FOR PREPARING THE SAME CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] The present application claims the benefit of priority to U.S. provisional patent application no. 62/644,664, filed on March 19, 2018, which is hereby incorporated by reference in its entirety.

FIELD

[0002] Embodiments relate to silicon-terminated organo-metal compositions and processes for preparing the same.

BACKGROUND

[0003] In recent years, advances in polymer design have been seen with the use of compositions capable of chain shuttling and/or chain transfer. For example, chain shuttling agents having reversible or partial reversible chain transfer ability with transition metal catalysts have enabled the production of novel olefin block copolymers (OBCs). Typical compositions capable of chain shuttling and/or chain transfer are simple metal alkyls, such as diethyl zinc and triethyl aluminum. Upon polymerization of a chain shuttling agent, polymeryl-metal intermediates can be produced, including but not limited to compounds having the formula Q ₂ Zn or Q3AI, with Q being an oligo- or polymeric substituent. These polymeryl-metal intermediates can enable the synthesis of novel end-functional polyolefins, including novel silicon-terminated organo-metal compositions.

SUMMARY

[0004] In certain embodiments, the present disclosure relates to a silicon-terminated organo- metal composition comprising a compound of formula (I):

wherein:

MB is a trivalent metal selected from the group consisting of Al, B, and Ga;

each Z is independently a substituted or unsubstituted divalent Ci to C ₂₀ hydrocarbyl group that is linear, branched, or cyclic;

each subscript m is a number from 1 to 100,000; each J is independently a hydrogen atom or a monovalent Ci to C20 hydrocarbyl group;

each R ^A , R ^B , and R ^c is independently a hydrogen atom, a substituted or unsubstituted Ci to C10 monovalent hydrocarbyl group that is linear, branched, or cyclic, a vinyl group, an alkoxy group, or one or more siloxy units selected from M, D, and T units:

unit), wherein each

R is independently a hydrogen atom, a substituted or unsubstituted Ci to C10 monovalent hydrocarbyl group that is linear, branched, or cyclic, a vinyl group, or an alkoxy group; two or all three of R ^A , R ^B , and R ^c of one silicon atom may optionally be bonded together to form a ring structure when two or all three of R ^A , R ^B , and R ^c of one silicon atom are each independently one or more siloxy units selected from D and T units.

[0005] In certain embodiments, the present disclosure relates to a process for preparing a sili con-terminated organo-metal composition comprising combining starting materials at an elevated temperature, wherein the starting materials comprise:

(A) a vinyl-terminated silicon-based compound; and

(B) a chain shuttling agent, thereby obtaining a product comprising the silicon- terminated organo-metal composition.

[0006] In certain embodiments, the starting materials of the process may further comprise optional materials, such as (C) a solvent.

BRIEF DESCRIPTION OF DRAWINGS

[0007] FIG. 1 is the ¾ NMR spectra of Example 1.

[0008] FIG. 2 is the GCMS spectrum of Example 1.

[0009] FIG. 3 is the ¹³ C NMR of Example 2.

[0010] FIG. 4 is the ¾ NMR spectrum of Example 2.

[0011] FIG. 5 is the GPC of Example 2.

DETAILED DESCRIPTION

[0012] The present disclosure is directed to a process for preparing a silicon-terminated organo-metal composition, the process comprising 1) combining starting materials comprising (A) a vinyl-terminated silicon-based compound and (B) a chain shuttling agent. In farther embodiments, the starting materials of the process may further comprise (C) a solvent and any other optional materials.

[0013] Step 1) of combining the starting materials may be performed by any suitable means, such as mixing at elevated temperatures. In certain embodiments, step 1) of combining the starting materials may be conducted at a temperature of from 50 °C to 200 °C, or from 60 °C to 200 °C, or from 80 °C to 180 °C or from 100 °C to 150 °C, at ambient pressure. Heating may be performed under inert, dry conditions. In certain embodiments, step 1) of combining the starting materials may be performed for a duration of from 30 minutes to 20 hours, or from 30 minutes to 15 hours, or from 1 hour to 10 hours. In further embodiments, step 1) of combining the starting materials may be performed by solution processing (i.e., dissolving and/or dispersing the starting materials in a (C) solvent and heating) or melt extrusion (e.g., when a (C) solvent is not used or is removed during processing).

[0014] The process may optionally further comprise one or more additional steps. For example, the process may further comprise: 2) recovering the silicon-terminated telechelic polyolefin composition. Recovering may be performed by any suitable means, such as precipitation and filtration, thereby removing unwanted materials.

