Double-ended organoaluminum composition

Abstract

The present disclosure relates to double-headed organoaluminum compositions of formula (I) and methods of making the same. In at least one aspect, the composition of formula (I) may be used during olefin polymerization.

Description

[0001] This application is a divisional application of the Chinese patent application with application number 201880079526X (application date: December 27, 2018, invention name: double-headed organic aluminum composition).

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS

[0003] This application claims priority to and the benefit of U.S. Provisional Application No. 62 / 611,680, filed on December 29, 2017, which is incorporated herein in its entirety. Technical Field

[0004] Embodiments relate to double-headed organoaluminum compositions and methods for preparing the same. The compositions can undergo chain shuttling and / or chain transfer. In at least one aspect, the double-headed organoaluminum compositions can be used for olefin polymerization. Background Art

[0005] In recent years, advances in polymer design have been seen through the use of compositions capable of chain shuttling, i.e., chain shuttling agents (CSAs). For example, chain shuttling agents with reversible chain transfer capabilities with transition metal catalysts are able to produce new olefin block copolymers (OBCs). Currently, the best known compositions capable of chain shuttling are simple metal alkyls that typically contain only a single point of attachment to the metal for each polymer chain, such as diethylzinc that produces polymer chains terminated with zinc metal at one end. More complex compositions capable of chain shuttling are also known, such as double-headed chain shuttling agents, in which the alkane moiety is attached to two metals. Indeed, double-headed compositions capable of chain shuttling are of great interest because they are able to produce new polyolefins, such as telechelic functional polymers, triblock copolymers, and the like. Summary of the invention

[0006] In certain embodiments, the present disclosure relates to a double-headed organoaluminum composition of formula (I):

[0007] in:

[0008] n is a number from 1 to 100;

[0009] Y is a linear, branched or cyclic C4 to C 100 A linking group consisting of an alkylene group, the alkylene group optionally containing at least one heteroatom and being aliphatic or aromatic, wherein Y includes two points of attachment to the Al atom, and at least one of the two points of attachment is -CH2-;

[0010] Each J group is independently hydrogen or substituted or unsubstituted acyclic alkyl; and

[0011] Two J groups attached to the same Al atom may optionally be covalently linked together.

[0012] In a further embodiment, the present disclosure relates to a method for preparing a double-headed organoaluminum composition of formula (I), the method comprising: (a) combining an aluminum compound, a linker, and optionally a solvent at a temperature of 25° C. to 200° C., and (b) obtaining a composition of formula (I), wherein the aluminum compound has the formula Al(J)3, wherein each J is independently hydrogen or a substituted or unsubstituted acyclic alkyl group, and optionally, two J groups can be covalently linked together; and the linker is C4 to C 100 A hydrocarbon comprising at least two vinyl groups or one vinyl group and a cycloolefin group, and optionally containing at least one heteroatom.

[0013] In a further embodiment, the present disclosure relates to a double-headed organoaluminum composition of formula (I), comprising the reaction product of: an aluminum compound, a linker, and optionally a solvent, wherein the aluminum compound has the formula Al(J)3, wherein each J group is independently hydrogen or a substituted or unsubstituted acyclic alkyl group, and optionally, two J groups may be covalently linked together; and the linker is C4 to C 100 A hydrocarbon comprising at least two vinyl groups or one vinyl group and a cycloolefin group, and optionally containing at least one heteroatom. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 For example 1 1 H NMR spectroscopy.

[0015] Figure 2A and 2B This is the GC / MS spectrum of Example 1.

[0016] Figure 3 This is the reaction scheme of Example 1.

[0017] Figure 4 This is the GC / MS spectrum of Example 2.

[0018] Figure 5 is the NMR spectrum of Example 4.

[0019] definition

[0020] All references to the Periodic Table of the Elements refer to the Periodic Table of the Elements published and copyrighted by CRC Press, Inc., 2003. In addition, any reference to one or more groups should be the group or groups reflected in this Periodic Table of the Elements using the IUPAC system for group numbering. Unless otherwise stated, implied from the context, or customary in the art, all parts and percentages are by weight, and all test methods are current methods as of the filing date of this disclosure. For the purpose of U.S. patent practice, the contents of any referenced patent, patent application, or publication, especially those concerning synthetic techniques, product and process designs, polymers, catalysts, definitions (to the extent inconsistent with any definitions provided in particular in this disclosure), and common knowledge in the art, are incorporated by reference in their entirety (or their equivalent U.S. versions are so incorporated by reference).

[0021] Numerical ranges in the present disclosure are approximate values, and therefore, unless otherwise indicated, may include values ​​outside the range. Numerical ranges disclosed herein include all values ​​from the lower and upper limits, and include the lower and upper limits. For ranges containing exact values ​​(e.g., 1 or 2, or 3 to 5, or 6, or 7), any subranges between any two exact values ​​are included (e.g., 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6; etc.). Numerical ranges disclosed herein also include fractions between any two exact values.

[0022] In the event that the name of a compound herein does not correspond to its structural representation, the structural representation shall control.

[0023] The terms "chain shuttling agent" and "chain transfer agent" refer to those known to those of ordinary skill in the art. Specifically, the terms "shuttling agent" and "chain shuttling agent" refer to a compound or mixture of compounds that is capable of causing polymer transfer between various active catalyst sites under polymerization conditions. That is, the transfer of polymer fragments to and from the active catalyst sites occurs in a facile and reversible manner. In contrast to shuttling agents or chain shuttling agents, agents that act only as "chain transfer agents", such as some main group alkyl compounds, can exchange, for example, an alkyl group on the chain transfer agent with a growing polymer chain on the catalyst, which generally results in the termination of polymer chain growth. In this case, the main group center can act as a reservoir for failed polymer chains, and does not participate in the reversible transfer through the catalyst site in the manner in which a chain shuttling agent participates in the transfer. Ideally, the intermediate formed between the chain shuttling agent and the polymer base chain is not sufficiently stable relative to the exchange between this intermediate and any other growing polymer base chain, so that chain termination is relatively rare.

[0024] As used herein, the term "derivative" refers to the reaction product of a chemical species after the reactant of the chemical species has inserted a metal alkyl or metal hydride bond. For example, but not limited to, (R)2-Al[—YC —Al(R)] n —The “Y” in (R) C " can define a derivative of a linker CH2=CH(CH2)6CH=CH2, wherein the linker reacts with (iBu)2AlH to form (iBu)2-Al[-CH2(CH2)8CH2-Al(iBu)] n In this non-limiting example, Y C It is -CH2(CH2)8CH2-, and the linking group is a derivative of the linking agent CH2=CH(CH2)6CH=CH2 after the linking agent is inserted into the Al-H bond.

[0025] The term "linker" is a chemical substance whose derivatives link multiple metal species together in a molecule by inserting into the metal hydride bonds of each metal. In the above non-limiting example, CH2=CH(CH2)6CH=CH is a "linker" that links n+1 aluminum species to form the substance (iBu)2Al[—CH2(CH2)8CH2—Al(iBu)] n —iBu. After insertion, the linker becomes a linker group —CH2(CH2)8CH2—.

[0026] "Co-catalyst" refers to a compound that can activate the primary catalyst to form an active catalyst composition / system capable of polymerizing unsaturated monomers. "Co-catalyst" can be used interchangeably with "activator" and similar terms.

