Preparation and method of making amine-containing polybutadiene polymers

Abstract

The preparation of amine-containing polymers from commodity polyolefins has been achieved through the functionalization of polybutadiene. Pre-functionalized polybutadiene is composed of butadiene and, optionally, other monomers such as styrene. The butadiene monomers may be linked with a mixture of both 1,4- and 1,2-subunits. Amine functionalization of polybutadiene substrates has been provided using a single-step catalytic reaction called hydroaminoalkylation (HAA).

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to and the benefit of U.S. Provisional Patent Application No. 63 / 330,696, filed April 13, 2022, the contents of which are incorporated by reference in their entirety for all purposes.

[0002] The present disclosure provides a hydroaminoalkylation reaction of polybutadiene to produce aminated polybutadiene having branched pendant amine groups. [Background technology]

[0003] Functionalization of polyolefins with polar groups is useful for a myriad of applications. Franssen et al., Chem. Soc. Rev. 2013, 42(13):5809-5832. Incorporation of amine functionality into polyolefins is attractive but remains relatively elusive via traditional routes. For example, amine-containing monomers are typically not compatible with the most commonly practiced polymerization methods, e.g., Ziegler-Natta polymerization, metallocene polymerization, or radical polymerization. Rare tertiary amine-containing monomers can be incorporated using some metallocene catalysis. Postpolymerization methods typically have low selectivity and / or atom efficiency. In other cases, organoaluminum protection of pendant amines has allowed incorporation into the polyolefin chain via an olefin-protected amine linkage. This route has proven complicated by the difficulty of recycling the protected amine olefin, reactions of the protected amine olefin with impurities, and the expense and complexity of the deprotection step.

[0004] Thus, the synthesis of amine-functionalized polymers remains challenging due to the nucleophilic and basic nature of amines. Amines interfere with most polymerization mechanisms and are difficult to install directly and catalytically via metal-based reactions. In general, such routes are not straightforward and require multiple steps and expensive reagents. Rodriguez et al., Macromolecules 2021,54(11):4971-4985. Although challenging to install, amine functional groups can impart materials with modified polarity, hydrogen bonding ability, and / or amphiphilic properties. Franssen et al., Chem. Soc. Rev. 2013, 42(13):5809-5832; Pelton, Langmuir 2014, 30(51):15373-15382; Gilmour et al., ACS Applied Polymer Materials 2021, 3(5):2330-2335; Kuanr et al., Macromolecules 2020, 53(7):2649-2661. Such amine-containing materials may be useful as fuel additives and lubricants, in paints, adhesives, and coatings, as components in drug delivery systems, anion exchange membranes, and reactive polymer blends compatible with immiscible polymer blends.

[0005] A common method for introducing amines onto polyolefins involves functionalizing unsaturated polyolefins via a high-pressure reaction sequence of hydroformylation followed by reductive amination. This process is commonly referred to as a tandem process called hydroaminomethylation / aminomethylation. Rodriguez et al., Macromolecules 2021, 54(11):4971-4985; McGrath et al., Chem. Rev. 1995, 95(2):381-398. The hydroaminomethylation / hydroformylation reductive amination sequence typically favors C-C bond formation on the terminal carbons of the pendant vinyl groups of the 1,2-polybutadiene repeat units to provide "linear" amination variants. Although these are well-established methodologies in the industry, these reactions result in stoichiometric waste and poor control over amine incorporation.

[0006] U.S. Patent Application Publication No. US2021 / 0002407A1 discloses a hydroformylation / reductive amination reaction sequence (also known as hydroaminomethylation) for introducing amines onto polyolefin mixtures. The hydroaminomethylation reaction yielded primarily "linear" products.

[0007] Scheme 1: [ka] Hydroaminoalkylation offers several advantages as a one-step catalytic reaction that can result in direct amine functionalization on unsaturated polyolefins. Edwards et al., Chemical Communications 2018, 54(89):12543-12560. Recently, it has been reported that hydroaminoalkylation is an effective post-polymerization amination route to provide terminally aminated polyolefins from vinyl-terminated polypropylene. Scott et al., ACS Macro Letters 2021, 10(10):1266-1272; Daneshmand et al., J. Am. Chem. Soc. 2020, 142(37):15740-15750.

[0008] This disclosure presents a one-step catalytic method for introducing amine groups onto polymers containing a large number of unsaturation points, such as polybutadiene, which is unknown. Hydroaminoalkylation is a known method for functionalizing small molecules, but has only been reported for functionalizing polymers with polyolefins that have a single terminal reactive unsaturation. Recent advances in the production of highly electrophilic and robust early transition metal catalysts have enabled the ability to predictably and efficiently install amine groups onto challenging polymer substrates without forming stoichiometric waste products. This disclosure describes a highly electrophilic early transition metal catalyst for efficiently introducing amine groups onto polybutadiene substrates via hydroaminoalkylation, which was unknown prior to this disclosure herein. Summary of the Invention

[0009] The disclosure described herein is based on the discovery that catalytic hydroaminoalkylation of polybutadiene results in aminated polybutadienes with predominantly branched pendant amine functionality. This reaction can be applied with a wide range of amine and polybutadiene polymer reactants to yield products with controlled amine incorporation. The introduction of amines provides polar groups that improve the utility and applicability of these products.

[0010] The present disclosure includes the hydroaminoalkylation reaction of unsaturated polyolefins using catalysts such as tantalum urate complexes. Compared to related processes, such as the Ta(NMe2)5 and Ta(NEt2)2Cl3 catalysts of Hagadorn et al., U.S. Patent No. 8,669,326, the present process has shorter reaction times, lower temperatures, and expanded amine substrate ranges to obtain products with controlled amine incorporation. An additional advantage is that the reactions described herein can be carried out at ambient pressure. This reaction can enable new connection patterns by preferentially forming branched products selectively with pendant vinyl groups, thus providing new object compositions.

[0011] In a first embodiment, provided herein is a polymer comprising: Polybutadiene backbone, 1,2-alkene unit, 1,4-alkene units, and A branched substituted unit having a functional group of formula (I): [ka] A linear substituted unit having a functional group of formula (I): wherein the molar ratio of branched to linear substituted units is 6:1 or greater; R 1 is hydrogen, -C1 to -C 20 Alkyl or -C6~C 20 is aryl, R 2 -C1~C 20 Alkyl or -C6~C 20 is aryl, or R 1 and R 2 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 Form a heterocyclic ring, R 1 and R 2 are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OH, -OCH3, -OCF3, and -C1 to C6 thioalkyl, or a combination thereof; R 3 and R 4 is independently selected at each instance from H, -C1-C6 alkyl, and -C1-C6 heteroalkyl; The asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone; wherein the polymer optionally comprises other units, The units may be arranged contiguously, in blocks, or randomly distributed.

[0012] In a second embodiment, the present specification provides a compound of formula (II): [ka] or a fragment thereof, wherein R 5 If is present on the c unit, the dashed line indicates a single bond, and R 5 is absent on the c unit, the dashed line is a double bond, R 5 is optionally a compound of formula (I), [ka] During the ceremony, R 1 -C1~C 20 Alkyl or -C6~C 20 is aryl, or R 2 is hydrogen, -C1 to -C 20 Alkyl or -C6~C 20 is aryl, or R 1 and R 2 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 Form a heterocyclic ring, R 3 and R 4 are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3, and -C1-C6 thioalkyl, or a combination thereof; R 3 and R 4 is independently selected at each instance from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl; R 6 is hydrogen, -C1 to -C 20 Alkyl, -C6~C 20 Aryl, -C 1~6 Alkyl-C1~C 20 Alkyl, -C 1~6 Alkyl-C6~C 20 Aryl, -C 1~6 Heteroalkyl-C1~C 20Alkyl, or -C 1~6 Heteroalkyl-C6~C 20 is aryl, a, b, c, d, e, and f are, independently at each occurrence, integers from 0 to 100,000, the ratio of d:e is 6:1 or greater, and the units may be ordered or randomly distributed.

[0013] In a third embodiment, provided herein is a polymer comprising: Polybutadiene backbone, 1,2-alkene unit, 1,4-alkene units, and 1,4-addition units substituted with functional groups of formula (I): [ka] During the ceremony, R 1 is hydrogen, -C1 to -C 20 Alkyl or -C6~C 20 is aryl, R 2 -C1~C 20 Alkyl or -C6~C 20 is aryl, or R 1 and R 2 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 Form a heterocyclic ring, R 1 and R 2 are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3, and -SCH3, or combinations thereof; R 3 and R 4 is independently selected at each instance from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl; The asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone; wherein the polymer optionally comprises other units, The units may be ordered or randomly distributed.

[0014] In a fourth embodiment, provided herein is a polymer comprising: Polybutadiene backbone, Units containing 1,2-alkene repeat units, Units containing 1,4-alkene repeat units, and Branched units substituted with functional groups of formula (I): [ka] A linear substituted unit having a functional group of formula (I): R 1 is hydrogen, -C1 to -C 20 Alkyl or -C6~C 20 is aryl, R 2 -C1~C 20 Alkyl or -C6~C 20 is aryl, or R 1 and R 2 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 Form a heterocyclic ring, R 1 and R 2 are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OH, -OCH3, -OCF3, and -C1 to C6 thioalkyl, or a combination thereof; R 3 and R 4 is independently selected at each instance from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl; The asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone; wherein the polymer optionally comprises other units, The units may be ordered or randomly distributed.

[0015] In a fifth embodiment, there is provided herein a process for making a polymer, the process comprising: hydroaminoalkylating the polybutadiene polymer post polymerization in the presence of at least 5 mol % of a Group 4 or Group 5 transition metal catalyst and a secondary amine to form a functionalized polymer, the reaction temperature being between 110° C. and 165° C.; and forming a polymer comprising: Polybutadiene backbone, 1,2-alkene unit, 1,4-alkene units, and Branched units substituted with functional groups of formula (I): [ka] The linear substitution pattern of vinyl polymer units having functional groups of formula (I): wherein the molar ratio of branched units to linear units is at least 6:1; R 1 is hydrogen, -C1 to -C 20 Alkyl or -C6~C 20 is aryl, R 2 -C1~C 20 Alkyl or -C6~C 20 is aryl, or R 1 and R 2 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 Form a heterocyclic ring, R 1 and R 2 are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3, and thio-C1-C6 alkyl, or a combination thereof; R 2 the aryl group is optionally para-substituted; R 3 and R 4 is independently selected at each instance from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl; The asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone; wherein the polymer optionally comprises other units, The units may be ordered or randomly distributed.

[0016] In a sixth embodiment, there is provided herein a process for making a polymer, the process comprising: hydroaminoalkylating a polybutadiene polymer post polymerization in the presence of a Group 4 or Group 5 transition metal catalyst and a secondary amine to form a functionalized polymer, the reaction temperature being between 110° C. and 165° C.; and forming a polymer comprising: Polybutadiene backbone, 1,2-alkene unit, 1,4-alkene units, and Branched units substituted with functional groups of formula (I): [ka] The linear substitution pattern of vinyl polymer units having functional groups of formula (I): wherein the molar ratio of branched units to linear units is at least 6:1; R 1 is hydrogen, -C1 to -C 20 Alkyl or -C6~C 20 is aryl, R 2 -C1~C 20 Alkyl or -C6~C 20 is aryl, or R 1 and R 2 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 Form a heterocyclic ring, R 1 and R 2are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3, and thio-C1-C6 alkyl, or a combination thereof; R 2 the aryl group is optionally para-substituted; R 3 and R 4 is independently selected at each instance from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl; The asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone; wherein the polymer optionally comprises other units, The units may be ordered or randomly distributed.

[0017] In a seventh embodiment, there is provided herein a process for making a polymer, the process comprising: The method includes functionalizing an internal olefin of a polybutadiene polymer in the presence of at least 5 mol % of a Group 4 or Group 5 transition metal catalyst and a secondary amine to form a functionalized polymer, the reaction temperature being at least 140° C., the functionalized polymer comprising: Polybutadiene backbone, 1,2-alkene unit, 1,4-alkene units, and 1,4-addition units substituted with functional groups of formula (I): [ka] During the ceremony, R 1 is hydrogen, -C1 to -C 20 Alkyl, or -C6~C 20 is aryl, R 2 -C1~C 20 Alkyl or -C6~C 20 is aryl, or R 1 and R 2-C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 Form a heterocyclic ring, R 1 and R 2 are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3, and -SCH3, or combinations thereof; R 3 and R 4 is independently selected at each instance from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl; The asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone; wherein the polymer optionally comprises other units, The units may be ordered or randomly distributed.

[0018] In an eighth embodiment, there is provided herein a process for making a polymer, the process comprising: The method includes hydroaminoalkylating a polybutadiene polymer in the presence of at least 10 mol % of a Zr-based catalyst and a silyl-protected secondary amine to form a functionalized polymer, the reaction temperature being at least 140° C., the functionalized polymer comprising: Polybutadiene backbone, 1,2-alkene unit, 1,4-alkene units, and Branched units substituted with functional groups of formula (I): [ka] A linear substituted unit having a functional group of formula (I): R 1 is hydrogen, -C 1 ~C 20 Alkyl, or -C6~C 20 is aryl, R 2 -C1~C 20 Alkyl or -C6~C 20 is aryl, or R 1 and R 2 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 Form a heterocyclic ring, R 1 and R 2 are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3, and -C1-C6 thioalkyl, or a combination thereof; R 3 and R 4 is independently selected at each instance from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl; The asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone; wherein the polymer optionally comprises other units, The units may be ordered or randomly distributed.

[0019] In a ninth embodiment, there is provided herein a process for making a polymer, the process comprising: The method includes hydroaminoalkylating a polybutadiene polymer in the presence of at least 10 mol % of a Zr-based catalyst and a silyl-protected secondary amine to form a functionalized polymer, the reaction temperature being at least 140° C., the functionalized polymer comprising: Polybutadiene backbone, 1,2-alkene unit, 1,4-alkene units, and Branched units substituted with functional groups of formula (I): [ka] A linear substituted unit having a functional group of formula (I): R1 is hydrogen, -C 1 ~C 20 Alkyl, or -C6~C 20 is aryl, R 2 is hydrogen, -C1 to -C 20Alkyl or -C6~C 20 is aryl, or R 1 and R 2 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 Form a heterocyclic ring, R 1 and R 2 are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3, and -C1-C6 thioalkyl, or a combination thereof; R 3 and R 4 is independently, in each instance, hydrogen, -C1-C6 alkyl, -C1-C6 heteroalkyl, C 4~10 Aryl and C 4~10 heteroaryl; The asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone; wherein the polymer optionally comprises other units, The units may be ordered or randomly distributed. [Brief description of the drawings]