[0015] The amount of each starting material depends on various factors, including the specific selection of each starting material.

(A) Vinyl-terminated Silicon-based Compound

[0016] Starting material (A) of the present process may be a vinyl-terminated silicon-based compound having the formula (P):

(P), wherein:

Z is a substituted or unsubstituted divalent Ci to C ₂₀ hydrocarbyl group that is linear, branched, or cyclic;

R ^A , R ^B , and R ^c are each independently a hydrogen atom, a substituted or unsubstituted Ci to Cio monovalent hydrocarbyl group that is linear, branched, or cyclic, a vinyl group, an alkoxy group, or one or more siloxy units selected from M, D, and T units: (T unit), wherein each

R is independently a hydrogen atom, a substituted or unsubstituted Ci to Cio monovalent hydrocarbyl group that is linear, branched, or cyclic, a vinyl group, or an alkoxy group; and two or all three of R ^A , R ^B , and R ^c may optionally be bonded together to form a ring structure when two or all three of R ^A , R ^B , and R ^c are each independently one or more siloxy units selected from D and T units.

[0017] In certain embodiments of the vinyl-terminated silicon-based compound having the formula (P), at least one of R ^A , R ^B , and R ^c is a hydrogen atom or a vinyl group. In further embodiments, each of at least two of R ^A , R ^B , and R ^c is a linear Ci to Cio monovalent hydrocarbyl group. In further embodiments, Z is an unsubstituted divalent Ci to C ₂₀ hydrocarbyl group that is linear or branched.

[0018] Suitable vinyl-terminated silicon-based compounds include but are not limited to 7- octenylsilane, 7-octenyldimethylvinylsilane, and the like.

(B) Chain Shuttling Agent

[0019] Starting material (B) of the present process may be a chain shuttling agent having the formula Y ₃ MB, where MB may be a trivalent metal atom, and each X is independently a hydrocarbyl group of 1 to 20 carbon atoms. In certain embodiments, MB may be but is not limited to Al, B, or Ga. In further embodiments, MB may be Al. The monovalent hydrocarbyl group of 1 to 20 carbon atoms may be alkyl group exemplified by ethyl, propyl, octyl, and combinations thereof. Suitable chain shuttling agents include those disclosed in U.S. Patent Nos. 7,858,706 and 8,053,529, which are hereby incorporated by reference.

[0020] Suitable chain shuttling agents include but are not limited to trimethyl aluminum, triethyl aluminum, tripropyl aluminum, tributyl aluminum, triisobutyl aluminum, trihexyl aluminum, triisohexyl aluminum, trioctyl aluminum, triisooctyl aluminum, , tripentyl aluminum, tridecyl aluminum, tribranched alkyl aluminums, tricycloalkyl aluminums, triphenyl aluminum, tritolyl aluminum, dialkyl and aluminum hydrides.

(C) Solvent

[0021] Starting material (C) of the present process may optionally be used in step 1) of the process described above. The solvent may be a hydrocarbon solvent such as an aromatic solvent or an isoparaffinic hydrocarbon solvent. Suitable solvents include but are not limited to a non-polar aliphatic or aromatic hydrocarbon solvent selected from the group of pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclopentane,

methylcyclopentane, cyclohexane, methylcyclohexane, cycloheptane, cyclooctane, decalin, benzene, toluene, xylene, an isoparaffinic fluid including but not limited to Isopar^M , IsoparTM G, IsoparTM H, Isopar^M L IsoparTM M, a dearomatized fluid including but not limited to ExxsolTM p> _or isomers and mixtures of two or more thereof. Alternatively, the solvent may be toluene and/or IsoparTM E. The amount of solvent added depends on various factors including the type of solvent selected and the process conditions and equipment that will be used.

