FIELD OF THE INVENTION

[0001] This disclosure relates to methods for synthesizing copolymers such as graft or block copolymers, and polymeric materials provided by the methods.

BACKGROUND OF THE INVENTION

[0002] The ability to control the physical properties of polymers, such as the hydrophilicity, lipophilicity, density, general durability, or molecular weight, is desirable. For example, it may be necessary to adjust or impart a particular physical property or feature of a polymer that is potentially useful for a desired application. In recent years, the use of well-defined soluble catalyst precursors generally has allowed enhanced control over polymer properties, such as branching architecture, stereochemistry, and molecular weight and polydispersity control. Certain types of copolymers have been very challenging to tailor. For example, the ability to graft polymerize side chains onto a polymer material has been difficult, yet provides opportunity to adjust the physical characteristics and properties of a wide number of polymer materials.

[0003] The production of graft copolymers previously has been achieved using two general techniques, namely photochemical and chemical. Photochemical techniques include exposure of a polymer to low-temperature plasma, ultraviolet irradiation, or gamma-ray irradiation to initiate the polymerization process. Chemical techniques typically use free-radical polymerization or atom transfer radical polymerization to produce the grafted copolymer. Various aspects of producing graft copolymers can be found at, for example, Mika, et al., "A New Class of Polyelectrolyte-Filled Microfiltration Membranes with Environmentally Controlled Porosity," J. Memb. ScL, 108, 37- 56 (1995); Iwata, et al., "Preparation and Properties of Novel Environmental- Sensitive Membranes Prepared by Graft Polymerization Onto a Porous Membrane", J. Memb. ScL, 38, 185-199, 1988); and Hautojarvi, et al., (J. Memb. ScL, 108, 37, 1995) (PVDF membranes graft-modified with poly( acrylic acid)). [0004] Even with the advent of these techniques, there is a continued need in the polymer arts for additional graft polymerization techniques that may be applicable to producing various types of graft copolymers and for the materials and articles produced by these techniques. Challenges in tailoring the specific copolymer properties that one desires using graft polymerization techniques remain. Therefore, it is desirable to develop new graft polymerization techniques that might provide enhanced control over copolymer architecture and properties.

BRIEF SUMMARY OF THE INVENTION

[0005] This disclosure provides for methods of preparing block or graft copolymers and interpolymers, polymeric materials provided by these methods, and articles prepared from these polymeric materials. In one aspect, two or more separate polymerization processes are used to generate a graft copolymer. A first polymer containing main chain or pendant olefin groups at various locations along the polymer chain, a vinyl-terminated polymer, or a polymer that contains all these types of olefin functionalities is provided or is prepared by a first polymerization. This first polymer is contacted with an organometal hydride, for example a dialkyl aluminum hydride, which is capable of adding across the unsaturated groups to functionalize the olefin to afford a metalated polymer. A second polymerization reaction is then effected in the presence of the metalated polymer, in which the second polymerization catalyst is one that is capable of undergoing chain transfer with metalated polymer. Thus, the second polymerization catalyst is selected for its polymerization activity and for its ability to transfer or exchange polymeryl groups, including a polymeryl group, with the metalated polymer's organometal groups, thereby enabling the second polymer to attach to the first polymer. The resulting product can be considered a comb copolymer with the second polymer chains branching from the first polymer backbone.

[0006] Thus, in one aspect, this disclosure describes a process for the synthesis of graft copolymers, the process comprising: a) contacting a polymeric material comprising at least one unsaturated bond with an organometal species of the general formula:

(R ³⁰ ) _p M ^A H _q ; wherein

R ³⁰ , in each occurrence, is independently a C1-C20 hydrocarbyl group;

M ^A is a metal selected from aluminum, gallium, indium, or thallium;

H is hydrogen;

p is 1, 2, or 3;

q is 0, 1, or 2; and

the sum of p and q equals the valence of the metal;

to form a metalated polymeric material comprising at least one organometal substituent; and

b) contacting, under polymerization conditions, at least one polymerizable monomer, at least one catalyst, and the metalated polymeric material, wherein the organometal substituent facilitates polymeryl transfer to the at least one catalyst.

[0007] By way of one specific example, and not intending to be bound by any theory, a likely process for the synthesis of graft copolymers can be illustrated as follows. The chain transfer reactivity between an alkyl aluminum reagent and a particular polymerization catalyst typically is known or tested and confirmed, for example, the polymerization catalyst can be active for preparing syndiotactic polystyrene. A polybutadiene containing a certain percentage of pendant vinyl groups is contacted with an organometal compound, such as diisobutylaluminum hydride (DIBAL-H) to metalate the polymer, forming a diisobutyl aluminum-functionalized polybutadiene. This metalated polymer is then used as a chain transfer reagent, by conducting a styrene polymerization reaction to generate syndiotactic polystyrene in the presence of the metalated polymer. In this manner, the resulting copolymer is a comb copolymer having a polybutadiene backbone containing syndiotactic polystyrene grafts. Accordingly, this exemplary synthesis of block (graft) copolymers is effected by functionalizing polybutadiene and incorporating the functionalized polybutadiene into a polymerization reaction such that the second polymer becomes grafted to the polybutadiene through chain transfer.

[0008] Other objects, features, and advantages of the invention will be apparent from the following detailed description, drawings, and claims. Unless otherwise defined, all technical and scientific terms and abbreviations used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Although methods and compositions similar or equivalent to those described herein can be used in the practice of the present invention, suitable methods and compositions are described without intending that any such methods and compositions limit the disclosure herein.

BRIEF DESCRIPTION OF THE FIGURE

[0009] The Figure illustrates ¹ H NMR spectra of two aliquots extracted from the reaction of polybutadiene and DIBAL-H.

DETAILED DESCRIPTION OF THE INVENTION

[0010] One aspect of this disclosure provides for methods of preparing block or graft copolymers and interpolymers, polymeric materials provided by these methods, and articles prepared from these polymeric materials. For example, the methods of this disclosure can provide a comb copolymer with second polymer chains branching from a first polymer backbone. Generally, this disclosure describes a process for the synthesis of graft copolymers, the process comprising:

a) contacting a polymeric material comprising at least one unsaturated bond with an organometal species of the general formula:

(R ³⁰ ) _p M ^A H _q ; wherein

each R ³⁰ is selected independently from a C1-C20 hydrocarbyl group;

M ^A is a metal selected from aluminum, gallium, indium, or thallium;

H is hydrogen;

p is 1, 2, or 3; q is 0, 1, or 2; and

the sum of p and q equals the valence of the metal;

to form a metalated polymeric material comprising at least one organometal substituent; and

b) contacting, under polymerization conditions, at least one polymerizable monomer, at least one catalyst, and the metalated polymeric material, wherein the organometal substituent facilitates polymeryl transfer to the at least one catalyst.

[0011] The product of the methods described herein is a "graft copolymer." In a graft copolymer, one or more side chain polymers are connected to a main chain or "backbone" polymer. In this disclosure, the polymeric material that is metalated with the organometal species comprises the main chain or backbone polymer in the final graft copolymer. The side chains of the graft copolymers described herein are formed from the at least one polymerizable monomer of step b) above.

