Method for preparing hollow latexes

• US 4,973,670 A
• Filed: 11/22/1989
• Issued: 11/27/1990
• Est. Priority Date: 08/12/1988
• Status: Expired due to Term

• Current Assignee: The Dow Chemical Company (Dow, Inc.)
• Original Assignee: The Dow Chemical Company (Dow, Inc.)
• Inventors: MacWilliams, Dalton C., Chonde, Yohannes, McDonald, Charles J., Cohrs, William E.
• Primary Examiner(s): Kight, III, John
• Assistant Examiner(s): ACQUAH, SAMUEL A
• Application Number:
  US07/441,006
• Time in Patent Office: 370 Days
• Field of Search: 521/65, 521/69, 521/70, 521/71, 427/373, 428/402.22, 428/402, 428/407, 525/238, 525/239, 525/243
• US Class Current: 521/65
• CPC Class Codes: B01J 13/14 Polymerisation; cross-linking
• CPC Class Codes: C08F 2/22 Emulsion polymerisation
• CPC Class Codes: C08F 291/00 Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
• CPC Class Codes: Y10T 428/2982 Particulate matter [e.g., sphere, flake, etc.]
• CPC Class Codes: Y10T 428/2987 Addition polymer from unsaturated monomers only
• CPC Class Codes: Y10T 428/2998 including synthetic resin or polymer

Abstract

The present invention provides for a process for preparing hollow polymer latexes by a one stage emulsion polymerization. The first step invloves introducing an effective amount of a first charge of a organic phase to an aqueous phase. The first charge of the organic phase comprises monomer which is vertually insoluble in the aqeuous phase and an inert-nonpolymerizable hydrocarbon. The polymer formed from polymerizing the monomer is virtually insoluble in the hydrocarbon, the hydrocarbon is virtually insoluble in the aqueous phase and the monomer is miscible with the hydrocarbon. The monomer is polymerized to produce a low molecular weight polymer such that the low molecular weight polymer will phase separate from the organic phase and conentrates at the surface of the introduced organic phase forming a low molecular weight polymer phase. The second step involves introducing a second charge of the organic phase to the aqeuous phase, wherein the second charge of the organic phase comprises a crosslinking monomer. The crosslinking monomer is polymerized with the low molecular weight polymer to produce a hollow polymer latex particle.

Claims

1. A process which comprises preparing hollow latex polymers by a single stage emulsion polymerization of monomers in the presence of hydrocarbons, by:

(1) introducing to a polymerization vessel an initial reactor charge which comprises;

an organic phase and an aqueous phase;

the aqueous phase comprising water and an effective amount of water-soluble initiator;

the organic phase comprising;

(a) an effective amount of at least one monomer, having a solubility of less than about three percent in the aqueous phase under polymerization conditions and (b) an effective amount of an inert-nonpolymerizable hydrocarbon wherein the polymer formed from polymerizing the monomer is less than about three percent soluble in the hydrocarbon under polymerization conditions and wherein the hydrocarbon has less than about one percent solubility in the aqueous phase under polymerization conditions and wherein the monomer is miscible with the hydrocarbon under polymerization conditions; and

(2) polymerizing the monomer under conditions to produce a low molecular weight polymer such that when the low molecular weight polymer reaches a molecular weight sufficient to cause the low molecular weight polymer to phase separate from the first introduced organic phase, the low molecular weight polymer phase separates from the introduced organic phase and concentrates at the surface of the introduced organic phase forming a low molecular weight polymer phase; and

(3) introducing to the vessel a second reactor charge comprising an additional effective amount of the organic phase to the aqueous phase when the low molecular weight polymer reaches a conversion of monomer to polymer of equal to or less than about 80 weight percent, wherein the second charge of the organic phase additionally comprises a crosslinking monomer wherein the crosslinking monomer becomes imbibed in the low molecular weight polymer phase; and

(4) polymerizing the crosslinking monomer with the low molecular weight polymer under polymerization conditions sufficient to produce a hollow polymer latex particle.

2. The process of claim 1 wherein the aqueous phase additionally comprises an effective amount of chain transfer agent.

3. The process of claim 2 wherein the chain transfer agent is present in an amount of from about 0.1 to about 50 weight percent based on the total weight of the polymer.

4. The process of claim 1 wherein the water-soluble initiator is present in an amount of from about 0.4 to about 1.0 weight percent based on the total weight of the polymer.

5. The process of claim 1 wherein the monomer of the first charge of the organic phase is selected from the group consisting of:

monovinyl aromatic monomers;

aliphatic conjugated diene monomers;

acrylate monomers;

vinylidene halide and vinyl halide monomers;

vinyl ester monomers of carboxyl acids containing from 1 to 18 carbon atoms;

methacrylonitrile;

acrylonitrile; and

monoethylenically unsaturated carboxylic acid monomer.

6. The process of claim 2 wherein the second charge of the organic phase further comprises monomer selected from the group consisting of:

monovinyl aromatic monomers;

acrylate monomers;

aliphatic conjugated diene monomers;

vinylidene halide and vinyl halide monomers;

vinyl ester monomers of carboxyl acids containing from 1 to 18 carbon atoms;

methacrylonitrile;

acrylonitrile; and

monoethylenically unsaturated carboxylic acid monomer.

7. The process of claim 6 wherein the low molecular weight polymer of the low molecular weight polymer phase has an average number molecular weight of from about 1,000 to about 100,000.

8. The process of claim 6 wherein the second charge of the organic phase further comprises hydrocarbon.

9. The process of claim 1 wherein the chain transfer agent is an aliphatic alcohol and wherein the aliphatic alcohol is present in the aqueous phase in an amount of from about 2 to about 65 weight percent based on the total weight of the aqueous phase, the initiator is present in an amount of less than or equal to about 2 weight percent based on the total weight of the polymer and the water is present in an amount of from about 98 to about 35 weight percent based on the total weight of the aqueous phase.

10. The process of claim 1 wherein the monomer of the first hydrocarbon is a blend of a monovinyl aromatic monomer and a monoethylenically unsaturated carboxylic acid monomer.

11. The process of claim 10 wherein the monovinyl aromatic monomer is present in an amount of from about 0 to about 97 weight percent and the monoethylenically unsaturated carboxylic acid monomer is present in an amount of from about 2 to about 10 weight percent based on the total weight of the first charge of the organic phase.

12. The process of claim 8 wherein the monomer of the second charge of the organic phase is a monovinyl aromatic monomer and the crosslinking monomer is divinyl benzene.

13. The process of claim 12 wherein the monomer of the second charge of the organic phase is a blend of the monovinyl aromatic monomer and an aliphatic conjugated diene monomer.

14. The process of claim 12 wherein the monovinyl aromatic monomer is present in an amount of from about 0 to about 97 weight percent and the divinyl benzene is present in an amount of from about 4 to about 100 weight percent based on the total weight of second charge of the organic phase.

15. The process of claim 8 wherein the aqueous phase additionally comprises surfactant.

16. The process of claim 12 wherein the aqueous phase additionally comprises surfactant.

17. The process of claim 15 wherein the aqueous phase additionally comprises a seed.

18. The process of claim 17 wherein the polymer composition of the seed is similar to the polymer composition of the resultant hollow polymer latex particle and the seed is present in the aqueous phase at a concentration of equal to or less than about 2 weight percent based on total monomer.