Process for preparing polymer emulsions and polymers formed therefrom

• US 7,803,878 B2
• Filed: 09/04/2008
• Issued: 09/28/2010
• Est. Priority Date: 11/05/1997
• Status: Expired due to Fees

• Current Assignee: Rohm and Haas Company (Dow, Inc.)
• Original Assignee: Rohm and Haas Company (Dow, Inc.)
• Inventors: Bardman, James Keith, Blankenship, Robert Mitchell
• Primary Examiner(s): CHOI, LING SIU
• Application Number:
  US12/231,642
• Publication Number:
  US 20090012212A1
• Time in Patent Office: 754 Days
• Field of Search: 524/460, 524/461, 525/301, 525/302, 525/308, 525/309, 525/298
• US Class Current: 525/302
• CPC Class Codes: C08F 2/22 Emulsion polymerisation
• CPC Class Codes: C08F 265/04 on to polymers of esters
• CPC Class Codes: C08F 265/06 Polymerisation of acrylate or methacrylate esters on to polymers thereof
• 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: Y10S 525/902 Core-shell

Abstract

An aqueous polymer emulsion comprising water and swollen multi-stage polymer is provided. The swollen multi-stage polymer has low dry bulk density, as measured by centrifugation. To achieve the low dry bulk density, the polymer is highly swollen in such a way that it does not subsequently collapse. The polymer is useful in paint and paper coatings.

Claims

1. An aqueous polymer emulsion comprising water and swollen multi-stage emulsion polymer wherein the dry bulk density of the swollen multi-stage emulsion is:

less than 0.77 g/cc when the swollen multi-stage emulsion polymer has a particle size below 275 nm;

less than 0.74 g/cc when the swollen multi-stage emulsion polymer has a particle size of from 275 to 500 nm;

less than 0.59 g/cc when the swollen multi-stage emulsion polymer has a particle size of from 501 to 750 nm;

less than 0.46 g/cc when the swollen multi-stage emulsion polymer has a particle size of from 751 to 1300 nm;

wherein said multi-stage emulsion polymer comprises

(I) a core stage polymer that comprises, as polymerized units, from 5 to 100 percent by weight, based on the weight of the core stage polymer, of hydrophilic monoethylenically unsaturated monomer, and from 0 to 95 percent by weight, based on the weight of the core stage polymer, of at least one nonionic monoethylenically unsaturated monomer;

(II) a shell stage polymer that comprises, as polymerized units, at least 50 percent by weight of nonionic monoethylenically unsaturated monomer;

(III) an intermediate stage polymer that partially or fully encapsulates said core stage polymer and that is partially or fully encapsulated by said shell stage polymer, wherein said intermediate stage polymer consists of as polymerized units,

(a) 0.3 to 20 percent by weight, based on the weight of said core stage polymer, at least one hydrophilic monoethylenically unsaturated monomer,

(b) 80 to 99.7 percent by weight, based on the weight of said core stage polymer, at least one nonionic monoethylenically unsaturated monomer.

2. The aqueous polymer emulsion of claim 1, wherein said multi-stage emulsion polymer has particle size of 275 to 500 nm and dry bulk density of less than 0.74g/cc.

3. The aqueous polymer emulsion of claim 1, wherein said shell stage polymer resists shrinking when said water is removed from said multistage emulsion polymer.

4. An aqueous polymer emulsion comprising water and swollen multi-stage emulsion polymer wherein the dry bulk density of the swollen multi-stage emulsion is:

less than 0.77 g/cc when the swollen multi-stage emulsion polymer has a particle size below 275 nm;

less than 0.74 g/cc when the swollen multi-stage emulsion polymer has a particle size of from 275 to 500 nm;

less than 0.59 g/cc when the swollen multi-stage emulsion polymer has a particle size of from 501 to 750 nm;

less than 0.46 g/cc when the swollen multi-stage emulsion polymer has a particle size of from 751 to 1300 nm;

wherein said multi-stage emulsion polymer comprises

(I) a core stage polymer that comprises, as polymerized units, from 5 to 100 percent by weight, based on the weight of the core stage polymer, of hydrophilic monoethylenically unsaturated monomer, and from 0 to 95 percent by weight, based on the weight of the core stage polymer, of at least one nonionic monoethylenically unsaturated monomer;

(II) a shell stage polymer that comprises, as polymerized units, at least 50 percent by weight of nonionic monoethylenically unsaturated monomer;

wherein said swollen multi-stage emulsion polymer additionally comprises

(A) X ppm based on polymer solids of one or more polymerization inhibitors, and

(B) one or more reaction products of one or more radicals with Y ppm based on polymer solids of one or more polymerization inhibitors,

wherein the sum of X+Y is from 25 to 5,000.

5. The aqueous polymer emulsion of claim 4, wherein said multi-stage emulsion polymer has particle size of 275 to 500 nm and dry bulk density of less than 0.74 g/cc.

6. The aqueous polymer emulsion of claim 4, wherein said multi-stage emulsion polymer additionally comprises

(III) an intermediate stage polymer that partially or fully encapsulates said core stage polymer and that is partially or fully encapsulated by said shell stage polymer, wherein said intermediate stage polymer comprises as polymerized units,

(a) 0.3 to 20 percent by weight, based on the weight of said core stage polymer, at least one hydrophilic monoethylenically unsaturated monomer,

(b) 80 to 99.7 percent by weight, based on the weight of said core stage polymer, at least one nonionic monoethylenically unsaturated monomer.

7. The aqueous polymer emulsion of claim 6, wherein said intermediate stage polymer consists of as polymerized units,

(a) 0.3 to 20 percent by weight, based on the weight of said core stage polymer, at least one hydrophilic monoethylenically unsaturated monomer,

(b) 80 to 99.7 percent by weight, based on the weight of said core stage polymer, at least one nonionic monoethylenically unsaturated monomer.

8. The aqueous polymer emulsion of claim 6, wherein said multi-stage emulsion polymer has particle size of 275 to 500 nm and dry bulk density of less than 0.74 g/cc.