[0027] "Procatalyst" refers to a transition metal compound that is capable of polymerizing unsaturated monomers when combined with an activator. Suitable procatalysts of the present disclosure include those that require or do not require a cocatalyst to become an active catalyst capable of polymerizing unsaturated monomers. "Procatalyst" can be used interchangeably with "catalyst precursor", "transition metal catalyst", "transition metal catalyst precursor", "metal complex" and similar terms. Suitable procatalysts include those known in the art, such as those disclosed in WO 2005 / 090426, WO 2005 / 090427, WO 2007 / 035485, WO 2009 / 012215, WO 2014 / 105411, U.S. Patent Publication Nos. 2006 / 0199930, 2007 / 0167578, 2008 / 0311812, and U.S. Patent Nos. 7,355,089 B2, 8,058,373 B2, and 8,785,554 B2, all of which are incorporated herein by reference in their entirety.

[0028] "Catalyst system" refers to a procatalyst or a combination of a procatalyst and an activator, with or without a support, capable of polymerizing olefins. "Catalyst system" may be used interchangeably with "active catalyst," "active catalyst composition," "olefin polymerization catalyst," and similar terms.

[0029] "Polymer" refers to a compound prepared by polymerizing monomers, whether of the same or different types. Thus, the generic term polymer encompasses the term homopolymer, commonly used to refer to polymers prepared from only one type of monomer, and the term interpolymer as defined below. It also encompasses all forms of interpolymers, for example, random, block, homogeneous, heterogeneous, etc.

[0030] "Interpolymer" and "copolymer" refer to polymers prepared by polymerizing at least two different types of monomers. These general terms encompass classical copolymers, i.e., polymers prepared from two different types of monomers, and polymers prepared from more than two different types of monomers, for example, terpolymers, tetrapolymers, etc.

[0031] The term "block copolymer" or "segmented copolymer" refers to a polymer comprising two or more chemically distinct regions or segments (called "blocks") connected in a linear manner, i.e., a polymer comprising chemically differentiated units that are linked end-to-end (covalently bonded) according to polymeric functionality rather than in a side-linked or grafted manner. Blocks differ in the amount or type of comonomer incorporated therein, density, amount of crystallinity, type of crystallinity (e.g., polyethylene vs. polypropylene), crystallite size attributable to the polymer of the composition, type or degree of stereoisomerism (isotactic or syndiotactic), regioregularity or regioirregularity, amount of branching (including long chain branching or hyperbranching), homogeneity, and / or any other chemical or physical properties. Block copolymers are characterized by unique distributions of polymer polydispersity (PDI or Mw / Mn) and block length distribution, for example, based on the use of shuttling agents and the effects of the catalyst system. DETAILED DESCRIPTION

[0032] All schemes and discussions below are by way of example only and are not intended to be limiting in any way. As described herein, double-head compositions (e.g., double-head CSAs) are of great interest because they can produce telechelic functional polymers. By way of example and not limitation, reference is made to non-limiting Structure 1. Structure 1 represents an exemplary double-head composition in which the Y linking group is sandwiched between two aluminum atoms. Y can be, for example, a linear, branched, or cyclic C4 to C 100A hydrocarbylene group, which optionally contains at least one heteroatom ((B, O, S, N, F, Cl or Si)) and is aliphatic or aromatic. The Y linking group connects two independent Al atoms and is connected to each Al atom via a connection point. The connection point is a group (i.e., a fragment) within the Y linking group, and at least one connection point is an ethylene group, -CH2-. Each terminal J group can be hydrogen or a substituted or unsubstituted acyclic alkyl group. Two J groups connected to the same Al atom can optionally be covalently linked together. Then, during olefin polymerization, the Y linking group can grow into a polymer chain, both ends of which are bonded to the aluminum atom via a terminal polymer-metal bond. Subsequently, the terminal polymer-metal bond can be converted to the desired functional group via functionalization chemistry, thereby obtaining the desired bifunctional (telechelic) polymer chain. The composition of the non-limiting structure 1 can be in monomeric (n=1) or oligomeric (n>1) form.

[0033]

[0034] Method for preparing double-headed organoaluminum composition

[0035] The composition of formula (I) can be prepared by the reaction caused by combining an aluminum compound and a linker. The reaction can be carried out in the absence (free of solvent) or in the presence of a solvent. Suitable solvents include but are not limited to non-polar solvents such as xylene, toluene, hexane, pentane, benzene or a combination thereof.

[0036] Thus, the composition of formula (I) can be prepared by a process comprising: (a) combining an aluminum compound, a linker, and optionally a solvent, and (b) obtaining a composition of formula (I), wherein: the aluminum compound has the formula Al(J)3, wherein each J group is independently hydrogen or a substituted or unsubstituted acyclic alkyl group, and optionally, two J groups may be covalently linked together; and the linker is C4 to C 100 A hydrocarbon comprising at least two vinyl groups or one vinyl group and a cycloolefin group, and optionally containing at least one heteroatom.

[0037] The reaction caused by combining the aluminum compound, the linking group and the optional solvent can be carried out at a temperature of 25° C. to 200° C., or 80° C. to 180° C., or 100° C. to 150° C. The high temperature facilitates the removal of the J group (e.g., alkyl) of the aluminum compound via β-hydride elimination, resulting in the insertion of the linking agent into Al—H to form the composition of formula (I).

[0038] Thus, in certain embodiments, the composition of formula (I) can be prepared by a method comprising: (a) combining an aluminum compound, a linker, and an optional solvent at a temperature of 25°C to 200°C (or 80°C to 180°C or 100°C to 150°C), and (b) obtaining a composition of formula (I), wherein: the aluminum compound has the formula Al(J)3, wherein each J group is independently hydrogen or a substituted or unsubstituted acyclic alkyl group, and optionally, two J groups may be covalently linked together; and the linker is C4 to C 100 A hydrocarbon comprising at least two vinyl groups or one vinyl group and a cycloolefin group, and optionally containing at least one heteroatom.

[0039] The reaction caused by combining the aluminum compound, the linker and the optional solvent may require a reaction time of 30 minutes to 200 hours, depending on the temperature at which the reaction is carried out. For example, but not limited to, if the reaction is carried out at 150° C., a reaction time of 1 to 2 hours may be required, if the reaction is carried out at 120° C., a reaction time of 2 to 5 hours may be required, and if the reaction is carried out at 60° C., a reaction time of 20 to 200 hours may be required.

[0040] Thus, in certain embodiments, the composition of formula (I) can be prepared by a process comprising: (a) combining an aluminum compound, a linker, and an optional solvent at a temperature of 25°C to 200°C (or at 80°C to 180°C or 100°C to 150°C) for a time of 30 minutes to 200 hours (or 30 minutes to 100 hours, or 1 hour to 50 hours, or 1 hour to 30 hours, or 1 hour to 25 hours, or 1 hour to 15 hours, or 1 hour to 10 hours, or 1 hour to 5 hours), and (b) obtaining a composition of formula (I), wherein: the aluminum compound has the formula Al(J)3, wherein each J group is independently hydrogen or a substituted or unsubstituted acyclic alkyl group, and optionally, two J groups can be covalently linked together; and the linker is C4 to C 100 A hydrocarbon comprising at least two vinyl groups or one vinyl group and a cycloolefin group, and optionally containing at least one heteroatom.

[0041] In certain embodiments of the methods of the present disclosure, the linker:aluminum compound ratio is defined as n:(n+1), where n can be a number from 1 to 10.

[0042] Aluminum compounds

[0043] Aluminum compounds are defined herein as compounds with formula Al(J)3, wherein each J group is independently hydrogen or a substituted or unsubstituted acyclic alkyl group, wherein at least one J group is hydrogen or an acyclic alkyl group, and optionally, two J groups can be covalently linked together. Optionally, one J group or each of two or three J groups can be a hydrogen atom. In certain embodiments, one J group or each of two or three J groups is an acyclic alkyl group containing 1 to 30 carbon atoms or 2 to 20 carbon atoms. In certain embodiments, one J group or each of two or three J groups is not hydrogen. In further embodiments, one J group or each of two or three J groups is not methyl. In further embodiments, one J group or each of two or three J groups is C1 to C2. 30 Acyclic alkyl or C2 to C 20 In certain embodiments, one J group or each of two or three J groups is a branched C3 to C 30 In further embodiments, two J groups may be covalently linked together.

