CA2247837A1 - Catalytic polymerization process - Google Patents

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

CA 02247837 l998-08-2l W O97/31030 PCT~US97/02912 TIT~ ,F.
CATALYTIC POLYMERIZATION PROCESS

RACKGROUND OF TF~F, INVF.NTION
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 termin~l 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 10 weight in the polymeri7~tions of other vinylic monomers such as acrylates.
Copolymeri7~tions of methacrylate monomers with monosubstituted monomers in the presence of cobalt have been described in the art. However, the monosllhstihlt~l1 monomer is almost always present as a minor component. U.S.
4,680,354 describes molecular weight reduction using various Co(II) complexes 15 in MMA-BA, MMA-EA and MMA-BA-St copolymPri7~tions~ wherein the abbreviations l~pres~ll:
MMA=methyl m~th~crylate BA=butyl acrylate EA=ethyl acrylate Sl--~Lyl~ne.
U.S. 5,324,879 describes molecular weight reduction with Co(III) complexes in EA, St, and vinyl acetate (VAc) polym~ri7~tions, and MMA-EA
copolymerization.
U.S. 4,680,352 describes molecular weight reduction and 25 macromonomer (polymers or copolymers with nn~h~r~trll end-groups) synthesis in copolymeri7~ri~ns with acrylates and styrene with various Co(II) complexes.
Various terpoly., ~c; ,~1 ;ons OEe cited therein, however, no evidence of the nature or existence of t~rmin~l double bonds is given.
Gruel et al., Polymer PleP,;11L~, 1991, 32, p. 545, reports the use of 30 Co(II) cobaloximes in low conversion St-MMA copolymerizations at low telllyc;l~LLul~s with end group analysis.
The lerc.~ ces cited above cover the copolymerization of acrylates and styrene with m~th~rrylate monomers, but do not disclose synthetic conditionsfor production of high purity ..la~.vl..onomers based on acrylates and styrene7 nor 3 5 br~nchinp of the resllltinp products. The conditions disclosed are unlikely to yield high purity macromonomers for systems composed predominantly of monosubstituted monomers. Disclosed ~e.npt:,dl lres of less than 80~C OEe likely to W O 97131030 PCTrUS97/02912 provide substantial amounts of undesired graft copolymer at high conversion rates.

SUMl~IARY OF THF. INVFNTION
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 p~upcllies of molecular weight, brAnrtling~ and vinyl-t.onnin~tl-fl end groups, the monomers having the formula 1 0 wherein X is selected from the grûup concicting of H, CH},and CH2OH;
Y is selected from the group corlci.cfing of OR, 02CR, halogen, CO2H, COR, CO2R, CN, CONH2, CONHR, CONR2 and R';
R is selected from the group consisting of ~ul~sliLuL~d and unsubstituted aLkyl, ~ub~liluled and unsllbstitlltrd aryl, sllhstitl-tP~1 and w~ulJ~Liluled h~le~o~ 1 and unsubstituted aralkyl, substituted and unsubstituted alkaryl, and substituted and wls-~b~liluk;d organosilyl, the sllhstihlrnt.c being the same or dir~ .en~ and selected from the group con~icting of carboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, primary amino, secrln~l~ry 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 sllksti1~ltçd and lm~llkstitl7ted aryl, ~ d and unsubstituted heteroaryl, the substibuents being the same or dirr~,l- and selected from the group consisting of carboxylic acid, carboxylic ester, epoxy, llyd~o~yl, aLtcoxy, plilll~L ~ amino, secondary amino, tertiary amino, isocyanato, sulfonic acid, ~ lllrd and lm~--bstituted alkyl, s--hstit--t~d and lm~llkstituted aryl, sllhstihltrd and un~ub~lilulcd olefin andhalogen;
by cor~t~rtin~ said monomers with a cobalt-co.l~ g chain transfer agent and a free radical ;nitiator at a lw~ aLulc from about 80~ to 1 70~C;
the improvement which comprises controlling polymer arr.hit~ct~lre by introducing into the ~resellcc of the 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 3 5 methyl or hydroxymethyl; by one or more of the following steps:
decreasing the ratio of A:B from about 1,000:1 toward 2:1;
II increasing the te~ cldLLIre from above 80~C toward 170 ~C;

W O97/31030 PCTAUS97/~2912 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 conce~ alion 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-t~?rmin~te~ end groups, employ at least one of steps I, II, IV, and V; and to effect increased br~nrhing ~mploy at least one of steps I, II, IV, and V
with step III.
The nature of the derived products r,h~nges as a function of time. In the initial stages, linear macromonomers with one monomer-A in the termin~
position can be obtained ~ eesenti~lly the only product. If the cobalt CTC
catalyst levels are relatively low then CTC does not occur after every B-monomerinsertion and the product n~ixlul~ can include monomer-B units in the polymer chain as well as in the tPrmin~l position.
Cobalt chain transfer agent is employed in the form of cobalt complexes.
Their concentrations are provided in the Fx~mples in terms of ppm by weight of total reaction mass. Co.lr~ ion will vary from 10 ppm to 1,500 ppm, pl~,r~;Lably 10 to 1,000 ppm.
Later in the course of the reaction, when the concentration of the two above products is increased, then they can be reincolyuldled into a growing polymer chain. Thus, mono-branched product is obtained in the later stages of the reaction, usually around 90% conversion. At conversions above 95%, hr~nrh~c begin to appear on the br~nrh~, and the polymer becoll~es hy~ ~,ched as conversions approach 100%.
Preferred monomers A are selected from the group consisting of acrylates, acrylonitrile and acryi~mides, and pref~ d monomers B are selected from the group:
a) s1lhstitllt~d or unsubstituted a-methylstyrenes;
b) s~-hstit~lt~-d or unsubstituted alkyl methyacrylates, where alkyl is C ,-C i2;
c) methacrylonitrile;
d) sub~ililul~d or unsubstituted metiacrylamide;

CA 02247837 l998-08-2l W O 97/31030 PCT~US97/02912 e~ 2-chlolupl~ pclle, f) 2-fluo,~prope.,e, g) 2-bromo~lvpclle, h) methacrylic acid, i) itaconic acid, j) itaconic anhydride, and k) substituted or unsubstituted styrenics.
If brAnch~ polymers are the desired product, it is possible to initiate the described process in the presence of plerc "l~ed macromonomers. They canbe of 10 the type described in this patent. They canalso be macromonomers based entirely upon m~thAr~ylates or the related species described previously in U.S. 4,680,354.
Such a process would lead to products fitting the desc.i~lion above, but would allow for greater control over the polymer end-groups.

The brAnr-h~ polymers made by said process are polymers of this invention having the formula:
t ~ H2 H--CH2--C--~H2 Cl CH2--Cl--CHz--C

/ n ~ Im~ / p Y is as earlier ~7efin~-1 n= 1-20,m= 1-5,p=1-20,andn+m+p>3,and Z is stolect~-d from the group CH2CHYCH3, CH2CMeYCH3, and, optionally, I l CH2--I CH2--Cl CH2--C CH2 /n ~ ~m'~ ~ p' m'=0-5,p'=0-20;n+m'+p'>2;
and if m or m' > I, the m or m' insertions lc;,~e~ ely are not consecutive.
This invention also concPrn~ a process corn~ ing selecting A and B
so the ratio of their chain transfer Co~ L~iS less than 1, whereby functionalityderived from Monomer B will be located on the vinyl-tPrrninAtec~ end of the polymer.
This invention also concerns an improved process for the free-radical polymerization of at least two ~ ltl.~ monomers having the formula W O 97/31030 PCT~US97/02912 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, CO R, CN, CONH2, CONHR. CONR~, COR and R';
R is selected from the group consisting of substituted and b~Lilul~d alkyl, subst;t~t~ and un~lb .lilUL~d aryl, ~ubaliLuLed and un~ llb~ LiluLed heteroaryl, ~ ed and Imcu~stihltl-d aralkyl, substituted and u~.~lb~liluLed alkaryl, and ~,~h~ rl and un~ Liluled organosilyl, the ~ub .I;L~ being the sarne or different and se}ected from the group consisting ofcarboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, ~lhll~y 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 selectecl from the aromatic group concicting of s-lhstih-ted and unsubstituted aryl, ~ led and lmcllhstitllte~l heteroaryl, the substituents being the same or ~lirr~ and selected from the group concicting of carboxylic acid, carboxylic ester, epoxy, hydluxyl, alkoxy, ~ amino, secon-1~ry arnino, tertiary amino, s--hstihltecl and unsubstituted alkyl, s~lbstitllted and lm~l~bstit aryl, s--hsti1~-te~l and ll.l~lll)slil~ l olefin and halogen;
by cont~ting said monomers with a cobalt-col";.il,;.,g chain transfer agent and a free radical initiator at a te~ alule from about 80~C tol70~C;
the improvement which co. . ,~ controlling molecular weight of t_e polymer architech-re 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 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:
decf.,a~i~lg the ratio of C:D from about 1,000:1 toward 2:1; or a,hlg the temrer~h~re from above ~0~C toward 170 ~C.
Preferred monolll~ A are selectecl from the group consisting of ~rylates, acrylonitrile and acryl~mi-les;
and ~ler~ ,d monomers B are substituted and Im~llhstih-t~ll styrenics.
The polymers made by said process improvement are polyrners of this invention having the formula:
H
I l CH2--C CH2=C~

/n where Y~ R' and n 2 1.