[0020] [Figure 1A] The 1H NMR spectrum of compound 1 is shown. [Figure 1B] The 13C{1H} NMR spectrum of compound 1 is shown. [Figure 2A] The 1H NMR spectrum of compound 2 is shown. [Figure 2B] The 13C{1H} NMR spectrum of compound 2 is shown. [Figure 3A] The 1H NMR spectrum of compound 3 is shown. [Figure 3B] The 13C{1H} NMR spectrum of compound 3 is shown. [Figure 3C] The 1H-1H COSY NMR spectrum of compound 3 is shown. [Figure 3D] The 1H-13C{1H}HSQC NMR spectrum of compound 3 is shown. [Figure 3E] The 1H-13C{1H}HMBC NMR spectrum of compound 3 is shown. [Figure 4A] The 1H NMR spectrum of compound 4 is shown. [Figure 4B] The 13C{1H}NMR spectrum of compound 4 is shown. [Figure 5A] The 1H NMR spectrum of compound 5 is shown. [Figure 5B] The 13C{1H} NMR spectrum of compound 5 is shown. [Figure 6A] The 1H NMR spectrum of compound 6 is shown. [Figure 6B] The 13C{1H} NMR spectrum of compound 6 is shown. [Figure 7] The 1H NMR spectrum of compound 7 is shown. [Figure 8] The stacked 1H NMR spectra of compound 8 before and after the reaction are shown. [Figure 9A] The 1H NMR spectrum of compound 9 is shown. [Figure 9B] The 13C{1H} NMR spectrum of compound 9 is shown. [Figure 9C] The 1H-1H COSY NMR spectrum of compound 9 is shown. [Figure 9D] The 1H-13C{1H}HSQC NMR spectrum of compound 9 is shown. [Figure 9E] The 1H-13C{1H}HMBC NMR spectrum of compound 9 is shown. [Figure 10] The 1H NMR spectrum of compound P6 is shown. [Figure 11] The 1H NMR spectrum of compound P7 is shown. [Figure 12A] The 1H NMR spectrum (300MH, CDCl3, 298K) of compound P9A is shown. [Figure 12B] The 13C NMR (75 MHz, CDCl3, 298K) spectrum of P9A is shown. [Figure 12C] The IR spectrum of P9A is shown. [Figure 13] The overlaid IR spectra of P10 and P10A are shown. [Figure 14] 1 shows the FT-IR spectrum of compound P12A. [Figure 15A] The 1H NMR (300 MHz, CDCl3, 298K) spectrum of P13A is shown. [Figure 15B] The 13C NMR (75 MHz, CDCl3, 298K) spectrum of P13A is shown. [Figure 15C] The IR spectrum of P13A is shown. [Figure 16] The 1H NMR (300 MHz, CDCl3, 298K) spectrum of P14A is shown. [Figure 17A] The 1H NMR (300 MHz, CDCl3, 298K) spectrum of P15A is shown. [Figure 17B] The 13C{1H}NMR (75 MHz, CDCl3, 298K) spectrum of P15A is shown. [Figure 18A] The 1H NMR (300 MHz, CDCl3, 298K) spectrum of P16A is shown. [Figure 18B] 1 shows the FT-IR spectrum of compound P16A. [Figure 19A] The 1H NMR (300 MHz, CDCl3, 298K) spectrum of P17A is shown. [Figure 19B] The 13C{1H}NMR (75 MHz, CDCl3, 298K) spectrum of P17A is shown. [Figure 20] FT-IR spectrum of compound P18A. [Figure 21A] The 1H NMR (300 MHz, CD3OD, 298K) spectrum of P19A is shown. [Figure 21B] The 13C{1H}NMR (75 MHz, CD3OD, 298K) spectrum of P19A is shown. [Figure 21C] 1 shows the FT-IR spectrum of compound P19A. [Figure 22A] The 1H NMR (300 MHz, CDCL3, 298K) spectrum of P20A is shown. [Figure 22B] The 13C{1H}NMR (75 MHz, CDCl3, 298K) spectrum of P20A is shown. [Figure 22C] 1 shows the FT-IR spectrum of compound P20A. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] The present disclosure provides a hydroaminoalkylation reaction of polybutadiene to obtain aminated polybutadienes with branched pendant amine functionality. The reaction can be applied with a wide range of amine and polybutadiene polymer reactants to obtain products with controlled amine incorporation. The introduction of amines provides polar groups that improve the utility and applicability of these products.

[0022] definition Unless otherwise defined, all technical terms, notations, and other scientific terms used herein are intended to have the meaning commonly understood by those skilled in the art to which this disclosure pertains. In some cases, terms with commonly understood meanings are defined herein for clarity and / or ready reference. The techniques and procedures described or referred to herein are generally well understood and commonly used by those skilled in the art using conventional methodology. Where appropriate, procedures involving the use of commercially available kits and reagents are generally performed according to manufacturer-defined protocols and conditions unless otherwise noted.

[0023] As used herein, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.

[0024] The term "about" refers to and encompasses the indicated value and the range above and below that value. In certain embodiments, the term "about" refers to the indicated value ±10%, ±5%, or ±1% of the indicated value. In certain embodiments, the term "about" refers to the indicated value ±1 standard deviation of that value. In certain embodiments, for example, on a logarithmic scale (e.g., pH), the term "about" refers to the indicated value ±0.3, ±0.2, or ±0.1.

[0025] As used herein, [ka] The symbol is used to indicate the point at which a repeat unit within a polymeric material is attached to another group within the polymeric material, for example, another repeat unit or an end group.

[0026] An asterisk (*) indicates the point of attachment of the pendant group to the polymer chain, such as to a carbon atom in the polymer chain.

[0027] The term "polymer" refers to a macrostructure having a number average molecular weight (Mn) of at least 2,000 daltons, at least 5,000 daltons, at least 10,000 daltons, at least 25,000 daltons, at least 50,000 daltons, at least 100,000 daltons, at least 300,000 daltons, at least 500,000 daltons, at least 750,000 daltons, at least 1,000,000 daltons, or even at least 1,500,000 daltons. The polymer may be a homopolymer, copolymer, terpolymer, etc. The polymer may be a random copolymer or a block copolymer.

[0028] The term "polymer backbone" refers to the primary continuous chain of carbon-only atoms of a polymer.

[0029] When referring to the compounds provided herein, the following terms have the following meanings unless otherwise specified. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. In the event that there are multiple definitions for any term herein, the definition in this section shall prevail unless otherwise specified.

[0030] The term "alkyl," as used herein, unless otherwise specified, refers to a saturated straight or branched chain hydrocarbon. In certain embodiments, an alkyl group is a primary, secondary, or tertiary hydrocarbon. In certain embodiments, an alkyl group contains 1 to 10 carbon atoms (i.e., C1 to C6). 10 In certain embodiments, the alkyl is a lower alkyl, e.g., C 1~6 and alkyl. In certain embodiments, the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secbutyl, t-butyl, pentyl, isopentyl, neopentyl, hexyl, isohexyl, 3-methylpentyl, 2,2-dimethylbutyl, and 2,3-dimethylbutyl. In certain embodiments, "substituted alkyl" refers to an alkyl substituted with one, two, or three groups independently selected from halogen (e.g., fluoro (F), chloro (Cl), bromo (Br), or iodo (I)), alkyl, haloalkyl, hydroxyl, amino, alkylamino, alkoxy, aryl, heteroaryl, cycloalkyl, cyano, oxo, alkyne, and heterocycloalkylalkylene. In some embodiments, the alkyl is unsubstituted.

[0031] The term "alkylene," as used herein, unless otherwise specified, refers to a divalent alkyl group, as defined herein. "Substituted alkylene" refers to an alkylene group substituted as described herein for alkyl. In some embodiments, the alkylene is unsubstituted.

[0032] "Alkoxy" and "alkoxyl" refer to the group -OR", where R" is alkyl or cycloalkyl. In certain embodiments, alkoxy includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, sec-butoxy, n-pentoxy, n-hexoxy, 1,2-dimethylbutoxy, and the like.

[0033] "Amino" refers to -NH2.

[0034] The term "alkylamino," as used herein, unless otherwise specified, refers to the group -NHR", where R is, for example, C, as defined herein. 1~10 In certain embodiments, alkylamino is C 1~6 It is an alkylamino.

[0035] The term "dialkylamino," as used herein, unless otherwise specified, refers to the group -NR"R", where each R" is independently a C alkyl group, as defined herein. 1~10 In certain embodiments, the dialkylamino is di-C 1~6 It is an alkylamino.

[0036] The term "aryl" as used herein refers to phenyl, biphenyl, or naphthyl unless otherwise specified. The term includes both substituted and unsubstituted moieties. The aryl group may be substituted with any moiety, including but not limited to, one or more moieties (e.g., in some embodiments, one, two, or three moieties) selected from the group consisting of halogen (e.g., fluoro (F), chloro (Cl), bromo (Br), or iodo (I)), alkyl, haloalkyl, hydroxyl, amino, alkylamino, arylamino, alkoxy, aryloxy, nitro, cyano, sulfonic acid, sulfate, phosphonic acid, phosphate, and phosphonate, each moiety being independently unprotected or protected as necessary as would be understood by one of ordinary skill in the art (e.g., Greene, et al., Protective Groups in Organic Synthesis, John Wiley and Sons, Second Edition, 1991), and the aryl in the arylamino and aryloxy substituents is not further substituted.

[0037] As used herein, unless otherwise specified, the term "arylene" refers to a divalent aryl group, as defined herein.

[0038] The term "haloalkyl" refers to an alkyl group, as defined herein, substituted with one or more independently selected halogen atoms (e.g., in some embodiments, 1, 2, 3, 4, or 5).

[0039] The term "heteroalkyl" refers to an alkyl, as defined herein, in which one or more carbon atoms are replaced by a heteroatom. As used herein, "heteroalkenyl" refers to an alkenyl, as defined herein, in which one or more carbon atoms are replaced by a heteroatom. As used herein, "heteroalkynyl" refers to an alkynyl, as defined herein, in which one or more carbon atoms are replaced by a heteroatom. Suitable heteroatoms include, but are not limited to, nitrogen (N), oxygen (O), and sulfur (S) atoms. Heteroalkyl, heteroalkenyl, and heteroalkynyl are optionally substituted. Examples of heteroalkyl moieties include, but are not limited to, aminoalkyl, sulfonylalkyl, and sulfinylalkyl. Examples of heteroalkyl moieties also include, but are not limited to, methylamino, methylsulfonyl, and methylsulfinyl. "Substituted heteroalkyl" refers to a heteroalkyl substituted with one, two, or three groups independently selected from halogen (e.g., fluoro (F), chloro (Cl), bromo (Br), or iodo (I)), alkyl, haloalkyl, hydroxyl, amino, alkylamino, and alkoxy. In some embodiments, a heteroalkyl group can contain one, two, three, or four heteroatoms. One of ordinary skill in the art will appreciate that a 4-membered heteroalkyl can generally contain one or two heteroatoms, a 5- or 6-membered heteroalkyl can generally contain one, two, or three heteroatoms, and a 7- to 10-membered heteroalkyl can generally contain one, two, three, or four heteroatoms.

[0040] The terms "halo" or "halogen" or "halide," by themselves or as part of another substituent, mean, unless otherwise stated, fluorine, chlorine, bromine, or iodine atoms or ions.

[0041] As used herein, "oxo" refers to =O.

[0042] As used herein, the term "substituted", whether preceded by the term "optionally" or not, generally refers to replacing a hydrogen atom in a given structure with the radical of a specific substituent. Specific substituents are described above in the definitions and in the following compound description and examples thereof. Unless otherwise indicated, an optionally substituted group may have a substituent at each substitutable position of the group, and when two or more positions of any given structure may be substituted with two or more substituents selected from a specific group, the substituents may be the same or different at all positions. Substituents are not further substituted unless expressly stated.

[0043] As used herein, the term "catalyst" refers to a chemical compound that promotes a chemical reaction without itself being affected. "Catalyst" may be used interchangeably with terms such as "precatalyst," "catalyst system," or "catalytic system." As used herein, "catalyst" includes catalytic intermediates or species formed in situ.

[0044] As used herein, "Group 5 metal" refers to the d-electron containing transition metals listed in the Periodic Table of the Elements as Group 5, including the transition metals vanadium (V), niobium (Nb), tantalum (Ta), and dubium (Nb).

[0045] As used herein, "hydroaminoalkylation" refers to the reaction between a secondary amine-containing moiety and an olefin. A catalyst can often be used to facilitate such a reaction.

[0046] As used herein, a "secondary amine" refers to an amine in which an amino group is directly attached to the two C atoms of any hybridization. The two C atoms in the α-position to the N atom are sp 3 It can be hybridized.

[0047] As used herein, "olefin" or "alkene" refers to an unsaturated hydrocarbon containing one or more pairs of C atoms linked by a double bond.

[0048] The term "1,2-alkene repeat unit" or "1,2 alkene unit" refers to a polymer chain having butadiene monomers added via a 1,2-addition reaction pathway.

[0049] The term "1,4-alkene repeat unit" or "1,4 alkene unit" refers to a polymer chain having butadiene monomers added via a 1,4-addition reaction pathway.

[0050] As used herein, the term "branched substitution pattern of vinyl polymer units" refers to the product of an amination reaction pathway in which the alkene carbon alpha to the polymer backbone of the vinyl group is aminated to form the compound of formula III [ka] This gives a branched reaction unit as exemplified by:

[0051] As used herein, the term "linear substitution pattern of vinyl polymer units" refers to a group of units of formula IV [ka] The term "c" refers to the functionalization of the terminal alkene carbon of the vinyl group, as exemplified in: The subscript c characterizes the number of repeats, which can be in series or randomly distributed throughout the polymer.

[0052] As used herein, the term "branched unit" refers to the alkylation product of the hydroaminoalkylation reaction pathway, in which the alkene carbon alpha to the vinyl group of the polymer backbone is aminated to form the alkyl group of formula III. [ka] The subscript d characterizes the number of repeats, which can be in series or randomly distributed throughout the polymer.

[0053] As used herein, the term "linear unit" refers to a unit of formula IV [ka] This refers to the alkylation product from the functionalization of the terminal alkene carbon of a vinyl group, exemplified by:

[0054] The term "salts thereof" refers to quaternary ammonium salts of the polymers described herein, including, but not limited to, hydrochloride and oxalate salts of quaternary ammonium-containing polymers. The salts may include any ionic form of the polymers described herein. The salts refer to quaternary ammonium salts of the polymers described herein, unless expressly specified otherwise.

[0055] "-[PEG] 0~10 " or "-[PEG] 0~10 The term PEG used in "-(C2H4-O)" refers to the polymer chain - poly(ethylene) glycol. This polymer has the structure (-O-CH2-CH2-) n where n ranges from, and can be from 1 to 10, or where n ranges from, and can be from 1 to 50. In some embodiments, the PEG polymer chain is linked to an epoxide.

[0056] The term "reduced polybutadiene backbone" means that the residual alkene portion of the main alkyl chain (also known as the backbone), including the branched terminal alkenes, in the polybutadiene polymers described herein has been hydrogenated such that the alkene linkages become saturated, alkane linkages.

[0057] Polymer Production A typical primary branched unit polymer is prepared from a polymer hydroaminoalkylating the polybutadiene polymer post polymerization in the presence of at least 5 mol % of a Group 4 or Group 5 transition metal catalyst and a secondary amine to form a functionalized polymer, the reaction temperature being between 110° C. and 165° C.; and forming a polymer comprising: Polybutadiene backbone, 1,2-alkene unit, 1,4-alkene units, and Branched units substituted with functional groups of formula (I): [ka] The linear substitution pattern of vinyl polymer units having functional groups of formula (I): wherein the molar ratio of branched units to linear units is at least 6:1; R 1 is hydrogen, -C1 to -C 20 Alkyl or -C6~C 20 is aryl, R 2 -C1~C 20 Alkyl or -C6~C 20 is aryl, or R 1 and R 2 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 Form a heterocyclic ring, R 1 and R 2 are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3, and -C1-C6 thioalkyl, or a combination thereof; R 3 and R 4 is independently selected at each instance from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl; The asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone; wherein the polymer optionally comprises other units, The units may be ordered or randomly dispersed. In certain embodiments, the process is optionally solvent-free.

[0058] In certain embodiments, the temperature is between 110 and 165°C. In certain embodiments, the temperature is at least 110°C. In certain embodiments, the temperature is at least 115°C. In certain embodiments, the temperature is at least 120°C. In certain embodiments, the temperature is at least 125°C. In certain embodiments, the temperature is at least 130°C. In certain embodiments, the temperature is at least 135°C. In certain embodiments, the temperature is 140°C. In certain embodiments, the temperature is 145°C. In certain embodiments, the temperature is 150°C. In certain embodiments, the temperature is 155°C.

[0059] In certain embodiments, the temperature is between 110 and 165°C. In certain embodiments, the temperature is 110°C. In certain embodiments, the temperature is 115°C. In certain embodiments, the temperature is 120°C. In certain embodiments, the temperature is 125°C. In certain embodiments, the temperature is 130°C. In certain embodiments, the temperature is 135°C. In certain embodiments, the temperature is 140°C. In certain embodiments, the temperature is 145°C. In certain embodiments, the temperature is 150°C. In certain embodiments, the temperature is 155°C.