[0044] Suitable J groups include, but are not limited to, methyl, ethyl, propyl, butyl, isobutyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and all isomers thereof. Trialkylaluminum compounds and dialkylaluminum hydride compounds are suitable reagents. Useful trialkylaluminum compounds include, but are not limited to, trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, triisohexylaluminum, trioctylaluminum, triisooctylaluminum, tripentylaluminum, tridecylaluminum, etc. Useful dialkylaluminum hydride compounds include, but are not limited to, dimethylaluminum hydride, diethylaluminum hydride, diisobutylaluminum hydride, dibutylaluminum hydride, dipropylaluminum hydride, dihexylaluminum hydride, diisohexylaluminum hydride, dioctylaluminum hydride, diisooctylaluminum hydride, dipentylaluminum hydride, didecylaluminum hydride, etc.

[0045] Linking group

[0046] In the composition of formula (I), Y is a linking group, which is a linear, branched or cyclic C4 to C 100 A alkylene group, which optionally contains at least one heteroatom and is aliphatic or aromatic. The linking group Y is a derivative of a linker, wherein the linker is C4 to C 100A hydrocarbon comprising at least two vinyl groups or one vinyl group and a cycloolefin group, and optionally containing at least one heteroatom. Suitable linkers must be able to insert into aluminum-hydrogen bonds so that the derivative of the linker is sandwiched between two aluminum atoms. As described above, Y of the composition of formula (I) is a linking group that can be transferred to the active catalyst and grow into a polymer chain during olefin polymerization due to chain transfer / chain shuttling between the active catalyst and the aluminum species, thereby forming a precursor of a telechelic polymer. Subsequent functionalization will result in the formation of a telechelic polymer.

[0047] In certain embodiments, Y is a derivative of a diene. In other words, the linker is a diene. As used herein, the term diene refers to any compound containing two vinyl groups or one vinyl group and a cycloalkenyl group, and optionally, at least one heteroatom. Examples of suitable dienes include hydrocarbon-based dienes, hydrocarbon-based dienes containing heteroatoms such as 1,3-di(ω-alkenyl)-tetramethyldisiloxane and di(ω-alkenyl) ethers and dienes containing aromatic fragments, such as divinylbenzene.

[0048] Suitable hydrocarbon-based dienes referred to herein include, but are not limited to, those having the formula CH2=CH(CH2) m CH=CH2 or CH2=CH(Ar) m Dienes of CH=CH2, including cyclic and bicyclic analogs thereof, wherein m is an integer from 0 to 20, and Ar is an aryl group. Examples of these hydrocarbon-based dienes include, but are not limited to, 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, and the like, typically containing 5 to 40 carbon atoms.

[0049] The heteroatom-containing hydrocarbon-based dienes mentioned herein include dienes containing at least one B, O, S, N, F, Cl or Si atom or a combination of atoms. Specific examples of heteroatom-containing hydrocarbon-based dienes include, but are not limited to, dienes having the formula O[(CH2) m CH=CH2]2、S[(CH2) m CH=CH2]2、R A N[(CH2) m CH=CH2]2、(R B )2Si[(CH2) m CH=CH2]2、Ar[Si(R B )2(CH2) m CH=CH2]2、(CH2) m [Si(R B )2(CH2) m CH=CH2]2、(RB )3SiOSiR B [(CH2) m CH=CH2]2 and [Si(R B )2(CH2) m CH=CH2]2O; wherein m is independently an integer from 0 to 20, inclusive, preferably from 1 to 20, inclusive; R A is H or a hydrocarbon group having 1 to 12 carbon atoms, inclusive; R B is independently at each occurrence a hydrocarbyl group of 1 to 12 carbon atoms, inclusive; and Ar is an aryl group.

[0050] Examples of heteroatom-containing hydrocarbon-based dienes include, but are not limited to, divinyldiphenylsilane, 1,4-bis(dimethyl(vinyl)silyl)benzene, 1,5-bis(dimethyl(vinyl)silyl)pentane, divinyl ether, di(2-propenyl)ether, di(3-butenyl)ether, di(4-pentenyl)ether, di(5-hexenyl)ether, divinylamine, di(2-propenyl)amine, di(3-butenyl)amine, di(4-pentenyl)amine, di(5-hexenyl)amine, divinylmethylamine, di(2 di-(2-propenyl)dimethylsilane, di-(3-butenyl)dimethylsilane, di-(4-pentenyl)dimethylsilane, di-(5-hexenyl)dimethylsilane, and the like, typically containing 4 to 40 carbon atoms.

[0051] Other examples of suitable heteroatom-containing hydrocarbon-based dienes include, but are not limited to, disiloxane compounds such as divinyltetramethyldisiloxane (also referred to herein as di(ethyl-1,2-diyl)tetramethyldisiloxane, di(2-propenyl)tetramethyldisiloxane, di(3-butenyl)tetramethyldisiloxane, di(4-pentenyl)tetramethyldisiloxane, di(5-hexenyl)tetramethyldisiloxane, di(6-heptenyl)tetramethyldisiloxane, di(7-octenyl)tetramethyldisiloxane, di(8-nonenyl)tetramethyldisiloxane, di(9-octenyl)tetramethyldisiloxane, di(10-octenyl)tetramethyldisiloxane, di(11-octenyl)tetramethyldisiloxane, di(12-octenyl)tetramethyldisiloxane, di(13-nonenyl)tetramethyldisiloxane, di(14-octenyl)tetramethyldisiloxane, di(15-octenyl)tetramethyldisiloxane, di(16-octenyl)tetramethyldisiloxane, di(17-octenyl)tetramethyldisiloxane, di(18-nonenyl)tetramethyldisiloxane, di(19-octenyl)tetramethyldisiloxane, di(20-octenyl)tetramethyldisiloxane, di(21-octenyl)tetramethyldisiloxane, di(22- 1,1- and 1,3-isomers of bis(2-propenyl)tetraethyldisiloxane, bis(3-butenyl)tetraethyldisiloxane, bis(4-pentenyl)tetraethyldisiloxane, bis(5-hexenyl)tetraethyldisiloxane, bis(6-heptenyl)tetraethyldisiloxane, bis(7-octenyl)tetraethyldisiloxane, bis(8-nonenyl)tetraethyldisiloxane, bis(9-decenyl)tetraethyldisiloxane, etc.;

[0052] Diene compounds containing a cyclic olefin or cyclic alkane such as vinyl norbornene, 1,3-divinylcyclopentane and vinylcyclohexene;

[0053] Halogen-containing diene compounds, such as 3-chloro-1,4-pentadiene, 3-bromo-3-methyl-1,4-pentadiene, 3-chloro-1,4-hexadiene, 3-chloro-3-methyl-1,4-hexadiene, 3-bromo-4-methyl-1,4-hexadiene, 3-chloro-5-methyl-1,4-hexadiene, 3-bromo-4,5-dimethyl-1,4-hexadiene, 3-bromo-1,5-hexadiene, 3-chloro-3-methyl-1,5-hexadiene, 3-bromo-1,5-heptadiene, 3-chloro-3-methyl-1,5-heptadiene, 4-bromo-1,6-heptadiene, 3-chloro-4-methyl-1,6-heptadiene, 4-bromo-1, 6-octadiene, 3-chloro-4-methyl-1,6-octadiene, 4-bromo-7-methyl-1,6-octadiene, 4-chloro-1,7-octadiene, 3-chloro-4-methyl-1,7-octadiene, 4-bromo-1,7-nonadiene, 4-bromo-4-methyl-1,7-nonadiene, 4-bromo-1,8-nonadiene, 3-chloro-4-methyl-1,8-nonadiene, 5-bromo-1,8-decadiene, 3-chloro-5-methyl-1,8-decadiene, 5-bromo-1,9-decadiene, 3-chloro-5-methyl-1,9-decadiene, 5-bromo-1,10-undecadiene and 5-bromo-1,1'-dodecadiene;

