Sequential emulsion polymerization process

• US 4,325,856 A
• Filed: 01/02/1980
• Issued: 04/20/1982
• Est. Priority Date: 01/02/1980
• Status: Expired due to Term

• Current Assignee: The Dow Chemical Company (Dow, Inc.)
• Original Assignee: The Dow Chemical Company (Dow, Inc.)
• Inventors: Lee, Do I., Ishikawa, Tadayoshi
• Primary Examiner(s): Henderson, C. A.
• Application Number:
  US06/108,973
• Time in Patent Office: 839 Days
• Field of Search: 260/29.6 RB, 260/29.6 RW, 260/29.6 WB, 260/29.6 TA, 525/301, 525/302, 525/308, 525/309, 525/902, 525/313
• US Class Current: 524/458
• CPC Class Codes: C08F 263/02 on to polymers of vinyl esters with monocarboxylic acids
• CPC Class Codes: C08F 265/04 on to polymers of esters
• CPC Class Codes: D21H 19/58 Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
• CPC Class Codes: Y10T 428/31895 Paper or wood
• CPC Class Codes: Y10T 428/31906 Ester, halide or nitrile of addition polymer

Abstract

Aqueous copolymer latexes comprising colloidally dispersed, substantially spheroidal copolymer particles having a predominantly hydrophobic core portion and having a relatively hydrophilic polymeric portion which is preferentially oriented toward the outer surface thereof (e.g., a relatively hydrophilic shell portion) are prepared by (a) first emulsion polymerizing an initial monomer charge to form a first aqueous latex of a substantially linear, relatively hydrophilic polymer and (b) thereafter emulsion polymerizing a major proportion (e.g., from about 50 to about 95 parts by weight) of a second (and relatively more hydrophobic) monomer charge in the presence of a minor proportion (e.g., from about 5 to about 50 parts by weight on a polymer solids basis) of said first, relatively hydrophilic polymer latex.

Claims

1. A process for preparing an aqueous copolymer latex of colloidally dispersed, substantially spheroidal, heterogeneous copolymer particles which are individually composed of a relatively hydrophobic polymer core portion having a relatively hydrophilic, polymeric portion preferentially oriented toward the outer surface thereof, said process comprising the steps of:

(a) first preparing an initial aqueous latex of a substantially linear hydrophilic polymer by emulsion copolymerizing at a pH of from about 2 to about 6 in the substantial absence of a cross-linking agent an initial monomer charge comprising (1) one or more vinyl esters of a non-addition polymerizable carboxylic acid and/or one or more esters of an addition polymerizable carboxylic acid and (2) one or more relatively hydrophilic comonomers in an amount which renders the copolymer of said initial latex sufficiently hydrophilic that it ultimately becomes preferentially oriented toward the outer surface of the finished copolymer particles of the final copolymer latex product, said relatively hydrophilic comonomer having a solubility in water of at least about 3 weight percent on a total weight basis at 25°

C. and with the proviso that such hydrophilic comonomer can be excluded when the monomer component of step (a)(1) is exclusively vinyl acetate; and

(b) thereafter emulsion polymerizing, in the presence of from about 5 to about 50 parts by weight on a polymer solids basis of the initial hydrophilic polymer latex of step (a) and at a pH of from about 2 to about 6, from about 50 to about 95 parts by weight of a second monomer charge comprising (1) an aliphatic conjugated diene and/or an addition polymerizable monovinylidene monomer selected from the group consisting of monovinylidene aromatic monomers and vinylidene halide monomers and (2) from 0 to about 10 weight percent based upon the weight of such second monomer charge of a monoethylenically unsaturated carboxylic acid monomer.

2. The process of claim 1 wherein the second monomer charge comprises, based upon the weight thereof, (1) from about 20 to 100 weight percent of a monovinylidene monomer selected from the group consisting of monovinylidene aromatic monomers and vinylidene halide monomers and (2) from 0 to about 10 weight percent of a monoethylenically unsaturated carboxylic acid.

3. The process of claim 2 wherein the second monomer charge comprises from 0 to about 5 weight percent of a monoethylenically unsaturated carboxylic acid monomer based upon the weight of such second monomer charge.

4. The process of claim 1 wherein the second monomer charge comprises from about 25 to about 100 weight percent of an aliphatic conjugated diene based upon the weight of such second monomer charge.

5. The process of claim 1 wherein the second monomer charge comprises, based upon the total weight thereof, (1) from about 20 to about 75 weight percent of a monovinylidene aromatic monomer;

(2) from 25 to about 80 percent of the aliphatic conjugated diene and (3) from 0 to about 10 percent of the monoethylenically unsaturated carboxylic acid monomer.

6. The process of claim 1 wherein, in the initial monomer charge of step (a), the hydrophilic monomer is a monoethylenically unsaturated carboxylic acid monomer and is employed in the range of from about 1 to about 50 weight percent based upon the weight of such initial monomer charge.

7. The process of claim 1 wherein the initial monomer charge comprises from about 70 to about 99 weight percent of one or more vinyl esters of nonaddition polymerizable carboxylic acids and/or one or more saturated aliphatic or aromatic alcohol esters of a monoethylenically unsaturated carboxylic acid and (2) from about 1 to about 30 weight percent of a monoethylenically unsaturated carboxylic acid monomer;

both weight percentages being based upon the total weight of such initial monomer charge.

8. The process of claim 1 wherein the initial monomer charge of step (a) further comprises, based upon the weight of such initial monomer charge, from about 0.5 to about 20 weight percent of a modifying monomer suitable for providing the final copolymer latex with reactive sites adapted for subsequent curing or cross-linking of the final copolymer product via a non-addition polymerization type of reaction mechanism.

9. The process of claim 8 wherein the modifying monomer employed in step (a) is selected from the group consisting of N-methylol acrylamide or methacrylamide, N-isobutoxymethyl acrylamide or methacrylamide, glycidyl acrylate or methacrylate, acrolein or methacrolein and isopropenyl oxazoline.

10. The process of claim 1 wherein the weight ratio of the initial monomer charge to the second monomer charge is from about 5:

95 to about 20;

80.

11. The process of claim 10 wherein the initial monomer charge comprises, based on the total weight thereof, from about 70 to about 99 weight percent of a vinyl ester of a C₁ to about C₆ alkanoic acid or a C₁ to about C₃ alkyl ester of acrylic acid and from about 1 to about 30 weight percent of the monoethylenically unsaturated carboxylic acid monomer.