W O 97/31030 PCT~US97102912 This invention also concerns a process improvement for polymerizing monomer(s) in the presence of an excess of a nonpolymerizable olefin~
YIY2C=CY3Y4. The product in the initial stages of the polymerization will be composed primarily of ~ \
~y1 y3 ~ H // H 2 H--C--C C--C--C--C

wherein:
yl and Y3, and optionally y2 and Y, are each independently selectec~
from the group consisting of -CH(O), -CN, -C(O)OR, -C~O)NR R, -CR (O), alkyl, aryl, s~ d alkyl, ~ul~liLuL~d aryl; or where yl and Y3 or y2 and Y4 are combined in a cyclic structure which includes any of the above function~lities~ 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=I-12, R, R, R, R, or R are hydrogen, alkyl, aryl, substituted alkyl, or ~ub~LiluLed aryl; and where at least one of yl and Y3 is selected from the group consisting of -15 CH(O),-CN,-C(O)OR ,-C(O)NR R ,-CR (O),aryl,~ub~LiLuLedaryl;andthe .n~in;"g of y2 and Y4 are -H.
The polymers made by said process i~ ovellle.l~ are polymers of this invention produced at later stages of the polyll~.i~Lion process having the /y1 1 3~ f H ~ f Z ~ / H \ // H 2 H--C ~ C--C--C--C C--C C ~
H2 l H2 I H2 ~ H2 20\ y2 y4/< \ Y Jn \ Y / m ~ Y ~p Y
where Z = H, CH3, CH2CHYCH3, CH2CMeYCH3, or ~y1 y3 \ ~ H \ / Z ~ / H \
H- C C C C C C--~ C--C C
,~ H2 I J H2 1 1 ~ YJP
k=Oor 1,n=0-20,m=0-S,p=0-20;andk+n+m~p>2, if m>1, then it is not inten~.od to imply that the m insertions are consecutive;
25Y is selected from the group consisting of OR, O,CR, halogen. CO~H, COR, C02R, CN, CONH2, CONHR, CONR2 and R'; and Y' to Y~ and R, and R' are as defined above.

l-F.T~ OF TH~ INVF'NTION
We have discovered that, with addition of small amounts of an a-methylvinyl monomer and al~vlu~lidLt: choice of reaction conditions, polymerization of mono~-lb~Liluled monomers in the presence of a metal complex 5 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 ldul~sdLuldLcd macromonomers composed predo~ ~lLly of monosubstituted monomers. The llla~;lulllonomers are p~ep~cd by polym~n7ing a mono~ e~
monomer as the major component (for example styrene) in the presence of a disubstituted a-mcLhylvillyl monomer (for example, a-methylstyrene, herein also referred to as "AMS") and a catalytic arnount of a cobalt complex [for example, Co(II)(DMG-BF2)2] called CoII in Scheme 1. Reaction Scheme 1 illustrates the 15 process where monomer A=styrene and monomer B=a-methylstyrene. The process is applicable to a wide range of monosubstitllted monomers (for e~c~mpleacrylate esters, vinyl acetate (VAc)) and other non-a-mcLhylvillyl monomers.
Scheme 1:

H--CH2 ~ CH2 ~ ~ H--CH2--~--CH2 ~ Com 11 AMS¦

ComH St~ H - CH2 - ~ -CH2 ~ H - CH2 - ~-CH= C~ + Com - H

Ph ~I Ph ~1 H -cH2 - ~-CH2-C -Com Ph ~I Ph In Scheme 1, "Ph" lepl~sell~ a phenyl group, and "m" de~ign~t~ the nurnber of monomer units in the polymer, and is > 1.
The key features of the invention are the addition of small amounts of a-methylvinyl monomers and the use of high reaction tenlpeldlu~s in the presence of chain transfer catalysts.
The incorporation of a-methylvinyl monomers into the recipe allows formation of the desired macromonomer end group. In the absence of the a-methylvinyl monomer, polymerization of monosnhstihltpcl monomers give polymers with internal double bonds (styrenic monomer) or a stable alkyl-cobalt species (acrylate monomers) as chain ends.

W O 97/31030 PCTrUS97/02912 The use of high reaction t~lllpeldlul~s (>lO0 ~C) favors the formation of pure linear macromonomers from monosubstituted monomers (for example acrylates, vinyl esters, and styrene). At lower t~-pel~LIlres we have shown thatthe formed macromonomers can react further by copolymerization to give S bl~ched polymers. Even though the macromonomers can undergo further reaction, at reaction tt:-np~,.dl lres > l Oû ~C, the radicals so formed do not propagate to give branched polymers. Rather, they fi agm~nt to give back a ma~ monomer. ~t is possible that this ch~omictry will also reduce the polydispersity of the final product.
The invention also provides a route to block or graft copolymers as ill L~ lldted in Scheme 2. The product derived by copolymeri7~tion of the ...a~lu.llonomer in the presence of monomers can be ~et~rmin~d by a~lup~iate choice of the monomer and the reaction conditions.
Scheme 2:
grafl~ copolymer r ,Y I I ~l~.. eri~CHz--C--CH--Cj Y /CH,--~CH2--H
X m-1 ~ ~ ~CHz~--CH2--C\p Ph n X m h R CHz ~--CH2--C~+ ~1~-- CH2 I CH2--~

~C--Cl 1~ C Cl 1~ ~CH2 H
X ~ O Ph n block copoly~.,er In Scheme 2, "Ph" ~CPr~SGIIL . a phenyl group; "m", "n" and "o" ~1e~ign~t~o the number of monomer units in the polymer; and X and Y are as defined above.
We have demonstrated that styrene macromonomers ~lG~aled by the above mentioned copolym~ri7~tion route give chain transfer (by an addition 20 fr~gment~tiQn m~f h~niqm) and have acceptable chain L~ e, constants at W O97/31030 PCT~US97/02912 te,l,p~ Lu,cs >100 ~C. They should therefore be useful in the p,c~aldlion of block copolymers.
One further aspect of the invention is that by a~p,.~,iate choice of the a-methylvinyl monomer the method is also a route to end-functional polymers.
S For example. use of a hydroxyethyl- or glycidyl-~unctional monomer would yield polymers with ~-hydroxy or cD-epoxy groups, re~e~;Lively.
This method enables the versatility and robustness of the cobalt technology to be utilized to form macromnnc)m~r~ that are comprised predominantly of monosubstituted monomers. Additionally, it provides the key step in a new and less t;~ ~ive route to end-functional and block or graft copolymers based on monosubstituted monomers. Copolymerizations of monosubstituted monomers with other a-methylvinyl monomers (for example a-methylstyrene) in the ~res~.lce of cobalt are cc,ll~ lated.
The choice of the a-mt;Lllyvillyl comonomer is illlpOlL~ll in macromonomer synthesis. It must be chosen so that the reactivity towards cobalt ("catalytic chain transfer con~L~lL") of the derived prop~ting species is j,.h~ lly greater than that of the prop~gs~tin~ species derived from the monosub~LiLuL~d mon~mer~
Two factors influence this reactivity.
a) The rate of the chain transfer reaction between the prop~g~ting species and the cobalt complex;
b) The relative cnn- en~tinn~ of the prop~g~tin~ species. This is rl~ termine~l not only by the monomer co~ ;Qn but also by the propagation rate coll~l~lL~ and lea~iLiviLy ratios.
While methacrylate esters can be used as a-methylvinyl comonomers (see examples), in copolymerization with styrene, the values of the reactivity ratios and prop~t;c-n rate c~ S."l~; will favor the fonn~finn of styryl chain ends.
The product then has an internal rather than the desired terminal double bond.
MeLllac.ylate esters are acceptable comonomers in, for example, acrylate polym.on7~tions.
Thus, the use of a-methylvinyl comonomers (for example, a--methylstyrene, mt-th~-~rylonitrile) which have low propagation rate Co and high chain transfer rate col ,~ ; are preferred.
There are sllbst~nti~l cost improvements over ~It~rn~tive 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 me~ ted processes~ for W O 97/31030 PCTrUS97/02912 example, in graft, star, block and branched copolymer synthes~c, further extendsthe value of the process.
The nature of the derived products changes as a fimction of time. In the initial stages, the product S
H ~ //CH 2 H--C--C C--C
Y Jn Y

can be obtained as ~5~onti~l1y the only product. If the cobalt CTC catalyst levels are relatively low then CTC does not occur after every B-monomer insertion and 10 the product nuxture can include:
H \ ~H3lC \ ~ H \ //Cff 2 t H2 I H2 I H2 ¦ ~ H2 Later in the course of the reaction, when the col-c~ 1 ;on of the two 15 above products is hlcl~e~sed, they can be reinculyulaL~d into a growing polymer chain. Thus, the product r ~ ~CH2 H--CH2--f --CH2 _f _CH2--f--CH2=c~
Y Y Y
~n~ ~m\ , p 20 where Z can include -H, -CH3, CH2CHYCH3, CH~CMeYCH3, or H ~ / Z \ ~ H \
H C C C- C CC--C--H2 1 ~ H2 I H2 I H2 Y/n \ Y~m\ Y ~P