[0012] Generally, the polymeric material of step a), which is the backbone polymer, may be any straight or branched polymer or copolymer. According to this disclosure, the term "copolymer" is defined as any polymer or polymeric material that has a molecular structure containing two or more types of monomers; for example, terpolymers. Also, as defined herein, the term "copolymer" includes polymers containing a backbone polymer to which at least one side chain has been grafted, regardless of the molecular structure of the backbone and at least one side chain. In one aspect of this disclosure, the backbone polymer may have a linear molecular structure. In another aspect, the backbone polymer may have a branched molecular structure; for example, a star polymer.

[0013] Not wishing to be bound by any theory, it is believed that the at least one organometal substituent of the metalated polymeric material (or backbone polymer) facilitates polymeryl transfer to the at least one catalyst. As defined herein, "polymeryl transfer" refers to the contacting of the at least one organometal substituent of the metalated polymeric material with the at least one catalyst, and the subsequent grafting of the side-chain polymer formed from the polymerizable monomer onto the polymeric material. Therefore, the side chains of the present disclosure may graft onto the backbone polymer wherever the organometal species added to the at least one unsaturated bond. For the purposes of this disclosure, wherever the organometal species successfully reacted or added to the at least one unsaturated bond of the backbone polymer is referred to as an "organometal substituent."

[0014] Generally, the backbone polymer, after being contacted with an organometal species, contains at least one organometal substituent. The organometal substituent may be located at any position throughout the molecular structure of the backbone polymer. In one aspect, the at least one organometal substituent may be located at one or more terminal positions of the backbone polymer's molecular structure. In other aspects, the at least one organometal substituent may be dispersed randomly or evenly throughout the entire molecular structure of the backbone polymer. In yet another aspect, at least two organometal substituents may be located at one or more terminal positions of the backbone polymer's molecular structure, and disbursed randomly or evenly throughout the entire molecular structure of the backbone polymer.

[0015] In one aspect of this disclosure, the backbone polymer may be linear and the resulting graft copolymer may be a "comb polymer." If a multitude of organometal substituents are present in a linear backbone polymer at substantially regular intervals, the resulting graft copolymer may include side chains spaced at substantially regular intervals. Such graft copolymers resemble a comb and are typically termed "comb polymers."

[0016] Generally, the backbone polymer and the side chains that form from the polymerizable monomer of step b) above may comprise any monomer or monomers that facilitate the methods described herein. In one aspect of this disclosure, the backbone polymer and the side chains have a substantially similar molecular structure. It should be noted that even though the monomers of the backbone polymer and the side chains may possess a similar molecular structure in this aspect of the disclosure, such a product is covered by the term "graft copolymer" as defined herein. As defined herein, the term "copolymer" includes not only polymers containing at least two types of monomers, but also polymers containing a backbone polymer to which side chains have been grafted, regardless of the molecular structure of the backbone and side chains. In other aspects of this disclosure, the backbone polymer and the side chains have substantially different molecular structures or different tacticity. In still other aspects, each side chain may possess a molecular structure substantially different than the backbone polymer and each other side chain. In another aspect, each side chain may be a block copolymer.

[0017] In one aspect, the graft copolymer may be amphiphilic, i.e., one portion of the copolymer is hydrophobic, while another portion is hydrophilic; for example, the copolymer may have hydrophilic (polar) side chains and a hydrophobic (nonpolar) backbone. In another aspect, the graft copolymer may comprise a soft backbone polymer and rigid or hard side chains.

[0018] In a further aspect, the methods disclosed here allow for preparing a comb copolymer having a first polymer backbone, in which the polymer chain branches constitute a block copolymer of a second and a third monomer. In this aspect, the second and third polymerization reactions can be conducted at alternating instances along the same growing polymer branch, by using a chain shuttling agent in the presence of the second and third polymerization catalysts capable of chain transfer activity. The chain shuttling process passes a growing polymer chain between second and third polymerization catalyst sites, such that portions of a single polymer branch are synthesized by at least two different catalysts. A chain shuttling agent (CSA) can be a component such as a metal alkyl complex (e.g. a dialkyl zinc reagent) that facilitates this transfer. This approach can thus be used to prepare block copolymers pendent branches off the first polymer backbone, from a common monomer environment by using a mixture of catalysts of different selectivities, namely stereoselectivity or monomer selectivity. The chain shuttling process and various chain shuttling agents are described in, for example, Arriola, DJ. ; Carnahan, E.M.; Hustad, P. D.; Kuhlman, R.L.; and Wenzel, T.T. Science 2006, 312: 714-719, WO2005/090427 and in WO 2007/035493, all of which are incorporated by reference herein in their entireties.

[0019] Generally, the polymeric material of step a) of the present disclosure may be any polymer or copolymer with an unsaturated bond located at any position within the polymeric material's molecular structure. An unsaturated bond according to this disclosure is any chemical bond that is not a single bond. In a particular aspect of this disclosure, the unsaturated bond may be a double bond. In one aspect, the unsaturated bond may be a terminal double bond. In yet another aspect, the unsaturated bond may be a vinyl group. The polymeric material may be natural or synthetic. Additionally, the polymeric material may be a homopolymer or a copolymer.

[0020] In particular aspects of this disclosure, the polymeric material may include homopolymers of acyclic alkadienes, acyclic alkatrienes, cyclic alkadienes, and cyclic alkatrienes, in which the double bonds can be in either conjugated or non-conjugated arrangement, and copolymers of these monomers with each other or with one or more mono- 1 -olefins, for example styrene, alkyl substituted styrenes, vinylnaphthalenes, ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-nonene, isobutylene, 2-methyl- 1-hexene, and the like. Examples of suitable alkadiene and alkatriene monomers include: poly-l,3-butadiene; polyisoprene; poly-2,3-dimethyl- 1 ,3-butadiene; poly-2-methoxy- 1 ,3-butadiene; poly-2-phenyl-l,3-butadiene; poly-l,5-hexadiene; poly-l,4-pentadiene; poly-1,6- heptadiene; poly-2-ethyl-l,5-hexadiene; poly-l,4,7-octatriene; poly- 1,3- pentadiene; poly-l,3,7-octatriene; poly-l,3-cyclohexadiene; poly- cyclopentadiene; poly-l^J-cyclooctadiene; poly-l,3-dicyclopentadiene; poly- vinylnorbornene; any combination thereof; or any co-polymers thereof.

[0021] Generally, the organometal species of the present disclosure may be any species satisfying the formula:

(R ³⁰ ) _p M ^A H _q ;

wherein R ³⁰ is selected independently from a C ₁ -C ₂₀ hydrocarbyl group; M ^A is a metal selected from aluminum, gallium, indium, or thallium; H is hydrogen; p is 1, 2, or 3; q is 0, 1, or 2; and the sum of p and q equals the valence of the metal. In one aspect of this disclosure, q is equal to at least 1 and the organometal species is an organometal hydride. In another aspect, q is equal to zero, and the organometal species is an organometal compound.

