Process for preparing olefins from polymers
By mixing the dehydrogenated polymer with olefin metathesis reagent and isomerization reagent, metathesis and isomerization treatment, the problem of difficult cleavage of carbon-carbon bonds is solved, and the effective conversion of waste plastics into carbon raw materials is achieved.
Patent Information
- Application Number
- CN202380060927.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Priority Date
- 2022-09-15
- Filing Date
- 2023-07-14
- Publication Date
- 2025-04-04
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
The prior art is difficult to effectively crack the carbon-carbon bond, resulting in the challenge of converting waste plastics into carbon raw materials.
Metalysis and isomerization treatment are performed to destroy the carbon-carbon bond by mixing the dehydrogenated polymer with the olefin metathesis reagent and isomerization reagent.
The effective cracking of carbon-carbon bonds is achieved, the conversion of waste plastics into carbon raw materials is promoted, and an efficient method is provided to treat waste plastics.
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Figure CN119768385A_ABST
Abstract
Description
[0001] CROSS-REFERENCE TO RELATED APPLICATIONS
[0002] This application claims priority to U.S. Provisional Application No. 63 / 389,591, filed on July 15, 2022, and U.S. Provisional Application No. 63 / 407,055, filed on September 15, 2022, the disclosures of which are incorporated herein by reference in their entirety and for all purposes.
[0003] STATEMENT REGARDING RIGHTS TO INVENTS RESULTING FROM FEDERALLY SPONSORED RESEARCH AND DEVELOPMENT
[0004] This invention was made with Government support under Grant No. DE-AC02-05CH11231 awarded by the Department of Energy. The Government has certain rights in this invention. Background Art
[0005] Conversion of polyolefins to small molecules (e.g., monomers) would enable the largest fraction of waste plastics to become carbon feedstocks, but this task requires the cleavage of carbon-carbon bonds, which are often resistant to selective chemical conversion. Solutions to these and other problems in the art are disclosed herein. Summary of the invention
[0006] In one aspect, a method for preparing olefins is provided, the method comprising mixing a dehydrogenated polymer with one or more olefin metathesis agents. In an embodiment, the method comprises mixing a dehydrogenated polymer with one or more olefin metathesis agents and one or more isomerization agents. In an embodiment, the dehydrogenated polymer comprises up to 10% unsaturated olefin monomer units. In an embodiment, the dehydrogenated polymer comprises at least 20 carbon atoms. In an embodiment, before mixing, the method comprises mixing the polymer with one or more dehydrogenated agents, thereby forming a dehydrogenated polymer. In an embodiment, the method comprises mixing the dehydrogenated polymer with one or more olefin metathesis agents and one or more isomerization agents; wherein: (i) the dehydrogenated polymer comprises up to 10% unsaturated olefin monomer units; (ii) the dehydrogenated polymer comprises at least 20 carbon atoms; or (iii) before mixing, the method comprises mixing the polymer with one or more dehydrogenated agents, thereby forming a dehydrogenated polymer.
[0007] In one aspect, a method for preparing a dehydrogenated polymer is provided, the method comprising mixing a polymer with one or more dehydrogenating agents, wherein: (i) 0.01% to 1.5% of the monomer units in the dehydrogenated polymer are unsaturated. In embodiments, 1.7% to 2.3% of the monomer units in the dehydrogenated polymer are unsaturated. In embodiments, 2.4% to 4.3% of the monomer units in the dehydrogenated polymer are unsaturated. In embodiments, 4.5% to 13.2% of the monomer units in the dehydrogenated polymer are unsaturated. In embodiments, the method comprises mixing a polymer with one or more dehydrogenation agents, wherein: (i) a percentage of the monomer units in the dehydrogenation polymer of 0.01% to 1.5%, or 1.7% to 2.3%, or 2.4% to 4.3%, or 4.5% to 13.2% are unsaturated; (ii) the dehydrogenation polymer has a number average molecular weight of about 2,200 Da or greater; (iii) the dehydrogenation polymer has a number average molecular weight of about 2,200 Da to about 6,500 Da, and a percentage of the monomer units in the dehydrogenation polymer of 0.01% to 10% are unsaturated; or (iv) the dehydrogenation polymer has a number average molecular weight of about 1,000 Da to about 500,000 Da, and a percentage of the monomer units in the dehydrogenation polymer of 0.01% to 1.5%, or 1.7% to 2.3%, or 2.4% to 4.3%, or 4.5% to 10% are unsaturated. In embodiments, the dehydrogenation polymer has a number average molecular weight of about 100 Da to about 2,200 Da. In embodiments, the dehydrogenation polymer has a number average molecular weight of about 2,200 Da or more. In embodiments, the dehydrogenation polymer has a number average molecular weight of about 2,200 Da to about 6,500 Da. In embodiments, the dehydrogenation polymer has a number average molecular weight of about 1,000 Da to about 500,000 Da.
[0008] In one aspect, a method for degrading a substance is provided, the method comprising: (i) performing one or more reactions to form one or more olefin units in the substance; (ii) after step (i), subjecting to conditions for olefin metathesis; and (iii) after step (i), subjecting to conditions for olefin isomerization.
[0009] In one aspect, a method of preparing a substituted or unsubstituted olefin is provided, the method comprising subjecting a dehydrogenated polymer to conditions for metathesis and conditions for olefin isomerization.
[0010] In one aspect, a method for preparing substituted or unsubstituted olefins is provided, the method comprising subjecting a first substance to conditions for metathesis and conditions for olefin isomerization; wherein: (i) the first substance comprises at least 20 carbon atoms per molecule; or (ii) before subjecting the first substance to conditions for metathesis and conditions for olefin isomerization, the method comprises subjecting a second substance to conditions for dehydrogenation, thereby forming the first substance.
[0011] On the one hand, a substituted or unsubstituted dehydrogenated polyethylene is provided, wherein 0.01% to 1.5%, or 1.7% to 2.3%, or 2.4% to 4.3%, or 4.5% to 13.2% of the percentage of monomer units are unsaturated (e.g., olefinic, such as monoolefins). In embodiments, 0.01% to 1.5%, or 1.7% to 2.3%, or 2.4% to 4.3%, or 4.5% to 13.2% of the percentage of monomer units are olefinic. In embodiments, 0.01% to 1.5% of the percentage of monomer units are olefinic. In embodiments, 1.7% to 2.3% of the percentage of monomer units are olefinic. In embodiments, 1.7% to 2.3% of the percentage of monomer units are olefinic. In embodiments, 2.4% to 4.3% of the percentage of monomer units are olefinic. In embodiments, 4.5% to 13.2% of the percentage of monomer units are olefinic.
[0012] In one aspect, provided is a substituted or unsubstituted dehydrogenated polyethylene having a number average molecular weight of 2,200 Da or greater. BRIEF DESCRIPTION OF THE DRAWINGS
[0013] Figures 1A to 1D .PE waste utilization strategy. Figure 1A : Degradation of PE by alkane metathesis with n-hexane (Huang 2016, Román-Leshkov 2021). Figure 1B : Conversion of PE into alkyl aromatics by tandem hydrogenolysis / aromatization (Scott 2020). Figure 1C : Degradation of PE by hydrogenolysis. Figure 1D : Conversion of PE to propylene via DIE (x = IE turnover number).
[0014] FIG. 2A to FIG. 2D .Test the conditions of DIE. Figure 2A : Homogeneous dehydrogenation of PE. Conditions for dehydrogenation: 0.42 mol% Ir- tBu POCOP, 0.46 mol% NaOtBu, 0.6 M PE solution, reaction was carried out with 0.4 equivalent TBE for 12 hours (mol%, equivalent TBE and M of PE are calculated relative to PE monomer units). Figure 2BHeterogeneous dehydrogenation of PE (HDPE, M) using a bimetallic catalyst supported on alumina n =26.1 kDa). Conditions: 20 wt% catalyst, 350° C. The catalyst was first activated under H 2 flow for 1 hour and then dehydrogenated under Ar flow for 16 hours. Figure 2C : GPC chromatograms of HDPE before and after ethenolysis with M-1. The conditions used for ethenolysis were: 0.36 M unsaturated PE solution, 3.6 mol% M-1 in p-xylene, heated to 130°C under 25 bar ethylene for 16 hours. Figure 2D :Long chain alkanes (C 24 H 50 ). The initial dehydrogenation produced olefins in 10% yield, followed by ethenolysis with M-1 to produce a statistical distribution of shorter chain olefins.
[0015] Figure 3A-3C .Development of conditions for DIE of PE. Figure 3A : Optimization of catalyst combination for IE of 1-octadecene. Conditions: 1-octadecene (0.5 M) was combined with an isomerization catalyst (3.0 mol%) and a metathesis catalyst (6.0 mol%) in p-xylene and heated to 60°C under 25 bar ethylene for 16 hours. (a) I-2 (6 mol%) was combined with Pd(OAc)2 (3 mol%) and methanesulfonic acid (30 mol%) to produce the active isomerization catalyst (25). The reaction was also carried out in THF to ensure catalyst solubility. (b) I-3 was activated by adding 1.5 equivalents of HBP relative to I-3 (also carried out in THF to ensure catalyst solubility). Figure 3B : IE was applied to dehydrogenated-polyethylene, where dehydrogenated-HDPE produced up to 80% propylene with 1.96% dehydrogenation. Conditions for IE for dehydrogenated PE: 3.6% M-1, 2.2% I-1, 1.78M PE solution, heated to 130°C in p-xylene at 25 bar ethylene for 16 hours. Figure 3C : Used to check background reactivity 13 DIE of C-labeled HDPE (conditions and Figure 3B The same conditions as in ).
[0016] Figure 4 . DIE of PE after use (conditions and Figure 3BThe conditions in the same). The propylene yield is reported as XX% (YY), where X is the yield obtained from the polymer purified by precipitation from acetone and Y is the yield obtained from the unmodified polymer. In cases where a single yield is reported, dehydrogenation of the unpurified sample is ineffective. From left to right: recycled HDPE (rHDPE) from can lids; HDPE from milk jugs; HDPE from shampoo bottles; LDPE from food packaging.
[0017] FIG. 5A to FIG. 5E .Study of reaction range and kinetics. Figure 5A : Time course of IE using 1-octadecene (100% yield = 458.3 mBar). Figure 5B : Time course of IE using dehydrogenated HDPE (1.41% olefins) (100% yield = 193.5 mBar). Figure 5C : Yields of IE on small molecules 1a-1d designed to evaluate the effect of branching on IE. Figure 5D : Yield of IE on small molecules 1e-1f designed to test the effect of dienes on IE. Figure 5E :Experiments using poly(cyclooctene) PCO (M n = designed to demonstrate the effect of polymer unsaturation on IE yield in the absence of branching). FIG. 5C to FIG. 5E The conditions of IE in Figure 3C The conditions are the same as in . DETAILED DESCRIPTION
[0018] I. Definitions
[0019] Abbreviations used herein have their conventional meanings within the chemical and biological arts.Chemical structures and formulae set forth herein are constructed according to standard rules of chemical valency known in the chemical arts.
[0020] When substituent groups are described by their conventional chemical formula written from left to right, these substituents equally encompass the chemically identical substituents resulting from writing the structure from right to left, for example, -CH2O- is equivalent to -OCH2-.
[0021] Unless otherwise indicated, the term "alkyl", by itself or as part of another substituent, means a straight (i.e., unbranched) or branched carbon chain (or carbons), or combinations thereof, which may be fully saturated, monounsaturated, or polyunsaturated, and may include monovalent, divalent, and polyvalent groups. An alkyl group may contain a specified number of carbons (e.g., C1-C 10Meaning one carbon to ten carbons). Alkyl is an uncyclized chain. Examples of saturated hydrocarbon groups include, but are not limited to, groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, sec-butyl, methyl, homologues and isomers of, for example, n-pentyl, n-hexyl, n-heptyl, n-octyl, etc. Unsaturated alkyl groups are alkyl groups with one or more double or triple bonds. Examples of unsaturated alkyl groups include, but are not limited to, vinyl, 2-propenyl, crotyl, 2-isopentenyl, 2-(butadienyl), 2,4-pentadienyl, 3-(1,4-pentadienyl), ethynyl, 1- and 3-propynyl, 3-butynyl, and higher homologues and isomers. Alkoxy is an alkyl group connected to the rest of the molecule via an oxygen linker (-O-). The alkyl moiety may be an alkenyl moiety. The alkyl moiety may be an alkynyl moiety. The alkyl moiety may be fully saturated. An alkenyl group may comprise more than one double bond and / or one or more triple bonds in addition to one or more double bonds. An alkynyl group may comprise more than one triple bond and / or one or more double bonds in addition to one or more triple bonds.
[0022] Unless otherwise stated, the term "alkylene" alone or as part of another substituent means a divalent group derived from an alkyl group, such as, but not limited to -CH2CH2CH2CH2-. Typically, an alkyl (or alkylene) group will have 1 to 24 carbon atoms, with those groups having 10 or less carbon atoms being preferred in this article. "Lower alkyl" or "lower alkylene" is a short-chain alkyl or alkylene group typically having eight or less carbon atoms. Unless otherwise stated, the term "alkenylene" by itself or as part of another substituent means a divalent group derived from an alkene. Unless otherwise stated, the term "alkynylene" by itself or as part of another substituent means a divalent group derived from an alkyne.
[0023] Unless otherwise indicated, the term "heteroalkyl" alone or in combination with another term means a stable straight or branched chain or combination thereof comprising at least one carbon atom and at least one heteroatom (e.g., O, N, P, Si, and S), and wherein the nitrogen and sulfur atoms may be optionally oxidized, and the nitrogen heteroatom may be optionally quaternized. One or more heteroatoms (e.g., O, N, S, Si, or P) may be placed at any interior position of the heteroalkyl group or at the position where the alkyl group is connected to the rest of the molecule. Heteroalkyl is an uncyclized chain. Examples include, but are not limited to: -CH2-CH2-O-CH3, -CH2-CH2-NH-CH3, -CH2-CH2-N(CH3)-CH3, -CH2-S-CH2-CH3, -CH2-S-CH2, -S(O)-CH3, -CH2-CH2-S(O)2-CH3, -CH=CH-O-CH3, -Si(CH3)3, -CH2-CH=N-OCH3, -CH=CH-N(CH3)-CH3, -O-CH3, -O-CH2-CH3 and -CN. Up to two or three heteroatoms may be consecutive, such as, for example, -CH2-NH-OCH3 and -CH2-O-Si(CH3)3. The heteroalkyl moiety may contain one heteroatom (e.g., O, N, S, Si or P). The heteroalkyl moiety may contain two optionally different heteroatoms (e.g., O, N, S, Si or P). The heteroalkyl moiety may include three optionally different heteroatoms (e.g., O, N, S, Si or P). The heteroalkyl moiety may include four optionally different heteroatoms (e.g., O, N, S, Si or P). The heteroalkyl moiety may include five optionally different heteroatoms (e.g., O, N, S, Si or P). The heteroalkyl moiety may include up to 8 optionally different heteroatoms (e.g., O, N, S, Si or P). Unless otherwise stated, the term "heteroalkenyl" by itself or in combination with another term means a heteroalkyl group comprising at least one double bond. The heteroalkenyl group may optionally include more than one double bond and / or one or more triple bonds in addition to one or more double bonds. Unless otherwise stated, the term "heteroalkynyl" by itself or in combination with another term means a heteroalkyl group comprising at least one triple bond. The heteroalkynyl group may optionally include more than one triple bond and / or one or more double bonds in addition to one or more triple bonds.
[0024] Similarly, unless otherwise indicated, the term "heteroalkylene" by itself or as part of another substituent means a divalent radical derived from a heteroalkyl group, such as, but not limited to, -CH2-CH2-S-CH2-CH2- and -CH2-S-CH2-CH2-NH-CH2-. For heteroalkylene groups, heteroatoms may also occupy either or both of the chain termini (e.g., alkyleneoxy, alkylenedioxy, alkyleneamino, alkylenediamino, etc.). Still further, for alkylene and heteroalkylene linking groups, the direction in which the formula of the linking group is written does not imply the orientation of the linking group. For example, the formula -C(O)2R'- represents both -C(O)2R'- and -R'C(O)2-. As described above, heteroalkyl groups as used herein include those groups that are attached to the rest of the molecule through a heteroatom, such as -C(O)R', -C(O)NR', -NR'R", -OR', -SR' and / or -S02R'. It should be understood that where "heteroalkyl" is recited after reciting a specific heteroalkyl group such as -NR'R", the terms heteroalkyl and -NR'R" are not redundant or mutually exclusive. Rather, the recitation of specific heteroalkyl groups is for added clarity. Therefore, the term "heteroalkyl" should not be interpreted herein to exclude specific heteroalkyl groups, such as -NR'R", etc.
[0025] Unless otherwise stated, the terms "cycloalkyl" and "heterocycloalkyl" mean the cyclic forms of "alkyl" and "heteroalkyl" respectively, either alone or in combination with other terms. Cycloalkyl and heterocycloalkyl are not aromatic. In addition, for heterocycloalkyl, heteroatoms can occupy the position where the heterocycle is connected to the rest of the molecule. Examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-cyclohexenyl, 3-cyclohexenyl, cycloheptyl, etc. Examples of heterocycloalkyl include, but are not limited to, 1-(1,2,5,6-tetrahydropyridyl), 1-piperidyl, 2-piperidyl, 3-piperidyl, 4-morpholinyl, 3-morpholinyl, tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, tetrahydrothiophene-2-yl, tetrahydrothiophene-3-yl, 1-piperazinyl, 2-piperazinyl, etc. "Cycloalkylene" and "heterocycloalkylene" alone or as part of another substituent mean a divalent radical derived from cycloalkyl and heterocycloalkyl, respectively.
[0026] In embodiments, the term "cycloalkyl" means a monocyclic, bicyclic or polycyclic cycloalkyl ring system. In embodiments, a monocyclic ring system is a cyclic hydrocarbon group containing 3 to 8 carbon atoms, wherein such groups may be saturated or unsaturated, but not aromatic. In embodiments, a cycloalkyl group is fully saturated. Examples of monocyclic cycloalkyls include cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl and cyclooctyl. Bicyclic cycloalkyl ring systems are bridged monocyclic or fused bicyclic rings. In embodiments, a bridged monocyclic ring contains a monocyclic cycloalkyl ring in which two non-adjacent carbon atoms of the monocyclic ring are connected by an alkylene bridge between a carbon atom and three additional carbon atoms (i.e., in the form of (CH2) w In some embodiments, the fused bicyclic cycloalkyl ring system contains a monocyclic cycloalkyl ring fused to any of a phenyl, a monocyclic cycloalkyl, a monocyclic cycloalkenyl, a monocyclic heterocyclyl, or a monocyclic heteroaryl. In some embodiments, the bridged or fused bicyclic cycloalkyl is attached to the parent molecular moiety via any carbon atom contained within the monocyclic cycloalkyl ring. In some embodiments, the cycloalkyl group is optionally substituted with one or two groups that are independently oxo or thia. In an embodiment, the fused bicyclic cycloalkyl is a 5- or 6-membered monocyclic cycloalkyl ring fused to a benzene ring, a 5- or 6-membered monocyclic cycloalkyl, a 5- or 6-membered monocyclic cycloalkenyl, a 5- or 6-membered monocyclic heterocyclyl, or a 5- or 6-membered monocyclic heteroaryl, wherein the fused bicyclic cycloalkyl is optionally substituted by one or two groups that are independently oxo or thio. In an embodiment, the polycyclic cycloalkyl ring system is a monocyclic cycloalkyl ring (base ring) fused to the following items: (i) a ring system selected from the group consisting of bicyclic aryl, bicyclic heteroaryl, bicyclic cycloalkyl, bicyclic cycloalkenyl, and bicyclic heterocyclyl; or (ii) two other ring systems independently selected from the group consisting of phenyl, bicyclic aryl, monocyclic or bicyclic heteroaryl, monocyclic or bicyclic cycloalkyl, monocyclic or bicyclic cycloalkenyl, and monocyclic or bicyclic heterocyclyl. In an embodiment, the polycyclic cycloalkyl is connected to the parent molecular moiety through any carbon atom contained in the base ring. In an embodiment, the polycyclic cycloalkyl ring system is a monocyclic cycloalkyl ring (base ring) fused to: (i) one ring system selected from the group consisting of bicyclic aryl, bicyclic heteroaryl, bicyclic cycloalkyl, bicyclic cycloalkenyl and bicyclic heterocyclyl; or (ii) two other ring systems independently selected from the group consisting of phenyl, monocyclic heteroaryl, monocyclic cycloalkyl, monocyclic cycloalkenyl and monocyclic heterocyclyl. Examples of polycyclic cycloalkyl groups include, but are not limited to, tetradecahydrophenanthrenyl, perhydrophenothiazine-1-yl and perhydrophenoxazine-1-yl.
[0027] In an embodiment, cycloalkyl is a cycloalkenyl. The term "cycloalkenyl" is used according to its common general meaning. In an embodiment, cycloalkenyl is a monocyclic, bicyclic or polycyclic cycloalkenyl ring system. In an embodiment, a monocyclic cycloalkenyl ring system is a cyclic hydrocarbon group containing 3 to 8 carbon atoms, wherein such a group is unsaturated (i.e., contains at least one annular carbon-carbon double bond), but is not aromatic. Examples of monocyclic cycloalkenyl ring systems include cyclopentenyl and cyclohexenyl. In an embodiment, a bicyclic cycloalkenyl ring is a bridged monocyclic or fused bicyclic ring. In an embodiment, a bridged monocyclic ring contains a monocyclic cycloalkenyl ring in which two non-adjacent carbon atoms of the monocyclic ring are connected by an alkylene bridge between a carbon atom and three additional carbon atoms (i.e., in the form of (CH2) w In some embodiments, the bicyclic cycloalkenyl group is a bridging group of cycloalkenyl, wherein w is 1, 2 or 3). Representative examples of bicyclic cycloalkenyl groups include, but are not limited to, norbornenyl and bicyclo[2.2.2]oct2enyl. In embodiments, the fused bicyclic cycloalkenyl ring system contains a monocyclic cycloalkenyl ring fused to any of a phenyl, a monocyclic cycloalkyl, a monocyclic cycloalkenyl, a monocyclic heterocyclyl or a monocyclic heteroaryl. In embodiments, the bridged or fused bicyclic cycloalkenyl is attached to the parent molecular moiety via any carbon atom contained within the monocyclic cycloalkenyl ring. In embodiments, the cycloalkenyl group is optionally substituted with one or two groups that are independently oxo or thio. In an embodiment, the polycyclic cycloalkenyl ring contains a monocyclic cycloalkenyl ring (base ring) fused to (i) one ring system selected from the group consisting of bicyclic aryl, bicyclic heteroaryl, bicyclic cycloalkyl, bicyclic cycloalkenyl, and bicyclic heterocyclyl; or (ii) two ring systems independently selected from the group consisting of phenyl, bicyclic aryl, monocyclic or bicyclic heteroaryl, monocyclic or bicyclic cycloalkyl, monocyclic or bicyclic cycloalkenyl, and monocyclic or bicyclic heterocyclyl. In an embodiment, the polycyclic cycloalkenyl is attached to the parent molecular moiety via any carbon atom contained within the base ring. In an embodiment, the polycyclic cycloalkenyl ring contains a monocyclic cycloalkenyl ring (base ring) fused to (i) one ring system selected from bicyclic cycloalkyl, bicyclic cycloalkenyl, and bicyclic heterocyclyl; or (ii) two ring systems independently selected from monocyclic cycloalkyl, monocyclic cycloalkenyl, and monocyclic heterocyclyl.
[0028] In embodiments, heterocycloalkyl is a heterocyclic radical. As used herein, the term "heterocyclic radical" means monocyclic, bicyclic or polycyclic heterocycles. Heterocyclic radical monocyclic heterocycle is a 3-, 4-, 5-, 6- or 7-ring containing at least one heteroatom independently selected from the group consisting of O, N and S, wherein the ring is saturated and or unsaturated, but not aromatic. A 3- or 4-ring contains 1 heteroatom selected from O, N and S. A 5-ring can contain zero or one double bond and one, two or three heteroatoms selected from O, N and S. A 6- or 7-ring contains zero, one or two double bonds and one, two or three heteroatoms selected from O, N and S. A heterocyclic radical monocyclic heterocycle is connected to the parent molecular moiety by any carbon atom or any nitrogen atom contained in the heterocyclic radical monocyclic heterocycle. Representative examples of heterocyclyl monocyclic heterocycles include, but are not limited to, azetidinyl, azepanyl, aziridinyl, diazepanyl, 1,3-dioxanyl, 1,3-dioxolanyl, 1,3-dithiopentyl, 1,3-dithianyl, imidazolinyl, imidazolidinyl, isothiazolinyl, isothiazolidinyl, isoxazolyl, isoxazolidinyl, morpholinyl, oxadiazolinyl, oxadiazolidinyl, oxazolinyl, oxazolidinyl, piperazinyl, piperidinyl, pyranyl, pyrazolinyl, thiazolidinyl, pyrrolinyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydrothiophenyl, thiadiazolinyl, thiadiazolinyl, thiazolinyl, thiazolidinyl, thiamorpholinyl, 1,1-dioxidothiomorpholinyl (thiomorpholine sulfone), thiopyranyl, and trithianyl. Heterocyclyl bicyclic heterocycle is a monocyclic heterocycle fused to any one of phenyl, monocyclic cycloalkyl, monocyclic cycloalkenyl, monocyclic heterocycle or monocyclic heteroaryl.Heterocyclyl bicyclic heterocycle is connected to the parent molecular part by any carbon atom or any nitrogen atom contained in the monocyclic heterocyclic ring part of the bicyclic ring system.Representative examples of bicyclic heterocyclic radicals include but are not limited to 2,3-dihydrobenzofuran-2-yl, 2,3-dihydrobenzofuran-3-yl, indol-1-yl, indol-2-yl, indol-3-yl, 2,3-dihydrobenzothiophene-2-yl, decahydroquinolyl, decahydroisoquinolyl, octahydro-1H-indolyl and octahydrobenzofuranyl.In an embodiment, the heterocyclyl group is optionally substituted by one or two groups that are independently oxo or thio. In certain embodiments, the bicyclic heterocyclyl is a 5- or 6-membered monocyclic heterocycle, a 5- or 6-membered monocyclic cycloalkyl, a 5- or 6-membered monocyclic cycloalkenyl, a 5- or 6-membered monocyclic heterocyclyl, or a 5- or 6-membered monocyclic heteroaryl fused to a benzene ring, wherein the bicyclic heterocyclyl is optionally substituted by one or two groups that are independently oxo or thio. The polycyclic heterocyclyl ring system is a monocyclic heterocyclyl ring (base ring) fused to (i) a ring system selected from the group consisting of bicyclic aryl, bicyclic heteroaryl, bicyclic cycloalkyl, bicyclic cycloalkenyl, and bicyclic heterocyclyl; or (ii) two other ring systems independently selected from the group consisting of phenyl, bicyclic aryl, monocyclic or bicyclic heteroaryl, monocyclic or bicyclic cycloalkyl, monocyclic or bicyclic cycloalkenyl, and monocyclic or bicyclic heterocyclyl.The polycyclic heterocyclyl is attached to the parent molecular moiety via any carbon atom or nitrogen atom contained within the base ring. In an embodiment, the polycyclic heterocyclyl ring system is a monocyclic heterocyclyl ring (base ring) fused to (i) one ring system selected from the group consisting of bicyclic aryl, bicyclic heteroaryl, bicyclic cycloalkyl, bicyclic cycloalkenyl, and bicyclic heterocyclyl; or (ii) two other ring systems independently selected from the group consisting of phenyl, monocyclic heteroaryl, monocyclic cycloalkyl, monocyclic cycloalkenyl, and monocyclic heterocyclyl. Examples of polycyclic heterocyclyl groups include, but are not limited to, 10H-phenothiazin-10-yl, 9,10-dihydroacridin-9-yl, 9,10-dihydroacridin-10-yl, 10H-phenoxazin-10-yl, 10,11-dihydro-5H-dibenzo[b,f]azepin-5-yl, 1,2,3,4-tetrahydropyrido[4,3-g]isoquinolin-2-yl, 12H-benzo[b]phenoxazin-12-yl, and dodecahydro-1H-carbazol-9-yl.
[0029] Unless otherwise indicated, the term "halo" or "halogen" by itself or as part of another substituent means a fluorine, chlorine, bromine or iodine atom. Additionally, terms such as "haloalkyl" are meant to include monohaloalkyl and polyhaloalkyl. For example, the term "halo (C1-C4) alkyl" includes, but is not limited to, fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 4-chlorobutyl, 3-bromopropyl, and the like.
[0030] Unless otherwise indicated, the term "acyl" means -C(O)R, where R is substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.
[0031] Unless otherwise specified, the term "aryl" means a polyunsaturated aromatic hydrocarbon substituent, which can be a monocyclic or polycyclic ring (preferably 1 to 3 rings) fused together (i.e., fused ring aryl) or covalently linked. A fused ring aryl refers to a plurality of rings fused together, wherein at least one of the fused rings is an aryl ring. The term "heteroaryl" refers to an aryl group (or ring) containing at least one heteroatom (such as N, O or S), wherein the nitrogen atom and the sulfur atom are optionally oxidized, and the nitrogen atom is optionally quaternized. Therefore, the term "heteroaryl" includes fused ring heteroaryl groups (i.e., a plurality of rings fused together, wherein at least one of the fused rings is a heteroaromatic ring). 5,6-fused ring heteroaryl substituents refer to two rings fused together, wherein one ring has 5 members and the other ring has 6 members, and wherein at least one ring is a heteroaryl ring. Similarly, 6,6-fused ring heteroaryl substituents refer to two rings fused together, wherein one ring has 6 members and the other ring has 6 members, and wherein at least one ring is a heteroaryl ring. And 6,5-fused ring heteroarylene refers to two rings fused together, where one ring has 6 members and the other ring has 5 members, and where at least one ring is a heteroaryl ring. The heteroaryl group can be attached to the rest of the molecule through a carbon or heteroatom. Non-limiting examples of aryl and heteroaryl groups include phenyl, naphthyl, pyrrolyl, pyrazolyl, pyridazinyl, triazinyl, pyrimidinyl, imidazolyl, pyrazinyl, purinyl, oxazolyl, isoxazolyl, thiazolyl, furanyl, thienyl, pyridyl, pyrimidinyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzofuran, isobenzofuranyl, indolyl, isoindolyl, benzothienyl, isoquinolyl, quinoxalinyl, quinolyl, 1-naphthyl, 2-naphthyl, 4-biphenyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 2-imidazolyl, 4-imidazole Substituents for each of the above noted aryl and heteroaryl ring systems are selected from the group of acceptable substituents described below. "Arylene" and "heteroarylene" alone or as part of another substituent mean a divalent radical derived from aryl and heteroaryl, respectively. A heteroaryl group substituent may be -O- bonded to a ring heteroatom nitrogen.
[0032] A fused ring heterocycloalkyl-aryl is an aryl fused to a heterocycloalkyl. A fused ring heterocycloalkyl-heteroaryl is a heteroaryl fused to a heterocycloalkyl. A fused ring heterocycloalkyl-cycloalkyl is a heterocycloalkyl fused to a cycloalkyl. A fused ring heterocycloalkyl-heterocycloalkyl is a heterocycloalkyl fused to another heterocycloalkyl. A fused ring heterocycloalkyl-aryl, a fused ring heterocycloalkyl-heteroaryl, a fused ring heterocycloalkyl-cycloalkyl or a fused ring heterocycloalkyl-heterocycloalkyl may each independently be unsubstituted or substituted with one or more of the substituents described herein.
[0033] Spirocycle is two or more rings in which adjacent rings are connected by a single atom. The single ring in the spirocycle can be the same or different. The single ring in the spirocycle can be substituted or unsubstituted, and can have a substituent different from other single rings in the spirocycle set. The possible substituents of each ring in the spirocycle are possible substituents of the same ring (when not a part of the spirocycle) (for example, substituents of cycloalkyl rings or heterocycloalkyl rings). The spirocycle can be a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted cycloalkylene, a substituted or unsubstituted heterocycloalkyl or a substituted or unsubstituted heterocycloalkylene, and each ring in the spirocyclic group can be any ring of the previous list, including all rings with one type (for example, all rings are substituted heterocycloalkylene, wherein each ring can be the same or different substituted heterocycloalkylene). When referring to the spirocycle system, heterocyclic spirocycle means that at least one ring is a heterocycle and each ring can be a spirocycle of different rings. When referring to the spirocycle system, the substituted spirocycle means that at least one ring is substituted and each substituent can be optionally different.
[0034] symbol Indicates the point of attachment of a chemical moiety to the rest of a molecule or chemical formula.
[0035] As used herein, the term "oxo" means an oxygen double-bonded to a carbon atom.
[0036] The term "alkylarylene" is an arylene moiety covalently bonded to an alkylene moiety (also referred to herein as an alkylene linker). In an embodiment, the alkylarylene group has the formula:
[0037]
[0038] The alkylarylene moiety can be substituted (e.g., with a substituent group) on the alkylene moiety or the arylene linker (e.g., at carbon 2, 3, 4, or 6) with halogen, oxo, -N3, -CF3, -CCl3, -CBr3, -CI3, -CN, -C(O)H, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO2CH3, -SO3H, -OSO3H, -SO2NH2, -NHNH2, -ONH2, -NHC(O)NHNH2, substituted or unsubstituted C1-C5 alkyl, or substituted or unsubstituted 2- to 5-membered heteroalkyl. In an embodiment, the alkylarylene is unsubstituted.
[0039] As used herein, the term "alkylsulfonyl" means a moiety having the formula -S(O2)-R', wherein R' is a substituted or unsubstituted alkyl group as defined above. R' may have a specified number of carbons (eg, "C1-C4 alkylsulfonyl").
[0040] Each of the above terms (eg, "alkyl," "heteroalkyl," "cycloalkyl," "heterocycloalkyl," "aryl," and "heteroaryl") includes substituted and unsubstituted forms of the indicated radical. Preferred substituents for each type of radical are provided below.
[0041] Substituents for alkyl and heteroalkyl groups (including those groups often referred to as alkylene, alkenyl, heteroalkylene, heteroalkenyl, alkynyl, cycloalkyl, heterocycloalkyl, cycloalkenyl, and heterocycloalkenyl) may be one or more of a variety of groups selected from, but not limited to, -OR', =O, =NR', =N-OR', -NR'R", -SR', -halogen, -SiR'R"R"', -OC(O)R', -C(O)R', -C02R', -CONR'R", -O(O)R', ... C(O)NR'R", -NR"C(O)R', -NR'-C(O)NR"R"', -NR"C(O)2R', -NR-C(NR'R"R"')=NR"", -NR-C(NR'R")= NR"′, -S(O)R', -S(O)2R', -S(O)2NR'R", -NRSO2R', -NR'NR"R"', -ONR'R", -NR'C(O)NR"NR"′R"", -C N, -NO2, -NR'SO2R", -NR'C(O)R", -NR'C(O)OR", -NR'OR", the number of which ranges from zero to (2m'+1), where m' is the total number of carbon atoms in such groups. R, R', R", R'" and R"" each preferably independently represent hydrogen, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl (e.g., substituted with 1 to 3 halogens). substituted aryl), substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, alkoxy or thioalkoxy group or aralkyl group. When the compounds described herein contain more than one R group, for example, each of the R groups is independently selected, such as when there are more than one of these groups, each R' group, R" group, R"' group and R"" group are independently selected. When R' and R" are connected to the same nitrogen atom, they can be combined with the nitrogen atom to form a 4-, 5-, 6- or 7-membered ring. For example, -NR'R" includes but is not limited to 1-pyrrolidinyl and 4-morpholinyl. According to the above discussion of substituents, those skilled in the art will understand that the term "alkyl" is intended to include groups containing carbon atoms bound to groups other than hydrogen groups, such as haloalkyl (e.g., -CF3 and -CH2CF3) and acyl (e.g., -C(O)CH3, -C(O)CF3, -C(O)CH2OCH3, etc.).