[0060] In certain embodiments, the catalyst is a Ta-based catalyst. In certain embodiments, the catalyst is Ta(CH2SiMe3)3Cl2. In certain embodiments, the catalyst is [ka] It is.

[0061] In certain embodiments, the amount of catalyst is at least 5 mol%. In certain embodiments, the catalyst is 0.5 mol%. In certain embodiments, the catalyst is 1 mol%. In certain embodiments, the catalyst is 2 mol%. In certain embodiments, the catalyst is 3 mol%. In certain embodiments, the catalyst is 4 mol%. In certain embodiments, the catalyst is 5 mol%.

[0062] A typical 1,4-addition polymer unit is prepared from a polymer The method includes functionalizing an internal olefin of a polybutadiene polymer in the presence of at least 5 mol % of a metal-based catalyst and a secondary amine to form a functionalized polymer, the reaction temperature being at least 140° C., and the functionalized polymer comprising: Polybutadiene backbone, 1,2-alkene unit, 1,4-alkene units, and 1,4-addition units substituted with functional groups of formula (I): [ka] During the ceremony, R 1 is hydrogen, -C1 to -C 20 Alkyl or -C6~C 20 is aryl, R 2 -C1~C 20 Alkyl or -C6~C 20 is aryl, or R 1 and R 2 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 Form a heterocyclic ring, R 1 and R 2 are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3, and -SCH3, or combinations thereof; R 3 and R 4 is independently selected at each instance from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl; The asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone; wherein the polymer optionally comprises other units, The units may be ordered or randomly dispersed. In certain embodiments, the process is optionally solvent-free.

[0063] In certain embodiments, the substituted aminated polybutadiene is The present invention is prepared by hydroaminoalkylating a polybutadiene polymer in the presence of at least 10 mol % of a Zr-based catalyst and a silyl-protected secondary amine to form a functionalized polymer, the reaction temperature being at least 140° C., the functionalized polymer comprising: Polybutadiene backbone, 1,2-alkene unit, 1,4-alkene units, and Branched units substituted with functional groups of formula (I): [ka] and A linear substituted unit having a functional group of formula (I): R 1 is hydrogen, -C1 to -C 20 Alkyl or -C6~C 20 is aryl, R 2 -C1~C 20 Alkyl or -C6~C 20 is aryl, or R 1 and R 2 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 Form a heterocyclic ring, R 1 and R 2 are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3, and -C1-C6 thioalkyl, or a combination thereof; R 3 and R 4 is independently selected at each instance from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl; The asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone; wherein the polymer optionally comprises other units, The units may be ordered or randomly dispersed. In certain embodiments, the process is optionally solvent-free. In certain embodiments, the amine is an N-benzylsilylamine.

[0064] In some other embodiments, the substituted aminated polybutadiene is The present invention is prepared by hydroaminoalkylating a polybutadiene polymer in the presence of at least 10 mol % of a Zr-based catalyst and a silyl-protected secondary amine to form a functionalized polymer, the reaction temperature being at least 140° C., the functionalized polymer comprising: Polybutadiene backbone, 1,2-alkene unit, 1,4-alkene units, and Branched units substituted with functional groups of formula (I): [ka] and A linear substituted unit having a functional group of formula (I): R 1 is hydrogen, -C1 to -C 20 Alkyl or -C6~C 20 is aryl, R 2 is hydrogen, -C1 to -C 20 Alkyl or -C6~C 20 is aryl, or R 1 and R 2 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 Form a heterocyclic ring, R 1 and R 2 are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3, and -C1-C6 thioalkyl, or a combination thereof; R 3 and R 4 is independently, in each instance, hydrogen, -C1-C6 alkyl, -C1-C6 heteroalkyl, C4~10 Aryl and C 4~10 heteroaryl; The asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone; wherein the polymer optionally comprises other units, The units may be ordered or randomly dispersed. In certain embodiments, the process is optionally solvent-free. In certain embodiments, the amine is an N-benzylsilylamine.

[0065] How to use In certain embodiments, the aminated materials disclosed herein may be applied in adhesive and coating formulations. In certain embodiments, the aminated materials disclosed herein may have applications as additives to materials such as rubber, plastics, composites, waxes, and the like. In certain embodiments, the aminated materials disclosed herein may have applications as lubricants, polymer membranes, and filters. In certain embodiments, the aminated materials disclosed herein may have applications as polymer compatibilizers. In certain embodiments, the aminated materials disclosed herein may have applications as drug delivery agents. In certain embodiments, the aminated materials disclosed herein may have applications as rheology modifiers, fuel additives, or dispersants.

[0066] compound In one embodiment, provided herein is a polymer comprising: Polybutadiene backbone, 1,2-alkene unit, 1,4-alkene units, and A branched substituted unit having a functional group of formula (I): [ka] A linear substituted unit having a functional group of formula (I): In certain embodiments, The molar ratio of branched units to linear units is greater than or equal to 6:1.

[0067] In formula (I), R 1 is hydrogen, -C1 to -C 20 Alkyl or -C6~C 20 Aryl or R 2 -C1~C 20 Alkyl or -C6~C 20 aryl or R 1 and R 2 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 Form a heterocyclic ring, R 1 and R 2 are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3, and -C1 to C6 thioalkyl, or a combination thereof; R 3 and R 4 is independently selected at each instance from hydrogen, C1-C6 alkyl, and C1-C6 heteroalkyl, and the asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone. In certain embodiments, the polymer optionally comprises other units. In certain embodiments, the units may be arranged sequentially, in blocks, or randomly distributed.

[0068] In certain embodiments, R 1 is hydrogen. In certain embodiments, R 1 -C1~C 20 In certain embodiments, R 1 -C6~C 20 It is aryl.

[0069] In certain embodiments, R 2 -C1~C 20 In certain embodiments, R 2 -C6~C 20 In certain embodiments, R 1 and R 2 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen.20 In certain embodiments, R 1 and R 2 are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3, and -C1-C6 thioalkyl, or a combination thereof. 2 The aryl group in is optionally para-substituted.

[0070] In certain embodiments, R 3 and R 4 is independently selected at each instance from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl. 3 is hydrogen. In certain embodiments, R 3 is -C1-C6 alkyl. In certain embodiments, R 3 is -C1-C6 heteroalkyl. In certain embodiments, R 4 is -H. In certain embodiments, R 4 is -C1-C6 alkyl. In certain embodiments, R 4 is -C1-C6 heteroalkyl.

[0071] In certain embodiments, the molar ratio of branched units to linear units products is 6:1 or greater. In certain embodiments, the ratio of branched units to linear units products is 6:1. In certain embodiments, the ratio of branched units to linear units products is 9:1. In certain embodiments, the molar ratio of branched units to linear units products can be varied by changing the reaction conditions. In certain embodiments, the amount of 1,2-alkene units and 1,4-alkene units can be equal or variable. In certain embodiments, the polymer comprises 92% 1,4-alkene units and 8% 1,2-alkene units.

[0072] In certain embodiments, the polymer comprises at least 60% branched substituted units relative to linear substituted units, hi certain embodiments, the polymer comprises at least 90% branched substituted units relative to linear substituted units.

[0073] In certain embodiments, the polymer optionally includes other units. In certain embodiments, the other units include styrene units optionally substituted with alkyl, substituted alkyl, heteroalkyl, substituted heteroalkyl, styrene, substituted styrene, or mixtures. In certain embodiments, the other units include styrene units optionally substituted with alkyl. In certain embodiments, the other units include alkyl. In certain embodiments, the other units include heteroalkyl. In certain embodiments, the other units include substituted heteroalkyl. In certain embodiments, the other units include styrene. In certain embodiments, the other units include substituted styrene. In certain embodiments, the monomer units are linked in a head-to-head fashion. In certain embodiments, the monomer units are linked in a head-to-tail fashion. In certain embodiments, the monomer units are linked in a tail-to-tail fashion.

[0074] In certain embodiments, the units may be arranged contiguously, in blocks, or randomly distributed.

[0075] In one embodiment, the compound of formula (II) [ka] A polymer of the formula:

[0076] In one embodiment, the compound of formula (II) [ka] In some examples, the fragments form polymers having isoprene units. In certain examples, these polymers are formed by copolymerizing butadiene with isoprene to add amine functional groups, e.g., functional groups of formula (I), to the polymer(s) formed by the copolymerization of butadiene and isoprene.

[0077] In formula (II), R 5optionally having the formula (I): [ka] In certain embodiments, R 5 When R is present on the c unit, the dashed line represents a single bond. 5 If is not present on the c unit, the dashed line indicates a double bond.

[0078] In formula (I), R 1 is hydrogen, -C1 to -C 20 Alkyl or -C6~C 20 Aryl or R 2 -C1~C 20 Alkyl or -C6~C 20 aryl or R 1 and R 2 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 Form a heterocyclic ring, R 1 and R 2 are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3, and -C1 to C6 thioalkyl, or a combination thereof; R 3 and R 4 is independently selected at each instance from H, C1-C6 alkyl, and C1-C6 heteroalkyl, and the asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone.

[0079] In certain embodiments, R 1 is hydrogen. In certain embodiments, R 1 -C1~C 20 In certain embodiments, R 1 -C6~C 20 It is aryl.

[0080] In certain embodiments, R 2 -C1~C 20 In certain embodiments, R2 -C6~C 20 In certain embodiments, R 1 and R 2 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 In certain embodiments, R 1 and R 2 are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3, and -C1-C6 thioalkyl, or a combination thereof. 2 The aryl group in is optionally para-substituted.

[0081] In embodiments, R 3 and R 4 is independently selected at each instance from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl. 3 is hydrogen. In certain embodiments, R 3 is -C1-C6 alkyl. In certain embodiments, R 3 is -C1-C6 heteroalkyl. In certain embodiments, R 4 is -H. In certain embodiments, R 4 is -C1-C6 alkyl. In certain embodiments, R 4 is -C1-C6 heteroalkyl.

[0082] In formula (II), R6 is hydrogen, -C1-C 20 Alkyl, -C6~C 20 Aryl, -C 1~6 Alkyl-C1~C 20 Alkyl, -C 1~6 Alkyl-C6~C 20 Aryl, -C 1~6 Heteroalkyl-C1~C 20 Alkyl, or -C 1~6 Heteroalkyl-C6~C 20 In certain embodiments, R 6is hydrogen. In certain embodiments, R 6 -C1~C 20 In certain embodiments, R 6 -C6~C 20 In certain embodiments, R 6 is C 1~6 Alkyl-C1~C 20 In certain embodiments, R 6 is C 1~6 Heteroalkyl-C1~C 20 In certain embodiments, R 6 is C 1~6 Heteroalkyl-C1~C 20 It is aryl.

[0083] In formula (II), a, b, c, d, e, and f are, independently at each occurrence, 0 to 100,000. In certain embodiments, the ratio of d:e is 6:1 or greater. In certain embodiments, the ratio of d:e is >9:1. In certain embodiments, the blocks may be ordered or randomly distributed. In certain embodiments, the ratio of d:c can be varied by changing the reaction conditions. In certain embodiments, more c units are provided relative to d units in the starting polymer where "a" is much larger than "b". In certain embodiments, the d block is usually formed first, and when the reaction is stopped, the ratio of d is >>c. In certain embodiments, if the reaction has sufficient time and amine loading, more and more "a" will react, resulting in a ratio of d:c that is not necessarily d>>>c. In certain embodiments, the ratio of a:b (blocks resulting from 1,4 and 1,2 addition of butadiene in the polymer, respectively) in the starting polymer reactant can also be varied.

[0084] In formula (II), the units may be ordered or randomly distributed. In certain embodiments, the units are ordered. In certain embodiments, the units are randomly distributed.

[0085] In certain embodiments of Formula (II), the ratio of a:b is 0.1, 0.5, 1, 1.5, 2, or 10. In certain embodiments, the ratio of d:e is 6:1.

[0086] In certain embodiments, the compound of formula II has the formula (IIa): [ka] It has the structure:

[0087] In certain embodiments, the compound of formula II has the formula (IIb): [ka] It has the structure:

[0088] In certain embodiments, the compound of formula II has the formula (IIc): [ka] It has the structure:

[0089] In certain embodiments, the compound of formula II has the formula (IId): [ka] It has the structure:

[0090] In certain embodiments, the compound of formula II has the formula (IIe): [ka] It has the structure:

[0091] In certain embodiments of formula (IIa), (IIb), (IIc), (IId), or (IIe), R 5 optionally having the formula (I): [ka] It is a compound of the formula:

[0092] In formula (I), R 1 is hydrogen, -C1 to -C 20 Alkyl or -C6~C 20 Aryl or R 2 -C1~C 20 Alkyl or -C6~C 20 aryl or R 1 and R 2 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 Form a heterocyclic ring, R 1 and R 2 are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3, and -C1 to C6 thioalkyl, or a combination thereof; R 2 The aryl group in is optionally para-substituted, R 3 and R 4 is independently selected at each instance from H, C1-C6 alkyl, and C1-C6 heteroalkyl, and the asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone.

[0093] In certain embodiments, R 1 is hydrogen. In certain embodiments, R 1 -C1~C 20 In certain embodiments, R 1 -C6~C 20 It is aryl.

[0094] In certain embodiments, R 2 -C1~C 20 In certain embodiments, R 2 -C6~C 20 In certain embodiments, R 1 and R 2 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 In certain embodiments, R 1 and R2 are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3, and -C1-C6 thioalkyl, or a combination thereof. 2 The aryl group in is optionally para-substituted.

[0095] In embodiments, R 3 and R 4 is independently selected at each instance from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl. 3 is hydrogen. In certain embodiments, R 3 is -C1-C6 alkyl. In certain embodiments, R 3 is -C1-C6 heteroalkyl. In certain embodiments, R 4 is -H. In certain embodiments, R 4 is -C1-C6 alkyl. In certain embodiments, R 4 is -C1-C6 heteroalkyl.

[0096] In certain embodiments of Formula (IIa), (IIb), or (IIc), R 6 is hydrogen, -C1 to -C 20 Alkyl, -C6~C 20 Aryl, -C 1~6 Alkyl-C1~C 20 Alkyl, -C 1~6 Alkyl-C6~C 20 Aryl, -C 1~6 Heteroalkyl-C1~C 20 Alkyl, or -C 1~6 Heteroalkyl-C6~C 20 In certain embodiments, R 6 is hydrogen. In certain embodiments, R 6 -C1~C 20 In certain embodiments, R 6 -C6~C 20 In certain embodiments, R 6 is C 1~6 Alkyl-C1~C20 In certain embodiments, R 6 is C 1~6 Heteroalkyl-C1~C 20 In certain embodiments, R 6 is C 1~6 Heteroalkyl-C1~C 20 It is aryl.

[0097] In formula (IIa), (IIb), (IIc), (IId), or (IIe), a, b, c, d, e, and f are, independently at each occurrence, 0 to 100,000. In certain embodiments, the ratio of d:e is 6:1 or greater. In certain embodiments, the ratio of d:e is >9:1. In certain embodiments, the blocks may be ordered or randomly distributed. In certain embodiments, the ratio of d:c can be changed by modifying the reaction conditions. In certain embodiments, more c units are provided relative to d units in the starting polymer where "a" is much larger than "b". In certain embodiments, the d block is usually formed first, and when the reaction is stopped, the ratio of d is >>c. In certain embodiments, if the reaction has sufficient time and amine loading, more and more "a" will react, resulting in a ratio of d:c that is not necessarily d>>>c. In certain embodiments, the ratio of a:b (blocks resulting from 1,4 and 1,2 additions of butadiene in the polymer, respectively) in the starting polymer reactant may also vary.