[0054] Silane-containing dienes, such as bis(vinyloxy)silane, dimethylbis(vinyloxy)silane, bisallyloxysilane, dimethylbis(allyloxy)silane, bis(3-butenyl)dimethylsilane, bis(3-butenyloxy)silane, dimethylbis(3-butenyloxy)silane, bis(4-pentenyl)dimethylsilane, bis(4-pentenyloxy)silane, bis(4-pentenyloxy)dimethylsilane, bis(5-hexenyl)dimethylsilane, bis(5-hexenyloxy)silane and bis(5-hexenyloxy)dimethylsilane;

[0055] Ester-containing diene compounds, such as 3-butenyl-4-pentenoate, 4-pentenyl-4-pentenoate, 4-methoxycarbonyl-1,7-octadiene and 4-methoxycarbonyl-1,9-decadiene;

[0056] Ether-containing diene compounds such as divinyl ether, diallyl ether, di(4-butenyloxy)ether and di(5-hexenyloxy)ether; and

[0057] Silicon-containing alkoxy diene compounds such as 4-trimethylsiloxymethyl-1,7-octadiene and 4-trimethylsiloxymethyl-1,9-decadiene.

[0058] In further embodiments, Y is a derivative of a conjugated diene compound, such as 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 1,3-octadiene, 1-phenyl-1,3-butadiene, 1-phenyl-2,4-pentadiene, isoprene, 2-ethyl-1,3-butadiene, 2-propyl-1,3-butadiene, 2-butyl-1,3-butadiene, 2-pentyl-1,3-butadiene, 2-hexyl-1,3-butadiene, 2-heptyl-1,3-butadiene, 2-octyl-1,3-butadiene and 2-phenyl-1,3-butadiene.

[0059] In further embodiments, Y is a triene or a C4 to C 100 Derivatives of hydrocarbons, the C4 to C 100 The hydrocarbon includes three or more vinyl groups and optionally contains at least one heteroatom. In other words, the linker is a triene or a C4 to C 100 A hydrocarbon comprising three or more vinyl groups and optionally comprising at least one heteroatom. Suitable examples include, but are not limited to, 1,4,7-octatriene, 3-methyl-1,4,7-octatriene, 1,5,9-decatriene, 4-methyl-1,5,9-decatriene, 1,2,4-trivinylcyclohexane, and the like. In certain embodiments, the linker is 1,2,4-trivinylcyclohexane, resulting in a composition of formula (I) having the following structural formula, wherein J is as defined herein:

[0060]

[0061] All linking groups discussed herein are generally available or can be generated by known methods.

[0062] Aggregation methods

[0063] In certain embodiments, the composition of formula (I) may be used as a chain shuttling agent or chain transfer agent during an olefin polymerization process.

[0064] Therefore, the present disclosure relates to a polymerization method for polymerizing at least one addition polymerizable monomer (i.e., olefin monomer) to form a polymer composition, the method comprising: contacting at least one addition polymerizable monomer (olefin monomer) with a catalyst composition under polymerization conditions; wherein the catalyst composition comprises a contact product (reaction product) of at least one catalyst precursor, an optional cocatalyst and a composition of formula (I).

[0065] The double-headed organoaluminum composition of formula (I) described herein and the catalyst system using the composition of formula (I) are suitable for any prepolymerization and / or polymerization process within a wide range of temperature and pressure ranges. The temperature and pressure, as well as other polymerization process information described herein, can be referred to as "polymerization conditions". The temperature can be in the range of 50°C to about 280°C, preferably 50°C to about 200°C. In another embodiment, the polymerization temperature is above 0°C, above 50°C, above 80°C, above 100°C, above 150°C or above 200°C. In one embodiment, the pressure used can be in the range of 1 atmosphere to about 500 atmospheres or more. The polymerization process includes solution, gas phase, slurry phase and high pressure processes or combinations thereof.

[0066] In one embodiment, the disclosure relates to one or more solutions, high pressure, slurries or gas phase polymerization methods with 2 to 30 carbon atoms, preferably 2 to 12 carbon atoms and more preferably 2 to 8 carbon olefin monomers. The disclosure is particularly directed to the polymerization of two or more olefin monomers of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene and 1-decene. Useful monomers include olefinic unsaturated monomers, dienes, conjugated or non-conjugated dienes, polyenes, vinyl monomers and cyclic olefins with 4 to 18 carbon atoms. Non-limiting monomers can include norbornene, norbornadiene, isobutylene, isoprene, vinylbenzocyclobutane, styrene, alkyl-substituted styrene, ethylidene norbornene, dicyclopentadiene and cyclopentene. In another embodiment of the polymerization process of the present disclosure, copolymers of ethylene are produced, wherein a comonomer having at least one α-olefin having 4 to 15 carbon atoms, preferably 4 to 12 carbon atoms, and most preferably 4 to 8 carbon atoms is polymerized with ethylene in a solution process. In another embodiment of the process of the present disclosure, ethylene or propylene is polymerized with at least two different comonomers (optionally one of the comonomers may be a diene) to form a terpolymer.

[0067] In one aspect of the present disclosure, a polymerization process and resulting polymer are provided, the method comprising polymerizing one or more olefin monomers in a polymerization reactor or region in the presence of an olefin polymerization catalyst and a composition of formula (I), thereby causing the formation of at least a certain amount of polymer, the polymer being connected to the residue of the composition of formula (I). Exemplary non-limiting polymerization processes include those known in the art, those disclosed in U.S. Patent No. 8,501,885B2, and those known in the art for producing random copolymers. Exemplary non-limiting polymerization processes are included in those carried out in a single reactor or two reactors (in parallel or in series).

[0068] In yet another aspect, a process and resulting polymer are provided, the process comprising polymerizing one or more olefin monomers in the presence of an olefin polymerization catalyst and a composition of formula (I) in a polymerization reactor or zone, thereby causing the formation of at least a certain amount of initial polymer, which is connected to the residue of the composition of formula (I) in the reactor or zone; discharging the reaction product from the first reactor or zone to a second polymerization reactor or zone, the polymerization reactor or zone being operated under polymerization conditions that are different from the polymerization conditions of the first polymerization reactor or zone; transferring at least some of the initial polymer connected to the residue of the composition of formula (I) to active catalyst sites in the second polymerization reactor or zone by means of at least one remaining shuttling site of the composition of formula (I); and polymerizing in the second polymerization reactor or zone to form a second polymer segment, the second polymer segment being bonded to some or all of the initial polymer by means of the residue of the composition of formula (I), the second polymer segment having polymer properties distinguishable from the initial polymer segment.

[0069] During polymerization, the reaction mixture is contacted with an activated catalyst composition according to any suitable polymerization conditions. The method can be generally characterized by the use of high temperature and high pressure. If desired, hydrogen can be used as a chain transfer agent for molecular weight control according to known techniques. As in other similar polymerizations, it is generally desired that the monomers and solvents used have a sufficiently high purity that catalyst deactivation or premature chain termination will not occur. Any suitable technique for monomer purification can be used, such as devolatilization under reduced pressure, contact with molecular sieves or high surface area alumina, or a combination of the foregoing methods.