[0042] Similar to the substituents described for the alkyl radicals, the substituents for the aryl and heteroaryl groups are different and are selected from, for example: -OR', -NR'R", -SR', -halogen, -SiR'R"R"', -OC(O)R', -C(O)R', -C02R', -CONR'R", -OC(O)NR'R", -NR"C(O)R', -NR'-C(O)NR"R"', -NR"C(O)2R', -NR-C(NR'R"R"')=NR"", -NR-C(NR'R")=NR"', -S(O)R', -S(O)2R', -S(O)2NR'R", -NRSO2R', -NR'NR"R"', -ONR'R", -NR'C(O)NR"NR"'R"", -CN, -NO 2, -R', -N3, -CH(Ph)2, fluoro(C1-C4)alkoxy and fluoro(C1-C4)alkyl, -NR'SO2R", -NR'C(O)R", -NR'C(O)-OR", -NR'OR", in a number ranging from zero to the total number of open valences on the aromatic ring system; and wherein R', R", R"' and R"" are preferably independently selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl. When the compounds described herein contain more than one R group, for example, each of the R groups is independently selected as each R' group, R" group, R"' group and R"" group is independently selected when more than one of these groups is present.
[0043] The substituents of a ring (e.g., cycloalkyl, heterocycloalkyl, aryl, heteroaryl, cycloalkylene, heterocycloalkylene, arylidene or heteroarylidene) can be depicted as substituents on the ring rather than on a specific atom of the ring (commonly referred to as floating substituents). In this case, the substituent can be connected to any of the ring atoms (following the rules of chemical valence), and in the case of a fused ring or spiro ring, the substituent depicted as being associated with one member of the fused ring or spiro ring (floating substituent on a single ring) can be a substituent on any of the fused rings or spiro rings (floating substituents on multiple rings). When the substituent is connected to the ring rather than a specific atom (floating substituent) and the subscript of the substituent is an integer greater than one, multiple substituents can be located on the same atom, the same ring, different atoms, different fused rings, different spiro rings, and each substituent can be optionally different. In the case where the point of connection of the ring to the rest of the molecule is not limited to a single atom (floating substituent), the point of connection can be any atom of the ring, and in the case of a fused ring or spiro ring, it can be any atom of any of the fused rings or spiro rings (following the rules of chemical valence). In the case where a ring, fused ring or spiro ring contains one or more ring heteroatoms and the ring, fused ring or spiro ring is shown as having yet another floating substituent (including but not limited to a point of attachment to the rest of the molecule), the floating substituent may be bonded to the heteroatom. When a ring heteroatom is shown bonded to one or more hydrogens in a structure or formula having a floating substituent (e.g., a ring nitrogen with two bonds to a ring atom and a third bond to a hydrogen), when the heteroatom is bonded to the floating substituent, the substituent will be understood to replace the hydrogen while following chemical valence rules.
[0044] Two or more substituents can be optionally connected to form aryl, heteroaryl, cycloalkyl or heterocycloalkyl groups. This so-called ring-forming substituent is usually (although not necessarily) connected to the cyclic base structure. In one embodiment, the ring-forming substituent is connected to the adjacent members of the base structure. For example, two ring-forming substituents connected to the adjacent members of the cyclic base structure produce condensed ring structure. In another embodiment, the ring-forming substituent is connected to a single member of the base structure. For example, two ring-forming substituents connected to a single member of the cyclic base structure produce spirocyclic structure. In another embodiment, the ring-forming substituent is connected to the non-adjacent members of the base structure.
[0045] Two substituents on adjacent atoms of an aryl or heteroaryl ring may optionally form a group of the formula -TC(O)-(CRR') q -U-, wherein T and U are independently -NR-, -O-, -CRR'- or a single bond, and q is an integer from 0 to 3. Alternatively, two substituents on adjacent atoms of the aryl or heteroaryl ring may be optionally replaced by a substituent of the formula -A-(CH2) r-B-, wherein A and B are independently -CRR'-, -O-, -NR-, -S-, -S(O)-, -S(O)2-, -S(O)2NR'- or a single bond, and r is an integer from 1 to 4. One of the single bonds of the new ring so formed may optionally be replaced by a double bond. Alternatively, two substituents on adjacent atoms of the aryl or heteroaryl ring may optionally be replaced by a substituent of the formula -(CRR') s -X′-(C"R"R"′) d -, wherein s and d are independently integers from 0 to 3, and X' is -O-, -NR'-, -S-, -S(O)-, -S(O)2- or -S(O)2NR'-. The substituents R, R', R" and R"' are preferably independently selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl.
[0046] As used herein, the term "heteroatom" or "ring heteroatom" is meant to include oxygen (O), nitrogen (N), sulfur (S), phosphorus (P), and silicon (Si).
[0047] As used herein, "substituent group" means a group selected from the following moieties:
[0048] (A) oxo, halogen, -CCl3, -CBr3, -CF3, -CI3, CHCl2, -CHBr2, -CHF2, -CHI2, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, -NHNH2, -ONH2, -NHC(O)NHNH2, -NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -OCCl3, -OCF3, -OCBr3, -OCI3 , -OCHCl2, -OCHBr2, -OCHI2, -OCHF2, -OCH2Cl, -OCH2Br, -OCHI, -OCH2F, -N3, unsubstituted alkyl (e.g., C1-C8 alkyl, C1-C6 alkyl, or C1-C4 alkyl), unsubstituted heteroalkyl (e.g., 2- to 8-membered heteroalkyl, 2- to 6-membered heteroalkyl, or 2- to 4-membered heteroalkyl), unsubstituted cycloalkyl (e.g., C3-C8 cycloalkyl, C3-C6 cycloalkyl, or C5-C6 cycloalkyl), unsubstituted heterocycloalkyl (e.g., 3- to 8-membered heterocycloalkyl, 3- to 6-membered heterocycloalkyl, or 5- to 6-membered heterocycloalkyl), unsubstituted aryl (e.g., C6-C 10 Aryl, C 10aryl or phenyl) or unsubstituted heteroaryl (e.g., 5- to 10-membered heteroaryl, 5- to 9-membered heteroaryl, or 5- to 6-membered heteroaryl), and
[0049] (B) alkyl (e.g., C1-C 20 、C1-C 12 , C1-C8, C1-C6, C1-C4 or C1-C2), heteroalkyl (e.g., 2-20, 2-12, 2-8, 2-6, 4-6, 2-3 or 4-5), cycloalkyl (e.g., C3-C 10 , C3-C8, C3-C6, C4-C6 or C5-C6), heterocycloalkyl (e.g., 3-10, 3-8, 3-6, 4-6, 4-5 or 5-6), aryl (e.g., C6-C 12 、C6-C 10 or phenyl) or heteroaryl (e.g., 5- to 12-membered, 5- to 10-membered, 5- to 9-membered, or 5- to 6-membered), substituted with at least one substituent selected from:
[0050] (i) oxo, halogen, -CCl3, -CBr3, -CF3, -CI3, CHCl2, -CHBr2, -CHF2, -CHI2, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, -NHNH2, -ONH2, -NHC(O)NHNH2, -NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -OCCl3, -OCF3, -OCBr3, -OCI3 , -OCHCl2, -OCHBr2, -OCHI2, -OCHF2, -OCH2Cl, -OCH2Br, -OCHI, -OCH2F, -N3, unsubstituted alkyl (e.g., C1-C8 alkyl, C1-C6 alkyl, or C1-C4 alkyl), unsubstituted heteroalkyl (e.g., 2- to 8-membered heteroalkyl, 2- to 6-membered heteroalkyl, or 2- to 4-membered heteroalkyl), unsubstituted cycloalkyl (e.g., C3-C8 cycloalkyl, C3-C6 cycloalkyl, or C5-C6 cycloalkyl), unsubstituted heterocycloalkyl (e.g., 3- to 8-membered heterocycloalkyl, 3- to 6-membered heterocycloalkyl, or 5- to 6-membered heterocycloalkyl), unsubstituted aryl (e.g., C6-C 10 Aryl, C 10 aryl or phenyl) or unsubstituted heteroaryl (e.g., 5- to 10-membered heteroaryl, 5- to 9-membered heteroaryl, or 5- to 6-membered heteroaryl), and
[0051] (ii) alkyl (e.g., C1-C 20 、C1-C 12 , C1-C8, C1-C6, C1-C4 or C1-C2), heteroalkyl (e.g., 2-20, 2-12, 2-8, 2-6, 4-6, 2-3 or 4-5), cycloalkyl (e.g., C3-C 10 , C3-C8, C3-C6, C4-C6 or C5-C6), heterocycloalkyl (e.g., 3-10, 3-8, 3-6, 4-6, 4-5 or 5-6), aryl (e.g., C6-C 12 、C6-C 10 or phenyl) or heteroaryl (e.g., 5- to 12-membered, 5- to 10-membered, 5- to 9-membered, or 5- to 6-membered), substituted with at least one substituent selected from:
[0052] (a) oxo, halogen, -CCl3, -CBr3, -CF3, -CI3, CHCl2, -CHBr2, -CHF2, -CHI2, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, -NHNH2, -ONH2, -NHC(O)NHNH2, -NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -OCCl3, -OCF3, -OCBr3, -OCI3 , -OCHCl2, -OCHBr2, -OCHI2, -OCHF2, -OCH2Cl, -OCH2Br, -OCHI, -OCH2F, -N3, unsubstituted alkyl (e.g., C1-C8 alkyl, C1-C6 alkyl, or C1-C4 alkyl), unsubstituted heteroalkyl (e.g., 2- to 8-membered heteroalkyl, 2- to 6-membered heteroalkyl, or 2- to 4-membered heteroalkyl), unsubstituted cycloalkyl (e.g., C3-C8 cycloalkyl, C3-C6 cycloalkyl, or C5-C6 cycloalkyl), unsubstituted heterocycloalkyl (e.g., 3- to 8-membered heterocycloalkyl, 3- to 6-membered heterocycloalkyl, or 5- to 6-membered heterocycloalkyl), unsubstituted aryl (e.g., C6-C 10 Aryl, C 10 aryl or phenyl) or unsubstituted heteroaryl (e.g., 5- to 10-membered heteroaryl, 5- to 9-membered heteroaryl, or 5- to 6-membered heteroaryl), and
[0053] (b) alkyl (e.g., C1-C 20 、C1-C 12, C1-C8, C1-C6, C1-C4 or C1-C2), heteroalkyl (e.g., 2-20, 2-12, 2-8, 2-6, 4-6, 2-3 or 4-5), cycloalkyl (e.g., C3-C 10 , C3-C8, C3-C6, C4-C6 or C5-C6), heterocycloalkyl (e.g., 3-10, 3-8, 3-6, 4-6, 4-5 or 5-6), aryl (e.g., C6-C 12 、C6-C 10 or phenyl) or heteroaryl (e.g., 5-12 membered, 5-10 membered, 5-9 membered, or 5-6 membered) substituted with at least one substituent selected from the group consisting of oxo, halogen, -CCl3, -CBr3, -CF3, -CI3, -CHCl2, -CHBr2, -CHF2, -CHI2, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, -NHNH2, -ONH2, -NHC(O)NHNH2, -NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHO -H, -OCCl3, -OCF3, -OCBr3, -OCI3, -OCHCl2, -OCHBr2, -OCHI2, -OCHF2, -OCH2Cl, -OCH2Br, -OCHI, -OCH2F, -N3, unsubstituted alkyl (e.g., C1-C8 alkyl, C1-C6 alkyl, or C1-C4 alkyl), unsubstituted heteroalkyl (e.g., 2- to 8-membered heteroalkyl, 2- to 6-membered heteroalkyl, or 2- to 4-membered heteroalkyl), unsubstituted cycloalkyl (e.g., C3-C8 cycloalkyl, C3-C6 cycloalkyl, or C5-C6 cycloalkyl), unsubstituted heterocycloalkyl (e.g., 3- to 8-membered heterocycloalkyl, 3- to 6-membered heterocycloalkyl, or 5- to 6-membered heterocycloalkyl), unsubstituted aryl (e.g., C6-C 10 Aryl, C 10 The present invention also comprises unsubstituted heteroaryl (e.g., 5- to 10-membered heteroaryl, 5- to 9-membered heteroaryl, or 5- to 6-membered heteroaryl).
[0054] As used herein, "a substituent of limited size" or "a substituent group of limited size" means a group selected from all substituents described above for a "substituent group", wherein each substituted or unsubstituted alkyl group is a substituted or unsubstituted C1-C 20alkyl, each substituted or unsubstituted heteroalkyl is a substituted or unsubstituted 2- to 20-membered heteroalkyl, each substituted or unsubstituted cycloalkyl is a substituted or unsubstituted C3-C8 cycloalkyl, each substituted or unsubstituted heterocycloalkyl is a substituted or unsubstituted 3- to 8-membered heterocycloalkyl, each substituted or unsubstituted aryl is a substituted or unsubstituted C6-C 10 The aryl group is an aryl group, and each substituted or unsubstituted heteroaryl group is a substituted or unsubstituted 5- to 10-membered heteroaryl group.
[0055] As used herein, "lower substituent" or "lower substituent group" means a group selected from all substituents described above for "substituent group", wherein each substituted or unsubstituted alkyl is a substituted or unsubstituted C1-C8 alkyl, each substituted or unsubstituted heteroalkyl is a substituted or unsubstituted 2-membered to 8-membered heteroalkyl, each substituted or unsubstituted cycloalkyl is a substituted or unsubstituted C3-C7 cycloalkyl, each substituted or unsubstituted heterocycloalkyl is a substituted or unsubstituted 3-membered to 7-membered heterocycloalkyl, each substituted or unsubstituted aryl is a substituted or unsubstituted phenyl, and each substituted or unsubstituted heteroaryl is a substituted or unsubstituted 5-membered to 6-membered heteroaryl.
[0056] In some embodiments, each substituted group described in the compounds herein is substituted by at least one substituent group. More specifically, in some embodiments, each substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, substituted heteroaryl, substituted alkylene, substituted sub-assorted alkyl, substituted cycloalkylene, substituted sub-heterocycloalkylene, substituted arylene and / or substituted sub-heteroaryl described in the compounds herein is substituted by at least one substituent group. In other embodiments, at least one or all of these groups are substituted by at least one substituent group of limited size. In other embodiments, at least one or all of these groups are substituted by at least one low-level substituent group.
[0057] In other embodiments of the compounds herein, each substituted or unsubstituted alkyl group may be a substituted or unsubstituted C1-C 20 alkyl, each substituted or unsubstituted heteroalkyl is a substituted or unsubstituted 2- to 20-membered heteroalkyl, each substituted or unsubstituted cycloalkyl is a substituted or unsubstituted C3-C8 cycloalkyl, each substituted or unsubstituted heterocycloalkyl is a substituted or unsubstituted 3- to 8-membered heterocycloalkyl, each substituted or unsubstituted aryl is a substituted or unsubstituted C6-C 10 aryl, and / or each substituted or unsubstituted heteroaryl is a substituted or unsubstituted 5- to 10-membered heteroaryl. In some embodiments of the compounds herein, each substituted or unsubstituted alkylene is a substituted or unsubstituted C1-C 20alkylene, each substituted or unsubstituted heteroalkylene is a substituted or unsubstituted 2- to 20-membered heteroalkylene, each substituted or unsubstituted cycloalkylene is a substituted or unsubstituted C3-C8 cycloalkylene, each substituted or unsubstituted heterocycloalkylene is a substituted or unsubstituted 3- to 8-membered heterocycloalkylene, each substituted or unsubstituted arylene is a substituted or unsubstituted C6-C 10 The arylene group and / or each substituted or unsubstituted heteroarylene group is a substituted or unsubstituted 5- to 10-membered heteroarylene group.
[0058] In some embodiments, each substituted or unsubstituted alkyl is a substituted or unsubstituted C1-C8 alkyl, each substituted or unsubstituted heteroalkyl is a substituted or unsubstituted 2- to 8-membered heteroalkyl, each substituted or unsubstituted cycloalkyl is a substituted or unsubstituted C3-C7 cycloalkyl, each substituted or unsubstituted heterocycloalkyl is a substituted or unsubstituted 3- to 7-membered heterocycloalkyl, each substituted or unsubstituted aryl is a substituted or unsubstituted C6-C 10 In some embodiments, each substituted or unsubstituted alkylene group is a substituted or unsubstituted C1-C8 alkylene group, each substituted or unsubstituted heteroalkylene group is a substituted or unsubstituted 2- to 8-membered heteroalkylene group, each substituted or unsubstituted cycloalkylene group is a substituted or unsubstituted C3-C7 cycloalkylene group, each substituted or unsubstituted heteroalkylene group is a substituted or unsubstituted 3- to 7-membered heteroalkylene group, each substituted or unsubstituted arylene group is a substituted or unsubstituted C6-C8 alkylene group. 10 arylene, and / or each substituted or unsubstituted heteroarylene is a substituted or unsubstituted 5- to 9-membered heteroarylene. In some embodiments, the compound is a chemical species described in the present application (eg, the following Examples section, claims, examples, figures or tables).
[0059] In embodiments, a substituted or unsubstituted moiety (e.g., substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkylene, substituted or unsubstituted heteroalkylene, substituted or unsubstituted cycloalkylene, substituted or unsubstituted heterocycloalkylene, substituted or unsubstituted arylene and / or substituted or unsubstituted heteroarylene) is unsubstituted (e.g., unsubstituted alkyl, unsubstituted heteroalkyl, unsubstituted cycloalkyl, unsubstituted heterocycloalkyl, unsubstituted aryl, unsubstituted heteroaryl, unsubstituted alkylene, unsubstituted heteroalkylene, unsubstituted cycloalkylene, unsubstituted heterocycloalkylene, unsubstituted arylene and / or unsubstituted heteroalkylene, respectively). In embodiments, the substituted or unsubstituted moiety (e.g., substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkylene, substituted or unsubstituted heteroalkylene, substituted or unsubstituted cycloalkylene, substituted or unsubstituted heterocycloalkylene, substituted or unsubstituted arylene and / or substituted or unsubstituted heteroarylene) is substituted (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, substituted heteroaryl, substituted alkylene, substituted heteroalkylene, substituted cycloalkylene, substituted heterocycloalkylene, substituted arylene and / or substituted heteroarylene, respectively).
[0060] In an embodiment, the substituted part (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, substituted heteroaryl, substituted alkylene, substituted heteroalkylene, substituted cycloalkylene, substituted heterocycloalkylene, substituted arylene and / or substituted heteroarylene) is substituted with at least one substituent group, wherein if the substituted part is substituted with a plurality of substituent groups, each substituent group may optionally be different. In an embodiment, if the substituted part is substituted with a plurality of substituent groups, each substituent group is different.
[0061] In an embodiment, a substituted moiety (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, substituted heteroaryl, substituted alkylene, substituted heteroalkylene, substituted cycloalkylene, substituted heterocycloalkylene, substituted arylene, and / or substituted heteroarylene) is substituted with at least one size-restricted substituent group, wherein if the substituted moiety is substituted with a plurality of size-restricted substituent groups, each size-restricted substituent group may optionally be different. In an embodiment, if the substituted moiety is substituted with a plurality of size-restricted substituent groups, each size-restricted substituent group is different.
[0062] In an embodiment, a substituted portion (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, substituted heteroaryl, substituted alkylene, substituted heteroalkylene, substituted cycloalkylene, substituted heterocycloalkylene, substituted arylene and / or substituted heteroarylene) is substituted with at least one low substituent group, wherein if the substituted portion is substituted with a plurality of low substituent groups, each low substituent group may optionally be different. In an embodiment, if the substituted portion is substituted with a plurality of low substituent groups, each low substituent group is different.
[0063] In an embodiment, a substituted moiety (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, substituted heteroaryl, substituted alkylene, substituted heteroalkylene, substituted cycloalkylene, substituted heterocycloalkylene, substituted arylene, and / or substituted heteroarylene) is substituted with at least one substituent group, a substituent group of limited size, or a lower substituent group; wherein if the substituted moiety is substituted with multiple groups selected from substituent groups, substituent groups of limited size, or lower substituent groups; each substituent group, substituent group of limited size, and / or lower substituent group may optionally be different. In an embodiment, if the substituted moiety is substituted with multiple groups selected from substituent groups, substituent groups of limited size, or lower substituent groups; each substituent group, substituent group of limited size, and / or lower substituent group is different.
[0064] In the claims or formula descriptions described herein, each R substituent or L linker described as "substituted", without reference to the identity of any chemical moiety that constitutes the "substituted" group (also referred to herein as "open substitution" on the R substituent or L linker or "open substituted" R substituent or L linker), in embodiments, the R substituent or L linker may be substituted with one or more first substituent groups as defined below.
[0065] The first substituent is represented by the corresponding first decimal point numbering system, so that, for example, R 1 You can use one or more R 1.1 The first substituent group represents substitution, R 2 You can use one or more R 2.1 The first substituent group represents substitution, R 3 You can use one or more R 3.1 The first substituent group represents substitution, R 4 You can use one or more R 4.1 The first substituent group represents substitution, R 5 You can use one or more R5.1 The first substituent group represented by R may be substituted, and so on up to or beyond the first substituent group represented by R 100.1 The first substituent group substituted R 100 As another example, R 1A One or more R 1A.1 The first substituent group represents substitution, R 2A One or more R 2A.1 The first substituent group represents substitution, R 3A One or more R 3A.1 The first substituent group represents substitution, R 4A One or more R 4A.1 The first substituent group represents substitution, R 5A One or more R 5A.1 The first substituent group represents substitution, and so on until or beyond R 100A One or more R 100A.1 As another example, L 1 One or more R L1.1 The first substituent group represents substitution, L 2 One or more R L2.1 The first substituent group represents substitution, L 3 One or more R L3.1 The first substituent group represents substitution, L 4 One or more R L4.1 The first substituent group represents substitution, L 5 One or more R L5.1 The first substituent group represents substitution, and so on until or beyond L 100 One or more R L100.1 Thus, each numbered R group or L group (or R as referred to herein) described herein is substituted with the first substituent group represented by WW or L WW , wherein "WW" represents the superscript number of the subject R group or L group) can be respectively replaced by one or more groups generally referred to herein as R WW.1 or R LWW.1 Then, each first substituent group (e.g., R 1.1 , R 2.1 , R 3.1 , R 4.1 , R 5.1 …R 100.1 ; R 1A.1 , R 2A.1 , R 3A.1 , R4A.1 , R 5A.1 …R 100A.1 ; R L1.1 , R L2.1 , R L3.1 , R L4.1 , R L5.1 …R L100.1 ) may be replaced by one or more second substituent groups (e.g., R 1.2 , R 2.2 , R 3.2 , R 4.2 , R 5.2 …R 100.2 ; R 1A.2 , R 2A.2 , R 3A.2 , R 4A.2 , R 5A.2 …R 100A.2 ; R L1.2 , R L2.2 , R L3.2 , R L4.2 , R L5.2 …R L100.2 ) is further substituted. Thus, each first substituent group, which may alternatively be represented herein as R as described above WW.1 , which may be further substituted with one or more second substituent groups, which may alternatively be represented herein as R WW.2 .
[0066] Finally, each second substituent group (e.g., R 1.2 , R 2.2 , R 3.2 , R 4.2 , R 5.2 …R 100.2 ; R 1A.2 , R 2A.2 , R 3A.2 , R 4A.2 , R 5A.2 …R 100A.2 ; R L1.2 , R L2.2 , R L3.2 , R L4.2 , R L5.2 …R L100.2 ) may be replaced by one or more third substituent groups (e.g., R 1.3 , R 2.3 , R 3.3 , R 4.3 , R 5.3 …R 100.3 ; R 1A.3 , R 2A.3 , R 3A.3 , R4A.3 , R 5A.3 …R 100A.3 ; R L1.3 , R L2.3 , R L3.3 , R L4.3 , R L5.3 …R L100.3 ;) further substituted. Therefore, each second substituent group, which may be alternatively represented herein as R as described above WW.2 , may be further substituted by one or more third substituent groups, which may alternatively be represented herein as R WW.3 Each of the first substituent group may optionally be different. Each of the second substituent group may optionally be different. Each of the third substituent group may optionally be different.
[0067] Therefore, as used herein, R WW "WW" represents the substituents described in the claims or chemical formula descriptions herein. "WW" represents the superscript number of the subject R group (1, 2, 3, 1A, 2A, 3A, 1B, 2B, 3B, etc.). Similarly, L WW is an open substituted linker as described in the claims or in the chemical formula description herein. Likewise, "WW" represents the superscript number (1, 2, 3, 1A, 2A, 3A, 1B, 2B, 3B, etc.) of the subject L group. As described above, in embodiments, each R WW may be unsubstituted or independently substituted with one or more substituted radicals referred to herein as R WW.1 The first substituent group is substituted; each first substituent group R WW.1 may be unsubstituted or independently substituted with one or more substituted radicals referred to herein as R WW.2 and each second substituent group may be unsubstituted or independently substituted with one or more substituent groups referred to herein as R WW.3 Similarly, each L WW The linker may be unsubstituted or independently substituted with one or more substituted radicals referred to herein as R LWW.1 The first substituent group is substituted; each first substituent group R LWW.1 may be unsubstituted or independently substituted with one or more substituted radicals referred to herein as R LWW.2 and each second substituent group may be unsubstituted or independently substituted with one or more substituent groups referred to herein as R LWW.3 Each first substituent group is optionally different. Each second substituent group is optionally different. Each third substituent group is optionally different. For example, if R WWis phenyl, the phenyl group is optionally replaced by one or more R as defined below WW.1 Group substitution, for example, when R WW.1 For R WW.2 -substituted or unsubstituted alkyl, examples of such groups include, but are not limited to, itself optionally substituted with one or more R WW.2 Replace the R WW.2 Optionally one or more R WW.3 For example, when R WW The group is R WW.1 When phenyl is substituted, the methyl group may be further substituted to form groups including but not limited to the following:
[0068]
[0069] R WW.1 are independently oxo, halogen, -CX WW.1 3. -CHX WW.1 2. -CH2X WW.1 、-OCX WW.1 3. -OCH2X WW.1 、-OCHX WW.1 2. -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, -NHNH2, -ONH2, -NHC(O)NHNH2, -NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -N3, R WW.2 - substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4 or C1-C2), R WW.2 -substituted or unsubstituted heteroalkyl (e.g., 2- to 8-membered, 2- to 6-membered, 4- to 6-membered, 2- to 3-membered, or 4- to 5-membered), R WW.2 - substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6 or C5-C6), R WW.2 -substituted or unsubstituted heterocycloalkyl (e.g., 3- to 8-membered, 3- to 6-membered, 4- to 6-membered, 4- to 5-membered, or 5- to 6-membered), R WW.2 - substituted or unsubstituted aryl (e.g., C6-C 12 、C6-C 10 or phenyl) or R WW.2 - substituted or unsubstituted heteroaryl (e.g., 5- to 12-membered, 5- to 10-membered, 5- to 9-membered, or 5- to 6-membered). In an embodiment, R WW.1 are independently oxo, halogen, -CX WW.1 3. -CHXWW.1 2. -CH2X WW.1 、-OCX WW.1 3. -OCH2X WW.1 、-OCHX WW.1 2, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, -NHNH2, -ONH2, -NHC(O)NHNH2, -NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -N3, unsubstituted alkyl (e.g., C1-C8, C1- C6, C1-C4 or C1-C2), unsubstituted heteroalkyl (e.g., 2-8, 2-6, 4-6, 2-3 or 4-5 members), unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6 or C5-C6), unsubstituted heterocycloalkyl (e.g., 3-8, 3-6, 4-6, 4-5 or 5-6 members), unsubstituted aryl (e.g., C6-C 12 、C6-C 10 or phenyl) or unsubstituted heteroaryl (e.g., 5- to 12-membered, 5- to 10-membered, 5- to 9-membered, or 5- to 6-membered). WW.1 are independently -F, -Cl, -Br or -I.
[0070] R WW.2 are independently oxo, halogen, -CX WW.2 3. -CHX WW.2 2. -CH2X WW.2 、-OCX WW.2 3. -OCH2X WW.2 、-OCHX WW.2 2. -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, -NHNH2, -ONH2, -NHC(O)NHNH2, -NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -N3, R WW.3 - substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4 or C1-C2), R WW.3 -substituted or unsubstituted heteroalkyl (e.g., 2- to 8-membered, 2- to 6-membered, 4- to 6-membered, 2- to 3-membered, or 4- to 5-membered), R WW.3 - substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6 or C5-C6), R WW.3-substituted or unsubstituted heterocycloalkyl (e.g., 3- to 8-membered, 3- to 6-membered, 4- to 6-membered, 4- to 5-membered, or 5- to 6-membered), R WW.3 - substituted or unsubstituted aryl (e.g., C6-C 12 、C6-C 10 or phenyl) or R WW.3 - substituted or unsubstituted heteroaryl (e.g., 5- to 12-membered, 5- to 10-membered, 5- to 9-membered, or 5- to 6-membered). In an embodiment, R WW.2 are independently oxo, halogen, -CX WW.2 3. -CHX WW.2 2. -CH2X WW.2 、-OCX WW.2 3. -OCH2X WW.2 、-OCHX WW.2 2, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, -NHNH2, -ONH2, -NHC(O)NHNH2, -NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -N3, unsubstituted alkyl (e.g., C1-C8, C1- C6, C1-C4 or C1-C2), unsubstituted heteroalkyl (e.g., 2-8, 2-6, 4-6, 2-3 or 4-5 members), unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6 or C5-C6), unsubstituted heterocycloalkyl (e.g., 3-8, 3-6, 4-6, 4-5 or 5-6 members), unsubstituted aryl (e.g., C6-C 12 、C6-C 10 or phenyl) or unsubstituted heteroaryl (e.g., 5- to 12-membered, 5- to 10-membered, 5- to 9-membered, or 5- to 6-membered). WW.2 are independently -F, -Cl, -Br or -I.
[0071] R WW.3 are independently oxo, halogen, -CX WW.3 3. -CHX WW.3 2. -CH2X WW.3 、-OCX WW.3 3. -OCH2X WW.3 、-OCHX WW.32, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, -NHNH2, -ONH2, -NHC(O)NHNH2, -NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -N3, unsubstituted alkyl (e.g., C1-C8, C1- C6, C1-C4 or C1-C2), unsubstituted heteroalkyl (e.g., 2-8, 2-6, 4-6, 2-3 or 4-5 members), unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6 or C5-C6), unsubstituted heterocycloalkyl (e.g., 3-8, 3-6, 4-6, 4-5 or 5-6 members), unsubstituted aryl (e.g., C6-C 12 、C6-C 10 or phenyl) or unsubstituted heteroaryl (e.g., 5- to 12-membered, 5- to 10-membered, 5- to 9-membered, or 5- to 6-membered). WW.3 are independently -F, -Cl, -Br or -I.
[0072] In two different R WW Where substituents are joined together to form an open substituted ring (e.g., substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, or substituted heteroaryl), in embodiments, the open substituted ring may be independently replaced by one or more substituents referred to herein as R WW.1 The first substituent group is substituted; each first substituent group R WW.1 may be unsubstituted or independently substituted with one or more substituted radicals referred to herein as R WW.2 and each second substituent group R WW.2 may be unsubstituted or independently substituted with one or more substituted radicals referred to herein as R WW.3 and each third substituent group R WW.3 is unsubstituted. Each first substituent group is optionally different. Each second substituent group is optionally different. Each third substituent group is optionally different. WW When the substituents are joined together to form an open substituted ring, R WW.1 , R WW.2 and R WW.3 The "WW" symbol in the code refers to two different R WW A specified number of one of the substituents. For example, in R 100A and R 100B In embodiments where R is optionally joined to form an open substituted ring, WW.1 For R 100A.1 , R WW.2For R 100A.2 , and R WW.3 For R 100A.3 Alternatively, in R 100A and R 100B In embodiments where R is optionally joined to form an open substituted ring, WW.1 For R 100B.1 , R WW.2 For R 100B.2 , and R WW.3 For R 100B.3 . R in this paragraph WW.1 , R WW.2 and R WW.3 As defined in the preceding paragraph.
[0073] R LWW.1 are independently oxo, halogen, -CX LWW.1 3. -CHX LWW.1 2. -CH2X LWW.1 、-OCX LWW.1 3. -OCH2X LWW.1 、-OCHX LWW.1 2. -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, -NHNH2, -ONH2, -NHC(O)NHNH2, -NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -N3, R LWW.2 - substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4 or C1-C2), R LWW.2 -substituted or unsubstituted heteroalkyl (e.g., 2- to 8-membered, 2- to 6-membered, 4- to 6-membered, 2- to 3-membered, or 4- to 5-membered), R LWW.2 - substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6 or C5-C6), R LWW.2 -substituted or unsubstituted heterocycloalkyl (e.g., 3- to 8-membered, 3- to 6-membered, 4- to 6-membered, 4- to 5-membered, or 5- to 6-membered), R LWW.2 - substituted or unsubstituted aryl (e.g., C6-C 12 、C6-C 10 or phenyl) or R LWW.2 - substituted or unsubstituted heteroaryl (e.g., 5- to 12-membered, 5- to 10-membered, 5- to 9-membered, or 5- to 6-membered). In an embodiment, R LWW.1 are independently oxo, halogen, -CX LWW.1 3. -CHX LWW.1 2. -CH2X LWW.1 、-OCXLWW.1 3. -OCH2X LWW.1 、-OCHX LWW.1 2, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, -NHNH2, -ONH2, -NHC(O)NHNH2, -NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -N3, unsubstituted alkyl (e.g., C1-C8, C1- C6, C1-C4 or C1-C2), unsubstituted heteroalkyl (e.g., 2-8, 2-6, 4-6, 2-3 or 4-5 members), unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6 or C5-C6), unsubstituted heterocycloalkyl (e.g., 3-8, 3-6, 4-6, 4-5 or 5-6 members), unsubstituted aryl (e.g., C6-C 12 、C6-C 10 or phenyl) or unsubstituted heteroaryl (e.g., 5- to 12-membered, 5- to 10-membered, 5- to 9-membered, or 5- to 6-membered). LWW.1 are independently -F, -Cl, -Br or -I.
[0074] R LWW.2 are independently oxo, halogen, -CX LWW.2 3. -CHX LWW.2 2. -CH2X LWW.2 、-OCX LWW.2 3. -OCH2X LWW.2 、-OCHX LWW.2 2. -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, -NHNH2, -ONH2, -NHC(O)NHNH2, -NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -N3, R LWW.3 - substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4 or C1-C2), R LWW.3 -substituted or unsubstituted heteroalkyl (e.g., 2- to 8-membered, 2- to 6-membered, 4- to 6-membered, 2- to 3-membered, or 4- to 5-membered), R WW.3 - substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6 or C5-C6), R LWW.3 -substituted or unsubstituted heterocycloalkyl (e.g., 3- to 8-membered, 3- to 6-membered, 4- to 6-membered, 4- to 5-membered, or 5- to 6-membered), R LWW.3- substituted or unsubstituted aryl (e.g., C6-C 12 、C6-C 10 or phenyl) or R LWW.3 - substituted or unsubstituted heteroaryl (e.g., 5- to 12-membered, 5- to 10-membered, 5- to 9-membered, or 5- to 6-membered). In one embodiment, R LWW.2 are independently oxo, halogen, -CX LWW.2 3. -CHX LWW.2 2. -CH2X LWW.2 、-OCX LWW.2 3. -OCH2X LWW.2 、-OCHX LWW.2 2, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, -NHNH2, -ONH2, -NHC(O)NHNH2, -NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)-OH, -NHOH, -N3, unsubstituted alkyl (e.g., C1-C8, C1 C-C6, C1-C4 or C1-C2), unsubstituted heteroalkyl (e.g., 2-8, 2-6, 4-6, 2-3 or 4-5 members), unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6 or C5-C6), unsubstituted heterocycloalkyl (e.g., 3-8, 3-6, 4-6, 4-5 or 5-6 members), unsubstituted aryl (e.g., C6-C 12 、C6-C 10 or phenyl) or unsubstituted heteroaryl (e.g., 5- to 12-membered, 5- to 10-membered, 5- to 9-membered, or 5- to 6-membered). LWW.2 are independently -F, -Cl, -Br or -I.