[0022] As stated, R ³⁰ may be selected independently from a C1-C20 hydrocarbyl group. Since R ³⁰ may be selected independently, R ³⁰ groups that are structurally unique may be bonded to the metal when p is greater than 1. For example, if p is 2, R ³⁰ may represent two identical C ₁ -C ₂₀ hydrocarbyls or two structurally unique C1-C20 hydrocarbyls. Similarly, if p is 3, R ³⁰ may represent three identical C1-C20 hydrocarbyls; three structurally unique C1-C20 hydrocarbyls; or two identical C ₁ -C ₂₀ hydrocarbyls and one structurally unique C1-C20 hydrocarbyl.

[0023] Moreover, in each occurrence, R ³⁰ may be a C1-C20 hydrocarbyl which includes an aliphatic group, an aromatic or aryl group, a cyclic group, or any combination thereof; any substituted derivative thereof, including but not limited to any halide-, alkoxide-, or amide- substituted derivative thereof. Also included in the definition of the C1-C20 hydrocarbyl are any unsubstituted, branched, or linear analogs thereof. The C1-C20 hydrocarbyl may be substituted with one or more functional moieties selected from a halide, an ether, a ketone, an ester, an amide, a nitrile, a heterocycle comprising at least one N-, O-, or S- heteroatom, an aldehyde, a thioether, a thiol, an imine, a sulfone, a carbonate, a urethane, a urea, or an imide.

[0024] Examples of aliphatic groups, in each instance, include, but are not limited to, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an alkadienyl group, a cyclic group, and the like, and includes all substituted, unsubstituted, branched, and linear analogs or derivatives thereof, in each instance having from 1 to about 20 carbon atoms.

[0025] Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, isobutyl, pentyl, hexyl, isohexyl, heptyl, 4,4-dimethylpentyl, octyl, 2,2,4-trimethylpentyl, nonyl, decyl, undecyl and dodecyl. Cycloalkyl moieties may be monocyclic or multicyclic, and examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl. Additional examples of alkyl moieties have linear, branched and/or cyclic portions (e.g., l-ethyl-4-methyl-cyclohexyl). Representative alkenyl moieties include vinyl, allyl, 1-butenyl, 2-butenyl, isobutylenyl, 1-pentenyl, 2-pentenyl, 3- methyl-1-butenyl, 2-methyl-2-butenyl, 2,3-dimethyl-2-butenyl, 1-hexenyl, 2- hexenyl, 3-hexenyl, 1-heptenyl, 2-heptenyl, 3-heptenyl, 1-octenyl, 2-octenyl, 3- octenyl, 1-nonenyl, 2-nonenyl, 3-nonenyl, 1-decenyl, 2-decenyl and 3-decenyl. Representative alkynyl moieties include acetylenyl, propynyl, 1-butynyl, 2- butynyl, 1-pentynyl, 2-pentynyl, 3-methyl- 1-butynyl, 4-pentynyl, 1-hexynyl, 2- hexynyl, 5-hexynyl, 1-heptynyl, 2-heptynyl, 6-heptynyl, 1-octynyl, 2-octynyl, 7- octynyl, 1-nonynyl, 2-nonynyl, 8-nonynyl, 1-decynyl, 2-decynyl and 9-decynyl.

[0026] Examples of aryl or aromatic moieties include, but are not limited to, anthracenyl, azulenyl, biphenyl, fluorenyl, indan, indenyl, naphthyl, phenanthrenyl, phenyl, 1,2,3,4-tetrahydro-naphthalene, and the like, including substituted derivatives thereof, in each instance having from 6 to about 20 carbons. Substituted derivatives of aromatic compounds include, but are not limited to, tolyl, xylyl, mesityl, and the like, including any heteroatom substituted derivative thereof. Examples of cyclic groups, in each instance, include, but are not limited to, cycloparaffins, cycloolefins, cycloacetylenes, arenes such as phenyl, bicyclic groups and the like, including substituted derivatives thereof, in each instance having from about 3 to about 20 carbon atoms. Thus heteroatom- substituted cyclic groups such as furanyl are also included herein.

[0027] In each instance, the heterocycle comprising at least one N-, O-, or

S- heteroatom may be selected from the group consisting of: morpholinyl, thiomorpholinyl, thiomorpholinyl S-oxide, thiomorpholinyl S,S-dioxide, piperazinyl, homopiperazinyl, pyrrolidinyl, pyrrolinyl, tetrahydropyranyl, piperidinyl, tetrahydrofuranyl, tetrahydrothienyl, homopiperidinyl, homomorpholinyl, homothiomorpholinyl, homothiomorpholinyl S,S-dioxide, oxazolidinonyl, dihydropyrazolyl, dihydropyrrolyl, dihydropyrazinyl, dihydropyridinyl, dihydropyrimidinyl, dihydrofuryl, dihydropyranyl, tetrahydrothienyl S-oxide, tetrahydrothienyl S,S-dioxide, and homothiomorpholinyl S-oxide, pyridinyl, pyrimidinyl, quinolinyl, benzothienyl, indolyl, indolinyl, pryidazinyl, pyrazinyl, isoindolyl, isoquinolyl, quinazolinyl, quinoxalinyl, phthalazinyl, imidazolyl, isoxazolyl, pyrazolyl, oxazolyl, thiazolyl, indolizinyl, indazolyl, benzothiazolyl, benzimidazolyl, benzofuranyl, furanyl, thienyl, pyrrolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, oxazolopyridinyl, imidazopyridinyl, isothiazolyl, naphthyridinyl, cinnolinyl, carbazolyl, beta- carbolinyl, isochromanyl, chromanyl, tetrahydroisoquinolinyl, isoindolinyl, isobenzotetrahydrofuranyl, isobenzotetrahydrothienyl, isobenzothienyi, benzoxazolyl, pyridopyridinyl, benzotetrahydrofuranyl, benzotetrahydrothienyl, purinyl, benzodioxolyl, triazinyl, phenoxazinyl, phenothiazinyl, pteridinyl, benzothiazolyl, imidazopyridinyl, imidazothiazolyl, dihydrobenzisoxazinyl, benzisoxazinyl, benzoxazinyl, dihydrobenzisothiazinyl, benzopyranyl, benzothiopyranyl, coumarinyl, isocoumarinyl, chromonyl, chromanonyl, pyridinyl-N-oxide, tetrahydroquinolinyl, dihydroquinolinyl, dihydroquinolinonyl, dihydroisoquinolinonyl, dihydrocoumarinyl, dihydroisocoumarinyl, isoindolinonyl, benzodioxanyl, benzoxazolinonyl, pyrrolyl N-oxide, pyrimidinyl N-oxide, pyridazinyl N-oxide, pyrazinyl N-oxide, quinolinyl N-oxide, indolyl N- oxide, indolinyl N-oxide, isoquinolyl N-oxide, quinazolinyl N-oxide, quinoxalinyl N-oxide, phthalazinyl N-oxide, imidazolyl N-oxide, isoxazolyl N- oxide, oxazolyl N-oxide, thiazolyl N-oxide, indolizinyl N-oxide, indazolyl N- oxide, benzothiazolyl N-oxide, benzimidazolyl N-oxide, pyrrolyl N-oxide, oxadiazolyl N-oxide, thiadiazolyl N-oxide, triazolyl N-oxide, tetrazolyl N-oxide, benzothiopyranyl S-oxide, or benzothiopyranyl S,S-dioxide.

