WO1997031030A1

WO1997031030A1 - Catalytic polymerization process

Info

Publication number: WO1997031030A1
Application number: PCT/US1997/002912
Authority: WO
Inventors: Graeme Moad; Ezio Rizzardo; Catherine Louise Moad; Steven Dale Ittel; Lech Wilczek; Alexei A. Gridnev
Original assignee: E.I. Du Pont De Nemours And Company; Commonwealth Scientific & Industrial Research Organization
Priority date: 1996-02-23
Filing date: 1997-02-18
Publication date: 1997-08-28
Also published as: CA2246416A1; CN1240725C; KR19990087193A; JP2000514845A; KR100483087B1; EP0882070A1; US6100350A; CA2247837A1; TW378227B; NZ331312A; CN1506382A; CN1134455C; WO1997031031A1; ES2207717T3; KR19990087192A; AU1973497A; IL125876A0; BR9707658A; JP2000506189A; BR9707655A

Abstract

This invention relates to a process for controlling the architecture of copolymers of at least two unsaturated monomers, made by free-radical polymerization in the presence of a cobalt-containing chain transfer agent, including the control of molecular weight, degree of branching and vinyl end group termination, by varying at least one of the variables of molar ratio of monomers, their relative chain transfer constants, polymerization temperature and degree of conversion and amount of cobalt chain transfer agent; and polymers made thereby.

Description

XIILE

CATALYTIC POLYMERIZATION PROCESS

BACKGROUND OF THE INVENTION Catalytic chain transfer is an effective way to control the molecular weight of polymers of methacrylates and styrenes. It is known that chain transfer catalysis (CTC) products contain a terminal vinylidene bond. This feature makes these products attractive as macromonomers for a variety of applications. However, CTC has not been known to be applicable for reduction of molecular weight in the polymerizations of other vinylic monomers such as acrylates.

Copolymerizations of methacrylate monomers with monosubstituted monomers in the presence of cobalt have been described in the art. However, the monosubstituted monomer is almost always present as a minor component. U.S. 4.680,354 describes molecular weight reduction using various Co(II) complexes in MMA-BA, MMA-EA and MMA-BA-St copolymerizations, wherein the abbreviations represent:

MMA=methyl methacrylate BA=buryl acrylate EA=ethyl acrylate St=styrene.

U.S. 5,324,879 describes molecular weight reduction with Co(III) complexes in EA, St, and vinyl acetate (VAc) polymerizations, and MMA-EA copolymerization.

U.S. 4,680,352 describes molecular weight reduction and macromonomer (polymers or copolymers with unsaturated end-groups) synthesis in copolymerizations with acrylates and styrene with various Co(II) complexes. Various terpolymerizations are cited therein; however, no evidence ofthe nature or existence of terminal double bonds is given.

Gruel et al., Polymer Preprints, 1991, 32, p. 545, reports the use of Co(II) cobaloximes in low conversion St-MMA copolymerizations at low temperatures with end group analysis.

The references cited above cover the copolymerization of acrylates and styrene with methacrylate monomers, but do not disclose synthetic conditions for production of high purity macromonomers based on acrylates and styrene. nor branching of the resulting products. The conditions disclosed are unlikely to yield high purity macromonomers for systems composed predominantly of monosubstituted monomers. Disclosed temperatures of less than 80°C are likely to provide substantial amounts of undesired graft copolymer at high conversion rates.

SUMMARY OF THE INVENTION This invention concerns an improvement in a process for the free- radical polymerization of at least two unsaturated monomers to form a polymer whose molecular architecture comprises properties of molecular weight, branching, and vinyl-terminated end groups, the monomers having the formula

CH₂=CXY wherein

X is selected from the group consisting of H, CH₃,and CH₂OH; Y is selected from the group consisting of OR, O₂CR, halogen, CO₂H, COR, CO₂R, CN, CONH₂, CONHR, CONR₂ and R';

R is selected from the group consisting of substituted and unsubstituted alkyl, substituted and unsubstituted aryl, substituted and unsubstituted heteroaryl, substituted and unsubstituted aralkyl, substituted and unsubstituted alkaryl, and substituted and unsubstituted organosilyl, the substituents being the same or different and selected from the group consisting of carboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, primary amino, secondary amino, tertiary amino, isocyanato, sulfonic acid and halogen; and the number of carbons in said alkyl groups is from 1 to 12; and

R' is selected from the aromatic group consisting of substituted and unsubstituted aryl, substituted and unsubstituted heteroaryl, the substituents being the same or different and selected from the group consisting of carboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, primary amino, secondary amino, tertiary amino, isocyanato, sulfonic acid, substituted and unsubstituted alkyl, substituted and unsubstituted aryl, substituted and unsubstituted olefin and halogen; by contacting said monomers with a cobalt-containing chain transfer agent and a free radical initiator at a temperature from about 80° to 170°C; the improvement which comprises controlling polymer architecture by introducing into the presence ofthe chain transfer agent at least one each of monomers A and B in the molar ratio of A:B, said molar ratio lying in the range of about 1 ,000: 1 to 2: 1 , wherein for monomer A Xis H and for monomer B X is methyl or hydroxymethyl; by one or more ofthe following steps:

I decreasing the ratio of A:B from about 1 ,000: 1 toward 2:1 ; II increasing the temperature from above 80°C toward 170 °C; III increasing the conversion of monomer to polymer toward 100% from less than about 50%;

IV decreasing the ratio of the chain transfer constant of A:B to below 1 ; and V increasing the concentration of cobalt chain transfer agent;

whereby: to effect lower molecular weight, employ at least one of steps I, II, IV and

V; to effect a higher degree of vinyl-terminated end groups, employ at least one of steps I, II, IV, and V; and to effect increased branching,employ at least one of steps I, II, IV, and V with step III.

The nature ofthe derived products changes as a function of time. In the initial stages, linear macromonomers with one monomer-A in the terminal position can be obtained as essentially the only product. If the cobalt CTC catalyst levels are relatively low then CTC does not occur after every B-monomer insertion and the product mixture can include monomer-B units in the polymer chain as well as in the terminal position. Cobalt chain transfer agent is employed in the form of cobalt complexes.

Their concentrations are provided in the Examples in terms of ppm by weight of total reaction mass. Concentration will vary from 10 ppm to 1,500 ppm, preferably 10 to 1,000 ppm.

Later in the course ofthe reaction, when the concentration ofthe two above products is increased, then they can be reincorporated into a growing polymer chain. Thus, mono-branched product is obtained in the later stages ofthe reaction, usually around 90% conversion. At conversions above 95%, branches begin to appear on the branches, and the polymer becomes hyperbranched as conversions approach 100%. Preferred monomers A are selected from the group consisting of acrylates, acrylonitrile and acrylamides;

and preferred monomers B are selected from the group: a) substituted or unsubstituted α-methylstyrenes; b) substituted or unsubstituted alkyl methyacrylates, where alkyl is

c) methacrylonitrile; d) substituted or unsubstituted methacrylamide: e) 2-chloropropene, f) 2-fluoropropene, g) 2-bromopropene, h) methacrylic acid, i) itaconic acid, j) itaconic anhydride, and k) substituted or unsubstituted styrenics. If branched polymers are the desired product, it is possible to initiate the described process in the presence of preformed macromonomers. They canbe of the type described in this patent. They canalso be macromonomers based entirely upon methacrylates or the related species described previously in U.S. 4,680,354. Such a process would lead to products fitting the description above, but would allow for greater control over the polymer end-groups.

The branched polymers made by said process are polymers of this invenuon having the formula:

Y is as earlier defined; n = 1-20, m = 1-5, p=l-20, and n + m + p > 3, and Z is selected from the group CH₂CHYCH₃, CH₂CMeYCH₃, and, optionally,

m' = 0-5, p' = 0-20; n + m' + p' > 2; and if m or m' > 1, the m or m' insertions respectively are not consecutive.

This invention also concerns a process comprising selecting A and B so the ratio of their chain transfer constants is less than 1, whereby functionality derived from Monomer B will be located on the vinyl-terminated end of the polymer.

This invention also concerns an improved process for the free-radical polymerization of at least two unsaturated monomers having the formula

CH₂=CXY wherein

X is selected from the group consisting of H, CH₃, and CH₂OH;

Y is selected from the group consisting of OR, O₂CR, halogen, CO₂H, CO₂R, CN, CONH₂, CONHR. CONR₂, COR and R'; R is selected from the group consisting of substituted and unsubstituted alkyl, substituted and unsubstituted aryl, substituted and unsubstituted heteroaryl, substituted and unsubstituted aralkyl, substituted and unsubstituted alkaryl, and substituted and unsubstituted organosilyl, the substituents being the same or different and selected from the group consisting of carboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, primary amino, secondary amino, tertiary amino, isocyanato, sulfonic acid and halogen, and the number of carbons in said alkyl groups is from 1 to 12; and

R' is selected from the aromatic group consisting of substituted and unsubstituted aryl, substituted and unsubstituted heteroaryl, the substituents being the same or different and selected from the group consisting of carboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, primary amino, secondary amino, tertiary amino, substituted and unsubstituted alkyl, substituted and unsubstituted aryl, substituted and unsubstituted olefin and halogen; by contacting said monomers with a cobalt-containing chain transfer agent and a free radical initiator at a temperature from about 80°C to 170°C; the improvement which comprises controlling molecular weight ofthe polymer architecture by introducing into the presence ofthe chain transfer agent at least one each of monomers C and D in the molar ratio of C:D in the range of about 1 ,000: 1 to 2: 1 , in which for monomer C, X is H and Y ≠ R' and for monomer D, X is H and Y = R' by: decreasing the ratio of C:D from about 1,000:1 toward 2:1 ; or increasing the temperature from above 80°C toward 170 °C.

Preferred monomers A are selected from the group consisting of acrylates, acrylonitrile and acrylamides; and preferred monomers B are substituted and unsubstituted styrenics.