[0075] R LWW.3 are independently oxo, halogen, -CX LWW.3 3. -CHX LWW.3 2. -CH2X LWW.3 、-OCX LWW.3 3. -OCH2X LWW.3 、-OCHX LWW.32, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, -NHNH2, -ONH2, -NHC(O)NHNH2, -NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -N3, unsubstituted alkyl (e.g., C1-C8, C1- C6, C1-C4 or C1-C2), unsubstituted heteroalkyl (e.g., 2-8, 2-6, 4-6, 2-3 or 4-5 members), unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6 or C5-C6), unsubstituted heterocycloalkyl (e.g., 3-8, 3-6, 4-6, 4-5 or 5-6 members), unsubstituted aryl (e.g., C6-C 12 、C6-C 10 or phenyl) or unsubstituted heteroaryl (e.g., 5- to 12-membered, 5- to 10-membered, 5- to 9-membered, or 5- to 6-membered). LWW.3 are independently -F, -Cl, -Br or -I.
[0076] Any R group (R WW Substituents) are not specifically defined in the present disclosure, then the R group (R WW Groups) are defined herein independently as oxo, halogen, -CX WW 3. -CHX WW 2. -CH2X WW 、-OCX WW 3. -OCH2X WW 、-OCHX WW 2. -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, -NHNH2, -ONH2, -NHC(O)NHNH2, -NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -N3, R WW.1 - substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4 or C1-C2), R WW.1 -substituted or unsubstituted heteroalkyl (e.g., 2- to 8-membered, 2- to 6-membered, 4- to 6-membered, 2- to 3-membered, or 4- to 5-membered), R WW.1 - substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6 or C5-C6), R WW.1-substituted or unsubstituted heterocycloalkyl (e.g., 3- to 8-membered, 3- to 6-membered, 4- to 6-membered, 4- to 5-membered, or 5- to 6-membered), R WW.1 - substituted or unsubstituted aryl (e.g., C6-C 12 、C6-C 10 or phenyl) or R WW.1 - substituted or unsubstituted heteroaryl (eg, 5- to 12-membered, 5- to 10-membered, 5- to 9-membered, or 5- to 6-membered). X WW R is independently -F, -Cl, -Br or -I. Likewise, "WW" represents the superscript number of the subject R group (e.g., 1, 2, 3, 1A, 2A, 3A, 1B, 2B, 3B, etc.). WW.1 , R WW.2 and R WW.3 As defined above.
[0077] Any L linker group (i.e., L WW If the substituent is not specifically defined, the L group (L WW The groups) are defined herein independently as a bond, -O-, -NH-, -C(O)-, -C(O)NH-, -NHC(O)-, -NHC(O)NH-, -C(O)O-, -OC(O)-, -S-, -SO2-, -SO2NH-, R LWW.1 - substituted or unsubstituted alkylene (e.g., C1-C8, C1-C6, C1-C4 or C1-C2), R LWW.1 - substituted or unsubstituted heteroalkylene (e.g., 2- to 8-membered, 2- to 6-membered, 4- to 6-membered, 2- to 3-membered, or 4- to 5-membered), R LWW.1 - substituted or unsubstituted cycloalkylene (e.g., C3-C8, C3-C6, C4-C6 or C5-C6), R LWW.1 - substituted or unsubstituted heterocycloalkylene (e.g., 3- to 8-membered, 3- to 6-membered, 4- to 6-membered, 4- to 5-membered, or 5- to 6-membered), R LWW.1 - substituted or unsubstituted arylene (e.g., C6-C 12 、C6-C 10 or phenyl) or R LWW.1 - substituted or unsubstituted heteroarylene (e.g., 5- to 12-membered, 5- to 10-membered, 5- to 9-membered, or 5- to 6-membered). Likewise, "WW" represents the superscript number of the subject L group (1, 2, 3, 1A, 2A, 3A, 1B, 2B, 3B, etc.). R LWW.1 and R LWW.2 and R LWW.3 As defined above.
[0078] Certain compounds of the present disclosure have asymmetric carbon atoms (optical or chiral centers) or double bonds; enantiomers, racemates, diastereomers, tautomers, geometric isomers, stereoisomeric forms that can be defined as (R)- or (S)- of amino acids or as (D)- or (L)- in terms of absolute stereochemistry, and each isomer is included within the scope of the present disclosure. The compounds of the present disclosure do not include compounds that are too unstable to be synthesized and / or separated as known in the art. The present disclosure is intended to include compounds in racemic and optically pure forms. Optically active (R)- and (S)- or (D)- and (L)-isomers can be prepared using chiral synthons or chiral reagents, or resolved using conventional techniques. When the compounds described herein contain olefinic bonds or other centers of geometric asymmetry, and unless otherwise indicated, it is intended that these compounds contain both E and Z geometric isomers.
[0079] As used herein, the term "isomers" refers to compounds that have the same number and kind of atoms and therefore the same molecular weight but differ in the structural arrangement or configuration of the atoms.
[0080] As used herein, the term "tautomer" refers to one of two or more structural isomers that exist in equilibrium and are readily converted from one isomeric form to another.
[0081] It will be apparent to those skilled in the art that certain compounds of the present disclosure may exist in tautomeric forms and all such tautomeric forms of the compounds are within the scope of the present disclosure.
[0082] Unless otherwise stated, structures depicted herein are also intended to include all stereochemical forms of the structure; that is, the R and S configurations for each asymmetric center. Therefore, single stereochemical isomers as well as enantiomeric and diastereomeric mixtures of the present compounds are within the scope of the present disclosure.
[0083] Unless otherwise stated, structures depicted herein are also meant to include compounds that differ only in the presence or absence of one or more isotopically enriched atoms. 13 C-enriched or 14 Compounds of the present structures in which a C-enriched carbon replaces a carbon other than carbon are within the scope of the present disclosure.
[0084] The compounds of the present disclosure may also contain unnatural proportions of atomic isotopes at one or more atoms that constitute such compounds. For example, the compounds may be treated with, for example, tritium ( 3 H), iodine-125 ( 125 I) or carbon-14 ( 14C) and other radioactive isotopes. All isotopic variations of the compounds of the present disclosure, whether radioactive or non-radioactive, are encompassed within the scope of the present disclosure.
[0085] It should be noted that throughout the application, alternatives are written in Markush groups, such as in each amino acid position that contains more than one possible amino acid. It is specifically contemplated that each member of the Markush group should be considered individually, thereby comprising another embodiment, and that the Markush group should not be construed as a single unit.
[0086] "Analog" or "analogue" is used according to its ordinary general meaning within chemistry and biology, and refers to a compound that is structurally similar but compositionally different from another compound (i.e., the so-called "reference" compound), for example in the replacement of one atom by an atom of a different element, or in the presence of a particular functional group, or in the replacement of one functional group by another functional group, or in the absolute stereochemistry of one or more chiral centers of the reference compound. Thus, an analog is a compound that is similar or equivalent to the reference compound in function and appearance, but not similar or equivalent in structure or origin.
[0087] As used herein, the term "a" or "an" means one or more. In addition, as used herein, the phrase "substituted with [n]..." means that the specified group may be substituted with one or more of any or all of the named substituents. For example, in the case of a group such as an alkyl or heteroaryl group, "substituted with an unsubstituted C1-C 20 In the case of "substituted with alkyl or unsubstituted 2- to 20-membered heteroalkyl", the group may contain one or more unsubstituted C1-C 20 alkyl, and / or one or more unsubstituted 2- to 20-membered heteroalkyl groups.
[0088] In addition, when a moiety is substituted with an R substituent, the group may be referred to as "R-substituted". When a moiety is R-substituted, the moiety is substituted with at least one R substituent, and each R substituent is optionally different. When a specific R group is present in the description of a chemical species, such as Formula (I), a Roman letter symbol may be used to distinguish each appearance of the specific R group. For example, when multiple R 13 In the case of a substituent, each R 13 Substituents can be divided into R 13A , R 13B , R 13C , R 13D etc., where R 13A , R 13B , R 13C , R 13D Each of the above is in R13 and optionally different.
[0089] Radioactive materials (e.g., radioisotopes) that can be used as imaging agents and / or labeling agents according to embodiments of the present disclosure include, but are not limited to: 18 F. 32 P. 33 P. 45 Ti, 47 Sc, 52 Fe, 59 Fe, 62 Cu, 64 Cu, 67 Cu, 67 Ga, 68 Ga, 77 As, 86 Y. 90 Y. 89 Sr. 89 Zr, 94 Tc, 94 Tc, 99m Tc, 99 Mo, 105 Pd, 105 Rh, 111 Ag, 111 In, 123 I. 124 I. 125 I. 131 I. 142 Pr, 143 Pr, 149 Pm, 153 Sm, 154-1581 Gd, 161 Tb, 166 Dy, 166 Ho, 169 2. 175 Lu, 177 Lu, 186 Re, 188 Re, 189 Re, 194 Ir, 198 Au, 199 Au, 211 At 211 Pb, 212 Pb, 212 Bi, 213 Bi, 223 Ra and 225Ac. Paramagnetic ions that can be used as additional imaging agents according to embodiments of the present disclosure include, but are not limited to, ions of transition metals and lanthanide metals (e.g., metals with atomic numbers 21-29, 42, 43, 44, or 57-71). These metals include ions of Cr, V, Mn, Fe, Co, Ni, Cu, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.
[0090] The description of the disclosed compounds is limited by the principles of chemical bonding known to those skilled in the art. Thus, where a group may be substituted by one or more of a plurality of substituents, such substitutions are selected so as to conform to the principles of chemical bonding and to yield compounds that are not inherently unstable and / or that would be unstable under environmental conditions (such as aqueous, neutral, and several known physiological conditions) as known to those of ordinary skill in the art. For example, heterocycloalkyl or heteroaryl groups, in accordance with the principles of chemical bonding known to those skilled in the art, are connected to the rest of the molecule via a ring heteroatom, thereby avoiding inherently unstable compounds.
[0091] The term "leaving group" is used according to its common meaning in chemistry, and refers to a part (e.g., atom, functional group, molecule) separated from a molecule after a chemical reaction (e.g., bond formation, reduction elimination, condensation, cross-coupling reaction), which involves an atom or chemical part (also referred to herein as "leaving group reactive part") to which the leaving group is connected and a complementary reactive part (i.e., a chemical part reacted with the leaving group reactive part) to form a new key between the residual part of the leaving group reactive part and the complementary reactive part. Therefore, the leaving group reactive part and the complementary reactive part form a complementary reactive group pair. The non-limiting example of leaving group includes hydrogen, hydroxide, organotin part (e.g., organotin heteroalkyl), halogen (e.g., Br), perfluoroalkyl sulfonate (e.g., trifluoromethanesulfonate), toluenesulfonate, mesylate, water, alcohol, nitrate, phosphate, thioether, amine, ammonia, fluoride, carboxylate, phenolate, boric acid, borate and alkoxide. In embodiments, two molecules having a leaving group are contacted and upon reaction and / or bond formation (eg, keto-ol condensation, aldol condensation, Claisen condensation, Stiller reaction), the leaving group dissociates from the respective molecule.
[0092] One of ordinary skill in the art will understand that when a variable (e.g., a moiety or linker) of a compound or genus of compounds (e.g., a genus described herein) is described by the name or formula of an independent compound with all filled valences, the unfilled valence or valences of the variable will be determined by the context in which the variable is used. For example, when a variable of a compound described herein is connected (e.g., bonded) to the rest of the compound by a single bond, the variable should be understood to represent the monovalent form of the independent compound (i.e., capable of forming a single bond due to the unfilled valences) (e.g., in one embodiment, if a variable is named "methane", but it is known that the variable is connected to the rest of the compound by a single bond, one of ordinary skill in the art will understand that the variable is actually the monovalent form of methane, i.e., methyl or -CH3). Similarly, for linker variables (e.g., L as described herein), 1 , L 2 or L 3 ), one of ordinary skill in the art will understand that the variable is a divalent form of the independent compound (for example, in the embodiments, if a variable is designated as "PEG" or "polyethylene glycol", but the variable is connected to the rest of the compound by two separate bonds, one of ordinary skill in the art will understand that the variable is a divalent form of PEG (i.e., capable of forming two bonds through two unfilled valencies), rather than the independent compound PEG).
[0093] As used herein, the term "salt" refers to an acid or base salt of a compound used in the method of the present invention. Illustrative examples of acceptable salts are mineral acid (hydrochloric acid, hydrobromic acid, phosphoric acid, etc.) salts, organic acid (acetic acid, propionic acid, glutamic acid, citric acid, etc.) salts, quaternary ammonium (methyl iodide, ethyl iodide, etc.) salts.
[0094] Therefore, the compounds of the present disclosure may exist in the form of salts. The present disclosure includes such salts. Non-limiting examples of such salts include hydrochlorides, hydrobromides, phosphates, sulfates, methanesulfonates, nitrates, maleates, acetates, citrates, fumarates, propionates, tartrates (e.g., (+)-tartrates, (-)-tartrates or their mixtures comprising racemic mixtures), succinates, benzoates, and salts with amino acids (such as glutamic acid) and quaternary ammonium salts (e.g., methyl iodide, ethyl iodide, etc.). These salts can be prepared by methods known to those skilled in the art.
[0095] The neutral forms of the compounds are preferably regenerated by contacting the salt with a base or acid and isolating the parent compound in the conventional manner.The parent form of the compound may differ from the various salt forms in certain physical properties, such as solubility in polar solvents.
[0096] Some compounds of the present disclosure can exist in non-solvated form and solvated form (including hydrated form). Generally, the solvated form is equivalent to the non-solvated form and is included in the scope of the present disclosure. Some compounds of the present disclosure can exist in multiple crystals or amorphous forms. Generally, all physical forms are equivalent for the purposes contemplated by the present disclosure and are intended to be within the scope of the present disclosure.
[0097] As used herein, the term "about" means a range of values that include a specified value, which one of ordinary skill in the art would consider to be reasonably similar to the specified value. In embodiments, about means within the standard deviation using measurements generally acceptable in the art. In embodiments, about means a range extends to + / -10% of a specified value. In embodiments, about includes a specified value.
[0098] "Contacting" is used in its plain ordinary sense and refers to the process of allowing at least two different substances (e.g., compounds including biomolecules or cells) to become close enough to react, interact or come into physical contact. However, it should be understood that the resulting reaction product can be produced directly from a reaction between the added reagents or from intermediates that can be produced in the reaction mixture from one or more of the added reagents.
[0099] In the present disclosure, "comprising," "including," "containing," and "having," etc. may have the meaning ascribed to them in U.S. patent law and may refer to "including," "comprising," etc. "Consisting essentially of" or "consists essentially of" also have the meaning ascribed to them in U.S. patent law and the terms are open ended, allowing for more than what is recited, as long as the basic or novel features of what is recited are not altered by the presence of more than what is recited, but excluding prior art implementations.
[0100] The term "polymer" is used according to its ordinary general meaning in the art and refers to a molecule comprised of repeating subunits (eg, polymerized monomers).
[0101] As used herein, the term "dehydropolymer" refers to a polymer containing carbon-carbon double bonds.
[0102] The term "olefin metathesis" is used according to its ordinary general meaning in the art and refers to an organic reaction involving the redistribution of olefin fragments by cleavage and regeneration of carbon-carbon double bonds.
[0103] The term "olefin isomerization" is used according to its ordinary general meaning in the art and refers to an organic reaction involving the relocation of carbon-carbon double bonds in a molecule to a different part of the molecule. In an embodiment, olefin isomerization is the isomerization of terminal olefins to internal olefins.
[0104] The term "dehydrogenation" is used according to its ordinary general meaning in the art and refers to an organic reaction involving, for example, the removal of hydrogen from an organic molecule. In an embodiment, the dehydrogenation is the conversion of an alkane to an alkene.
[0105] The term "catalyst" is used according to its ordinary general meaning in the art and refers to a substance that increases the rate of a chemical reaction. The catalyst is not consumed in the reaction and can continue to work repeatedly.
[0106] The term "high-density polyethylene" or "HDPE" refers to a thermoplastic polymer produced from the monomer ethylene, which is known to have a high strength-to-density ratio. Typically, the density of HDPE ranges from 0.93 g / cm 3 To about 0.97g / cm 3 The polymer chain of HDPE has minimal branching and is therefore denser than low-density polyethylene.
[0107] The term "low density polyethylene" or "LDPE" refers to a thermoplastic polymer produced from the monomer ethylene. Typically, the density of LDPE ranges from 0.917 g / cm 3 To about 0.930g / cm 3 .
[0108] The term "linear low density polyethylene" or "LLDPE" refers to a substantially linear polyethylene with a large number of short chain branches. LLDPE differs from LDPE by the absence of long chain branching. Typically, the density of LLDPE ranges from 0.91 g / cm 3 To about 0.94g / cm 3 .
[0109] II. Methods
[0110] In one aspect, a method of degrading a substance is provided, the method comprising: (i) performing one or more reactions to form one or more olefin units in the substance; (ii) after step (i), subjecting to conditions for olefin metathesis; and (iii) after step (i), subjecting to conditions for olefin isomerization. In an embodiment, step (i) comprises subjecting the substance to conditions for dehydrogenation.
[0111] In one aspect, a method of preparing a substituted or unsubstituted olefin is provided, the method comprising subjecting a dehydrogenated polymer to conditions for olefin metathesis and conditions for olefin isomerization.
[0112] In one aspect, a method for preparing substituted or unsubstituted olefins is provided, the method comprising subjecting a first substance to conditions for olefin metathesis and conditions for olefin isomerization; wherein: (i) the first substance comprises at least 20 carbon atoms per molecule; or (ii) before subjecting the first substance to conditions for olefin metathesis and conditions for olefin isomerization, the method comprises subjecting a second substance to conditions for dehydrogenation, thereby forming the first substance.
[0113] In one aspect, a method for preparing substituted or unsubstituted olefins is provided, the method comprising subjecting a first substance to conditions for olefin metathesis and conditions for olefin isomerization; wherein: (i) the first substance comprises up to 10% unsaturated olefin monomer units; (ii) the first substance comprises at least 20 carbon atoms per molecule; or (iii) before subjecting the first substance to conditions for olefin metathesis and conditions for olefin isomerization, the method comprises subjecting a second substance to conditions for dehydrogenation, thereby forming the first substance.
[0114] In embodiments, subjecting to conditions for olefin metathesis and subjecting to conditions for olefin isomerization are performed simultaneously. In embodiments, subjecting to conditions for olefin metathesis and subjecting to conditions for olefin isomerization are performed simultaneously by orthogonal tandem catalysis.
[0115] In an embodiment, the substance comprises one or more polymers. In an embodiment, the substance comprises a polymer. In an embodiment, the substance comprises multiple polymers. In an embodiment, the substance comprises one or more polyolefins. In an embodiment, the substance comprises a polyolefin. In an embodiment, the substance comprises multiple polyolefins. In an embodiment, the substance is a polyolefin.
[0116] In an embodiment, the substance comprises one or more polymers comprising one or more monomer units selected from the group consisting of ethylene units, propylene units, 1-butene units, 2-butene units, isobutylene units, 1-pentene units, 2-pentene units, 1-hexene units, 2-hexene units, 3-hexene units, 1-heptene units, 1-octene units, 1-nonene units, 1-decene units, styrene units, vinyl chloride units, vinyl fluoride units, cyclopentene units, cyclohexene units, cycloheptene units, cyclooctene units, cyclononane units, cyclodecene units, cycloundecene units, cyclododecene units, and norbornene units. In an embodiment, the substance comprises one or more monomer units selected from the group consisting of ethylene, propylene, styrene, and vinyl chloride. In an embodiment, the substance comprises one or more monomer units selected from the group consisting of ethylene and propylene. In an embodiment, the substance comprises one or more monomer units selected from the group consisting of ethylene.
[0117] In an embodiment, the substance comprises one or more copolymers comprising one or more monomer units selected from the group consisting of ethylene units, propylene units, 1-butene units, 2-butene units, isobutylene units, 1-pentene units, 2-pentene units, 1-hexene units, 2-hexene units, 3-hexene units, 1-heptene units, 1-octene units, 1-nonene units, 1-decene units, styrene units, vinyl chloride units, vinyl fluoride units, cyclopentene units, cyclohexene units, cycloheptene units, cyclooctene units, cyclononane units, cyclodecene units, cycloundecene units, cyclododecene units, and norbornene units. In an embodiment, the substance comprises one or more copolymers comprising one or more monomeric units selected from the group consisting of ethylene units, propylene units, 1-butene units, 2-butene units, isobutylene units, 1-pentene units, 2-pentene units, 1-hexene units, 2-hexene units, 3-hexene units, 1-heptene units, 1-octene units, 1-nonene units, 1-decene units, styrene units, and vinyl chloride units. In an embodiment, the substance comprises one or more copolymers comprising one or more monomeric units selected from the group consisting of ethylene units, propylene units, styrene units, and vinyl chloride units. In an embodiment, the substance comprises one or more copolymers comprising one or more monomeric units selected from the group consisting of ethylene units and propylene units. In an embodiment, the substance comprises one or more copolymers comprising one or more monomeric units selected from the group consisting of ethylene units.
[0118] In an embodiment, the material comprises one or more block copolymers comprising one or more blocks selected from the group consisting of polyethylene blocks, polypropylene blocks, poly(vinyl chloride) blocks, polybutylene blocks, polyisobutylene blocks, poly(1-butene) blocks, poly(2-butene) blocks, polypentene blocks, poly(4-methyl-1-pentene) blocks, polystyrene blocks, poly(cyclopentene) blocks, poly(cyclohexene) blocks, poly(cycloheptene) blocks, poly(cyclooctene) blocks, poly(cyclononene) blocks, poly(cyclodecene) blocks, poly(cycloundecene) blocks, poly(cyclododecene) blocks, and polynorbornene. In an embodiment, the substance comprises one or more block copolymers, the one or more block copolymers comprising one or more blocks selected from the group consisting of polyethylene blocks, polypropylene blocks, poly(vinyl chloride) blocks, polyisobutylene blocks, poly(4-methyl-1-pentene) blocks, polystyrene blocks, and poly(cyclooctene) blocks. In an embodiment, the substance comprises one or more block copolymers, the one or more block copolymers comprising one or more blocks selected from the group consisting of polyethylene blocks, polypropylene blocks, poly(vinyl chloride) blocks, and polystyrene blocks. In an embodiment, the substance comprises one or more block copolymers, the one or more block copolymers comprising one or more blocks selected from the group consisting of polyethylene blocks and polypropylene blocks. In an embodiment, the substance comprises one or more block copolymers, the one or more block copolymers comprising one or more blocks selected from the group consisting of polyethylene blocks.
[0119] In embodiments, the material comprises one or more homopolymers selected from the group consisting of polyethylene, polypropylene, polystyrene, poly(vinyl chloride), polybutene, polyisobutylene, polybutene, poly(1-butene), poly(2-butene), polyisobutylene, polypentene, poly(4-methyl-1-pentene), polystyrene, and poly(vinyl chloride). In embodiments, the material comprises polyethylene. In embodiments, the material is polyethylene. In embodiments, the material comprises waste polyethylene. In embodiments, the material comprises one or more polyethylenes. In embodiments, the material is one or more polyethylenes. In embodiments, the material comprises one or more polyethylenes selected from the group consisting of high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and copolymers thereof. In embodiments, the material comprises one or more polyethylenes selected from the group consisting of high-density polyethylene, low-density polyethylene, and copolymers thereof. In embodiments, the material comprises one or more polyethylenes selected from the group consisting of high-density polyethylene and low-density polyethylene. In embodiments, the material comprises high-density polyethylene. In embodiments, the material comprises low-density polyethylene. In embodiments, the material comprises linear low-density polyethylene. In embodiments, the material is high-density polyethylene. In embodiments, the material is low-density polyethylene. In embodiments, the substance is linear low density polyethylene.
[0120] In an embodiment, the substance comprises polypropylene. In an embodiment, the substance comprises syndiotactic polypropylene. In an embodiment, the substance comprises atactic polypropylene. In an embodiment, the substance comprises isotactic polypropylene.
[0121] In embodiments, the material comprises plastic waste. In embodiments, the material comprises plastic waste selected from the group consisting of milk jugs, shampoo bottles, lawn chairs, food containers, trash bags, buckets, drain tubes, grocery bags, and cereal bin liners.
[0122] In embodiments, the formation of one or more olefin units in the substance includes subjecting the substance to conditions for dehydrogenation. In embodiments, the formation of one or more olefin units in the substance includes performing one or more dehydrogenation reactions on the substance. In embodiments, the one or more dehydrogenation reactions include one or more reactions that include removing one or more proton-hydride pairs, wherein each proton-hydride pair in the one or more proton-hydride pairs includes a proton and a hydride. In embodiments, the one or more dehydrogenation reactions convert reactants into dehydrogenated substances. In embodiments, the one or more dehydrogenation reactions include one or more acceptor-free dehydrogenation reactions. In embodiments, the one or more dehydrogenation reactions include one or more transfer dehydrogenation reactions. In embodiments, the one or more dehydrogenation reactions include one or more transfer dehydrogenation reactions, and the one or more transfer dehydrogenation reactions include treating the substance with one or more hydrogen acceptors. In embodiments, the one or more dehydrogenation reactions include one or more oxidative dehydrogenation reactions. In embodiments, the one or more dehydrogenation reactions include treating the substance with one or more hydrogen acceptors. In embodiments, the one or more dehydrogenation reactions produce dehydrogenated substances. In embodiments, the dehydrogenated substances are purified. In embodiments, the dehydrogenated material is purified by one or more techniques selected from the group consisting of distillation or precipitation from one or more organic solvents or precipitation from water.
[0123] In embodiments, the one or more transfer dehydrogenation reactions comprise treatment with one or more hydrogen acceptors comprising: one or more bonds independently selected from the group consisting of: C-C, C=C, C≡C, NN, N=N, N≡N, OO, O=O, CN, C=N, C≡N, CO, C=O, C≡O, SS, CS, and C=S; or one or more rings. In embodiments, the one or more hydrogen acceptors comprise: one or more bonds independently selected from the group consisting of: C=C, C≡C, N=N, N≡N, OO, O=O, C=N, C≡N, C=O, C≡O, SS, and C=S; or one or more rings. In embodiments, the one or more hydrogen acceptors include: one or more bonds independently selected from the group consisting of C=C, C≡C, N=N, N≡N, OO, O=O, C=N, C=O, C≡O, SS, and C=S; or one or more rings. In embodiments, the one or more hydrogen acceptors include: one or more bonds independently selected from the group consisting of C=C, C≡C, N=N, OO, O=O, C=N, C=O, C≡O, SS, and C=S; or one or more rings. In embodiments, the one or more hydrogen acceptors include: one or more bonds independently selected from the group consisting of C=C, C≡C, N=N, OO, O=O, C=O, and C≡; or one or more rings. In embodiments, the one or more hydrogen acceptors include: one or more bonds independently selected from the group consisting of C=C, C≡C, OO, O=O, C=O, and C≡; or one or more rings. In embodiments, the one or more hydrogen acceptors include: one or more bonds independently selected from the group consisting of C=C, C≡C, O=O, C=O, and C≡O; or one or more rings. In embodiments, the one or more hydrogen acceptors include: one or more bonds independently selected from the group consisting of C=C, C≡C, C=O, and C≡O; or one or more rings. In embodiments, the one or more hydrogen acceptors include: one or more bonds independently selected from the group consisting of C=C and C≡C; or one or more rings. In embodiments, the one or more hydrogen acceptors include: one or more bonds independently selected from the group consisting of C=C and C≡C. In embodiments, the one or more hydrogen acceptors include: one or more C=C bonds.
[0124] In embodiments, the one or more transfer dehydrogenation reactions include treatment with one or more hydrogen acceptors selected from the group consisting of ethylene, propylene, butene, tert-butylethylene, norbornene, norbornadiene, butadiene, styrene, acetylene, O2, CO2, CO, optionally substituted benzoquinone, and N2. In embodiments, the one or more hydrogen acceptors are independently selected from ethylene, propylene, butene, tert-butylethylene, norbornene, norbornadiene, butadiene, and styrene. In embodiments, the one or more hydrogen acceptors are independently selected from ethylene, propylene, tert-butylethylene, norbornene, and norbornadiene. In embodiments, the one or more hydrogen acceptors are independently selected from ethylene, propylene, tert-butylethylene, and norbornene. In embodiments, the one or more hydrogen acceptors are independently selected from ethylene, tert-butylethylene, and norbornene. In embodiments, the one or more hydrogen acceptors are independently selected from tert-butylethylene and norbornene. In embodiments, the one or more hydrogen acceptors are independently selected from tert-butylethylene and norbornene. In embodiments, the one or more hydrogen acceptors are independently selected from norbornene. In embodiments, the one or more hydrogen acceptors are independently selected from tert-butylethylene. In embodiments, the one or more hydrogen acceptors are ethylene. In embodiments, the one or more hydrogen acceptors are propylene.
[0125] In embodiments, the conditions for dehydrogenation include performing one or more reactions at a temperature ranging from 20°C to 1000°C. In embodiments, the conditions for dehydrogenation include performing one or more reactions at a temperature ranging from 50°C to 500°C. In embodiments, the conditions for dehydrogenation include performing one or more reactions at a temperature ranging from 100°C to 400°C. In embodiments, the conditions for dehydrogenation include performing one or more reactions at a temperature ranging from 100°C to 300°C. In embodiments, the conditions for dehydrogenation include performing one or more reactions at a temperature ranging from 100°C to 200°C. In embodiments, dehydrogenation is performed at a temperature of at least 20°C, at least 50°C, at least 65°C, at least 80°C, at least 100°C, at least 120°C, at least 200°C, at least 250°C, at least 300°C, at least 350°C, at least 400°C, at least 500°C, at least 600°C, at least 1000°C or more. Alternatively or in addition, in embodiments, the dehydrogenation is conducted at a temperature of at most 20°C, at most 50°C, at most 65°C, at most 80°C, at most 100°C, at most 120°C, at most 200°C, at most 250°C, at most 300°C, at most 350°C, at most 400°C, at most 500°C, at most 600°C, at most 1000°C, or less.
[0126] In embodiments, conditions for dehydrogenation include performing one or more reactions at a temperature of about 20°C to about 1000°C. In embodiments, conditions for dehydrogenation include performing one or more reactions at a temperature of at least about 20°C. In embodiments, conditions for dehydrogenation include performing one or more reactions at a temperature of up to about 1000°C. In embodiments, conditions for dehydrogenation include performing one or more reactions at a temperature of about 20°C to about 65°C, about 20°C to about 100°C, about 20°C to about 150°C, about 20°C to about 200°C, about 20°C to about 300°C, about 20°C to about 350°C, about 20°C to about 400°C, about 20°C to about 450°C, about 20°C to about 500°C, about 20°C to about 600°C, about 20°C to about 1000°C, about 65°C to about 100°C, about 65°C to about 150°C, about 65°C to about 200°C, about 65°C to about 3 ... ℃, about 65 ℃ to about 400 ℃, about 65 ℃ to about 450 ℃, about 65 ℃ to about 500 ℃, about 65 ℃ to about 600 ℃, about 65 ℃ to about 1000 ℃, about 100 ℃ to about 150 ℃, about 100 ℃ to about 200 ℃, about 100 ℃ to about 300 ℃, about 100 ℃ to about 350 ℃, about 100 ℃ to about 400 ℃, about 100 ℃ to about 450 ℃, about 100 ℃ to about 500 ℃, about 100 ℃ to about 600 ℃, about 100 ℃ to about 1,000 ℃, about 150 ℃ to about 200 ℃, about 150 ℃ to about 300 ℃, about 150 ℃ to about 350 ℃ ℃, about 150 ℃ to about 400 ℃, about 150 ℃ to about 450 ℃, about 150 ℃ to about 500 ℃, about 150 ℃ to about 600 ℃, about 150 ℃ to about 1,000 ℃, about 200 ℃ to about 300 ℃, about 200 ℃ to about 350 ℃, about 200 ℃ to about 400 ℃, about 200 ℃ to about 450 ℃, about 200 ℃ to about 500 ℃, about 200 ℃ to about 600 ℃, about 200 ℃ to about 1,000 ℃, about 300 ℃ to about 350 ℃, about 300 ℃ to about 400 ℃, about 300 ℃ to about 450 ℃, about 300 ℃ to about 500 ℃, about 300 ℃ to about 600 ℃, From about 600°C, from about 300°C to about 1000°C, from about 350°C to about 400°C, from about 350°C to about 450°C, from about 350°C to about 500°C, from about 350°C to about 600°C, from about 350°C to about 1,000°C, from about 400°C to about 450°C, from about 400°C to about 500°C, from about 400°C to about 600°C, from about 400°C to about 1000°C, from about 450°C to about 500°C, from about 450°C to about 600°C, from about 450°C to about 1000°C, from about 500°C to about 600°C, from about 500°C to about 1000°C, or from about 600°C to about 1000°C.In embodiments, conditions for dehydrogenation include conducting one or more reactions at a temperature of about 20°C, about 65°C, about 100°C, about 150°C, about 200°C, about 300°C, about 350°C, about 400°C, about 450°C, about 500°C, about 600°C, or about 1000°C.
[0127] In an embodiment, the conditions for dehydrogenation include subjecting a pure substance to one or more dehydrogenation reactions. In an embodiment, the conditions for dehydrogenation include melting the substance. In an embodiment, the conditions for dehydrogenation include melting the polymer. In an embodiment, the conditions for dehydrogenation include melting the polyethylene.
[0128] In embodiments, the conditions for dehydrogenation include contacting the substance with one or more solvents. In embodiments, the conditions for dehydrogenation include contacting the substance with one or more organic solvents. In embodiments, the conditions for dehydrogenation include contacting the substance with one or more hydrocarbon solvents. In embodiments, the conditions for dehydrogenation include contacting the substance with one or more solvents selected from the following: benzene, toluene, o-xylene, m-xylene, p-xylene, dichlorobenzene (e.g., o-dichlorobenzene), trichlorobenzene (e.g., 1,2,4-trichlorobenzene), dioxane, tetrahydrofuran, tetrahydropyran, acetone, chloroform, carbon tetrachloride, methylene chloride, ethyl acetate, pentane, pentanes, hexane, hexanes, heptane, heptanes, octane, octanes, nonane, nonanes, decane, decanes, undecane, undecanes, dodecane and dodecanes. In embodiments, the conditions for dehydrogenation include contacting the substance with a mixture of multiple organic solvents.
[0129] In embodiments, the conditions for dehydrogenation include conducting a batch reaction. In embodiments, the conditions for dehydrogenation include flowing one or more gases through a headspace of a batch reaction. In embodiments, the conditions for dehydrogenation include flowing one or more gases selected from helium, argon, nitrogen, and hydrogen through a headspace of a batch reaction.
[0130] In embodiments, the conditions for dehydrogenation include contacting the substance with one or more dehydrogenation catalysts. In embodiments, the one or more dehydrogenation catalysts include homogeneous catalysts. In embodiments, the one or more dehydrogenation catalysts include heterogeneous catalysts. In embodiments, the one or more dehydrogenation catalysts are immobilized catalysts.