W O 97/31030 PCTrUS97/02912 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 of the higher molecular weight species as branches. At conversions above 95%, branches begin to appear on the branches, and the polymer becomes hyperbranched as 5 conversions approach 100%.
Metal complexes are those that give catalytic chain transfer with a-methylvinyl mon-)me-S Examples include, but are not limited to, cobalt(II) and cobalt(lII) chelates:
J ~ K
o N~ ~N--O /F

K~
L J
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 J ~K

F\ / ~ / /B~
F/ ~~ ~ ~N~

L J
Qco(III)(DpG-BF2)2 J=K=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=K=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 commomy known in 25 coordination ch~mi.ctry. Examples include water, arnines, ammonia, phosphines, The catalysts can also include cobalt complexes of a variety of porphyrin CA 02247837 l998-08-2l moiecules such as tetraphenylporphyrin, le~ ylporphyrin~
tetrarnesitylporphyrin and other substituted species.

a-Methylvinyl monomers (B monomers) have the general structure ~H3 ~CH20H

Y y where Y is as described above in the l'Sul,lu,~". R is an optionally substitutedalkyl (such as fluoroalkyl, hydroxyalkyl, or epoxyalkyl), organosilyl, or aryl group. Preferred examples of a-methylvinyl monomers (B monomers) include metnacrylate esters, a-methylstyrene and methacrylnnitrile "A" mollul~c~.. have the general .Llu~;Lulc:

where Y is as described above in the "S~
The ~nh,.nrerl utility ofthe poly...~ lion method dis-;ussed in this invention is that it extends each of these general CTC methodologies:
15 i) molecular weight control is ~ten-le~l from m~th~rrylates and styrenes to include acrylates, vinyl esters, and other higher activity monomer species;
ii) ",a,lo",onomer ylllhc~is is ç~tl-nrled to the monomers in (i) while ref~ining the desirable vinyl l~ ..,i~.z.l;on ofthe resulting species;
iii) end-functional polymer synthesis is also e~t~n~ed to the mon-~mers in (i);
iv) the use of ,,,a;lu,llonomers as chain transfer agents is e~t--n-l~d 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 of t'nis invention. The process can be run in batch, semi-batch, continuous, bulk, emulsion or suspension mode.
Most p~ cd A-monomers are:

W O 97131030 PCTrUS97/02912 methyl acrylate~ ethyl acrylate, propyl acrylate (all isomers), butyl acrylate (all isomers), 2-ethylhexyl acrylate~ isobornyl acrylate, acrylic acid, benzyl acrylate, phenyl acrylate, acrylonitrile. glycidyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate (all isomers), hydroxybutyl acrylate (all isomers), S diethylaminoethyl acrylate, triethyieneglycol acrylate, N-tert-butyl acrylamide, N-n-butyl acrylamide, N-methyl-ol acrylamide, N-ethyl-ol acrylamide, trimethoxysilylpropyl acrylate, triethoxysilylpropyl acrylate, tributoxysilyll,iol,yl acrylate, ~lim~th~xymethylsilylpropyl acrylate, diethoxymethylsilylpropyl acrylate, dibuto~y,l,.flhylsilylpropyl acrylate, diisopropoxymethylsilylpropyl 10 acrylate, dimethoxysilylpropyl acrylate, diethoxysilylpropyl acrylate, dibutoxysilylpropyl acrylate, diisopropoxysilylpropyl acrylate, vinyl acetate, styrene, diethylamino styrene, P--methylstyrene, vinyl ben_oic acid, vinylbell7in~lllfonic acid, vinyl propionate, vinyl butyrate, vinyl ben70~t~7 vinyl chloride, vinyl fluoride, vinyl bromide~
Most preferred B-monomers are:
methyl methacrylate, ethyl meth~rrylate, propyl methacrylate (all isomers), butyl m~th~rrylate (all isomers), 2-ethylhexyl meth~.rylate, isobornyl m~th~rylate, methacrylic acid, benzyl methacrylate, phenyl methacrylate, methacrylonitrile, alpha methyl styrene, trimethoxysilylulu~yl methacrylate, triethoxysilyl~,u~yl methacrylate, tributoxysilylpropyl m~th~f~rylate, dimethoxymethylsilylpropyl methacrylate, diethoxymethyl-silyllulupyllllethacrylate, dibutoxymethyls;lylpropyl meth~rylate, diisopropoxymethylsilylpropyl methacrylate, flimethoxysilylpru~yl methacrylate, diethoxysilylpropyl methacrylate, dibutoxysilyl~lu~yl mPfh~rylate,diisopropoxysilylpropyl methacrylate, is-~lup~ yl bu~yl~L~, isoplopellyl acetate, isoplupellyl bel~o~Lle;, iso~-lbp~ yl chloride, iso~lupenyl fluoride, isopropellvl bromideitaconic aciditaconic anhydridedimethyl itaconate. methyl itaconateN-tert-butyl m~th~crylamide~ N-n-butyl methacrylamide, N-methyl-ol meth~ rylamide~
N-ethyl-ol methacrylamide, iso~.b~.,ylbenzoic acid (all isomers), diethylamino alph~methylstyrene (all isomers~, para-methyl-alpha-methylstyrene (all isomers),diisoplu~nylbel~.lc (all isomers), isu~lup~nylbenzene 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-Isoplu~;l.ylbenzyl Isocyanate.
Preferred C monomers are those from the list of A monomers minus the styrenic family.
Preferred D monomers include the following styrenes:

W O 97/31030 PCTrUS97/~2912 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 aclylate and methyl methacrylate:

H--C--C C C
H2 l H2 \ CO 2M~ n CO 2Me from butyl acrylate and alpha-methylstyrene:
_,~ H \ // H 2 HC--C C C
H2 l H2 CO 2Bu/ n Ph from hy~o~y~lyl acrylate and alpha-methylsty-rene:

H~2--11 \ C--CO 2CH 2CH 20H~ n Ph fiom vinyl be~oa~ and butyl me;l~ ac~

H~C I C C//

ocoPh Jn CO 2BU

-W O 97/31030 PCTrUS97/02912 Typical products of the reaction at lower conversions include the linear products from butyl acrylate and methyl methacrylate:

H--CH2{; ~H2 C02Bu/
~CH2 H ~Hz~l CH2--C CHz--C CH2--C
CO2Bu~ n ~ CO2Me~ \ CO2Bu/ p CO2Me from methyl acrylate and alpha-me~ylstyrene:
H
H--CHz~ CH2 CO2Me/ m H--CHz--Cl ~H2--Cl CH2~l CH --C ~ 2 CO2Me/ n \ Ph / \ CO2Me/p When the polym~-ri7~t;0n (for example butyl acrylate as A-monomer and methyl m~th~ rylate as B-monomer) is carried out in the ~lese.lce of a 10 nonpolymeri7able olefin such as 2-p~nt~n~nitril~ the product in the initial stages of the polymeri_ation will be:

H ~ H H2 //
BU--f c_f c c~
CN ~ CO 2BuJ n CO 2Me W O 97/31030 PCT~US97/02912 and later in the polymerization. the product will be:

Bu--f ~ CH2 CN ~ C02Bu/
m Bu--C--CH~ I CH2--f CH~I CH2--c ~
CN \ CO2Bu/n \ CO2Mel \ C02Bu/p CO2Me It becomes imrrs~rtical to draw sch~"itl ;çs of any of the higher degrees of br~nchin~ that are obtained as the conversion of the polymeri7~ti~ n 5 approaches 100%.
Oligomers, ~l,a~lol,lonomers 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 m~teri~l~, multilayer coatings, photopolym~-ri7~hle materials, 10 photoresists, surface active agents, di~c~ x~ adhesives, adhesion promoters, coupling agents, compatibilizers and others. End products taking advantage of available ch~ tics can jnrl~lA~, for example, automotive and arrl~
coatings or finich.Q~, in~ ng high solids, aqueous or solvent based fini~hl-~Polymers, such as those produced in this invention, will find use in, for example, 15 structured polymers for use in pigment di~
K+IDS mass ~e.i~lu~co~y is an ionization method that produces pseudomolecular ions in the form of [MlK+ with little or no fr~gm,ont~tion. Intact organic molecules are desorbed by rapid h~iqting In the gas phase, the organic molecules are ionized by potassium att~h.,.~lL Potas~ ll ions are ge.~dLed 20 from an ~lumin~silic~t~ matrix that cotlt~in~ K20. All of these ~x~,~ . ;,~nt~ were p~,.r~ led on a FinnPg~n Model 4615 GC/MS quadrupole mass spe~ uln~Lel (Finn~g~n MAT (USA), San Jose, CA). An electron impact source configuration ope~dl~lg at 200 ~C and a source pre ,~ule of <lx10-6 torr was used. MALDl was also p~,~ro~ ed on this instrument.
All MW and DP mea~uLGnl~,.ll~ were based on gel permeation chromatography (GPC) using styrene as a standard.