Product and Polymerization

[0022] The present process described herein results a silicon-terminated organo-metal composition comprising a compound of formula (I):

wherein:

MB is a trivalent metal selected from the group consisting of Al, B, and Ga;

each Z is independently a substituted or unsubstituted divalent Ci to C20 hydrocarbyl group that is linear, branched, or cyclic;

each subscript m is a number from 1 to 100,000;

each J is independently a hydrogen atom or a monovalent Ci to C ₂₀ hydrocarbyl group;

each R ^A , R ^B , and R ^c is independently a hydrogen atom, a substituted or unsubstituted Ci to C10 monovalent hydrocarbyl group that is linear, branched, or cyclic, a vinyl group, an alkoxy group, or one or more siloxy units selected from M, D, and T units:

^ (M unit) ^ (D unit) ® (T unit), wherein each

R is independently a hydrogen atom, a substituted or unsubstituted Ci to C10 monovalent hydrocarbyl group that is linear, branched, or cyclic, a vinyl group, or an alkoxy group; two or all three of R ^A , R ^B , and R ^c of one silicon atom may optionally be bonded together to form a ring structure when two or all three of R ^A , R ^B , and R ^c of one silicon atom are each independently one or more siloxy units selected from D and T units.

[0023] In certain embodiments of formula (I), MB is Al. In certain embodiments, each subscript m is a number from 1 to 75,000, from 1 to 50,000, from 1 to 25,000, from 1 to 15,000, from 1 to 10,000, from 1 to 5,000, from 1 to 2,500, or from 1 to 1,000. In certain embodiments, each J is a hydrogen atom. In certain embodiments, each Z is an unsubstituted Cl to C 10 divalent hydrocarbyl group that is linear.

[0024] In certain embodiments, at least one of R ^A , R ^B , and R ^c of each silicon atom may be a hydrogen atom or a vinyl group. In further embodiments, each of at least two of R ^A , R ^B , and R ^c of each silicon atom may be a linear Ci to C10 monovalent hydrocarbyl group. In further embodiments, each of at least two of R ^A , R ^B , and R ^c of each silicon atom may be a methyl group.

[0025] Examples of the -SiR ^A R ^B R ^c groups of the compounds of formulas (I) and (II) include but are not limited to the following, where the squiggly line " ^L< denotes the attachment of the group to the Z group of the compounds of formulas (I) and (P).

, | ₂ o ,

[0026] In farther embodiments, the process for preparing the silicon-terminated organo-metal composition of the present disclosure may be followed by a subsequent polymerization step to form a silicon terminated polymeryl-metal, which still falls under the definition of the sili con-terminated organo-metal composition of the present disclosure. Specifically, the sili con-terminated organo-metal of the present disclosure may be combined with a procatalyst, an activator, at least one olefin monomer, and optional materials, such as solvents and/or scavengers. Such a polymerization step will be performed under polymerization process conditions known in the art, including but not limited to those disclosed in U.S.

Patent No 7,858,706 and U.S. Patent No. 8,053,529. Such a polymerization step essentially increases the subscript m in the formula (I).

[0027] The procatalyst may be any compound or combination of compounds capable of, when combined with an activator, polymerization of unsaturated monomers. Suitable procatalysts include but are not limited to those disclosed in WO 2005/090426, WO

2005/090427, WO 2007/035485, WO 2009/012215, WO 2014/105411, WO 2017/173080, 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.

[0028] Suitable procatalysts include but are not limited to the following structures labeled as procatalysts (Al) to (A8):

[0029] Procatalysts (Al) and (A2) may be prepared according to the teachings of WO 2017/173080 Al or by methods known in the art. Procatalyst (A3) may be prepared according to the teachings of WO 03/40195 and U.S. Patent No. 6,953,764 B2 or by methods known in the art. Procatalyst (A4) may be prepared according to the teachings of

Macromolecules (Washington, DC, United States), 43(19), 7903-7904 (2010) or by methods known in the art. Procatalysts (A5), (A6), and (A7) may be prepared according to the teachings of WO 2018/170138 Al or by methods known in the art. Procatalyst (A8) may be prepared according to the teachings of WO 2011/102989 Al or by methods known in the art.

[0030] The activator may be any compound or combination of compounds capable of activating a procatalyst to form an active catalyst composition or system. Suitable activators include but are not limited to Brpnsted acids, Lewis acids, carbocationic species, or any activator known in the art, including but limited to those disclosed in WO 2005/090427 and U.S. Patent No. 8,501,885 B2. In exemplary embodiments of the present disclosure, the co catalyst is [(Ci6-i8H33-37)2CH3NH] tetrakis(pentafluorophenyl)borate salt.

