Multistage polymers and compositions thereof

Patent metadata

Field	Value
Publication number	US-2016355698-A1
Application number	US-201415103963-A
Country	US
Kind code	A1
Filing date	Dec 3, 2014
Priority date	Dec 13, 2013
Publication date	Dec 8, 2016
Grant date	—

Abstract

Provided are multistage polymers that comprise (i) a first stage comprising a first copolymer having a first theoretical T g , the first copolymer being derived from a soft ethylenically-unsaturated monomer, a phosphorus-containing monomer, and an acetoacetoxy monomer; and (ii) a second stage comprising a second polymer having a second theoretical T g , the second polymer being derived from one or more hard ethylenically-unsaturated monomers. The multistage polymers can be in the form of multilayer particles that comprise (i) a first layer comprising the first copolymer; and (ii) a second layer surrounding at least a portion of the first layer comprising the second polymer. Also provided are aqueous compositions including one or more of the multistage polymers (or multilayer particles) described herein, as well as methods for making the multistage polymers (or multilayer particles) described herein.

First claim

1 . An aqueous composition comprising an aryl phosphate surfactant and a multistage polymer, wherein the multistage polymer comprises
(i) a first stage comprising a first copolymer having a first theoretical glass transition temperature (T g ), the first copolymer being derived from a soft ethylenically-unsaturated monomer, a phosphorus-containing monomer, and an acetoacetoxy monomer; and (ii) a second stage comprising a second polymer having a second theoretical T g , the second polymer being derived from one or more hard ethylenically-unsaturated monomers.

2 . The composition of claim 1 , wherein the aryl phosphate surfactant comprises a tristyrylphenol alkoxylated phosphate.

3 . A multilayer particle comprising
(i) a first layer comprising a first copolymer having a first theoretical glass transition temperature (T g ), the first copolymer being derived from a soft ethylenically-unsaturated monomer, a phosphorus-containing monomer, and an acetoacetoxy monomer; and (ii) a second layer surrounding at least a portion of the first layer comprising a second polymer having a second theoretical T g , the second polymer being derived from at least 50% by weight of one or more hard ethylenically-unsaturated monomers, based on the total weight of monomers used to form the second polymer;
wherein the second theoretical T g is at least 40° C. greater than the first theoretical T g .

4 . The particle of claim 3 , wherein the multistage particle exhibits a single T g , measured using differential scanning calorimetry (DSC), ranging from −10° C. to 25° C.

5 . A multilayer particle comprising
(i) a first layer comprising a first copolymer derived from a soft ethylenically-unsaturated monomer, a phosphorus-containing monomer, and an acetoacetoxy monomer; and (ii) a second layer surrounding at least a portion of the first layer comprising a second polymer derived from at least 90% by weight of one or more hard ethylenically-unsaturated monomers selected from the group consisting of methyl methacrylate, styrene, and combinations thereof, based on the total weight of monomers used to form the second polymer; wherein the particle exhibits a single T g , measured using DSC, ranging from −10° C. to 25° C.

6 . The particle of claim 3 ,
wherein the first theoretical T g of the first copolymer is 30° C. or less.

7 . The particle of claim 3 ,
wherein the second theoretical T g of the second copolymer is at least 60° C.

8 . The particle of claim 3 ,
wherein the second theoretical T g is at least 50° C. greater than the first theoretical T g .

9 . The particle of claim 3 ,
wherein the first copolymer is derived from (i) greater than 80% by weight of one or more (meth)acrylate monomers; (ii) greater than 0% by weight to 5% by weight of one or more carboxylic acid-containing monomers; (iii) greater than 0% by weight to 10% by weight of one or more acetoacetoxy monomers; (iv) greater than 0% by weight to 5% by weight of one or more phosphorus-containing monomers; and (v) optionally one or more additional ethylenically-unsaturated monomers, excluding monomers (i), (ii), (iii), and (iv).

10 . The particle of claim 3 , wherein the one or more (meth)acrylate monomers are selected from the group consisting of methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, and combinations thereof.

11 . The particle of claim 3 , wherein
the one or more carboxylic acid-containing monomers are selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and combinations thereof; the one or more phosphorus-containing monomers are selected from the group consisting of 2-phosphoethyl methacrylate (PEM), 2-phosphopropyl methacrylate, 3-phosphopropyl methacrylate, phosphobutyl methacrylate, 3-phospho-2-hydroxypropyl methacrylate, and combinations thereof; and the one or more acetoacetoxy monomers are selected from the group consisting of acetoacetoxyethyl (meth)acrylate (AAEM), acetoacetoxypropyl (meth)acrylate, acetoacetoxybutyl (meth)acrylate, 2,3-di(acetoacetoxy)propyl (meth)acrylate, allyl acetoacetate, vinyl acetoacetate, and combinations thereof.

12 . The particle of claim 3 ,
wherein the one or more hard ethylenically-unsaturated monomers are selected from the group consisting of methyl methacrylate, styrene, and combinations thereof.

13 . The particle of claim 3 ,
wherein the second polymer is derived from at least 90% by weight of one or more hard ethylenically-unsaturated monomers selected from the group consisting of methyl methacrylate, styrene, and combinations thereof, based on the total weight of monomers used to form the second polymer.

14 . An aqueous composition comprising a plurality of particles defined by claim 3 dispersed in an aqueous medium.

15 . A coating comprising a plurality of particles defined by claim 3 .

16 . A method of making a multilayer particle, comprising
(i) polymerizing a soft ethylenically-unsaturated monomer, a phosphorus-containing monomer, and an acetoacetoxy monomer in a first emulsion polymerization step to produce a first copolymer having a first theoretical T g ; and (ii) polymerizing one or more hard ethylenically-unsaturated monomers in a second emulsion polymerization step to produce a second polymer having a second theoretical T g that is at least 40° C. greater than the first theoretical T g , wherein the one or more hard ethylenically-unsaturated monomers comprise at least 50% by weight of the monomers polymerized to form the second polymer.

17 . The method of claim 16 , wherein the particle exhibits a T g , measured using DSC, ranging from −10° C. to 25° C.

18 . The method of claim 16 , wherein the first emulsion polymerization step further comprises an aryl phosphate surfactant.

19 . The method of claim 18 , wherein the aryl phosphate surfactant comprises a tristyrylphenol alkoxylated phosphate surfactant.

20 . The method of claim 16 , wherein the first polymerization step is carried out at a first polymerization temperature of less than or equal to 85° C., and the second polymerization step is carried out at a second polymerization temperature of less than or equal to 85° C.

Assignees

• Basf Se

Inventors

• Harris Paul J
• Drewery Michael J
• Casebolt Eric
• Foley Nicholas

Classifications

• C08F265/06 Primary

  Polymerisation of acrylate or methacrylate esters on to polymers thereof · CPC title

• C09D151/003 Primary

  grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds (C09D151/04, C09D151/06 take precedence) · CPC title

• C08K5/523

  with hydroxyaryl compounds · CPC title

• C09D151/06

  grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond · CPC title

• C08K5/521

  Esters of phosphoric acids, e.g. of H3PO4 · CPC title