[0070] A support may be used in the present process, particularly in slurry phase or gas phase polymerization. Suitable supports include solid, particulate, high surface area metal oxides, metalloid oxides, or mixtures thereof (interchangeably referred to herein as inorganic oxides). Examples include, but are not limited to, talc, silica, alumina, magnesia, titania, zirconia, Sn2O3, aluminosilicates, borosilicates, clays, and any combination or mixture thereof. The surface area of ​​a suitable support is preferably 10 to 1000 m2 as determined by nitrogen porosimetry using the BET method. 2 / g, and preferably 100 to 600 m 2 The average particle size is usually 0.1 to 500 μm, preferably 1 to 200 μm, more preferably 10 to 100 μm.

[0071] In one aspect of the present disclosure, the catalyst and optional support may be spray dried or recovered in a solid particulate form to provide a composition that is easy to transport and handle. Suitable methods for spray drying a slurry containing a liquid are well known in the art and are effectively used herein. Preferred techniques for spray drying the catalyst composition for use herein are described in U.S. Pat. Nos. 5,648,310 and 5,672,669.

[0072] It is desirable to carry out polymerization in a continuous polymerization, such as a continuous solution polymerization, in which catalyst components, monomers and optional solvents, adjuvants, scavengers and polymerization aids are continuously supplied to one or more reactors or zones, and polymer products are continuously removed therefrom. The terms "continuously" and "continuously" as used in this context include those processes in which reactants are intermittently added and products are removed at small regular or irregular time intervals, so that over time, the entire process is substantially continuous. The composition of formula (I) can be added at any point during the polymerization (if used), including in the first reactor or zone, at the outlet of the first reactor or slightly before the outlet of the first reactor, between the first reactor or zone and any subsequent reactor or zone, or even only the second reactor or zone. If there are any differences in monomers, temperature, pressure or other polymerization conditions within a reactor or between two or more reactors or zones connected in series, polymer segments with different compositions (such as comonomer content), crystallinity, density, stereoisomerism, regioregularity or other chemical or physical differences in the same molecule can be formed in the polymer of the present disclosure. In such cases, the size of the individual segments or blocks is determined by the polymer reaction conditions and is generally the maximum possible distribution of polymer sizes.

[0073] If multiple reactors are used, each can be operated independently under high pressure, solution, slurry or gas phase polymerization conditions. In a multi-zone polymerization, all zones are operated under the same polymerization type (such as solution, slurry or gas phase), but optionally under different process conditions. With respect to solution polymerization processes, it is desirable to employ a uniform dispersion of the catalyst components in a liquid diluent in which the polymer is soluble under the polymerization conditions employed. One such process utilizing extremely fine silica or similar dispersants to produce such homogeneous catalyst dispersions, in which the metal complex or co-catalyst is generally only poorly soluble, is disclosed in U.S. Pat. No. 5,783,512. High pressure processes are generally conducted at temperatures of 100° C. to 400° C. and at pressures above 500 bar (50 MPa). Slurry processes generally employ an inert hydrocarbon diluent and a temperature of 0° C. to a temperature slightly below the temperature at which the resulting polymer is substantially soluble in the inert polymerization medium. For example, typical temperatures in slurry polymerizations are 30° C., generally 60° C. to 115° C., including up to 100° C., depending on the polymer being produced. Pressures are typically in the range of atmospheric pressure (100 kPa) to 500 psi (3.4 MPa).

[0074] In all of the foregoing processes, continuous or substantially continuous polymerization conditions are generally employed. The use of such polymerization conditions, particularly continuous solution polymerization processes, permits the use of elevated reactor temperatures, which allows the block copolymers of the present invention to be produced at high yields and high efficiency at low cost.

[0075] The catalyst can be prepared as a homogeneous composition by adding the necessary metal complex or complexes to the solvent in which the polymerization will be carried out or to a diluent compatible with the final reaction mixture. The desired cocatalyst or activator and the optional composition of formula (I) can be combined with the catalyst composition before, simultaneously or after the catalyst is combined with the monomer to be polymerized and any additional reaction diluent. Ideally, if present, the composition of formula (I) is added simultaneously.

[0076] The individual ingredients as well as any active catalyst composition are always protected from oxygen, moisture and other catalyst poisons.Thus, the catalyst components, the composition of formula (I) and the activated catalyst are prepared and stored in an atmosphere free of oxygen and moisture, typically under a dry inert gas, such as nitrogen.

[0077] Without limiting the scope of the present disclosure in any way, one means for carrying out the polymerization process is as follows. In one or more well-stirred tank reactors or loop reactors operating under solution polymerization conditions, the monomer to be polymerized is continuously introduced into one part of the reactor together with any solvent or diluent. The reactor contains a relatively uniform liquid phase consisting essentially of the monomer and any solvent or diluent and dissolved polymer. Preferably, the solvent comprises C 4-10A hydrocarbon or a mixture thereof, particularly an alkane such as hexane or a mixture of alkanes, and one or more monomers used in the polymerization. Examples of suitable loop reactors and various suitable operating conditions for use therewith, including the use of multiple loop reactors, operating in series, are found in U.S. Pat. Nos. 5,977,251, 6,319,989 and 6,683,149.

[0078] The catalyst and the cocatalyst and the composition of formula (I) are continuously or intermittently introduced into the lowest position in the reactor liquid phase or any recycle component thereof. The reactor temperature and pressure can be controlled, for example, by adjusting the solvent / monomer ratio or the catalyst addition rate, and by using cooling or heating coils, jackets or both. The polymerization rate can be controlled by the catalyst addition rate. The content of a given monomer in the polymer product is affected by the ratio of each monomer in the reactor, which is controlled by manipulating the individual feed rates of these components to the reactor. The polymer product molecular weight is optionally controlled by controlling other polymerization variables (such as temperature, monomer concentration), or by the previously mentioned composition of formula (I), or a chain terminator (such as hydrogen), as known in the art.

[0079] In one aspect of the present disclosure, the second reactor is optionally connected to the discharge port of the first reactor by means of a pipeline or other transfer means so that the reaction mixture prepared in the first reactor is discharged to the second reactor without substantially terminating polymer growth. Between the first and second reactors, a difference in at least one process condition can be established. Typically, for forming a copolymer of two or more monomers, the difference is the presence or absence of one or more comonomers or comonomer concentrations. Additional reactors each arranged in a manner similar to the second reactor in the series can also be provided. Further polymerization is terminated by contacting the reactor effluent with a catalyst killer, such as water, steam or alcohol or with a coupling agent (if a coupling reaction product is desired).

[0080] The resulting polymer product is recovered by flashing off volatile components such as residual monomers or diluents in the reaction mixture under reduced pressure and, if necessary, further devolatilization in a device such as a venting barrel. In a continuous process, the average retention time of the catalyst and polymer in the reactor is generally from 5 minutes to 8 hours, for example from 10 minutes to 6 hours.

[0081] In another aspect of the present disclosure, as an alternative, the aforementioned polymerization may be carried out in a plug flow reactor, which is optionally carried out with monomer, catalyst, composition of formula (I), temperature or other gradients established in different zones or between zones thereof, further optionally accompanied by separate addition of catalyst and / or composition of formula (I), and operated under adiabatic or non-adiabatic polymerization conditions.