[0131] In embodiments, the formation of one or more olefin units in the substance includes subjecting the substance to conditions for cracking. In embodiments, (i) performing one or more reactions to form one or more olefin units in the substance includes subjecting the substance to conditions for cracking. In embodiments, cracking is thermal cracking. In embodiments, cracking is catalytic cracking. In embodiments, cracking is fluid catalytic cracking. In embodiments, cracking includes hydrocracking. In embodiments, conditions for cracking include heating to a temperature of 100°C to 900°C. In embodiments, conditions for cracking include heating to a temperature of 300°C to 700°C. In embodiments, conditions for cracking include heating to a temperature of 300°C to 600°C. In embodiments, conditions for cracking include heating to a temperature of 400°C to 650°C. In embodiments, conditions for cracking include treatment with one or more catalysts selected from alumina, silica, X-type zeolite, and Y-type zeolite. In embodiments, conditions for cracking include selective formation of olefins from paraffins. In embodiments, conditions for cracking include selective formation of monoolefins or non-conjugated dienes from paraffins. In embodiments, the conditions for cracking include the selective formation of mono-olefins from paraffins.
[0132] In an embodiment, the formation of one or more olefin units includes polymerization. In an embodiment, polymerization includes terminating chain growth. In an embodiment, polymerization includes terminating chain growth to release one or more olefin units. In an embodiment, terminating chain growth includes β-hydride elimination. In an embodiment, terminating chain growth includes chain transfer to a monomer. In an embodiment, the formation of one or more olefin units includes polymerizing one or more monomer units or comonomer units including two or more degrees of unsaturation. In an embodiment, the one or more monomer units comonomer units including two or more degrees of unsaturation are polyenes (e.g., dienes) or alkynes. In an embodiment, the one or more monomer units comonomer units including two or more degrees of unsaturation are selected from butadiene, acetylene and norbornadiene.
[0133] In embodiments, the formation of one or more olefin units comprises post-polymerization modification. In embodiments, the post-polymerization modification comprises one or more reaction sequences selected from the group consisting of: (i) C—H olefination; (ii) C—H functionalization to install heteroatom X followed by elimination of HX; (iii) C—H formylation to install aldehydes followed by Wittig coupling; (iv) C—H carboxylation to install esters followed by treatment with Tebbe reagent or Petasis reagent; (v) Julia olefination; and (vi) C—H acetylation to install one or more alkynes followed by reduction of the one or more alkynes to alkenes. In embodiments, the post-polymerization modification comprises C—H functionalization to install heteroatom X followed by elimination of HX. In embodiments, the post-polymerization modification comprises C—H halogenation followed by elimination. In embodiments, the post-polymerization modification comprises C—H halogenation followed by base-promoted elimination.
[0134] In an embodiment, the formation of one or more olefin units includes the installation of a leaving group on a substance. In an embodiment, the formation of one or more olefin units includes the installation of a leaving group on a substance and the elimination of a leaving group. In an embodiment, the leaving group is selected from -F, -Cl, -Br, -I, -OTf, -OTs, -OMs, -(OR2) + 、-(NR3) + , OC(O)R, OC(O)OR, OC(O)X and SO2R, wherein R and X are independently selected from H, substituted or unsubstituted C 1- C 30 In one embodiment, the leaving group is selected from -F, -Cl, -Br and -I. In one embodiment, the leaving group is selected from -Cl, -Br and -I. In one embodiment, the leaving group is -I.
[0135] In embodiments, the method further comprises a pre-metathesis step performed after (i) forming the one or more olefins, before (ii) subjecting to conditions for olefin metathesis, and before (iii) subjecting to conditions for olefin isomerization. In embodiments, the pre-metathesis step comprises treating with one or more olefin metathesis catalysts. In embodiments, the pre-metathesis step comprises treating with one or more olefins. In embodiments, the pre-metathesis step comprises treating with ethylene. In embodiments, the pre-metathesis step comprises treating with ethylene and one or more olefin metathesis catalysts.
[0136] In embodiments, the conditions for olefin metathesis include treatment with one or more olefins. In embodiments, the conditions for olefin metathesis include treatment with one or more exogenously added olefins. In embodiments, the conditions for olefin metathesis include treatment with 0.1 equivalent to 1000 equivalents of the one or more olefins. In embodiments, the conditions for olefin metathesis include treatment with an independently selected C 2- C 40 In embodiments, the conditions for olefin metathesis include treatment with an optionally substituted C2 olefin. In embodiments, the conditions for olefin metathesis include treatment with one or more olefins independently selected from the group consisting of ethylene, propylene, 1-butene, 2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, 3-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 2-octene, 3-octene, 4-octene, 1-nonene, 2-nonene, 3-nonene, 4-nonene, 1-decene, 2-decene, 3-decene, 4-decene, 5-decene, 1-undecene, 2-undecene, 3-undecene, 4-un ... 1-Tetradecene, 2-Tetradecene, 3-Tetradecene, 4-Tetradecene, 5-Tetradecene, 6-Tetradecene, and 7-Tetradecene.
[0137] In embodiments, the one or more olefins include one or more gaseous olefins. In embodiments, the conditions for olefin metathesis include processing with the one or more gaseous olefins of 0.1 bar to 1000 bar. In embodiments, the conditions for olefin metathesis include processing with the one or more gaseous olefins of 5 bar to 100 bar. In embodiments, the conditions for olefin metathesis include processing with the one or more gaseous olefins of 10 bar to 100 bar. In embodiments, the conditions for olefin metathesis include processing with ethylene. In embodiments, the conditions for olefin metathesis include processing with ethylene under a pressure of 0.1 bar to 1000 bar. In embodiments, the conditions for olefin metathesis include conditions for the decomposition of ethylene alcohol. In embodiments, the conditions for olefin metathesis include processing with propylene. In embodiments, the conditions for olefin metathesis include processing with propylene under a pressure of 0.1 bar to 1000 bar. In embodiments, the conditions for olefin metathesis include conditions for the decomposition of propylene alcohol. In embodiments, the conditions for olefin metathesis include processing with butene. In embodiments, the conditions for olefin metathesis include treatment with butenes at a pressure of 0.1 bar to 1000 bar. In embodiments, the conditions for olefin metathesis include conditions for butene alcohol decomposition. In embodiments, the conditions for olefin metathesis include treatment with 2-butene. In embodiments, the conditions for olefin metathesis include treatment with 2-butene at a pressure of 0.1 bar to 1000 bar. In embodiments, the conditions for olefin metathesis include conditions for 2-butene alcohol decomposition. In embodiments, the conditions for olefin metathesis include treatment with ethylene and one or more olefin metathesis catalysts.
[0138] In embodiments, the conditions for olefin metathesis include heating at 20°C to 500°C. In embodiments, the conditions for olefin metathesis include heating at 20°C to 200°C. In embodiments, the conditions for olefin metathesis include heating at 40°C to 170°C. In embodiments, the conditions for olefin metathesis include heating at 40°C to 160°C. In embodiments, the conditions for olefin metathesis include heating at 140°C to 170°C. In embodiments, the conditions for olefin metathesis include heating at 40°C to 100°C.
[0139] In embodiments, the pure material is subjected to conditions for olefin metathesis. In embodiments, the conditions for olefin metathesis include melt dehydrogenation of the material. In embodiments, the conditions for olefin metathesis include melting the polymer. In embodiments, the conditions for olefin metathesis include contacting the material with one or more solvents. In embodiments, the conditions for olefin metathesis include contacting the material with one or more organic solvents. In embodiments, the conditions for olefin metathesis include contacting the material with one or more hydrocarbon solvents. In embodiments, conditions for olefin metathesis comprise contacting the material with one or more solvents selected from the group consisting of benzene, toluene, o-xylene, m-xylene, p-xylene, dichlorobenzene (e.g., o-dichlorobenzene), trichlorobenzene (e.g., 1,2,4-trichlorobenzene), dioxane, tetrahydrofuran, tetrahydropyran, acetone, chloroform, carbon tetrachloride, methylene chloride, ethyl acetate, pentane, pentanes, hexane, hexanes, heptane, heptanes, octane, octanes, nonane, nonanes, decane, decanes, undecane, undecanes, dodecane, and dodecanes.
[0140] In embodiments, the conditions for olefin metathesis include conducting a batch reaction. In embodiments, the conditions for olefin metathesis include flowing one or more gases through a headspace of a batch reaction. In embodiments, the conditions for olefin metathesis include conducting a continuous flow reaction. In embodiments, the conditions for olefin metathesis include flowing one or more gases selected from helium, argon, nitrogen, and hydrogen through a headspace of a batch reaction.
[0141] In embodiments, the conditions for olefin metathesis include contacting the substance with one or more olefin metathesis catalysts. In embodiments, the one or more olefin metathesis catalysts include one or more homogeneous catalysts. In embodiments, the one or more olefin metathesis catalysts include one or more heterogeneous catalysts. In embodiments, one or more of the one or more olefin metathesis catalysts are immobilized catalysts. In embodiments, the one or more olefin metathesis catalysts are selected from Schrock-type olefin metathesis catalysts, Grubbs-type olefin metathesis catalysts, Hoveyda / Grubbs-type olefin metathesis catalysts, and heterogeneous olefin metathesis catalysts. In embodiments, the one or more olefin metathesis catalysts include Hoveyda Grubbs II. In embodiments, the one or more olefin metathesis catalysts are Hoveyda Grubbs II. In embodiments, the one or more olefin metathesis catalysts include Ultra-Nitro-Cat. In embodiments, the one or more olefin metathesis catalysts include Re2O7. In embodiments, the one or more olefin metathesis catalysts include Re2O7 on alumina. In embodiments, the one or more olefin metathesis catalysts include Re2O7 on silica. In embodiments, the one or more olefin metathesis catalysts include Re2O7 on a zeolite. In embodiments, the one or more olefin metathesis catalysts include Re2O7 on a Y-type zeolite. In embodiments, the one or more olefin metathesis catalysts include tungsten.
[0142] In embodiments, the conditions for olefin metathesis include performing more than one metathesis reaction for each molecule present in the substance. In embodiments, the conditions for olefin metathesis include performing more than one non-degenerate metathesis reaction for each molecule present in the substance. In embodiments, the conditions for olefin metathesis include performing from 2 to 100,000 non-degenerate metathesis reactions for each molecule present in the substance.
[0143] In an embodiment, the conditions for olefin isomerization include conditions for positional olefin isomerization. In an embodiment, the conditions for olefin isomerization include conditions for positional long-range olefin isomerization. In an embodiment, the conditions for olefin isomerization include conditions for positional short-range olefin isomerization. In an embodiment, the conditions for olefin isomerization include conditions for isomerizing terminal olefins to internal olefins. In an embodiment, the conditions for olefin isomerization include carrying out one or more olefin isomerizations, carried out by one or more intermediates independently selected from the following: metal-hydride intermediates, metal-allyl intermediates, cationic intermediates, carbonic cation intermediates, anionic intermediates, carbonic anionic intermediates, free radical intermediates, metal-radical intermediates, free radical cation intermediates and free radical anionic intermediates. In an embodiment, the one or more olefin isomerizations are carried out by one or more metal-hydride intermediates. In an embodiment, the one or more olefin isomerizations are carried out by one or more metal-allyl intermediates. In an embodiment, the one or more olefin isomerizations are carried out by one or more cationic intermediates.
[0144] In embodiments, conditions for olefin isomerization comprise heating at 20°C to 1000°C. In embodiments, conditions for olefin isomerization comprise heating at 20°C to 200°C. In embodiments, conditions for olefin isomerization comprise heating at 20°C to 175°C.
[0145] In embodiments, pure substances are subjected to conditions for olefin isomerization. In embodiments, conditions for olefin isomerization include melt dehydrogenation substances. In embodiments, conditions for olefin isomerization include melting the polymer. In embodiments, conditions for olefin isomerization include contacting substances with one or more solvents. In embodiments, conditions for olefin isomerization include contacting substances with one or more solvents selected from the following: benzene, toluene, o-xylene, m-xylene, p-xylene, dichlorobenzene (e.g., o-dichlorobenzene), trichlorobenzene (e.g., 1,2,4-trichlorobenzene), dioxane, tetrahydrofuran, tetrahydropyran, acetone, chloroform, carbon tetrachloride, methylene chloride, ethyl acetate, pentane, pentanes, hexane, hexanes, heptanes, heptanes, octane, octanes, nonanes, nonanes, decane, decanes, undecane, undecanes, dodecane and dodecanes. In embodiments, conditions for olefin isomerization include treatment with one or more bases.
[0146] In embodiments, the conditions for olefin isomerization include contacting the material with one or more olefin isomerization catalysts. In embodiments, the one or more olefin isomerization catalysts include homogeneous catalysts. In embodiments, the one or more olefin isomerization catalysts include heterogeneous catalysts. In embodiments, the one or more olefin isomerization catalysts include immobilized catalysts. In embodiments, the conditions for olefin isomerization include treatment with one or more olefin isomerization catalysts. In embodiments, the conditions for olefin isomerization include treatment with one or more homogeneous olefin isomerization catalysts. In embodiments, the conditions for olefin isomerization include treatment with one or more heterogeneous olefin isomerization catalysts.
[0147] In embodiments, the conditions for olefin isomerization include conducting a batch reaction. In embodiments, the conditions for olefin isomerization include flowing one or more gases through the headspace of the batch reaction. In embodiments, the conditions for olefin isomerization include conducting a continuous flow reaction. In embodiments, the conditions for olefin isomerization include flowing one or more gases selected from helium, argon, nitrogen, and hydrogen through the headspace of the batch reaction.
[0148] In embodiments, (b) being subjected to conditions for olefin metathesis and (c) being subjected to conditions for olefin isomerization are performed together as isomerized olefin metathesis. In embodiments, the one or more olefins formed in (a) forming one or more olefins are subjected to isomerized olefin metathesis. In embodiments, isomerized olefin metathesis includes isomerized ethylene alcohol decomposition. In embodiments, isomerized olefin metathesis is isomerized ethylene alcohol decomposition. In embodiments, isomerized olefin metathesis includes repeating a cycle including (i) olefin metathesis and (ii) olefin isomerization. In embodiments, the cycle including (i) olefin metathesis and (ii) olefin isomerization is repeated 1 to 500,000 times. In embodiments, the cycle including (i) olefin metathesis and (ii) olefin isomerization is repeated 1 to 200,000 times. In embodiments, the cycle including (i) olefin metathesis and (ii) olefin isomerization is repeated 1 to 100,000 times. In embodiments, the cycle comprising (i) olefin metathesis and (ii) olefin isomerization is repeated from 1 to 50,000 times. In embodiments, the cycle comprising (i) olefin metathesis and (ii) olefin isomerization is repeated from 1 to 5,000 times. In embodiments, the cycle comprising (i) olefin metathesis and (ii) olefin isomerization is repeated from 500 times. In embodiments, the cycle comprising (i) olefin metathesis and (ii) olefin isomerization is repeated from 1 to 50 times. In embodiments, the cycle comprising (i) olefin metathesis and (ii) olefin isomerization is repeated at least 1 time, at least 50 times, at least 100 times, at least 500 times, at least 2000 times, at least 10,000 times, at least 50,000 times, at least 100,000 times, at least 500,000 times, or more times. Alternatively or additionally, in embodiments, the cycle comprising (i) olefin metathesis and (ii) olefin isomerization is repeated at most 1 time, at most 50 times, at most 100 times, at most 500 times, at most 2000 times, at most 10,000 times, at most 50,000 times, at most 100,000 times, at most 500,000 times, or less.
[0149] In embodiments, the cycle comprising (i) olefin metathesis and (ii) olefin isomerization is repeated from about 1 time to about 500,000 times. In embodiments, the cycle comprising (i) olefin metathesis and (ii) olefin isomerization is repeated at least about 1 time. In embodiments, the cycle comprising (i) olefin metathesis and (ii) olefin isomerization is repeated up to about 500,000 times. In embodiments, the cycle comprising (i) olefin metathesis and (ii) olefin isomerization is repeated about 1 time to about 50 times, about 1 time to about 100 times, about 1 time to about 500 times, about 1 time to about 1,000 times, about 1 time to about 5,000 times, about 1 time to about 10,000 times, about 1 time to about 25,000 times, about 1 time to about 50,000 times, about 1 time to about 100,000 times, about 1 time to about 250,000 times, about 1 time to about 500,000 times, about 50 times to about 100 times, about 50 times to about 500 times, about 50 times to about 1,000 times, about 50 times to about 5,000 times, about 50 times to about 5,000 times, about 50 times to about 10,000 times, about 50 times to about 250,000 times, about 1 time to about 500,000 times, about 50 times to about 100 times, about 50 times to about 500 times, about 50 times to about 1,000 times, about 50 times to about 5,000 times, about 50 times to about 5,000 times. times to about 10,000 times, about 50 times to about 25,000 times, about 50 times to about 50,000 times, about 50 times to about 100,000 times, about 50 times to about 250,000 times, about 50 times to about 500,000 times, about 100 times to about 500 times, about 100 times to about 1,000 times, about 100 times to about 5,000 times, about 100 times to about 10,000 times, about 100 times to about 25,000 times, about 100 times to about 50,000 times, about 100 times to about 100,000 times, about 100 times to about 250,000 times, about 100 times to about 500,000 times, From about 500 to about 1,000 times, from about 500 to about 5,000 times, from about 500 to about 10,000 times, from about 500 to about 25,000 times, from about 500 to about 50,000 times, from about 500 to about 100,000 times, from about 500 to about 250,000 times, from about 500 to about 500,000 times, from about 1,000 to about 5,000 times, from about 1,000 to about 10,000 times, from about 1,000 to about 25,000 times, from about 1,000 to about 50,000 times, from about 1,000 to about 100,000 times, from about 1,000 to about 25 0,000 times, about 1,000 times to about 500,000 times, about 5,000 times to about 10,000 times, about 5,000 times to about 25,000 times, about 5,000 times to about 50,000 times, about 5,000 times to about 100,000 times, about 5,000 times to about 250,000 times, about 5,000 times to about 500,000 times, about 10,000 times to about 25,000 times, about 10,000 times to about 50,000 times, about 10,000 times to about 100,000 times, about 10,000 times to about 250,000 times, about 10,000 times to about 500,000 timesThe present invention relates to a method for treating a patient's skin with a plurality of different kinds of adhesives. The method comprises the following steps: first, step 1, step 2, step 3, step 4, step 5, step 6, step 7, step 8, step 9, step 10, step 11, step 12, step 13, step 14, step 15, step 16, step 17, step 18, step 19, step 20, step 21, step 22, step 23, step 24, step 25, or a plurality of different kinds of adhesives. The method comprises the following steps: first, step 1, step 2, step 3, step 4, step 5, step 6, step 7, step 8, step 9, step 10, step 11, step 12, step 13, step 14, step 15, step 16, step 17, step 18, step 19, step 20, step 21, step 22, step 23, step 24, step 25, In embodiments, the cycle comprising (i) olefin metathesis and (ii) olefin isomerization is repeated about 1 time, about 50 times, about 100 times, about 500 times, about 1,000 times, about 5,000 times, about 10,000 times, about 25,000 times, about 50,000 times, about 100,000 times, about 250,000 times, or about 500,000 times.
[0150] In embodiments, the isomerized olefin metathesis is conducted at 20°C to 500°C. In embodiments, the pure material is subjected to the conditions for isomerized olefin metathesis. In embodiments, the conditions for isomerized olefin metathesis include melt dehydrogenating the material. In embodiments, the conditions for isomerized olefin metathesis include melting the polymer. In embodiments, the conditions for isomerized olefin metathesis include contacting the material with one or more solvents. In embodiments, conditions for isomerization olefin metathesis include contacting the material with one or more solvents selected from the group consisting of benzene, toluene, o-xylene, m-xylene, p-xylene, dichlorobenzene (e.g., o-dichlorobenzene), trichlorobenzene (e.g., 1,2,4-trichlorobenzene), dioxane, tetrahydrofuran, tetrahydropyran, acetone, chloroform, carbon tetrachloride, methylene chloride, ethyl acetate, pentane, pentanes, hexane, hexanes, heptane, heptanes, octane, octanes, nonane, nonanes, decane, decanes, undecane, undecanes, dodecane, dodecanes. In embodiments, conditions for isomerization olefin metathesis include treatment with one or more bases.
[0151] In embodiments, conditions for isomerizing olefin metathesis include contacting the material with one or more olefin metathesis catalysts. In embodiments, one or more of the one or more olefin metathesis catalysts are capable of olefin isomerization. In embodiments, conditions for isomerizing olefin metathesis include contacting the material with one or more olefin isomerization catalysts. In embodiments, one or more of the one or more olefin isomerization catalysts are capable of catalyzing olefin metathesis. In embodiments, conditions for isomerizing olefin metathesis include contacting the material with one or more olefin metathesis catalysts and contacting with one or more olefin isomerization catalysts.
[0152] In embodiments, the conditions for isomerization olefin metathesis include performing a batch reaction. In embodiments, the conditions for isomerization olefin metathesis include flowing one or more gases through the head space of the batch reaction. In embodiments, the conditions for isomerization olefin metathesis include performing a continuous flow reaction. In embodiments, the conditions for isomerization olefin metathesis include flowing one or more gases selected from helium, argon, nitrogen and hydrogen through the head space of the batch reaction. In embodiments, the conditions for isomerization olefin metathesis include continuously removing one or more gases. In embodiments, the conditions for isomerization olefin metathesis include continuously removing propylene. In embodiments, the conditions for isomerization olefin metathesis include continuously adding one or more gases. In embodiments, the conditions for isomerization olefin metathesis include continuously adding ethylene.
[0153] In embodiments, the method produces olefins. In embodiments, the method produces olefins containing less carbon per molecule than the substance. In embodiments, the method further comprises reactive distillation. In embodiments, the method produces propylene. In embodiments, the method produces propylene at a yield of 0.1% to 100%. In embodiments, the method produces propylene at a yield of 50% to 100%. In embodiments, the method produces propylene at a yield of 50% to 99.9%. In embodiments, the method produces propylene at a yield of 50% to 99%. In embodiments, the method produces propylene at a yield of 60% to 95%. In embodiments, the method produces propylene at a selectivity of 0% to 100%. In embodiments, the method produces propylene at a selectivity of 0.01% to 99.99%. In embodiments, the method produces propylene at a selectivity of 1% to 99.99%. In embodiments, the method produces propylene at a selectivity of 50% to 99.99%.
[0154] In one aspect, a method for preparing olefins is provided, the method comprising mixing a dehydrogenated polymer with one or more olefin metathesis agents and one or more isomerization agents; wherein: (i) the dehydrogenated polymer comprises at least 20 carbon atoms; or (ii) prior to mixing, the method comprises mixing the polymer with one or more dehydrogenation agents to form the dehydrogenated polymer.
[0155] In one aspect, a method for preparing olefins is provided, the method comprising mixing a dehydrogenated polymer with one or more olefin metathesis agents and one or more isomerization agents; wherein: (i) the dehydrogenated polymer comprises up to 10% unsaturated olefin monomer units; (ii) the dehydrogenated polymer comprises at least 20 carbon atoms; or (iii) prior to mixing, the method comprises mixing the polymer with one or more dehydrogenation agents to form the dehydrogenated polymer.
[0156] In one aspect, a method for preparing a dehydrogenated polymer is provided, the method comprising mixing a polymer with one or more dehydrogenating agents, wherein: (i) a percentage of monomer units in the dehydrogenated polymer of 0.01% to 1.5%, or 1.7% to 2.3%, or 2.4% to 4.3%, or 4.5% to 13.2% are unsaturated; (ii) the dehydrogenated polymer has a number average molecular weight of about 2,200 Da or greater; (iii) the dehydrogenated polymer has a number average molecular weight of about 2,200 Da to about 6,500 Da, and a percentage of monomer units in the dehydrogenated polymer of 0.01% to 10% are unsaturated; or (iv) the dehydrogenated polymer has a number average molecular weight of about 1,000 Da to about 500,000 Da, and a percentage of monomer units in the dehydrogenated polymer of 0.01% to 1.5%, or 1.7% to 2.3%, or 2.4% to 4.3%, or 4.5% to 10% are unsaturated.
[0157] In an embodiment, the substituted or unsubstituted olefin is a substituted or unsubstituted propylene. In an embodiment, the first material is a substituted or unsubstituted dehydrogenated polyethylene.
[0158] In embodiments, the dehydrogenation polymer has a number average molecular weight of about 2,200Da to about 6,500Da or about 6,700Da to about 15,000Da. In embodiments, the dehydrogenation polymer has a number average molecular weight of about 2,200Da to about 6,500Da. In embodiments, the dehydrogenation polymer has a number average molecular weight of about 2,200Da to about 6,000Da. In embodiments, the dehydrogenation polymer has a number average molecular weight of about 2,200Da to about 5,000Da. In embodiments, the dehydrogenation polymer has a number average molecular weight of about 2,200Da to about 4,000Da. In embodiments, the dehydrogenation polymer has a number average molecular weight of about 2,200Da to about 4,000Da. In embodiments, the dehydrogenation polymer has a number average molecular weight of about 6,700Da to about 500,000Da. In embodiments, the dehydrogenation polymer has a number average molecular weight of about 6,700Da to about 400,000Da. In embodiments, the dehydrogenation polymer has a number average molecular weight of about 6,700Da to about 300,000Da. In embodiments, the dehydrogenation polymer has a number average molecular weight of about 6,700Da to about 200,000Da. In embodiments, the dehydrogenation polymer has a number average molecular weight of about 6,700Da to about 100,000Da. In embodiments, the dehydrogenation polymer has a number average molecular weight of about 6,700Da to about 80,000Da. In embodiments, the dehydrogenation polymer has a number average molecular weight of about 6,700Da to about 60,000Da. In embodiments, the dehydrogenation polymer has a number average molecular weight of about 6,700Da to about 40,000Da. In embodiments, the dehydrogenation polymer has a number average molecular weight of about 6,700Da to about 20,000Da. In embodiments, the dehydrogenation polymer has a number average molecular weight of about 6,700Da to about 15,000Da.
[0159] In embodiments, the dehydrogenation polymer has a number average molecular weight of 2,200Da to 6,500Da or 6,700Da to 15,000Da. In embodiments, the dehydrogenation polymer has a number average molecular weight of 2,200Da to 6,500Da. In embodiments, the dehydrogenation polymer has a number average molecular weight of 2,200Da to 6,000Da. In embodiments, the dehydrogenation polymer has a number average molecular weight of 2,200Da to 5,000Da. In embodiments, the dehydrogenation polymer has a number average molecular weight of 2,200Da to 4,000Da. In embodiments, the dehydrogenation polymer has a number average molecular weight of 2,200Da to 4,000Da. In embodiments, the dehydrogenation polymer has a number average molecular weight of 6,700Da to 500,000Da. In embodiments, the dehydrogenation polymer has a number average molecular weight of 6,700Da to 400,000Da. In embodiments, the dehydrogenation polymer has a number average molecular weight of 6,700Da to 300,000Da. In embodiments, the dehydrogenation polymer has a number average molecular weight of 6,700Da to 200,000Da. In embodiments, the dehydrogenation polymer has a number average molecular weight of 6,700Da to 100,000Da. In embodiments, the dehydrogenation polymer has a number average molecular weight of 6,700Da to 80,000Da. In embodiments, the dehydrogenation polymer has a number average molecular weight of 6,700Da to 60,000Da. In embodiments, the dehydrogenation polymer has a number average molecular weight of 6,700Da to 40,000Da. In embodiments, the dehydrogenation polymer has a number average molecular weight of 6,700Da to 20,000Da. In embodiments, the dehydrogenation polymer has a number average molecular weight of 6,700Da to 15,000Da.
[0160] In embodiments, about 10% or less of the monomer units in the dehydrogenated polymer are unsaturated. In embodiments, about 0.01% to about 11% of the monomer units in the dehydrogenated polymer are unsaturated. In embodiments, about 0.01% to about 10% of the monomer units in the dehydrogenated polymer are unsaturated. In embodiments, about 0.01% to about 9% of the monomer units in the dehydrogenated polymer are unsaturated. In embodiments, about 0.01% to about 8% of the monomer units in the dehydrogenated polymer are unsaturated. In embodiments, about 0.01% to about 1.5% of the monomer units in the dehydrogenated polymer are unsaturated. In embodiments, about 2.4% to about 4.3% of the monomer units in the dehydrogenated polymer are unsaturated. In embodiments, about 4.5% to about 13.2% of the monomer units in the dehydrogenated polymer are unsaturated. In embodiments, about 1% to about 3% of the monomer units in the dehydrogenated polymer are unsaturated. In embodiments, about 1.5% to about 3% of the percentage of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, about 1.7% to about 2.3% of the percentage of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, about 1.7% to about 2.1% of the percentage of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, about 1.9% to about 2.1% of the percentage of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, about 1.7% of the percentage of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, about 1.8% of the percentage of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, about 1.9% of the percentage of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, about 2% of the percentage of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, about 2.1% of the percentage of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, about 2.2% of the percentage of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, about 2.3% of the monomer units in the dehydrogenated polymer are unsaturated.
[0161] In an embodiment, 10% or less of the monomer units in the dehydrogenated polymer are unsaturated. In an embodiment, 0.01% to 11% of the monomer units in the dehydrogenated polymer are unsaturated. In an embodiment, 0.01% to 10% of the monomer units in the dehydrogenated polymer are unsaturated. In an embodiment, 0.01% to 9% of the monomer units in the dehydrogenated polymer are unsaturated. In an embodiment, 0.01% to 8% of the monomer units in the dehydrogenated polymer are unsaturated. In an embodiment, 0.01% to 1.5% of the monomer units in the dehydrogenated polymer are unsaturated. In an embodiment, 2.4% to 4.3% of the monomer units in the dehydrogenated polymer are unsaturated. In an embodiment, 4.5% to 13.2% of the monomer units in the dehydrogenated polymer are unsaturated. In an embodiment, 1% to 3% of the monomer units in the dehydrogenated polymer are unsaturated. In an embodiment, 1.5% to 3% of the monomer units in the dehydrogenated polymer are unsaturated. In an embodiment, 1.7% to 2.3% of the monomer units in the dehydrogenated polymer are unsaturated. In an embodiment, 1.7% to 2.1% of the monomer units in the dehydrogenated polymer are unsaturated. In an embodiment, 1.9% to 2.1% of the monomer units in the dehydrogenated polymer are unsaturated. In an embodiment, 1.7% of the monomer units in the dehydrogenated polymer are unsaturated. In an embodiment, 1.8% of the monomer units in the dehydrogenated polymer are unsaturated. In an embodiment, 1.9% of the monomer units in the dehydrogenated polymer are unsaturated. In an embodiment, 2% of the monomer units in the dehydrogenated polymer are unsaturated. In an embodiment, 2.1% of the monomer units in the dehydrogenated polymer are unsaturated. In an embodiment, 2.2% of the monomer units in the dehydrogenated polymer are unsaturated. In an embodiment, 2.3% of the monomer units in the dehydrogenated polymer are unsaturated.
[0162] In embodiments, the dehydrogenated polymer has a number average molecular weight of about 1,000 Da to about 500,000 Da, and a percentage of the monomer units in the dehydrogenated polymer of 0.01% to 1.5%, or 1.7% to 2.3%, or 2.4% to 4.3%, or 4.5% to 10% are unsaturated. In embodiments, the dehydrogenated polymer has a number average molecular weight of about 2,200 Da to about 100,000 Da, and a percentage of the monomer units in the dehydrogenated polymer of 0.01% to 1.5%, or 1.7% to 2.3%, or 2.4% to 4.3%, or 4.5% to 10% are unsaturated. In embodiments, the dehydrogenated polymer has a number average molecular weight of about 2,200 Da to about 50,000 Da, and a percentage of the monomer units in the dehydrogenated polymer of 0.01% to 1.5%, or 1.7% to 2.3%, or 2.4% to 4.3%, or 4.5% to 10% are unsaturated. In embodiments, the dehydrogenated polymer has a number average molecular weight of about 2,200 Da to about 20,000 Da, and a percentage of the monomer units in the dehydrogenated polymer of 0.01% to 1.5%, or 1.7% to 2.3%, or 2.4% to 4.3%, or 4.5% to 10% are unsaturated. In embodiments, the dehydrogenated polymer has a number average molecular weight of about 2,200 Da to about 10,000 Da, and a percentage of the monomer units in the dehydrogenated polymer of 0.01% to 1.5%, or 1.7% to 2.3%, or 2.4% to 4.3%, or 4.5% to 10% are unsaturated. In embodiments, the dehydrogenated polymer has a number average molecular weight of about 2,200 Da to about 6,500 Da, and a percentage of the monomer units in the dehydrogenated polymer of 0.01% to 1.5%, or 1.7% to 2.3%, or 2.4% to 4.3%, or 4.5% to 10% are unsaturated.
[0163] In embodiments, the method further comprises mixing the dehydrogenated polymer with one or more olefin metathesis agents and one or more isomerization agents to form olefins.
[0164] In an embodiment, the dehydrogenated polymer is a substituted or unsubstituted dehydrogenated polyethylene. In an embodiment, the olefin is a substituted or unsubstituted propylene.
[0165] In embodiments, the dehydrogenating polymer, the one or more olefin metathesis reagents, and the one or more isomerization reagents are mixed simultaneously. In embodiments, the dehydrogenating polymer and the one or more olefin metathesis reagents are mixed prior to adding the one or more isomerization reagents. In embodiments, the dehydrogenating polymer and the one or more additional olefin metathesis reagents are mixed prior to adding the one or more olefin metathesis reagents and the one or more isomerization reagents.
[0166] In embodiments, the one or more olefin metathesis reagents include an ethenolysis catalyst. In embodiments, the one or more olefin metathesis reagents include one or more homogeneous olefin metathesis catalysts or one or more heterogeneous olefin metathesis catalysts. In embodiments, the one or more olefin metathesis reagents include one or more homogeneous olefin metathesis catalysts. In embodiments, the one or more olefin metathesis reagents include ... also include ethylene.
[0167] In embodiments, the homogeneous olefin metathesis catalyst is
[0168]
[0169] In embodiments, the homogeneous olefin metathesis catalyst is In embodiments, the homogeneous olefin metathesis catalyst is In embodiments, the homogeneous olefin metathesis catalyst is In embodiments, the homogeneous olefin metathesis catalyst is
[0170] In embodiments, the heterogeneous olefin metathesis catalyst is Re2O7 / Al2O3 or WO3 / Al2O3. In embodiments, the heterogeneous olefin metathesis catalyst is Re2O7 / Al2O3. In embodiments, the heterogeneous olefin metathesis catalyst is WO3 / Al2O3.
[0171] In embodiments, the one or more isomerization agents include one or more homogeneous isomerization catalysts or one or more heterogeneous isomerization catalysts. In embodiments, the one or more isomerization agents include one or more homogeneous isomerization catalysts. In embodiments, the one or more isomerization agents include one or more heterogeneous isomerization catalysts.
[0172] In embodiments, the one or more homogeneous isomerization catalysts are selected from: In embodiments, the one or more homogeneous isomerization catalysts are In embodiments, the one or more homogeneous isomerization catalysts are In embodiments, the one or more homogeneous isomerization catalysts are [Rh(cod)2]BF4. In embodiments, the one or more homogeneous isomerization catalysts are
[0173] In embodiments, the one or more heterogeneous isomerization catalysts are selected from the group consisting of: Na / Al2O3, K / Al2O3, Mg / Al2O3, MgO, NaO2, and KO2. In embodiments, the one or more heterogeneous isomerization catalysts are Na / Al2O3. In embodiments, the one or more heterogeneous isomerization catalysts are K / Al2O3. In embodiments, the one or more heterogeneous isomerization catalysts are Mg / Al2O3. In embodiments, the one or more heterogeneous isomerization catalysts are MgO. In embodiments, the one or more heterogeneous isomerization catalysts are NaO2. In embodiments, the one or more heterogeneous isomerization catalysts are KO2.
[0174] In embodiments, the one or more heterogeneous isomerization catalysts include a Group VI or Group VII metal (W, Mo, Re) on SiO2 or Al2O3. In embodiments, the Group VI or Group VII metal (W, Mo, Re) on SiO2 or Al2O3 is first treated with a weak base (e.g., Na2CO3). Without being bound by any particular theory, in embodiments, the weak base is sufficient to neutralize the acidic sites. In embodiments, the one or more heterogeneous isomerization catalysts include K, Na, Na / K alloy, or Li supported on Al2O3. In embodiments, the one or more heterogeneous isomerization catalysts include an alkali metal (e.g., a Group VI or Group VII metal such as W, Mo, Re) and a SiO2 support. In embodiments, the one or more heterogeneous isomerization catalysts include K, Na, Na / K alloy, or Li supported on SiO2.
