Polymer synthesis

Details Polymer synthesis Polymer synthesis

1997-11-20

2001-09-18

Wu, David W. (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S288000, C526S243000, C526S329000, C526S078000, C526S079000, C526S082000, C526S083000, C526S084000, C526S209000, C526S213000, C526S214000, C526S215000

Reexamination Certificate

active

06291620

ABSTRACT:

1. FIELD OF THE INVENTION
This invention relates to a process for the synthesis of block copolymers and polymers of narrow polydispersity based on radical polymerization of monomers in the presence of unsaturated chain transfer agents.
2. BACKGROUND
Block copolymers are useful as pigment dispersants, surfactants, compatibilizers for polymer blends, thermoplastic elastomers and in a variety of other applications. Polymers with narrow molecular weight dispersity can enhance melt viscosity behavior, solids-viscosity relationships of polymer solutions and sharper melt transitions than the same composition at a higher polydispersity.
Conventional commercial techniques for synthesizing narrow polydispersed polymers and block copolymers include free-radical polymerization. Radical polymerization may be accomplished: (1) through the use of pseudo or quasi-living polymerization. These techniques make use of low molecular weight transfer agents and/or chain terminators; (2) through the use of transformation chemistry; (3) through the use of multifunctional or polymeric initiators.
This invention provides a method of employing certain vinyl compounds in the synthesis of polymers with narrow molecular weight distribution and block copolymers by free radical polymerization Block copolymerization by radical polymerization has been described in PCT Application No WO 93/2355. This PCT application describes the mechanism of block copolymer formation but does not define conditions necessary for the preparation of high purity block copolymers, nor formation of narrow polydispersity resins.
SUMMARY OF THE INVENTION
This invention is directed to a process for the synthesis of polymers (block, homo- and copolymers) of the general formula:
comprising contacting:
(i) a vinyl monomer of the formula
CH
2
=CUV
(ii) a vinyl-terminated compound of formula
 and
(iii) free radicals, produced from a free radical source; and increasing the molar amount of polymers, 1, by one or both of:
(a) decreasing the molar amount of (iii) for any given conversion of (i); and
(b) decreasing the molar amount of (i) for any given conversion of (iii);
wherein:
Q is selected from the group H, R, OR, O
2
CR, halogen CO
2
H, CO
2
R, CN, CONH
2
, CONHR and CONR
2
;
U is selected from H and R;
V is selected from R, OR, O
2
CR, halogen, CO
2
H, CO
2
R, CN, CONH
2
, CONHR and CONR
2
;
X is selected from H and R;
Y is selected from R, OR, O
2
CR, halogen, CO
2
R, CO
2
R, CN, CONH
2
, CONHR and CONR
2
;
Z is selected from the group H, SR
1
, S(O)R, S(O)
2
R, R
2
and R
3
;
R is selected from the group substituted and unsubstituted alkyl, aryl, aralkyl, alkaryl and organosilyl groups wherein the substituent(s) are independently selected from the group carboxyl, epoxy, hydroxyl, alkoxy, amino and halogen;
R
1
is selected from the group H, substituted and unsubstituted alkyl, aryl, aralkyl, alkaryl, organosilyl wherein the substituent(s) are independently selected from the group carboxyl, epoxy, hydroxyl, alkoxy, amino and halogen;
R
2
is selected from the group free radical initiator-derived fragments of substituted and unsubstituted alkyl, cycloalkyl, aryl, aralkyl alkaryl, organosilyl, alkoxyalkyl, alkoxyaryl, sulfate groups wherein the substituent(s) are independently selected from R, OR
1
, O
2
CR, halogen, CO
2
H (and salts), CO
2
R, CN, CONH
2
,
R
3
is selected from the group radical chain transfer agent-derived fragments of substituted and unsubstituted alkyl, cycloalkyl, aryl, aralkyl, alkaryl, organosilyl, alkoxyalkyl, alkoxyaryl, and PR
2
groups wherein the substituent(s) are independently selected from R OR
1
, SR, NR
2
, NHR, O
2
CR, halogen, CO
2
H, CO
2
R, CN, CONH
2
, CONHR, and CONR
2
;
m and n are independently ≧1; and