W O 97/31030 PCTrUS97/02912 nefinitinl-q The following abbreviations have been used and are defined as:
TAPCo = meso-tetra(4-methoxyphenyl)porphyrin-Co; VAZO(g)-88 = 1,1'-azobis(cyclohexane-l-carbonitrile) (DuPont Co., Wilmington, DE); VRO-110 =
2,2'-azobis(2,4,4-~ Lllylpentane) (Wako Pure Chemical industries, Ltd., Osaka, Japan);
DP = degree of polymeri_ation. Mn is number average molecular weight and Mw is weight average molecular weight. AIBN is azoisol,uLyl~ ;le. THF is tetrahydrofilran. MA = methylacrylate.
F.XAMPT,F~, Synthesis of low molecular weight styrene macromonomers AMS comonomer Feed polymeri7~tion Examples 1 -3 and Control 1 show tnat molecular weight control is obtained in the absence of added a-methylstyrene. The products have structure 1 with an internal double bond and do not function as macromonomers.

,H ~'~r'~'H ,~ ~/ ~H
H~ b b ~3 Solution polym~ri7~tion of styrene with a-methylstyrene (10:1) and 20 iPrCo(III)(DMG-BF2)2 isopropylcobalt(III)(DMG) (100 ppm3 in n-butyl acetate at 125 ~C
n-butyl acetate 20.04 g styrene (sty) 10.03 g a-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-cycloh~c~n~rbonitrile) 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 m~/min a-methylstyrene 1.57 g over 120 min) W O 97/31030 PCT~US97/02912 The butyl ace~ate was degRc~ed in a 5 neck 250 m~ reactor, equipped with condenser, stirred, and N2 purge. The monomers were added and deg~c~ed for a fi~rther 10 minllt~ 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 5 started imm~-liAtcoly The reactor was sampled at regular intervals to monitor intennt~iAt~ molecular weights (GPC, THF) and conversions (IH NMR, CDC13).
A sarnple of this low viscosity yellow liquid was ~lt;ci~ L~d into a twenty foldexcess of metha~lol, and the macromonomer recovered as a fine white powder. M
n 1270, M w/M n 1.43, 34 % conversion. The precipitated sarnples were c:.xA.
10 by 'H NMR (200 ME~z, CDCl3) to establish the nature of the chain ends.
The ~ A~ A~d end groups give rise to signals as follows: styryl end group internal double bond (1): o6.1 -CH(Ph)-CH=CH-Ph; ~3.1 CH(Ph)-CH=CH-Ph. Alpha methyl styrene- ~AMS)-derived terminal methylene double bond (2):
~4.8 1 H and a5.2 lH, -C(Ph)=CH2 (the ratio of the signa~s at â6.1 and ~4.8 was 15 found to give the best e~l ;I l ~AI~ of tenninAI double bond content. Although this utilises a signal on the fringe of the broad aromatic re~onAn~e ~7.6-7.2, a series of coll-pa~isons of the 'H-NM~ molecular weights calculated from the end groups with those obtained by GPC showed that this gave better results than the signal at ~3.1). This may be due to the internal double bond product being a L~ Ul~ of (1)20 and (3).
Table 1.1: Polyrnerization of styrene in presence of AMS and iPrCo(III) (DMG-BF2)2 at 125~C
Example Time [Co(III)~ Sty: M n M w M w/M n conv l% [2~2%
(min) ppm AMS
100 - 1050 2290 2.18 100 1150 2540 2.21 3 120 100 1100 2590 2.18 5 ppt 100 1630 1.69 0 2 60 50 - 20104150 2.06 3 120 50 1720 3980 2.30 5 ppt 50 1940 2.03 o 3 60 25 - 327011153 3.41 3 ppt 25 - 2750 3.26 0 IDetr~ninrdby~H NMR
2%2,remainderisland3~ bylH NMR

Table 1.1 (Cont'd) Example Time ~Co(III)l Sty: Mn Mw MW/M n Conv ~ [2]%~
(min! ppmAMS %
Control 1 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 0 4 30 100 10:17301840 2.38 lO0 740 1670 2.25 120 100 690 1430 2.06 3 ppt 100 1270 1.43 32 10:111702540 2.17 2 120 50 1040 2300 2.21 4 ppt 50 1470 1.80 56 6 60 25 10:113702890 2.11 2 120 25 1270 2690 2.11 3 ppt 25 1660 1.89 65 Control 2 20 0 10:119696 50460 2.56 n.d 0 14860 37950 2.55 n.d 0 17060 38g90 2.28 120 0 24430 42040 1.72 3 240 27440 51420 1.87 4 360 0 29400 52930 1.80 6 0 7 60 100 5:1380 930 2.45 120 100 140 870 2.10 ppt 100 1310 1.83 8 60 50 5:1810 1670 2.06 120 50 780 1530 1.96 2 ppt 50 1180 1.53 68 9 60 25 5:117603480 1.98 2 120 25 1640 3160 1.93 3 ppt 25 2140 1.60 100 Conkol 3 60 0 5:1 16740 32450 1.94 120 0 19540 35020 1.79 ppt 0 19570 1.83 0 -Synthesis of high molecular weight styrene macromonomers AMS comonomer Feed polymerization 5These Examples were run according to the sarne procedure of Examples l through 3.
Table 1.2: Polymerization of styrene in presence of AMS and iPrCo~III)(DMG-BF2)2 at 125 ~C. Numbers in par~?nth~si~ indicate reaction times.
Ex. reaction[Co(III)] Sty/AMM nc M w/M % conv. % termins time (h) (ppm) S alkene 2 8 5/17~55 (120) 2.4 14 (0.13/0.37)3 944~ (ppt) 1.95 >705 14 1 8 5/1 4648 (60) 1.81 12 (0.13/0.37~3 5160 (ppt) 1.64 >705 12 2 13 5/12660 (120) 1.87 20 (0.2s/0.75)3 3300 (ppt) 1.63 >705 10EXAMPLES 13-18, Control 4-6 Synthesis of styrene macromQnnm~
AMS comonomer Batch polymPri7~tiorls in sealed tube - Effect of reaction ~ aLule Batch poly..a ~ iQn~ were con~ cted in sealed tubes to establish the 15 effect of te.llp~,~a~ulc on nla~ilu" ,c nQm~r purity (% 2). Molecular weights and macromonomer purities are similar to those obtained in the feed polylll.,~i~Lion entc (refer Table 1.1).
A mixture of styrene (1.3g, 12.5 mmol), a-methylstyrene (O.lSg, 1.27 mmol) (monomer ratio: 10/1), n-butyl acetate (3 g), VR'~9-110 (8.9xlO-5 g, 20 20 ppm) and iPrCo(III)(DMG-BF2)2 (for con~Pntr~tiQns see Table 1.3) was placed in an ampoule and de~esed 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 IH-r~nrand GPC.

3 arnount, in mg, added in (shot~feed).
rate of cobalt complex feed twice that fior example l o.

5 internal methylene was not visible in the 'H-nmr spectrum.

