Alkali-soluble polymers and process for producing same

• US 4,921,934 A
• Filed: 05/12/1989
• Issued: 05/01/1990
• Est. Priority Date: 12/23/1987
• Status: Expired due to Fees

• Current Assignee: SC Johnson & Son Incorporated
• Original Assignee: SC Johnson & Son Incorporated
• Inventors: Bixler, Kathleen J., Scholsky, Kevin M.
• Primary Examiner(s): Bleutge, John C.
• Assistant Examiner(s): BUTTNER, DAVID J
• Application Number:
  US07/353,202
• Time in Patent Office: 354 Days
• Field of Search: 528/354, 528/355, 528/359, 525/386
• US Class Current: 528/355
• CPC Class Codes: C08F 212/08 Styrene
• CPC Class Codes: C08F 212/12 Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
• CPC Class Codes: C08F 212/18 Chlorine
• CPC Class Codes: C08F 220/06 Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• CPC Class Codes: C08F 2800/20 as weight or mass percentages
• CPC Class Codes: C08F 8/00 Chemical modification by after-treatment graft polymers, block polymers, crosslinking with unsaturated monomers or with polymers C08F251/00 - C08F299/00; of conjugated diene rubbers C08C
• CPC Class Codes: C08G 63/08 Lactones or lactides

Abstract

A process for producing an alkali-soluble graft polymer is disclosed. The graft polymer has at least one main chain and a plurality of side chains attached thereto. The process comprises combining at least one vinylic monomer that is capable of forming free radicals, at least one ethylenically-unsaturated carboxylic acid monomer that is capable of addition-copolymerization with the vinylic monomer in the presence of the thus-formed free radicals, and cyclic ester molecules that are capable of ring-opening in the presence of the carboxylic acid monomer, to produce a polymerizable mixture. the polymerizable mixture to subjected to a preselected temperature and pressure for causing the monomers to free-radically addition-copolymerize to form the main chain while the cyclic ester molecules graft thereon, thereby forming the side chains of the graft polymer. The process is characterized in that the main-chain and side-chain formations of the graft polymer occur substantially simultaneously.

Claims

1. A process for producing an alkali-soluble graft polymer having at least one main chain and a plurality of side chains attached thereto, the process comprising the steps of:

combining, in a solvent contained within an agitated reaction zone, (1) at least one vinylic monomer that is capable of forming free radicals, (2) at least one ethylenically-unsaturated carboxylic acid monomer that is capable of addition-copolymerizing with the vinylic monomer in the presence of the thus-formed free radicals, and (3) cyclic ester molecules that are capable of ring-opening in the presence of the carboxylic acid monomer, thereby producing a reactant-initiatable polymerizable mixture; and

subjecting the reactant-initiatable polymerizable mixture to a preselected temperature and pressure effective to cause the vinylic monomer and the ethylenically-unsaturated carboxylic acid monomer to free-radically addition-copolymerize to form the graft polymer one main chain and to cause the cyclic ester molecules to ring-open at the inner ester bonds thereof and to graft onto the polymer main chain, thereby forming the side chains of the graft polymer,

the process being characterized in that the main-chain and side-chain formations of the graft polymer occur substantially simultaneously, the process further being characterized in that the graft polymer is formed expressly excluding utilization of a polymerization catalyst for the cyclic ester molecule.

2. The process in accordance with claim 1 wherein the solvent is selected from the group consisting of methyl amyl ketone, xylene, propylene glycol monomethyl ether acetate, toluene, cellosolve acetate, ethoxy ethyl acetate, diethyl cellosolve, ethyl benzene, and mixtures thereof.

3. The process in accordance with claim 1 wherein the solvent is selected from the group consisting of propylene glycol monomethyl ether acetate, ethyl benzene, methyl amyl ketone, xylene, and cellosolve acetate.

4. The process in accordance with claim 1 wherein the vinylic monomer is selected from the group consisting of vinyl toluene, alpha-methyl styrene, tertiary-butyl styrene, ortho-chlorostyrene, styrene, and mixtures thereof.

5. The process in accordance with claim 2 wherein the ethylenically-unsaturated carboxylic acid monomer is selected from the group consisting of maleic acid, itaconic acid, crotonic acid, acrylic acid, methacrylic acid, and mixtures thereof.

6. The process in accordance with claim 1 wherein the ethylenically-unsaturated carboxylic acid monomer is selected from the group consisting of methacrylic acid and acrylic acid.

7. The process in accordance with claim 1 wherein the cyclic ester is selected from the group consisting of gamma-butyrolactone, delta-valerolactone, pivalolactone, thio-butyrolactone, beta-butyrolactone, epsilon-caprolactone, and mixtures thereof.

8. The process in accordance with claim 1 wherein the cyclic ester is selected from the group consisting of epsilon-caprolactone, delta-valerolactone, pivalolactone, and thio-butyrolactone.

9. The process in accordance with claim 1 wherein the preselected temperature is about 160°

to about 300°

C.

10. The process in accordance with claim 1 wherein the preselected temperature is about 200°

to about 240°

C.

11. The process in accordance with claim 1 wherein the pressure is about 14.7 psia up to about 2000 psia.

12. The process in accordance with claim 1 wherein the pressure is about 14.7 psia up to about 300 psia.

13. The alkali-soluble graft polymer made in accordance with the process of claim 1.

14. The alkali-soluble graft polymer of claim 13 wherein the carboxylic acid monomer is acrylic acid, wherein the cyclic ester molecule is epsilon-caprolactone, and wherein the graft polymer possesses an epsilon-caprolactone to acrylic acid mole ratio of 0.76 or less.

15. The alkali-soluble graft polymer of claim 13 wherein the carboxylic acid monomer is acrylic acid, wherein the cyclic ester molecule is epsilon-caprolactone, and wherein the graft polymer possesses an epsilon-caprolactone to acrylic acid mole ratio of more than about 0.76.

16. An alkali-soluble graft polymer that is formed expressly excluding utilization of a polymerization catalyst, the graft polymer having a number-average molecular weight of about 500 to about 30,000 and which is structurally represented as:

##STR7## where R is an end-cap which is based upon an unstable Diels-Alder adduct that is selected from the group consisting of vinyl toluene, alpha-methyl styrene, tertiary-butyl styrene, ortho-chlorostyrene, styrene, and mixtures thereof;

where R₁ and R₂ are --H, --CH₃ or --COOH;

where R₃ is --H, --CH₃, --COOH, --CH₂ COOH, ##STR8## where R₄ and R₅ are --H or --CH₃ ;

where i and j are each about 1 to about 500;

where K is 0 to 50; and

where m is 2 to 11.

17. The graft polymer of claim 16 wherein the number-average molecular weight is about 750 to about 20,000.

18. The graft polymer of claim 16 wherein the number-average molecular weight is about 1,000 to about 10,000.