The polymers made by said process improvement are polymers ofthis invention having the formula:

where Y≠ R' and n > 1. This invention also concerns a process improvement for polymerizing monomer(s) in the presence of an excess of a nonpolymerizable olefin,

Y Y C=CY x . The product in the initial stages ofthe polymerization will be composed primarily of

wherein:

1 3 1 A

Y and Y , and optionally Y and Ύ , are each independently selected from the group consisting of -CH(O), -CN, -C(O)OR⁵, -C(O)NR⁶R⁷, -CR⁸(O), alkyl, aryl, substituted alkyl, substituted aryl; or where Y and Y or Y and x are combined in a cyclic structure which includes any of the above functionalities, or can be -C(O)-(CH2)_x-, -C(O)- O-(CH₂)_x-, -C(O)O-C(O)-, -C(O)(CH₂)_x-, -C(O)NR⁹-(CH₂)_x-, wherein x=l-12,

R , R , R , R , or R are hydrogen, alkyl, aryl, substituted alkyl, or substituted aryl; and where at least one of Y and Y is selected from the group consisting of - CH(O), -CN, -C(O)OR⁵, -C(O)NR⁶R⁷, -CR⁸(O), aryl, substituted aryl; and the remaining of Y and Y are -H.

The polymers made by said process improvement are polymers of this invention produced at later stages ofthe polymerization process having the formula:

then it is not intended to imply that the m insertions are consecutive;

Y is selected from the group consisting of OR, O₂CR, halogen. CO₂H, COR, CO₂R, CN, CONH₂, CONHR, CONR₂ and R'; and

Y¹ to Y and R. and R' are as defined above. DETAILS OF THE INVENTION

We have discovered that, with addition of small amounts of an α- methylvinyl monomer and appropriate choice of reaction conditions, polymerization of monosubstituted monomers in the presence of a metal complex can provide high yield of macromonomers. These macromonomers can subsequently be used for the synthesis of a wide range of block and graft copolymers.

This invention concerns a method for the synthesis of ωunsaturated macromonomers composed predominantly of monosubstituted monomers. The macromonomers are prepared by polymerizing a monosubstituted monomer as the major component (for example styrene) in the presence of a disubstituted α-methylvinyl monomer (for example, α-methylstyrene, herein also referred to as "AMS") and a catalytic amount of a cobalt complex [for example, Co(II)(DMG-BF2)2] called Coll in Scheme 1. Reaction Scheme 1 illustrates the process where monomer A=styrene and monomer B=α-methylstyrene. The process is applicable to a wide range of monosubstituted monomers (for example acrylate esters, vinyl acetate (VAc)) and other non-α-methylvinyl monomers. Scheme 1 :

In Scheme 1, "Ph" represents a phenyl group, and "m" designates the number of monomer units in the polymer, and is > 1.

The key features of the invention are the addition of small amounts of α-methylvinyl monomers and the use of high reaction temperatures in the presence of chain transfer catalysts. The incoφoration of α-methylvinyl monomers into the recipe allows formation of the desired macromonomer end group. In the absence of the α- methylvinyl monomer, polymerization of monosubstituted monomers give polymers with internal double bonds (styrenic monomer) or a stable alkyl-cobalt species (acrylate monomers) as chain ends. The use of high reaction temperatures (>100 °C) favors the formation of pure linear macromonomers from monosubstituted monomers (for example acrylates, vinyl esters, and styrene). At lower temperatures we have shown that the formed macromonomers can react further by copolymerization to give branched polymers. Even though the macromonomers can undergo further reaction, at reaction temperatures > 100 °C, the radicals so formed do not propagate to give branched polymers. Rather, they fragment to give back a macromonomer. It is possible that this chemistry will also reduce the polydispersity ofthe final product.

The invention also provides a route to block or graft copolymers as illustrated in Scheme 2. The product derived by copolymerization ofthe macromonomer in the presence of monomers can be determined by appropriate choice ofthe monomer and the reaction conditions. Scheme 2: graft copolymer

block copolymer

In Scheme 2, "Ph" represents a phenyl group; "m", "n" and "o" designate the number of monomer units in the polymer; and X and Y are as defined above.

We have demonstrated that styrene macromonomers prepared by the above mentioned copolymerization route give chain transfer (by an addition fragmentation mechanism) and have acceptable chain transfer constants at temperatures > 100 °C. They should therefore be useful in the preparation of block copolymers.

One further aspect of the invention is that by appropriate choice ofthe α-methylvinyl monomer the method is also a route to end-functional polymers. For example, use of a hydroxyethyl- or giycidyl-functional monomer would yield polymers with ω-hydroxy or ω-epoxy groups, respectively.

This method enables the versatility and robustness ofthe cobalt technology to be utilized to form macromonomers that are comprised predominantly of monosubstituted monomers. Additionally, it provides the key step in a new and less expensive route to end-functional and block or graft copolymers based on monosubstituted monomers. Copolymerizations of monosubstituted monomers with other α-methylvinyl monomers (for example α- methylstyrene) in the presence of cobalt are contemplated.

The choice ofthe α-methyvinyl comonomer is important in macromonomer synthesis. It must be chosen so that the reactivity towards cobalt ("catalytic chain transfer constant") ofthe derived propagating species is substantially greater than that ofthe propagating species derived from the monosubstituted monomer.

Two factors influence this reactivity. a) The rate of the chain transfer reaction between the propagating species and the cobalt complex; b) The relative concentrations ofthe propagating species. This is determined not only by the monomer concentration but also by the propagation rate constants and reactivity ratios. While methacrylate esters can be used as α-methylvinyl comonomers

(see examples), in copolymerization with styrene, the values ofthe reactivity ratios and propagation rate constants will favor the formation of styryl chain ends. The product then has an internal rather than the desired terminal double bond. Methacrylate esters are acceptable comonomers in, for example, acrylate polymerizations.

Thus, the use of α-methylvinyl comonomers (for example, α — methylstyrene, methacrylonitrile) which have low propagation rate constants and high chain transfer rate constants are preferred.

There are substantial cost improvements over alternative technologies which involve the use of stoichiometric amounts of an organic transfer agent. The ability to use acrylate/styrenic rich macromonomers, in contexts similar to those developed for methacrylate monomers products by cobalt mediated processes, for example, in graft, star, block and branched copolymer syntheses, further extends the value ofthe process.

The nature ofthe derived products changes as a function of time. In the initial stages, the product

can be obtained as essentially the only product. If the cobalt CTC catalyst levels are relatively low then CTC does not occur after every B-monomer insertion and the product mixture can include:

Later in the course ofthe reaction, when the concentration ofthe two above products is increased, they can be reincoφorated into a growing polymer chain. Thus, the product

where Z can include -H, -CH₃, CH₂CHYCH₃, CH CMeYCH₃, or

is obtained. In the early stages of the reaction, Z is most often H, but as the reaction proceeds toward 90% conversion, Z begins to include more ofthe higher molecular weight species as branches. At conversions above 95%, branches begin to appear on the branches, and the polymer becomes hyperbranched as conversions approach 100%.

Metal complexes are those that give catalytic chain transfer with α- methylvinyl monomers. Examples include, but are not limited to, cobalt(II) and cobalt(III) chelates:

Co(II)(DPG-BF₂)₂ J=K=Ph, L= ligand

Co(II)(DMG-BF₂)₂ J=K=Me, L= ligand

Co(II)(EMG-BF₂)₂ J=Me, K=Et, L= ligand

Co(II)(DEG-BF₂)₂ J=K=Et, L= ligand

Co(II)(CHG-BF₂)₂ J=K=-(CH₂)₄-, L= ligand

QCo(III)(DPG-BF₂)₂ J= =Ph, R=alkyl, L= ligand

QCo(III)(DMG-BF₂)₂ J=K=Me, R= alkyl, L= ligand

QCo(III)(EMG-BF₂)₂ J=Me, K=Et, R=alkyl, L= ligand

QCo(III)(DEG-BF₂)₂ J= =Et, R=alkyl, L= ligand

QCo(III)(CHG-BF₂)₂ J=K=-(CH₂)₄-, R=alkyl, L= ligand

QCo(III)(DMG-BF₂)₂ J=K=Me, R=halogen, L= ligand

L can be a variety of additional neutral ligands commonly known in coordination chemistry. Examples include water, amines, ammonia, phosphines. The catalysts can also include cobalt complexes of a variety of poφhyrin molecules such as tetraphenylpoφhyrin, tetraanisyipoφhyrin, tetramesitylpoφhyrin and other substituted species.

α-Methylvinyl monomers (B monomers) have the general structure

where Y is as described above in the "Summary". R is an optionally substituted alkyl (such as fluoroalkyl, hydroxyalkyl, or epoxyalkyl), organosilyl, or aryl group. Preferred examples of α-methylvinyl monomers (B monomers) include methacrylate esters, α-methylstyrene and methacrylonitrile. "A" monomers have the general structure:

where Y is as described above in the "Summary". The enhanced utility ofthe polymerization method discussed in this invention is that it extends each of these general CTC methodologies: i) molecular weight control is extended from methacrylates and styrenes to include acrylates, vinyl esters, and other higher activity monomer species; ii) macromonomer synthesis is extended to the monomers in (i) while retaining the desirable vinyl termination ofthe resulting species; iii) end-functional polymer synthesis is also extended to the monomers in (i); iv) the use of macromonomers as chain transfer agents is extended to include monomer classes heretofore unavailable through CTC technology; and v) not only are a wider range of block and graft copolymers available through the use of CTC technology, but now it is possible to prepare branched and even hyperbranched species through single-pot reactions. It is preferred to employ free-radical initiators and solvents in the process ofthis invention. The process can be run in batch, semi-batch, continuous, bulk, emulsion or suspension mode. Most preferred A-monomers are: methyl acrylate. ethyl acrylate, propyl acrylate (all isomers), butyl acrylate (all isomers), 2-ethyihexyl acrylate. isobornyl acrylate, acrylic acid, benzyl acrylate, phenyl acrylate, acrylonitrile, glycidyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate (all isomers), hydroxybutyl acrylate (all isomers), diethylaminoethyl acrylate, triethyleneglycol acrylate. N-tert-butyl acrylamide, N- n-butyl acrylamide, N-methyl-ol acrylamide, N-ethyl-ol acrylamide, trimethoxysilylpropyl acrylate, triethoxysilylpropyl acrylate, tributoxysilylpropyl acrylate, dimethoxymethylsilylpropyl acrylate, diethoxymethylsilylpropyl acrylate, dibutoxymethylsilylpropyl acrylate, diisopropoxymethylsilylpropyl acrylate, dimethoxysilylpropyl acrylate, diethoxysilylpropyl acrylate, dibutoxysilylpropyl acrylate, diisopropoxysilylpropyl acrylate, vinyl acetate, styrene, diethylamino styrene, P — methylstyrene, vinyl benzoic acid, vinylbeuzinsulfonic acid, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl chloride, vinyl fluoride, vinyl bromide. Most preferred B-monomers are: methyl methacrylate, ethyl methacrylate, propyl methacrylate (all isomers), butyl methacrylate (all isomers), 2-ethylhexyl methacrylate, isobornyl methacrylate, methacrylic acid, benzyl methacrylate, phenyl methacrylate, methacrylonitrile, alpha methyl styrene, trimethoxysilylpropyl methacrylate, triethoxysilylpropyl methacrylate, tributoxysilylpropyl methacrylate, dimethoxymethylsilylpropyl methacrylate, diethoxymethyl-silylpropylmethacrylate, dibutoxymethylsilylpropyl methacrylate, diisopropoxymethylsilylpropyl methacrylate, dimethoxysilylpropyl methacrylate, diethoxysilylpropyl methacrylate, dibutoxysilylpropyl methacrylate, diisopropoxysilylpropyl methacrylate, isopropenyl butyrate, isopropenyl acetate, isopropenyl benzoate, isopropenyl chloride, isopropenyl fluoride, isopropenyl bromideitaconic aciditaconic anhydridedimethyl itaconate. methyl itaconateN-tert- butyl methacrylamide, N-n-butyl methacrylamide, N-methyl-ol methacrylamide, N-ethyl-ol methacrylamide, isopropenylbenzoic acid (all isomers), diethylamino alphamethylstyrene (all isomers), para-methyl-alpha-methylstyrene (all isomers), diisopropenylbenzene (all isomers), isopropenylbenzene sulfonic acid (all isomers), methyl 2-hydroxymethylacrylate, ethyl 2-hydroxymethylacrylate, propyl 2-hydroxymethylacrylate (all isomers), butyl 2-hydroxymethylacrylate (all isomers), 2-ethylhexyl 2-hydroxymethylacrylate, isobornyl 2- hydroxymethylacrylate, and TMI dimethyl Meta-Isopropenylbenzyl Isocyanate. Preferred C monomers are those from the list of A monomers minus the styrenic family.

Preferred D monomers include the following styrenes: styrene, vinyl benzoic acid (all isomers), diethylamino styrene (all isomers), para- methylstyrene (all isomers), and vinyl benzene sulfonic acid (all isomers),

Typical products of the reaction at lower conversions include the linear products from methyl acrylate and methyl methacrylate:

from hydroxyethyl acrylate and alpha-methylstyrene:

from vinyl benzoate and butyl methacrylate:

Typical products of the reaction at lower conversions include the linear products from butyl acrylate and methyl methacrylate:

from methyl acrylate and alpha-methylstyrene:

When the polymerization (for example butyl acrylate as A-monomer and methyl methacrylate as B-monomer) is carried out in the presence of a nonpolymerizable olefin such as 2-pentenenitrile, the product in the initial stages ofthe polymerization will be:

and later in the polymerization, the product will be:

It becomes impractical to draw schematics of any ofthe higher degrees of branching that are obtained as the conversion ofthe polymerization approaches 100%.

Oligomers, macromonomers and polymers made by the present process are useful in a wide variety of coating and molding resins. Other potential uses can include cast, blown, spun or sprayed applications in fiber, film, sheet, composite materials, multilayer coatings, photopolymerizable materials, photoresists, surface active agents, dispersants, adhesives. adhesion promoters, coupling agents, compatibilizers and others. End products taking advantage of available characteristics can include, for example, automotive and architectural coatings or finishes, including high solids, aqueous or solvent based finishes. Polymers, such as those produced in this invention, will find use in, for example, structured polymers for use in pigment dispersants. ⁺IDS mass spectroscopy is an ionization method that produces pseudomolecular ions in the form of [M]K⁺ with little or no fragmentation. Intact organic molecules are desorbed by rapid heating. In the gas phase, the organic molecules are ionized by potassium attachment. Potassium ions are generated from an aluminosilicate matrix that contains K₂O. All ofthese experiments were performed on a Finnegan Model 4615 GC/MS quadrupole mass spectrometer (Finnegan MAT (USA), San Jose, CA). An electron impact source configuration op^erating at 200 °C and a source pressure of <lxl0^" torr was used. MALDI was aL performed on this instrument. All MW and DP measurements were based on gel permeation chromatography (GPC) using styrene as a standard. Definitions

The following abbreviations have been used and are defined as: TAPCo = rneso-tetra(4-methoxyphenyl)poφhyrin-Co; VAZOΘ-88 = 1,1 '- azobis(cyclohexane-l-carbonitrile) (DuPont Co., Wilmington, DE); VRO-1 10 = 2,2'-azobis(2,4,4-trimethylpentane) (Wako Pure Chemical Industries, Ltd., Osaka, Japan);

DP = degree of polymerization. M_π is number average molecular weight and M_w is weight average molecular weight. AIBN is azoisobutyronitrile. THF is tetrahydrofuran. MA = methy lacry late.

EXAMPLES EXAMPLES 1-9 Synthesis of low molecular weight styrene macromonomers AMS comonomer Feed polymerization Examples 1-3 and Control 1 show that molecular weight control is obtained in the absence of added α-methylstyrene. The products have structure 1 with an internal double bond and do not function as macromonomers.

Solution polymerization of styrene with α-methylstyrene (10: 1) and iPrCo(III)(DMG-BF₂)₂ isopropylcobalt(III)(DMG) ( 100 ppm) in n-butyl acetate at 125 °C

n-butyl acetate 20.04 g styrene (sty) 10.03 g α-methylstyrene 1.00 g

Shot: iPrCo(III)(DMG-BF₂)2 1.4 mg n-butyl acetate 5.00 g

Feed 1 : 1 , 1 ^,-azobis(4-cyclohexanecarbonitrile) 0.093 g

(0.063 mL/min n-butyl acetate 6.73 g over 120 min) iPrCo(III)(DMG-BF₂)₂ 4.6 mg

Feed 2: styrene 13.57 g

(0.139 mL/min α-methylstyrene 1.57 g over 120 min) The butyl acetate was degassed in a 5 neck 250 mL reactor, equipped with condenser, stirred, and N₂ purge. The monomers were added and degassed for a further 10 minutes. The reactor was heated to reflux (ca 125°C) and the shot of iPrCo(III)(DMG-BF2)₂/solvent added. The monomer and initiator feeds were started immediately. The reactor was sampled at regular intervals to monitor intermediate molecular weights (GPC, THF) and conversions (Η NMR, CDCI3). A sample of this low viscosity yellow liquid was precipitated into a twenty fold excess of methanol, and the macromonomer recovered as a fine white powder. M n 1270, M /M _n 1.43, 34 % conversion. The precipitated samples were examined by 'H NMR (200 MHz, CDCI3) to establish the nature of the chain ends.

The unsaturated end groups give rise to signals as follows: styryl end group internal double bond (1): 66.1 -CH(Ph)-CH=CH-Ph; 53.1 CH(Ph)-CH=CH- Ph. Alpha methyl styrene- (AMS)-derived terminal methylene double bond (2): 64.8 IH and 65.2 IH, -C(Ph)=CH₂ (the ratio ofthe signals at 66.1 and 64.8 was found to give the best estimate of terminal double bond content. Although this utilises a signal on the fringe ofthe broad aromatic resonance 67.6-7.2, a series of comparisons ofthe 'H-NMR molecular weights calculated from the end groups with those obtained by GPC showed that this gave better results than the signal at 63.1). This may be due to the internal double bond product being a mixture of (1) and (3).

Table 1.1: Polymerization of styrene in presence of AMS and iPrCo(III) (DMG-BF₂)₂ at l25°C

Example Time [Co(III)] Sty: Conv.'%

M _n M _w M _W M _n [2?% (min) ppm AMS

1 30 100 - 1050 2290 2.18

60 100 1 150 2540 2.21 3

120 100 1100 2590 2.18 5 ppt 100 1630 1.69 0

2 60 50 - 2010 4150 2.06 3

120 50 1720 3980 2.30 5 ppt 50 1940 2.03 0

3 60 25 - 3270 11153 3.41 •_^ j

120 25 2710 9540 3.52 5 ppt 25 2750 3.26 0

¹ Determined by 'H NMR

² % 2, remainder is 1 and 3 estimated by Η NMR Table 1.1 (Cont'd)

Example Time [Co(III)] Sty: M _n M w M w/ _n Conv. [2]%° (min) ppm AMS %

Control 60 0 32230 54760 1.70 2 120 0 33830 59450 1.76 4 180 0 38060 63750 1.68 5 240 0 39510 67150 1.70 6 300 0 37420 67630 1.81 7 360 0 39420 67070 1.70 8

30 100 10:1 730 1840 2.38 60 100 740 1670 2.25 120 100 690 1430 2.06 ppt 100 1270 1.43 32

5 60 50 10:1 1170 2540 2.17 2

120 50 1040 2300 2.21 4 ppt 50 1470 1.80 56

6 60 25 10:1 1370 2890 2.11 2

120 25 1270 2690 2.11 3 ppt 25 1660 1.89 65

Control 2 20 0 10:1 19696 50460 2.56 n.d

40 0 14860 37950 2.55 n.d

60 0 17060 38890 2.28 1

120 0 24430 42040 1.72 3

240 27440 51420 1.87 4

360 0 29400 52930 1.80 6

7 60 100 5:1 380 930 2.45

120 100 140 870 2.10 ppt 100 1310 1.83 -

8 60 50 5:1 810 1670 2.06 1

120 50 780 1530 1.96 2 ppt 50 1180 1.53 68

9 60 25 5:1 1760 3480 1.98 2

120 25 1640 3160 1.93 J ppt 25 2140 1.60 100

Control 3 60 0 5:1 16740 32450 1.94

120 0 19540 35020 1.79 ppt 0 19570 1.83 EXAMPLES 10-12 Synthesis of high molecular weight styrene macromonomers AMS comonomer Feed polymerization These Examples were run according to the same procedure of

Examples 1 through 3. Table 1.2: Polymerization of styrene in presence of AMS and iPrCo(III)(DMG-

BF;)₂ at 125 °C. Numbers in parenthesis indicate reaction times.