[0098] In one embodiment, provided herein is a polymer comprising: Polybutadiene backbone, 1,2-alkene unit, 1,4-alkene units, and 1,4-addition units substituted with functional groups of formula (I): [ka] During the ceremony, R 1 is hydrogen, -C1 to -C 20 Alkyl or -C6~C 20is aryl, R 2 -C1~C 20 Alkyl or -C6~C 20 is aryl, or R 1 and R 2 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 Form a heterocyclic ring, R 1 and R 2 are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3, and -SCH3, or combinations thereof; R 3 and R 4 is independently selected at each instance from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl; The asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone; wherein the polymer optionally comprises other units, The units may be ordered or randomly distributed.

[0099] In another embodiment, provided herein is a polymer comprising: Polybutadiene backbone, Units containing 1,2-alkene repeat units, Units containing 1,4-alkene repeat units, and Branched units substituted with functional groups of formula (I): [ka] Linear substituted units having a functional group of formula (I): In certain embodiments, the polymer optionally includes other units. In certain embodiments, the units may be ordered or randomly distributed.

[0100] In formula (I), R 1 is hydrogen, -C1 to -C 20Alkyl or -C6~C 20 Aryl or R 2 -C1~C 20 Alkyl or -C6~C 20 aryl or R 1 and R 2 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 Form a heterocyclic ring, R 1 and R 2 are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3, and -C1 to C6 thioalkyl, or a combination thereof; R 3 and R 4 is independently selected at each instance from hydrogen, C1-C6 alkyl, and C1-C6 heteroalkyl, and the asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone.

[0101] In certain embodiments, R 1 is hydrogen. In certain embodiments, R 1 -C1~C 20 In certain embodiments, R 1 -C6~C 20 It is aryl.

[0102] In certain embodiments, R 2 -C1~C 20 In certain embodiments, R 2 -C6~C 20 In certain embodiments, R 1 and R 2 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 In certain embodiments, R 1 and R 2are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3, and -C1-C6 thioalkyl, or a combination thereof. 2 The aryl group in is optionally para-substituted.

[0103] In certain embodiments, R 3 and R 4 is independently selected at each instance from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl. 3 is hydrogen. In certain embodiments, R 3 is -C1-C6 alkyl. In certain embodiments, R 3 is -C1-C6 heteroalkyl. In certain embodiments, R 4 is -H. In certain embodiments, R 4 is -C1-C6 alkyl. In certain embodiments, R 4 is -C1-C6 heteroalkyl.

[0104] In certain embodiments, the compound is [ka] where the sum of the subscripts d and e is 9.

[0105] In certain embodiments, provided herein are compounds in the following table: [Table 1-1] [Table 1-2] [Table 1-3]

[0106] Embodiment Embodiment 1: A polymer comprising: Polybutadiene backbone, 1,2-alkene unit, 1,4-alkene units, and A branched substituted unit having a functional group of formula (I): [ka] A linear substituted unit having a functional group of formula (I): wherein the molar ratio of branched units to linear units is at least 6:1; R 1 is hydrogen, -C1 to -C 20 Alkyl or -C6~C 20 is aryl, R 2 -C1~C 20 Alkyl or -C6~C 20 is aryl, or R 1 and R 2 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 Forming a heterocyclic ring, In the formula, R 1 and R 2 are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OH, -OCH3, -OCF3, and -C1 to C6 thioalkyl, or a combination thereof; R 3 and R 4 is independently selected at each instance from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl; The asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone; wherein the polymer optionally comprises other units, The units may be arranged sequentially, in blocks or randomly distributed in the polymer.

[0107] Embodiment 2: The polymer of embodiment 1, wherein the product contains at least 60% branched substituted units relative to linear substituted units.

[0108] Embodiment 3: A polymer according to embodiment 1 or 2, wherein the amount of 1,2-alkene units and 1,4-alkene units can be equal or variable.

[0109] Embodiment 4: A polymer according to any one of embodiments 1 to 3, comprising 92% 1,4-alkene units and 8% 1,2-alkene units.

[0110] Embodiment 5: The polymer of any one of embodiments 1 to 4, wherein the other units comprise styrene units optionally substituted with alkyl, substituted alkyl, heteroalkyl, substituted heteroalkyl, styrene, substituted styrene, or mixtures thereof.

[0111] Embodiment 6: The polymer of embodiment 5, wherein the other units comprise styrene units.

[0112] Embodiment 7: The polymer of embodiment 1, wherein the other units are isoprene units.

[0113] Embodiment 8: R 2 The polymer of any one of the preceding embodiments, wherein the aryl group in

[0114] Embodiment 9: Formula (II) [ka] or a fragment thereof, wherein R 5 is either present or absent, R 5 If is present on the c unit, the dashed line indicates a single bond, and R 5 is absent on the c unit, the dashed line indicates a double bond, R 5 is optionally a compound of formula (I), [ka] During the ceremony, R 1-C1~C 20 Alkyl or -C6~C 20 is aryl, or R 2 is hydrogen, -C1 to -C 20 Alkyl or -C6~C 20 is aryl, or R 1 and R 2 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 Form a heterocyclic ring, R 3 and R 4 are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3, and -C1-C6 thioalkyl, or a combination thereof; R 2 the aryl group in is optionally para-substituted; R 3 and R 4 is independently selected at each instance from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl; R 6 is hydrogen, -C1 to -C 20 Alkyl, -C6~C 20 Aryl, -C 1~6 Alkyl-C1~C 20 Alkyl, -C 1~6 Alkyl-C6~C 20 Aryl, -C 1~6 Heteroalkyl-C1~C 20 Alkyl, or -C 1~6 Heteroalkyl-C6~C 20 is aryl, a, b, c, d, e, and f, independently at each occurrence, are integers from 0 to 100,000, the ratio of d:e is 6:1 or greater, and the units may be ordered or randomly dispersed in the polymer.

[0115] Embodiment 10: The polymer of embodiment 9, wherein the ratio of a:b is 0.1, 0.5, 1, 1.5, 2, or 10.

[0116] Embodiment 11: The polymer of embodiment 9 or 10, wherein the ratio of d:e is 6:1.

[0117] Embodiment 12: R 2 12. The polymer of any one of embodiments 9-11, wherein the aryl group in

[0118] Embodiment 13: The polymer of formula (II) having the structure of formula (IIa): [ka]

[0119] Embodiment 14: The polymer of formula (II) having the structure of formula (IIb): [ka]

[0120] Embodiment 15: The polymer of formula (II) having a structure of formula (IIc): [ka]

[0121] Embodiment 16: The polymer of formula (II) having a structure of formula (IId): [ka]

[0122] Embodiment 17: The polymer of formula (II) having a structure of formula (IIe): [ka]

[0123] Embodiment 18: The polymer of embodiment 1 or 9, selected from the following compounds: [Table 2-1] [Table 2-2] [Table 2-3]

[0124] Embodiment 19: A polymer comprising: Polybutadiene backbone, 1,2-alkene unit, 1,4-alkene units, and 1,4-addition units substituted with functional groups of formula (I): [ka] During the ceremony, R 1 is hydrogen, -C1 to -C 20 Alkyl or -C6~C 20 is aryl, R 2 -C1~C 20 Alkyl or -C6~C 20 is aryl, or R 1 and R 2 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 Form a heterocyclic ring, R 1 and R 2 are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3, and -SCH3, or combinations thereof; R 3 and R 4 is independently selected at each instance from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl; The asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone; wherein the polymer optionally comprises other units, The units may be ordered or randomly distributed in the polymer.

[0125] Embodiment 20: A polymer comprising: Polybutadiene backbone, Units containing 1,2-alkene repeat units, Units containing 1,4-alkene repeat units, and Branched units substituted with functional groups of formula (I): [ka] comprising a linear substituted unit having a functional group of formula (I), R 1 is hydrogen, -C1 to -C 20 Alkyl or -C6~C 20 is aryl, R 2 -C1~C 20 Alkyl or -C6~C 20 is aryl, or R 1 and R 2 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 Form a heterocyclic ring, R 1 and R 2 are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OH, -OCH3, -OCF3, and -C1 to C6 thioalkyl, or a combination thereof; R 3 and R 4 is independently selected at each instance from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl; an asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone; wherein the polymer optionally comprises other units, The units may be ordered or randomly distributed in the polymer.

[0126] Embodiment 21: A compound having the structure [ka] 21. The polymer of embodiment 20, having the formula: wherein the sum of subscripts d and e is 9.

[0127] Embodiment 22: A process for making a polymer, comprising: hydroaminoalkylating the polybutadiene polymer post polymerization in the presence of at least 5 mol % of a Group 4 or Group 5 transition metal catalyst and a secondary amine to form a functionalized polymer, the reaction temperature being between 110° C. and 165° C.; and forming a polymer comprising: Polybutadiene backbone, 1,2-alkene unit, 1,4-alkene units, and Branched units substituted with functional groups of formula (I): [ka] A linear unit substituted with a functional group of formula (I): wherein the molar ratio of branched units to linear units is at least 6:1; R 1 is hydrogen, -C1 to -C 20 Alkyl or -C6~C 20 is aryl, R 2 -C1~C 20 Alkyl or -C6~C 20 is aryl, or R 1 and R 2 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 Form a heterocyclic ring, R 1 and R 2are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3, and -C1-C6 thioalkyl, or a combination thereof; R 3 and R 4 is independently selected at each instance from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl; an asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone; wherein the polymer optionally comprises other units, The units may be ordered or randomly distributed.

[0128] Embodiment 23: The process of embodiment 22, wherein the catalyst is a Ta-based catalyst.

[0129] Embodiment 24: A process for making a polymer, comprising: The method includes functionalizing an internal olefin of a polybutadiene polymer in the presence of at least 5 mol % of a Group 4 or Group 5 transition metal catalyst and a secondary amine to form a functionalized polymer, the reaction temperature being at least 140° C., and the functionalized polymer comprising: Polybutadiene backbone, 1,2-alkene unit, 1,4-alkene units, and 1,4-addition units substituted with functional groups of formula (I): [ka] During the ceremony, R 1 is hydrogen, -C1 to -C 20 Alkyl or -C6~C 20 is aryl, R 2 -C1~C 20 Alkyl or -C6~C 20 is aryl, or R 1 and R 2-C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 Form a heterocyclic ring, R 1 and R 2 are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3, and -SCH3, or combinations thereof; R 3 and R 4 is independently selected at each instance from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl; an asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone; wherein the polymer optionally comprises other units, The units may be ordered or randomly distributed.

[0130] Embodiment 25: A process for making a polymer, comprising: The method includes hydroaminoalkylating a polybutadiene polymer in the presence of a Zr-based catalyst and a silyl-protected secondary amine to form a functionalized polymer, the reaction temperature being at least 140° C., the functionalized polymer being Polybutadiene backbone, 1,2-alkene unit, 1,4-alkene units, and Branched units substituted with functional groups of formula (I): [ka] comprising a linear substituted unit having a functional group of formula (I), R 1 is hydrogen, -C1 to -C 20 Alkyl or -C6~C 20 is aryl, R 2 -C1~C 20 Alkyl or -C6~C 20 is aryl, or R 1and R 2 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 Form a heterocyclic ring, R 1 and R 2 are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3, and -C1-C6 thioalkyl, or a combination thereof; R 3 and R 4 is independently selected at each instance from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl; an asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone; wherein the polymer optionally comprises other units, The units may be ordered or randomly distributed.

[0131] In some other embodiments, provided herein is a process for making a polymer, the process comprising: The method includes hydroaminoalkylating a polybutadiene polymer in the presence of a Zr-based catalyst and a silyl-protected secondary amine to form a functionalized polymer, the reaction temperature being at least 140° C., the functionalized polymer being Polybutadiene backbone, 1,2-alkene unit, 1,4-alkene units, and Branched units substituted with functional groups of formula (I): [ka] comprising a linear substituted unit having a functional group of formula (I), R 1 is hydrogen, -C1 to -C 20 Alkyl or -C6~C 20 is aryl, R 2 is hydrogen, -C1 to -C 20 Alkyl or -C6~C20 is aryl, or R 1 and R 2 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 Form a heterocyclic ring, R 1 and R 2 are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3, and -C1-C6 thioalkyl, or a combination thereof; R 3 and R 4 is independently, in each instance, hydrogen, -C1-C6 alkyl, -C1-C6 heteroalkyl, C 4~10 Aryl and C 4~10 heteroaryl; an asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone; wherein the polymer optionally comprises other units, The units may be ordered or randomly distributed.

[0132] Embodiment 26: The process of embodiment 25, wherein the amine is an N-benzylsilylamine.

[0133] Embodiment 27: A polymer produced by the process of any one of embodiments 22 to 26.

[0134] Embodiment 28: A polymer produced by the process of any one of embodiments 22-26, wherein the process is optionally solvent-free.

[0135] Embodiment 29: A polymer comprising: Polybutadiene backbone, 1,2-alkene unit, 1,4-alkene units, and A branched substituted unit having a functional group of formula (I) or a salt thereof: [ka] A linear substituted unit having a functional group of formula (I) or a salt thereof: wherein the molar ratio of branched to linear substituted units is 6:1 or greater; R 1 is hydrogen, -C1 to -C 20 Alkyl or -C6~C 20 is aryl, R 2 -L 1 -C1-C 20 Alkyl, -L 1 -C2-C 20 Alkenyl, or -L 1 -C6-C 20 is aryl, or R 1 and R 2 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 Forming a heterocyclic ring, In the formula, R 1 and R 2 are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OH, -OCH3, -OCF3, and -C1 to C6 thioalkyl, or a combination thereof; R 3 and R 4 is independently selected at each instance from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl; L 1 is independently, at each instance, a bond, C1-C3 alkylene, -(C=O)-C2-C4 alkylene, or -(C=O)(NR 3 )-C1 to C3 alkylene; an asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone; wherein the polymer optionally comprises one or more other units, The units may be arranged sequentially, in blocks or randomly distributed in the polymer.

[0136] Embodiment 30: L 1 is a bond.

[0137] Embodiment 31: R 2 But -C1~C 20 Alkyl, or -C6~C 20 The polymer of embodiment 29 or 30, which is aryl.

[0138] Embodiment 32: The polymer of any one of embodiments 29 to 31, wherein the polymer contains at least 60% branched substituted units relative to linear substituted units.

[0139] Embodiment 33: The polymer of any one of embodiments 29 to 32, wherein the amount of 1,2-alkene units and 1,4-alkene units can be equal or variable. The polymer of any one of embodiments 1 to 5, comprising 92% 1,4-alkene units and 8% 1,2-alkene units.

[0140] Embodiment 34: A polymer according to any one of embodiments 29 to 33, wherein the one or more other units comprise a styrene unit optionally substituted with alkyl, substituted alkyl, heteroalkyl, substituted heteroalkyl, styrene, substituted styrene, or mixtures thereof.

[0141] Embodiment 35: The polymer of embodiment 34, wherein the one or more other units comprises a styrene unit.

[0142] Embodiment 36: A polymer according to any one of embodiments 29 to 35, wherein the one or more other units are isoprene units.

[0143] Embodiment 37: R 2 37. The polymer of any one of embodiments 29-36, wherein the aryl group in

[0144] Embodiment 38: Polymer of Formula (II) [ka] or a fragment thereof, R 5 is either present or absent, R 5 If is present on the c unit, the dashed line indicates a single bond, and R 5 is absent on the c unit, the dashed line indicates a double bond, R 5 is a compound of formula (I) or a salt thereof: [ka] During the ceremony, R 1 -C1~C 20 Alkyl or -C6~C 20 is aryl, or R 2 is hydrogen, -L 1 ~C1~C 20 Alkyl, -L 1 ~C2~C 20 Alkenyl, or -L 1 ~C6~C 20 is aryl, or R 1 and R 2 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 Form a heterocyclic ring, R 3 and R 4 are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3, and -C1-C6 thioalkyl, or a combination thereof; R 2 wherein the aryl group is optionally para-substituted; R 3 and R 4 is independently selected at each instance from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl; L 1is independently, at each instance, a bond, C1-C3 alkylene, -(C=O)-C2-C4 alkylene, or -(C=O)(NR 3 )-C1 to C3 alkylene; R 6 is hydrogen, -C1 to -C 20 Alkyl, -C6~C 20 Aryl, -C 1~6 Alkyl-C1~C 20 Alkyl, -C 1~6 Alkyl-C6~C 20 Aryl, -C 1~6 Heteroalkyl-C1~C 20 Alkyl, or -C 1~6 Heteroalkyl-C6~C 20 is aryl, a, b, c, d, e, and f, independently at each occurrence, are integers from 0 to 100,000, the ratio of d:e is 6:1 or greater, and the units may be ordered or randomly dispersed in the polymer.