when either or both of m and n are greater than 1, the repeat units are the same or different.
Each alkyl in the defined substituents is independently selected from branched, unbranched, and cyclical hydrocarbons having 1 to 20, preferably 1-12, and most preferably 1-8 carbon atoms; halo or halogen refers to bromo, iodo, chloro and fluoro, preferably chloro and fluoro, and organosilyl includes —SiR
4
(R
5
)(R
6
) and the like, wherein R
4
, R
5
, and R
6
are independently alkyl, phenyl, alkyl ether, or phenyl ether, preferably at least two of R
4
, R
5
, and R
6
being a hydrolyzable group, more preferably two of which are alkyl ether, wherein alkyl is preferably methyl or ethyl. A plurality of silyl groups can be condensed; for example, an organopolysiloxane such as —Si(R
4
)
2
—O—Si(R
5
)
2
R
6
, wherein R
4
, R
5
, and R
6
are independently alkyl.
Preferred 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, methyl acrylate, ethyl acrylate, propyl acrylate (all isomers), butyl acrylate (all isomers), 2-ethylhexyl acrylate, isobornyl acrylate, acrylic acid, benzyl acrylate, phenyl acrylate, acrylonitrile, styrene, functional methacrylate, acrylates and styrene selected from glycidyl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate (all isomers), hydroxybutyl methacrylate (all isomers), diethylaminoethyl methacrylate, triethyleneglycol methylacrylate, itaconic anhydride, itaconic acid, glycidyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate (all isomers), hydroxybutyl acrylate (all isomers), diethylaminoethyl acrylate, triethyleneglycol acrylate, methacrylamide, N-tert-butyl methacrylamide, N-n-butyl methacrylamide, N-methyl-ol methacrylamide, N-ethyl-ol methacrylamide, N-tert-butyl acrylamide, N-n-butyl acrylamide, N-methyl-ol acrylamide, N-ethyl-ol acrylamide, vinyl benzoic acid (all isomers), diethylamino styrene (all isomers), alphamethylvinyl benzoic acid (all isomers), diethylamino alphamethylstyrene (all isomers), para-methylstyrene, p-vinyl benzene sulfonic acid, trimethoxysilylpropyl methacrylate, triethoxysilylpropyl methacrylate, triethoxysilylpropyl methacrylate, dimethoxymethylsilylpropyl methacrylate, diethoxymethyl-silylpropylmethacrylate, dimethoxymethylsilylpropyl methacrylate, diisopropoxymethylsilylpropyl methacrylate, dimethoxysilylpropyl methacrylate, diethoxysilylpropyl methacrylate, dibutoxysilylpropyl methacrylate, diisopropoxysilylpropyl methacrylate tributoxysilylpropyl acrylate, triethoxysilylpropyl acrylate, tributoxysilylpropyl acrylate, dimethoxymethylsilylpropyl acrylate, dimethoxymethylsilylpropyl acrylate, dibutoxymethylsilylpropyl acrylate, diisopropoxymethylsilylpropyl acrylate, dimethoxysilylpropyl acrylate, diethoxysilylpropyl acrylate, dibutoxysilylpropyl acrylate, diisopropoxysilylpropyl acrylate, vinyl acetate, and vinyl butyrate, vinyl chloride, vinyl fluoride, vinyl bromide.
In a preferred process, (ii) is selected where Q, —XYC—CH
2
— and Z are independently selected from one or more of the following:
Q=H, methyl ethyl, butyl, (all isomers), cyclohexyl, methoxy, ethoxy, propoxy, butoxy (all isomers), phenoxy, acetate, propionate, butyrate (all isomers), benzoate, carboxylate, chlorine, bromine, fluorine, iodine, nitrile, amide, N-methylamide, N-ethylamide, N-propylamide, N,N-dimethylamide, N,N-diethylamide, N,N-dibutylamide, N-methyl-N-ethylamide, carboxylate ester of methyl, ethyl, propyl, butyl (all isomers), benzyl, phenyl, 2-hydroxyethyl 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxy-butyl (all isomers), 3-hydroxybutyl (all isomers), 2-hydroxybutyl, 3-trimethoxysilylpropyl, 3-triethoxysilylpropyl, 3-tributoxy-silylpropyl, 3-tri(isopropoxy)silylpropyl, 2-aminoethyl, 3-amino-propyl, 2-aminopropyl, 4-aminobutyl (all isomers), 3-aminobutyl (all isomers), 2-aminobutyl (all isomers), 2-epoxypropyl, or 3-epoxypropyl;
—XYC—CH
2
—=derived from one or more of the following monomers: methyl methacrylate, ethyl methacrylate propyl methacrylate (all isomers), butyl methacrylate (all isomers), 2-ethylhexyl methacrylate, isobornyl methacrylate, methacrylate acid, benzyl methacrylate, ph

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