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US 2003/0195313 A1Published application
Catalytic polymerization process
AssigneesE. I. Du Pont de Nemours and Company, Commonwealth Scientific and Industrial Research Organisation
InventorsGraeme Moad, Ezio Rizzardo, Catherine Louise Moad, Steven Dale Ittel, Lech Wilczek, Alexei A. Gridnev
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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.
Claims10
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 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 X is 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.
19 more elements
A polymer having the formula:.
- 29
- 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,
- 30
- 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.
5 more elements
A polymer having the formula:
- 31
- where Z═H, CH3, CH2CHYCH3, CH2CMeYCH3, or
- 32
- 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 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.
14 more elements
A polymer having the formula:
- 33
- 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.
3 more elements
Dependencies are inferred from the claim text.