[0145] Embodiment 39: L 1 The polymer of embodiment 38, wherein is a bond.

[0146] Embodiment 40:R 2 But -C1~C 20 Alkyl, or -C6~C 20 40. The polymer of embodiment 38 or 39, which is aryl.

[0147] Embodiment 41: The polymer of any one of embodiments 38-40, wherein the ratio of a:b is 0.1, 0.5, 1, 1.5, 2, or 10.

[0148] Embodiment 42: The polymer of any one of embodiments 38 to 41, wherein the ratio of d:e is 6:1.

[0149] Embodiment 43: R 2 43. The polymer of any one of embodiments 38-42, wherein the aryl group in

[0150] Embodiment 44: Formula (II) has the structure of formula (IIa) [ka] 44. The polymer of any one of embodiments 38 to 43, having the following structure:

[0151] Embodiment 45: Formula (II) has the structure of formula (IIb) [ka] 45. The polymer of any one of embodiments 38 to 44, having the following structure:

[0152] Embodiment 46: Formula (II) has the structure of formula (IIc) [ka] 46. ​​The polymer of any one of embodiments 38 to 45, having the following structure:

[0153] Embodiment 47: Formula (II) has the structure of formula (IId) [ka] 47. The polymer of any one of embodiments 38 to 46, having the following structure:

[0154] Embodiment 48: Formula (II) has the structure of formula (IIe) [ka] 49. The polymer of any one of embodiments 38 to 48, having the following structure:

[0155] Embodiment 49: The polymer of any one of embodiments 38 and 48, wherein the polymer is selected from the following compounds: [Table 3-1] [Table 3-2] [Table 3-3]

[0156] Embodiment 50: A polymer comprising: Polybutadiene backbone, 1,2-alkene unit, 1,4-alkene units, and A 1,4-addition unit substituted with a functional group of formula (I) or a salt thereof: [ka] wherein R 1 is hydrogen, -C1 to -C 20 Alkyl or -C6~C 20 is aryl, R 2 -L 1 -C1-C 20 Alkyl, -L 1 -C2-C 20 Alkenyl, or -L 1 -C6-C 20 is aryl, or R 1 and R 2 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 Form a heterocyclic ring, R 1 and R 2 are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3, and -SCH3, or combinations thereof; R 3 and R 4 is independently selected at each instance from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl; L1, independently at each instance, is a bond, C1-C3 alkylene, -(C=O)-C2-C4 alkylene, or -(C=O)(NR3)-C1-C3 alkylene; an asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone; wherein the polymer optionally comprises one or more other units, The units may be ordered or randomly distributed in the polymer.

[0157] Embodiment 51: R 2 But -C1~C 20 Alkyl, or -C6~C 20 The polymer of embodiment 50, which is aryl.

[0158] Embodiment 52: A polymer comprising: Polybutadiene backbone, Units containing 1,2-alkene repeat units, Units containing 1,4-alkene repeat units, and A branched substituted unit having a functional group of formula (I) or a salt thereof: [ka] A linear substituted unit having a functional group of formula (I) or a salt thereof: During the ceremony, R 1 is hydrogen, -C1 to -C 20 Alkyl or -C6~C 20 is aryl, R 2 -L 1 -C1-C 20 Alkyl, -L 1 -C2-C 20 Alkenyl, or -L 1 -C6-C 20 is aryl, or R 1 and R 2 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 Form a heterocyclic ring, R 1 and R 2 are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OH, -OCH3, -OCF3, and -C1 to C6 thioalkyl, or a combination thereof; R 3 and R 4 is independently selected at each instance from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl; L 1 is independently, at each instance, a bond, C1-C3 alkylene, -(C=O)-C2-C4 alkylene, or -(C=O)(NR 3 )-C1 to C3 alkylene; an asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone; wherein the polymer optionally comprises one or more other units, The units may be ordered or randomly distributed in the polymer.

[0159] Embodiment 53: R 2 But -C1~C 20 Alkyl, or -C6~C 20 The polymer of embodiment 52, wherein the polymer is aryl.

[0160] Embodiment 54: A compound having the structure: [ka] 53. The polymer of embodiment 52, having the formula: wherein the sum of subscripts d and e is 9.

[0161] Embodiment 55: A process for making a polymer, comprising: hydroaminoalkylating the polybutadiene polymer post polymerization in the presence of at least 5 mol % of a Group 4 or Group 5 transition metal catalyst and a secondary amine to form a functionalized polymer, the reaction temperature being between 110° C. and 165° C.; and forming the functionalized polymer, the functionalized polymer comprising: Polybutadiene backbone, 1,2-alkene unit, 1,4-alkene units, and A branched substituted unit having a functional group of formula (I) or a salt thereof: [ka] A linear substituted unit having a functional group of formula (I) or a salt thereof: wherein the molar ratio of branched to linear substituted units is 6:1 or greater; R 1 is hydrogen, -C1 to -C 20 Alkyl or -C6~C 20 is aryl, R 2 -L 1 -C1-C 20 Alkyl, -L 1 -C2-C 20 Alkenyl, or -L 1 -C6-C 20 is aryl, or R 1 and R 2 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 Form a heterocyclic ring, R 1 and R 2 are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3, and -C1-C6 thioalkyl, or a combination thereof; R 3 and R 4 is independently selected at each instance from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl; L 1 is independently, at each instance, a bond, C1-C3 alkylene, -(C=O)-C1-C3 alkylene, or -(C=O)(NR 3 )-C1 to C3 alkylene; an asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone; wherein the polymer optionally comprises one or more other units, The units may be ordered or randomly distributed in the polymer.

[0162] Embodiment 56: The process of embodiment 55, wherein the catalyst is a Ta-based catalyst.

[0163] Embodiment 57: R 2 But -C1~C 20 Alkyl, or -C6~C 20 57. The process of embodiment 56, wherein the is aryl.

[0164] Embodiment 58: A process for making a polymer, comprising: The method includes functionalizing an internal olefin of a polybutadiene polymer in the presence of at least 5 mol % of a Group 4 or Group 5 transition metal catalyst and a secondary amine to form a functionalized polymer, the reaction temperature being at least 140° C., and the functionalized polymer comprising: Polybutadiene backbone, 1,2-alkene unit, 1,4-alkene units, and A 1,4-addition unit substituted with a functional group of formula (I) or a salt thereof: [ka] wherein R 1 is hydrogen, -C1 to -C 20 Alkyl or -C6~C 20 is aryl, R 2 -L 1 -C1-C 20 Alkyl, -L 1 -C2-C 20 Alkenyl, or -L 1 -C6-C 20 is aryl, or R 1 and R 2 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 Form a heterocyclic ring, R 1 and R 2are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3, and -SCH3, or combinations thereof; R 3 and R 4 is independently selected at each instance from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl; L 1 is independently, at each instance, a bond, C1-C3 alkylene, -(C=O)-C1-C3 alkylene, or -(C=O)(NR 3 )-C1 to C3 alkylene; an asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone; wherein the polymer optionally comprises one or more other units, The units may be ordered or randomly distributed.

[0165] Embodiment 59: R 2 But -C1~C 20 Alkyl, or -C6~C 20 59. The process of embodiment 58, wherein the is aryl.

[0166] Embodiment 60: A process for making a polymer, comprising: The method includes hydroaminoalkylating a polybutadiene polymer in the presence of a Zr-based catalyst and a silyl-protected secondary amine to form a functionalized polymer, the reaction temperature being at least 140° C., the functionalized polymer being Polybutadiene backbone, 1,2-alkene unit, 1,4-alkene units, and A branched substituted unit having a functional group of formula (I) or a salt thereof: [ka] A linear substituted unit having a functional group of formula (I) or a salt thereof: During the ceremony, R 1 is hydrogen, -C1 to -C20 Alkyl or -C6~C 20 is aryl, R 2 -L 1 -C1-C 20 Alkyl, -L 1 -C2-C 20 Alkenyl, or -L 1 -C6-C 20 is aryl, or R 1 and R 2 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 Form a heterocyclic ring, R 1 and R 2 are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3, and -C1-C6 thioalkyl, or a combination thereof; R 3 and R 4 is independently selected at each instance from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl; L 1 is independently, at each instance, a bond, C1-C3 alkylene, -(C=O)-C1-C3 alkylene, or -(C=O)(NR 3 )-C1 to C3 alkylene; an asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone; wherein the polymer optionally comprises other units, The units may be ordered or randomly distributed.

[0167] Embodiment 61: The process of embodiment 60, wherein the amine is an N-benzylsilylamine.

[0168] Embodiment 62: R 2 But -C1~C 20 Alkyl, or -C6~C 20 The process of embodiment 60, wherein the is aryl.

[0169] Embodiment 63: A polymer produced by the process of any one of embodiments 55 to 62.

[0170] Embodiment 64: A polymer produced by the process of any one of embodiments 55 to 62, wherein the process is solventless.

[0171] Embodiment 65: A process for hydrogenating the backbone of a polybutadiene polymer to prepare an aliphatic backbone polymer, comprising reacting a polybutadiene polymer as described herein under hydrogenation conditions, thereby preparing said aliphatic backbone polymer.

[0172] Embodiment 66: The process of embodiment 65, wherein the hydrogenation conditions comprise using p-toluenesulfonyl hydrazide, tripropylamine, xylene, or a combination thereof.

[0173] Embodiment 67: The process of any one of embodiments 65-66, wherein the hydrogenation conditions comprise a N2 atmosphere.

[0174] Embodiment 68: The process of any one of embodiments 65-67, wherein the hydrogenation conditions comprise heating the polymer of any one of embodiments 1-21 or 27-28 to at least 100° C. under hydrogenation conditions.

[0175] Embodiment 69: The process of any one of embodiments 65-32, wherein the hydrogenation conditions comprise heating the polymer of any one of embodiments 1-21 or 27-28 to 100° C.-150° C. under hydrogenation conditions.

[0176] Embodiment 70: The process of any one of embodiments 65-69, wherein the hydrogenation conditions comprise heating the polymer of any one of embodiments 1-21 or 27-28 to at least 130° C. under hydrogenation conditions.

[0177] Embodiment 71: The process of any one of embodiments 65-70, wherein the hydrogenation conditions comprise heating the polymer of any one of embodiments 1-21 or 27-28 under hydrogenation conditions for 24 hours.

[0178] Embodiment 72: The process of any one of embodiments 65 to 71, wherein the process further comprises reducing at least one or both of R1 or R2 such that at least one or both of R1 or R2 is H.

[0179] Embodiment 73: The process of any one of embodiments 65 to 72, wherein the process further comprises reducing the polymer by reacting the polymer with cerium(II) ammonium nitrate.

[0180] Embodiment 74: A polymer produced by the process herein.

[0181] In some embodiments, including any of the above, the hydrogenation process may be accomplished using a catalyst. For example, in some embodiments, including any of the above, the hydrogenation is accomplished using a palladium on carbon catalyst. See one reaction scheme below: [ka]

[0182] Other metal catalyzed hydrogenation processes are known and include, but are not limited to, Martin P. McGrath, Erik D. Sall, and Samuel J. Tremont. Chemical Reviews 1995 95(2), 381-398, which is incorporated herein by reference in its entirety for all purposes.

[0183] In some embodiments, including any of the foregoing, the hydrogenation process may be accomplished using electrochemical methods.

[0184] Embodiment 75: A process for preparing an epoxide resin, comprising reacting a polymer as described herein with at least one epoxide monomer or a precursor thereof to prepare the epoxide resin.

[0185] Embodiment 76: A process for preparing a mixture, comprising preparing the mixture by providing a polymer as described herein and at least one epoxide monomer or a precursor thereof.

[0186] Embodiment 77: The epoxide monomer or precursor thereof is [ka] (In the formula, R 30 is hydrogen, C 1~6 Alkyl, [ka] 77. The process of embodiment 75 or 76, wherein the compound has a structure selected from:

[0187] Embodiment 78: The epoxide monomer or precursor thereof is [ka] (In the formula, R 30 teeth, [ka] The process of any one of embodiments 75 to 77, wherein the compound has a structure selected from:

[0188] Embodiment 79: The process of any one of embodiments 75 to 78, wherein the epoxide monomer or precursor is a poly(ethylene glycol) diglycidyl ether epoxide.

[0189] Embodiment 80: The process of any one of embodiments 75 to 78, wherein the epoxide monomer or precursor is trimethylolpropane triglycidyl ether epoxide.

[0190] Embodiment 81: The process of any one of embodiments 75 to 78, wherein the one or more epoxide monomers or precursors thereof comprise epichlorohydrin or a derivative thereof.

[0191] Embodiment 82: The process of any one of embodiments 75-78, wherein the one or more epoxide monomers or precursors thereof comprise bisphenol A, a derivative thereof, or a combination thereof. In some embodiments, including any of the foregoing, the epoxide monomers or precursors thereof are bisphenol A diglycidyl ether resin, butoxymethyl butyl glycidyl ether resin, bisphenol A-epichlorohydrin resin, bisphenol F resin, polyepoxide resin, bisphenol epoxy resin, volatile resin, polyester resin, aldehyde resin, phenolic resin, terpolymer of phenol, phenol aldehyde resin, phenol formaldehyde resin, urea aldehyde resin, furan resin, furfuryl alcohol resin, urethane resin, or glycidyl ether resin.

[0192] Embodiment 83: The process of any one of embodiments 75 to 78, wherein the one or more epoxide monomers or precursors have the following structure: [ka]

[0193] Embodiment 84: The process of any one of embodiments 75 to 78, wherein the one or more epoxide monomers or precursors have the following structure: [ka]

[0194] Embodiment 85: The one or more epoxide monomers or precursors have the following structure: [ka] wherein R 5 , R 6 , R 7 , and R 8 Each of the following is independently selected from the group consisting of -C1 to -C 20 Alkyl, -C1~C 20 Alkoxy, -[PEG] 0~10 , -[PEG] 0~10 -(C2H4-O), C1~C 10 Heteroalkyl, C6-C 20 C3-C with 0-2 additional heteroatoms selected from aryl, nitrogen and oxygen 20 heterocycle, which may be a fused bicyclic ring, wherein R 5 , R 6 , R 7 , and R 8

[0081] The process of any one of embodiments 75-78, wherein each is independently at each instance optionally substituted with 1 to 6 members selected from the group consisting of: -F, -Cl, -I, -Br, -OH, -OCH3, -OCF3, -C1-C6 thioalkyl, and combinations thereof.

[0195] Embodiment 86: The process of any one of embodiments 75 to 85, wherein the mixture further comprises a combination of epoxide monomers.

[0196] Embodiment 87: The process of any one of embodiments 75 to 86, wherein the mixture further comprises one or more additional curing agents.

[0197] Embodiment 88: The process of any one of embodiments 75 to 87, further comprising curing the mixture.

[0198] Embodiment 89: The process of any one of embodiments 75 to 88, further comprising crosslinking the polymer of any one of embodiments 1 to 21, 27 to 28, or 38 to 59.

[0199] Embodiment 90: The process of any one of embodiments 75 to 89, further comprising hardening the mixture.

[0200] In some embodiments, including any of the foregoing, the process comprises the following reaction: [ka]

[0201] In the above reaction, in some preferred embodiments, R 1 is H.