[0031] Suitable monomers for the polymerization step include any addition polymerizable monomer, generally any olefin or diolefin monomer. Suitable monomers can be linear, branched, acyclic, cyclic, substituted, or unsubstituted. In one aspect, the olefin can be any a- olefin, including, for example, ethylene and at least one different copolymerizable comonomer, propylene and at least one different copolymerizable comonomer having from 4 to 20 carbons, or 4-methyl- l-pentene and at least one different copolymerizable comonomer having from 4 to 20 carbons. Examples of suitable monomers include, but are not limited to, straight-chain or branched a-olefins having from 2 to 30 carbon atoms, from 2 to 20 carbon atoms, or from 2 to 12 carbon atoms. Specific examples of suitable monomers include, but are not limited to, ethylene, propylene, 1 -butene, l-pentene, 3-methyl- 1 -butene, 1 -hexane, 4- methyl-l-pentene, 3-methyl- l-pentene, l-octene, l-decene, l-dodecene, l-tetradecene, 1- hexadecene, l-octadecene, and l-eicosene. Suitable monomers also include cycloolefins having from 3 to 30, from 3 to 20 carbon atoms, or from 3 to 12 carbon atoms. Examples of cycloolefins that can be used include, but are not limited to, cyclopentene, cycloheptene, norbomene, 5-methyl-2-norbomene, tetracyclododecene, and 2-methyl- 1,4, 5, 8-dimethano- l,2,3,4,4a,5,8,8a-octahydronaphthalene. Suitable monomers also include di- and poly-olefins having from 3 to 30, from 3 to 20 carbon atoms, or from 3 to 12 carbon atoms. Examples of di- and poly-olefins that can be used include, but are not limited to, butadiene, isoprene, 4- methyl-l,3-pentadiene, l,3-pentadiene, l,4-pentadiene, l,5-hexadiene, l,4-hexadiene, 1,3- hexadiene, l,3-octadiene, l,4-octadiene, l,5-octadiene, l,6-octadiene, l,7-octadiene, ethylidene norbomene, vinyl norbomene, dicyclopentadiene, 7-methyl- l,6-octadiene, 4- ethylidene-8-methyl-l,7-nonadiene, and 5,9-dimethyl-l,4,8-decatriene. In a further aspect, aromatic vinyl compounds also constitute suitable monomers for preparing the copolymers disclosed here, examples of which include, but are not limited to, mono- or poly- alkylstyrenes (including styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p- dimethylstyrene, o-ethylstyrene, m-ethylstyrene and p-ethylstyrene), and functional group- containing derivatives, such as methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene, 3-phenylpropene, 4-phenylpropene and a-methylstyrene, vinylchloride, 1,2- difluoroethylene, l,2-dichloroethylene, tetrafluoroethylene, and 3,3,3-trifluoro-l-propene, provided the monomer is polymerizable under the conditions employed.

[0032] Silicon-terminated organo-metals prepared as described above followed by a polymerization step include but are not limited to silicon-terminated-tri-polyethylene aluminum, silicon-terminated-tri-poly(ethylene/octene) aluminum, and mixtures thereof.

[0033] Any subsequent polymerization step to prepare the silicon-terminated organo-metal composition of the present disclosure may be followed by hydrolysis or use of alcohol to remove the metal resulting in a silicon-terminated polymer.

[0034] The silicon-terminated organo-metal composition may include any or all

embodiments disclosed herein. Industrial Applicability

[0035] The present disclosure and below examples show inventive processes for preparing inventive silicon-terminated organo-metal compositions. These inventive silicon-terminated organo-metal compositions may be used in a variety of commercial applications, including facilitation of further functionalization or preparation of subsequent polymers, such as telechelic polymers.

Definitions

[0036] All references to the Periodic Table of the Elements refer to the Periodic Table of the Elements published and copyrighted by CRC Press, Inc., 1990. Also, any references to a Group or Groups shall be to the Group or Groups reflected in this Periodic Table of the Elements using the IUPAC system for numbering groups. Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percentages are based on weight and all test methods are current as of the filing date of this disclosure. For purposes of United States patent practice, the contents of any referenced patent, patent application or publication are incorporated by reference in their entirety (or its equivalent U.S. version is so incorporated by reference in its entirety), especially with respect to the disclosure of synthetic techniques, product and processing designs, polymers, catalysts, definitions (to the extent not inconsistent with any definitions specifically provided in this disclosure), and general knowledge in the art.

[0037] Number ranges in this disclosure are approximate and, thus, may include values outside of the ranges unless otherwise indicated. Number ranges include all values from and including the lower and the upper values, including fractional numbers or decimals. The disclosure of ranges includes the range itself and also anything subsumed therein, as well as endpoints. For example, disclosure of a range of 1 to 20 includes not only the range of 1 to 20 including endpoints, but also 1, 2, 3, 4, 6, 10, and 20 individually, as well as any other number subsumed in the range. Furthermore, disclosure of a range of, for example, 1 to 20 includes the subsets of, for example, 1 to 3, 2 to 6, 10 to 20, and 2 to 10, as well as any other subset subsumed in the range.