[0175] In embodiments, the one or more heterogeneous metathesis catalysts further include a tin promoter. In embodiments, the tin promoter is a tetraalkyltin promoter. In embodiments, the one or more heterogeneous metathesis catalysts further include a tetramethyltin promoter. In embodiments, the one or more metathesis isomerization catalysts further include a tetraethyltin promoter. In embodiments, the one or more heterogeneous metathesis catalysts further include a tetrapropyltin promoter. In embodiments, the one or more heterogeneous metathesis catalysts further include a tetrabutyltin promoter. In embodiments, the one or more heterogeneous metathesis catalysts further include a tetrabenzyltin promoter.
[0176] In an embodiment, the substituted or unsubstituted polymer is a high density polyethylene, a low density polyethylene or a linear low density polyethylene or a copolymer thereof. In an embodiment, the substituted or unsubstituted polymer is a high density polyethylene. In an embodiment, the substituted or unsubstituted polymer is a low density polyethylene. In an embodiment, the substituted or unsubstituted polymer is a linear low density polyethylene.
[0177] In embodiments, the one or more dehydrogenation agents include a transfer dehydrogenation catalyst.
[0178] In embodiments, the one or more dehydrogenation agents include a hydrogen acceptor. In embodiments, the hydrogen acceptor comprises a CC bond, a C=C bond, a C≡C bond, a NN bond, a N=N bond, a N≡N bond, an OO bond, an O=O bond, a CN bond, a C=N bond, a C≡N bond, a CO bond, a C=O bond, a C≡O bond, an SS bond, a CS bond, or a C=S bond. In embodiments, the hydrogen acceptor comprises a CC bond. In embodiments, the hydrogen acceptor comprises a C=C bond. In embodiments, the hydrogen acceptor comprises a C≡C bond. In embodiments, the hydrogen acceptor comprises a NN bond. In embodiments, the hydrogen acceptor comprises an N=N bond. In embodiments, the hydrogen acceptor comprises an N≡N bond. In embodiments, the hydrogen acceptor comprises an OO bond. In embodiments, the hydrogen acceptor comprises an O=O bond. In embodiments, the hydrogen acceptor comprises a CN bond. In embodiments, the hydrogen acceptor comprises a C=N bond. In embodiments, the hydrogen acceptor comprises a C≡N bond. In embodiments, the hydrogen acceptor comprises a CO bond. In embodiments, the hydrogen acceptor comprises a C=O bond. In an embodiment, the hydrogen acceptor comprises a C≡O bond. In an embodiment, the hydrogen acceptor comprises a SS bond. In an embodiment, the hydrogen acceptor comprises a CS bond. In an embodiment, the hydrogen acceptor comprises a C=S bond.
[0179] In embodiments, the hydrogen acceptor is ethylene, propylene, butene, tert-butylethylene, norbornene, norbornadiene, butadiene, styrene, acetylene, O2, CO2, CO, substituted or unsubstituted benzoquinone, or N2. In embodiments, the hydrogen acceptor is ethylene. In embodiments, the hydrogen acceptor is propylene. In embodiments, the hydrogen acceptor is butane. In embodiments, the hydrogen acceptor is tert-butylethylene. In embodiments, the hydrogen acceptor is norbornene. In embodiments, the hydrogen acceptor is norbornadiene. In embodiments, the hydrogen acceptor is butadiene. In embodiments, the hydrogen acceptor is styrene. In embodiments, the hydrogen acceptor is acetylene. In embodiments, the hydrogen acceptor is O2. In embodiments, the hydrogen acceptor is CO2. In embodiments, the hydrogen acceptor is CO. In embodiments, the hydrogen acceptor is substituted or unsubstituted benzoquinone. In embodiments, the hydrogen acceptor is N2.
[0180] In embodiments, the one or more dehydrogenation agents include a heterogeneous dehydrogenation catalyst. In embodiments, the heterogeneous dehydrogenation catalyst includes multiple metal elements. In embodiments, the heterogeneous dehydrogenation catalyst is a bimetallic catalyst. In embodiments, the heterogeneous dehydrogenation catalyst is a Pt / Sn catalyst or a Pt / Zn catalyst. In embodiments, the heterogeneous dehydrogenation catalyst is a Pt / Sn catalyst. In embodiments, the heterogeneous dehydrogenation catalyst is a Pt / Zn catalyst. In embodiments, the heterogeneous dehydrogenation catalyst is a Pt / Sn-Al2O3. In embodiments, the heterogeneous dehydrogenation catalyst is Pt / Zn-SiO2.
[0181] In embodiments, the one or more dehydrogenation agents comprise a homogeneous dehydrogenation catalyst. In embodiments, the homogeneous dehydrogenation catalyst comprises an iridium catalyst. In embodiments, the homogeneous dehydrogenation catalyst comprises a rhodium catalyst. In embodiments, the homogeneous dehydrogenation catalyst comprises a ruthenium catalyst.
[0182] In an embodiment, the one or more dehydrogenation agents include (R)-(-)-5,5′-bis[di(3,5-di-tert-butyl-4-methoxyphenyl)phosphino]-4,4′-bis-1,3-benzodioxole, [(4R)-(4,4′-bis-1,3-benzodioxole)-5,5′-diyl]bis[bis(3,5-di-tert-butyl-4-methoxyphenyl)phosphine] (also commonly referred to as (R)-DTBM-SEGPHOS). In an embodiment, the one or more dehydrogenation reagents include (R)-(-)-5,5′-bis[di(3,5-di-tert-butyl-4-methoxyphenyl)phosphino]-4,4′-bis-1,3-benzodioxole, [(4R)-(4,4′-bis-1,3-benzodioxole)-5,5′-diyl]bis[bis(3,5-di-tert-butyl-4-methoxyphenyl)phosphine] and an iridium catalyst.
[0183] In embodiments, the homogeneous dehydrogenation catalyst has the formula:
[0184]
[0185] M is Ir, Rh, Ru or Os.
[0186] L 1 and L 2 are independently -O-, -S-, -NR 6 - or substituted or unsubstituted alkylene (eg, C1-C8, C1-C6, C1-C4 or C1-C2).
[0187] Each R 3 and R 4The alkyl radicals are independently substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4, or C1-C2), substituted or unsubstituted heteroalkyl (e.g., 2- to 8-membered, 2- to 6-membered, 4- to 6-membered, or 2- to 3-membered), substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6, or C5-C6), substituted or unsubstituted heterocycloalkyl (e.g., 3- to 8-membered, 3- to 6-membered, 4- to 6-membered, 4- to 5-membered, or 5- to 6-membered), substituted or unsubstituted aryl (e.g., C6-C 10 or phenyl) or a substituted or unsubstituted heteroaryl (e.g., 5- to 10-membered, 5- to 9-membered, or 5- to 6-membered).
[0188] R 5 are independently halogen, -CX 5 3. -CHX 5 2. -CH2X 5 、-OCX 5 3. -OCH2X 5 、-OCHX 5 2. -CN, -SO n5 R 5D 、-SO v5 NR 5A R 5B 、-NR 5C NR 5A R 5B 、-ONR 5A R 5B 、-NR 5C C(O)NR 5A R 5B 、-N(O) m5 、-NR 5A R 5B 、-C(O)R 5C 、-C(O)OR 5C 、-OC(O)R 5C 、-OC(O)OR 5C 、-C(O)NR 5A R 5B 、-OC(O)NR 5A R 5B 、-OR 5D 、-SR 5D 、-NR 5A S02R 5D 、-NR 5A C(O)R 5C 、-NR 5A C(O)OR 5C 、-NR 5A OR 5C 、-P(O)2(OR5A )、-OP(O)2(OR 5A )、-OP(R 5A )(R 5B ),-BR 5A R 5B 、-SiR 5A R 5B R 5C , substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4, or C1-C2), substituted or unsubstituted heteroalkyl (e.g., 2- to 8-membered, 2- to 6-membered, 4- to 6-membered, or 2- to 3-membered), substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6, or C5-C6), substituted or unsubstituted heterocycloalkyl (e.g., 3- to 8-membered, 3- to 6-membered, 4- to 6-membered, 4- to 5-membered, or 5- to 6-membered), substituted or unsubstituted aryl (e.g., C6-C 10 or phenyl) or a substituted or unsubstituted heteroaryl (e.g., 5- to 10-membered, 5- to 9-membered, or 5- to 6-membered).
[0189] Each R 6 are independently hydrogen, halogen, -CCl3, -CBr3, -CF3, -CI3, -CHCl2, -CHBr2, -CHF2, -CHI2, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CN, -OH, -NH2, -COOH, -CONH2, -OCCl3, -OCF3, -OCBr3, -OCI3, -OCHCl2, -OCHBr2, -OCHI2, -OCHF2, -OCH2Cl, -OCH2Br, -OCH2I, -OCH CH2F, substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4, or C1-C2), substituted or unsubstituted heteroalkyl (e.g., 2- to 8-membered, 2- to 6-membered, 4- to 6-membered, 2- to 3-membered, or 4- to 5-membered), substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6, or C5-C6), substituted or unsubstituted heterocycloalkyl (e.g., 3- to 8-membered, 3- to 6-membered, 4- to 6-membered, 4- to 5-membered, or 5- to 6-membered), substituted or unsubstituted aryl (e.g., C6-C 10 or phenyl) or a substituted or unsubstituted heteroaryl (e.g., 5- to 10-membered, 5- to 9-membered, or 5- to 6-membered).
[0190] Each R 5A , R 5B , R 5C and R 5Dare independently hydrogen, -CCl3, -CBr3, -CF3, -CI3, -CHCl2, -CHBr2, -CHF2, -CHI2, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CN, -OH, -NH2, -COOH, -CONH2, -OCCl3, -OCF3, -OCBr3, -OCI3, -OCHCl2, -OCHBr2, -OCHI2, -OCHF2, -OCH2Cl, -OCH2Br, -OCH2I, -OCH2F, substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4, or C1-C2), substituted or unsubstituted heteroalkyl (e.g., 2- to 8-membered, 2- to 6-membered, 4- to 6-membered, or 2- to 3-membered), substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6, or C5-C6), substituted or unsubstituted heterocycloalkyl (e.g., 3- to 8-membered, 3- to 6-membered, 4- to 6-membered, 4- to 5-membered, or 5- to 6-membered), substituted or unsubstituted aryl (e.g., C6-C 10 or phenyl) or substituted or unsubstituted heteroaryl (e.g., 5- to 10-membered, 5- to 9-membered, or 5- to 6-membered); or R 5A and R 5B The substituents are joined to form a substituted or unsubstituted heterocycloalkyl (e.g., 3-8, 3-6, 4-6, 4-5, or 5-6 membered) or a substituted or unsubstituted heteroaryl (e.g., 5-10, 5-9, or 5-6 membered).
[0191] Each X 5 are independently -Cl, -Br, -I or -F.
[0192] The symbol n5 is 0, 1, 2, 3 or 4.
[0193] Each m5 and v5 is independently 1 or 2.
[0194] The symbol z5 is 0, 1, 2 or 3.
[0195] In embodiments, the homogeneous dehydrogenation catalyst has the formula:
[0196] M.L 1 , L 2 , R 3 , R 4 and R 5 As described herein (including in the embodiments).
[0197] In embodiments, M is Ir, Rh or Ru. In embodiments, M is Ir. In embodiments, M is Rh. In embodiments, M is Ru. In embodiments, M is Os.
[0198] In an embodiment, substituted L 1 (e.g., substituted alkylene) is substituted with at least one substituent group, a substituent group of limited size, or a lower substituent group; wherein if the substituted L 1 is substituted with a plurality of groups selected from a substituent group, a substituent group of limited size, and a lower substituent group; each substituent group, a substituent group of limited size, and / or a lower substituent group may optionally be different. In an embodiment, when L 1 When L is substituted, it is substituted with at least one substituent group. 1 When substituted, it is substituted with at least one substituent group of limited size. 1 When substituted, it is substituted with at least one lower substituent group.
[0199] In an embodiment, L 1 -O-, -S-, -NR 6 - or unsubstituted C1-C 10 In an embodiment, L 1 In the embodiment, L 1 In the embodiment, L 1 For-NR 6 -. In an embodiment, L 1 In the embodiment, L 1 For unsubstituted C1-C 10 In an embodiment, L 1 is an unsubstituted methylene group. In the embodiment, L 1 is unsubstituted ethylene. In the embodiment, L 1 is unsubstituted propylene. In the embodiment, L 1 is unsubstituted n-propylene. In the embodiment, L 1 is an unsubstituted isopropylidene group. 1 is unsubstituted butylene. In the embodiment, L 1 is unsubstituted n-butylene. In the embodiment, L 1 is an unsubstituted isobutylene group. 1 is unsubstituted tert-butylene. 1 For the replacement of C1-C 10 In an embodiment, L 1is a substituted methylene. In the embodiment, L 1 is a substituted ethylene group. 1 is substituted propylene. In the embodiment, L 1 is substituted n-propylene. In the embodiment, L 1 is substituted isopropylidene. In the embodiment, L 1 is substituted butylene. 1 is substituted n-butylene. 1 is substituted isobutylene. 1 is a substituted tert-butylene. In an embodiment, the substituted alkylene is substituted with a substituent group.
[0200] In an embodiment, substituted L 2 (e.g., substituted alkylene) is substituted with at least one substituent group, a substituent group of limited size, or a lower substituent group; wherein if the substituted L 2 is substituted with a plurality of groups selected from a substituent group, a substituent group of limited size, and a lower substituent group; each substituent group, a substituent group of limited size, and / or a lower substituent group may optionally be different. In an embodiment, when L 2 When L is substituted, it is substituted with at least one substituent group. 2 When substituted, it is substituted with at least one substituent group of limited size. 2 When substituted, it is substituted with at least one lower substituent group.
[0201] In an embodiment, L 2 -O-, -S-, -NR 6 - or unsubstituted C1-C 10 In an embodiment, L 2 In the embodiment, L 2 In the embodiment, L 2 For-NR 6 -. In an embodiment, L 2 In the embodiment, L 2 For unsubstituted C1-C 10 In an embodiment, L 2 is an unsubstituted methylene group. In the embodiment, L 2 is unsubstituted ethylene. In the embodiment, L 2 is unsubstituted propylene. In the embodiment, L 2 is unsubstituted n-propylene. In the embodiment, L 2is an unsubstituted isopropylidene group. 2 is unsubstituted butylene. In the embodiment, L 2 is unsubstituted n-butylene. In the embodiment, L 2 is an unsubstituted isobutylene group. 2 is unsubstituted tert-butylene. 2 For the replacement of C1-C 10 In an embodiment, L 2 is a substituted methylene. In the embodiment, L 2 is a substituted ethylene group. 2 is substituted propylene. In the embodiment, L 2 is substituted n-propylene. In the embodiment, L 2 is substituted isopropylidene. In the embodiment, L 2 is substituted butylene. 2 is substituted n-butylene. 2 is substituted isobutylene. 2 is a substituted tert-butylene. In an embodiment, the substituted alkylene is substituted with a substituent group.
[0202] In an embodiment, substituted R 3 (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl and / or substituted heteroaryl) is substituted with at least one substituent group, a substituent group of limited size, or a lower substituent group; wherein if the substituted R 3 is substituted with a plurality of groups selected from a substituent group, a substituent group of limited size, and a lower substituent group; each substituent group, a substituent group of limited size, and / or a lower substituent group may optionally be different. In an embodiment, when R 3 When substituted, it is substituted with at least one substituent group. 3 When substituted, it is substituted with at least one substituent group of limited size. 3 When substituted, it is substituted with at least one lower substituent group.
[0203] In an embodiment, R 3 For unsubstituted C1-C 10 alkyl, unsubstituted 2- to 10-membered heteroalkyl, unsubstituted C3-C 10 In one embodiment, R 3 For unsubstituted C1-C 10 In an embodiment, R3 is an unsubstituted methyl group. In an embodiment, R 3 is an unsubstituted ethyl group. In an embodiment, R 3 is unsubstituted propyl. In the embodiment, R 3 is unsubstituted n-propyl. In the embodiment, R 3 is unsubstituted isopropyl. In the embodiment, R 3 is an unsubstituted butyl group. In an embodiment, R 3 is unsubstituted n-butyl. 3 is unsubstituted isobutyl. In the embodiment, R 3 is an unsubstituted tert-butyl group. 3 is unsubstituted neopentyl. In the embodiment, R 3 is an unsubstituted 2- to 10-membered heteroalkyl group. 3 is an unsubstituted methoxy group. In an embodiment, R 3 is an unsubstituted ethoxy group. In an embodiment, R 3 is an unsubstituted propoxy group. In an embodiment, R 3 In an embodiment, R 3 is unsubstituted isopropoxy. In an embodiment, R 3 is an unsubstituted butoxy group. 3 is unsubstituted n-butyloxy. In an embodiment, R 3 is an unsubstituted isobutyloxy group. 3 is unsubstituted tert-butyloxy. 3 For unsubstituted C3-C 10 In one embodiment, R 3 is unsubstituted adamantyl. In an embodiment, R 3 is unsubstituted 1-adamantyl. In an embodiment, R 3 is an unsubstituted 2-adamantyl group. In an embodiment, R 3 It is an unsubstituted phenyl group.
[0204] In an embodiment, substituted R 4 (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl and / or substituted heteroaryl) is substituted with at least one substituent group, a substituent group of limited size, or a lower substituent group; wherein if the substituted R 4is substituted with a plurality of groups selected from a substituent group, a substituent group of limited size, and a lower substituent group; each substituent group, a substituent group of limited size, and / or a lower substituent group may optionally be different. In an embodiment, when R 4 When substituted, it is substituted with at least one substituent group. 4 When substituted, it is substituted with at least one substituent group of limited size. 4 When substituted, it is substituted with at least one lower substituent group.
[0205] In an embodiment, R 4 For unsubstituted C1-C 10 alkyl, unsubstituted 2- to 10-membered heteroalkyl, unsubstituted C3-C 10 In one embodiment, R 4 For unsubstituted C1-C 10 In an embodiment, R 4 is an unsubstituted methyl group. In an embodiment, R 4 is an unsubstituted ethyl group. In an embodiment, R 4 is unsubstituted propyl. In the embodiment, R 4 is unsubstituted n-propyl. In the embodiment, R 4 is unsubstituted isopropyl. In the embodiment, R 4 is an unsubstituted butyl group. In an embodiment, R 4 is unsubstituted n-butyl. 4 is unsubstituted isobutyl. In the embodiment, R 4 is an unsubstituted tert-butyl group. 4 is unsubstituted neopentyl. In the embodiment, R 4 is an unsubstituted 2- to 10-membered heteroalkyl group. 4 is an unsubstituted methoxy group. In an embodiment, R 4 is an unsubstituted ethoxy group. In an embodiment, R 4 is an unsubstituted propoxy group. In an embodiment, R 4 In an embodiment, R 4 is unsubstituted isopropoxy. In an embodiment, R 4 is an unsubstituted butoxy group. 4 is unsubstituted n-butyloxy. In an embodiment, R 4 is an unsubstituted isobutyloxy group. 4 is unsubstituted tert-butyloxy. 4For unsubstituted C3-C 10 In one embodiment, R 4 is unsubstituted adamantyl. In an embodiment, R 4 is unsubstituted 1-adamantyl. In an embodiment, R 4 is an unsubstituted 2-adamantyl group. In an embodiment, R 4 It is an unsubstituted phenyl group.
[0206] In an embodiment, substituted R 5 (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl and / or substituted heteroaryl) is substituted with at least one substituent group, a substituent group of limited size, or a lower substituent group; wherein if the substituted R 5 is substituted with a plurality of groups selected from a substituent group, a substituent group of limited size, and a lower substituent group; each substituent group, a substituent group of limited size, and / or a lower substituent group may optionally be different. In an embodiment, when R 5 When substituted, it is substituted with at least one substituent group. 5 When substituted, it is substituted with at least one substituent group of limited size. 5 When substituted, it is substituted with at least one lower substituent group.
[0207] In an embodiment, R 5are independently hydrogen, -CCl3, -CBr3, -CF3, -CI3, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CHCl2, -CHBr2, -CHF2, -CHI2, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, -NHNH2, -ONH2, -NHC(O)NHNH2, -NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -OCCl3, -OCBr3, -OCF3, -OCI3, -OCH2C l, -OCH2Br, -OCH2F, -OCHI, -OCHCl2, -OCHBr2, -OCHF2, -OCHI2, substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4, or C1-C2), substituted or unsubstituted heteroalkyl (e.g., 2-8, 2-6, 4-6, 2-3, or 4-5), substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6, or C5-C6), substituted or unsubstituted heterocycloalkyl (e.g., 3-8, 3-6, 4-6, 4-5, or 5-6), substituted or unsubstituted aryl (e.g., C6-C 10 or phenyl) or a substituted or unsubstituted heteroaryl (e.g., 5- to 10-membered, 5- to 5-membered, or 5- to 6-membered).
[0208] In an embodiment, R 5 are independently halogen. In an embodiment, R 5 is independently -F. In an embodiment, R 5 is independently -Cl. In an embodiment, R 5 is independently -Br. In an embodiment, R 5 is independently -I. In an embodiment, R 5 is independently -CCl3. In an embodiment, R 5 is independently -CBr3. In an embodiment, R 5 is independently -CF3. In an embodiment, R 5 is independently -CI3. In an embodiment, R 5 is independently -CH2Cl. In an embodiment, R 5 is independently -CH2Br. In an embodiment, R 5 are independently -CH2F. In an embodiment, R 5 are independently -CH2I. In an embodiment, R 5 is independently -CHCl2. In an embodiment, R 5is independently -CHBr2. In an embodiment, R 5 are independently -CHF2. In an embodiment, R 5 are independently -CHI2. In an embodiment, R 5 is independently -CN. In an embodiment, R 5 Independently -OR 5D In an embodiment, R 5 is independently -OCH3. In an embodiment, R 5 is independently -OH. In an embodiment, R 5 is independently -NH2. In an embodiment, R 5 is independently -COOH. In an embodiment, R 5 are independently -CONH2. In an embodiment, R 5 is independently -NO2. In an embodiment, R 5 are independently -SH. In an embodiment, R 5 is independently -SO3H. In an embodiment, R 5 is independently -OSO3H. In an embodiment, R 5 is independently -SO2NH2. In an embodiment, R 5 is independently -NHNH2. In an embodiment, R 5 is independently -ONH2. In an embodiment, R 5 is independently -NHC(O)NHNH2. In an embodiment, R 5 is independently -NHC(O)NH2. In an embodiment, R 5 is independently -NHSO2H. In an embodiment, R 5 is independently -NHC(O)H. In an embodiment, R 5 is independently -NHC(O)OH. In an embodiment, R 5 is independently -NHOH. In an embodiment, R 5 is independently -OCCl3. In an embodiment, R 5 is independently -OCBr3. In an embodiment, R 5 is independently -OCF3. In an embodiment, R 5 is independently -OCI3. In an embodiment, R 5 is independently -OCH2Cl. In an embodiment, R 5 is independently -OCH2Br. In an embodiment, R 5 is independently -OCH2F. In an embodiment, R 5 is independently -OCH2I. In an embodiment, R 5is independently -OCHCl2. In an embodiment, R 5 is independently -OCHBr2. In an embodiment, R 5 is independently -OCHF2. In an embodiment, R 5 is independently -OCHI2. In an embodiment, R 5 Independently -OP(R 5A )(R 5B ). In an embodiment, R 5 is independently -OP(C(CH3)3)2. In an embodiment, R 5 are independently unsubstituted C1-C 10 In an embodiment, R 5 is independently unsubstituted methyl. 5 is independently unsubstituted ethyl. In an embodiment, R 5 is independently unsubstituted propyl. 5 is independently unsubstituted n-propyl. 5 is independently unsubstituted isopropyl. 5 is independently unsubstituted butyl. 5 is independently unsubstituted n-butyl. 5 is independently unsubstituted isobutyl. 5 is independently unsubstituted tert-butyl. 5 is independently unsubstituted 2 to 4 membered heteroalkyl. 5 is independently unsubstituted methoxy. 5 is independently unsubstituted ethoxy. 5 is independently unsubstituted propoxy. 5 is independently unsubstituted n-propoxy. 5 is independently unsubstituted isopropoxy. 5 is independently unsubstituted butoxy. 5 is independently unsubstituted n-butyloxy. 5 is independently unsubstituted isobutyloxy. 5 and is independently unsubstituted tert-butoxy.
[0209] In an embodiment, substituted R 5A(e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl and / or substituted heteroaryl) is substituted with at least one substituent group, a substituent group of limited size, or a lower substituent group; wherein if the substituted R 5A is substituted with a plurality of groups selected from a substituent group, a substituent group of limited size, and a lower substituent group; each substituent group, a substituent group of limited size, and / or a lower substituent group may optionally be different. In an embodiment, when R 5A When substituted, it is substituted with at least one substituent group. 5A When substituted, it is substituted with at least one substituent group of limited size. 5A When substituted, it is substituted with at least one lower substituent group.
[0210] In an embodiment, substituted R 5B (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl and / or substituted heteroaryl) is substituted with at least one substituent group, a substituent group of limited size, or a lower substituent group; wherein if the substituted R 5B is substituted with a plurality of groups selected from a substituent group, a substituent group of limited size, and a lower substituent group; each substituent group, a substituent group of limited size, and / or a lower substituent group may optionally be different. In an embodiment, when R 5B When substituted, it is substituted with at least one substituent group. 5B When substituted, it is substituted with at least one substituent group of limited size. 5B When substituted, it is substituted with at least one lower substituent group.
[0211] In an embodiment, when R bonded to the same nitrogen atom 5A and R 5B The substituted ring formed when the substituents are joined (e.g., substituted heterocycloalkyl and / or substituted heteroaryl) is substituted with at least one substituent group, a substituent group of limited size, or a lower substituent group; wherein if R 5A and R 5B The substituted ring formed when the substituents are joined is substituted with a plurality of groups selected from a substituent group, a substituent group of limited size, and a lower substituent group; each substituent group, a substituent group of limited size, and / or a lower substituent group may optionally be different. In an embodiment, when R bonded to the same nitrogen atom 5A and R 5BWhen the substituted ring formed when the substituents are joined is substituted, it is substituted with at least one substituent group. In an embodiment, when R bonded to the same nitrogen atom 5A and R 5B When the substituted ring formed when the substituents are joined is substituted, it is substituted with at least one substituent group of limited size. In an embodiment, when R bonded to the same nitrogen atom 5A and R 5B When the substituted ring formed when the substituents are attached is substituted, it is substituted with at least one lower substituent group.
[0212] In an embodiment, substituted R 5C (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl and / or substituted heteroaryl) is substituted with at least one substituent group, a substituent group of limited size, or a lower substituent group; wherein if the substituted R 5C is substituted by a plurality of groups selected from a substituent group, a substituent group of limited size, or a lower substituent group; then each substituent group, substituent group of limited size, and / or lower substituent group may optionally be different. In an embodiment, when R 5C When substituted, it is substituted with at least one substituent group. 5C When substituted, it is substituted with at least one substituent group of limited size. 5C When substituted, it is substituted with at least one lower substituent group.
[0213] In an embodiment, substituted R 5D (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl and / or substituted heteroaryl) is substituted with at least one substituent group, a substituent group of limited size, or a lower substituent group; wherein if the substituted R 5D is substituted with a plurality of groups selected from a substituent group, a substituent group of limited size, or a lower substituent group; each substituent group, substituent group of limited size, and / or lower substituent group may optionally be different. In an embodiment, when R 5D When substituted, it is substituted with at least one substituent group. 5D When substituted, it is substituted with at least one substituent group of limited size. 5D When substituted, it is substituted with at least one lower substituent group.
[0214] In an embodiment, R 5A is independently hydrogen or unsubstituted C1-C4 alkyl. 5Aare independently hydrogen. In an embodiment, R 5A is independently unsubstituted C1-C4 alkyl. 5A is independently unsubstituted methyl. 5A is independently unsubstituted ethyl. In an embodiment, R 5A is independently unsubstituted propyl. 5A is independently unsubstituted n-propyl. 5A is independently unsubstituted isopropyl. 5A is independently unsubstituted butyl. 5A is independently unsubstituted n-butyl. 5A is independently unsubstituted isobutyl. 5A and is independently unsubstituted tert-butyl.
[0215] In an embodiment, R 5B is independently hydrogen or unsubstituted C1-C4 alkyl. 5B are independently hydrogen. In an embodiment, R 5B is independently unsubstituted C1-C4 alkyl. 5B is independently unsubstituted methyl. 5B is independently unsubstituted ethyl. In an embodiment, R 5B is independently unsubstituted propyl. 5B is independently unsubstituted n-propyl. 5B is independently unsubstituted isopropyl. 5B is independently unsubstituted butyl. 5B is independently unsubstituted n-butyl. 5B is independently unsubstituted isobutyl. 5B and is independently unsubstituted tert-butyl.
[0216] In an embodiment, R 5C is independently hydrogen or unsubstituted C1-C4 alkyl. 5C are independently hydrogen. In an embodiment, R 5C is independently unsubstituted C1-C4 alkyl. 5C is independently unsubstituted methyl. 5C is independently unsubstituted ethyl. In an embodiment, R 5C is independently unsubstituted propyl.5C is independently unsubstituted n-propyl. 5C is independently unsubstituted isopropyl. 5C is independently unsubstituted butyl. 5C is independently unsubstituted n-butyl. 5C is independently unsubstituted isobutyl. 5C and is independently unsubstituted tert-butyl.
[0217] In an embodiment, R 5D is independently hydrogen or unsubstituted C1-C4 alkyl. 5D are independently hydrogen. In an embodiment, R 5D is independently unsubstituted C1-C4 alkyl. 5D is independently unsubstituted methyl. 5D is independently unsubstituted ethyl. In an embodiment, R 5D is independently unsubstituted propyl. 5D is independently unsubstituted n-propyl. 5D is independently unsubstituted isopropyl. 5D is independently unsubstituted butyl. 5D is independently unsubstituted n-butyl. 5D is independently unsubstituted isobutyl. 5D and is independently unsubstituted tert-butyl.
[0218] In an embodiment, z5 is 0. In an embodiment, z5 is 1. In an embodiment, z5 is 2. In an embodiment, z5 is 3.
[0219] In an embodiment, substituted R 6 (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl and / or substituted heteroaryl) is substituted with at least one substituent group, a substituent group of limited size, or a lower substituent group; wherein if the substituted R 6 is substituted with a plurality of groups selected from a substituent group, a substituent group of limited size, and a lower substituent group; each substituent group, a substituent group of limited size, and / or a lower substituent group may optionally be different. In an embodiment, when R 6 When substituted, it is substituted with at least one substituent group. 6When substituted, it is substituted with at least one substituent group of limited size. 6 When substituted, it is substituted with at least one lower substituent group.
[0220] In an embodiment, R 6 is independently hydrogen or unsubstituted C1-C4 alkyl. 6 are independently hydrogen. In an embodiment, R 6 is independently unsubstituted C1-C4 alkyl. 6 is independently unsubstituted methyl. 6 is independently unsubstituted ethyl. In an embodiment, R 6 is independently unsubstituted propyl. 6 is independently unsubstituted n-propyl. 6 is independently unsubstituted isopropyl. 6 is independently unsubstituted butyl. 6 is independently unsubstituted n-butyl. 6 is independently unsubstituted isobutyl. 6 and is independently unsubstituted tert-butyl.
[0221] In embodiments, the homogeneous dehydrogenation catalyst is
[0222] In an embodiment, the dehydrogenation polymer comprises at least one -C(R 1 )=C(R 2 )-monomer unit.
[0223] R 1 are independently hydrogen, halogen, -CX 1 3. -CHX 1 2. -CH2X 1 、-OCX 1 3. -OCH2X 1 、-OCHX 1 2. -CN, -SO n1 R 1D 、-SO v1 NR 1A R 1B 、-NR 1C NR 1A R 1B 、-ONR 1A R 1B 、-NR 1C C(O)NR 1A R 1B、-N(O) m1 、-NR 1A R 1B 、-C(O)R 1C 、-C(O)OR 1C 、-OC(O)R 1C 、-OC(O)OR 1C 、-C(O)NR 1A R 1B 、-OC(O)NR 1A R 1B 、-OR 1D 、-SR 1D 、-NR 1A S02R 1D 、-NR 1A C(O)R 1C 、-NR 1A C(O)OR 1C 、-NR 1A OR 1C 、-P(O)2(OR 1A )、-OP(O)2(OR 1A ),-BR 1A R 1B 、-SiR 1A R 1B R 1C , substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4, or C1-C2), substituted or unsubstituted heteroalkyl (e.g., 2- to 8-membered, 2- to 6-membered, 4- to 6-membered, or 2- to 3-membered), substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6, or C5-C6), substituted or unsubstituted heterocycloalkyl (e.g., 3- to 8-membered, 3- to 6-membered, 4- to 6-membered, 4- to 5-membered, or 5- to 6-membered), substituted or unsubstituted aryl (e.g., C6-C 10 or phenyl) or a substituted or unsubstituted heteroaryl (e.g., 5- to 10-membered, 5- to 9-membered, or 5- to 6-membered).
[0224] R 2 are independently hydrogen, halogen, -CX 2 3. -CHX 2 2. -CH2X 2 、-OCX 2 3. -OCH2X 2 、-OCHX 2 2. -CN, -SO n2 R 2D 、-SO v2 NR 2A R 2B 、-NR 2C NR2A R 2B 、-ONR 2A R 2B 、-NR 2C C(O)NR 2A R 2B 、-N(O) m2 、-NR 2A R 2B 、-C(O)R 2C 、-C(O)OR 2C 、-OC(O)R 2C 、-OC(O)OR 2C 、-C(O)NR 2A R 2B 、-OC(O)NR 2A R 2B 、-OR 2D 、-SR 2D 、-NR 2A S02R 2D 、-NR 2A C(O)R 2C 、-NR 2A C(O)OR 2C 、-NR 2A OR 2C 、-P(O)2(OR 2A )、-OP(O)2(OR 2A ),-BR 2A R 2B 、-SiR 2A R 2B R 2C , substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4, or C1-C2), substituted or unsubstituted heteroalkyl (e.g., 2- to 8-membered, 2- to 6-membered, 4- to 6-membered, or 2- to 3-membered), substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6, or C5-C6), substituted or unsubstituted heterocycloalkyl (e.g., 3- to 8-membered, 3- to 6-membered, 4- to 6-membered, 4- to 5-membered, or 5- to 6-membered), substituted or unsubstituted aryl (e.g., C6-C 10 or phenyl) or a substituted or unsubstituted heteroaryl (e.g., 5- to 10-membered, 5- to 9-membered, or 5- to 6-membered).
[0225] Each R 1A , R 1B , R 1C , R 1D , R 2A , R 2B , R 2C and R 2Dare independently hydrogen, -CCl3, -CBr3, -CF3, -CI3, -CHCl2, -CHBr2, -CHF2, -CHI2, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CN, -OH, -NH2, -COOH, -CONH2, -OCCl3, -OCF3, -OCBr3, -OCI3, -OCHCl2, -OCHBr2, -OCHI2, -OCHF2, -OCH2Cl, -OCH2Br, -OCH2I, -OCH2F, substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4, or C1-C2), substituted or unsubstituted heteroalkyl (e.g., 2- to 8-membered, 2- to 6-membered, 4- to 6-membered, or 2- to 3-membered), substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6, or C5-C6), substituted or unsubstituted heterocycloalkyl (e.g., 3- to 8-membered, 3- to 6-membered, 4- to 6-membered, 4- to 5-membered, or 5- to 6-membered), substituted or unsubstituted aryl (e.g., C6-C 10 or phenyl) or substituted or unsubstituted heteroaryl (e.g., 5- to 10-membered, 5- to 9-membered, or 5- to 6-membered); or R 1A and R 1B The substituents are joined to form a substituted or unsubstituted heterocycloalkyl (e.g., 3-8, 3-6, 4-6, 4-5, or 5-6) or a substituted or unsubstituted heteroaryl (e.g., 5-10, 5-9, or 5-6); or R bonded to the same nitrogen atom 2A and R 2B The substituents are joined to form a substituted or unsubstituted heterocycloalkyl (e.g., 3-8, 3-6, 4-6, 4-5, or 5-6 membered) or a substituted or unsubstituted heteroaryl (e.g., 5-10, 5-9, or 5-6 membered).