Ex. reaction [Co(III)] Sty/AM M _n ^c M _W/M % conv. % terminal time (h) (ppm) S alkene

10 2 8 5/1 7455 (120) 2.4 14 -

(0.13/0.37)³ 9442 (ppt) 1.95 >70⁵ l l⁴ 1 8 5/1 4648 (60) 1.81 12 -

(0.13/0.37)³ 5160 (ppt) 1.64 >70⁵

12 2 13 5/1 2660 (120) 1.87 20 -

(0.25/0.75)³ 3300 (ppt) 1.63 >70⁵

EXAMPLES 13-18, Control 4-6

Synthesis of styrene macromonomers

AMS comonomer

Batch polymerizations in sealed tube - Effect of reaction temperature

Batch polymerizations were conducted in sealed tubes to establish the effect of temperature on macromonomer purity (% 2). Molecular weights and macromonomer purities are similar to those obtained in the feed polymerization experiments (refer Table 1.1).

A mixture of styrene (1.3g, 12.5 mmol), α-methylstyrene (0.15g, 1.27 mmol) (monomer ratio: 10/1), n-butyl acetate (3 g), VR^®-110 (8.9x10'⁵ g, 20 ppm) and iPrCo(III)(DMG-BF₂)₂ (for concentrations see Table 1.3) was placed in an ampoule and degassed by 4 freeze-thaw cycles. The ampoule was sealed and the mixture heated at 125 °C for 2 hours. The ampoule was cooled, opened and the reaction mixture reduced in vacuo to a residue which was analysed by 'H-nmr and GPC.

³ amount, in mg, added in (shot/feed).

⁴ rate of cobalt complex feed twice that for example 10.

⁵ internal methylene was not visible in the Η-nmr spectrum. Table 1.3: Batch polymerization of styrene in presence of AMS and iPrCo(III)(DMG-BF₂)₂ at 125 °C with VR*-1 10 initiator

Example Sty/AMS [Co(III)] M _{n w}/M _n % conv % terminal ratio ppm AMS

Control 4 10/1 0 64547 1.72 5 - 9 -

Control 5 5/1 0 53498 1.77 4 - 7 -

13 10/1 100 445 1.61 1 - 4 36

14 10/1 50 751 1.76 4 - 6 39

15 10/1 25 1408 1.79 7 - 9 54

Table 1.4: Batch polymerization of styrene in presence of AMS and iPrCo(III)(DMG-BF₂)₂ at 80 °C with AIBN initiator.

Example Sty/AM [Co(III)] M _n M /M % conv % terminal ratio ppm AMS⁶

Control 6 10/1 0 32,60 1.97 4 0 0

16 10/1 100 660 1.30 5 22

17 10/1 50 1090 1.52 7 33

18 10/1 25 1456 1.63 7 45

EXAMPLES 19-22, CONTROL 7-9 Synthesis of styrene macromonomers AMS comonomer Batch polymerizations in sealed tube - Effect of cobalt complex

A mixture of styrene (l.Og, 9.6mmol), α-methylstyrene (0.12g, .96mmol) (monomer ratio: 10/1), n-butyl acetate (2g), VR^®-1 10 (3.12X10^"4 g, lOOppm) and the cobalt species (for all experiments 50ppm, 2.44x10^"7 mol of cobalt species was used) was placed in an ampoule and degassed by 4 freeze-thaw cycles. The ampoule was sealed and the mixture heated at 125 °C for 2 hours. The ampoule was cooled, opened and the reaction mixture reduced in vacuo to a residue which was analysed by Η-nmr and GPC.

⁶ Calculated as [terminal AMS units]/[ terminal AMS units + terminal Sty units] X 100. From 'NMR. Table 1.5: Batch polymerization of styrene in presence of AMS and various cobalt complexes at 125 °C with VR^®1 10 initiator.

Example Co species⁷ [Co] ppm Mn Mw PD % conv % terminal AMS units⁸

Control 7 Co(III)DMG 0 58,288 104,916 1.8 13 0

19 50 1065 1730 1.62 19 71

Control 8 Co(III)DEG 0 72,284 125,129 1.73 15 0

20 50 1388 2368 1.7 19 . 85

Control 9 Co(II) DPG 0 71,869 122,098 1.7 12 0

21 50 1454 2532 1.74 23 91

22 Co(III)DMG 50 1470 - 1.8 39 74 Feed Expt⁹

EXAMPLES 23-24, CONTROL 10 Synthesis of styrene macromonomers

Methacrylate comonomer Feed polymerization The polymerization recipe for examples 23-24 and their control was similar to that given for Examples 1 -3 with the modification that BMA was used in place of AMS. Conversions obtained are similar. Good molecular weight control is observed however little specificity for formation of a terminal macromonomer double bond is observed.

⁷ Co(HI)DMG = iPrCo(III)(DMG-BF₂)₂, Co(III)DEG = MeCo(HI)(DEG-BF₂)₂, Co(IIIDPG Co(II)(DPG-BF₂)₂

⁸ Calculated as [terminal AMS units]/[terminal AMS units + terminal Sty units] X 100 from NMR.

⁹ Data ex Table 1.1 Table 1.7: Polymerization of styrene in presence of BMA and iPrCo(III)(DMG-

BF2)2 at 125 °C with l ,r-azobis(4-cyclohexanecarbonitrile) as initiator

Sample Time [Co(III)] Sty:BMA¹⁰ M „u M _w M _W/M _n % Conv.¹² (min) ppm

Control 10 30 0 10:1 35870 60580 1.69 25

60 0 34970 58090 1.66 35

120 0 36360 61770 1.70 51 ppt 0 35750 1.73

23 30 100 10:1 1170 2130 1.81 20

60 100 1220 3410 1.82 37

120 100 1190 2230 1.88 51 ppt 100 1560 1.69

24 60 25 10:1 4800 9440 1.97 38

120 25 3750 8290 2.21 53 ppt 25 4190 8270 1.97

EXAMPLES 25-30 Synthesis of styrene macromonomers

Isopropenyl acetate comonomer Batch polymerization Sty/iPA macromonomer formation at 80 °C: A mixture of styrene (lg, 9.6mmol), isopropenyl acetate (0.19g, 1.9mmol) (monomer ratio: 5/1), n- butyl acetate (2g), AIBN (3.19x10^"^, lOOppm) and isopropylcobalt(III)DMG (for concentrations see Table 1.8) was placed in an ampoule and degassed by 4 freeze- thaw cycles. The ampoule was sealed and the mixture heated at 80 °C for 2 hours. The ampoule was cooled, opened and the reaction mixture reduced in vacuo to a residue which was analysed by ' H-nmr and GPC. Η-nmr (d6-acetone): styryl end group internal double bond (1): 66.1 -CH(Ph)- CH=CH-Ph; 63.1 CH(Ph)-CH=CH-Ph.

¹⁰ Molar ratio of comonomers

¹ ' Determined by GPC calibrated with narrow polydispersity polystyrene standards. ¹² Determined by 1H NMR Table 1.8: Sty/iPA macromonomer formation at 80 °C for 2h with AIBN and iPrCo(III)(DMG-BF₂)₂.

Example Sty/iPA Co(III) Mn Mw PD % conv % terminal ratio ppm iPA units¹³

Control 1 1 5/1 0 57,425 91,753 1.6 6.00 0

25 5/1 400 338 364 1.07 4.00 0

26 5/1 100 698 1045 1.49 4.00 0

27 5/1 25 5188 1 1,611 2.24 6.00 0

Control 12 1/1 0 32,782 52,987 1.61 3.00 0

28 1/1 400 323 343 1.07 2.00 0

29 1/1 100 465 586 1.26 3.00 0

30 1/1 25 1560 2825 1.81 3.00 0

EXAMPLES 31-45, CONTROLS 13-16 Synthesis of butyl acrylate macromonomers

AMS comonomer at 80 °C Batch polymerization - Effect of comonomer and complex concentration

A mixture of butyl acrylate (1.3g, lOmmol), a-methylstyrene (50mg, 0.4mmol) (monomer ratio: 25/1), n-butyl acetate (2g), AIBN (3.74xl0"⁴ g, 1 OOppm) and isopropylcobalt(III)DMG (for concentration see Table 2.1) was placed in an ampoule and degassed by 4 freeze-thaw cycles. The ampoule was sealed and the mixture heated at 80 °C for 2 hours. The ampoule was cooled, opened and the reaction mixture reduced in vacuo to a residue which was analysed by ' H-nmr and GPC. Η-nmr (d6-acetone): d 0.9, CH₃; 1.25, CH₂; 1.5, CH₂; 1.95, CH; 2.3, backbone CH₂; 2.55, allyl CH₂; 3.95, OCH₂; 5.0, vinyl H; 5.2, vinyl H; 7.15-7.25, ArH.

¹³ No terminal alkene derived from iPA were detectable by 1 H NMR. Table 2.1 Polymerization of butyl acrylate in presence of AMS and iPrCo(III)(DMG-BF2)2 at 80 °C

Ex. BA AM Co(III) M n¹⁴ PD % % term. % AMS % term.

S ratio ppm Conv AMS units¹⁵ inc.¹⁶ alkene¹⁷

Ctrl 13 5/1 0 23,500 1.75 3 0 39 0

31 5/1 100 475 1.20 3 64 43 100

32 5/1 50 487 1.20 4 60 38 100

33 5/1 25 495 1.20 4 54 41 100

Ctrl 14 10/1 0 28,200 1.64 4 0 38 0

34 10/1 100 551 1.27 3 67 36 100

35 10/1 50 605 1.31 5 63 35 100

36 10/1 25 635 1.33 5 60 36 100

Ctrl 15 25/1 0 41,423 1.69 9 0 17 0

37 25/1 200 943 1.37 6 92 15 91

38 25/1 100 961 1.39 5 77 17 96

39 25/1 50 1062 1.42 6 71 18 100

40 25/1 25 1152 1.48 7 57 20 100

Ctrl 16 50/1 0 56,071 1.76 14 0 12 0

41 50/1 400 1168 1.64 10 78 9 80

42 50/1 200 1207 1.76 10 75 9 85

43 50/1 100 1481 1.80 13 61 9 91

44 50/1 50 1600 1.82 11 59 10 100

45 50/1 25 1876 1.96 11 45 10 100

EXAMPLES 46-54, CONTROLS 17, 18,

Synthesis of butyl acrylate macromonomers

AMS comonomer at 125 °C

Batch polymerization - Effect of reaction temperature

A mixture of butyl acrylate (1.3g, lOmmol), α-methylstyrene (50mg,

0.4mmol) (monomer ratio: 25/1), n-butyl acetate (2g), VR^®-110 (3.74xl0"⁴ g,

¹⁴ Polystyrene equivalents.