[0038] Similarly, the disclosure of Markush groups includes the entire group and also any individual members and subgroups subsumed therein. For example, disclosure of the Markush group a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group, includes the member alkyl individually; the subgroup hydrogen, alkyl and aryl; the subgroup hydrogen and alkyl; and any other individual member and subgroup subsumed therein. [0039] In the event the name of a compound herein does not conform to the structural representation thereof, the structural representation shall control.

[0040] The term“comprising” and derivatives thereof means including and is not intended to exclude the presence of any additional component, starting material, step or procedure, whether or not the same is disclosed therein.

[0041] The terms "group," "radical," and "substituent" are also used interchangeably in this disclosure.

[0042] The term“hydrocarbyl” means groups containing only hydrogen and carbon atoms, where the groups may be linear, branched, or cyclic, and, when cyclic, aromatic or non aromatic.

[0043] The term "substituted" means that a hydrogen group has been replaced with a hydrocarbyl group, a heteroatom, or a heteroatom containing group. For example, methyl cyclopentadiene (Cp) is a Cp group substituted with a methyl group and ethyl alcohol is an ethyl group substituted with an -OH group.

[0044]“Catalyst precursors” include those known in the art and 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. The terms“transition metal catalysts,”“transition metal catalyst precursors,”“catalysts,”“catalyst precursors,”“polymerization catalysts or catalyst precursors,”“procatalysts,”“metal complexes,”“complexes,”“metal-ligand complexes,” and like terms are to be interchangeable in the present disclosure.

[0045]“Co-catalyst” refers to those known in the art, e.g., those disclosed in WO

2005/090427 and U.S. Patent No. 8,501,885 B2, that can activate the catalyst precursor to form an active catalyst composition.“Activator” and like terms are used interchangeably with“co-catalyst.”

[0046] The term“catalyst system,”“active catalyst,”“activated catalyst,”“active catalyst composition,”“olefin polymerization catalyst,” and like terms are interchangeable and refer to a catalyst precursor/co-catalyst pair. Such terms can also include more than one catalyst precursor and/or more than one activator and optionally a co-activator. Likewise, these terms can also include more than one activated catalyst and one or more activator or other charge balancing moiety, and optionally a co-activator.

[0047] The terms“polymer,”“polymer,” and the like refer to a compound prepared by polymerizing monomers, whether of the same or a different type. The generic term polymer thus embraces the term homopolymer, usually employed to refer to polymers prepared from only one type of monomer, and the term interpolymer as defined below. It also embraces all forms of interpolymers, e.g., random, block, homogeneous, heterogeneous, etc.

[0048] "Interpolymer" and "copolymer" refer to a polymer prepared by the polymerization of at least two different types of monomers. These generic terms include both classical copolymers, i.e., polymers prepared from two different types of monomers, and polymers prepared from more than two different types of monomers, e.g., terpolymers, tetrapolymers, etc.

EXAMPLES

Methods

[0049] NMR: ¾ NMR spectra are recorded on a Bruker AV-400 spectrometer at ambient temperature. ¾ NMR chemical shifts in benzene- <5 are referenced to 7.16 ppm (C6D5H) relative to TMS (0.00 ppm).

[0050] ¹³ C NMR: ¹³ C NMR spectra of polymers are collected using a Bruker 400 MHz spectrometer equipped with a Bruker Dual DUL high-temperature CryoProbe. The polymer samples are prepared by adding approximately 2.6g of a 50/50 mixture of tetrachloroethane- d2/orthodichlorobenzene containing 0.025M chromium trisacetylacetonate (relaxation agent) to 0.2 g of polymer in a lOmm NMR tube. The samples are dissolved and homogenized by heating the tube and its contents to 150 °C. The data is acquired using 320 scans per data file, with a 7.3 second pulse repetition delay with a sample temperature of 120 °C.