[0226] Each X 1 and X 2 are independently -Cl, -Br, -I or -F.
[0227] Each n1 and n2 is independently 0, 1, 2, 3 or 4.
[0228] Each of m1, m2, v1 and v2 is independently 1 or 2.
[0229] In an embodiment, substituted R 1 (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl and / or substituted heteroaryl) is substituted with at least one substituent group, a substituent group of limited size, or a lower substituent group; wherein if the substituted R 1is substituted with a plurality of groups selected from a substituent group, a substituent group of limited size, and a lower substituent group; each substituent group, a substituent group of limited size, and / or a lower substituent group may optionally be different. In an embodiment, when R 1 When substituted, it is substituted with at least one substituent group. 1 When substituted, it is substituted with at least one substituent group of limited size. 1 When substituted, it is substituted with at least one lower substituent group.
[0230] In an embodiment, R 1 are independently hydrogen, halogen, -CCl3, -CBr3, -CF3, -CI3, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CHCl2, -CHBr2, -CHF2, -CHI2, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, -NHNH2, -ONH2, -NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -OCCl3, -OCBr3, -OCF3, -OCI3, -OCH2Cl, -OCH2Br, -OCH2F, -OCHI, -OCHCl2, -OCHBr2, -OCHF2, -OCHI2, substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4, or C1-C2), substituted or unsubstituted heteroalkyl (e.g., 2- to 8-membered, 2- to 6-membered, 4- to 6-membered, or 2- to 3-membered), substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6, or C5-C6), substituted or unsubstituted heterocycloalkyl (e.g., 3- to 8-membered, 3- to 6-membered, 4- to 6-membered, 4- to 5-membered, or 5- to 6-membered), substituted or unsubstituted aryl (e.g., C6-C 10 or phenyl) or a substituted or unsubstituted heteroaryl (e.g., 5- to 10-membered, 5- to 9-membered, or 5- to 6-membered).
[0231] In an embodiment, R 1are independently hydrogen, halogen, -CCl3, -CBr3, -CF3, -CI3, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CHCl2, -CHBr2, -CHF2, -CHI2, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, -NHNH2, -ONH2, -NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -OCCl3, -OCBr3, -OCF3, -OCI3, -OCH2Cl, -OCH2Br, -OCH2F, -OCHI, -OCHCl2, -OCHBr2, -OCHF2, -OCHI2, or substituted or unsubstituted C1-C 20 alkyl.
[0232] In an embodiment, R 1 are independently hydrogen. In an embodiment, R 1 are independently substituted or unsubstituted C1-C 1000 In an embodiment, R 1 are independently substituted or unsubstituted C1-C 500 In an embodiment, R 1 are independently substituted or unsubstituted C1-C 100 In an embodiment, R 1 are independently substituted or unsubstituted C1-C 50 In an embodiment, R 1 are independently substituted or unsubstituted C1-C 20 In an embodiment, R 1 are independently substituted or unsubstituted C1-C 10 In an embodiment, R 1 are independently substituted or unsubstituted C1-C5 alkyl. 1 is independently unsubstituted methyl. 1 is independently unsubstituted ethyl. In an embodiment, R 1 is independently unsubstituted propyl. 1 is independently unsubstituted n-propyl. 1 is independently unsubstituted isopropyl. 1 is independently unsubstituted butyl. 1 is independently unsubstituted n-butyl. 1 and is independently unsubstituted tert-butyl.
[0233] In an embodiment, substituted R 1A (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl and / or substituted heteroaryl) is substituted with at least one substituent group, a substituent group of limited size, or a lower substituent group; wherein if the substituted R 1A is substituted with a plurality of groups selected from a substituent group, a substituent group of limited size, and a lower substituent group; each substituent group, a substituent group of limited size, and / or a lower substituent group may optionally be different. In an embodiment, when R 1A When substituted, it is substituted with at least one substituent group. 1A When substituted, it is substituted with at least one substituent group of limited size. 1A When substituted, it is substituted with at least one lower substituent group.
[0234] In an embodiment, substituted R 1B (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl and / or substituted heteroaryl) is substituted with at least one substituent group, a substituent group of limited size, or a lower substituent group; wherein if the substituted R 1B is substituted with a plurality of groups selected from a substituent group, a substituent group of limited size, and a lower substituent group; each substituent group, a substituent group of limited size, and / or a lower substituent group may optionally be different. In an embodiment, when R 1B When substituted, it is substituted with at least one substituent group. 1B When substituted, it is substituted with at least one substituent group of limited size. 1B When substituted, it is substituted with at least one lower substituent group.
[0235] In an embodiment, when R bonded to the same nitrogen atom 1A and R 1B The substituted ring formed when the substituents are joined (e.g., substituted heterocycloalkyl and / or substituted heteroaryl) is substituted with at least one substituent group, a substituent group of limited size, or a lower substituent group; wherein if R 1A and R 1B The substituted ring formed when the substituents are joined is substituted with a plurality of groups selected from a substituent group, a substituent group of limited size, and a lower substituent group; each substituent group, a substituent group of limited size, and / or a lower substituent group may optionally be different. In an embodiment, when R bonded to the same nitrogen atom 1A and R1B When the substituted ring formed when the substituents are joined is substituted, it is substituted with at least one substituent group. In an embodiment, when R bonded to the same nitrogen atom 1A and R 1B When the substituted ring formed when the substituents are joined is substituted, it is substituted with at least one substituent group of limited size. In an embodiment, when R bonded to the same nitrogen atom 1A and R 1B When the substituted ring formed when the substituents are attached is substituted, it is substituted with at least one lower substituent group.
[0236] In an embodiment, substituted R 1C (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl and / or substituted heteroaryl) is substituted with at least one substituent group, a substituent group of limited size, or a lower substituent group; wherein if the substituted R 1C is substituted with a plurality of groups selected from a substituent group, a substituent group of limited size, or a lower substituent group; each substituent group, substituent group of limited size, and / or lower substituent group may optionally be different. In an embodiment, when R 1C When substituted, it is substituted with at least one substituent group. 1C When substituted, it is substituted with at least one substituent group of limited size. 1C When substituted, it is substituted with at least one lower substituent group.
[0237] In an embodiment, substituted R 1D (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl and / or substituted heteroaryl) is substituted with at least one substituent group, a substituent group of limited size, or a lower substituent group; wherein if the substituted R 1D is substituted with a plurality of groups selected from a substituent group, a substituent group of limited size, or a lower substituent group; each substituent group, substituent group of limited size, and / or lower substituent group may optionally be different. In an embodiment, when R 1D When substituted, it is substituted with at least one substituent group. 1D When substituted, it is substituted with at least one substituent group of limited size. 1D When substituted, it is substituted with at least one lower substituent group.
[0238] In an embodiment, R 1A are independently hydrogen. In an embodiment, R 1Aare independently substituted or unsubstituted C1-C5 alkyl. 1A is independently unsubstituted methyl. 1A is independently unsubstituted ethyl. In an embodiment, R 1A is independently unsubstituted propyl. 1A is independently unsubstituted n-propyl. 1A is independently unsubstituted isopropyl. 1A is independently unsubstituted butyl. 1A is independently unsubstituted n-butyl. 1A and is independently unsubstituted tert-butyl.
[0239] In an embodiment, R 1B are independently hydrogen. In an embodiment, R 1B are independently substituted or unsubstituted C1-C5 alkyl. 1B is independently unsubstituted methyl. 1B is independently unsubstituted ethyl. In an embodiment, R 1B is independently unsubstituted propyl. 1B is independently unsubstituted n-propyl. 1B is independently unsubstituted isopropyl. 1B is independently unsubstituted butyl. 1B is independently unsubstituted n-butyl. 1B and is independently unsubstituted tert-butyl.
[0240] In an embodiment, R 1C are independently hydrogen. In an embodiment, R 1C are independently substituted or unsubstituted C1-C5 alkyl. 1C is independently unsubstituted methyl. 1C is independently unsubstituted ethyl. In an embodiment, R 1C is independently unsubstituted propyl. 1C is independently unsubstituted n-propyl. 1C is independently unsubstituted isopropyl. 1C is independently unsubstituted butyl. 1C is independently unsubstituted n-butyl. 1C and is independently unsubstituted tert-butyl.
[0241] In an embodiment, R 1D are independently hydrogen. In an embodiment, R 1D are independently substituted or unsubstituted C1-C5 alkyl. 1D is independently unsubstituted methyl. 1D is independently unsubstituted ethyl. In an embodiment, R 1D is independently unsubstituted propyl. 1D is independently unsubstituted n-propyl. 1D is independently unsubstituted isopropyl. 1D is independently unsubstituted butyl. 1D is independently unsubstituted n-butyl. 1D and is independently unsubstituted tert-butyl.
[0242] In an embodiment, substituted R 2 (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl and / or substituted heteroaryl) is substituted with at least one substituent group, a substituent group of limited size, or a lower substituent group; wherein if the substituted R 2 is substituted with a plurality of groups selected from a substituent group, a substituent group of limited size, and a lower substituent group; each substituent group, a substituent group of limited size, and / or a lower substituent group may optionally be different. In an embodiment, when R 2 When substituted, it is substituted with at least one substituent group. 2 When substituted, it is substituted with at least one substituent group of limited size. 2 When substituted, it is substituted with at least one lower substituent group.
[0243] In an embodiment, R 2are independently hydrogen, halogen, -CCl3, -CBr3, -CF3, -CI3, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CHCl2, -CHBr2, -CHF2, -CHI2, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, -NHNH2, -ONH2, -NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -OCCl3, -OCBr3, -OCF3, -OCI3, -OCH2Cl, -OCH2Br, -OCH2F, -OCHI, -OCHCl2, -OCHBr2, -OCHF2, -OCHI2, substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4, or C1-C2), substituted or unsubstituted heteroalkyl (e.g., 2- to 8-membered, 2- to 6-membered, 4- to 6-membered, or 2- to 3-membered), substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6, or C5-C6), substituted or unsubstituted heterocycloalkyl (e.g., 3- to 8-membered, 3- to 6-membered, 4- to 6-membered, 4- to 5-membered, or 5- to 6-membered), substituted or unsubstituted aryl (e.g., C6-C 10 or phenyl) or a substituted or unsubstituted heteroaryl (e.g., 5- to 10-membered, 5- to 9-membered, or 5- to 6-membered).
[0244] In an embodiment, R 2 are independently hydrogen, halogen, -CCl3, -CBr3, -CF3, -CI3, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CHCl2, -CHBr2, -CHF2, -CHI2, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, -NHNH2, -ONH2, -NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -OCCl3, -OCBr3, -OCF3, -OCI3, -OCH2Cl, -OCH2Br, -OCH2F, -OCHI, -OCHCl2, -OCHBr2, -OCHF2, -OCHI2, or substituted or unsubstituted C1-C 20 alkyl.
[0245] In an embodiment, R 2 are independently hydrogen. In an embodiment, R 2 are independently substituted or unsubstituted C1-C 1000 In an embodiment, R 2are independently substituted or unsubstituted C1-C 500 In an embodiment, R 2 are independently substituted or unsubstituted C1-C 100 In an embodiment, R 2 are independently substituted or unsubstituted C1-C 50 In an embodiment, R 2 are independently substituted or unsubstituted C1-C 20 In an embodiment, R 2 are independently substituted or unsubstituted C1-C 10 In an embodiment, R 2 are independently substituted or unsubstituted C1-C5 alkyl. 2 is independently unsubstituted methyl. 2 is independently unsubstituted ethyl. In an embodiment, R 2 is independently unsubstituted propyl. 2 is independently unsubstituted n-propyl. 2 is independently unsubstituted isopropyl. 2 is independently unsubstituted butyl. 2 is independently unsubstituted n-butyl. 2 and is independently unsubstituted tert-butyl.
[0246] In an embodiment, substituted R 2A (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl and / or substituted heteroaryl) is substituted with at least one substituent group, a substituent group of limited size, or a lower substituent group; wherein if the substituted R 2A is substituted with a plurality of groups selected from a substituent group, a substituent group of limited size, and a lower substituent group; each substituent group, a substituent group of limited size, and / or a lower substituent group may optionally be different. In an embodiment, when R 2A When substituted, it is substituted with at least one substituent group. 2A When substituted, it is substituted with at least one substituent group of limited size. 2A When substituted, it is substituted with at least one lower substituent group.
[0247] In an embodiment, substituted R 2B(e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl and / or substituted heteroaryl) is substituted with at least one substituent group, a substituent group of limited size, or a lower substituent group; wherein if the substituted R 2B is substituted with a plurality of groups selected from a substituent group, a substituent group of limited size, and a lower substituent group; each substituent group, a substituent group of limited size, and / or a lower substituent group may optionally be different. In an embodiment, when R 2B When substituted, it is substituted with at least one substituent group. 2B When substituted, it is substituted with at least one substituent group of limited size. 2B When substituted, it is substituted with at least one lower substituent group.
[0248] In an embodiment, when R bonded to the same nitrogen atom 2A and R 2B The substituted ring formed when the substituents are joined (e.g., substituted heterocycloalkyl and / or substituted heteroaryl) is substituted with at least one substituent group, a substituent group of limited size, or a lower substituent group; wherein if R 2A and R 2B The substituted ring formed when the substituents are joined is substituted with a plurality of groups selected from a substituent group, a substituent group of limited size, and a lower substituent group; each substituent group, a substituent group of limited size, and / or a lower substituent group may optionally be different. In an embodiment, when R bonded to the same nitrogen atom 2A and R 2B When the substituted ring formed when the substituents are joined is substituted, it is substituted with at least one substituent group. In an embodiment, when R bonded to the same nitrogen atom 2A and R 2B When the substituted ring formed when the substituents are joined is substituted, it is substituted with at least one substituent group of limited size. In an embodiment, when R bonded to the same nitrogen atom 2A and R 2B When the substituted ring formed when the substituents are attached is substituted, it is substituted with at least one lower substituent group.
[0249] In an embodiment, substituted R 2C (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl and / or substituted heteroaryl) is substituted with at least one substituent group, a substituent group of limited size, or a lower substituent group; wherein if the substituted R 2Cis substituted with a plurality of groups selected from a substituent group, a substituent group of limited size, or a lower substituent group; each substituent group, substituent group of limited size, and / or lower substituent group may optionally be different. In an embodiment, when R 2C When substituted, it is substituted with at least one substituent group. 2C When substituted, it is substituted with at least one substituent group of limited size. 2C When substituted, it is substituted with at least one lower substituent group.
[0250] In an embodiment, substituted R 2D (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl and / or substituted heteroaryl) is substituted with at least one substituent group, a substituent group of limited size, or a lower substituent group; wherein if the substituted R 2D is substituted with a plurality of groups selected from a substituent group, a substituent group of limited size, or a lower substituent group; each substituent group, substituent group of limited size, and / or lower substituent group may optionally be different. In an embodiment, when R 2D When substituted, it is substituted with at least one substituent group. 2D When substituted, it is substituted with at least one substituent group of limited size. 2D When substituted, it is substituted with at least one lower substituent group.
[0251] In an embodiment, R 2A are independently hydrogen. In an embodiment, R 2A are independently substituted or unsubstituted C1-C5 alkyl. 2A is independently unsubstituted methyl. 2A is independently unsubstituted ethyl. In an embodiment, R 2A is independently unsubstituted propyl. 2A is independently unsubstituted n-propyl. 2A is independently unsubstituted isopropyl. 2A is independently unsubstituted butyl. 2A is independently unsubstituted n-butyl. 2A and is independently unsubstituted tert-butyl.
[0252] In an embodiment, R 2B are independently hydrogen. In an embodiment, R 2Bare independently substituted or unsubstituted C1-C5 alkyl. 2B is independently unsubstituted methyl. 2B is independently unsubstituted ethyl. In an embodiment, R 2B is independently unsubstituted propyl. 2B is independently unsubstituted n-propyl. 2B is independently unsubstituted isopropyl. 2B is independently unsubstituted butyl. 2B is independently unsubstituted n-butyl. 2B and is independently unsubstituted tert-butyl.
[0253] In an embodiment, R 2C are independently hydrogen. In an embodiment, R 2C are independently substituted or unsubstituted C1-C5 alkyl. 2C is independently unsubstituted methyl. 2C is independently unsubstituted ethyl. In an embodiment, R 2C is independently unsubstituted propyl. 2C is independently unsubstituted n-propyl. 2C is independently unsubstituted isopropyl. 2C is independently unsubstituted butyl. 2C is independently unsubstituted n-butyl. 2C and is independently unsubstituted tert-butyl.
[0254] In an embodiment, R 2D are independently hydrogen. In an embodiment, R 2D are independently substituted or unsubstituted C1-C5 alkyl. 2D is independently unsubstituted methyl. 2D is independently unsubstituted ethyl. In an embodiment, R 2D is independently unsubstituted propyl. 2D is independently unsubstituted n-propyl. 2D is independently unsubstituted isopropyl. 2D is independently unsubstituted butyl. 2D is independently unsubstituted n-butyl. 2D and is independently unsubstituted tert-butyl.
[0255] In embodiments, the method is performed under continuous flow conditions.
[0256] In an embodiment, when R 1 When replaced, R 1 By one or more R 1.1 The first substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 1.1 When the substituent group is substituted, R 1.1 The substituent group is composed of one or more R 1.2 The second substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 1.2 When the substituent group is substituted, R 1.2 The substituent group is composed of one or more R 1.3 The third substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In the above embodiment, R 1 , R 1.1 , R 1.2 and R 1.3 The values corresponding to R WW , R WW.1 , R WW.2 and R WW.3 The value of is as explained in the definition section in the description of the “first substituent group” above, wherein R WW , R WW.1 , R WW.2 and R WW.3 Corresponding to R 1 , R 1.1 , R 1.2 and R 1.3 .
[0257] In an embodiment, when R 1A When replaced, R 1A By one or more R 1A.1 The first substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 1A.1 When the substituent group is substituted, R 1A.1 The substituent group is composed of one or more R 1A.2 The second substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 1A.2 When the substituent group is substituted, R 1A.2 The substituent group is composed of one or more R 1A.3The third substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In the above embodiment, R 1A , R 1A.1 , R 1A.2 and R 1A.3 The values corresponding to R WW , R WW.1 , R WW.2 and R WW.3 The value of is as explained in the definition section in the description of the “first substituent group” above, wherein R WW , R WW.1 , R WW.2 and R WW.3 Corresponding to R 1A , R 1A.1 , R 1A.2 and R 1A.3 .
[0258] In an embodiment, when R 1B When replaced, R 1B By one or more R 1B.1 The first substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 1B.1 When the substituent group is substituted, R 1B.1 The substituent group is composed of one or more R 1B.2 The second substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 1B.2 When the substituent group is substituted, R 1B.2 The substituent group is composed of one or more R 1B.3 The third substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In the above embodiment, R 1B , R 1B.1 , R 1B.2 and R 1B.3 The values corresponding to R WW , R WW.1 , R WW.2 and R WW.3 The value of is as explained in the definition section in the description of the “first substituent group” above, wherein R WW , R WW.1 , R WW.2 and R WW.3 Corresponding to R 1B , R 1B.1 , R 1B.2 and R 1B.3 .
[0259] In an embodiment, when R bonded to the same nitrogen atom 1A and R 1B When substituents are optionally joined to form a substituted moiety (e.g., substituted heterocycloalkyl or substituted heteroaryl), the moiety is replaced by one or more R 1A.1 The first substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 1A.1 When the substituent group is substituted, R 1A.1 The substituent group is composed of one or more R 1A.2 The second substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 1A.2 When the substituent group is substituted, R 1A.2 The substituent group is composed of one or more R 1A.3 The third substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In the above embodiment, R 1A.1 , R 1A.2 and R 1A.3 The values corresponding to R WW.1 , R WW.2 and R WW.3 The value of is as explained in the definition section in the description of the “first substituent group” above, wherein R WW.1 , R WW.2 and R WW.3 Corresponding to R 1A.1 , R 1A.2 and R 1A.3 .
[0260] In an embodiment, when R bonded to the same nitrogen atom 1A and R 1B When substituents are optionally joined to form a substituted moiety (e.g., substituted heterocycloalkyl or substituted heteroaryl), the moiety is replaced by one or more R 1B.1 The first substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 1B.1 When the substituent group is substituted, R 1B.1 The substituent group is composed of one or more R 1B.2 The second substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 1B.2 When the substituent group is substituted, R 1B.2 The substituent group is composed of one or more R 1B.3The third substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In the above embodiment, R 1B.1 , R 1B.2 and R 1B.3 The values corresponding to R WW.1 , R WW.2 and R WW.3 The value of is as explained in the definition section in the description of the “first substituent group” above, wherein R WW.1 , R WW.2 and R WW.3 Corresponding to R 1B.1 , R 1B.2 and R 1B.3 .
[0261] In an embodiment, when R 1C When replaced, R 1C By one or more R 1C.1 The first substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 1C.1 When the substituent group is substituted, R 1C.1 The substituent group is composed of one or more R 1C.2 The second substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 1C.2 When the substituent group is substituted, R 1C.2 The substituent group is composed of one or more R 1C.3 The third substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In the above embodiment, R 1C , R 1C.1 , R 1C.2 and R 1C.3 The values corresponding to R WW , R WW.1 , R WW.2 and R WW.3 The value of is as explained in the definition section in the description of the “first substituent group” above, wherein R WW , R WW.1 , R WW.2 and R WW.3 Corresponding to R 1C , R 1C.1 , R 1C.2 and R 1C.3 .
[0262] In an embodiment, when R 1D When replaced, R 1D By one or more R 1D.1The first substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 1D.1 When the substituent group is substituted, R 1D.1 The substituent group is composed of one or more R 1D.2 The second substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 1D.2 When the substituent group is substituted, R 1D.2 The substituent group is composed of one or more R 1D.3 The third substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In the above embodiment, R 1D , R 1D.1 , R 1D.2 and R 1D.3 The values corresponding to R WW , R WW.1 , R WW.2 and R WW.3 The value of is as explained in the definition section in the description of the “first substituent group” above, wherein R WW , R WW.1 , R WW.2 and R WW.3 Corresponding to R 1D , R 1D.1 , R 1D.2 and R 1D.3 .
[0263] In an embodiment, when R 2 When replaced, R 2 By one or more R 2.1 The first substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 2.1 When the substituent group is substituted, R 2.1 The substituent group is composed of one or more R 2.2 The second substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 2.2 When the substituent group is substituted, R 2.2 The substituent group is composed of one or more R 2.3 The third substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In the above embodiment, R 2 , R 2.1 , R 2.2 and R 2.3 The values corresponding to R WW , RWW.1 , R WW.2 and R WW.3 The value of is as explained in the definition section in the description of the “first substituent group” above, wherein R WW , R WW.1 , R WW.2 and R WW.3 Corresponding to R 2 , R 2.1 , R 2.2 and R 2.3 .
[0264] In an embodiment, when R 2A When replaced, R 2A By one or more R 2A.1 The first substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 2A.1 When the substituent group is substituted, R 2A.1 The substituent group is composed of one or more R 2A.2 The second substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 2A.2 When the substituent group is substituted, R 2A.2 The substituent group is composed of one or more R 2A.3 The third substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In the above embodiment, R 2A , R 2A.1 , R 2A.2 and R 2A.3 The values corresponding to R WW , R WW.1 , R WW.2 and R WW.3 The value of is as explained in the definition section in the description of the “first substituent group” above, wherein R WW , R WW.1 , R WW.2 and R WW.3 Corresponding to R 2A , R 2A.1 , R 2A.2 and R 2A.3 .
[0265] In an embodiment, when R 2B When replaced, R 2B By one or more R 2B.1 The first substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 2B.1 When the substituent group is substituted, R2B.1 The substituent group is composed of one or more R 2B.2 The second substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 2B.2 When the substituent group is substituted, R 2B.2 The substituent group is composed of one or more R 2B.3 The third substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In the above embodiment, R 2B , R 2B.1 , R 2B.2 and R 2B.3 The values corresponding to R WW , R WW.1 , R WW.2 and R WW.3 The value of is as explained in the definition section in the description of the “first substituent group” above, wherein R WW , R WW.1 , R WW.2 and R WW.3 Corresponding to R 2B , R 2B.1 , R 2B.2 and R 2B.3 .
[0266] In an embodiment, when R bonded to the same nitrogen atom 2A and R 2B When substituents are optionally joined to form a substituted moiety (e.g., substituted heterocycloalkyl or substituted heteroaryl), the moiety is replaced by one or more R 2A.1 The first substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 2A.1 When the substituent group is substituted, R 2A.1 The substituent group is composed of one or more R 2A.2 The second substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 2A.2 When the substituent group is substituted, R 2A.2 The substituent group is composed of one or more R 2A.3 The third substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In the above embodiment, R 2A.1 , R 2A.2 and R 2A.3 The values corresponding to R WW.1 , R WW.2 and R WW.3The value of is as explained in the definition section in the description of the “first substituent group” above, wherein R WW.1 , R WW.2 and R WW.3 Corresponding to R 2A.1 , R 2A.2 and R 2A.3 .
[0267] In an embodiment, when R bonded to the same nitrogen atom 2A and R 2B When substituents are optionally joined to form a substituted moiety (e.g., substituted heterocycloalkyl or substituted heteroaryl), the moiety is replaced by one or more R 2B.1 The first substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 2B.1 When the substituent group is substituted, R 2B.1 The substituent group is composed of one or more R 2B.2 The second substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 2B.2 When the substituent group is substituted, R 2B.2 The substituent group is composed of one or more R 2B.3 The third substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In the above embodiment, R 2B.1 , R 2B.2 and R 2B.3 The values corresponding to R WW.1 , R WW.2 and R WW.3 The value of is as explained in the definition section in the description of the “first substituent group” above, wherein R WW.1 , R WW.2 and R WW.3 Corresponding to R 2B.1 , R 2B.2 and R 2B.3 .
[0268] In an embodiment, when R 2C When replaced, R 2C By one or more R 2C.1 The first substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 2C.1 When the substituent group is substituted, R 2C.1 The substituent group is composed of one or more R 2C.2 The second substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R2C.2 When the substituent group is substituted, R 2C.2 The substituent group is composed of one or more R 2C.3 The third substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In the above embodiment, R 2C , R 2C.1 , R 2C.2 and R 2C.3 The values corresponding to R WW , R WW.1 , R WW.2 and R WW.3 The value of is as explained in the definition section in the description of the “first substituent group” above, wherein R WW , R WW.1 , R WW.2 and R WW.3 Corresponding to R 2C , R 2C.1 , R 2C.2 and R 2C.3 .
[0269] In an embodiment, when R 2D When replaced, R 2D By one or more R 2D.1 The first substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 2D.1 When the substituent group is substituted, R 2D.1 The substituent group is composed of one or more R 2D.2 The second substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 2D.2 When the substituent group is substituted, R 2D.2 The substituent group is composed of one or more R 2D.3 The third substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In the above embodiment, R 2D , R 2D.1 , R 2D.2 and R 2D.3 The values corresponding to R WW , R WW.1 , R WW.2 and R WW.3 The value of is as explained in the definition section in the description of the “first substituent group” above, wherein R WW , R WW.1 , R WW.2 and R WW.3 Corresponding to R 2D , R2D.1 , R 2D.2 and R 2D.3 .
[0270] In an embodiment, when R 3 When replaced, R 3 By one or more R 3.1 The first substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 3.1 When the substituent group is substituted, R 3.1 The substituent group is composed of one or more R 3.2 The second substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 3.2 When the substituent group is substituted, R 3.2 The substituent group is composed of one or more R 3.3 The third substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In the above embodiment, R 3 , R 3.1 , R 3.2 and R 3.3 The values corresponding to R WW , R WW.1 , R WW.2 and R WW.3 The value of is as explained in the definition section in the description of the “first substituent group” above, wherein R WW , R WW.1 , R WW.2 and R WW.3 Corresponding to R 3 , R 3.1 , R 3.2 and R 3.3 .
[0271] In an embodiment, when R 4 When replaced, R 4 By one or more R 4.1 The first substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 4.1 When the substituent group is substituted, R 4.1 The substituent group is composed of one or more R 4.2 The second substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 4.2 When the substituent group is substituted, R 4.2 The substituent group is composed of one or more R 4.3The third substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In the above embodiment, R 4 , R 4.1 , R 4.2 and R 4.3 The values corresponding to R WW , R WW.1 , R WW.2 and R WW.3 The value of is as explained in the definition section in the description of the “first substituent group” above, wherein R WW , R WW.1 , R WW.2 and R WW.3 Corresponding to R 4 , R 4.1 , R 4.2 and R 4.3 .
[0272] In an embodiment, when R 5 When replaced, R 5 By one or more R 5.1 The first substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 5.1 When the substituent group is substituted, R 5.1 The substituent group is composed of one or more R 5.2 The second substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 5.2 When the substituent group is substituted, R 5.2 The substituent group is composed of one or more R 5.3 The third substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In the above embodiment, R 5 , R 5.1 , R 5.2 and R 5.3 The values corresponding to R WW , R WW.1 , R WW.2 and R WW.3 The value of is as explained in the definition section in the description of the “first substituent group” above, wherein R WW , R WW.1 , R WW.2 and R WW.3 Corresponding to R 5 , R 5.1 , R 5.2 and R 5.3 .
[0273] In an embodiment, when R 5A When replaced, R 5A By one or more R 5A.1 The first substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 5A.1 When the substituent group is substituted, R 5A.1 The substituent group is composed of one or more R 5A.2 The second substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 5A.2 When the substituent group is substituted, R 5A.2 The substituent group is composed of one or more R 5A.3 The third substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In the above embodiment, R 5A , R 5A.1 , R 5A.2 and R 5A.3 The values corresponding to R WW , R WW.1 , R WW.2 and R WW.3 The value of is as explained in the definition section in the description of the “first substituent group” above, wherein R WW , R WW.1 , R WW.2 and R WW.3 Corresponding to R 5A , R 5A.1 , R 5A.2 and R 5A.3 .
[0274] In an embodiment, when R 5B When replaced, R 5B By one or more R 5B.1 The first substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 5B.1 When the substituent group is substituted, R 5B.1 The substituent group is composed of one or more R 5B.2 The second substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 5B.2 When the substituent group is substituted, R 5B.2 The substituent group is composed of one or more R 5B.3 The third substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In the above embodiment, R 5B , R5B.1 , R 5B.2 and R 5B.3 The values corresponding to R WW , R WW.1 , R WW.2 and R WW.3 The value of is as explained in the definition section in the description of the “first substituent group” above, wherein R WW , R WW.1 , R WW.2 and R WW.3 Corresponding to R 5B , R 5B.1 , R 5B.2 and R 5B.3 .
[0275] In an embodiment, when R bonded to the same nitrogen atom 5A and R 5B When substituents are optionally joined to form a substituted moiety (e.g., substituted heterocycloalkyl or substituted heteroaryl), the moiety is replaced by one or more R 5A.1 The first substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 5A.1 When the substituent group is substituted, R 5A.1 The substituent group is composed of one or more R 5A.2 The second substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 5A.2 When the substituent group is substituted, R 5A.2 The substituent group is composed of one or more R 5A.3 The third substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In the above embodiment, R 5A.1 , R 5A.2 and R 5A.3 The values corresponding to R WW.1 , R WW.2 and R WW.3 The value of is as explained in the definition section in the description of the “first substituent group” above, wherein R WW.1 , R WW.2 and R WW.3 Corresponding to R 5A.1 , R 5A.2 and R 5A.3 .
[0276] In an embodiment, when R bonded to the same nitrogen atom 5A and R 5BWhen substituents are optionally joined to form a substituted moiety (e.g., substituted heterocycloalkyl or substituted heteroaryl), the moiety is replaced by one or more R 5B.1 The first substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 5B.1 When the substituent group is substituted, R 5B.1 The substituent group is composed of one or more R 5B.2 The second substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 5B.2 When the substituent group is substituted, R 5B.2 The substituent group is composed of one or more R 5B.3 The third substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In the above embodiment, R 5B.1 , R 5B.2 and R 5B.3 The values corresponding to R WW.1 , R WW.2 and R WW.3 The value of is as explained in the definition section in the description of the “first substituent group” above, wherein R WW.1 , R WW.2 and R WW.3 Corresponding to R 5B.1 , R 5B.2 and R 5B.3 .
[0277] In an embodiment, when R 5C When replaced, R 5C By one or more R 5C.1 The first substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 5C.1 When the substituent group is substituted, R 5C.1 The substituent group is composed of one or more R 5C.2 The second substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 5C.2 When the substituent group is substituted, R 5C.2 The substituent group is composed of one or more R 5C.3 The third substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In the above embodiment, R 5C , R 5C.1 , R 5C.2 and R 5C.3 The values corresponding to R WW , RWW.1 , R WW.2 and R WW.3 The value of is as explained in the definition section in the description of the “first substituent group” above, wherein R WW , R WW.1 , R WW.2 and R WW.3 Corresponding to R 5C , R 5C.1 , R 5C.2 and R 5C.3 .
[0278] In an embodiment, when R 5D When replaced, R 5D By one or more R 5D.1 The first substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 5D.1 When the substituent group is substituted, R 5D.1 The substituent group is composed of one or more R 5D.2 The second substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 5D.2 When the substituent group is substituted, R 5D.2 The substituent group is composed of one or more R 5D.3 The third substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In the above embodiment, R 5D , R 5D.1 , R 5D.2 and R 5D.3 The values corresponding to R WW , R WW.1 , R WW.2 and R WW.3 The value of is as explained in the definition section in the description of the “first substituent group” above, wherein R WW , R WW.1 , R WW.2 and R WW.3 Corresponding to R 5D , R 5D.1 , R 5D.2 and R 5D.3 .
[0279] In an embodiment, when R 6 When replaced, R 6 By one or more R 6.1 The first substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 6.1 When the substituent group is substituted, R6.1 The substituent is composed of one or more R 6.2 The second substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R 6.2 When the substituent group is substituted, R 6.2 The substituent group is composed of one or more R 6.3 The third substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In the above embodiment, R 6 , R 6.1 , R 6.2 and R 6.3 The values corresponding to R WW , R WW.1 , R WW.2 and R WW.3 The value of is as explained in the definition section in the description of the “first substituent group” above, wherein R WW , R WW.1 , R WW.2 and R WW.3 Corresponding to R 6 , R 6.1 , R 6.2 and R 6.3 .
[0280] In the embodiment, when L 1 When replaced, L 1 By one or more R L1.1 The first substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R L1.1 When the substituent group is substituted, R L1.1 The substituent group is composed of one or more R L1.2 The second substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R L1.2 When the substituent group is substituted, R L1.2 The substituent group is composed of one or more R L1.3 The third substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. 1 , R L1.1 , R L1.2 and R L1.3 The values corresponding to L WW , R LWW.1 , R LWW.2 and R LWW.3 The value of L is as explained in the definition section in the description of the "first substituent group" above, wherein LWW , R LWW.1 , R LWW.2 and R LWW.3 Corresponding to L 1 , R L1.1 , R L1.2 and R L1.3 .