¹⁵ Calculated as (terminal AMS units)/(total AMS units) X 100.

¹⁶ Calculated as (total AMS units)/(total BA units + total AMS) X 100.

¹⁷ Calculated as (terminal AMS units)/( terminal AMS units + terminal BA units) X 100. A Value of 100% indicates that terminal BA could not be detected by Η NMR. lOOppm) and iPrCo(III)(DMG-BF₂)₂ (for concentration see Table 2.2) was placed in an ampoule and degassed by 4 freeze-thaw cycles. The ampoule was sealed and the mixture heated at 125 °C for 2 hours. The ampoule was cooled, opened and the reaction mixture reduced in vacuo to a residue which was analysed by H-nmr and GPC.

Table 2.2 Polymerization of butyl acrylate in presence of AMS and iPrCo(III)(DMG-BF₂)₂ at 125 °C

Ex. BA/AMS Co(III) M _n PD % % term. % AMS % terminal ratio ppm conv AMS inc.¹⁹ alkene²⁰ units¹⁸

Control 17 25/1 0 18,069 1.77 36 0 13 0

46 25/1 200 973 1.58 19 77 12 85

47 25/1 100 967 1.73 29 68 13 93

48 25/1 50 1402 1.68 32 57 13 100

49 25/1 25 2230 2.10 23 20 100

Control 18 50/1 0 18,891 1.85 6 0 5 0

50 50/1 400 1069 1.65 21 84 6 not calc.

51 50/1 200 1200 1.72 21 72 7 73

52 50/1 100 1624 1.81 30 58 6 77

53 50/1 50 1948 1.92 32 55 6 87

54 50/1 25 3463 2.10 43 32 5 100

EXAMPLES 55-58, CONTROL 19 Synthesis of butyl acrylate macromonomers

AMS comonomer at 80°C Batch polymerization - Effect of cobalt complex A mixture of butyl acrylate (1.3g, lOmmol), a-methylstyrene (24mg, 0.2mmol) (monomer ratio: 50/1), n-butyl acetate (2g), AIBN (3.74xl0^" g, 1 OOppm) and MeCo(lll)(DEG-BF₇)₂ (for concentration see table 2.3 ) was placed in an ampoule and degassed by 4 freeze-thaw cycles. The ampoule was sealed and the mixture heated at 80°C for 2 hours. The ampoule was cooled, opened and the reaction mixture reduced in vacuo to a residue which was analysed by H-nmr and GPC.

¹⁸ Calculated as (terminal AMS units)/( total AMS units) X 100.

¹⁹ Calculated as (total AMS units )/(total BA units + total AMS) X 100.

²⁰ Calculated as (terminal AMS units)/( terminal AMS units ^■+^• terminal BA units) X 100. Table 2.3 Polymenzation of butyl acrylate in presence of AMS and MeCo(III)(DEG-BF₂)₂ at 80°C

Ex. BA/AMS Co(III) M _n PD % % term. % AMS % terminal ratio ppm conv AMS inc.²² alkene²³ units²¹

Control 19 50/1 0 49,342 1.74 1 1 0 25 0

55 50/1 200 1128 1.57 4 79 12 100

56 50/1 100 1162 1.66 5 75 12 100

57 50/1 50 1647 1.70 10 57 12 100

58 50/1 25 2369 1.85 11 31 13 100

EXAMPLES 59-63, CONTROL 20 BA/AMS macromonomer formation at 80°C with Co(II)(DPG-BF₂)₂.

A mixture of butyl acrylate (1.3g, lOmmol), α-methylstyrene (24mg, 0.2mmol) (monomer ratio: 50/1), n-butyl acetate (2g), AIBN (3.74x1 O^g, lOOppm) and Co(II)(DPG-BF₂)₂ (for concentrations see Table 2.4) was placed in an ampoule and degassed by 4 freeze-thaw cycles. The ampoule was sealed and the mixture heated at 80 °C for 2 hours. The ampoule was cooled, opened and the reaction mixture reduced under vacuum to a residue which was analysed by H- nmr and GPC.

Table 2.4 Polymerization of butyl acrylate in presence of AMS (50/1) and Co(II)(DPG-BF₂)₂ at 80°C

Ex. Co(II) M _n M _w PD % % term. % AMS % ppm conv AMS inc.²⁵ terminal units²⁴ alkene²⁶

Control 20 0 50,575 104,679 2.07 17 0 9 0

59 400 796 1262 1.58 1 79 1 1 89

60 200 864 1419 1.64 1 73 12 100

61 100 1064 1817 1.71 1 66 13 100

62 50 1126 1957 1.73 1 60 14 100

63 25 2076 5407 2.10 J 35 13 100

²¹ Calculated as (terminal AMS units )/(total AMS units) X 100

²² Calculated as (total AMS untts)/(total BA units + total AMS) X 100

²³ Calculated as (terminal AMS units )/(termιnal AMS units + terminal BA units) X 100

²⁴ Calculated as (terminal AMS units )/(totai AMS units) X 100

²⁵ Calculated as (total AMS units )/( total BA units + total AMS) X 100

²⁶ Calculated as (terminal AMS units )/( terminal AMS units + terminal BA units) X 100 EXAMPLES 64-68, CONTROL 21 Synthesis of butyl acrylate macromonomers MAN comonomer at 80 °C - Batch polymerization A mixture of butyl acrylate (lg, 7.58mmol), methacrylonitrile (51mg, 0.758mmol), n-butyl acetate (2g), AIBN (3.54xlθ"g, lOOppm) and iPrCo(III)(DMG-BF )₂ (for concentration see Table 2.5) was placed in an ampoule and degassed by 4 freeze-thaw cycles. The ampoule was sealed and the mixture heated at 80 °C for 2 hours. The ampoule was cooled, opened and the reaction mixture reduced in vacuo to a residue which was analysed by 1 H-nmr and GPC. Η-nmr (CDCLJ: d 0.95, CH₃; 1.35, CH₂; 1.65, CH₂; 1.95, CH; 2.3, backbone CH₂; 2.6, allyl CH₂; 4.0, OCH₂; 5.7, vinyl H; 5.85, vinyl H. Table 2.5 Polymerization of butyl acrylate in presence of MAN and iPrCo(III)(DMG-BF₂)₂ at 80 °C

Ex. BA/MAN [Co(III)] M _n M PD % % terminal

Ratio ppm conv. methylene²⁷

Control 21 10/1 0 9306 17,653 1.90 8 0

64 10/1 400 669 1004 1.50 6 86

65 10/1 200 802 1179 1.47 7 87

66 10/1 100 959 1432 1.49 8 80

67 10/1 50 1036 1676 1.62 8 76

68 10/1 25 1301 2008 1.54 8 81

EXAMPLES 69-83, CONTROLS 22 to 24 Synthesis of butyl acrylate macromonomers MMA comonomer at 60-125 °C - Batch polymerization BA/MMA macromonomer formation at BA/MMA 10/1. A mixture of butyl acrylate (lg, 7.58mmol), methyl methacrylate (76mg, 0.758mmol), n-butyl acetate (2g), initiator (see Table 2.6 for initiator type) and isopropylcobalt(III)DMG (for concentration see Table 2.6) was placed in an ampoule and degassed by 4 freeze-thaw cycles. The ampoule was sealed and the mixture heated at the indicated temperature for either 2 or 3 hours. The ampoule was rapidly cooled, opened and the reaction mixture reduced in vacuo to a residue which was analysed by ^l H-nmr and GPC.

²⁷ Calculated as (terminal MAN units )/( terminal MAN units + terminal BA units) X 100 lH-nmr (CDCl₃): d 0.9, CH₃; 1.35. CH₂; 1.65. CH₂: 1.85, CH. 2.25. backbone CH₂; 2.55. allyl CH₂; 3.6, OCH₃; 4.0, OCH₂; 5.5. vinyl H; 6.15, vinyl H.

Table 2.6 Polymerization of butyl acrylate in presence of MMA (10: 1) and iPrCo(HI)(DMG-BF₂)₂ at various temperatures

Ex. Temp °C React. Co(III) M _n PD % % term. % MMA — cal M n ^ T

(initiator) Time h ppm conv alkene²⁸ incorp.²⁹^ ¹¹ ob

Ctrl 22 (AIBN) 3 0 170,75 2.08 25 0 19 - 4

69 60 3 400 891 1.55 6 83 18 1.04

70 60 3 200 1051 1.56 5 87 19 1.05

71 60 3 100 1567 1.70 4 91 20 0.83

72 60 3 50 2610 1.80 7 100 19 0.98

73 60 3 25 7702 1.87 16 100 18 1.0

Ctrl 23 (AIBN) 2 0 75,501 2.08 54 0 14 -

74 80 2 400 917 1.31 8 75 17 0.92

75 80 2 200 1196 1.43 10 86 17 0.93

76 80 2 100 1520 1.50 9 92 18 0.92

77 80 2 50 2602 1.66 21 94 17 1.00

78 80 2 25 12,117 1.82 53 100 14 1.09

Ctrl 24 (VR^®-110) 2 0 10,410 2.56 76 0 1 1 -

79 125 2 400 832 1.51 9 79 16 1.04

80 125 2 200 1032 1.73 15 87 17 1.00

81 125 2 100 1224 1.60 14 91 17 1.05

82 125 2 50 1994 1.70 32 92 15 1.01

83 125 2 25 3513 1.74 45 93 14 0.88

EXAMPLES 84-91, CONTROL 25 and 26 Synthesis of functional butyl acrylate macromonomers HEMA comonomer at 80 °C - Batch polymerization A mixture of butyl acrylate ( 1.3g; 1 Ommol), 2-hydroxyethyl methacrylate, HEMA (65mg; 0.5mmol) (monomer ratio 20: 1), n-butyl acetate (2g), AIBN (3.74xl0-4g, lOOppm) and isopropylcobalt(III)DMG (for concentration see Table 2.7) was placed in an ampoule and degassed by 4 freeze-

²⁸ Calculated as (terminal MMA units )/( terminal MMA units -t- terminal BA units) X 100

²⁹ Calculated as (total MMA unιts)/(total MMA units + total BA units) x 100 thaw cycles. The ampoule was sealed and the mixture heated at 80 °C for 1 or 2 hours. The ampoule was cooled, opened and the reaction mixture reduced in vacuo to a residue which was analysed by ' H-nmr and GPC.