[0082] The use of functionalized derivatives of polymers is also included in the present disclosure. Examples include Al-terminated polymers produced by compositions of formula (I). Because most of the polymer products leaving the reactor are terminated with metals, further functionalization is relatively easy. Metallated polymer species can be used for well-known chemical reactions, such as those applicable to other alkylaluminum compounds, to form those of amine-, hydroxyl-, epoxy-, silane, vinyl and other functionalized terminated polymer products. Polymers with Al termini can also be functionalized via thermal elimination of mono- and di-unsaturated polymers by heating the Al-terminated polymer to a temperature causing β-hydride elimination in the presence of a sacrificial monomer (such as ethylene), preferably to 150-250° C., which reacts with the resulting aluminum-hydride species to prevent the eliminated mono- or di-unsaturated polymer from undergoing a reverse reaction (i.e., inserting into the aluminum-hydride species).

[0083] Olefin Monomers

[0084] Suitable monomers for preparing the polymer product of the present disclosure in a polymerization process include any addition polymerizable monomers, generally any olefin or diene monomers. Suitable monomers can be straight chain, branched, acyclic, cyclic, substituted or unsubstituted. In one aspect, olefin can be any alpha-olefin, including, for example, ethylene and at least one different copolymerizable comonomer, propylene and at least one different copolymerizable comonomer with 4 to 20 carbon atoms or 4-methyl-1-pentene and at least one different copolymerizable comonomer with 4 to 20 carbon atoms. Examples of suitable monomers include, but are not limited to, straight or branched alpha-olefins with 2 to 30 carbon atoms, 2 to 20 carbon atoms, or 2 to 12 carbon atoms. Specific examples of suitable monomers include, but are not limited to, ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexane, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Suitable monomers for preparing copolymers disclosed herein also include cycloolefins having 3 to 30, 3 to 20 carbon atoms, or 3 to 12 carbon atoms. Examples of usable cycloolefins include, but are not limited to, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and 2-methyl-1,4,5,8-dimethyl-1,2,3,4,4a,5,8,8a-octahydronaphthalene. Suitable monomers for preparing the copolymers disclosed herein also include dienes and polyolefins having 3 to 30, 3 to 20, or 3 to 12 carbon atoms. Examples of dienes and polyolefins that can be used include, but are not limited to, butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinyl norbornene, dicyclopentadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, and 5,9-dimethyl-1,4,8-decatriene.In another aspect, aromatic vinyl compounds also constitute suitable monomers for preparing the copolymers disclosed herein, examples of which include, but are not limited to, monoalkylstyrenes or polyalkylstyrenes (including styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-dimethylstyrene, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene and p-ethylstyrene), and derivatives containing functional groups, such as methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene, 3-phenylpropylene, 4-phenylpropylene and α-methylstyrene, vinyl chloride, 1,2-difluoroethylene, 1,2-dichloroethylene, tetrafluoroethylene and 3,3,3-trifluoro-1-propylene, provided that the monomers are polymerizable under the conditions used.

[0085] In addition, in one aspect, suitable monomers or monomer mixtures suitable for combination with at least the composition of formula (I) disclosed herein include ethylene; propylene; mixtures of ethylene and one or more monomers selected from propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and styrene; and mixtures of ethylene, propylene and conjugated or non-conjugated dienes. In this aspect, the copolymer or interpolymer may contain two or more intramolecular regions comprising different chemical or physical properties, particularly regions that distinguish comonomer incorporation, which are connected in a dimeric, linear, branched or multi-branched polymer structure. The polymer can be prepared by varying the polymerization conditions during the polymerization of the composition comprising formula (I), for example by using two reactors with different comonomer ratios, a variety of catalysts with different comonomer incorporation capabilities, or a combination of the process conditions, and optionally a multifunctional coupling agent.

[0086] Polymer products

[0087] As disclosed herein, polymer product refers to the polymer product after polymerization, which is usually chemically treated to consume the reactive metal alkyl and release the polymer product no longer attached to the transition or main group metal. This method includes hydrolysis with water to produce saturated polymer end groups. Alternatively, various organic or inorganic reagents can be added to consume the metal alkyl and produce reactive functional end groups on the polymer chain.

[0088] The polymers produced by the methods of the present disclosure can be used in a variety of products and end-use applications. The resulting polymers can be homopolymers and copolymers of ethylene and propylene and include linear low density polyethylene, elastomers, plastomers, high density polyethylene, medium density polyethylene, low density polyethylene, polypropylene and polypropylene copolymers. The propylene-based polymers produced include isotactic polypropylene, atactic polypropylene, and random, block or impact copolymers.

[0089] Using the polymerization method disclosed herein, it is easy to prepare a novel polymer composition comprising a block copolymer of one or more olefin monomers having a molecular weight distribution of the present invention. Exemplary polymers include at least one monomer selected from ethylene, propylene and 4-methyl-1-pentene in polymerized form. Illustratively, the polymer is a block copolymer comprising ethylene, propylene or 4-methyl-1-pentene in polymerized form and at least one different C 2-20 Interpolymers of alpha-olefin comonomers and optionally one or more additional copolymerizable comonomers. Suitable comonomers are selected from dienes, cyclic olefins and cyclic dienes, halogenated vinyl compounds, vinylidene aromatic compounds and combinations thereof. Exemplary polymers are interpolymers of ethylene with propylene, 1-butene, 1-hexene or 1-octene. Illustratively, based on the total weight of the polymer, the polymer composition disclosed herein has an ethylene content of 1 to 99 percent, a diene content of 0 to 10 percent, and a styrene and / or C3-8 alpha-olefin content of 99 to 1 percent. According to conventional GPC methods, the polymers disclosed herein may have a weight average molecular weight (Mw) of 500 to 2,500,000. Typically, the polymers of the present disclosure have a weight average molecular weight (Mw) of 500 to 250,000 (eg, 2,000 to 150,000, 3,000 to 100,000, 1,000 to 25,000, 5,000 to 25,000, etc.) according to conventional GPC methods.

[0090] The polymers prepared according to the present disclosure may have a melt index, I2, of 0.01 to 2000 g / 10 minutes, typically 0.01 to 1000 g / 10 minutes, more typically 0.01 to 500 g / 10 minutes, and especially 0.01 to 100 g / 10 minutes, according to ASTM D-792, Method B. Desirably, the polymers of the present disclosure may have a molecular weight, Mw, of 1,000 g / mol to 5,000,000 g / mol, typically 1000 g / mol to 1,000,000 g / mol, more typically 1000 g / mol to 500,000 g / mol, and especially 1,000 g / mol to 300,000 g / mol, according to conventional GPC methods.

[0091] The density of the polymers of the present disclosure may range from 0.80 to 0.99 g / cc according to ASTM D-792, Method B, and for ethylene containing polymers, may typically range from 0.85 to 0.97 g / cc (e.g., 0.853 to 0.970 g / cc).

[0092] The polymers according to the present disclosure can be distinguished from conventional random copolymers, physical blends of polymers, and block copolymers prepared via sequential monomer addition, rheological catalysts, or by anionic or cationic living polymerization techniques, particularly by their narrow molecular weight distribution. In this regard, for example, the polymer composition prepared according to the present disclosure can be characterized by a polydispersity index (PDI) of 1.5 to 10.0 (e.g., 2.0 to 8.0, 2.0 to 6.0, 2.0 to 5.0, 2.0 to 4.0, etc.). For example, the polydispersity index (PDI) of the polymer composition can be 1.5 to 2.8, 1.5 to 2.5, or 1.5 to 2.3.

[0093] If present, the individual regions or blocks within each polymer are relatively uniform, depending on the consistency of the reactor conditions, and are chemically distinct from each other. That is, the comonomer distribution, stereoisomerism, or other characteristics of the segments in the polymer are relatively consistent within the same block or segment. However, the average block length can be a narrow distribution, but is not required to be so. The average block length can also be the largest possible distribution.