[0281] In the embodiment, when L 2 When replaced, L 2 By one or more R L2.1 The first substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R L2.1 When the substituent group is substituted, R L2.1 The substituent group is composed of one or more R L2.2 The second substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In an embodiment, when R L2.2 When the substituent group is substituted, R L2.2 The substituent group is composed of one or more R L2.3 The third substituent group represented by is substituted as explained in the definition section in the description of the "first substituent group" above. In the above embodiment, L 2 , R L2.1 , R L2.2 and R L2.3 The values corresponding to L WW , R LWW.1 , R LWW.2 and R LWW.3 The value of L is as explained in the definition section in the description of the "first substituent group" above, wherein L WW , R LWW.1 , R LWW.2 and R LWW.3 Corresponding to L 2 , R L2.1 , R L2.2 and R L2.3 .
[0282] In one aspect, a method for quantifying propylene is provided, the method comprising (a) conducting a chemical reaction to produce propylene at a known pressure in the presence of a gaseous internal standard; (b) analyzing a crude reaction mixture produced by the chemical reaction by gas chromatography; and (c) measuring signal intensity.
[0283] III. Composition
[0284] On the one hand, a substituted or unsubstituted dehydrogenated polyolefin is provided. On the one hand, a substituted or substituted dehydrogenated polyethylene or polypropylene is provided. On the one hand, dehydrogenated polyethylene is produced by the dehydrogenation of polyethylene. Alternatively, in some embodiments, dehydrogenated polyethylene is not produced by the dehydrogenation of polyethylene. In some embodiments, dehydrogenated polyethylene is produced by installing a leaving group and then eliminating it. In some embodiments, dehydrogenated polyethylene is produced by breaking a precursor into fragments (e.g., cracking, pyrolysis, fluid catalytic cracking, catalytic cracking). In some embodiments, dehydrogenated polyethylene comprises an olefin moiety. On the one hand, a substituted or unsubstituted dehydrogenated polyethylene is provided, wherein 0.01% to 1.5%, or 1.7% to 2.3%, or 2.4% to 4.3%, or 4.5% to 13.2% of the percentage of monomer units is unsaturated (e.g., olefinic, such as monoolefin). In an embodiment, 0.01% to 1.5%, or 1.7% to 2.3%, or 2.4% to 4.3%, or 4.5% to 13.2% of the monomeric units are olefinic. In an embodiment, 0.01% to 1.5% of the monomeric units are olefinic. In an embodiment, 1.7% to 2.3% of the monomeric units are olefinic. In an embodiment, 1.7% to 2.3% of the monomeric units are olefinic. In an embodiment, 2.4% to 4.3% of the monomeric units are olefinic. In an embodiment, 4.5% to 13.2% of the monomeric units are olefinic.
[0285] In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at least 0.001%, at least 0.01%, at least 0.1%, at least 0.2%, at least 0.5%, at least 0.75%, at least 0.9%, at least 1%, at least 1.1%, at least 1.3%, at least 1.5% or more. In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at most 0.001%, at most 0.01%, at most 0.1%, at most 0.2%, at most 0.5%, at most 0.75%, at most 0.9%, at most 1%, at most 1.1%, at most 1.3%, at most 1.5% or less.
[0286] In an embodiment, the percentage of olefinic carbon units in the dehydrogenated polyethylene is from about 0.001% to about 1.5%. In an embodiment, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at least about 0.001%. In an embodiment, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at most about 1.5%. In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is from about 0.001% to about 0.01%, from about 0.001% to about 0.1%, from about 0.001% to about 0.2%, from about 0.001% to about 0.5%, from about 0.001% to about 0.75%, from about 0.001% to about 0.9%, from about 0.001% to about 1%, from about 0.001% to about 1.1%, from about 0.001% to about 1.3%, from about 0.001% to about 1.4%, from about 0.001% to about 1.5%, from about 0.01% to about 0.1%, from about 0.01% to about 0.2%, from about 0.01% to about 0.5%. to about 0.5%, about 0.01% to about 0.75%, about 0.01% to about 0.9%, about 0.01% to about 1%, about 0.01% to about 1.1%, about 0.01% to about 1.3%, about 0.01% to about 1.4%, about 0.01% to about 1.5%, about 0.1% to about 0.2%, about 0.1% to about 0.5%, about 0.1% to about 0.75%, about 0.1% to about 0.9%, about 0.1% to about 1%, about 0.1% to about 1.1%, about 0.1% to about 1.3%, about 0.1% to about 1.4%, about 0.1% to about 1.5%, about 0.2% to about 0.5%, about 0.2% to about 0.75%, about 0.2% to about 0.9%, about 0.2% to about 1%, about 0.2% to about 1.1%, about 0.2% to about 1.3%, about 0.2% to about 1.4%, about 0.2% to about 1.5%, about 0.5% to about 0.75%, about 0.5% to about 0.9%, about 0.5% to about 1%, about 0.5% to about 1.1%, about 0.5% to about 1.3%, about 0.5% to about 1.4%, about 0.5% to about 1.5%, about 0.75% to about 0.9%, about 0.75% to about 1%, about 0.75% to about 1%. , about 0.75% to about 1.3%, about 0.75% to about 1.4%, about 0.75% to about 1.5%, about 0.9% to about 1%, about 0.9% to about 1.1%, about 0.9% to about 1.3%, about 0.9% to about 1.4%, about 0.9% to about 1.5%, about 1% to about 1.1%, about 1% to about 1.3%, about 1% to about 1.4%, about 1% to about 1.5%, about 1.1% to about 1.3%, about 1.1% to about 1.4%, about 1.1% to about 1.5%, about 1.3% to about 1.4%, about 1.3% to about 1.5%, or about 1.4% to about 1.5%.In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is about 0.001%, about 0.01%, about 0.1%, about 0.2%, about 0.5%, about 0.75%, about 0.9%, about 1%, about 1.1%, about 1.3%, about 1.4%, or about 1.5%.
[0287] In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at least 1.7%, at least 1.8%, at least 1.9%, at least 2.0%, at least 2.1%, at least 2.2%, at least 2.3% or more. In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at most 1.7%, at most 1.8%, at most 1.9%, at most 2.0%, at most 2.1%, at most 2.2%, at most 2.3% or less.
[0288] In an embodiment, the percentage of olefinic carbon units in the dehydrogenated polyethylene is from about 1.7% to about 2.3%. In an embodiment, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at least about 1.7%. In an embodiment, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at most about 2.3%. In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is from about 1.7% to about 1.8%, from about 1.7% to about 1.9%, from about 1.7% to about 2%, from about 1.7% to about 2.1%, from about 1.7% to about 2.2%, from about 1.7% to about 2.3%, from about 1.8% to about 1.9%, from about 1.8% to about 2%, from about 1.8% to about 2.1%, from about 1.8% to about 2.2%, from about 1.8% to about 2.3%, from about 1.9% to about 2%, from about 1.9% to about 2.1%, from about 1.9% to about 2.2%, from about 1.9% to about 2.3%, from about 2% to about 2.1%, from about 2% to about 2.2%, from about 2% to about 2.3%, from about 2.1% to about 2.2%, from about 2.1% to about 2.3%, or from about 2.2% to about 2.3%. In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is about 1.7%, about 1.8%, about 1.9%, about 2%, about 2.1%, about 2.2%, or about 2.3%.
[0289] In embodiments, the percentage of olefinic carbon units in dehydrogenated polyethylene is at least 2.4%, at least 2.5%, at least 2.6%, at least 2.7%, at least 2.8%, at least 2.9%, at least 3%, at least 3.3%, at least 3.5%, at least 3.7%, at least 4%, at least 4.3% or more. In embodiments, the percentage of olefinic carbon units in dehydrogenated polyethylene is at most 2.4%, at most 2.5%, at most 2.6%, at most 2.7%, at most 2.8%, at most 2.9%, at most 3%, at most 3.3%, at most 3.5%, at most 3.7%, at most 4%, at most 4.3% or less. In embodiments, the percentage of olefinic carbon units in dehydrogenated polyethylene is about 2.4% to about 4.3%. In embodiments, the percentage of olefinic carbon units in dehydrogenated polyethylene is at least about 2.4%. In embodiments, the percentage of olefinic carbon units in dehydrogenated polyethylene is at most about 4.3%.In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is from about 2.4% to about 2.5%, from about 2.4% to about 2.6%, from about 2.4% to about 2.7%, from about 2.4% to about 2.8%, from about 2.4% to about 2.9%, from about 2.4% to about 3%, from about 2.4% to about 3.3%, from about 2.4% to about 3.5%, from about 2.4% to about 3.7%, from about 2.4% to about 4%, from about 2.4% to about 4.3%, from about 2.5% to about 2.6%, from about 2.5% to about 2.7%, from about 2.5% to about 2.8%, from about 2.5 ... to about 2.9%, about 2.5% to about 3%, about 2.5% to about 3.3%, about 2.5% to about 3.5%, about 2.5% to about 3.7%, about 2.5% to about 4%, about 2.5% to about 4.3%, about 2.6% to about 2.7%, about 2.6% to about 2.8%, about 2.6% to about 2.9%, about 2.6% to about 3%, about 2.6% to about 3.3%, about 2.6% to about 3.5%, about 2.6% to about 3.7%, about 2.5% to about 4%, about 2.5% to about 4.3%, about 2.6% to about 2.7%, about 2.6% to about 2.8%, about 2.6% to about 2.9%, about 2.6% to about 3%, about 2.6% to about 3.3%, about 2.6% to about 3.5%, about 2.6% to about 3.7%, about 2.6% to about 4%, about 2.6% to about 4.3%, about 2.7% to about 2.8%, about 2 .7% to about 2.9%, about 2.7% to about 3%, about 2.7% to about 3.3%, about 2.7% to about 3.5%, about 2.7% to about 3.7%, about 2.7% to about 4%, about 2.7% to about 4.3%, about 2.8% to about 2.9%, about 2.8% to about 3%, about 2.8% to about 3.3%, about 2.8% to about 3.5%, about 2.8% to about 3.7%, about 2.8% to about 4%, about 2.8% to about 4.3%, about 2.9% to about 3%, about 2.9% to about 3.3%, about 2.9% to about 3.5%, about % to about 3.7%, about 2.9% to about 4%, about 2.9% to about 4.3%, about 3% to about 3.3%, about 3% to about 3.5%, about 3% to about 3.7%, about 3% to about 4%, about 3% to about 4.3%, about 3.3% to about 3.5%, about 3.3% to about 3.7%, about 3.3% to about 4%, about 3.3% to about 4.3%, about 3.5% to about 3.7%, about 3.3% to about 4%, about 3.3% to about 4.3%, about 3.5% to about 3.7%, about 3.5% to about 4%, about 3.5% to about 4.3%, about 3.7% to about 4%, about 3.7% to about 4.3%, or about 4% to about 4.3%. In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is about 2.4%, about 2.5%, about 2.6%, about 2.7%, about 2.8%, about 2.9%, about 3%, about 3.3%, about 3.5%, about 3.7%, about 4%, or about 4.3%.
[0290] In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at least 4.5%, at least 4.7%, at least 5%, at least 5.2%, at least 5.5%, at least 6%, at least 7%, at least 8%, at least 9%, at least 10%, at least 11%, at least 12%, at least 13%, at least 13.3% or more. In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at most 4.5%, at most 4.7%, at most 5%, at most 5.2%, at most 5.5%, at most 6%, at most 7%, at most 8%, at most 9%, at most 10%, at most 11%, at most 12%, at most 13%, at most 13.3% or more.
[0291] In an embodiment, the percentage of olefinic carbon units in the dehydrogenated polyethylene is from about 4.5% to about 13.3%. In an embodiment, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at least about 4.5%. In an embodiment, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at most about 13.3%. In an embodiment, the percentage of olefinic carbon units in the dehydrogenated polyethylene is from about 4.5% to about 4.7%, from about 4.5% to about 5%, from about 4.5% to about 5.2%, from about 4.5% to about 5.5%, from about 4.5% to about 6%, from about 4.5% to about 7%, from about 4.5% to about 8%, from about 4.5% to about 9%, from about 4.5% to about 10%, from about 4.5% to about 12%, from about 4.5% to about 13.3%, from about 4.7% to about 5%, from about 4.7% to about 5.2%, from about 4.7% to about 5.5%, about 4.7% to about 6%, about 4.7% to about 7%, about 4.7% to about 8%, about 4.7% to about 9%, about 4.7% to about 10%, about 4.7% to about 12%, about 4.7% to about 13.3%, about 5% to about 5.2%, about 5% to about 5.5%, about 5% to about 6%, about 5% to about 7%, about 5% to about 8%, about 5% to about 9%, about 5% to about 10%, about 5% to about 12%, about 5% to about 13.3%, about 5.2% to about 5.5%, about 5% to about 6%, about 5% to about 7%, about 5% to about 8%, about 5% to about 9%, about 5% to about 10%, about 5% to about 12%, about 5% to about 13.3%, about 5.2% to about 5.5%, about 5.2% to about 6%, about 5.2% to about 7%, about 5.2% to about 8%, about 5.2% to about 9%, about 5.2% to about 10%, about 5.2% to about 12%, about 5.2% to about 13.3%, about 5.5% to about 6%, about 5.5% to about 7%, about 5.5% to about 8%, about 5.5% to about 9%, about 5.5% to about 10%, about 5.5% to about 12%, about 5.5% to about 13.3%, about 6% to about 7%, about 6% to about 8%, about 6% to about 9%, From about 6% to about 10%, from about 6% to about 12%, from about 6% to about 13.3%, from about 7% to about 8%, from about 7% to about 9%, from about 7% to about 10%, from about 7% to about 12%, from about 7% to about 13.3%, from about 8% to about 9%, from about 8% to about 10%, from about 8% to about 12%, from about 8% to about 13.3%, from about 9% to about 10%, from about 9% to about 12%, from about 9% to about 13.3%, from about 10% to about 12%, from about 10% to about 13.3%, or from about 12% to about 13.3%. In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is about 4.5%, about 4.7%, about 5%, about 5.2%, about 5.5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 12%, or about 13.3%.
[0292] In one aspect, there is provided a substituted or unsubstituted dehydrogenated polyethylene wherein a percentage of the repeating ethylene units of the polymer of 0.01% to 1.5%, or 1.7% to 2.3%, or 2.4% to 4.3%, or 4.5% to 13.2% is olefinic.
[0293] In some embodiments, the percentage of olefinic carbon in the dehydrogenated polyethylene is at least 0.62%, at least 0.81%, at least 1.06%, at least 1.09%, at least 1.34%, at least 1.42%, at least 1.46%, at least 1.76%, at least 2.17%, at least 2.3%, at least 2.38%, at least 2.55%, at least 3.54% or more. In some embodiments, the percentage of olefinic carbon in the dehydrogenated polyethylene is at most 0.62%, at most 0.81%, at most 1.06%, at most 1.09%, at most 1.34%, at most 1.42%, at most 1.46%, at most 1.76%, at most 2.17%, at most 2.3%, at most 2.38%, at most 2.55%, at most 3.54% or less.
[0294] In some embodiments, the percentage of olefinic carbon in the dehydrogenated polyethylene is about 0.1% to about 2.38%. In some embodiments, the percentage of olefinic carbon in the dehydrogenated polyethylene is at least about 0.1%. In some embodiments, the percentage of olefinic carbon in the dehydrogenated polyethylene is up to about 2.38%.In some embodiments, the percentage of olefinic carbon in the dehydrogenated polyethylene is from about 0.1% to about 0.62%, from about 0.1% to about 0.81%, from about 0.1% to about 1.06%, from about 0.1% to about 1.09%, from about 0.1% to about 1.34%, from about 0.1% to about 1.42%, from about 0.1% to about 1.46%, from about 0.1% to about 1.76%, from about 0.1% to about 2.17%, from about 0.1% to about 2.3%, from about 0.1% to about 2.38%, from about 0.62% to about 0.81%, from about 0.62% to about 1.06%, from about 0.62% to about 1.09%, from about 0.1% to about 1.34%, from about 0.1% to about 1.42%, from about 0.1% to about 1.46%, from about 0.1% to about 1.76%, from about 0.1% to about 2.17%, from about 0.1% to about 2.3%, from about 0.1% to about 2.38%, from about 0.62% to about 0.81%, from about 0.62% to about 1.06%, from about 0.62% to about 1.09%, from about 0.62% to about 1.34%. 42%, about 0.62% to about 1.46%, about 0.62% to about 1.76%, about 0.62% to about 2.17%, about 0.62% to about 2.3%, about 0.62% to about 2.38%, about 0.81% to about 1.06%, about 0.81% to about 1.09%, about 0.81% to about 1.34%, about 0.81% to about 1.42%, about 0.81% to about 1.46%, about 0.81% to about 1.76%, about 0.81% to about 2.17%, about 0.81% to about 2.3%, about 0.81% to about 2.38%, about 1.06% to about 1.09%, about 1.06% to about 1.34%, about 1.06 % to about 1.42%, about 1.06% to about 1.46%, about 1.06% to about 1.76%, about 1.06% to about 2.17%, about 1.06% to about 2.3%, about 1.06% to about 2.38%, about 1.09% to about 1.34%, about 1.09% to about 1.42%, about 1.09% to about 1.46%, about 1.09% to about 1.76%, about 1.09% to about 2.17%, about 1.09% to about 2.3%, about 1.09% to about 2.38%, about 1.34% to about 1.42%, about 1.34% to about 1.46%, about 1.34% to about 1.76%, about 1.34% to about 2.17%, From about 1.34% to about 2.3%, from about 1.34% to about 2.38%, from about 1.42% to about 1.46%, from about 1.42% to about 1.76%, from about 1.42% to about 2.17%, from about 1.42% to about 2.3%, from about 1.42% to about 2.38%, from about 1.46% to about 1.76%, from about 1.46% to about 2.17%, from about 1.46% to about 2.3%, from about 1.46% to about 2.38%, from about 1.76% to about 2.17%, from about 1.46% to about 2.3%, from about 1.46% to about 2.38%, from about 1.76% to about 2.17%, from about 1.76% to about 2.3%, from about 1.76% to about 2.38%, from about 2.17% to about 2.3%, from about 2.17% to about 2.38%, or from about 2.3% to about 2.38%.In some embodiments, the percentage of olefinic carbon in the dehydrogenated polyethylene is about 0.1%, about 0.62%, about 0.81%, about 1.06%, about 1.09%, about 1.34%, about 1.42%, about 1.46%, about 1.76%, about 2.17%, about 2.3%, or about 2.38%.
[0295] In some embodiments, the percentage of olefinic carbon in the dehydrogenated polyethylene is about 0.1% to about 10%. In some embodiments, the percentage of olefinic carbon in the dehydrogenated polyethylene is at least about 0.1%. In some embodiments, the percentage of olefinic carbon in the dehydrogenated polyethylene is up to about 10%. In some embodiments, the percentage of olefinic carbon in the dehydrogenated polyethylene is from about 0.1% to about 0.62%, from about 0.1% to about 0.81%, from about 0.1% to about 1.34%, from about 0.1% to about 1.09%, from about 0.1% to about 1.34%, from about 0.1% to about 1.76%, from about 0.1% to about 2.38%, from about 0.1% to about 2.55%, from about 0.1% to about 3.54%, from about 0.1% to about 4%, from about 0.1% to about 10%, from about 0.62% to about 0.81%, from about 0.62% to about 1.34%, from about 0.1% to about 1.09%, from about 0.1% to about 1.34%, from about 0.1% to about 1.76%, from about 0.1% to about 2.38%, from about 0.1% to about 2.55%, from about 0.1% to about 3.54%, from about 0.1% to about 4%, from about 0.1% to about 10%, from about 0.62% to about 0.81%, from about 0.62% to about 1.34%, from about 0.1% to about 1.76%. 62% to about 1.76%, about 0.62% to about 2.38%, about 0.62% to about 2.55%, about 0.62% to about 3.54%, about 0.62% to about 4%, about 0.62% to about 10%, about 0.81% to about 1.34%, about 0.81% to about 1.09%, about 0.81% to about 1.34%, about 0.81% to about 1.76%, about 0.81% to about 2.38%, about 0.81% to about 2.55%, about 0.81% to about 3.54%, about 0.81% to about 4%, about 0.81% to about 10%, about 1.34% to about 1.09%, about 1.34% to about 1. .34%, about 1.34% to about 1.76%, about 1.34% to about 2.38%, about 1.34% to about 2.55%, about 1.34% to about 3.54%, about 1.34% to about 4%, about 1.34% to about 10%, about 1.09% to about 1.34%, about 1.09% to about 1.76%, about 1.09% to about 2.38%, about 1.09% to about 2.55%, about 1.09% to about 3.54%, about 1.09% to about 4%, about 1.09% to about 10%, about 1.34% to about 1.76%, about 1.34% to about 2.38%, about 1.34% to about 2.55%, about 1.09% to about 3.54%, about 1.09% to about 4%, about 1.09% to about 10%, about 1.34% to about 1.76%, about 1.34% to about 2.38%, about 1.34% to about 2.55%, about From about 1.34% to about 3.54%, from about 1.34% to about 4%, from about 1.34% to about 10%, from about 1.76% to about 2.38%, from about 1.76% to about 2.55%, from about 1.76% to about 3.54%, from about 1.76% to about 4%, from about 1.76% to about 10%, from about 2.38% to about 2.55%, from about 2.38% to about 3.54%, from about 2.38% to about 4%, from about 2.38% to about 10%, from about 2.55% to about 3.54%, from about 2.55% to about 4%, from about 2.55% to about 10%, from about 3.54% to about 4%, from about 3.54% to about 10%, or from about 4% to about 10%.In some embodiments, the percentage of olefinic carbon in the dehydrogenated polyethylene is about 0.1%, about 0.62%, about 0.81%, about 1.34%, about 1.09%, about 1.34%, about 1.76%, about 2.38%, about 2.55%, about 3.54%, about 4%, or about 10%.
[0296] In some embodiments, the percentage of olefinic carbon in the dehydrogenated polyethylene is from about 0.1% to about 20%. In some embodiments, the percentage of olefinic carbon in the dehydrogenated polyethylene is at least about 0.1%. In some embodiments, the percentage of olefinic carbon in the dehydrogenated polyethylene is up to about 20%. In some embodiments, the percentage of olefinic carbon in the dehydrogenated polyethylene is from about 0.1% to about 1%, from about 0.1% to about 1.5%, from about 0.1% to about 1.75%, from about 0.1% to about 2%, from about 0.1% to about 2.5%, from about 0.1% to about 3%, from about 0.1% to about 4%, from about 0.1% to about 5%, from about 0.1% to about 7.5%, from about 0.1% to about 10%, from about 0.1% to about 20%, from about 1% to about 1.5%, from about 1% to about 1.75%, from about 1% to about 2%, From about 1% to about 2.5%, from about 1% to about 3%, from about 1% to about 4%, from about 1% to about 5%, from about 1% to about 7.5%, from about 1% to about 10%, from about 1% to about 20%, from about 1.5% to about 1.75%, from about 1.5% to about 2%, from about 1.5% to about 2.5%, from about 1.5% to about 3%, from about 1.5% to about 4%, from about 1.5% to about 5%, from about 1.5% to about 7.5%, from about 1.5% to about 10%, from about 1.5% to about 20%, from about 1.5% to about 1.75%, from about 1.5% to about 2%, from about 1.5% to about 2.5%, from about 1.5% to about 3%, from about 1.5% to about 4%, from about 1.5% to about 5%, from about 1.5% to about 7.5%, from about 1.5% to about 10%, from about 1.5% to about 20%, .75% to about 2.5%, about 1.75% to about 3%, about 1.75% to about 4%, about 1.75% to about 5%, about 1.75% to about 7.5%, about 1.75% to about 10%, about 1.75% to about 20%, about 2% to about 2.5%, about 2% to about 3%, about 2% to about 4%, about 2% to about 5%, about 2% to about 7.5%, about 2% to about 10%, about 2% to about 20%, about 2.5% to about 3%, about 2.5% to about 4%, about 2% to about 5%, about 2% to about 7.5%, about 2% to about 10%, about 2% to about 20%, about 2.5% to about 3%, about 2.5% to about 4%, about 2.5% to about 5%, From about 2.5% to about 7.5%, from about 2.5% to about 10%, from about 2.5% to about 20%, from about 3% to about 4%, from about 3% to about 5%, from about 3% to about 7.5%, from about 3% to about 10%, from about 3% to about 20%, from about 4% to about 5%, from about 4% to about 7.5%, from about 4% to about 10%, from about 4% to about 20%, from about 5% to about 7.5%, from about 5% to about 10%, from about 5% to about 20%, from about 7.5% to about 10%, from about 7.5% to about 20%, or from about 10% to about 20%.
[0297] In some embodiments, the percentage of olefinic carbon in the dehydrogenated polyethylene is about 0.1%, about 1%, about 1.5%, about 1.75%, about 2%, about 2.5%, about 3%, about 4%, about 5%, about 7.5%, about 10%, or about 20%.
[0298] In embodiments, the percentage of olefinic carbon in the dehydrogenated polyethylene is at least about 0.01%, at least about 0.05%, at least about 0.1%, at least about 0.15%, at least about 0.17%, at least about 0.19%, at least about 0.2%, at least about 0.22%, at least about 0.25%, at least about 0.3%, at least about 0.35%, at least about 0.38%, at least about 0.4%, at least about 0.45%, at least about 0.5%, at least about 0.52%, at least about 0.55%, at least about 0.56%, at least about 0.6%, at least about 0.65%, at least about 0.75%, at least about 1%, at least about 2%, at least about 3%, at least about 4%, at least about 5%, at least about 10%, or more.
[0299] In embodiments, the percentage of olefinic carbon in the dehydrogenated polyethylene is at most about 0.01%, at most about 0.05%, at most about 0.1%, at most about 0.15%, at most about 0.17%, at most about 0.19%, at most about 0.2%, at most about 0.22%, at most about 0.25%, at most about 0.3%, at most about 0.35%, at most about 0.38%, at most about 0.4%, at most about 0.45%, at most about 0.5%, at most about 0.52%, at most about 0.55%, at most about 0.56%, at most about 0.6%, at most about 0.65%, at most about 0.75%, at most about 1%, at most about 2%, at most about 3%, at most about 4%, at most about 5%, at most about 10%, or less.
[0300] In some embodiments, the percentage of olefinic carbon in the dehydrogenated polyethylene is about 0.01% to about 10%. In some embodiments, the percentage of olefinic carbon in the dehydrogenated polyethylene is at least about 0.01%. In some embodiments, the percentage of olefinic carbon in the dehydrogenated polyethylene is up to about 10%. In some embodiments, the percentage of olefinic carbon in the dehydrogenated polyethylene is from about 0.01% to about 0.05%, from about 0.01% to about 0.1%, from about 0.01% to about 0.19%, from about 0.01% to about 0.22%, from about 0.01% to about 0.25%, from about 0.01% to about 0.38%, from about 0.01% to about 0.52%, from about 0.01% to about 0.56%, from about 0.01% to about 1%, from about 0.01% to about 2%, from about 0.01% to about 10%, from about 0.05% to about 0.1%, from about 0.05% to about 0.19%, from about 0.05 ...%. 0.05% to about 0.25%, about 0.05% to about 0.38%, about 0.05% to about 0.52%, about 0.05% to about 0.56%, about 0.05% to about 1%, about 0.05% to about 2%, about 0.05% to about 10%, about 0.1% to about 0.19%, about 0.1% to about 0.22%, about 0.1% to about 0.25%, about 0.1% to about 0.38%, about 0.1% to about 0.52%, about 0.1% to about 0.56%, about 0.1% to about 1%, about 0.1% to about 2%, about 0.1% to about 10%, about 0.19% to about 0.22%, about 0.1% to about 0. .19% to about 0.25%, about 0.19% to about 0.38%, about 0.19% to about 0.52%, about 0.19% to about 0.56%, about 0.19% to about 1%, about 0.19% to about 2%, about 0.19% to about 10%, about 0.22% to about 0.25%, about 0.22% to about 0.38%, about 0.22% to about 0.52%, about 0.22% to about 0.56%, about 0.22% to about 1%, about 0.22% to about 2%, about 0.22% to about 10%, about 0.25% to about 0.38%, about 0.25% to about 0.52%, about 0.25% to about 0.56%, about 0.22% to about 1%, about 0.22% to about 2%, about 0.22% to about 10%, about 0.25% to about 0.38%, about 0.25% to about 0.52%, about 0.25% to about To about 0.56%, about 0.25% to about 1%, about 0.25% to about 2%, about 0.25% to about 10%, about 0.38% to about 0.52%, about 0.38% to about 0.56%, about 0.38% to about 1%, about 0.38% to about 2%, about 0.38% to about 10%, about 0.52% to about 0.56%, about 0.52% to about 1%, about 0.52% to about 2%, about 0.52% to about 10%, about 0.56% to about 1%, about 0.56% to about 2%, about 0.56% to about 10%, about 1% to about 2%, about 1% to about 10%, or about 2% to about 10%.In some embodiments, the percentage of olefinic carbon in the dehydrogenated polyethylene is about 0.01%, about 0.05%, about 0.1%, about 0.19%, about 0.22%, about 0.25%, about 0.38%, about 0.52%, about 0.56%, about 1%, about 2%, or about 10%.
[0301] In one aspect, provided is a substituted or unsubstituted dehydrogenated polyethylene having a number average molecular weight of 2,200 Da or greater.
[0302] In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of about 1,000Da to about 500,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of about 1,000Da to about 400,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of about 1,000Da to about 300,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of about 1,000Da to about 200,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of about 1,000Da to about 100,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of about 1,000Da to about 50,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of about 1,000Da to about 40,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of about 1,000Da to about 30,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of about 1,000Da to about 20,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of about 1,000Da to about 10,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of about 2,200Da to about 500,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of about 2,200Da to about 400,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of about 2,200Da to about 300,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of about 2,200Da to about 200,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of about 2,200Da to about 100,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of about 2,200Da to about 50,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of about 2,200Da to about 40,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of about 2,200Da to about 30,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of about 2,200Da to about 20,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of about 2,200Da to about 10,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of about 2,200Da to about 6,500Da or greater than about 6,700Da.
[0303] In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of 1,000Da to 500,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of 1,000Da to 400,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of 1,000Da to 300,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of 1,000Da to 200,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of 1,000Da to 100,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of 1,000Da to 50,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of 1,000Da to 40,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of 1,000Da to 30,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of 1,000Da to 20,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of 1,000Da to 10,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of 2,200Da to 500,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of 2,200Da to 400,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of 2,200Da to 300,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of 2,200Da to 200,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of 2,200Da to 100,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of 2,200Da to 50,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of 2,200Da to 40,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of 2,200Da to 30,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of 2,200Da to 20,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of 2,200Da to 10,000Da. In an embodiment, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of 2,200Da to 6,500Da or greater than 6,700Da.
[0304] In embodiments, the substituted or unsubstituted dehydropolyethylene has a number average molecular weight of at least about 0.5 kDa, at least about 1 kDa, at least about 2 kDa, at least about 4 kDa, at least about 5 kDa, at least about 5.22 kDa, at least about 6 kDa, at least about 7 kDa, at least about 8 kDa, at least about 9 kDa, at least about 10 kDa, at least about 11 kDa, at least about 12 kDa, at least about 13 kDa, at least about 14 kDa, at least about 15 kDa, at least about 16 kDa, at least about 17 kDa, at least about 18 kDa, at least about 18.2 kDa, at least about 19 kDa, at least about 20 kDa, at least about 21 kDa, at least about 25 kDa, at least about 30 kDa, at least about 35 kDa, at least about 40 kDa, at least about 45 kDa, or at least about 50 kDa or more.
[0305] Alternatively or in addition, in embodiments, the substituted or unsubstituted dehydropolyethylene has a number average molecular weight of at most about 0.5 kDa, at most about 1 kDa, at most about 2 kDa, at most about 4 kDa, at most about 5 kDa, at most about 5.22 kDa, at most about 6 kDa, at most about 7 kDa, at most about 8 kDa, at most about 9 kDa, at most about 10 kDa, at most about 11 kDa, at most about 12 kDa, at most about 13 kDa, at most about 14 kDa, at most about 15 kDa, at most about 16 kDa, at most about 17 kDa, at most about 18 kDa, at most about 19 kDa, at most about 20 kDa, at most about 21 kDa, at most about 22 kDa, at most about 23 kDa, at most about 24 kDa, at most about 25 kDa, at most about 26 kDa, at most about 27 kDa, at most about 28 kDa, at most about 29 kDa, at most about 30 kDa, at most about 31 kDa, at most about 32 kDa, at most about 33 kDa, at most about 34 kDa, at most about 35 kDa At most about 13 kDa, at most about 14 kDa, at most about 15 kDa, at most about 16 kDa, at most about 17 kDa, at most about 18 kDa, at most about 18.2 kDa, at most about 19 kDa, at most about 20 kDa, at most about 21 kDa, at most about 25 kDa, at most about 30 kDa, at most about 35 kDa, at most about 40 kDa, at most about 45 kDa, at least about 50 kDa or less.
[0306] In embodiments, the substituted or unsubstituted dehydropolyethylene has a number average molecular weight of up to about 5.22 kDa or at least about 18.2 kDa or greater. In embodiments, the substituted or unsubstituted dehydropolyethylene has a number average molecular weight of at least about 5.22 kDa or at least about 18.2 kDa or less.
[0307] In an embodiment, the number average molecular weight of the substituted or unsubstituted dehydrogenated polyethylene is from about 2 kDa to about 50 kDa. In an embodiment, the number average molecular weight of the substituted or unsubstituted dehydrogenated polyethylene is at least about 2 kDa. In an embodiment, the number average molecular weight of the substituted or unsubstituted dehydrogenated polyethylene is at most about 50 kDa.In embodiments, the substituted or unsubstituted dehydropolyethylene has a number average molecular weight of about 2 kDa to about 4 kDa, about 2 kDa to about 5 kDa, about 2 kDa to about 5.22 kDa, about 2 kDa to about 8 kDa, about 2 kDa to about 10 kDa, about 2 kDa to about 12 kDa, about 2 kDa to about 15 kDa, about 2 kDa to about 18.2 kDa, about 2 kDa to about 20 kDa, about 2 kDa to about 35 kDa, about 2 kDa to about 50 kDa, about 4 kDa to about 5 kDa, about 4 kDa to about 5.22 kDa, about 4 kDa to about 8 kDa, about 4 kDa to about 10 kDa, about 4 kDa to about 12 kDa, about 4 ... kDa to about 15 kDa, about 4 kDa to about 18.2 kDa, about 4 kDa to about 20 kDa, about 4 kDa to about 35 kDa, about 4 kDa to about 50 kDa, about 5 kDa to about 5.22 kDa, about 5 kDa to about 8 kDa, about 5 kDa to about 10 kDa, about 5 kDa to about 12 kDa, about 5 kDa to about 15 kDa, about 5 kDa to about 18.2 kDa, about 5 kDa to about 20 kDa, about 5 kDa to about 35 kDa, about 5 kDa to about 50 kDa, about 5.22 kDa to about 8 kDa, about 5.22 kDa to about 10 kDa, about 5.22 kDa to about 12 kDa. kDa to about 15 kDa, about 5.22 kDa to about 18.2 kDa, about 5.22 kDa to about 20 kDa, about 5.22 kDa to about 35 kDa, about 5.22 kDa to about 50 kDa, about 8 kDa to about 10 kDa, about 8 kDa to about 12 kDa, about 8 kDa to about 15 kDa, about 8 kDa to about 18.2 kDa, about 8 kDa to about 20 kDa, about 8 kDa to about 35 kDa, about 8 kDa to about 50 kDa, about 10 kDa to about 12 kDa, about 10 kDa to about 15 kDa, about 10 kDa to about 18.2 kDa, about 10 kDa to about 20 kDa, about 10 kDa to about 35 kDa, about 10 kDa to about 50 kDa, about 12 kDa to about 15 kDa, about 12 kDa to about 18.2 kDa, about 12 kDa to about 20 kDa, about 12 kDa to about 35 kDa, about 12 kDa to about 50 kDa, about 15 kDa to about 18.2 kDa, about 15 kDa to about 20 kDa, about 15 kDa to about 35 kDa, about 15 kDa to about 50 kDa, about 18.2 kDa to about 20 kDa, about 18.2 kDa to about 35 kDa, about 18.2 kDa to about 50 kDa, about 20 kDa to about 35 kDa, about 20 kDa to about 50 kDa, or about 35 kDa to about 50 kDa.In embodiments, the substituted or unsubstituted dehydropolyethylene has a number average molecular weight of about 2 kDa, about 4 kDa, about 5 kDa, about 5.22 kDa, about 8 kDa, about 10 kDa, about 12 kDa, about 15 kDa, about 18.2 kDa, about 20 kDa, about 35 kDa, or about 50 kDa.
