Multistage polymers and compositions thereof
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.
1. 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.
2. The multilayer particle of claim 1 , 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).
3. The multilayer particle of claim 2 , 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.
4. The multilayer particle of claim 2 , 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.
5. An aqueous composition comprising a plurality of multilayer particles defined by claim 1 dispersed in an aqueous medium.
6. The aqueous composition of claim 5 , wherein the aqueous composition further comprises an aryl phosphate surfactant.
7. The composition of claim 6 , wherein the aryl phosphate surfactant comprises a tristyrylphenol alkoxylated phosphate.
8. A coating comprising a plurality of multilayer particles defined by claim 1 .
9. 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; and
(ii) polymerizing one or more hard ethylenically-unsaturated monomers selected from the group consisting of methyl methacrylate, styrene, and combinations thereof in a second emulsion polymerization step to produce a second polymer, wherein the one or more hard ethylenically-unsaturated monomers comprise at least 90% by weight of the monomers polymerized to form the second polymer,
wherein the particle exhibits a single T g , measured using DSC, ranging from −10° C. to 25° C.
10. The method of claim 9 , wherein the first emulsion polymerization step further comprises an aryl phosphate surfactant.
11. The method of claim 10 , wherein the aryl phosphate surfactant comprises a tristyrylphenol alkoxylated phosphate surfactant.
12. The method of claim 9 , 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.