CA 02247837 l998-08-2l W O 97/31030 PCT~US97/02912 Table 1.3: Batch polymerization of styrene in pl~ s~.lce of AMS and iPrCo(IlI)(l:~MG-BF2)2 at 125 ~C with VR~-110 initiator Example Sty/AMS [Co(III)I M n M w/M n % conv % termin~l 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 10/1 25 1408 1.79 7 - 9 54 Table 1.4: Batch poly",~ ;nn of styrene in ~ e-~ce of AMS and iPrCo(III)(DMG-BF2)2 at 80 ~C with AIBN initiator.
Example Sty/AM [Co(III)] M n M w/M n % conv %
ratio ppm AMS6 Control 6 10/1 0 32,60 1.97 4 0 o 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 macrom--nnm~-.s AMS comonomer Batch poly".~ ions in sealed tube - Effect of cobalt complex A mixture of styrene (l.Og, 9.6mmol), a-methylstyrene (0.12g, .96mmol) (monomer ratio: 10/1), n-butyl acetate (2g), VR~9-110 (3.12x10 ' g, 100ppm) and the cobalt species (for all ~ i 50ppm, 2.44x10-7 mol of cobalt species was used) was placed in an ampoule and deg~e~l by 4 freeze-thaw 15 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 IH-nmr and GPC.

6 f~lrll~ ' ' as [terminal AMS units]/tterminal AMS units + terrninal Sty units] X 100. From INMR.

W O 97/31030 ~C~r~S97/02912 Table 1.5: Batch polymerization of styrene in presence of AMS and various cobalt complexes at 125 ~C with VR~110 initiator.
Example Co species7 ~Co] ppm Mn Mw PD % conv % tPrrnin~t AMS units8 Control 7Co(III)DMG 058,288 104,916 1.8 13 0 19 " 501065 1730 1.62 19 71 Control 8Co(III)DEG 072,284 125,129 1.73 15 0 " 501388 2368 1.7 19 . 85 Control 9Co(II) DPG 071,869 122,098 1.7 12 0 21 " 501454 2532 1.74 23 91 22 Co~III)DMG 501470 - 1.8 39 74 Feed Expt9 EXAMPLES 23-24, CONI ROL 10 5Synthesis of styrene macromonomers M~LIlac~ LLe comonomer Feed poly...~ n The poly~ I ;on recipe for ex~mrles 23-24 and their control was similar to that given for Fx~ Cs 1-3 with the mo~l;fi~-~ti~ n that BMA was used 10 in place of AMS. Conversions obtained are similar. Good molecular weight control is observed however little specificitv for formation of a terrnin~l aclulllonomer double bond is observed.

7Co(IlI)DMG =iPrCo(lll)(DMG-BF2)2,Co(lll)DEG = MeCo(lll)(DEG-BFl)2,Co(lllDPG

Co(lI)(DPG-BF2)2.
8 (~lr~ tPd as [terrninal AMS units]/[terminal AMS units + tenninal Sty units] X 100 from NMR.
9 Data ex ~able 1.1 CA 02247837 l998-08-2l W O 97/31030 PCTrUS97/02912 Table 1.7: Polymerization of styrene in presence of BMA and iPrCo(llI)(DMG-BF2)2 at 125 ~C with 1,1'-azobis~4-cycloh~ nPc~rbonitrile) as initiator Sarnple T;me [Co(lII)] Sty:BMA~~ M nll 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 20 100 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 EXAMP~ES 25-30 S Synthesis of styrene macrom~ n~mers Iso~,u~cllyl acetate comonom~r Batch polyrn~ri7~tio~
Sty/iPA .llaclulllonomer formation at 80 ~C: A mixture of styrene (lg, 9.6mrnol), iSO~ yl acetate (0.19g, 1.9mmol) (monomer ratio: 5/1), n-butyl acetate (2g), AIBN (3.19xlO 4g, lOOppm) and isopropylcobalt(III)DMG (for con~entr~fi~ ns see Table 1.8) was placed in an ampoule and de~ied 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 IH-nmr and GPC.
~H-nmr (d6-acetone): styryl end group internal double bond (1): ~6.1 -CH(Ph)-CH=CH-Ph; ~3.1 CH(Ph)-CH=CH-Ph.

10 Molar ratio of c~
Il Det~ i..cd by GPC calibrated with narrow polydi~y~ity polystyrene standards 12 De~rrnin~(l by I H NMR

CA 02247837 l998-08-2l W O 97/31030 PCT~US97/02912 Table 1.8: Sty/iPA macromonomer formation at 80 ~C for 2h with AIBN and iPrCo(III)(DMG-BF2)2-Exarnple StyfiPA Co(III) Mn Mw PD % conv % ~errnin~ql ratioppm iPA unitsl3 Control 11 5/1 0 57,425 91,753 1.6 6.00 0 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 11,611 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 1/1 25 1560 2825 1.81 3.00 0 EXAMPLES 31 -45, CONTROLS 13- 16 Synthesis of butyl acrylate macromonomers AMS cnmonf m~r at 80 ~C
Batch poly. . .~ ;on - Effect of comonomer and complex conc~ alion A mixture of butyl acrylate (1.3g, 10mmol), a-methylstyrene (SOmg, 0.4mmol) (monom~r ratio: 25/1), n-butyl acetate (2g), AIBN (3 74x10-4 g, 100ppm) and isopropylcobalt(III)DMG (for conc~ntr~tir~n see Table 2.1) was placed in an ampoule and de~e~e~i by 4 freeze-thaw cycles. The arnpoule was sealed and the mixture heated at 80 ~C for 2 hours. The arnpoule was cooled, opened and the reaction mixture reduced in vacuo to a residue which was analysedby 'H-nmr and GPC.
IH-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 terrninal alkene derived from iPA were detectable byIH 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 nl4 PD % % tenn. % AMS % terrn.
S ratio ppm Conv AMS unitslS inc.l6 alkene~7 Ctrl 13 5/1 023,500 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 Ctrll4 10/1 028,200 1.64 4 0 38 0 34 10/1100 551 1.27 3 67 36 100 10/1 50 605 1.31 5 63 35 100 36 10/1 25 635 1.33 5 60 36 100 Ctrl 15 25/l 041,423 1.69 9 0 17 0 37 25/1200 943 1.37 6 92 15 91 38 25/1100 96~ 1.39 5 77 17 96 39 25/1 50 1062 1.42 6 7~ 18 100 25/1 25 1152 1.48 7 57 20 100 Ctrl 16 50/1 056,071 1.76 14 0 12 0 41 50/1400 1168 1.64 10 78 9 80 42 50/1200 1207 1.76 10 75 9 85 43 50/1100 1481 1.80 13 61 9 91 44 50/1 50 1600 1.82 11 59 10 100 50/1 25 1876 1.96 11 45 10 100 EXAMPLES 46-54, CONTROLS 17, 18, Synthesis of butyl acrylate .. lacl.,l.lonomers AMS comonomer at 125 ~C
Batch pol~ ;on - Effect of reaction ~ alule A mixture of butyl acrylate (1.3g, 10rnmol), a-methylstyrene ~SOmg, 0.4mrnol) (monomer ratio: 25/1), n-butyl acetate (2g~, VRZ9-110 (3.74x10-4 g, 14 Polystyrene e~uival~,..t~.

5 ('AlrlllAt~-d âS (terrninal AMS units)~(total AMS units) X lOO.
16 CAlr~ Pd as (total AMS units)/(total BA units + total AMS) X lOO.
17 CAlr~lAtPd as (tenninal AMS units)/(tenninal AMS units + tenninal BA units) X lOO.
A Value of 100% indicates that tenninal BA could not be detected by 'H NMR.

W O 97/31030 PCTrUS97/02912 100ppm) and iPrCo(III)(DMG-BF~)2 (for concentration see Table 2.2) was placed in an ampoule and 11eg~ee~l by 4 fireeze-thaw cycles. The ampoule was sealed andehe 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 IH-nrnr5 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 % terrnin~l ratio ppm conv AMS inc. 19 alkene20 unitsl8 Control 17 25/1 Q 18,069 1.77 36 0 13 0 46 25/1 Z00 973 1.58 ~9 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 3 23 20 100 Control 18 50/1 0 18,891 1.85 6 0 5 0 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 10Synthesis of butyl acrylate nlac~ llonomers AM~ comon~me.r at 80~C
Batch polym~r-7~tion - Effect of cobalt complex A mixture of butyl acrylate (1.3g, 10mmol), a-methylstyrene (24mg, 0.2rnmol) (monomer ratio: 50/1), n-butyl acetate (2g), AlBN (3.74x10 4g, 15100ppm) and MeCo(III)(DEG-BF2)2 (for concc~ dlion see table 2.3) was placed in an ampoule and Atog~ed by 4 freeze-thaw cycles. The ampoule was sealed and the llli~ULG heated at 80~C for 2 hours. The arnpoule was cooled, opened and thereac~ion mixture reduced in vacuo to a residue which was analysed by I H-nrnr and GPC.

18 t'~lr~ t~d as (tcrtninal AMS units)/~total AMS units) X IOQ.
19 ('zllr~l ' ' as (total AMS units)/(total BA units + total AMS~ X IOO.
20 ~l~ull a' as (te~ninal AMS units~/~tenninal AMS units + tenninal BA units) X IO0.