[0094] Illustratively, these interpolymers may be characterized in that the terminal blocks or segments of the polymer have a higher stereoisomerism or crystallinity than at least some of the remaining blocks or segments.Illustratively, the polymer may be a triblock copolymer containing a central polymer block or segment that is relatively amorphous or even elastomeric.

[0095] In another aspect of the present disclosure, a polymer composition is provided, which includes: (1) an organic or inorganic polymer, preferably a homopolymer of ethylene or propylene and / or a copolymer of ethylene or propylene with one or more copolymerizable comonomers, and (2) a polymer or a combination of polymers prepared according to the present disclosure or according to the method disclosed herein.

[0096] The polymer product comprises a combination of two or more polymers comprising regions or segments (blocks) having different chemical compositions. In addition, at least one of the components of the polymer combination may contain a linking group, which is a residue of the composition of formula (I), so that the polymer has certain physical properties.

[0097] Various additives can be effectively incorporated into the compositions of the present invention in amounts that do not detract from the properties of the resulting composition. These additives include, for example, reinforcing agents, fillers including conductive and non-conductive materials, flame retardant additives, antioxidants, heat and light stabilizers, colorants, extenders, crosslinking agents, foaming agents, plasticizers, flame retardants, anti-drip agents, lubricants, slip additives, anti-caking agents, anti-degradants, softeners, waxes, pigments, and the like, including combinations thereof.

[0098] The resulting polymer may be a block interpolymer characterized by an average block index, for example, as discussed in U.S. Pat. Nos. 7,947,793, 7,897,698, and 8,293,859. The resulting polymer may be a block composite characterized by a block composite index, for example, as discussed in U.S. Pat. Nos. 8,563,658, 8,476,366, 8,686,087, and 8,716,400. The resulting polymer may be a crystalline block composite characterized by a crystalline block composite index, for example, as discussed in U.S. Pat. Nos. 8,785,554, 8,822,598, and 8,822,599. The resulting polymer may be a specific block composite characterized by a microstructure index, for example, as discussed in WO2016 / 028957. The resulting polymer may be a specific block composite that can be characterized by a modified block composite index, for example, as discussed in WO2016 / 028970.

[0099] In certain embodiments, the methods for preparing the compositions of formula (I) can be combined with functionalization chemistry to develop telechelic polymers. In certain embodiments, the compositions of formula (I) can generate and grow telechelic polymer chains bonded at both ends to the compositions of formula (I); subsequent conversion of the terminal polymer group-metal bonds to the desired diterminal functional groups can then occur to form telechelic polymers.

[0100] The application of the method for preparing the composition of formula (I) of the present disclosure in combination with the functionalization chemistry is by no means limited to the production of telechelic polymers and the above examples. In certain embodiments, the method for preparing the composition of formula (I) of the present disclosure can be combined with, for example, coordination chain transfer polymerization to produce functionalized polyolefins.

[0101] The polymers of the present disclosure may be blended and / or coextruded with any other polymer. Non-limiting examples of other polymers include linear low density polyethylene, elastomers, plastomers, high pressure low density polyethylene, high density polyethylene, isotactic polypropylene, ethylene propylene copolymers, and the like.

[0102] The polymers and blends thereof prepared by the process of the present disclosure are suitable for such forming operations as film, sheet and fiber extrusion and coextrusion as well as blow molding, injection molding, rotational molding. The films include blown or cast films formed by coextrusion or by lamination, suitable for use as shrink films, cling films, stretch films, sealing films or oriented films.

[0103] Examples

[0104] method

[0105] 1 H NMR: 1H NMR spectra were recorded on a Bruker AV-400 spectrometer at ambient temperature. 1 The H NMR chemical shift was set at 7.16 ppm (C6D5H).

[0106] 13 C NMR: The polymer spectra were collected using a Bruker 400 MHz spectrometer equipped with a Bruker Dual DUL high-temperature and low-temperature probe. 13 C NMR spectroscopy. The polymer samples were prepared by adding approximately 2.6 g of a 50 / 50 mixture of tetrachloroethane-d2 / o-dichlorobenzene containing 0.025 M chromium triacetylacetonate (relaxant) to 0.2 g of polymer in a 10 mm NMR tube. The sample was dissolved and homogenized by heating the tube and its contents to 150° C. Data were acquired using 320 scans / data file at a sample temperature of 120° C. with a pulse repetition delay of 7.3 seconds.

[0107] GC / MS: Combined gas chromatography / low resolution mass spectrometry analysis using electron impact ionization (EI) was performed at 70 eV on an Agilent Technologies 6890N series gas chromatograph equipped with an Agilent Technologies 5975 Inert XL mass selective detector and an Agilent Technologies capillary column (HP1MS, 15 m x 0.25 mm, 0.25 micron) with respect to:

[0108] Programming method:

[0109] Oven equilibration time 0.5min

[0110] 50℃ for 0min

[0111] Then, heat at 25°C / min to 200°C for 5 minutes

[0112] Running time: 11 minutes

[0113] GPC:The gel permeation chromatography system consists of a Polymer Laboratories model PL-210 or a Polymer Laboratories model PL-220 instrument. The column and transfer chamber are operated at 140°C. Three Polymer Laboratories 10 micron Mixed-B columns are used. The solvent is 1,2,4-trichlorobenzene. The sample is prepared at a concentration of 0.1 gram of polymer in 50 milliliters of a solvent containing 200 ppm of butylated hydroxytoluene (BHT). The sample is prepared by gently stirring at 160°C for 2 hours. The injection volume used is 100 microliters and the flow rate is 1.0 ml / min.

[0114] The GPC column set was calibrated using 21 narrow molecular weight distribution polystyrene standards with molecular weights ranging from 580 to 8,400,000, arranged in a mixture of 6 "cocktails" with individual molecular weights differing by at least a factor of ten. The standards were purchased from Polymer Laboratories (Shropshire, UK). The polystyrene standards were prepared at 0.025 g in 50 mL of solvent for molecular weights equal to or greater than 1,000,000 and 0.05 g in 50 mL of solvent for molecular weights less than 1,000,000. Gently stir at 80°C for 30 minutes to allow the polystyrene standards to dissolve. The narrow standards mixture was run first and in order of decreasing highest molecular weight component to minimize degradation. The polystyrene standard peak molecular weights were converted to polyethylene molecular weights using the following equation (as described by Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)): M 聚丙烯 =0.431(M 聚苯乙烯 ) Polyethylene equivalent molecular weight calculations were performed using Viscotek TriSEC software version 3.0.

[0115] Molecular Weight: Molecular weight is determined by optical analytical techniques, including deconvolution gel permeation chromatography coupled with a low angle laser light scattering detector (GPC-LALLS), as described by Rudin, A., "Modern Methods of Polymer Characterization", John Wiley & Sons, New York (1991) pp. 103-112.

[0116] Material

[0117] Unless otherwise stated, all performance of the examples discussed herein was performed under an inert atmosphere using dry box techniques.

[0118] The following materials were obtained from Sigma-Aldrich and purified as needed before use: diisobutylaluminum hydride (DIBAL-H); triisobutylaluminum (TIBA); 1,2,4-trivinylcyclohexane (TVCH); 1,9-decadiene; 1,7-octadiene; 3-methyl-1,4-pentadiene; p-xylene; C6D6; toluene; methanol; hexane; benzene; and D2O. 1,3-divinylcyclopentane was prepared according to the method published in Designed Monomers and Polymers, 2004, 7, 661-676.