[0028] Unless otherwise indicated, the term "substituted," when used to describe a chemical structure or moiety, refers to a derivative of that structure or moiety wherein one or more of its hydrogen atoms is substituted with a chemical moiety or functional group such as, but not limited to, alcohol, alkoxy, alkanoyloxy, alkoxycarbonyl, alkenyl, alkyl (e.g., methyl, ethyl, propyl, t-butyl), alkynyl, alkylcarbonyloxy (-OC(O)alkyl), amide (-C(O)NH-alkyl- or - alkylNHC(O)alkyl), tertiary amine (such as alkylamino, arylamino, arylalkylamino), aryl, aryloxy, azo, carbamoyl (-NHC(O)O-alkyl- or -OC(O)NH- alkyl), carbamyl (e.g., CONH ₂ , as well as CONH-alkyl, CONH-aryl, and CONH- arylalkyl), carboxyl, carboxylic acid, cyano, ester, ether (e.g., methoxy, ethoxy), halo, haloalkyl (e.g., -CCI ₃ , -CF ₃ , -C(CF ₃ ) ₃ ), heteroalkyl, isocyanate, isothiocyanate, nitrile, nitro, phosphodiester, sulfide, sulfonamido (e.g., SO ₂ NH ₂ ), sulfone, sulfonyl (including alkylsulfonyl, arylsulfonyl and arylalkylsulfonyl), sulfoxide, thiol (e.g., sulfhydryl, thioether) or urea (-NHCONH-alkyl-). Also unless otherwise indicated, the particular size of the unsubstituted chemical moiety, for example as designated by the number of carbon atoms, is also generally applicable to the substituted chemical moiety.

[0029] In the formula above, M ^A is a boron, lanthanum, magnesium, zinc or a Group 13 metal selected from aluminum, gallium, indium or thallium. Therefore, the organometal species that may be used include, but are not limited to, the following: trimethylaluminum; triethylaluminum; methylaluminum dihydride; dimethylaluminum hydride; ethylaluminum dihydride; diethylaluminum hydride; propylaluminum dihydride; n-butylaluminum dihydride; diisobutylaluminum hydride; n-hexylaluminum dihydride; dioctylaluminum hydride; cyclopentylaluminum dihydride; decylaluminum dihydride; tetradecylaluminum dihydride; heptadecylaluminum dihydride; di(octadecyl) aluminum hydride; eicosylaluminum dihydride; cyclohexylaluminum dihydride; cycloheptyaluminum dihydride; dicyclodecylaluminum hydride; cyclodecylaluminum dihydride; cycloeicosylaluminum dihydride; cyclooctylaluminum dihydride; phenylaluminum dihydride; diphenylaluminum hydride; 1-naphthylaluminum dihydride; biphenylaluminum dihydride; o-tolylaluminum dihydride; 1,3,4,5- tetramethylphenylaluminum dihydride; methylgallium dihydride; dimethylgallium hydride; diethylgallium hydride; ethylgallium dihydride; propylgallium dihydride; isobutylgallium dihydride; di-n-butylgallium hydride; di-n-hexylgallium hydride; octylgallium dihydride; decylgallium dihydride; di(tetradecyl) gallium hydride; heptadecylgallium dihydride; dieicosylgallium hydride; octadecylgallium dihydride; dicyclopentylgallium hydride; dicyclohexylgallium hydride; cyclodecylgallium dihydride; (2,6-dipropyl-4-octyl) cyclohexylgallium dihydride; phenylgallium dihydride; naphthylgallium dihydride; methylindium dihydride; dimethylindium hydride; ethylindium dihydride; diethylindium hydride; n-butylindium dihydride; dihexylindium hydride; decylindium dihydride; diheptylindium hydride; dieicosylindium hydride; dicyclohexylindium hydride; cyclohexylindium dihydride; cyclodecylinium dihydride; 5,8-dibutyldodecylindium dihydride; phenylindium dihydride; naphthylindium dihydride; 1,2,3,4-tetramethylphenylindium dihydride; and the like.

[0030] Generally, the organometal species adds to the at least one unsaturated bond in the polymeric material. The addition of an organometal species to unsaturated bonds is well known in the prior art. U.S. Patent 3,347,834 to Naylor, et al. and U.S. Patent 6,344,524 to Robert, et al. both describe polymer functionalization techniques that require the addition of an organometal species to an unsaturated bond. Both of these references are hereby incorporated by reference in their entirety. In one aspect of this disclosure, the organometal species is an organometal hydride that adds to the at least one unsaturated bond via a hydroalumination reaction. In another aspect of this disclosure, the organometal species is an organometal compound that adds to the at least one unsaturated bond via a carboalumination reaction. As illustrated in Scheme 1, the hydroalumination reaction between a vinyl group of the polymeric material and diisobutylaluminum hydride (DIBAL-H) produces the metalated polymeric material.

Scheme 1

[0031] Similarly, Scheme 2 illustrates the carboalumination reaction between a vinyl group of the polymeric material and trimethylaluminum hydride. Scheme 2

[0032] Generally, the amount of organometal species utilized in the present disclosure may vary over a wide range depending upon the particular polymeric material and organometal species used, as well as the desired characteristics of the final graft copolymer. Larger or smaller quantities of the organometal species relative to the number of unsaturated bonds in the polymeric material (backbone polymer) may be employed if desired. In one aspect of this disclosure, an excess of the organometal species may be used in order to substitute substantially all of the polymeric material's unsaturated bonds with an organometal substituent. In another aspect of this disclosure, a lower relative amount of organometal species may be used in order to substitute only a percentage of the polymeric material's unsaturated bonds with an organometal substituent. Not wishing to be bound by any theory, it is believed that the side chains may add to the polymeric material wherever an organometal substituent is located due to the polymeryl transfer described hereinabove. The organometal substituents are located on the polymeric material (backbone polymer) wherever an organometal species successfully added to the at least one unsaturated bond. Therefore, in one aspect of this disclosure, altering the amount of organometal species contacted with a polymeric material with at least one unsaturated bond may be used to control, limit, or maximize the number of side chains that may graft on to the polymeric material (backbone polymer).

[0033] Generally, the organometal species and the polymeric material may be contacted in the presence or absence of any solvent. Typically, any inert hydrocarbon solvent is suitable. In particular aspects of this disclosure, the organometal species and the polymeric material may be contacted in toluene, xylene, heptane, cyclohexane, or any combination thereof.

[0034] In one aspect of this disclosure, the contacting of the polymeric material with the organometal species may be carried out at suitable temperatures, generally in the range of 5° to 15O ⁰ C, with temperatures in the range of 5O ⁰ C to 100 ⁰ C being preferred in order to minimize any decomposition of the reactants and increase the rate of reaction. The reactants may be agitated or stirred to facilitate contact. Generally, reaction time will be dependent upon the temperature and the particular organometal species and polymeric material employed. Typically, the reaction time will range from about 1 minute to about 15 days, and is preferably in the range of about 5 minutes to about 30 hours, and most preferably 10 to 15 minutes.