W O 97/31030 PCT~US97102912 Table 2.3 Polymerization 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 % terrnin~l ratio ppm conv AMS inc.2' alkene23 units21 Contlol 19 50/1 0 49,342 1.74 11 0 25 0 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 .llaclulllonomer fonn~tion at 80~C with Co(II)(DPG-BF2)2.
Amixture of butyl acrylate (1.3g, 10mmol), a-methylstyrene ~24mg, 0.2rnmol) (monomer ratio: 50/1), n-butyl acetate (2g), AIBN (3.74x10 '~g, 100ppm) and Cû(lI)(DPG-BF2)2 (for c"llr~ .,I".Iic~n~ see Table 2.4) was placed in an ampoule and ~ g~ed by 4 freeze-thaw cycles. The ampoule was sealed and the ll~ heated at 80 ~C for 2 hours. The ampoule was cooled, opened and the reaction ~ e reduced under vacuum to a residue which was analysed by IH-nmr and GPC.
Table 2.4 Poly., .~ . ;".1 ion 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 t~min~l units24 aLkene26 Control 20 0 50,575 104,679 2.07 17 0 9 0 59 400 796 1262 1.58 1 79 11 89 200 864 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 3 35 13 100 21 (~lr~ d as (terrninal AMS units)/(total AMS units) X 100.
22 C~ t~d as (total AMS units)/(total BA units + total AMS)XIOO.
23 C~lr~ t~d as (tenninal AMS units)/(terTninal AMS units + tenninal BA units) X 100.
Z4 t'~ rd as (tenninal AMS units)/(total AMS units) X 100.
25 C~ t~d as (total AMS units)/(total BA units + total AMS)XIOO.
26 C~ t~d as (tenninal AMS units)/(tenninal AMS units + tenninal BA units) X 100.

CA 02247837 l998-08-2l W O97/31030 PCT~US97/02912 EXAMPLES 64-68, CONTROL 21 Synthesis of butyl acrylate macromonomers MAN comonomer at 80 ~C - Batch polymerization SA mixture of butyl acrylate (lg, 7.58rnmol), methacrylonitrile (51mg, 0.758mmol), n-butyl acetate (2g), AIBN (3.54x10 4g, 100ppm) and iPrCo(III)(DMG-BF23z (for con~ontr7~tion see Table 2.5) was placed in an ampouleand c~eg~ed by 4 freeze-thaw cycles. The ampoule was sealed and the llli~LLLle heated at 80 ~C for 2 hours. The arnpoule was cooled, opened and the reaction 10 mixture reduced in vacuo to a residue which was analysed by 1 H-mnr and GPC.
IH-r~nr (CDCl3): 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 Polylne~ ion of butyl acrylate in presence of MAN and iPrCo(III)(DMG-BF2)2 at 80 ~C
Ex. BA/MAN [Co(m)] M n M w PD % % terrnin~l Ratio ppm conv. methylene27 Q . . ~ _ ,,, W O 97/31V30 PCTrUS97/02912 lH-nmr (CDCI3): d 0.9, CH3; 1.35. CH2; 1.65. CH2; 1.85, CH: 2.25, backbone CH2; 2.55. allyl CH7; 3.6, OCH3; 4.0, OCH2; 5.5. vinyl H; 6.15, vinyl H.
Table 2.6 Polym~ri7~tion of butyl acrylate in presence of MMA (10: 1) and S iPrCo(III)(DMG-BF2) at various te~ dlules Ex. Temp ~C React. Co(III) M n PD % % tenn % MMA M n c b (initiatOr) Time h ppm conv alkene28 incorp 292 Ctrl 22 (AIBN) 3 0 170,75 2.08 25 0 19 -69 60 3 400 891 1.55 6 83 18 1.04 3 2001051 1.56 5 87 19 1.05 71 60 3 1001567 1.70 4 91 20 0.83 72 60 3 502610 1.80 7 100 19 0.98 73 60 3 257702 1.87 16 100 18 1.0 Ctrl 23 (AIBN3 2 0 75,5012.08 54 0 14 -74 80 2 400 917 1.31 8 75 17 0.92 2 2001196 1.43 10 86 17 0.93 76 80 2 1001520 1.50 9 92 18 0 92 77 80 2 502602 1.66 21 94 17 1.00 78 80 2 2512,117 1.82 53 100 14 1.09 Ctrl 24 (VR~-110) 2 0 10,4102.56 76 0 11 79 125 2 400 832 1.51 9 79 16 1.04 125 2 2001032 1.73 15 87 17 1.00 81 125 2 1001224 1.60 14 91 17 1.05 82 125 2 501994 1.70 32 92 15 1.01 83 125 2 253513 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 polymen7~tion A mixture of butyl ac.-yiate (1.3g; 10mmol), 2-hydroxyethyl metnaciylate, ~IEMA (65mg; 0.5mmol) (monomer ratio 20: 1), n-butyl acetate (2g), AIBN (3.74x10-4g, 100ppm) and isopropylcobalt(lII)DMG (for concentration see Table 2.73 was placed in an ampoule and ~leg~sed by 4 freeze-28 (~ as (terrninal MMA units)/(tenninal MMA units + terrninal BA units) X 100.
~9 CAlr~ t~d as (total MMA units)/(total MMA units + total BA units~ x 100.
2~

W O 97/31030 PCT~US97/0~912 thaw cycles. The ampoule was sealed and the mixture heated at 80 ~C for I 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.
lH-nmr (CDCl3): d 0.95, CH3; 1.40, CH,; 1.65, CH2; 1.85, backbone CH; 2.25, backbone CH2; 3.80, CH2; 4.00, CH~; 4.22, CH2; 5.50, externz-l vinyl*;5.80, 5.90, E&Z internal vinyl*; 6.20, e~t~ l vinyl*.
(~xt~ l vinyl signals due to HEMA derived vinyl end group and internal vinyl signals due to BA derived vinyl group).

Table 2.7 Polym~n7~ti~-n of butyl acrylate in presence of HEMA (20: 1) and iPrCo(III)(DMG-BF2)2 at 80 ~C
F~s~mrle Reaction Co(lII) Mn Mw PD % %
Time ppm conv tt-~rnins~l (hours) alkene30 Control 25 1 0 169,846 403,699 2.38 53 0 84 1 200 1695 3011 1.78 6 80 1 50 12,glg 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.~2 13 71 88 2 200 1545 3207 2.08 19 73 89 2 100 2219 5215 2.35 24 78 2 50 21,852 46,133 2.11 79 a 91 2 25 38,369 95,492 2.49 97 a a Terminal aL~cene protons were not visible in IH-mnr spectrum.

EXAMPLES 92-94, CONTROL 27 Synthesis of functional acrylate copolymer n.a loll-onomers AMS comonomer at 80 ~C - Batch poly...~ I;on ~ mixture of butyl acry}ate (1.3g; 10mmol), 2-hydroxyethylacrylate, HEA (116mg; lmmol), cc-methylstyrene (26mg; 2.2xlO-4mol) (monomer ratio 10/1/0.22), n-butyl acetate (2g), AIBN (3.65x10-4g, 100ppm) and 20 isopropylcobalt(III)DMG (for concentration see Table 2.8) was placed in an ampoule and ~ieg~e~i 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 ~ t~d as (terminal HEMA units)/(terrninal HEMA units + tenninal BA units~ X 100.

W O97/31030 PCTrUS97/02912 reaction mixture reduced in vacuo to a residue which was analysed by I H-nmr and GPC.
~H-nmr(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, S 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 Copolym~ri7~tion of butyl acrylate and hydlvxyethyl acrylate in presence of AMS and iPrCo(III)(DMG-BF2)2 at 80 ~C
Example BAtHEAt Co(~II) Mn PD % % % %
AMS ratio ppm (MwtMn) conv te~rnjn~l AMS termin~
AMS inc.32 aL~cene33 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 10ll/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 polym~n7~tion A mixture of vinyl b~n7 ~te, VB (1.3g, 8.77mmol), butyl methacrylate (0.125g, 0.877mmol) (mon~m~r ratio: 10/1), n-butyl acetate (3g), AIBN (4.43x10 4g, 100ppm) and isopropylcobalt(III)DMG (for concentration see Table 3.1) was placed in an ampoule and ~ e~1 by 4 freeze-thaw cycles. The ampoule was sealed and the l..ixlu-c heated at 80 ~C for 2 hours. The ampoule was cooled, opened and the reaction llliXLul~ reduced in vacuo to a residue which was 20 analysed by IH-nmr and GPC.
IH-nmr (d6-acetone): ~ 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 C~lr~ tPd as (telTninal AMS units)/(total AMS units) X 100.
32 ~-~lrl~l~tPd as (total AMS units)/(total BA+total HEA units) X 100.
33 (-~Ir~ tPd as (termjnal AMS units)/(tenninal AMS units + tertninal BA units) X 100.