Η-nmr (CDCLJ: d 0.95, CH₃; 1.40, CH₂; 1.65, CH₂; 1.85, backbone CH; 2.25, backbone CH₂; 3.80, CH₂; 4.00, CH,; 4.22, CH₂; 5.50, external vinyl*; 5.80, 5.90, E&Z internal vinyl*; 6.20, external vinyl*.

('external vinyl signals due to HEMA derived vinyl end group and internal vinyl signals due to BA derived vinyl group).

Table 2.7 Polymerization of butyl acrylate in presence of HEMA (20:1) and iPrCo(III)(DMG-BF2)2 at 80 °C

Example Reaction Co(III) M_n M_w PD % %

Time ppm conv terminal

(hours) alkene³⁰

Control 25 1 0 169,846 403,699 2.38 53 0

84 1 200 1695 3011 1.78 6 80

85 1 50 12,919 25,390 1.97 23 100

86 1 25 35,421 68,294 1.93 37 100

Control 26 2 0 58,522 200,100 3.42 98 0

87 2 400 1116 2144 1.92 13 71

88 2 200 1545 3207 2.08 19 73

89 2 100 2219 5215 2.35 24 78

90 2 50 21,852 46,133 2.11 79 a

91 2 25 38,369 95,492 2.49 97 a ^a Terminal alkene protons were not visible in ' H-nmr spectrum.

EXAMPLES 92-94, CONTROL 27 Synthesis of functional acrylate copolymer macromonomers

AMS comonomer at 80 °C - Batch polymerization A mixture of butyl acrylate (1.3g; lOmmol), 2-hydroxyethylacrylate, HEA (116mg; Immol), α-methylstyrene (26mg; 2.2xl0'⁴mol) (monomer ratio 10/1/0.22), n-butyl acetate (2g), AIBN (3.65xl0"⁴g, lOOppm) and isopropylcobalt(III)DMG (for concentration see Table 2.8) was placed in an ampoule and degassed by 4 freeze-thaw cycles. The ampoule was sealed and the mixture heated at 80 °C for 2 hours. The ampoule was cooled, opened and the

³⁰ Calculated as (terminal HEMA unιts)/( ter inal HEMA units + terminal BA units) X 100 reaction mixture reduced in vacuo to a residue which was analysed by ' H-nmr and GPC. ^lH-nmτ(CDCl₃): d 0.90, CH₃; 1.30, CH₂; 1.50, CH₂; 1.80, backbone CH: 2.22, backbone CH₂; 3.80, CH₂; 3.85, CH2; 4.98, external vinyl*; 5.20. external vinyl*; 5.80, 5.85, internal vinyl*; 6.60-7.00, internal vinyl*; 7.30, ArH. ⁽'external vinyl signals due to aMS derived vinyl end group and internal vinyl signals due to BA derived vinyl group).

Table 2.8 Copolymerization of butyl acrylate and hydroxyethyl acrylate in presence of AMS and iPrCo(III)(DMG-BF₂>2 at 80 °C

Example BA/HEA/ Co(III) M_n PD % % % %

AMS ratio ppm (Mw/Mn) conv terminal AMS terminal

AMS inc.³² alkene³³ units³¹ 3

Control 27 10/1/0.22 0 66,642 1.96 30 0 9 0

92 10/1/0.22 200 1255 1.55 16 72 10 78

93 10/1/0.22 100 1712 1.76 22 19 8 100

94 10/1/0.22 50 1835 1.80 22 49 10 100

EXAMPLES 95-100, CONTROLS 28 and 29 Synthesis of vinyl benzoate macromonomers BMA comonomer at 80 °C - Batch polymerization A mixture of vinyl benzoate, VB (1.3g, 8.77mmol), butyl methacrylate (0.125g, 0.877mmol) (monomer ratio: 10/1), n-butyl acetate (3g), AIBN (4.43x1 O^g, lOOppm) and isopropylcobalt(III)DMG (for concentration see Table 3.1) was placed in an ampoule and degassed by 4 freeze-thaw cycles. The ampoule was sealed and the mixture heated at 80 °C for 2 hours. The ampoule was cooled, opened and the reaction mixture reduced in vacuo to a residue which was analysed by ^x H-nmr and GPC.

Η-nmr (d6-acetone): δ 0.9, CH₃; 1.35, CH₂; 1.65, CH₂; 1.95, CH; 2.25, backbone CH₂; 2.55, allyl CH₂; 4.0, OCH₂; 5.2, CH; 5.45, vinyl H; 6.15, vinyl H; 6.9-7.7, ArH.

³¹ Calculated as (terminal AMS units)/(total AMS units) X 100.

³² Calculated as (total AMS units )/( total BA+total HEA units) X 100.

³³ Calculated as (terminal AMS units)/(terminal AMS units + terminal BA units) X 100. Table 3.1 Polymerization of vinyl benzoate in presence of BMA and iPrCo(III)(DMG-BF₂), at 80°C

Example VB/BMA [Co(III)] M _n M _w PD % % terminal ratio ppm conv. methylene

34

Control 28 10/1 0 67,070 106,547 1.59 12 0

95 10/1 100 3168 4942 1.56 5 87

96 10/1 50 6679 12,475 1.87 7 85

97 10/1 25 12,344 24,349 1.97 8 63

Control 29 5/1 0 86,701 137,600 1.58 19 0

98 5/1 100 1720 2526 1.47 8 100

99 5/1 50 3464 6151 1.76 7 100

100 5/1 25 9094 16,155 1.78 9 86 ^a Calculated as (terminal BMA units)/( terminal BMA unιts+ terminal VB units) X 100.

EXAMPLES 101-108, CONTROLS 30 and 31

Synthesis of vinyl acetate macromonomers methacrylate comonomers at 80°C - Butyl methacrylate comonomers at 80°C Batch polymerization VAc/BMA macromonomer synthesis with monomer ratio of 10/1. A mixture of vinyl acetate (lg; 11.6mmol), butyl methacrylate (0.165g; 1.16mmol) (monomer ratio: 10/1 ), n-butyl acetate (2g), AIBN (3.17x10" g, lOOppm) and isopropylcobalt(III)DMG (for concentration see Table 3.2) was placed in an ampoule and degassed by 3 freeze-thaw cycles. The ampoule was sealed and the mixture heated at 80 °C for 2 hours. The ampoule was cooled, opened and the reaction mixture reduced in vacuo to a residue which was analysed by 'H-nmr and GPC.

1H-nmr(CDCl₃): d 0.95, CH₃; 1.30, CH₂; 1.60, CH₂; 3.90, CH₂; 5.40, 6.10, external vinyl CH₂*. ('external vinyl signals due to BMA derived vinyl end group).

³⁴ Calculated as (terminal BMA unιts)/(terminal BMA units* terminal VB units) X 100. Table 3.2 Polymerization of vinyl benzoate in presence of BMA and iPrCo(III)(DMG-BF₂)₂ at 80°C (VAc:BMA = lO l

Example Co(III) M , PD %o %BMA BMA % term. M _n ppm conv terminal^{35 36} (%) alkene³⁷ £^ obs

Control 30 0 62,363 1.78 10 0 67 0 0

101 400 499 1.40 5 33 80 100 0.9

102 200 1917 1.37 6 16 69 100 0.55

103 100 2127 2.3 7 7 72 100 1.02

104 50 4435 3.0 7 4 73 100 1.03

105 25 10,331 2.88 10 1 71 100 1.3

VAc/MMA macromonomer synthesis with monomer ratio of 5/1.

A mixture of vinyl acetate (0.75g; 8.77mol), methyl methacrylate (0.175g; 1.75mmol) (monomer ratio: 5/1), n-butyl acetate (2g), AIBN (2.93x10- ⁴g, lOOppm) and isopropylcobalt(III)DMG (for concentration see Table 3.3) was placed in an ampoule and degassed by 3 freeze-thaw cycles. The ampoule was sealed and the mixture heated at 80°C for 2 hours. The ampoule was cooled, opened and the reaction mixture reduced in vacuo to a residue which was analysed by ^l H-nmr and GPC.

¹ H-nmr (d_j-acetone): δ 0.6-2.1, CH₃CO₂ and backbone CH₂; 3.60, COOCH₃; 4.80-5.30, multiplet, various methine signals; 5.42, 6.10 external vinyl CH₂*. ('external vinyl signal due to MMA derived vinyl end group).

³⁵ Calculated as [terminal BMA units ]/[total BMA units incoφorated] X 100.

³⁶ Calculated as (total BMA units)/( total VAc units + total BMA units) X 100.

³⁷ VAc derived internal alkene not detectable by Η-nmr. Table 3.3 Polymerization of vinyl acetate in presence of MMA and iPrCo(III)(DMG-BF₂)₂ at 80°C (VAc:MMA = 5^

Example Co(III) M _n PD % conv %MMA % MMA % term. \ MΛ n T ^Cal ob~^C s ppm terminal inc.³⁹ alkene⁴⁰

38

Control 31 0 40,448 1.87 8 0 87 0 -

106 100 11,806 2.26 5 0.9 87 100 1.0

107 50 12,487 2.38 8 0.8 88 100 1.06

108 25 30,782 1.92 8 Q41 87 0⁴¹ -

EXAMPLES 109-116, CONTROLS 32 and 33 Synthesis of vinyl acetate macromonomers isopropenyl acetate, iPA comonomer at 125 °C - Batch polymerization A mixture of vinyl acetate (l.Og; 1 l.όmmol), isopropenyl acetate (23mg; 0.232mmol) (monomer ratio: 50/1), n-butyl acetate (2g), VR^®-110 (3.4x10' g, lOOppm) and isopropylcobalt(III)DMG (for concentration see Table 3.4) was placed in an ampoule and degassed by 3 freeze-thaw cycles. The ampoule was sealed and the mixture heated at 125 °C for 2 hours. The ampoule was cooled, opened and the reaction mixture reduced in vacuo to a residue which was analysed by 'H-nmr and GPC.