[0035] Generally, the at least one polymerizable monomer of step b) above may be of any composition so long as the monomers form a polymer side chain upon contact with the at least one catalyst that may be grafted on to the polymer backbone in accordance with the methods described herein. Typically, a polymerizable monomer is chosen to affect a property of the resultant graft copolymer, such as its hydrophilicity or hydrophobicity; hardness or softness, tacticity, etc.

[0036] Suitable polymerizable monomers for use in preparing the side chains of the present disclosure include any addition polymerizable monomer, generally any olefin or diolefin monomer. Suitable polymerizable monomers can be linear, branched, acyclic, cyclic, substituted, or unsubstituted. In one aspect, the olefin can be any α-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 α-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, 1- pentene, 3 -methyl- 1-butene, 1-hexane, 4-methyl-l-pentene, 3-methyl-l-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

[0037] Suitable polymerizable 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, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and 2- methyl-l,4,5,8-dimethano-l,2,3,4,4a,5,8,8a-octahydro-naphtha lene. Suitable polymerizable 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, 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, dicyclopenta-diene, 7-methyl- 1 ,6-octadiene, 4-ethylidene- 8 -methyl- 1,7- nonadiene, and 5,9-dimethyl-l,4,8-decatriene.

[0038] In a further aspect, aromatic vinyl compounds also constitute suitable polymerizable monomers for performing the methods 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, A- phenylpropene and α-methylstyrene, vinylchloride, 1,2- difluoroethylene, 1,2- dichloroethylene, tetrafluoroethylene, and 3,3,3-trifluoro-l-propene, provided the monomer is polymerizable under the conditions employed.

[0039] Generally, the at least one catalyst of step b) described above may be any catalyst that catalyzes the polymerization of the polymerizable monomer and undergoes polymeryl transfer with the metalated polymeric material. Both heterogeneous and homogeneous catalysts may be employed. In one aspect of this disclosure, suitable catalysts for carrying out the processes described herein include those described in WO 2007/035493, which is incorporated by reference herein in its entirety.

[0040] Examples of heterogeneous catalysts include the well known Ziegler-Natta compositions, including the Group 4 metal halides and their derivatives, and including Group 4 metal halides supported on Group 2 metal halides or mixed halides and alkoxides, including the well-known chromium- or vanadium-based catalysts. However, for ease of use and for production of narrow molecular weight polymer segments in solution, especially useful catalysts include the homogeneous catalysts including a relatively pure organometallic compound or metal complex, especially compounds or complexes based on metals selected from Groups 3-15 or the Lanthanide series of the Periodic Table of the Elements.

[0041] Suitable catalysts and catalyst precursors for use in the present invention also include those disclosed in WO2005/090427, in particular, those disclosed starting on page 25, line 19 through page 55, line 10. Suitable catalysts are also disclosed in US 2006/0199930; US 2007/0167578; US 2008/0311812; US 7,355,089 B2; or WO 2009/012215.

[0042] One aspect of this disclosure provided for particularly useful polymerization catalyst precursors, including but not limited to:

combination thereof.

[0043] S Catalysts having high comonomer incorporation properties are also known to reincorporate in situ prepared long chain olefins resulting incidentally during the polymerization through β-hydride elimination and chain termination of growing polymer, or other process. The concentration of such long chain olefins is particularly enhanced by use of continuous solution polymerization conditions at high conversions, especially ethylene conversions of 95 percent or greater, and more particularly at ethylene conversions of 97 percent or greater. Under such conditions a small but detectable quantity of vinyl group terminated polymer may be reincorporated into a growing polymer chain, resulting in the formation of long chain branches, that is, branches of a carbon length greater than would result from other deliberately added comonomer. Moreover, such chains reflect the presence of other comonomers in the reaction mixture. That is, the chains may include short chain or long chain branching as well, depending on the comonomer composition of the reaction mixture.

Cocatalysts

[0044] Each of the metal complexes (also interchangeably referred to here as procatalysts or catalyst precursors) may be activated to form the active catalyst composition by combination with a cocatalyst, preferably a cation forming cocatalyst, a strong Lewis acid, or a combination thereof. Thus, this disclosure also provides for the use of at least one cocatalyst in a catalyst composition and various methods, along with at least one polymerization catalyst precursor, and at least one chain shuttling agent as disclosed herein.

[0045] Suitable cation forming cocatalysts include those previously known in the art for metal olefin polymerization complexes. Examples include neutral Lewis acids, such as Ci_ ₃ o hydrocarbyl substituted Group 13 compounds, especially tri(hydrocarbyl)aluminum- or tri(hydrocarbyl)boron compounds and halogenated (including perhalogenated) derivatives thereof, having from 1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group, more especially perfluorinated tri(aryl)boron compounds, and most especially tris(pentafluoro- phenyl)borane; nonpolymeric, compatible, noncoordinating, ion forming compounds (including the use of such compounds under oxidizing conditions), especially the use of ammonium-, phosphonium-, oxonium-, carbonium-, silylium- or sulfonium- salts of compatible, noncoordinating anions, or ferrocenium-, lead- or silver salts of compatible, noncoordinating anions; and combinations of the foregoing cation forming cocatalysts and techniques. The foregoing activating cocatalysts and activating techniques have been previously taught with respect to different metal complexes for olefin polymerizations in the following references: EP-A-277,003; US 5,153,157; US 5,064,802; US 5,321,106; US 5,721,185; US 5,350,723; US 5,425,872; US 5,625,087; US 5,883,204; US 5,919,983; US 5,783,512; WO 99/15534, and WO99/42467.

[0046] Combinations of neutral Lewis acids, especially the combination of a trialkyl aluminum compound having from 1 to 4 carbons in each alkyl group and a halogenated tri(hydrocarbyl)boron compound having from 1 to 20 carbons in each hydrocarbyl group, especially tris(pentafluorophenyl)borane, further combinations of such neutral Lewis acid mixtures with a polymeric or oligomeric alumoxane, and combinations of a single neutral Lewis acid, especially tris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxane may be used as activating cocatalysts. Preferred molar ratios of metal complex:tris(pentafluorophenyl-borane:alumoxane are from 1:1:1 to 1:5:20, more preferably from 1:1:1.5 to 1:5:10. [0047] Suitable ion forming compounds useful as cocatalysts in one embodiment of the present disclosure comprise a cation which is a Brønsted acid capable of donating a proton, and a compatible, noncoordinating anion, A ^" . As used herein, the term "noncoordinating" refers to an anion or substance which either does not coordinate to the Group 4 metal containing precursor complex and the catalytic derivative derived there from, or which is only weakly coordinated to such complexes thereby remaining sufficiently labile to be displaced by a neutral Lewis base. A noncoordinating anion specifically refers to an anion which when functioning as a charge balancing anion in a cationic metal complex does not transfer an anionic substituent or fragment thereof to said cation thereby forming neutral complexes. "Compatible anions" are anions which are not degraded to neutrality when the initially formed complex decomposes and are noninterfering with desired subsequent polymerization or other uses of the complex.