[0202] In the above reaction, in some preferred embodiments, R 1 is H and R 2 is an alkyl group, e.g., C 1~20 Alkyl or C 1~20 In some embodiments, R 2 is methyl. In some embodiments, R 2 is ethyl. In some embodiments, R 2 is propyl. In some embodiments, R 2 is butyl. In some embodiments, R 2 is pentyl. In some embodiments, R 2 is hexyl. In some embodiments, R 2 is cyclohexyl.

[0203] In the above reaction, in some preferred embodiments, R 1 and R 2 are both H.

[0204] In some embodiments, including any of the foregoing, the mixture is cured or hardened by the amine-functionalized polybutadiene. In this regard, curing agents are used interchangeably herein with hardeners, unless otherwise specified.

[0205] In some embodiments, including any of the foregoing, the final cured mixture has improved properties, such as mechanical, adhesive, etc., and improved processability.

[0206] In some embodiments, including any of the foregoing, the product of the foregoing epoxide ring opening reaction has a molecular weight of 1090 cm -1 ~1115cm -1 It features a unique infrared (IR) mode in

[0207] In some embodiments, including any of the foregoing, the product of the epoxide ring opening reaction may have a 1110 cm ring assigned to a C-O stretch from the reaction product. -1 It features a unique infrared (IR) mode in

[0208] In some embodiments, including any of the foregoing, the product of the epoxide ring opening reaction may have a 1095 cm ring assigned to a C-O stretch from the reaction product. -1 It features a unique IR mode at

[0209] In some embodiments, including those described above, the polybutadiene starting material (ie, reagent) is a liquid having an average molecular weight of 2,500 to 4,500 g / mol.

[0210] In some other embodiments, including those mentioned above, the polybutadiene starting material (ie, reagent) is a solid having an average molecular weight of 70,000 to 80,000 g / mol.

[0211] In some other embodiments, including those mentioned above, the polybutadiene starting material (ie, reagent) is a solid having an average molecular weight of 72,000 g / mol.

[0212] In some other embodiments, including those mentioned above, the polybutadiene starting material (ie, reagent) is a solid having an average molecular weight of 65,000 g / mol. EXAMPLES

[0213] Additional embodiments are disclosed in further detail in the following examples, which are not intended to limit the scope of the claims in any way.

[0214] Analytical methods and instruments Proton nuclear magnetic resonance (NMR) spectra were obtained on a Bruker Avance™ 300 or 400 MHz spectrometer. NMR spectra are reported as follows: chemical shift δ (ppm), multiplicity, coupling constant J (Hz), and integral. The abbreviations s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, and br = broadline are used throughout. COSY, HSQC, and HMBC 2D NMR spectroscopy experiments were used to obtain 1 H and 13 C NMR resonances were unambiguously assigned.

[0215] Mass spectrometry data was measured using a JeolAccuTOF-GCv4G spectrometer equipped with a field desorption / ionization (FD / FI) ion source. Samples were dissolved in DCM, loaded into the FD probe, and then introduced into the ion source of the GC-TOFMS. Mass spectra were acquired in positive mode, and fragments are expressed as mass per charge (m / z). FT-IR data were recorded at room temperature on a PerkinElmer FT-IR equipped with an ATR accessory for direct measurements on oils and polymeric materials.

[0216] Experimental conditions Air- and moisture-sensitive reactions were prepared in an MBraunLABmaster glovebox filled with N2 atmosphere. All glassware was dried overnight in a 160°C oven before being transferred to the glovebox or used in a Schlenk manifold. Toluene was passed through an activated alumina column under N2 gas, collected in a Teflon-sealed Straus flask, and sparged with N2 for 30 minutes before use. Toluene-d8 was dried over sodium metal, distilled under N2 atmosphere, collected in a Teflon-sealed Straus flask, and degassed before use. Screening of hydroaminoalkylation reactions was carried out in J-Young tubes (8" x 5mm) sealed with Teflon screw caps.

[0217] material Liquid polybutadiene materials, Ricon® 100 (PBD-co-PS4.5-54) R1, Ricon® 130 (PBD2.5-28) R2, and Ricon® 150 (PBD3.9-70) R3 (as shown in Scheme 2). The number of repeat units was calculated based on the molecular weight and weight percent (wt%) content reported by Cray Valley (see example calculation in the Formula section). The reported repeat unit values ​​are rounded to the nearest integer. These materials were dissolved in hexane, dried with CaH2, filtered, degassed by three freeze-pump-thaw cycles, and the solvent was removed in vacuum. The materials were stored under an inert N2 atmosphere before use. The tantalum precatalyst was synthesized as described in the prior art and generated in situ before use. Daneshmand et al., J. Am. Chem. Soc. 2020, 142(37):15740-15750. N-Methylaniline was purchased from MillaporeSigma, N-methylcyclohexylamine and N-methylbutylamine were purchased from Oakwood Chemical, and all amine reagents were dried over CaH2 and distilled before being stored in an inert N2 glovebox atmosphere. 1,3,5-Trimethoxybenzene was commercially available from Oakwood Chemical and sublimed prior to storage in the glovebox.

[0218] Scheme 2 [ka] Unless otherwise stated, Ricon® materials were used herein.

[0219] Abbreviations used in the examples include the following: [Table 4]

[0220] General scheme for preparing branched HAA products Method A1 [ka] Scheme A1. In certain embodiments, hydroamino alkylation involves alkylating polymer P1a with an amine using a suitable catalyst to obtain alkylation product P1, as shown in Scheme A1. In certain embodiments, variable degrees of functionalization (ratio of b:d in the product) can be achieved by adjusting the reaction conditions. In certain embodiments, the ratio of a:b (blocks resulting from 1,4 and 1,2 addition of butadiene in the polymer, respectively) in the starting polymer reactant can also be varied. In certain embodiments, the alkylation product can contain >90% branched HAA product. In certain embodiments, the % vinyl consumption ( 1 1 H NMR spectroscopy) is up to 100%.

[0221] General scheme for preparing polymers with additional blocks ("e" blocks) Scheme A2 [ka] Scheme A2. In certain embodiments, the functionalized polymer may contain optional additional blocks such as polystyrene ("e" units). In certain embodiments, the hydroaminoalkylation involves alkylating the polymer precursor P2a with an amine using a suitable catalyst to give the alkylation product P2.

[0222] General scheme for preparing primary amine products Scheme A3 [ka] Scheme A3. In certain embodiments, the functionalized polymer may contain a primary amine product. In certain embodiments, the polymer precursor P3a may be subjected to hydroaminoalkylation reaction conditions using a Zr-based catalyst and benzylamine to provide the primary amine product P3.

[0223] General scheme for preparing 1,4-addition products Scheme A4 [ka] Scheme A4. In certain embodiments, 1,4 addition products such as P4 can be prepared from the functionalization of internal olefins such as P4a.

[0224] Catalyst: Hydroaminoalkylation Scheme A5 [ka] Scheme A5. In Scheme A5, p is an integer from 0 to 4, q is an integer from 0 to 4, or the sum of p and q is 3 or 4; each W is a halogen substituent; R 7 and R 8 are each independently hydrogen or a substituted or unsubstituted -C 40 Straight chain alkyl, substituted or unsubstituted -C1-C 40 Branched alkyl, substituted or unsubstituted -C1-C 40Cyclic alkyl, substituted or unsubstituted -C1-C 40 Alkenyl, substituted or unsubstituted -C1-C 40 alkynyl, substituted or unsubstituted aryl, or substituted or unsubstituted heterocycle, or R 7 and R 8 together with the nitrogen to which they are both attached form a heterocyclic ring; R 9 is hydrogen, substituted or unsubstituted -C1-C 40 Straight chain alkyl, substituted or unsubstituted -C1-C 40 Branched alkyl, substituted or unsubstituted -C1-C 40 Cyclic alkyl, substituted or unsubstituted -C1-C 40 Alkenyl, substituted or unsubstituted -C1-C 40 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, or R 9 R 7 and / or R 8 together with the to form a heterocycle.

[0225] In some embodiments, including any of the foregoing, R 7 and R 8 is R in the above embodiment. 1 or R 2 For example, in some embodiments, R 7 Or R 8 In certain embodiments, either or both of R 7 Or R 8 Either or both of -C1~C 20 In certain embodiments, R 7 Or R 8 Either or both of -C6~C 20 It is aryl.

[0226] In certain embodiments, R 7 -C1~C 20 In certain embodiments, R 7 -C6~C 20 In certain embodiments, R8 -C1~C 20 In certain embodiments, R 8 -C6~C 20 In certain embodiments, R 7 and R 8 -C3-C, which together with the nitrogen to which they are both attached, has 0-2 additional heteroatoms selected from nitrogen and oxygen. 20 In certain embodiments, R 7 and R 8 are each independently optionally substituted with 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3, and -C1-C6 thioalkyl, or a combination thereof. 7 The aryl group in is optionally para-substituted. In certain embodiments, R 8 The aryl group in is optionally para-substituted.

[0227] In certain embodiments, p is an integer from 0 to 4, and q is an integer from 0 to 4. In certain embodiments, p is an integer from 0 to 4. In certain embodiments, q is an integer from 0 to 4. In certain embodiments, the sum of p and q is 3 or 4. In certain embodiments, the sum of p and q is 3. In certain embodiments, the sum of p and q is 4.

[0228] In certain embodiments, each W is a halogen substituent.

[0229] In certain embodiments, R 7 and R 8 are each independently hydrogen or a substituted or unsubstituted -C 40 Straight chain alkyl, substituted or unsubstituted -C1-C 40 Branched alkyl, substituted or unsubstituted -C1-C 40 Cyclic alkyl, substituted or unsubstituted -C1-C 40 Alkenyl, substituted or unsubstituted -C1-C 40alkenyl, substituted or unsubstituted aryl, or substituted or unsubstituted heterocycle. In certain embodiments, R 7 and R 8 together with the nitrogen to which they are both attached form a heterocyclic ring.

[0230] In certain embodiments, R 7 is hydrogen. In certain embodiments, R 7 is a substituted or unsubstituted -C1~C 40 In certain embodiments, R 7 is a substituted or unsubstituted -C1~C 40 In certain embodiments, R 7 is a substituted or unsubstituted -C1~C 40 In certain embodiments, R 7 is a substituted or unsubstituted -C1~C 40 alkenyl. In certain embodiments, R 7 is a substituted or unsubstituted -C1~C 40 In certain embodiments, R 7 is substituted or unsubstituted aryl. In certain embodiments, R 7 is a substituted or unsubstituted heterocycle.

[0231] In certain embodiments, R 8 is hydrogen. In certain embodiments, R 8 is a substituted or unsubstituted -C1~C 40 In certain embodiments, R 8 is a substituted or unsubstituted -C1~C 40 In certain embodiments, R 8 is a substituted or unsubstituted -C1~C 40 In certain embodiments, R 8 is a substituted or unsubstituted -C1~C 40 alkenyl. In certain embodiments, R 8 is a substituted or unsubstituted -C1~C 40 In certain embodiments, R 8is substituted or unsubstituted aryl. In certain embodiments, R 8 is a substituted or unsubstituted heterocycle.

[0232] In certain embodiments, R 9 is hydrogen. In certain embodiments, R 9 is a substituted or unsubstituted -C1~C 40 In certain embodiments, R 9 is a substituted or unsubstituted -C1~C 40 In certain embodiments, R 9 is a substituted or unsubstituted -C1~C 40 In certain embodiments, R 9 is a substituted or unsubstituted -C1~C 40 alkenyl. In certain embodiments, R 9 is a substituted or unsubstituted -C1~C 40 In certain embodiments, R 9 is substituted or unsubstituted aryl. In certain embodiments, R 9 is a substituted or unsubstituted heterocycle.

[0233] In Scheme A5, the Ta-based catalyst for carrying out the hydroaminoalkylation reaction is selected from catalysts C1, C2, and C3. In certain embodiments, functionalization of the polymer is provided by the use of reactive group 4 or 5 hydroaminoalkylation catalysts. In certain embodiments, the formation of a highly reactive electrophilic catalyst using an N,O-chelating ligand, such as cyclic urea C1 or C2, is required to obtain reactivity. In certain embodiments, the N,O-chelating catalyst is Ta(CH2SiMe3)3C l2 The catalyst can be isolated or generated in situ by providing one equivalent of an alkali salt of the N,O-chelate (e.g., sodium urate) to C2. In certain embodiments, the catalyst is C2.

[0234] General scheme: Hydroaminoalkylation Scheme A6 [ka] Scheme A6. In a particular embodiment, Scheme A5 shows the reaction conditions for hydroaminoalkylation on 5000 g / mol liquid polybutadiene with 92% 1,4-repeating units and 8% 1,2-repeating units. In a particular embodiment, the alkylation product P5 is obtained by treating the polymer P5a with N-methylaniline (P5c) in the presence of Ta-based catalyst and ligand P5b. The following describes the detailed reaction procedure and additional examples that can be prepared according to Scheme A6.

[0235] General Procedure 1: For in situ catalyst generation The tantalum precursor (TaCl2(CH2SiMe3)) was added to a vial containing the ligand and toluene-d8 (0.10 mL). The mixture was stirred to produce a green pre-catalyst. Liquid polybutadiene (Ricon® 100, Ricon® 130, Ricon® 150) (0.10 g), amine (various amounts), and 1,3,5-trimethoxybenzene (0.016 mg) were weighed separately. See Scheme 2 above for the chemical structures of these polybutadiene polymers. The amine was transferred to the pre-catalyst mixture, which was then quantitatively transferred to a J-Young NMR spectrometer tube with toluene-d8 along with liquid polybutadiene and 1,3,5-trimethoxybenzene internal standard. The total mass of each reaction solution was 0.60 mg. 1 H NMR spectra were recorded at t=0 hours before heating. Reactions were heated to 140° C. (unless otherwise noted) in a silicon oil bath with the solvent line aligned with the oil bath level. After heating for 1 hour, 1 H NMR spectra were recorded at t=1 h. For selected reactions, the reaction vessel was heated for an additional 2, 4, and 23 h to obtain the reaction mixture at t=3, t=5, and t=24 h, respectively. 1H NMR spectra were acquired. The reaction was stopped by removing it from the heat source and exposing it to air to oxidize the catalyst. The material was isolated by filtering through a 1 inch Celite® pad and precipitating three times from a concentrated DCM solution into either cold MeOH or acetone. The final product was collected and dried overnight in vacuum before characterization. In certain embodiments, the molar ratio of tantalum precursor to ligand is 1:1.

[0236] Example 1: Synthesis of Compound 1 Compound 1 was synthesized using the same procedure as general procedure 1, using Ricon® 130R2 and N-methylaniline (50 mg), using catalytic C2 in situ generation (12 mg Ta(CH2SiMe3)3Cl2 and 3.8 mg uric acid ligand salt). For the chemical structure of these polybutadiene polymers, see scheme 2 above. Compound 1 (91 mg, 81%) was obtained. 1 H NMR(300MHz,CDCl3,298K)δ=7.16(t,br,H1);6.67-6.61(overlapping t and d,br,2H);5.56(m,br,1H);5.38(m,br ,2H);4.96(m,br,1H);3.08-2.94(d,m,br,1H);2.03(m,br,2H);1.63-0.85(m,br,7);0.88(duplications,3H); 13 C{ 1 H}NMR(300MHz,CDCl3,298K)δ=148.6,142.8,131.4,128.5,117.1,114.4,112.8,48.3,38.3,34.2,32.9,32.8,30.3,27.5,25.0,22.7 and 14.3;LCMS: Required C 17 H 25 N3O4: 335, measured value: m / z=336 [M+H] + In certain embodiments, 13 C{ 1 Some of the {H} NMR chemical shifts were difficult to see, so the values ​​were determined in conjunction with the spectrum in Figure 1A. Figure 1B shows the structure of compound 1. 13 C{ 1 The H}NMR spectrum is shown.