W O 97/31030 PCTrUS97/02912 Table 3.1 Polymerization of vinyl benzoate in presence of ~MA and iPrCo(lII)(DMG-BF2)2 at 80~C
Exarnple VB/BMA [Co(III)~ M n M w PD % % terrninal ratio ppm conv. methylene Control 28 10/1 0 67,070 106,547 1.59 12 0 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 Contro} 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 (~lr~ d as (tenninal BMA units)/(tenninai BMA units+ tenninal VB units) X 100.
S EXAMPLES 101-108, CONTROLS 30 and 31 Synthesis of vinyl acetate ll~a ;lu-llonomers meth~rrylate comonomers at 80~C -Butyl m~ ylaLt: comono~ at 80~C Batch poly.. ~ ;on VAc/BMA ll.a,.vnlonomer synthesis with monomer ratio of 10/1.
A mixture of vinyl acetate (1 g; 11.6mmol), butyl ~ late (0.165g; 1.16mmol) (monomer ratio: 10/1), n-butyl acetate (2g), AIBN (3.17x10-4g, 100ppm) and iso~lol,ylcobalt(III)DMG (for concentration see Table 3.2~ was placed in an arnpoule and lle~esed by 3 freeze-thaw cycles. The ampoule was sealed and the rnixture 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 IH-nmr and GPC.
l~I-nrnr(CDCI3): d 0.95, CH3; 1.30, CEI2; 1.60, CH2; 3.90, CH2; 5.40, 6.10, ~xt.orn~l vinyl CH2*.
(*PYt~ l vinyl signals due to BMA derived vinyl end group).

34 ('~ d as (tenninal BMA units)/(tenninal BMA units+ tertninal VB units) X 100.

W O 97/31030 PCTrUS97/02912 Table 3.2 Polymerization of vinyl benzoate in presence of BMA and iPrCo(III)~DMG-BF2)z at 80~C (VAc:BMA = 10: 1) Exarnple Co(III) M n PD% %BMA BMA % term- M n ppm conv terminal35 3fi (%~ alkene37 calc 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 10~ 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 YAc/MA~4 macromonomer synthesis with monomer ratio of 5/1.
A mixture of vinyl acetate (0.75g; 8.77mol), methy} m.ofha~rylate (0.175g, 1.75rnrnol~ (m~n- m~r ratio: 5/1), n-butyl acetate (2g), AlBN (2.93x10-4g, 100ppm) and iso~.u~lcobalt(III)DMG (for concentration see Table 3.3) was placed in an ampoule and ~ga-~e~l by 3 freeze-thaw cycles. The ampoule was sealed and the rnixture heated at 80~C for 2 hours. The arnpoule was cooled, opened and the reaction mixture reduced in vacuo to a residue which was ~ys~d by ~ r~h~ ~d GPC.
lH-nmr (d6-acetone): o 0.6-2.1, CH3CO2 and backbone CH2, 3.60, COOCH3; 4.80-5.30, multiplet, various m~thm~ signals, 5.42, 6.10 e~Cte'llal vinyl CH2*. (*~t~rnal vinyl signal due to MMA derived vinyl end group).

35 ~'alr~llat~d as [terrninal BMA units ]/[total BMA units i.,cu~,u..,~ ] X 100.
- 36 Calr~lat~d as (total BMA units)/(total VAc units + total BMA units) X 100.
37 VAc derived internal alkene not detectable by ' H-nmr.

W O 97/31030 PCTrUS97102912 Table 3.3 Polym~ti7~tion of vinyl acetate in presence of MMA and iPrCo(IIl)(DMG-BF2)2 at 80~C (VAc:MMA = 5: 1) Example Co(III) M n PD % conv %MMA % MMA % terrn. M n calc ppm te~l inc.39 alkene~~ s Control 31 0 40,44~ 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 1~0 1.06 108 25 30,782 1.92 8 041 87 o4~ _ EXAMPLES 109-116, CONTROLS 32 and 33 Synthesis of vinyl acetate lnacl~ monomers iso~.o~c.~yl acetate, iPA comonomer at 125 ~C - Batch polymf~ri7~tic)n A nuxture of vinyl acetate ~l.Og; 11.6mmol), iso~lu~ yl acetate (23mg; 0.232mmol) (monomer ratio: 50/1), n-butyl acetate (2g), VR'I9-110 (3.4xlO-~g, lOOppm) and isoy~ ylcobalt(III)DMG (for c~l.cenlldlion see Table 3.4) was placed in an ampoule and ~leg~ecl by 3 freeze-thaw cycles. The ampoule was sealed and the llli~Lul~; heated at 125 ~C for 2 hours. The ~mpoule was cooled, opened and the reaction ll~i~Lu~; reduced in vac7lo to a residue which was analysed by IH-nmr and GPC.
IH-nmr (CDCl3): d 1.2-2.1, CH2 +CH3CO; 4.7-5.2, multiplet, vanous backbone methine.

38 ~ r~ tPd as (terminal MMA units )/(total MMA units inco.~ t~,d) X 100.
39 ~ t~d as (total MMA units)/(total VAc units + total MMA units) X 100.
40 C~lr~ tPd as (tenninal MMA units)/(tenninal VAc units + terminal MMA units) X 100. VAc derived internal alkene not d.,t~,c~ lc by ~H-nmr.
41 Terminal vinyl signals could not be detected by '~I-nmr.

W O 97/31030 PCTrUS97/02912 Table 3.4 Polymerization of vinyl acetate in presence of iPA and iPrCo(lII)(DMG-E~F2)2 at 125~C
Example Vac/iPA Co(III) Mn Mw PD % % term.
ratio ppm conv iPA
Control32 5/1 0 11,964 21,818 1.82 47 0 109 5/1 200 502 983 1.40 2 b 110 5/1 100 696 1124 1.61 2 b 111 5/1 50 1240 2278 1.84 2 b 112 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 oL~ d but reliable ~ n not possible.
b no end group signals det~c~

EXAMPLES 117-128, CONTROLS34 to 36 Synthesis of vinyl acetate macromonomers isop~ l chloride comonomer at 125 ~C - Batch polymerization VAc/iPrCl macromonomer formation at 125 ~C with VR'19-110 and 1 0 iPrCo(lII)(DMG-BF2)2 A mixture of vinyl acetate ~lg, 11.6mmol), isopropenyl chloride ~0.18g, 2.32mmol) (monnm~:r ratio: 5/1), n-butyl acetate (2g), VR~9-110 (3.18x10g, 100ppm) and iPrCo(III)(DMG-BF2)2 (for con~ntr~tion see table 3.5) was placed in an ampoule and ~l.og~c~ed by 4 freeze-thaw cycles. The ampoule was 15 sealed and the mixture hea~ed at 125~C for 2 hours. The ampoule was cooled, opened and the reaction mixture reduced in vacuo to a residue which was analysedby IH-nmr and GPC.

W O 97/31030 PCTrUS97102912 Table 3.5 Polymerization o f vinyl acetate in presence of iPCI and iPrCo(III)(DMG-BF2)2 at 125 ~C
Example VAc/iPrCI Co(III) Mn Mw PD %
ppm conv Control 34 S/l 0 3969 74751.88 3 117 5/1 200350 434 1.24 118 5/1 100552 1323 2.40<1 119 5/1 501355 3833 2.82 120 5/1 251791 5143 2.87<I
Control 35 50/1 0 15,712 27,346 1.74 14 121 50/1 200717 973 1.35<1 122 50/1 1001230 1843 1.49<1 123 50/1 5026g2 4594 1.71 124 50/1 2512,24321.771 1.788 VAc/iPrCl macromonomer formation at 125 ~C with VR'~ O and MRCo(III)(DEG-BF2)2 A mixture of vinyl acetate (lg, 11.6mmol), iso~ yl chloride (18mg, 0.232mmol) (m~-nomer ratio: 50/1), n-butyl acetate (2g), VR2-l lO
(3.1 Sx104 g, 1 OOppm) and MeCoaII)(DEG-BF2)2 (for conc~ 1 ;on see table 3.6) was placed in an ampoule and ~leg~e~ed by 4 ~eeze-thaw cycles. The ampoule was sealed and the mixture heated at 125~9 for 2 hours. The ampoule was cooled, opened and the reaction mixture reduced in vacuo to a residue which was analysedby GPC.