[0048] Preferred anions are those containing a single coordination complex comprising a charge-bearing metal or metalloid core which anion is capable of balancing the charge of the active catalyst species (the metal cation) which may be formed when the two components are combined. Also, said anion should be sufficiently labile to be displaced by olefinic, diolefinic and acetylenically unsaturated compounds or other neutral Lewis bases such as ethers or nitriles. Suitable metals include, but are not limited to, aluminum, gold and platinum. Suitable metalloids include, but are not limited to, boron, phosphorus, and silicon. Compounds containing anions which comprise coordination complexes containing a single metal or metalloid atom are, of course, well known and many, particularly such compounds containing a single boron atom in the anion portion, are available commercially.

[0049] In one aspect, suitable cocatalysts may be represented by the following general formula:

(L*-H) _g ⁺ (A) ^g~ , wherein:

L* is a neutral Lewis base;

(L* -H)+ is a conjugate Brønsted acid of L*; A ^g~ is a noncoordinating, compatible anion having a charge of g-, and

g is an integer from 1 to 3.

More particularly, A ^g~ corresponds to the formula: [MiQ ₄ ] ^" ; wherein:

Mi is boron or aluminum in the +3 formal oxidation state; and

[0050] Q independently in each occurrence is selected from hydride, dialkylamido, halide, hydrocarbyl, hydrocarbyloxide, halo sub stituted- hydrocarbyl, halosubstituted hydrocarbyloxy, and halo- substituted silylhydrocarbyl radicals (including perhalogenated hydrocarbyl- perhalogenated hydrocarbyloxy- and perhalogenated silylhydrocarbyl radicals), each Q having up to 20 carbons with the proviso that in not more than one occurrence is Q halide. Examples of suitable hydrocarbyloxide Q groups are disclosed in US-A-5,296,433.

[0051] In a more preferred embodiment, d is one, that is, the counter ion has a single negative charge and is A ^" . Activating cocatalysts comprising boron which are particularly useful in the preparation of catalysts of this disclosure may be represented by the following general formula:

(L* -H) ⁺ (BQ ₄ ) ^" ; wherein:

L* is as previously defined;

B is boron in a formal oxidation state of 3; and

Q is a hydrocarbyl-, hydrocarbyloxy-, fluorinated hydrocarbyl-, fluorinated hydrocarbyloxy-, or fluorinated silylhydrocarbyl-group of up to 20 nonhydrogen atoms, with the proviso that in not more than one occasion is Q hydrocarbyl.

[0052] Especially useful Lewis base salts are ammonium salts, more preferably trialkylammonium salts containing one or more C ₁₂ - ₄₀ alkyl groups. In this aspect, for example, Q in each occurrence can be a fluorinated aryl group, especially, a pentafluorophenyl group. [0053] Illustrative, but not limiting, examples of boron compounds which may be used as an activating cocatalyst in the preparation of the improved catalysts of this disclosure include the tri-substituted ammonium salts such as: trimethylammonium tetrakis(pentafluorophenyl) borate,

triethylammonium tetrakis(pentafluorophenyl) borate,

tripropylammonium tetrakis(pentafluorophenyl) borate,

tri(n-butyl) ammonium tetrakis(pentafluorophenyl) borate,

tri(sec-butyl)ammonium tetrakis(pentafluorophenyl) borate,

N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate,

N,N-dimethylanilinium n-butyltris(pentafluorophenyl) borate,

N,N-dimethylanilinium benzyltris(pentafluorophenyl) borate,

N,N-dimethylanilinium tetrakis(4-(t-butyldimethylsilyl)-2, 3, 5, 6 tetrafluorophenyl) borate,

N,N-dimethylanilinium tetrakis(4-(triisopropylsilyl)-2, 3, 5, 6- tetrafluorophenyl) borate,

N,N-dimethylanilinium pentafluorophenoxytris(pentafluorophenyl) borate,

N,N-diethylanilinium tetrakis(pentafluorophenyl) borate,

N,N-dimethyl-2,4,6-trimethylanilinium tetrakis(pentafluorophenyl) borate, dimethyloctadecylammonium tetrakis(pentafluorophenyl) borate, methyldioctadecylammonium tetrakis(pentafluorophenyl) borate;

a number of dialkyl ammonium salts such as:

di-(i-propyl)ammonium tetrakis(pentafluorophenyl) borate,

methyloctadecylammonium tetrakis(pentafluorophenyl) borate, methyloctadodecylammonium tetrakis(pentafluorophenyl) borate, and dioctadecylammonium tetrakis(pentafluorophenyl) borate;

various tri-substituted phosphonium salts such as:

triphenylphosphonium tetrakis(pentafluorophenyl) borate,

methyldioctadecylphosphonium tetrakis(pentafluorophenyl) borate, and tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl) borate; di-substituted oxonium salts such as: diphenyloxonium tetrakis(pentafluorophenyl) borate, di(o-tolyl)oxonium tetrakis(pentafluorophenyl) borate, and

di(octadecyl)oxonium tetrakis(pentafluorophenyl) borate; and

di-substituted sulfonium salts such as:

di(o-tolyl)sulfonium tetrakis(pentafluorophenyl) borate, and

methylcotadecylsulfonium tetrakis(pentafluorophenyl) borate.

[0054] Further to this aspect of the disclosure, examples of useful (L* -H) ⁺ cations include, but are not limited to, methyldioctadecylammonium cations, dimethyloctadecylammonium cations, and ammonium cations derived from mixtures of trialkyl amines containing one or two Ci ₄ _i ₈ alkyl groups.

[0055] Another suitable ion forming, activating cocatalyst comprises a salt of a cationic oxidizing agent and a noncoordinating, compatible anion represented by the formula:

(Ox ^h+ ) _g (A ^g -) _h,

wherein:

Ox ^h+ is a cationic oxidizing agent having a charge of h+;

h is an integer from 1 to 3; and

A ^g~ and g are as previously defined.

Examples of cationic oxidizing agents include: ferrocenium, hydrocarbyl-substituted ferrocenium, Ag ⁺ , or Pb ⁺ . Particularly useful examples of A ^g~ are those anions previously defined with respect to the Brønsted acid containing activating cocatalysts, especially tetrakis(pentafluorophenyl)borate.

[0056] Another suitable ion forming, activating cocatalyst can be a compound which is a salt of a carbenium ion and a noncoordinating, compatible anion represented by the following formula:

[C] ⁺ A ^"

wherein:

[C] ⁺ is a Ci_ ₂ o carbenium ion; and

A ^" is a noncoordinating, compatible anion having a charge of -1. For example, one carbenium ion that works well is the trityl cation, that is triphenylmethylium. [0057] A further suitable ion forming, activating cocatalyst comprises a compound which is a salt of a silylium ion and a noncoordinating, compatible anion represented by the formula:

(Q ¹ _S Si) ⁺ A ^"

wherein:

Q ¹ is C _1-1O hydrocarbyl, and A ^" is as previously defined.