[0308] In embodiments, the substituted or unsubstituted dehydropolyethylene has a number average molecular weight of at least about 0.5 kDa, at least about 1 kDa, at least about 1.23 kDa, at least about 1.67 kDa, at least about 2 kDa, at least about 2.24 kDa, at least about 3 kDa, at least about 3.9 kDa, at least about 4 kDa, at least about 4.07 kDa, at least about 5 kDa, at least about 5.22 kDa, at least about 6 kDa, at least about 7 kDa, at least about 8 kDa, at least about 9 kDa, at least about 10 kDa, at least about 11 kDa, at least about 13 kDa, at least about 15 kDa, at least about 16 kDa, at least about 17 kDa, at least about 18 kDa, at least about 19 kDa, at least about 20 kDa, at least about 21 kDa, at least about 23 kDa, at least about 24 kDa, at least about 26 kDa, at least about 28 kDa, at least about 29 kDa, at least about 30 kDa, at least about 31 kDa, at least about 32 kDa, at least about 34 kDa, at least about 36 kDa, at least about 38 kDa, at least about 39 kDa, at least about 40 kDa, at least about 41 kDa, at least about 42 kDa, at least about 43 kDa, at least about 44 kDa, at least about 45 kDa kDa, at least about 12 kDa, at least about 13 kDa, at least about 14 kDa, at least about 15 kDa, at least about 16 kDa, at least about 17 kDa, at least about 18 kDa, at least about 18.2 kDa, at least about 19 kDa, at least about 20 kDa, at least about 21 kDa, at least about 25 kDa, at least about 30 kDa, at least about 35 kDa, at least about 40 kDa, at least about 45 kDa, or at least about 50 kDa, or at least about 100 kDa, or at least about 200 kDa or more.
[0309] Alternatively or in addition, in embodiments, the substituted or unsubstituted dehydropolyethylene has a number average molecular weight of at most about 0.5 kDa, at most about 1 kDa, at most about 1.23 kDa, at most about 1.67 kDa, at most about 2 kDa, at most about 2.24 kDa, at most about 3 kDa, at most about 3.9 kDa, at most about 4 kDa, at most about 4.07 kDa, at most about 5 kDa, at most about 5.22 kDa, at most about 6 kDa, at most about 7 kDa, at most about 8 kDa, at most about 9 kDa, at most about 10 kDa , at most about 11 kDa, at most about 12 kDa, at most about 13 kDa, at most about 14 kDa, at most about 15 kDa, at most about 16 kDa, at most about 17 kDa, at most about 18 kDa, at most about 18.2 kDa, at most about 19 kDa, at most about 20 kDa, at most about 21 kDa, at most about 25 kDa, at most about 30 kDa, at most about 35 kDa, at most about 40 kDa, at most about 45 kDa, or at most about 50 kDa, or at most about 100 kDa, or at most about 200 kDa or less.
[0310] In an embodiment, the number average molecular weight of the substituted or unsubstituted dehydropolyethylene is from about 0.5 kDa to about 50 kDa. In an embodiment, the number average molecular weight of the substituted or unsubstituted dehydropolyethylene is at least about 0.5 kDa. In an embodiment, the number average molecular weight of the substituted or unsubstituted dehydropolyethylene is at most about 50 kDa. In an embodiment, the number average molecular weight of the substituted or unsubstituted dehydropolyethylene is from about 0.5 kDa to about 1 kDa, from about 0.5 kDa to about 1.23 kDa, from about 0.5 kDa to about 1.67 kDa, from about 0.5 kDa to about 2 kDa, from about 0.5 kDa to about 2.24 kDa, from about 0.5 kDa to about 3 kDa, from about 0.5 kDa to about 3.9 kDa, from about 0.5 kDa to about 4.07 kDa, from about 0.5 kDa to about 5.22 kDa, from about 0.5 kDa to about 10 kDa, from about 0.5 kDa to about 50 kDa, from about 1 kDa to about 1.23 kDa, about 1 kDa to about 1.67 kDa, about 1 kDa to about 2 kDa, about 1 kDa to about 2.24 kDa, about 1 kDa to about 3 kDa, about 1 kDa to about 3.9 kDa, about 1 kDa to about 4.07 kDa, about 1 kDa to about 5.22 kDa, about 1 kDa to about 10 kDa, about 1 kDa to about 50 kDa, about 1.23 kDa to about 1.67 kDa, about 1.23 kDa to about 2 kDa, about 1.23 kDa to about 2.24 kDa, about 1.23 kDa to about 3 kDa, about 1.23 kDa to about 3.9 kDa, about 1.23 kDa to about 4.07 kDa a to about 4.07 kDa, about 1.23 kDa to about 5.22 kDa, about 1.23 kDa to about 10 kDa, about 1.23 kDa to about 50 kDa, about 1.67 kDa to about 2 kDa, about 1.67 kDa to about 2.24 kDa, about 1.67 kDa to about 3 kDa, about 1.67 kDa to about 3.9 kDa, about 1.67 kDa to about 4.07 kDa, about 1.67 kDa to about 5.22 kDa, about 1.67 kDa to about 10 kDa, about 1.67 kDa to about 50 kDa, about 2 kDa to about 2.24 kDa, about 2 kDa to about 3 kDa. about 3 kDa, about 2 kDa to about 3.9 kDa, about 2 kDa to about 4.07 kDa, about 2 kDa to about 5.22 kDa, about 2 kDa to about 10 kDa, about 2 kDa to about 50 kDa, about 2.24 kDa to about 3 kDa, about 2.24 kDa to about 3.9 kDa, about 2.24 kDa to about 4.07 kDa, about 2.24 kDa to about 5.22 kDa, about 2.24 kDa to about 10 kDa, about 2.24 kDa to about 50 kDa, about 3 kDa to about 3.9 kDa, about 3 kDa to about 4.07 kDa, about 3 kDa to about 5.kDa, about 3 kDa to about 10 kDa, about 3 kDa to about 50 kDa, about 3.9 kDa to about 4.07 kDa, about 3.9 kDa to about 5.22 kDa, about 3.9 kDa to about 10 kDa, about 3.9 kDa to about 50 kDa, about 4.07 kDa to about 5.22 kDa, about 4.07 kDa to about 10 kDa, about 4.07 kDa to about 50 kDa, about 5.22 kDa to about 10 kDa, about 5.22 kDa to about 50 kDa, or about 10 kDa to about 50 kDa. In embodiments, the substituted or unsubstituted dehydropolyethylene has a number average molecular weight of about 0.5 kDa, about 1 kDa, about 1.23 kDa, about 1.67 kDa, about 2 kDa, about 2.24 kDa, about 3 kDa, about 3.9 kDa, about 4.07 kDa, about 5.22 kDa, about 10 kDa, or about 50 kDa.
[0311] In embodiments, the polydispersity of the dehydrogenated polyethylene is at least about 1.001, at least about 1.01, at least about 1.05, at least about 1.1, at least about 1.25, at least about 1.5, at least about 1.6, at least about 1.7, at least about 1.75, at least about 1.8, at least about 1.84, at least about 1.9, at least about 2, at least about 2.1, at least about 2.25, at least about 2.5, at least about 2.75, at least about 3, at least about 3.25, at least about 3.35, at least about 3.4, at least about 3.45, at least about 3.48, at least about 3.5, at least about 3.55, at least about 3.75, at least about 4, at least about 4.25, at least about 4.5, at least about 4.75, at least about 5, or more.
[0312] In embodiments, the polydispersity of the dehydrogenated polyethylene is at most about 1.001, at most about 1.01, at most about 1.05, at most about 1.1, at most about 1.25, at most about 1.5, at most about 1.6, at most about 1.7, at most about 1.75, at most about 1.8, at most about 1.84, at most about 1.9, at most about 2, at most about 2.1, at most about 2.25, at most about 2.5, at most about 2.75, at most about 3, at most about 3.25, at most about 3.35, at most about 3.4, at most about 3.45, at most about 3.48, at most about 3.5, at most about 3.55, at most about 3.75, at most about 4, at most about 4.25, at most about 4.5, at most about 4.75, at most about 5, or less.
[0313] In embodiments, the polydispersity of the dehydrogenated polyethylene is from about 1.1 to about 8. In embodiments, the polydispersity of the dehydrogenated polyethylene is at least about 1.1. In embodiments, the polydispersity of the dehydrogenated polyethylene is at most about 8. In embodiments, the polydispersity of the dehydrogenated polyethylene is from about 1.1 to about 1.3, from about 1.1 to about 1.5, from about 1.1 to about 1.7, from about 1.1 to about 1.8, from about 1.1 to about 1.84, from about 1.1 to about 1.9, from about 1.1 to about 2.5, from about 1.1 to about 3.25, from about 1.1 to about 3.48, from about 1.1 to about 5, from about 1.1 to about 8, from about 1.3 to about 1.5, from about 1.3 to about 1.7, from about 1.1 to about 1.8, from about 1.3 to about 1.8 4, about 1.3 to about 1.9, about 1.3 to about 2.5, about 1.3 to about 3.25, about 1.3 to about 3.48, about 1.3 to about 5, about 1.3 to about 8, about 1.5 to about 1.7, about 1.5 to about 1.8, about 1.5 to about 1.84, about 1.5 to about 1.9, about 1.5 to about 2.5, about 1.5 to about 3.25, about 1.5 to about 3.48, about 1.5 to about 5, about 1.5 to about 8, about 1.7 to about 1.8, about 1.7 to about 1.8. 84, about 1.7 to about 1.9, about 1.7 to about 2.5, about 1.7 to about 3.25, about 1.7 to about 3.48, about 1.7 to about 5, about 1.7 to about 8, about 1.8 to about 1.84, about 1.8 to about 1.9, about 1.8 to about 2.5, about 1.8 to about 3.25, about 1.8 to about 3.48, about 1.8 to about 5, about 1.8 to about 8, about 1.84 to about 1.9, about 1.84 to about 2.5, about 1.84 to about 3.25, about 1.84 to about 1.84 In some embodiments, the polydispersity of the dehydrogenated polyethylene is about 1.1, about 1.3, about 1.5, about 1.7, about 1.8, about 1.84, about 1.84 to about 3.48, about 1.84 to about 8, about 1.9 to about 2.5, about 1.9 to about 3.25, about 1.9 to about 3.48, about 1.9 to about 5, about 1.9 to about 8, about 2.5 to about 3.25, about 2.5 to about 3.48, about 2.5 to about 5, about 2.5 to about 8, about 3.25 to about 3.48, about 3.25 to about 5, about 3.25 to about 8, about 3.48 to about 5, about 3.48 to about 8, or about 5 to about 8. In embodiments, the polydispersity of the dehydrogenated polyethylene is about 1.1, about 1.3, about 1.5, about 1.7, about 1.8, about 1.84, about 1.9, about 2.5, about 3.25, about 3.48, about 5, or about 8.
[0314] In an embodiment, about 0.01% to about 11% of the monomer units of the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, about 0.01% to about 10% of the monomer units of the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, about 0.01% to about 9% of the monomer units of the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, about 0.01% to about 8% of the monomer units of the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, about 8% or less of the monomer units of the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, about 0.01% to about 1.5% of the monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, about 2.4% to about 4.3% of the monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, about 4.5% to about 13.2% of the monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, about 1% to about 3% of the monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, about 1.5% to about 3% of the monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, about 1.9% of the monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, about 1.7% to about 2.3% of the monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, about 1.7% to about 2.1% of the monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, about 1.9% to about 2.1% of the monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, about 1.7% of the monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, about 1.8% of the monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, about 1.9% of the monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, about 2% of the monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, about 2.1% of the monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, about 2.2% of the monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, about 2.3% of the monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated.
[0315] In an embodiment, 0.01% to 11% of the monomer units of the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, 0.01% to 10% of the monomer units of the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, 0.01% to 9% of the monomer units of the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, 0.01% to 8% of the monomer units of the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, 8% or less of the monomer units of the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, 0.01% to 1.5% of the monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, 2.4% to 4.3% of the monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, 4.5% to 13.2% of the monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, 1% to 3% of the monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, 1.5% to 3% of the monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, 1.9% of the monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, 1.7% to 2.3% of the monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, 1.7% to 2.1% of the monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, 1.9% to 2.1% of the monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, 1.7% of the monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, 1.8% of the monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, 1.9% of the monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, 2% of the monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, 2.1% of the monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, 2.2% of the monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In an embodiment, 2.3% of the monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated.
[0316] In some embodiments, the percentage of aromatic carbon in the dehydrogenated polyethylene is at least about 0%, at least about 0.0001%, at least about 0.001%, at least about 0.01%, at least about 0.02%, at least about 0.03%, at least about 0.04%, to At least about 0.05%, at least about 0.06%, at least about 0.07%, at least about 0.08%, at least about 0.09%, at least about 0.1%, at least about 0.11%, at least about 0.12%, at least about 0.13%, at least about 0.14%, at least about 0.15%, at least about 0.16%, to At least about 0.17%, at least about 0.18%, at least about 0.19%, at least about 0.2%, at least about 0.22%, at least about 0.24%, at least about 0.30%, at least about 0.35%, at least about 0.36%, at least about 0.37%, at least about 0.38%, at least about 0.39%, at least about 0.40%, at least about 0.50%, at least At least about 0.26%, at least about 0.28%, at least about 0.3%, at least about 0.32%, at least about 0.33%, at least about 0.34%, at least about 0.5 At least about 0.35%, at least about 0.4%, at least about 0.5%, at least about 0.54%, at least about 0.55%, at least about 0.6%, at least about 0.7%, at least about 0.75%, at least about 0.77%, at least about 0.8%, at least about 0.9%, at least about 1%, at least about 1.1%, at least about 1.2%, at least about 1.23%, at least about 1.3%, at least about 1.39%, at least about 1.4%, at least about 1.43%, at least about 1.47%, at least about 1.5%, at least about 1.75%, at least about 2%, at least about 3%, at least about 4%, to At least about 5%, at least about 6%, at least about 7%, at least about 8%, at least about 9%, at least about 10%, at least about 12.5%, at least About 15%, at least about 17.5%, at least about 20%, at least about 50%, at least about 75% or more .
[0317] In some embodiments, the percentage of aromatic carbon in the dehydrogenated polyethylene is at most about 0%, at most about 0.0001%, at most about 0.001%, at most about 0.01%, at most about 0.02%, at most about 0.03%, at most about 0.04%, at most about 0.05%, at most about 0.06%, at most about 0.07%, at most about 0.08%, at most about 0.09, at most about 0.1%, at most about 0.11 %, up to about 0.12%, up to about 0.13%, up to about 0.14%, up to about 0.15%, up to about 0.16%, up to about 0.17%, up to about 0.18%, up to about 0.19%, up to about 0.2%, up to about 0.22%, up to about 0.24%, up to about 0.26%, up to about 0.28%, up to about 0.3%, up to about 0.32%, up to about 0.33%, up to about 0.34%, up to about 0.35%, up to about 0.4%, up to about 0.5%, up to about 0.54%, up to about 0.55%, up to about 0.6%, up to about 0.7%, up to about 0.75%, up to about 0.77%, up to about 0.8%, up to about 0.9%, up to about 1%, up to about 1.1%, up to about 1.2%, up to about 1.23%, up to about 1.3%, up to about 1.39%, At most about 1.4%, at most about 1.43%, at most about 1.47%, at most about 1.5%, at most about 1.75%, at most about 2%, at most about 3%, at most about 4%, at most about 5%, at most about 6%, at most about 7%, at most about 8%, at most about 9%, at most about 10%, at most about 12.5%, at most about 15%, at most about 17.5%, at most about 20%, at most about 50%, at most about 75% or more.
[0318] In some embodiments, the percentage of aromatic carbon in the dehydrogenated polyethylene is about 0.001% to about 10%. In some embodiments, the percentage of aromatic carbon in the dehydrogenated polyethylene is at least about 0.001%. In some embodiments, the percentage of aromatic carbon in the dehydrogenated polyethylene is up to about 10%.In some embodiments, the percentage of aromatic carbon in the dehydrogenated polyethylene is from about 0.001% to about 0.01%, from about 0.001% to about 0.02%, from about 0.001% to about 0.04%, from about 0.001% to about 0.08%, from about 0.001% to about 0.09%, from about 0.001% to about 0.1%, from about 0.001% to a...
Claims
1. A method for degrading a substance, the method comprising: (iv) performing one or more reactions to form one or more olefin units in the substance; (v) after step (i), subjecting to conditions for olefin metathesis; as well as (vi) after step (i), subjecting to conditions for olefin isomerization.
2. The process of claim 1, wherein step (i) comprises subjecting the substance to conditions for dehydrogenation.
3. A process for preparing substituted or unsubstituted olefins, the process comprising subjecting a dehydrogenated polymer to conditions for metathesis and to conditions for olefin isomerization.
4. A method for preparing a substituted or unsubstituted olefin, the method comprising subjecting a first material to conditions for olefin metathesis and conditions for olefin isomerization; wherein: (iii) the first substance contains at least 20 carbon atoms per molecule; or (iv) prior to subjecting the first substance to conditions for olefin metathesis and conditions for olefin isomerization, the process includes subjecting the second substance to conditions for dehydrogenation, thereby forming the first substance.
5. The method according to claim 4, wherein the substituted or unsubstituted olefin is substituted or unsubstituted propylene.
6. The method according to claim 4, wherein the first substance is substituted or unsubstituted dehydrogenated polyethylene.
7. A method for preparing olefins, the method comprising mixing a dehydrogenated polymer with one or more olefin metathesis agents and one or more isomerization agents; wherein: (iii) the dehydrogenated polymer comprises at least 20 carbon atoms; or (iv) prior to said mixing, said method comprises mixing a polymer with one or more dehydrogenating agents, thereby forming said dehydrogenated polymer.
8. A method for preparing a dehydrogenated polymer, the method comprising mixing a polymer with one or more dehydrogenating agents, wherein (v) a percentage of the monomer units in the dehydrogenated polymer of 0.01% to 1.5%, or 1.7% to 2.3%, or 2.4% to 4.3%, or 4.5% to 13.2% are unsaturated; (vi) the dehydrogenated polymer has a number average molecular weight of about 2,200 Da or greater; (vii) the dehydrogenated polymer has a number average molecular weight of about 2,200 Da to about 6,500 Da, and a percentage of the monomer units of 0.01% to 10% are unsaturated; or (viii) the dehydrogenated polymer has a number average molecular weight of about 1,000 Da to about 500,000 Da, and a percentage of the monomer units in the dehydrogenated polymer of 0.01% to 1.5%, or 1.7% to 2.3%, or 2.4% to 4.3%, or 4.5% to 10% are unsaturated.
9. The method of claim 8, wherein the dehydrogenated polymer has a number average molecular weight of about 2,200 Da to about 6,500 Da or about 6,700 Da to about 15,000 Da.
10. The method of claim 8, wherein the dehydrogenating polymer has a number average molecular weight of about 2,200 Da to about 6,500 Da.
11. The method of claim 8, further comprising mixing the dehydrogenated polymer with one or more olefin metathesis agents and one or more isomerization agents to form olefins.
12. The method of claim 7, wherein the dehydrogenated polymer is a substituted or unsubstituted dehydrogenated polyethylene.
13. The method of claim 7, wherein the olefin is substituted or unsubstituted propylene.
14. The process of claim 7, wherein the dehydrogenating polymer, the one or more olefin metathesis agents, and the one or more isomerization agents are mixed simultaneously.
15. The process of claim 7, wherein the dehydrogenated polymer and the one or more olefin metathesis agents are mixed prior to adding the one or more isomerization agents.
16. The process of claim 15, wherein the dehydrogenated polymer and one or more additional olefin metathesis agents are mixed prior to adding the one or more olefin metathesis agents and the one or more isomerization agents.
17. The method of claim 7, wherein the one or more olefin metathesis agents comprises an ethenolysis catalyst.
18. The method of claim 7, wherein the one or more olefin metathesis agents comprise one or more homogeneous olefin metathesis catalysts or one or more heterogeneous olefin metathesis catalysts.
19. The method of claim 18, wherein the one or more olefin metathesis reagents further comprises ethylene.
20. The process of claim 18, wherein the homogeneous olefin metathesis catalyst is 21. The process of claim 19, wherein the homogeneous olefin metathesis catalyst is 22. The process of claim 18, wherein the heterogeneous olefin metathesis catalyst is Re2O7 / Al2O3 or WO3 / Al2O3.
23. The method of claim 7, wherein the one or more isomerization agents comprise one or more homogeneous isomerization catalysts or one or more heterogeneous isomerization catalysts.
24. The process of claim 23, wherein the one or more homogeneous isomerization catalysts are selected from:
25. The process of claim 23, wherein the one or more homogeneous isomerization catalysts are 26. The process of claim 23, wherein the one or more heterogeneous isomerization catalysts are selected from the group consisting of: Na / Al2O3, K / Al2O3, Mg / Al2O3, MgO, NaO2, and KO2.
27. The method of claim 7, wherein the substituted or unsubstituted polymer is high density polyethylene, low density polyethylene or linear low density polyethylene or a copolymer thereof.
28. The method of claim 7, wherein the one or more dehydrogenation reagents comprise a transfer dehydrogenation catalyst.
29. The method of claim 7, wherein the one or more dehydrogenation reagents comprise a hydrogen acceptor.
30. The method of claim 29, wherein the hydrogen acceptor comprises a C-C bond, a C=C bond, a C≡C bond, a NN bond, a N=N bond, a N≡N bond, an OO bond, an O=O bond, a CN bond, a C=N bond, a C≡N bond, a CO bond, a C=O bond, a C≡O bond, an SS bond, a CS bond, or a C=S bond.
31. The method of claim 29, wherein the hydrogen acceptor comprises a C=C bond.
32. The method of claim 29, wherein the hydrogen acceptor is ethylene, propylene, butene, tert-butylethylene, norbornene, norbornadiene, butadiene, styrene, acetylene, O2, CO2, CO, substituted or unsubstituted benzoquinone, or N2.
33. The method of claim 7, wherein the one or more dehydrogenation agents comprise a heterogeneous dehydrogenation catalyst.
34. The method of claim 33, wherein the heterogeneous dehydrogenation catalyst comprises a plurality of metal elements.
35. The process of claim 33, wherein the heterogeneous dehydrogenation catalyst is a bimetallic catalyst.
36. The method of claim 33, wherein the heterogeneous dehydrogenation catalyst is a Pt / Sn catalyst or a Pt / Zn catalyst.
37. The method of claim 33, wherein the heterogeneous dehydrogenation catalyst is Pt / Sn-Al2O3 or Pt / Zn-SiO2.
38. The method of claim 7, wherein the one or more dehydrogenation agents comprise a homogeneous dehydrogenation catalyst.
39. The method of claim 38, wherein the homogeneous dehydrogenation catalyst comprises an iridium catalyst, a rhodium catalyst, or a ruthenium catalyst.
40. The method of claim 38, wherein the homogeneous dehydrogenation catalyst comprises an iridium catalyst.
41. The method of claim 38, wherein the homogeneous dehydrogenation catalyst has the formula: in M is Ir, Rh, Ru or Os; L 1 and L 2 are independently -O-, -S-, -NR 6 - or a substituted or unsubstituted alkylene group; Each R 3 and R 4 are independently substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; R 5 are independently halogen, -CX 5 3. -CHX 5 2. -CH2X 5 、-OCX 5 3. -OCH2X 5 、-OCHX 5 2. -CN, -SO n5 R 5D 、-SO v5 NR 5A R 5B 、-NR 5C NR 5A R 5B 、-ONR 5A R 5B 、-NR 5C C(O)NR 5A R 5B 、-N(O) m5 、-NR 5A R 5B 、-C(O)R 5C 、-C(O)OR 5C 、-OC(O)R 5C 、-OC(O)OR 5C 、-C(O)NR 5A R 5B 、-OC(O)NR 5A R 5B 、-OR 5D 、-SR 5D 、-NR 5A S02R 5D 、-NR 5A C(O)R 5C 、-NR 5A C(O)OR 5C 、-NR 5A OR 5C 、-P(O)2(OR 5A )、-OP(O)2(OR 5A )、-OP(R 5A )(R 5B ),-BR 5A R 5B 、-SiR 5A R 5B R 5C , substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; Each R 6 are independently hydrogen, halogen, -CCl3, -CBr3, -CF3, -CI3, -CHCl2, -CHBr2, -CHF2, -CHI2, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CN, -OH, -NH2, -COOH, -CONH2, -OCCl3, -OCF3, -OCBr3, -OCI3, -OCHCl2, -OCHBr2, -OCHI2, -OCHF2, -OCH2Cl, -OCH2Br, -OCH2I, -OCH2F, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; Each R 5A , R 5B , R 5C and R 5D are independently hydrogen, -CCl3, -CBr3, -CF3, -CI3, -CHCl2, -CHBr2, -CHF2, -CHI2, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CN, -OH, -NH2, -COOH, -CONH2, -OCCl3, -OCF3, -OCBr3, -OCI3, -OCHCl2, -OCHBr2, -OCHI2, -OCHF2, -OCH2Cl, -OCH2Br, -OCH2I, -OCH2F, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; or R bonded to the same nitrogen atom 5A and R 5B The substituents are joined to form a substituted or unsubstituted heterocycloalkyl or a substituted or unsubstituted heteroaryl; Each X 5 are independently -Cl, -Br, -I or -F; n5 is 0, 1, 2, 3 or 4; Each m5 and v5 is independently 1 or 2; and z5 is 0, 1, 2, or 3.
42. The process of claim 38, wherein the homogeneous dehydrogenation catalyst is 43. The method of claim 7, wherein a percentage of 1% to 3% of the monomer units in the dehydrogenated polymer are unsaturated.
44. The method of claim 7, wherein a percentage of 1.7% to 2.1% of the monomer units in the dehydrogenated polymer are unsaturated.
45. The method of claim 7, wherein a percentage of 1.9% to 2.1% of the monomer units in the dehydrogenated polymer are unsaturated.
46. The method of claim 7, wherein the dehydrogenation polymer comprises at least one -C(R 1 )=C(R 2 )-monomer unit, wherein R 1 are independently hydrogen, halogen, -CX 1 3. -CHX 1 2. -CH2X 1 、-OCX 1 3. -OCH2X 1 、-OCHX 1 2. -CN, -SO n1 R 1D 、-SO v1 NR 1A R 1B 、-NR 1C NR 1A R 1B 、-ONR 1A R 1B 、-NR 1C C(O)NR 1A R 1B 、-N(O) m1 、-NR 1A R 1B 、-C(O)R 1C 、-C(O)OR 1C 、-OC(O)R 1C 、-OC(O)OR 1C 、-C(O)NR 1A R 1B 、-OC(O)NR 1A R 1B 、-OR 1D 、-SR 1D 、-NR 1A S02R 1D 、-NR 1A C(O)R 1C 、-NR 1A C(O)OR 1C 、-NR 1A OR 1C 、-P(O)2(OR 1A )、-OP(O)2(OR 1A ),-BR 1A R 1B 、-SiR 1A R 1B R 1C , substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; R 2 are independently hydrogen, halogen, -CX 2 3. -CHX 2 2. -CH2X 2 、-OCX 2 3. -OCH2X 2 、-OCHX 2 2. -CN, -SO n2 R 2D 、-SO v2 NR 2A R 2B 、-NR 2C NR 2A R 2B 、-ONR 2A R 2B 、-NR 2C C(O)NR 2A R 2B 、-N(O) m2 、-NR 2A R 2B 、-C(O)R 2C 、-C(O)OR 2C 、-OC(O)R 2C 、-OC(O)OR 2C 、-C(O)NR 2A R 2B 、-OC(O)NR 2A R 2B 、-OR 2D 、-SR 2D 、-NR 2A S02R 2D 、-NR 2A C(O)R 2C 、-NR 2A C(O)OR 2C 、-NR 2A OR 2C 、-P(O)2(OR 2A )、-OP(O)2(OR 2A ),-BR 2A R 2B 、-SiR 2A R 2B R 2C , substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; Each R 1A , R 1B , R 1C , R 1D , R 2A , R 2B , R 2C and R 2D R is independently hydrogen, -CCl3, -CBr3, -CF3, -CI3, -CHCl2, -CHBr2, -CHF2, -CHI2, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CN, -OH, -NH2, -COOH, -CONH2, -OCCl3, -OCF3, -OCBr3, -OCI3, -OCHCl2, -OCHBr2, -OCHI2, -OCHF2, -OCH2Cl, -OCH2Br, -OCH2I, -OCH2F, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; or R bonded to the same nitrogen atom 1A and R 1B The substituents are joined to form a substituted or unsubstituted heterocycloalkyl or a substituted or unsubstituted heteroaryl; or R 2A and R 2B The substituents are joined to form a substituted or unsubstituted heterocycloalkyl or a substituted or unsubstituted heteroaryl; Each X 1 and X 2 are independently -Cl, -Br, -I or -F; Each n1 and n2 is independently 0, 1, 2, 3 or 4; and Each of m1, m2, v1 and v2 is independently 1 or 2.
47. The method of claim 46, wherein R 1 and R 2 are independently hydrogen, halogen, -CCl3, -CBr3, -CF3, -CI3, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CHCl2, -CHBr2, -CHF2, -CHI2, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, -NHNH2, -ONH2, -NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -OCCl3, -OCBr3, -OCF3, -OCI3, -OCH2Cl, -OCH2Br, -OCH2F, -OCH2I, -OCHCl2, -OCHBr2, -OCHF2, -OCHI2, or substituted or unsubstituted C1-C 20 alkyl.
48. The method of claim 46, wherein R 1 and R 2 are independently hydrogen or substituted or unsubstituted C1-C 1000 alkyl.
49. The method of claim 46, wherein R 1 and R 2 For hydrogen.
50. The method of claim 1 performed under continuous flow conditions.
51. A substituted or unsubstituted dehydrogenated polyethylene wherein a percentage of the monomer units is unsaturated from 0.01% to 1.5%, or from 1.7% to 2.3%, or from 2.4% to 4.3%, or from 4.5% to 13.2%.
52. The dehydrogenated polyethylene of claim 51, having a number average molecular weight of 1,000 Da to 500,000 Da.
53. A substituted or unsubstituted dehydrogenated polyethylene having a number average molecular weight of 2,200 Da or more.
54. The dehydrogenated polyethylene of claim 53, having a number average molecular weight of 2,200 Da to 500,000 Da.
55. The dehydrogenated polyethylene of claim 53, having a number average molecular weight of 2,200 Da to 6,500 Da or a number average molecular weight greater than 6,700 Da.
56. The dehydrogenated polyethylene of claim 53, wherein a percentage of the monomer units is unsaturated from 0.01% to 11%.
57. The dehydrogenated polyethylene of claim 53, wherein a percentage of the monomer units is unsaturated from 0.01% to 10%.
58. The dehydrogenated polyethylene of claim 53, wherein 8% or less of the monomer units are unsaturated.
59. The dehydrogenated polyethylene of claim 53, wherein a percentage of the monomer units is unsaturated from 1.5% to 3%.
60. The dehydrogenated polyethylene of claim 53, wherein a percentage of 1.9% of the monomer units are unsaturated.
61. The dehydrogenated polyethylene of claim 51, wherein the distribution of the unsaturated monomer units is irregular.
62. The dehydrogenated polyethylene of claim 51, comprising at least one -C(R 1 )=C(R 2 )-monomer unit, wherein R 1 are independently hydrogen, halogen, -CX 1 3. -CHX 1 2. -CH2X 1 、-OCX 1 3. -OCH2X 1 、-OCHX 1 2. -CN, -SO n1 R 1D 、-SO v1 NR 1A R 1B 、-NR 1C NR 1A R 1B 、-ONR 1A R 1B 、-NR 1C C(O)NR 1A R 1B 、-N(O) m1 、-NR 1A R 1B 、-C(O)R 1C 、-C(O)OR 1C 、-OC(O)R 1C 、-OC(O)OR 1C 、-C(O)NR 1A R 1B 、-OC(O)NR 1A R 1B 、-OR 1D 、-SR 1D 、-NR 1A S02R 1D 、-NR 1A C(O)R 1C 、-NR 1A C(O)OR 1C 、-NR 1A OR 1C 、-P(O)2(OR 1A )、-OP(O)2(OR 1A ),-BR 1A R 1B 、-SiR 1A R 1B R 1C , substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; R 2 are independently hydrogen, halogen, -CX 2 3. -CHX 2 2. -CH2X 2 、-OCX 2 3. -OCH2X 2 、-OCHX 2 2. -CN, -SO n2 R 2D 、-SO v2 NR 2A R 2B 、- NR 2C NR 2A R 2B 、-ONR 2A R 2B 、-NR 2C C(O)NR 2A R 2B 、-N(O) m2 、- NR 2A R 2B 、-C(O)R 2C 、-C(O)OR 2C 、-OC(O)R 2C 、-OC(O)OR 2C 、-C(O)NR 2A R 2B 、-OC(O)NR 2A R 2B 、-OR 2D 、-SR 2D 、-NR 2A SO2R 2D 、- NR 2A C(O)R 2C 、-NR 2A C(O)OR 2C 、-NR 2A OR 2C 、-P(O)2(OR 2A )、-OP(O)2(OR 2A ),-BR 2A R 2B 、-SiR 2A R 2B R 2C , substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; Each R 1A , R 1B , R 1C , R 1D , R 2A , R 2B , R 2C and R 2D R is independently hydrogen, -CCl3, -CBr3, -CF3, -CI3, -CHCl2, -CHBr2, -CHF2, -CHI2, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CN, -OH, -NH2, -COOH, -CONH2, -OCCl3, -OCF3, -OCBr3, -OCI3, -OCHCl2, -OCHBr2, -OCHI2, -OCHF2, -OCH2Cl, -OCH2Br, -OCH2I, -OCH2F, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; or R bonded to the same nitrogen atom 1A and R 1B The substituents are joined to form a substituted or unsubstituted heterocycloalkyl or a substituted or unsubstituted heteroaryl; or R 2A and R 2B The substituents are joined to form a substituted or unsubstituted heterocycloalkyl or a substituted or unsubstituted heteroaryl; Each X 1 and X 2 are independently -Cl, -Br, -I or -F; Each n1 and n2 is independently 0, 1, 2, 3 or 4; and Each of m1, m2, v1 and v2 is independently 1 or 2.
63. The dehydrogenated polyethylene according to claim 62, wherein R 1 and R 2 are independently hydrogen, halogen, -CCl3, -CBr3, -CF3, -CI3, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CHCl2, -CHBr2, -CHF2, -CHI2, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, -NHNH2, -ONH2, -NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -OCCl3, -OCBr3, -OCF3, -OCI3, -OCH2Cl, -OCH2Br, -OCH2F, -OCH2I, -OCHCl2, -OCHBr2, -OCHF2, -OCHI2, or substituted or unsubstituted C1-C 10 alkyl.
64. The dehydrogenated polyethylene according to claim 62, wherein R 1 and R 2 are independently hydrogen or substituted or unsubstituted C1-C 1000 alkyl.
65. The dehydrogenated polyethylene according to claim 62, wherein R 1 and R 2 For hydrogen.