Process for producing polymers useful in thermoset coatings and polymer so produced

• US 4,933,430 A
• Filed: 05/19/1989
• Issued: 06/12/1990
• Est. Priority Date: 03/05/1987
• Status: Expired due to Fees

• Current Assignee: SC Johnson & Son Incorporated
• Original Assignee: SC Johnson & Son Incorporated
• Inventors: Kessler, Lisa M., Scholsky, Kevin M.
• Primary Examiner(s): Michl, Paul R.
• Assistant Examiner(s): Doody, Patrick A.
• Application Number:
  US07/356,647
• Time in Patent Office: 389 Days
• Field of Search: 528/323, 528/326, 528/354, 528/359, 528/370, 528/392, 528/393
• US Class Current: 528/323
• CPC Class Codes: C08G 63/08 Lactones or lactides
• CPC Class Codes: C08G 85/00 General processes for preparing compounds provided for in this subclass

Abstract

A polymerization process to produce polyol polymer useful in the formulation of thermoset coatings, including the polymer so produced, is disclosed. The polymers are characterized as having at least one main chain and a plurality of side chains attached thereto. The polymerization process comprises combining in a solvent, at an elevated temperature and for a predetermined period of time, an addition-polymerizable monomer (that is also a free-radical initiator) together with an ethylenically-unsaturated monomer (having a nucleophilic or an electrophilic moiety), to initiate addition copolymerization of the addition-polymerizable monomer with the ethylenically-unsaturated monomer, whereby propagation of the reaction forms the main chain of the polymer. Meanwhile, also combined in the solvent is a polymerizable, carbonyl carbon-containing, ringed molecule--such as a lactone--which, at the elevated temperature, has a ring portion that opens to initiate ionic-copolymerization (of the now-opened ring molecule) with the nucleophilic-containing or electrophilic-containing moiety, whereby propagation of this reaction forms the side chains of the polyol polymer. Termination of the addition-copolymerization and ionic-copolymerization reactions is effected when the polyol polymer attains a predetermined number-average and/or weight-average molecular weight. The polymerization process is characterized in that each of the main-chain and side-chain propagations occurs substantially simultaneously, relative to the other, without using a catalyst.

Claims

1. A polymerization process to produce a graft polymer useful in the production of a thermoset coating, the graft polymer being characterized as having at least one main chain and a plurality of side chains attached thereto, the polymerization process comprising the steps of:

combining in a solvent, at an elevated temperature and for a predetermined period of time an (1) addition-polymerizable monomer that is also a free-radical initiator together with an (2) ethylenically-unsaturated monomer having a nucleophilic or an electrophilic moiety, the elevated temperature being effective for initiating addition copolymerization of the addition-polymerizable monomer with the ethylenically-unsaturated monomer, wherein propagation by the addition-copolymerization reaction forms the main chain of the graft polymer;

while also combining in the solvent a polymerizable, carbonyl carbon-containing, ringed molecule at a pressure effective, at the elevated temperature, to cause the ring portion of the ringed molecule to open in the vicinity of the carbonyl carbon thereof in response to the presence of the nucleophilic or the electrophilic moiety of the ethylenically-unsaturated monomer, for initiating ionic-copolymerization of the polymerizable, ringed molecule with the nucleophilic-containing or electrophilic-containing moiety of the ethylenically-unsaturated monomer, wherein propagation by the ionic-copolymerization reaction forms the side chains of the graft polymer; and

terminating both of the addition-copolymerization and the ionic-copolymerization reactions when the thus-produced graft polymer attains a predetermined number-average and/or weight-average molecular weight, the polymerization process being characterized in that each of the main-chain and side-chain propagations occurs substantially simultaneously, relative to the other, and wherein the polymerization process is further characterized in that the ionic-copolymerization reaction occurs expressly excluding utilization of a catalyst for the carbonyl carbon-containing ringed molecule.

2. The process of claim 1 further comprising the steps of:

separating the polymer from the solvent; and

recovering the polymer.

3. The process of claim 1 wherein the elevated temperature is about 100°

to about 350°

Centigrade, when styrene monomer is the addition-polymerizable monomer.

4. The process of claim 1 wherein the elevated temperature is about 150°

to about 300°

Centigrade, when styrene monomer is the addition-polymerizable monomer.

5. The process of claim 1 wherein the elevated temperature is about 190°

to about 270°

Centigrade, when styrene monomer is the addition-polymerizable monomer.

6. The process of claim 1 wherein the combining steps take place utilizing agitation.

8. The process of claim 1 wherein the polymerizable, carbonyl carbon-containing ringed molecule is selected from the group consisting of caprolactam, cyclic ether, cyclic anhydride, cyclic carbonate, cyclic oxalate, and lactone.

9. The process of claim 1 wherein the polymerizable, carbonyl carbon-containing ringed molecule is selected from the group consisting of beta-propiolactone, alpha,alpha-bis(chloromethyl)propiolactone, beta-butyrolactone, delta-valerolactone, alpha,beta,gamma-trimethoxy-delta-valerolactone, 1,4-dioxane-2-one, glycolide, lactide, 1,4-dithiane-2,5-dione, trimethylene carbonate, neopentyl carbonate, ethylene oxalate, beta-methyl-epsilon-isopropyl-epsilon-caprolactone, propylene oxalate, epsilon-caprolactone, and lactones of 4-hydroxylcyclohexanecarboxylic acid, cis-disalicylide, di-o-cresotide, and trisalicylide.

10. The process of claim 1 wherein the nucleophilic moiety comprises a hydroxyl moiety.

11. The process of claim 10 wherein the monomer having the hydroxyl moiety is selected from the group consisting of hydroxyalkyl acrylates, hydroxyalkyl methacrylates, and methyl alpha-hydroxyalkyl acrylates.

12. The process of claim 1 wherein the ethylenically-unsaturated monomer is selected from the group consisting of an acrylate, a methacrylate, and other monomers capable of being polymerized by free-radical addition polymerization.

13. The process of claim 1 wherein the polymerizable free-radical initiator is selected from the group consisting of styrene, alpha-methyl styrene, vinyl toluene, para-methyl styrene, and tertiary-butyl styrene.

14. The process of claim 1 wherein the terminating step is effected when the number-average molecular weight of the polymer is about 700 to about 15,000.

15. The process of claim 1 wherein the terminating step is effected when the number-average molecular weight of the polymer is about 1,000 to about 10,000.

16. The process of claim 1 wherein the terminating step is effected when the number-average molecular weight of the polymer is about 1,500 to about 7,000.

17. Polyol polymer made according to the process of claim 1.

7. The process of claim wherein the solvent is selected from the group consisting of butyl acetate, MAK, PM acetate, toluene, xylene, dimethyl cellosolve, glyme, diglyme, triglyme, diethyl carbitol, diethyl cellosolve, and cellosolve acetate.