[0051] GC/MS: Tandem gas chromatography/low resolution mass spectroscopy using electron impact ionization (El) is 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, l5m X 0.25mm, 0.25 micron) with respect to the following:

Programed method:

Oven Equilibration Time 0.5 min

50 °C for 0 min

then 25 °C/min to 200 °C for 5 min

Run Time 11 min

[0052] GPC: The gel permeation chromatographic system consists of either a Polymer Laboratories Model PL-210 or a Polymer Laboratories Model PL-220 instrument. The column and carousel compartments are operated at 140 °C. Three Polymer (Laboratories 10- micron Mixed-B columns are used. The solvent is 1,2,4 trichlorobenzene. The samples are prepared at a concentration of 0.1 grams of polymer in 50 milliliters of solvent containing 200 ppm of butylated hydroxytoluene (BHT). Samples are prepared by agitating lightly for 2 hours at 160 °C. The injection volume used is 100 microliters and the flow rate is 1.0 ml/minute.

[0053] Calibration of the GPC column set is performed with 21 narrow molecular weight distribution polystyrene standards with molecular weights ranging from 580 to 8,400,000, arranged in 6“cocktail” mixtures with at least a decade of separation between individual molecular weights. The standards are purchased from Polymer Laboratories (Shropshire, UK). The polystyrene standards are prepared at 0.025 grams in 50 milliliters of solvent for molecular weights equal to or greater than 1,000,000 and 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000. The polystyrene standards are dissolved at 80 °C. with gentle agitation for 30 minutes. The narrow standards mixtures are run first and in order of decreasing highest molecular weight component to minimize degradation. The polystyrene standard peak molecular weights are converted to polyethylene molecular weights using the following equation (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)): Mpoiyethyiene=0.43l(Mpoiy _Styrene ). Polyethylene equivalent molecular weight calculations are performed using Viscotek TriSEC software Version 3.0.

[0054] Molecular Weight: Molecular weights are determined by optical analysis techniques including deconvoluted gel permeation chromatography coupled with a low angle laser light scattering detector (GPC-LALLS) as described by Rudin, A.,“Modem Methods of Polymer Characterization”, John Wiley & Sons, New York (1991) pp. 103-112.

[0055] Unless noted otherwise, all starting materials for the examples described below are commercially available from, for example, Sigma- Aldrich and Gelest.

Example 1

[0056] Synthesis of tris(8-dimethylsilyloctyl)aluminum. An exemplary silicon-terminated organo-metal composition is prepared as follows and as seen in Reaction Scheme 1. In a nitrogen-filled drybox, 7-octenyldimethylsilane (4.05 g, 23.78 mmol) and

triisobutylaluminum (2.0 mL, 7.9 mmol) are mixed in 10 mL of p-xylene in a 40 mL glass vial with a stirbar and a venting needle on the cap. The mixture is heated to and held at 130 °C for 2 h with stirring. After 2 h, NMR (FIG. 1) shows that all vinyl groups disappeared. GCMS analysis (FIG. 2) of a hydrolyzed sample shows a major peak at m/z of 171, which is consistent to the expected reaction product.

Reaction Scheme 1.

Example 2 - Ethylene Polymerization:

[0057] Subsequent ethylene polymerization of the silicon-terminated organo-metal prepared in Example 1 is performed as follows and as seen in Reaction Scheme 2. In a nitrogen-filled drybox, a 40 mL vial equipped with a stirbar was charged with Isopar E (10 mL) and the activator [(Ci6-i8H33-37)2CH3NH] tetrakis(pentafluorophenyl)borate salt available from Boulder Scientific (Act. A in Reaction Scheme 2) (0.063 mL of 0.064 M solution in MCH, 0.004 mmol). The vial is sealed with a septum cap and placed in a heating block set to 100 °C. The ethylene line (from a small cylinder) is connected and the vial headspace is slowly purged via a needle. Solutions of the silicon-terminated organo-metal of Example 1 (0.4 mL, 0.20 mmol) and Procatalyst (A4) (0.002 mmol) as defined above and labeled as PCA in Reaction Scheme 2 are injected and the purge needle is removed to maintain a total pressure at 12 psig. The reaction mixture is stirred for 30 min, then taken out of the drybox and quenched with MeOH (100 mL). The precipitated white polymer is stirred in methanol for 3 hours, followed by filtration and drying of the polymer under vacuum overnight. 0.73 g white polymer is collected. ¹³ C NMR (FIG. 3) and ¾ NMR (FIG. 4) confirmed the polymer structure with terminal SiMe2H group. GPC results: M _n = 1,273, M _w = 1,534, PDI = 1.21. The GPC chromatogram is shown in FIG. 5.

Reaction Scheme 2.