Η-nmr (CDClj: d 1.2-2.1, CH₂ +CH₃CO; 4.7-5.2, multiplet, various backbone methine.

³⁸ Calculated as (terminal MMA units )/(total MMA units incoφorated) X 100

³⁹ Calculated as (total MMA unιts)/(total VAc units + total MMA units) X 100

⁴⁰ Calculated as (terminal MMA umts)/( terminal VAc units + terminal MMA units) X 100 VAc denved internal alkene not detectable by Η-nmr.

⁴¹ Terminal vinyl signals could not be detected by Η-nmr Table 3.4 Polymerization of vinyl acetate in presence of iPA and iPrCo(III)(DMG-BF₂)₂ at 125°C

Example Vac/iPA Co(III) M_n Mw PD % % term. ratio ppm conv iPA

Control 32 5/1 0 11,964 21,818 1.82 47 0

109 5/1 200 502 983 1.40 2 b

1 10 5/1 100 696 1124 1.61 2 b

1 11 5/1 50 1240 2278 1.84 2 b

1 12 5/1 25 z 4781 11,189 2.34 9 b

Control 33 50/1 0 15,271 29,423 1.93 90 0

113 50/1 200 772 1329 1.72 2 a

114 50/1 100 1295 2517 1.94 3 a

115 50/1 50 2353 6484 2.76 5 b

116 50/1 25 13,518 23,737 1.76 16 b a end group signals observed but reliable quantitation not possible, b no end group signals detected.

EXAMPLES 117-128, CONTROLS34 to 36

Synthesis of vinyl acetate macromonomers isopropenyl chloride comonomer at 125 °C - Batch polymerization

VAc/iPrCl macromonomer formation at 125 °C with VR^®-110 and iPrCo(IH)(DMG-BF₂)₂

A mixture of vinyl acetate (lg, 1 l.όmmol), isopropenyl chloride

(0.18g, 2.32mmol) (monomer ratio: 5/1), n-butyl acetate (2g), VR^®-110 (3.18X10^*4 g, lOOppm) and iPrCo(III)(DMG-BF₂)₂ (for concentration see table 3.5) was placed in an ampoule and degassed by 4 freeze-thaw cycles. The ampoule was sealed and the mixture heated at 125°C for 2 hours. The ampoule was cooled, opened and the reaction mixture reduced in vacuo to a residue which was analysed by 'H-nmr and GPC.

Table 3.5 Polymerization of vinyl acetate in presence of iPCl and iPrCo(III)(DMG-BF,)₂ at 125 °C

Example VAc/iPrCl Co(III) M_n Mw PD % ppm conv

Control 34 5/1 0 3969 7475 1.88 3

1 17 5/1 200 350 434 1.24 1

118 5/1 100 552 1323 2.40 <1

119 5/1 50 1355 3833 2.82 1

120 5/1 25 1791 5143 2.87 <1

Control 35 50/1 0 15,712 27,346 1.74 14

121 50/1 200 717 973 1.35 <1

122 50/1 100 1230 1843 1.49 <1

123 50/1 50 2692 4594 1.71 1

124 50/1 25 12,243 21,771 1.78 8

VAc/iPrCl macromonomer formation at 125 °C with VR -1 10 and MRCo(III)(DEG-BF₂)₂ A mixture of vinyl acetate (lg, 1 l.όmmol), isopropenyl chloride (18mg, 0.232mmol) (monomer ratio: 50/1), n-butyl acetate (2g), VR^®-110 (3.15X10^" g, lOOppm) and MeCo(III)(DEG-BF₂)₂ (for concentration see table 3.6) was placed in an ampoule and degassed by 4 freeze-thaw cycles. The ampoule was sealed and the mixture heated at 125^® for 2 hours. The ampoule was cooled, opened and the reaction mixture reduced in vacuo to a residue which was analysed by GPC.

Table 3.6 Polymerization of vinyl acetate in presence of iPCl and MeCo(III)(DEG-BF₂)₂ at 125 °C

Example VAc/ Co(III) M_n M w PD % conv iPrCl ppm ratio

Control 36 50/1 0 13,984 24,811 1.77 46

125 50/1 200 935 1502 1.60 <1

126 50/1 100 1627 3001 1.84 1

127 50/1 50 10,605 19,522 1.84 6

128 50/1 25 12,740 22.831 1.79 10 EXAMPLES 129-132, CONTROL 37

Synthesis of functional styrene macromonomer

TMI^®- Cytec Incorporated comonomer

Feed polymerization A mixture of styrene ( 1 g, 9.6mmol), TMI (0.2g, 0.96mmol)

(monomer ratio: 10/1), n-butyl acetate (2g), VR^®-110 (3.2x10"* g, lOOppm) and isopropylcobalt(IH)DMG (at 0, 25, 50, 100 and 200ppm) was placed in an ampoule and degassed by 4 freeze-thaw cycles. The ampoule was sealed and the mixture heated at 125 °C for 2 hours. The ampoule was cooled, opened and the reaction mixture reduced in vacuo to a residue which was analysed by Η-nmr and GPC.

¹H-nmr(d6-acetone): δ 4.9, external vinyl*; 5.20, external vinyl*; 6.0- 6.2, internal vinyl*; 6.6-7.4, ArH.

(*external vinyl signals due to TMI derived vinyl end group and internal vinyl signals due to Sty derived vinyl end group).

Table 4.1 : Polymerization of styrene in presence of TMI^® and iPrCo(III)(DMG- BF₂)₂ at 125 °C

Example Sty/ Co(IH) M_n M_w PD % terminal

TMI^® ppm TMI^® units⁴² ratio

Control 37 10/1 0 85,912 133,091 1.67 0

129 10/1 200 475 602 1.27 47

130 10/1 100 640 903 1.41 53

131 10/1 50 887 1373 1.55 60

132 10/1 25 1274 2155 1.73 75

EXAMPLE 133

A mixture of 2.5 mL MA, 0.5 mL 2-chloro-2-propenol, 14 mg TAPCo, 20 mg VAZO-88 and 5 mL chloroform was degassed by three freeze-pump-thaw cycles. The reaction mixture was kept at 90 °C until 10-15% conversion was attained. GPC analysis showed Mn * 2150, PD = 2.0.

EXAMPLE 134 A mixture of 2.5 mL MA, 0.5 mL ethyl 2-hydroxymethylacryiate, 14 mg TAPCo, 20 mg VAZO-88 and 5 mL chloroform was degassed by three freeze-pump-thaw

⁴² Calculated as (terminal TMI units)/(terminal TMI units+terminal Sty units). cycles. The reaction mixture was kept at 90 °C until 10-15% conversion was attained. GPC analysis showed Mn « 1600, PD = 3.2.

EXAMPLE 135 A mixture of 2.5 mL MA, 0.5 mL styrene. 14 mg TAPCo, 20 mg VAZO-88 and 5 mL chloroform was degassed by three freeze-pump-thaw cycles. The reaction mixture was kept at 90 °C until 10-15% conversion was attained. GPC analysis showed Mn * 700, PD = 2.4.

EXAMPLE 136

A mixture of 2.5 mL MA, 0.5 mL 2 -hydroxyethyl methacrylate, 14 mg TAPCo, 20 mg VAZO-88 and 5 mL chloroform was degassed by three freeze-pump-thaw cycles. The reaction mixture was kept at 90°C until 10-15% conversion was attained. GPC analysis showed Mn « 2150, PD = 2.0. CONTROL 38

A mixture of 2.5 mL MA, 14 mg TAPCo, 20 mg VAZO^®-88 and 5 mL chloroform was degassed by three freeze-pump-thaw cycles. The reaction mixture was kept at 90°C until 10-15% conversion was attained. GPC analysis showns Mn * 21,700, PD=2.4.

EXAMPLE 137 High Conversion Copolymerization of BA and MMA to Branched and Hyperbranched Polymers The reincorporation of initially- formed macromonomers back into the growing polymer is demonstrated.

Identical solutions of 32 mg of VAZO^®-88 and 4 mg Co(II)(DPG-BF₂)₂ in 7.7 mL of butyl acrylate (BA), 1.5 mL MMA and 8 mL of 1 ,2-dichloroethane were degassed and kept in a 90 °C oil bath. The samples were removed from the temperature bath at various times shown in Table 5.1. Then each reaction mixture was chilled and evaporated in high vacuum till constant weight. The results, shown in Table 5.1, indicates that MW increases sharply at the end ofthe polymerization process. Because most ofthe monomer had been consumed before the increase in molecular weight, the only way that it could occur is through reincorporation ofthe macromonomers formed at the beginning ofthe reaction. GPC and K⁺IDS data are consistent. Table 5.1

Conversion M„ M_n/M_v

12% 540 2.08

20% 640 2.08

55% 890 2.06

93% 2270 2.84

The catalyst remained active during the course of the polymerization. Sudden inactivation ofthe catalyst at conversion >60% cannot account for an increase of the Mn from 890 at 55% conversion to 2270 at 93% conversion. Less than doubling ofthe conversion (93% vs 55%) cannot provide a 2.6 fold increase ofthe Mn (2270 vs 890) maintaining a unimodal distribution.

The linear macromonomers formed at 55% conversion were incoφorated into the polymer at higher conversions. The incorporation of macromonomer into growing polymer chains provides branched polymer. With continuous termination of polymeric radicals by the cobalt catalyst, such an incoφoration leads to polymer with a structure containing "branches-on-branches" - in the extreme, it is hyperbranched.