[0237] Example 2: Synthesis of Compound 2 Compound 2 was synthesized using the same general procedure 1 with Ricon® 130R2. 1 H NMR(300MHz,CDCl3,298K)δ=6.77,6.75(H3);6.59,6.56,6.53(H4);5.83(H14);5.36(H17&H18);4.96(H15);3 .73(H1);3.03,2.88(H7);2.06,2.02(H16&H19);1.63,1.60,1.44,1.37,1.26,0.88(H8-H13overlapping)ppm; 13 C{ 1 H}NMR (75MHz, CDCl3, 298K) δ = 152.0, 142.9, 130.2, 115.1, 114.2, 56.0, 49.3, 34.3, 32.9, 30.4, 27.6, 14.3 ppm. Figure 2A shows the structure of compound 2. 1 FIG. 2B shows the H NMR spectrum of compound 2. 13 C{ 1 The H}NMR spectrum is shown.

[0238] Example 3: Synthesis of Compound 3 Compound 3 was synthesized using the same procedure as general procedure 1, using Ricon® 130R2 and 150 wt% N-methylcyclohexylamine (150 mg) in the presence of tantalum catalyst (34 mg Ta(CH2SiMe3)3Cl2 and 10.9 mg uric acid ligand salt), and the reaction mixture was heated at 140° C. for 1 h. Compound 3 (82 g, 65%) was obtained. 1H NMR (300MHz, CDCl3, 298K) δ = 5.64, 5.62, 5.61, 5.58, 5.56, 5.54, 5.54, 5.50, (m, br, H13); 5.42, 5.41, 5.39, 5.37 (m, br, H16 & H17); 5.01, 5.00, 4.99, 4.97, 4.96, 4.95, 4.94, 4.93, 4.91 (m, br, H14); 2.62, 2.61, 2.59, 2.57, 2.47, 2.44, 2.41 (d, m, br, H6 overlaps with H4); 2.12, 2.08, 2.04 (m, br, H15 & H1 8 overlaps with H3);1.78,1.76,1.75,1.74,1.72,1.70(H2);1.65,1.64,1.62,1.61,1.60,1.59(H1);1.57(H7);1.54,1.52,1.51,1.50,1.49,1.47,1.45,1.43,1.42,1.39,1.37,1.36,1.34,1.33,1.31,1.30,1.28,1.27,1.25,1.23(H9-H12);0.98,0.96(d,H8);0.91,0.89,0.86,0.84(m,br,endgroups)ppm. 13 C{ 1 H}NMR(75MHz,CDCl3,298K)δ=143.2,142.8,142.7(C13);131.4,131.1,130.7,130.6,130.5,130.2,120.1,129 .9,129.7,129.5,129.4,128.6,128.5,128.3,128.2,128.0(C16,C17 duplicate);115.0,114.4,114.3,114.0(C14);57. 1 (C4); 51.0 (C6); 43.9, 43.7, 43.6 (C11); 41.7, 41.2, 40.9 (C9); 34.8, 34.2, 34.1 (C7, C12 overlap); 32.8 (C15 & C18-trans); 31.7 (C10); 30.3, 30.2 (C3); 27.5 (C15 & C18-cis); 26.3 (C1); 25.4, 25.2, 25.1, 25.0 (C2) ppm. C8 was not determined. Figure 3A shows the chromatogram of compound 3. 1 1 H NMR spectrum of compound 3. 13 FIG. 3C shows the C{1H} NMR spectrum of compound 3. 1 H-1 1 H COSY NMR spectrum of compound 3. 1 H- 13 C{ 1 FIG. 3E shows the {H} HSQC NMR spectrum of compound 3. 1 H- 13 C{ 1 The H}HMBC NMR spectrum is shown.

[0239] Example 4: Synthesis of Compound 4 Compound 4 was synthesized using the same procedure as general procedure 1 with Ricon® 130R2 and N-methylbutylamine using in situ generation of catalyst C2. 1 H NMR(300MHz,CDCl3,298K)δ=5.42,5.41,5.40,5.37,5.36,5.34(H16&H17 overlap);4.99,4.98,4.95,4.91(H1 4);2.60,2.57,2.55,2.53,2.51,2.48,2.40,2.37(H4&H6 overlap);2.08,2.07,2.02,1.89(H15&H18shouldero verlappingwithH9&H11);1.64,1.63,1.60,1.58;1.45,1.43(H3);1.39,1.37,1.35,1.33,1.32,1.30,1. 27,1.25(H2,H10,H12 overlap);0.98,0.96,0.93,0.91,0.88,0.85,0.83,0.82,0.81,0.67(H1,H8&end group overlap)ppm. 13 C{ 1 H}NMR (75 MHz, CDCl3, 298 K) δ = 130.3, 129.7, 129.6 (C14); 114.4 (C13 observed through HSQC); 68.8 (C4 when activated to form methine in HAA); 50.0 (C4); 48.4 (C6); 32.9 (C15 & C18-trans); 32.4 (C3); 27.5 (C15 & C18-cis); 20.8, 20.7 (C2); 18.1; 14.2 (C1) ppm. Unobserved: C9-C12. Figure 4A shows the structure of compound 4. 1 1 H NMR spectrum of compound 4. 13 C{ 1The H}NMR spectrum is shown.

[0240] Example 5: Synthesis of Compound 5 Compound 5 was synthesized using the same procedure as general procedure 1 with Ricon® 100R1 and N-methylaniline using in situ generation of catalyst C2. 1 H NMR(300MHz,CDCl3,298K)δ=7.18(H2&H13 overlap);6.71(H1);6.61(H3);5.83(H16);5.37(H19&H20);4.98(H17);3.8 0,3.79;3.08,2.92,2.57(H6);2.04(H18&H121);1.39,1.38,1.29,1.28,(H7,H9-H12, overlap);0.92(H8, end group overlap)ppm. 13 C{ 1 H}NMR (75 MHz, CDCl3, 298 K) δ = 148.4 (C4); 142.8 (C16); 129.4, 129.4, 128.3, 127.9, 126.0 (C2, C16, C17 overlap); 117.3 (C1); 112.9 (C3); 48.4 (C6); 38.0 (C7); 32.9 (C18 & C21-trans); 34.4, 30.6, 29.8, 22.7, (C9-C12 overlap); 27.7 (C18 & C21-trans); 16.7, 14.3 (C8) ppm. Not observed: C17. Figure 5A shows the structure of compound 5. 1 1 H NMR spectrum of compound 5. 13 C{ 1 The H}NMR spectrum is shown.

[0241] Example 4: Synthesis of Compound 6 Compound 6 was synthesized using the same procedure as general procedure 1 with in situ generation of catalyst C2 (24.2 mg Ta(CH2SiMe3)3Cl2 and 7.7 mg uric acid ligand salt), Ricon® 100R1 and N-methylaniline (101 mg). Compound 6 (124 mg, 71%) was obtained. 1H NMR(300MHz,CDCl3,298K)δ=7.18(H2&H13 overlap);6.71(H1);6.61(H3);5.83(H16);5.37(H19&H20);4.98(H17);3.8 0,3.79;3.08,2.92,2.57(H6);2.04(H18&H121);1.39,1.38,1.29,1.28,(H7,H9-H12, overlap);0.92(H8, end group overlap)ppm. 13 C{ 1 H}NMR (75 MHz, CDCl3, 298 K) δ = 148.4 (C4); 142.8 (C16); 129.4, 129.4, 128.3, 127.9, 126.0 (C2, C16, C17 overlap); 117.3 (C1); 112.9 (C3); 48.4 (C6); 38.0 (C7); 32.9 (C18 & C21-trans); 34.4, 30.6, 29.8, 22.7, (C9-C12 overlap); 27.7 (C18 & C21-trans); 16.7, 14.3 (C8) ppm. Not observed: C17. Figure 6A shows the structure of compound 6. 1 FIG. 6B shows the H NMR spectrum of compound 6. 13 C{ 1 The H}NMR spectrum is shown.

[0242] Example 7: Synthesis of Compound 7 Compound 7 was synthesized using the same procedure as general procedure 1 with Ricon® 100R1 and N-methylcyclohexylamine using in situ generation of catalyst C2. 1 H NMR (300MHz, CDCl3, 298K) δ = 7.13 (H13), 5.79, 5.52 (H16); 5.34 (H19&H20); 4.95 (H17); 2.56, 2.36, 2.26 (H4&H6 overlap); 2.02 (H18&H21); 1.70, 1.63, 1.59, 1.35, 1.28, 1.26, 1.23, 1.20, 0.88, 0.85, 0.83 (H1-H3, H9-H15 overlap) ppm. Figure 7 shows the structure of compound 7. 1 The H NMR spectrum is shown.

[0243] Example 8: Synthesis of Compound 8 Compound 8 was synthesized using 9.4 wt% Zr(NMe2)4, 42 wt% N-benzyltrimethylsilylamine, and 0.1 g of Ricon130R1. The reaction was heated at 145°C for up to 400 hours for maximum reaction of the vinyl groups. A mixture of branched and linear products was obtained. 1 H NMR (300 MHz, C6D6, 298 K) δ 7.08, δ 5.45, δ 4.99, δ 3.99, δ 3.75, δ 2.37, δ 2.09-1.00. Figure 8 shows stacked images of the reaction of compound 8 before and after heating. 1 The H NMR spectrum is shown.

[0244] Example 5: Synthesis of Compound 9 Compound 9 was synthesized using the same procedure as general procedure 1, using Ricon® 130R1 and 200 wt% N-methylaniline (200 mg) in the presence of 5 mol% tantalum catalyst (47.9 mg Ta(CH2SiMe3)3Cl2 and 15.3 mg uric acid ligand salt), and the reaction mixture was heated at 140° C. for 1 h. Compound 9 (42.3 mg, 23%) was obtained. 1 H NMR(300MHz,CDCl3,298K)δ=7.18(H2&H13overlapping);6.71(H1);6.61(H3);5.83(H16);5.37(H19&H20);4.98(H17) );3.80,3.79;3.08,2.92,2.57(H6);2.04(H18&H121);1.39,1.38,1.29,1.28,(H7,H9-H12, overlap);0.92(H8, end group overlap)ppm. 13 C{ 1 H}NMR (75 MHz, CDCl3, 298 K) δ = 148.4 (C4); 142.8 (C16); 129.4, 129.4, 128.3, 127.9, 126.0 (C2, C16, C17 overlap); 117.3 (C1); 112.9 (C3); 48.4 (C6); 38.0 (C7); 32.9 (C18 & C21-trans); 34.4, 30.6, 29.8, 22.7, (C9-C12 overlap); 27.7 (C18 & C21-trans); 16.7, 14.3 (C8) ppm. Not observed: C17. Figure 9A shows the structure of compound 9. 11 H NMR spectrum of compound 9. 13 C{ 1 FIG. 9C shows the {H} NMR spectrum of compound 9. 1 H- 1 FIG. 9D shows the HCOSY NMR spectrum of compound 9. 1 H- 13 C{ 1 FIG. 9E shows the H}HSQC NMR spectrum of compound 9. 1 H- 13 C{ 1 The H}HMBC NMR spectrum is shown.

[0245] Example 9: Hydrogenation Scheme A7 [ka] Scheme A7. In certain embodiments, the functionalized polymer can be subjected to hydrogenation reaction conditions to obtain a saturated polymer backbone. In certain embodiments, the saturated polymer backbone product is generally expected to exhibit higher thermal oxidative stability. In certain embodiments, subjecting polymer P1 to suitable hydrogenation conditions leads to saturated polymer P6.

[0246] Example 10: Synthesis of P6 A Schlenk flask containing P1 (500 mg, 0.088 mmol) was heated in vacuum at 100° C. overnight to dry and degas the compound. A thick-walled vessel was charged with tosylhydrazide (2.9 g, 15.6 mmol) and dried in vacuum overnight. Tripropylamine (TPA) was dried over CaH2, distilled, and degassed by three freeze-pump-thaw cycles before use. Xylene was dried over CaH2, distilled, and degassed by three freeze-pump-thaw cycles before use. 3 mL of xylene was transferred to the Schlenk flask to dissolve P1, and the solution was transferred to the thick-walled vessel containing the dried tosylhydrazide. An additional 6 mL of xylene was added to the reaction vessel via syringe. TPA (1.9 mL, 10.0 mmol) was transferred to the thick-walled reaction vessel via syringe technique. The vessel was sealed under N2 with an airtight PTFE valve and heated to 130°C for 24 hours. The reaction was removed from the heat and cooled to room temperature. The solution was collected in a separatory funnel with 20 mL of dichloromethane (DCM). The organic layer was washed three times with 15 mL of 1 M NaOH. The aqueous layer was washed once with 20 mL of DCM and the organic layers were collected and combined. The organic layers were dried over MgSO4, gravity filtered and concentrated under reduced pressure. The product was precipitated from the concentrated DCM solution into cold MeOH to remove the by-product paratoluenesulfonic acid. The product P6 was collected and dried in vacuum to give a dark red viscous oil (0.443 mg, 86%). 1 H NMR spectrum (300 MHz, CDCl3) (Figure 10). δ = 7.26, 6.78, 6.76, 6.58, 6.55, 3.74, 3.03, 3.02, 2.86, 2.32, 1.85, 1.62, 1.26, 1.23, 1.10, 1.08, 0.83, 0.08 ppm.

[0247] Example 11: Reduction of branched p-methoxyarylamines to branched primary amine products Scheme A8 [ka] Scheme A8. In certain embodiments, the functionalized polymer can be subjected to reduction reaction conditions to afford a primary amine product.

[0248] Synthesis of P7A P7 (0.500 g, 0.190 mmol) was weighed into a round bottom flask and dissolved in 2 mL of toluene. Ceric ammonium nitrate (II) was added neat, followed by 2 mL of deionized water. The reaction was stirred at room temperature overnight. The dark purple solution was concentrated under reduced pressure, and the product was then isolated by filtering the dichloromethane solution through a short Celite and activated charcoal plug. The solution was dried under vacuum and the product P7A was isolated as a dark brown oil in 43% yield. 1 No aryl signals were observed by 1 H NMR spectroscopy (Figure 11). 1 H NMRspectrum(300MHz,CDCl3)δ=7.26,5.65,5.56,5.50,5.42,5.38,4.96,4.92,2.24,2.07, 2.03,1.65,1.64,1.59,1.43,1.30,1.28,1.28,1.26,1.01,0.91,0.88,0.87,0.83,0.07ppm.

[0249] Example 12: General scheme: Epoxide ring opening Scheme A9 [ka] Scheme A9. In certain embodiments, the functionalized polymer can be reacted with an epoxide. In certain embodiments, the functionalized polymer can be used to perform epoxide ring opening, which is a key step in the curing process of epoxy-based resins used in adhesives and coatings.

[0250] Example 13: Epoxide ring opening of poly(ethylene glycol) diglycidyl ether Scheme A10 [ka] Scheme A10. P9 (0.254 g, 0.053 mmol) was weighed into a round bottom flask and dissolved in 3 mL of THF. Poly(ethylene glycol) diglycidyl ether (0.052 g, 0.104 mmol) was weighed separately and quantitatively transferred to the flask containing the amine-functionalized polybutadiene as a solution in 2 mL of THF. The solution was stirred at room temperature overnight to obtain an aliquot of the solution. 1 This resulted in minimal conversion as observed by 1 H NMR spectroscopy. The reaction solution was then heated to 80 °C overnight, which gave nearly quantitative conversion. Figure 12A shows the structure of P9A. 1 1 H NMR (300 MHz, CDCl3, 298 K) spectrum of P9A. 13 C NMR (75 MHz, CDCl3, 298K) spectrum of P9A is shown. Figure 12C shows the IR spectrum of P9A.