[0058] Suitable silylium salt activating cocatalysts include trimethylsilylium tetrakispentafluorophenylborate, triethylsilylium tetrakispentafluorophenylborate, and ether substituted adducts thereof. Silylium salts have been previously generically disclosed in /. Chem. Soc. Chem. Comm. 1993, 383-384, as well as in Lambert, J. B., et al., Organometallics 1994, 13, 2430-2443. The use of the above silylium salts as activating cocatalysts for addition polymerization catalysts is also described in U.S. Patent No. 5,625,087.

[0059] Certain complexes of alcohols, mercaptans, silanols, and oximes with tris(pentafluorophenyl)borane are also effective catalyst activators and may be used according to the present disclosure. Such cocatalysts are disclosed in U.S. Patent No. 5,296,433.

[0060] Suitable activating cocatalysts for use herein also include polymeric or oligomeric alumoxanes (also called aluminoxanes), especially methylalumoxane (MAO), triisobutyl aluminum modified methylalumoxane (MMAO), or isobutylalumoxane; Lewis acid modified alumoxanes, especially perhalogenated tri(hydrocarbyl)aluminum- or perhalogenated tri(hydrocarbyl)boron modified alumoxanes, having from 1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group, and most especially tris(pentafluorophenyl)borane modified alumoxanes. Such cocatalysts are previously disclosed in U.S. Patents No. 6,214,760, 6,160,146, 6,140,521, and 6,696,379.

[0061] A class of cocatalysts comprising non-coordinating anions generically referred to as expanded anions, further disclosed in U.S. Patent No. 6,395,671, may be suitably employed to activate the metal complexes of the present disclosure for olefin polymerization. Generally, these cocatalysts (illustrated by those having imidazolide, substituted imidazolide, imidazolinide, substituted imidazolinide, benzimidazolide, or substituted benzimidazolide anions) may be depicted as follows:

wherein:

A ⁺ is a cation, especially a proton containing cation, and can be trihydrocarbyl ammonium cation containing one or two Cio- ₄ 0 alkyl groups, especially a methyldi(Ci ₄ _ ₂ o alkyl) ammonium cation,

Q ³ , independently in each occurrence, is hydrogen or a halo, hydrocarbyl, halocarbyl, halohydrocarbyl, silylhydrocarbyl, or silyl, (including for example mono-, di- and tri(hydrocarbyl)silyl) group of up to 30 atoms not counting hydrogen, such as Ci_ ₂ o alkyl, and

Q ² is tris(pentafluorophenyl)borane or tris(pentafluorophenyl)alumane).

[0062] Examples of these catalyst activators include trihydrocarbylammonium- salts, especially, methyldi(C ₁₄ . ₂₀ alkyl)ammonium-salts of:

bis(tris(pentafluorophenyl)borane)imidazolide,

bis(tris(pentafluorophenyl)borane)-2-undecylimidazolide, bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolide, bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazoli de, bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidaz olide, bis(tris(pentafluorophenyl)borane)imidazolinide,

bis(tris(pentafluorophenyl)borane)-2-undecylimidazolinide, bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolinide , bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazoli nide, bis(tris(pentafluorophenyl)borane)-4,5- bis(heptadecyl)imidazolinide,

bis(tris(pentafluorophenyl)borane)-5,6-dimethylbenzimidazoli de, bis(tris(pentafluorophenyl)borane)-5,6- bis(undecyl)benzimidazolide,

bis(tris(pentafluorophenyl)alumane)imidazolide,

bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolide, bis(tris(pentafluorophenyl)alumane)-2-heptadecylimidazolide, bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazol ide, bis(tris(pentafluorophenyl)alumane)-4,5- bis(heptadecyl)imidazolide,

bis(tris(pentafluorophenyl)alumane)imidazolinide, bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolinide, bis(tris(pentafluorophenyl)alumane)-2-heptadecylimidazolinid e, bis(tris(pentafluorophenyl)alumane)-4,5- bis(undecyl)imidazolinide,

bis(tris(pentafluorophenyl)alumane)-4,5- bis(heptadecyl)imidazolinide,

bis(tris(pentafluorophenyl)alumane)-5,6-dimethylbenzimidazol ide, and

bis(tris(pentafluorophenyl)alumane)-5,6- bis(undecyl)benzimidazolide.

[0063] Other activators include those described in the PCT publication

WO 98/07515, such as tris (2,2',2"-nonafluorobiphenyl)fluoroaluminate.

Combinations of activators are also contemplated by the disclosure, for example, alumoxanes and ionizing activators in combinations, see for example, EP-A-O

573120, PCT publications WO 94/07928 and WO 95/14044, and U.S. Patents No.

5,153,157 and 5,453,410. For example, and in general terms, WO 98/09996 describes activating catalyst compounds with perchlorates, periodates and iodates, including their hydrates. WO 99/18135 describes the use of organoboroaluminum activators. WO 03/10171 discloses catalyst activators that are adducts of Brønsted acids with Lewis acids. Other activators or methods for activating a catalyst compound are described in, for example, U.S. Patents No. 5,849,852, 5,859, 653, and 5,869,723, in EP-A-615981, and in PCT publication WO 98/32775. All of the foregoing catalyst activators as well as any other known activator for transition metal complex catalysts may be employed alone or in combination according to the present disclosure. In one aspect, however, the cocatalyst can be alumoxane-free. In another aspect, for example, the cocatalyst can be free of any specifically-named activator or class of activators as disclosed herein.

Test Methods

[0064] In one aspect of the foregoing disclosure and the examples that follow, the following analytical techniques may be employed to characterize the resulting polymer.

Molecular Weight Determination

[0065] 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., "Modern Methods of Polymer Characterization", John Wiley & Sons, New York (1991) pp. 103-112.

Standard CRYSTAF Method

[0066] Branching distributions are determined by crystallization analysis fractionation (CRYSTAF) using a CRYSTAF 200 unit commercially available from PolymerChar, Valencia, Spain. The samples are dissolved in 1,2,4 trichlorobenzene at 160 ⁰ C (0.66 mg/mL) for 1 hr and stabilized at 95 ⁰ C for 45 minutes. The sampling temperatures range from 95 to 30 ⁰ C at a cooling rate of 0.2 °C/min. An infrared detector is used to measure the polymer solution concentrations. The cumulative soluble concentration is measured as the polymer crystallizes while the temperature is decreased. The analytical derivative of the cumulative profile reflects the short chain branching distribution of the polymer. The CRYSTAF peak temperature and area are identified by the peak analysis module included in the CRYSTAF Software (Version 2001. b, PolymerChar, Valencia, Spain). The CRYSTAF peak finding routine identifies a peak temperature as a maximum in the dW/dT and the area between the largest positive inflections on either side of the identified peak in the derivative curve.

DSC Standard Method

[0067] Differential Scanning Calorimetry results are determined using a TAI model QlOOO DSC equipped with an RCS cooling accessory and an autosampler. A nitrogen purge gas flow of 50 ml/min is used. The sample is pressed into a thin film and melted in the press at 175 ⁰ C and then air-cooled to room temperature (25 ⁰ C). About 10 mg of material in the form of a 5-6 mm diameter disk is accurately weighed and placed in an aluminum foil pan (ca 50 mg) which is then crimped shut. The thermal behavior of the sample is investigated with the following temperature profile. The sample is rapidly heated to 180 ⁰ C and held isothermal for 3 minutes in order to remove any previous thermal history. The sample is then cooled to -40 ⁰ C at 10 °C/min cooling rate and held at -40 ⁰ C for 3 minutes. The sample is then heated to 150 ⁰ C at 10°C/min heating rate. The cooling and second heating curves are recorded.