Confirmation ofthe macromonomer reincoφoration into the polymer back-bone was provided by MALDI mass spectroscopy. As seen on the MALDI spectra, at conversions <50% the polymer contains from 1 to 5 MMA units per chain. For Mn «900, it means that the polymer is enriched with MMA vs composition ofthe initial monomer solution. As a result, the concentration of unreacted MMA monomer in the solution decreases faster than that of BA. At 55% conversion, more than 70% ofthe original MMA is consumed. Fewer MMA units are available to be incoφorated into the high molecular weight polymer formed at conversions >60% than at lower conversions if polymer that forms at high conversion does not incoφorate previously formed macromonomer. Incoφoration ofthe previously-formed macromonomer would provide MMA to the high molecular weight polymer. The MALDI spectrum of the polymer at 93% conversion demonstrated this clearly. The MALDI spectrum ofthe polymer at 93% conversion becomes unresolved at masses >2500 due to the high levels of MMA incoφoration. EXAMPLE 138 A reaction mixture containing 4 mg ofthe CTC-catalyst (COBF), 32 mg of VAZO^®-88, 2 ml of butyl acrylate, 6 ml MMA-trimer, 0.2 ml of methyl methacrylate and 4 ml of 1 ,2-dichloroethane was degassed by three freeze-pump- thaw cycles and put into an oil bath at 90°C. Samples of the reaction mixture were taken after 1.5 hours, 3 hours, 7 hours and 22 hours. Initial GPC analysis shows that molecular weight ofthe polymeric product increases with time. Comparision of GPC data with that of KIDS and MALDI shows that in the first case the average measured MW are lower than expected in case of higher conversion samples. The first samples had readily observable quantities of vinylene protons (IH NMR spectra), indicating the formation of methacrylate- terminated polymer at the beginning ofthe CTC process. All ofthese observations are consistent with the proposed scheme.

Claims

WHAT IS CLAIMED IS:

1. In a process for the free-radical polymerization of at least two unsaturated monomers to form a polymer whose molecular architecture comprises properties of molecular weight, branching, and vinyl-terminated end groups, the monomers having the formula

CH₂=CXY wherein

X is selected from the group consisting of H, CH₃,and CH₂OH; Y is selected from the group consisting of OR, O₂CR. halogen, CO₂H, COR, CO₂R, CN, CONH₂, CONHR, CONR₂ and R;

R' is selected from the aromatic group consisting of substituted and unsubstituted aryl, substituted and unsubstituted heteroaryl, the substituents being the same or different and selected from the group consisting of carboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, primary amino, secondary amino, tertiary amino, isocyanato, sulfonic acid, substituted and unsubstituted alkyl, substituted and unsubstituted aryl, substituted and unsubstituted olefin and halogen; by contacting said monomers with a cobalt-containing chain transfer agent and a free radical initiator at a temperature from about 80° to 170°C; the improvement which comprises controlling polymer architecture by introducing into the presence ofthe chain transfer agent at least one each of monomers A and B in the molar ratio of A:B, said molar ratio lying in the range of about 1,000:1 to 2:1, wherein for monomer A Xis H and for monomer B X is methyl or hydroxymethyl; by one or more of the following steps:

I decreasing the ratio of A:B from about 1 ,000: 1 toward 2:1; II increasing the temperature from above 80°C toward 170 °C; III increasing the conversion of monomer to polymer toward 100% from less than about 50%; IV decreasing the ratio ofthe chain transfer constant of A:B to below 1 ; and V increasing the concentration of cobalt chain transfer agent; whereby: to effect lower molecular weight, employ at least one of steps I, II, IV and V; to effect a higher degree of vinyl-terminated end groups, employ at least one of steps I, II, IV, and V; and to effect increased branching,employ at least one of steps I, II, IV, and V with step III.

2. A process according to Claim 1 wherein the improvement comprises: controlling molecular weight ofthe polymer by introducing into the presence of the chain transfer agent at least one each of monomers C and D in the molar ratio of C:D lying in the range of about 1,000:1 to 2:1, in which for monomer C, X is H, and Y≠R' and for monomer D, X is H, and Y=R' by: decreasing the ratio of C:D from about 1 ,000: 1 toward 2: 1 ; or increasing the temperature from above 80°C toward 170 °C.

3. A process according to Claim 1 wherein the improvement comprises polymerizing monomer(s) in the presence of an excess of a nonpolymerizable olefin, Y¹Y²C=CY³Y⁴. The product in the initial stages ofthe polymerization will be composed primarily of

wherein: Y¹ and Y , and optionally Y and \ , are each independently selected from the group consisting of -CH(O), -CN, -C(O)OR , -C(O)NR R , -CR (O), alkyl, aryl, substituted alkyl, substituted aryl; or where Y and Y or Y and i are combined in a cyclic structure which includes any ofthe above functionalities, or can be -C(O)-(CH2)_x-, -C(O)- O-(CH₂)_x-, -C(O)O-C(O)-, -C(O)(CH₂)_x-, -C(O)NR -(CH₂)_X-, wherein x= 1 - 12,

5 6 7 8 9

R , R , R , R , or R are hydrogen, alkyl, aryl, substituted alkyl, or substituted aryl; and where at least one of Y and Y is selected from the group consisting of -

CH(O), -CN, -C(O)OR , -C(O)NR R , -CR (O), aryl, substituted aryl; and the remaining of Y and Y are -H.

4. A process according to Claim 1 comprising selecting A and B so the ratio of their chain transfer constants is less than 1 , whereby functionality derived from monomer B will be located on the vinyl-terminated end ofthe polymer.

5. The process according to Claim 1 in which monomer A is at least one member selected from the group substituted and unsubstituted alkyl acrylates, substituted and unsubstituted acrylamides, acrylonitrile, and vinyl esters; and monomer B is at least one of: a) substituted and unsubstituted α-methyl styrenes; b) alkyl methacrylates c) methacrylonitrile; d) substituted or unsubstituted methacrylamide; e) 2-chloropropene, f) 2-fluoropropene, g) 2-bromopropene h) methacrylic acid, i) itaconic acid, j) itaconic anhydride, k) substituted and unsubstituted styrenics, and

1) isopropenyl esters; alkyl being Ci to C,₂ and substituents being selected from the group carboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, primary amino, secondary amino, tertiary amino, isocyananto, sulfonic acid and hydrogen.

6. A process according to Claim 5 in which monomer A is at least one member selected from the group alkyl acrylate, acrylamide, acrylonitrile and vinyl ester.

7. A process according to Claim 2 in which monomer A is at least one member selected from the group substituted and unsubstituted alkyl acrylates substituted and unsubstituted acrylamides, acrylonitrile, and vinyl esters; and monomer B is at least one of: a) substituted and unsubstituted α-methyi styrenes; b) alkyl methacrylates c) methacrylonitrile; d) substituted and unsubstituted methacrylamide; e) 2-chloropropene, f) 2-fluoropropene, g) 2-bromopropene h) methacrylic acid, i) itaconic acid, j) itaconic anhydride, k) substituted and unsubstituted styrenics, and

1) isopropenyl esters; alkyl being C] to C₁₂ and substituents being selected from the group carboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, primary amino, secondary amino, tertiary amino, isocyananto, sulfonic acid and hydrogen.

8. A polymer having the formula:

Y is selected from the group consisting of OR, O₂CR, halogen, CO₂H, COR, CO₂R, CN, CONH₂, CONHR, CONR₂ and R'; n = 1-20, m = 1-5, p=l-20, and n + m + p > 3, and

Z is selected from the group CH₂CHYCH₃, CH₂CMeYCH₃, and, optionally,

m' = 0-5, p' = 0-20; n + m' + p' > 2; and if m or m' > 1 , the m or m' insertions respectively are not consecutive.

9. A polymer having the formula:

wherein:' k = 0 or 1, n = 0-20, m = 0-5, p = 0-20; and k + n + m + p > 2; if m>l, the m insertions are consecutive; Y is selected from the group consisting of OR, O₂CR, halogen, CO₂H,

COR, CO₂R, CN, CONH₂, CONHR, CONR₂ and R'; and

Y 1 and Y3 , and optionally Y 2 and Y 4 , are each independently selected from the group consisting of -CH(O), -CN, -C(O)OR⁵, -C(O)NR⁶R⁷, -CR⁸(O), alkyl, aryl, substituted alkyl, substituted aryl; or where Y and Y or Y and i are combined in a cyclic structure which includes any ofthe above functionalities, or can be -C(O)-(CH2)_x-, -C(O)- O-( (O)-, -C(O)(CH₂)_x-, -C(O)NR⁹-(CH₂)_x-, wherein x=l-12,

R ,

are hydrogen, alkyl, aryl, substituted alkyl, or substituted aryl; and where at least one of Y 1 and Y 3 is selected from the group consisting of - CH(O), -CN, -C(O)OR⁵, -C(O)NR⁶R⁷, -CR⁸(O), aryl, substituted aryl; and the remaining of Y and Y^ are -H;

R is selected from the group consisting of substituted and unsubstituted alkyl, substituted and unsubstituted aryl, substituted and unsubstituted heteroaryl, substituted and unsubstituted aralkyl, substituted and unsubstituted alkaryl, and substituted and unsubstituted organosilyl, the substituents being the same or different and selected from the group consisting of carboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, primary amino, secondary amino, tertiary amino, isocyanato, sulfonic acid and halogen; and the number of carbons in said alkyl groups is from 1 to 12; and R' is selected from the aromatic group consisting of substituted and unsubstituted aryl, substituted and unsubstituted heteroaryl, the substituents being the same or different and selected from the group consisting of carboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, primary amino, secondary amino, tertiary amino, isocyanato, sulfonic acid, substituted and unsubstituted alkyl, substituted and unsubstituted aryl, substituted and unsubstituted olefin and halogen.

10. A polymer having the formula:

where Y≠ R' and n > 1 ; in which

Y is selected from the group consisting of OR, O₂CR, halogen, CO₂H, COR, CO₂R, CN, CONH₂, CONHR and CONR₂; and

R' is selected from the aromatic group consisting of substituted and unsubstituted aryl, substituted and unsubstituted heteroaryl, the substituents being the same or different and selected from the group consisting of carboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, primary amino, secondary amino, tertiary amino, isocyanato, sulfonic acid, substituted and unsubstituted alkyl, substituted and unsubstituted aryl, substituted and unsubstituted olefin and halogen.