[0119] Example 1

[0120] In a nitrogen-filled dry box, TVCH (0.324 mL, 1.67 mmol) and DIBAL-H (5 mL of a 1 M solution in hexane, 5 mmol) were mixed in a capped scintillation vial with a stirring bar. This mixture was heated to 70°C and kept stirring for 21 hours, and a small needle was inserted through the septum cap for ventilation. The reaction proceeded as expected (see non-limiting reaction scheme 1) to form a double-headed organoaluminum composition. To confirm the reaction, a sample (about 0.1 mL) was mixed with C6D6 (0.5 mL) for 1 H NMR ( Figure 1 ), which showed that all vinyl groups were consumed. Another sample was quenched with H2O and the organic phase was analyzed by GC / MS ( Figure 2A ), GC / MS showed a set of clean peaks at m / z = 166. A third sample was quenched with D2O and analyzed by GC / MS ( Figure 2B ), GC / MS showed the peak shifted to m / z=168. Figure 2A and 2B The peak and Figure 3 The multiplicity of peaks is due to the presence of multiple chiral centers in the structure.

[0121]

[0122] Example 2

[0123] In a nitrogen filled dry box, TIBA (1 mL, 3.96 mmol) and 1,9-decadiene (0.55 mL, 2.97 mmol) were mixed in 2 mL of p-xylene in a capped scintillation vial with a stirring bar. This mixture was heated to 130°C and kept stirring for 2 hours, and a small needle was inserted through the septum cap for ventilation. The reaction proceeded as expected (see non-limiting reaction scheme 2) to form a double-headed organoaluminum composition (the product structure shown in scheme 2 represents the average composition). To confirm the reaction, a sample was removed and mixed with C6D6 (0.5 mL) for 1 H NMR, which showed a reduction in the vinyl groups of 1,9-decadiene. Figure 4 As seen in FIG. 1 , a sample was also hydrolyzed and analyzed by GC / MS, which showed a clean peak at m / z 142, consistent with the expected hydrolysis product of the double-headed organoaluminum composition.

[0124]

[0125] Example 3

[0126] In a nitrogen-filled dry box, DIBAL-H (0.5 g, 3.5 mmol) and 1,7-octadiene (0.39 mL, 2.6 mmol) were mixed in 5 mL of p-xylene in a capped scintillation vial with a stirring bar. This mixture was heated to 70°C and kept stirring for 3 hours, then heated to 130°C and kept stirring for 1 hour; a needle was inserted through the septum cap for ventilation. The reaction proceeded as expected (see non-limiting reaction scheme 3) to form a double-headed organoaluminum composition (the product structure shown in scheme 3 represents the average composition). To confirm the reaction, a sample of the mixture was taken for 1 H NMR analysis. 1 H NMR showed that the vinyl groups of 1,7-octadiene were completely consumed. In addition, a sample of the mixture was hydrolyzed and analyzed by GC / MS, which showed a clean peak at m / z 114, which was consistent with the expected hydrolysis product of the double-headed organoaluminum composition.

[0127]

[0128] Example 4

[0129] In a nitrogen-filled dry box, solvent-free DIBAL-H (4.0 g, 28.13 mmol) and 3-methyl-1,4-pentadiene (1.72 mL, 14.06 mmol, d=0.673) were mixed in 12 mL of p-xylene in a capped scintillation vial with a stirring bar. This mixture was heated to 60°C and kept stirring for 14 hours, and a needle was inserted through the septum cap for ventilation. The reaction proceeded as expected (see non-limiting reaction scheme 4) to form a double-headed organoaluminum composition. To confirm the reaction, an aliquot of the mixture was diluted with C6D6, hydrolyzed with water, and passed through 1 H NMR analysis ( Figure 5 ). 1 H NMR showed the expected hydrolysis products of the double-headed organoaluminum composition, isobutane and 3-methylpentane. Note: This reaction can also be carried out in toluene or without solvent.

[0130]

[0131] Example 5

[0132] In a nitrogen-filled dry box, solvent-free DIBAL-H (1.00 mL, 5.61 mmol, d = 0.798) and 1,3-divinylcyclopentane solution (30.9 wt% in toluene, 1.11 g, 2.81 mmol) were mixed in a capped scintillation vial with a stirring bar. This mixture was heated to 90°C and kept stirring for 18 hours. The reaction proceeded as expected (see non-limiting reaction scheme 5) to form a double-headed organoaluminum composition. To confirm the reaction, an aliquot of the mixture was diluted with C6D6, hydrolyzed with 10 wt% NaOD in D2O, and filtered by 1 H NMR and 13 C NMR analysis. 1 H NMR and 13 C NMR showed the expected hydrolysis product of the double-headed organoaluminum composition, 1,3-bis(ethyl-2-d)cyclopentane. The hydrolyzed sample was also analyzed by GC / MS, which showed a clean peak at m / z 128, which was consistent with the expected hydrolysis product of the double-headed organoaluminum composition.

[0133]

Claims

1. A composition having formula (I): in: n is a number from 1 to 100; Y is a linear, branched or cyclic C4 to C 100 A linking group consisting of an alkylene group, the alkylene group optionally containing at least one heteroatom and being aliphatic or aromatic, wherein Y includes two points of attachment to the Al atom, and at least one of the two points of attachment is -CH2-; Each J group is independently hydrogen or substituted or unsubstituted acyclic alkyl; and Two J groups attached to the same Al atom may optionally be covalently linked together.

2. The composition according to claim 1, wherein Y has formula (II): -CH2CH2(CHR1) m CH2CH2-(II), wherein: R1 is hydrogen or C1 to C 20 alkyl or aryl; and m is a number from 0 to 20.

3. The composition according to claim 1, having the formula: wherein n is a number from 1 to 100, each J group is independently hydrogen or a substituted or unsubstituted acyclic alkyl group, and two J groups attached to the same Al atom may be optionally covalently linked together.

4. The composition according to claim 1, having the formula: wherein n is a number from 1 to 100, each J group is independently hydrogen or a substituted or unsubstituted acyclic alkyl group, and two J groups attached to the same Al atom may be optionally covalently linked together.

5. A composition according to any one of the preceding claims, wherein each J is hydrogen or C1 to C 20 Acyclic alkyl.

6. A composition according to any one of the preceding claims, wherein n is a number from 1 to 10.

7. A composition according to any one of the preceding claims, wherein n is a number from 1 to 3.

8. A method for preparing an organoaluminum composition, the method comprising: (a) combining an aluminum compound, a linker and optionally a solvent at a temperature of 25°C to 200°C, and (b) obtaining the organoaluminum composition, wherein: The aluminum compound has the formula Al(J)3, wherein each J group is independently hydrogen or a substituted or unsubstituted acyclic alkyl group, and optionally, two J groups can be covalently linked together; and the linker is C4 to C 100 A hydrocarbon comprising at least two vinyl groups or one vinyl group and a cycloolefin group, and optionally containing at least one heteroatom.

9. The method of claim 8, wherein the linker is an α,ω-diene.

10. The method of claim 8, wherein the linker is 1,2,4-trivinylcyclohexane.

11. The method of claim 8, wherein the linker is 1,3-divinylcyclopentane.

12. An organoaluminum composition comprising the reaction product of: an aluminum compound, a linker, and optionally a solvent, wherein: The aluminum compound has the formula Al(J)3, wherein each J group is independently hydrogen or a substituted or unsubstituted acyclic alkyl group, and optionally, two J groups attached to the same Al atom may be covalently linked together; and The linker is C4 to C 100 A hydrocarbon comprising at least two vinyl groups or one vinyl group and a cycloolefin group, and optionally containing at least one heteroatom.

13. The composition of claim 12, wherein the linker is an α,ω diene.

14. The composition of claim 12, wherein the linker is 1,2,4-trivinylcyclohexane.

15. The composition of claim 12, wherein the linker is 1,3-divinylcyclopentane.

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