Table 3.6 Polymeri7~tio~ of vinyl acetate in ~lcsc;llce of iPCl and MeCo(III)~l:)EG-BF2)2 at 125 ~C
Example VAc/ Co(III) MnMw PD% conv iPrCI ppm ratio Control 36 50/1 0 13,984 24,811 1.77 46 125 50/1 200 935 15021.60 <1 126 S0/1 100 1627 30011.84 127 50/1 50 10,605 19,522 1.84 6 128 S0/1 25 12.740 Z2.831 1.79 10 W O 97/31030PCTrUS97/02912 EXAMPLES 129-132, CONTROL 37 Synthesis of functional styrene macromonomer TMIQ- Cytec incol~o.dlt:d comonomer Feed polymPri7~tion 5A mixture of styrene (Ig, 9.6mmol), TMI'9 (0.2g, 0.96mmol) (monomer ratio: 10/1), n-butyl acetate (2g), VR'!9-110 (3.2x10 4 g, 100ppm) and isopropylcobalt(III)DMG (at 0, 25, 50, 100 and 200ppm) was placed in an ampoule and deg~c~ed 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 10 reaction mixture reduced in vacuo to a residue which was analysed by 'H-nmr and GPC.
~H-r~nr(d6-acetone): ~ 4.9, ç~t~ vinyl*; 5.20, e~t~ l vinyl*; 6.0-6.2, internal vinyl*; 6.6-7.4, ArH.
(*t~xt~ l vinyl signals due to TMI'I9 derived vinyl end group and internal vinyl15 signals due to Sty derived vinyl end group).

Table 4.1: Polym~ri7~tion of styrene in presence of TMI~9 and iPrCo(III)(DMG-BF2)2 at 125 ~C
Example Sty/ Co(III) Mn Mw PD % t~rmin:~l TMI~9 ppm TMI~9 nits42 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 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 ~leg~c~ed by three freeze-pump-thaw cycles.
The reaction mixture was kept at 90 ~C until 10-15% conversion was ~ in GPC analysis showed Mn ~ 2150, PD = 2Ø

A mixture of 2.5 mL MA. 0.5 mL ethyl 2-hydro~cy~ ylacrylate, 14 mg TAPCo, 20 mg VAZO-88 and 5 mL chloroform was ~eg~c~ed by three freeze-pump-thaw 42 ~ t~d as (tenninai TMI units~/(tenninal TMI units+tenninal Sty units).

W 097/31030 PCT~US97/02912 cycles. The reaction mixture was kept at 90 ~C until 10- 15% conversion was ;ne~1 GPC analysis showed Mn ~ 1600, PD = 3.2.

A mixture of 2.5 mL MA, 0.5 rnL styrene, 14 mg TAPCo, 20 mg VAZ0-88 and 5 rnL chloroform was ~le~cced by three freeze-purnp-thaw cycles. The reaction mixture was kept at 90 ~C until 10- 15% conversion was ~tt~in~rl GPC analysis showed Mn ~ 700, PD = 2.4.

A mixture of 2.5 mL MA, 0.5 mL 2-hy~ yeLhyl methacrylate, 14 mg TAPCo, 20 mg VAZO-88 and 5 rnL chloroforrn was c~eg~cce~l by three freeze-pump-thaw cycles. The reaction mixture was kept at 90~C until 10-15% conversion was ~tt:~in~?~ GPC analysis showed Mn ~ 2150, PD = 2.û.

A n~ ule of 2.5 mL MA, 14 mg TAPCo, 20 mg VAZo~9-88 and 5 rnL
chloroform was Aeg~cce~l by three freeze-pump-thaw cycles. The reaction rnixturewas kept at 90~C until 10-15% con\,~ ion was attained. GPC analysis showns Mn ~ 21,700, PD=2.4.

High Conversion Copolyrneri7~tion of BA and MMA to Br~nrhed and Hyperbranched Polymers The reincorporation of initially-formed lllacl~,lllonomers back into the growing polymer is d~n~ e~
IdPnti~l solutions of 32 mg of VAZO'!9-88 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-dichlo~o~lhdlle were tleg~cs~ and kept in a 90 ~C oil bath. The samples were removed from the dlul~: bath at various times shown in Table 5.1. Then each reaction mixb~re 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 of the pol~ "i,dlion process. Because most of the monomer had been consumed before the increase in molecular weight, the only way that it could occur is through .ehlcc,l~"dlion of the macromonomers formed at the beginning of the reaction. GPC and K+lDS data are consistent.

W 097/31030 PCTrUS97/02912 Table 5.1 Conversion Mn Mn/MW
12% 540 2.08 20% 640 2.08 55% 890 2.06 93% 2270 2.84 The catalyst rem~in~ active during the course of the polymerization.
Sudden inactivation of the 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 of the conversion (93% vs 55%) cannot provide a 2.6 fold increase ofthe Mn (2270 vs 890) m~ .g a ur~imodal distribution.
The lineamllacl~lllonomers formed at 55% conversion were incorporated into the polymer at higher co~ ions. The incul~olaLion of ma l u~ - -nl~o- - ~r into growing polymer chains provides l,.,~ polymer. With continuous 0 te.,.~ l ion of polymeric radicals by the cobalt catalyst, such an incorporation leads to polymer with a structure Cf~ bla~1cl~es-on-branches" - in the c2~Llcll.C, it is lly~cll~ h~ofl cu~.ri....i., ;nn ofthe macromonom~r reincol~u.d~ion into the polymer back-bone was provided by MALDI mass s~,e~ Llu~copy. As seen on the MALDI
spectra, at conversions C50% the polymer collldil~ from 1 to 5 M M A units per chain. For Mn ~900, it means that the polymer is .onricllPcl with MMA vs composition of the initial monomer solution. As a result, the conc~ n of a~;lcd MMA monomer in the solution decreases f&ster than that of BA. At 55% co~ ion, more than 70% of the original MMA is con~llme(1 Fewer MMA units are available to be hlcol~uldled into the high molecular weight polymer formed at conversions >60% than at lower conversions if polymer that forms at high conversion does not incc~llJulaLe previously formed ma.;lumollulllc~ Incorporation of the previously-formed macromonomer would provide MMA to the high molecular weight polymer. The MALDI spectrum of the polymer at g3% conversion demonstrated this clearly. The MALDI spe-;L.u.ll of the polymer at 93% conversion becomes unresolved at masses >2500 due to the high levels of MMA incorporation.

W O 97/31030 PCTrUS97/02912 E~h9M PLE 138 A reaction mixture cont~inin~ 4 mg of the CTC-catalyst (COBF), 32 mg of VAZOQ-~8, 2 ml of butyl acrylate, 6 ml MMA-trimer, 0.2 ml of methyl meth~f rylate and 4 ml of 1,2-dichloroethane was cleg~eee(l by th~ree freeze-purnp-5 thaw cycles and put into an oil bath at 90~C. Samples of the reaction mixturewere taken after 1.5 hours, 3 hours, 7 hours and 22 hours. Initial GPC analysis shows that molecular weight of the polymeric product increases with time.
C.~l.p~. ;xion of GPC data with that of NDS and MALDI shows that in the first case the average l~ea~ ,d MW are lower than ç~recte~l in case of higher 10 conversion samples. The first samples had readily observable quantities of vinylene protons (lH NMR srectr~)7 inr~ tinF~ the form~tion of mPth~ ylate-t. . ~"i~ 1 polymer at the be~ .g of the CTC process. All of these observations are coneiet~nt with the proposed scheme.

Claims (10)

WHAT IS CLAIMED IS:
I . 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 andunsubstituted 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 of the 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 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.

2. A process according to Claim 1 wherein the improvement comprises:
controlling molecular weight of the 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;
wherein:
Y1 and Y3, and optionally Y2 and Y4, 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 Y1 and Y3 or Y2 and Y4 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=1-12, R5, R6, R7, R8, orR9 are hydrogen, alkyl, aryl, substituted alkyl, or substituted aryl; and whereat least one of Y1 and Y3 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 Y2 and Y4 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 of the 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 .alpha.-methyl styrenes;
b) alkyl methacrylates c) methacrylonitrile;
d) substituted or unsubstituted methacrylamide;
e) 2-chloropropene, f) 2-fluropropene, g) 2-bromopropene h) methacrylic acid, i) itaconic acid, j) itaconic anhydride, k) substituted and unsubstituted styrenics, and l) isopropenyl esters;
alkyl being C1 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.

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 .alpha.-methyl 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 l) isopropenyl esters;
alkyl being C1 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=1-20, 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:

where Z = H, CH3, CH2CHYCH3, CH2CMeYCH3, or wherein:
k = 0 or 1,n = 0-20, m = 0-5, p = 0-20; and k + n + m + p ~ 2; if m>1, 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 and Y3, and optionally Y2 and Y4, 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 Y1 and Y3 or Y2 and Y4 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=1-12, R5, R6, R7, R8, or R9 are hydrogen, alkyl, aryl, substituted alkyl, or substituted aryl; and where at least one of Y1 and Y3 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 Y2 and Y4 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 andunsubstituted 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.