[0251] Example 14: Epoxide ring opening of trimethylolpropane triglycidyl ether Scheme A11 [ka] Scheme A11. Amine-functionalized polybutadiene (0.650 g, 0.135 mmol) was weighed into a Schlenk flask and dissolved in 5 mL of THF. Trimethylolpropane triglycidyl ether (1 mL, 3.83 mmol) was added via syringe. The solution was heated to 40° C. overnight, forming an orange solid, gel-like, insoluble material. Figure 13 shows the overlaid IR spectrum of P10 and P10A.

[0252] Example 15: Reactivity of Isocyanates to Form Polyureas Scheme A12 [ka] Scheme A12. In certain embodiments, the functionalized polymer can be reacted with an isocyanate. The reaction between an amine functional group and an isocyanate functional group can produce a urea functional group. In some embodiments, R 5is hydrogen, -C1 to -C 20 Alkyl, or -C6~C 20 In some other embodiments, R 5 is -C1-C6 alkyl, -C1-C6 heteroalkyl, C 4~10 Aryl and C 4~10 It is heteroaryl.

[0253] Example 16: Reaction with 4,4'-methylenebis(cyclohexyl isocyanate) Scheme A13 [ka] Scheme A13. P12 (0.25 g, 0.055 mmol) was weighed into a round bottom flask and dissolved in 3 mL of DCM. 4,4'-methylenebis(cyclohexyl isocyanate) (1.3 mL, 5.28 mmol) was transferred to the reaction flask via syringe. The solution was stirred overnight at room temperature. The next morning, the material was concentrated under reduced pressure to give a hard, brittle, insoluble material, P12A. The product was characterized by FTIR spectroscopy (Figure 14).

[0254] Example 17: Reaction with tosylated polyethylene glycol Scheme A14 [ka] Scheme A14. P13 (290 mg, 0.060 mmol) was weighed into a round bottom flask and dissolved in 3 mL of THF. Tosylated polyethylene glycol (180 mg, 0.43 mmol) was weighed separately and quantitatively transferred to the round bottom flask containing P13 along with 2 mL of THF. KI (0.138 g, 0.83 mmol) and Cs2SO3 (0.407 mg, 0.13 mmol) were weighed separately and added directly to the round bottom flask. The solution was stirred and refluxed overnight. An off-white precipitate formed overnight. The solution was cooled to room temperature and then filtered through a 1-inch Celite® pad. The resulting solution was concentrated under reduced pressure and then dissolved in DCM and liquid-liquid extraction was performed with DI-H2O. The organic layer was collected and concentrated under reduced pressure. The resulting product was redissolved in concentrated DCM solution and precipitated in MeOH. The insoluble material was collected by decanting the MeOH and then collecting it as a solution in DCM. The product was concentrated under reduced pressure and then dried in vacuum overnight. Figure 15A shows the elution of P13A. 1 1 H NMR (300 MHz, CDCl3, 298 K) spectrum of P13A. 13 C NMR (75 MHz, CDCl3, 298K) spectrum is shown. Figure 15C shows the IR spectrum of P13A.

[0255] Example 18: Preparation of quaternary amine groups using methyl iodide Scheme A15 [ka] Scheme A15. P14 (0.252 g, 0.053 mmol) was weighed into a round bottom flask and dissolved in 3 mL of DCM. Iodomethane (0.1 mL, 1.55 mmol) and 2,6-lutidine (0.15 mL, 1.30 mmol) were added to the reaction vessel via syringe. The solution was stirred at room temperature overnight. A precipitate formed and was removed by filtration through Celite. The solution was concentrated under reduced pressure to give more precipitate. These were removed by filtration over Celite with hexane. The solution was concentrated under reduced pressure and dried in vacuum overnight to give P14A (247 mg, 92%). Figure 16. Synthesis of P14A. 1 H NMR (300 MHz, CDCl3, 298 K) spectrum.

[0256] Example 19: Scheme: Reaction with benzyl chloride Scheme A16 [ka] Scheme A16. P15 (251 mg, 0.044 mmol) was weighed into a round bottom flask and dissolved in 3 mL of THF. Sodium iodide (0.097 mg, 0.647 mmol) was weighed separately and added neat to the reaction flask. Benzyl chloride (0.077 mL, 0.669 mmol) was delivered to the reaction flask via syringe. The solution was stirred vigorously and refluxed overnight. A precipitate formed and was removed by filtering through Celite. The solution was concentrated under reduced pressure and the product was precipitated from the concentrated DCM solution into cold MeOH. The MeOH was decanted and the product was collected in a vial with DCM, concentrated under reduced pressure, and dried in vacuum overnight. The resulting material P15A was hard and amber in color (0.077 g, 25%). Figure 17A. 1 H NMR (300 MHz, CDCl3, 298 K) spectrum. 13 C{1H}NMR (75MHz, CDCl3, 298K) spectrum.

[0257] Example 20: Reaction with triphosgene Scheme A17 [ka] Scheme A17. P16 (0.25 g, 0.055 mmol) was weighed into a round bottom flask and dissolved in 3 mL of DCM. Triphosgene (0.77 g, 0.26 mmol) was weighed separately in a sealed vial and then added directly to the reaction vessel. The solution was stirred at room temperature overnight. The next morning, the solution was washed with deionized H2O (3x5 mL) and the organic layer was collected and dried over MgSO4. The solution was gravity filtered and concentrated under reduced pressure before being dried in vacuum overnight. The resulting material P16A was oily, sticky and brown (0.22 g, 84%). Figure 18A. 1 H NMR (300 MHz, CDCl3, 298 K) spectrum. Figure 18B. FT-IR spectrum of P16A.

[0258] Example 21: Reaction with linoleic acid Scheme A18: [ka] Scheme A18. P17 (0.102 g, 0.0210 mmol) was weighed into a round bottom flask. Linoleic acid (0.121 g, 0.431 mmol) was weighed separately and quantitatively transferred into the round bottom flask containing DCM. The two were mixed for 1 hour and then N,N'-dicyclohexylcarbodiimide (DCC) (0.095 g, 0.46 mmol) was added neat. The reaction was stirred overnight at room temperature. The next morning the solution was cloudy and the precipitate (N,N'-dicyclohexylurea-DCU) was removed by filtration. The product, P17A, was concentrated under reduced pressure and precipitated from the concentrated DCM solution into acetone. This formed a persistent dispersion and the product was separated by centrifugation and the acetone was decanted from the product. The product P17A was isolated as a yellow oil in 0.156 g (0.0145 mmol, 69%). Figure 19A.P17A 1 H NMR (300 MHz, CDCl3, 298 K) spectrum. 13 C{1H}NMR (75MHz, CDCl3, 298K) spectrum.

[0259] Example 22: Reaction with oxalic acid to obtain a pH-responsive material Scheme A19 [ka] Scheme A19. P18 (0.50 g, 0.10 mmol) was weighed into a round bottom flask and dissolved in hexane. Oxalic acid (0.10 g, 1.1 mmol) was weighed separately and transferred to a round bottom flask with 0.1 mL of MeOH. One minute after the addition, a white solid waxy precipitate formed at the bottom of the round bottom flask. This precipitate persisted. Then, 1 mL of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) was added, and the precipitate immediately redissolved. The solution remained homogeneous. An excess of oxalic acid was then added to the solution, which reformed the precipitate and made the supernatant clear after 10 minutes. The product P18A was insoluble in most organic solvents (Hexane, MeOH, EtOAc, CDCl3). Figure 20. FT-IR spectrum of P18A.

[0260] Example 23: Reaction with hydrochloric acid Scheme A20 [ka] Scheme A20. P19 (0.29 g, 0.064 mmol) was weighed into a round bottom flask and dissolved in 3 mL of DCM. 0.61 mL of 2.0 M HCl in ether was transferred to the reaction flask via syringe. An insoluble precipitate formed immediately and the reaction was stirred at room temperature overnight. The next morning, the solvent was removed under reduced pressure and the material was dried in vacuum overnight to give a solid, flaky, amber material, P19A (0.306 g, 0.059 mmol). Figure 21A. 1 H NMR (300 MHz, CD3OD, 298 K) spectrum. 13 C{1H}NMR (75 MHz, CD3OD, 298K) spectrum. Figure 21C. FT-IR spectrum of P19A.

[0261] Example 24: Reaction with polybutadienes having various molecular weights The following reactions were carried out on polybutadiene starting materials of various molecular weights: [ka] [ka]

[0262] Example 25: Reaction with acid anhydrides The following reactions were carried out: [ka] P20 (0.247 g, 0.055 mmol) was weighed into a round bottom flask and then dissolved in 3 mL of THF. Succinic anhydride (0.054 g, 0.540 mmol) was then weighed separately and added to the solution. Two drops of 1M HCl (水溶液) was added to the solution. The solution was stirred at room temperature overnight. The solution was concentrated under reduced pressure, then the viscous product was dissolved in concentrated DCM solution and precipitated in DI-H2O. The DI-H2O was decanted, and the product was recovered as a DCM solution, concentrated under reduced pressure, and then dried in vacuum overnight to give P20A (0.262 g). Figure 22A. 1 H NMR (300 MHz, CD3OD, 298 K) spectrum. 13 C{1H}NMR (75 MHz, CD3OD, 298K) spectrum. Figure 22C. FT-IR spectrum of P20A.

[0263] The above embodiments and examples are intended to be merely illustrative and non-limiting. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, numerous equivalents to the specific compounds, materials, and procedures. All such equivalents are considered to be within the scope of the invention and are covered by the appended claims.

Claims

1. It is a polymer, Polybutadiene skeleton, 1,2-Alkene units, 1,4-Alkene units, and Branched substitutional units having the functional group of formula (I) or a salt thereof: 【Chemistry 1】 Linear substitutional units having the functional group of formula (I) or a salt thereof: Includes, In the formula, the molar ratio of the branched substitution unit to the linear substitution unit is 6:1 or greater. R １ is hydrogen, -C １ ~C ２０ Alkyl, or -C ６ ~C ２０ Is it an allele? R ２ is -C １ ~C ２０ alkyl, or -C ６ ~C ２０ aryl, or R １ and R ２ Together with the nitrogen to which both are bonded, it has 0 to 2 additional heteroatoms selected from nitrogen and oxygen -C ３ ~C ２０ Forming a complex ring, In the formula, R １ and R ２ These are, independently, -F, -Cl, -I, -Br, -OH, and -OCH. ３ , -OCF ３ , and -C １ ~C ６ Optionally substituted with 1 to 6 groups selected from thioalkyl groups or combinations thereof, R ３ and R ４ In each example, hydrogen and -C are independently involved. １ ~C ６ Alkyl and -C １ ~C ６ Selected from heteroalkyl groups, The asterisk (*) indicates the bonding point of the functional group to the carbon atoms in the polymer skeleton. Here, the polymer optionally includes one or more other units, The polymer, wherein the units may be arranged in a continuous sequence, in blocks, or randomly dispersed.

2. The polymer according to claim 1, wherein the polymer contains at least 60% branched substitution units relative to linear substitution units.

3. The polymer according to claim 1, wherein the amounts of 1,2-alkene units and 1,4-alkene units may be equal or variable.

4. The polymer according to claim 1, comprising 92% 1,4-alkene units and 8% 1,2-alkene units.

5. The polymer according to claim 1, wherein one or more of the other units comprises a styrene unit which is optionally substituted with alkyl, substituted alkyl, heteroalkyl, substituted heteroalkyl, styrene, substituted styrene, or a mixture thereof.

6. The polymer according to claim 1, wherein one or more of the other units include styrene units.

7. The polymer according to claim 1, wherein one or more of the other units are isoprene units.

8. R2 is a -C6 to C20 aryl, and R ２ The polymer according to claim 1, wherein the aryl group in is para-substituted.

9. Polymer of formula (II) 【Chemistry 2】 or a fragment thereof, in the formula, R ５ It is either present or absent. R ５ When it exists on a c unit, the dashed line indicates a single bond, R ５ If the c unit is absent, the dashed line indicates a double bond. R ５ is a compound or salt thereof having the structure of formula (I): 【Transformation 3】 During the ceremony, R １ is, -C １ ~C ２０ Alkyl, or -C ６ ~C ２０ Is it an allele, or R ２ is hydrogen, -C １ ~C ２０ Alkyl, or -C ６ ~C ２０ Is it an allele, or R １ and R ２ Together with the nitrogen to which both are bonded, it has 0 to 2 additional heteroatoms selected from nitrogen and oxygen -C ３ ~C ２０ Forming a heteroalgebra, R ３ and R ４ These are, independently, -F, -Cl, -I, -Br, and -OCH. ３ , -OCF ３ , -C １ ~C ６ It is optionally substituted with 1 to 6 groups selected from the group consisting of thioalkyl groups and combinations thereof. R ２ The aryl group in the above is optionally para-substituted, R ３ and R ４ In each example, hydrogen and -C are independently involved. １ ~C ６ Alkyl and -C １ ~C ６ Selected from heteroalkyl groups, R ６ is hydrogen, -C1 to C ２０ Alkyl, -C ６ ~C ２０ Ariel, -C １～６ Alkyl-C １ ~C ２０ Alkyl, -C １～６ Alkyl-C ６ ~C ２０ Ariel, -C １～６ Heteroalkyl-C １ ~C ２０ Alkyl, or -C １～６ Heteroalkyl-C ６ ~C ２０ It is Ariel, The polymer according to claim 1, wherein a, b, c, d, e, and f are independent integers between 0 and 100,000 for each occurrence, the ratio of d:e is 6:1 or greater, and the units may be ordered or randomly distributed.

10. The polymer according to claim 9, wherein the a:b ratio is 0.1, 0.5, 1, 1.5, 2, or 10.

11. The polymer according to claim 1, wherein the ratio of d to e is 6:

1.

12. Structure of equation (IIa) 【Chemistry 4】

13. The polymer according to claim 1, selected from the group consisting of the following compounds: Table 1-1 Table 1-2 Table 1-3

14. The following structure: 【Chemistry 11】 The polymer according to claim 1, having (wherein the formula, the sum of the subscripts d and e is 9).

15. The polymer according to claim 1, wherein the polymer has a molecular weight of 2,500 to 4,500 g / mol.

16. The polymer according to claim 1, wherein the polymer has a molecular weight of 70,000 to 80,000 g / mol.

17. A process for producing polymers, The process involves hydroaminoalkylating a polybutadiene polymer after polymerization in the presence of a Group 4 or Group 5 transition metal catalyst and a secondary amine to form a functionalized polymer, with a reaction temperature of 110°C to 165°C. The process includes producing the functionalized polymer, wherein the functionalized polymer is Polybutadiene skeleton, 1,2-Alkene units, 1,4-Alkene units, and Branched substitutional units having the functional group of formula (I) or a salt thereof: 【Chemistry 12】 A linear substitutional unit having a functional group of formula (I) or a salt thereof: In the formula, the molar ratio of the branched substitution unit to the linear substitution unit is 6:1 or greater. R １ is hydrogen, -C １ ~C ２０ Alkyl, or -C ６ ~C ２０ Is it an allele? R ２ is, -C １ ~C ２０ Alkyl, or -C ６ ~C ２０ Is it an allele, or R １ and R ２ together with the nitrogen to which they are both attached, have 0 to 2 additional heteroatoms selected from nitrogen and oxygen and form a -C ３ -C ２０ heterocyclic ring, and R １ and R ２ are each independently optionally substituted with 1 to 6 groups selected from the group consisting of -F, -Cl, -I, -Br, -OCH ３ , -OCF ３ , and -C １ -C ６ [[ID=二十]]thioalkyl, and combinations thereof. R ３ and R ４ each independently, in each case, is hydrogen, -C １ to -C ６ alkyl, and -C １ to -C ６ heteroalkyl, and is selected from The asterisk (*) indicates the bonding point of the functional group to the carbon atoms in the polymer skeleton. Here, the polymer optionally includes one or more other units, The process, wherein the units may be ordered or randomly distributed.

18. A process for preparing functionalized polymers, A reaction mixture comprising the polymer described in claim 1 and an electrophile is prepared. The process comprising reacting the polymer with the electrophile to produce the functionalized polymer.

Images