[0068] The DSC melting peak is measured as the maximum in heat flow rate (W/g) with respect to the linear baseline drawn between -30 ⁰ C and end of melting. The heat of fusion is measured as the area under the melting curve between -30 ⁰ C and the end of melting using a linear baseline.

GPC Method

[0069] 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 ⁰ C. The injection volume used is 100 microliters and the flow rate is 1.0 ml/minute. [0070] 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 ⁰ 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. ScL, Polym. Let., 6, 621 (1968)): Mpoiyethyiene = 0.431(Mp _O iy _S tyrene)- Polyethylene equivalent molecular weight calculations are performed using Viscotek TriSEC software Version 3.0. Density

[0071] Density measurement are conducted according to ASTM D 1928.

Measurements are made within one hour of sample pressing using ASTM D792, Method B.

Flexural/Secant Modulus

[0072] Samples are compression molded using ASTM D 1928. Flexural and 2 percent secant moduli are measured according to ASTM D-790.

Dynamic Mechanical Analysis (DMA)

[0073] Dynamic Mechanical Analysis (DMA) is measured on compression molded disks formed in a hot press at 180 ⁰ C at 10 MPa pressure for 5 minutes and then water cooled in the press at 90 ⁰ C / min. Testing is conducted using an ARES controlled strain rheometer (TA instruments) equipped with dual cantilever fixtures for torsion testing.

[0074] A 1.5 mm plaque is pressed and cut in a bar of dimensions 32 mm x 12 mm. The sample is clamped at both ends between fixtures separated by 10 mm (grip separation ΔL) and subjected to successive temperature steps from -100 ⁰ C to +200 ⁰ C (5 ⁰ C per step). At each temperature the torsion modulus G' is measured at an angular frequency of 10 rad/s, the strain amplitude being maintained between 0.1 percent and 4 percent to ensure that the torque is sufficient and that the measurement remains in the linear regime.

[0075] An initial static force of 10 g is maintained (auto-tension mode) to prevent slack in the sample when thermal expansion occurs. As a consequence, the grip separation ΔL increases with the temperature, particularly above the melting or softening point of the polymer sample. The test stops at the maximum temperature or when the gap between the fixtures reaches 65 mm.

Melt Properties

[0076] Melt Flow Rate (MFR) and Melt index (MI or I ₂ ) are measured in accordance with ASTM D1238, Condition 190 °C/2.16 kg.

Analytical Temperature Rising Elution Fractionation (ATREF)

[0077] Analytical temperature rising elution fractionation (ATREF) analysis is conducted according to the method described in U.S. Patent No. 4,798,081, the relevant portion of which is incorporated herein by reference. The composition to be analyzed is dissolved in trichlorobenzene and allowed to crystallize in a column containing an inert support (stainless steel shot) by slowly reducing the temperature to 20 ⁰ C at a cooling rate of 0.1 °C/min. The column is equipped with an infrared detector. An ATREF chromatogram curve is then generated by eluting the crystallized polymer sample from the column by slowly increasing the temperature of the eluting solvent (trichlorobenzene) from 20 ⁰ C to 120 ⁰ C at a rate of 1.5 °C/min.

[0078] The present invention is further illustrated by the following examples, which are not to be construed in any way as imposing limitations upon the scope thereof. On the contrary, it is to be clearly understood that resort may be had to various other aspects, embodiments, modifications, and equivalents thereof which, after reading the description herein, may suggest themselves to one of ordinary skill in the art without departing from the spirit of the present invention or the scope of the appended claims. Thus, other aspects of this invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein.

[0079] In the following examples, unless otherwise specified, the syntheses and preparations described therein were carried out under an inert atmosphere such as nitrogen or argon. Solvents were purchased from commercial sources and were typically dried prior to use. Unless otherwise specified, reagents were obtained from commercial sources.

Examples

Example 1

Addition of aluminum hydride to terminal double bonds in polybutadiene

[0080] In a glovebox under N ₂ gas, a solution of polybutadiene (32 mL of a 6.26% solution in cyclohexane with 20 ppm methanol and 25 ppm lithium methoxide) is transferred to ajar with a Teflon coated stirbar. The solvent is then removed in vacuo, and the remaining residue is dissolved in toluene (15 mL). DIBAL-H is then added, and the mixture stirred for 2 hours at 6O ⁰ C.

[0081] A first aliquot is then removed from the jar and transferred to a vial. After removing the solvent from the aliquot, an ¹ H NMR is performed in d- toluene. The NMR spectrum contained a peak corresponding to DIBAL-H. The reaction is then allowed to continue for an additional 14 hours before a second aliquot is removed. The spectra of the two aliquots are then compared. The NMR spectrum of the second aliquot did not contain a peak corresponding to the Al-H in the DIBAL-H. As illustrated in Figure 3, the peaks assigned to R- CH=CH ₂ decreased in intensity by roughly 50% compared to R-CH=CH-R. Therefore, the aluminum added across the terminal double bonds in the polybutadiene.

Example 2

Polymerization of styrene in the presence of functionalized polybutadiene

[0082] After cooling the reaction mixture produced by the procedure of

Example 1 to room temperature, pentamethylcyclopentadienyl titanium trichloride (CsMe _S )TiCl ₃ (4.9 mg, Strem Chemicals, Inc.) is added as a solid, followed by an additional 5 mL of toluene. The solution is then stirred for approximately 3 minutes. The reaction mixture is then briefly stirred after the addition of methyaluminoxane (MAO) (0.8 mL, 10% solution in toluene). Styrene (1.5 mL filtered through Alumina) is then added and the jar sealed with a PTFE-lined cap. The mixture thickens as it is stirred for 45 minutes at 6O ⁰ C. The mixture is then placed in a freezer for 5 minutes.

[0083] The mixture is then removed from the freezer. While stirring, methanol is added dropwise to the reaction mixture. A glass pipet is used to stir the mixture by hand as it becomes more viscous as more methanol is added. Excess methanol (30 mL) is then added. After soaking in the excess methanol for 30 minutes, the reaction mixture is removed from the glovebox. The solid is filtered through a polyethylene fritted funnel. The collected solid is rinsed with methanol and dried under vacuum at 6O ⁰ C. Once dry, the polymer is returned to the glovebox. The polymer is then suspended in THF and stirred for 1 hour at 5O ⁰ C to dissolve any unreacted polybutadiene. After removing the THF, the solid is stirred in d2-tetrachloroethane overnight at 100 ⁰ C. A ¹ H NMR was then taken of the solution. According to the chemical literature, the peaks correspond to syndiotactic polystyrene (δ = 7.1, 6.6, 1.9, 1.3 ppm) and polybutadiene (δ = 5.4 and 2.1 ppm).

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