Dispersion of adsorbing emulsion polymer particles
US-9303161-B2 · Apr 5, 2016 · US
US9856372B2 · US · B2
| Field | Value |
|---|---|
| Publication number | US-9856372-B2 |
| Application number | US-201615075241-A |
| Country | US |
| Kind code | B2 |
| Filing date | Mar 21, 2016 |
| Priority date | Mar 24, 2015 |
| Publication date | Jan 2, 2018 |
| Grant date | Jan 2, 2018 |
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The present invention relates to an in situ method for preparing a bimorphological aqueous dispersion of first polymer particles with protuberating phosphorus acid cores and second polymer particles without protuberating cores. The method provides a more efficient way of making compositions for pigmented coating formulations.
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The invention claimed is: 1. An in situ method for preparing a bimorphological aqueous dispersion of polymer particles comprising the steps of: a) mixing together an aqueous dispersion of phosphorus acid-functionalized acrylic-based first seed polymer particles having a volume average particle size in the range of from 40 nm to 85 nm with an aqueous dispersion of acrylic-based second seed polymer particles comprising a substantial absence of phosphorus acid functionality and having a volume average particle size in the range of from 20 nm to 80 nm; b) contacting monomers with the aqueous dispersions of the first and second seed polymer particles under emulsion polymerization conditions to form a dispersion of 1) polymer particles with a protuberating phosphorus acid functionalized core; and 2) polymer particles without a protuberating core; and wherein the weight-to-weight ratio of particles with the protuberating phosphorus acid functionalized core to particles without a protuberating core is in the range of 25:75 to 75:25. 2. The method of claim 1 wherein the phosphorus acid-functionalized acrylic-based first seed polymer particles comprise structural units of: a) methyl methacrylate or styrene or a combination thereof; b) one or more acrylate monomers selected from the group consisting of ethyl acrylate, butyl acrylate, 2-propylheptyl acrylate, and 2-ethylhexyl acrylate; and c) phosphoethyl methacrylate; and wherein the monomers comprise: a) methyl methacrylate or styrene or a combination thereof; b) one or more acrylate monomers selected from the group consisting of ethyl acrylate, butyl acrylate, 2-propylheptyl acrylate, and 2-ethylhexyl acrylate; and c) a substantial absence of a phosphorus acid monomer, based on the weight of the second seed polymer particles. 3. The method of claim 2 wherein the phosphorus acid-functionalized acrylic-based first seed polymer particles further comprise: d) structural units of a carboxylic acid monomer or a salt thereof; and e) structural units of a multiethylenically unsaturated monomer. 4. The method of claim 3 wherein the monomers further comprises a carboxylic acid monomer or a sulfur acid monomer or a salt thereof or a combination thereof. 5. The method of claim 4 wherein the phosphorus acid-functionalized acrylic-based first seed polymer particles comprise, based on the weight of the first seed polymer particles: a) 3 to 8 weight percent structural units of phosphoethyl methacrylate or a salt thereof; b) from 1 to 5 weight percent structural units of acrylic acid or methacrylic acid or a salt thereof; c) from 0.2 to 5 weight percent structural units of a multiethylenically unsaturated monomer; d) from 50 to 65 weight percent structural units of butyl acrylate; and e) 25 to 45 weight percent structural units of methyl methacrylate; and wherein the monomers are added as a monomer emulsion and comprises, based on the weight of the monomers: a) from 40 to 60 weight percent butyl acrylate or 2-ethylhexyl acrylate or a combination thereof; b) from 40 to 60 weight percent methyl methacrylate or styrene or a combination thereof; c) from 0.1 to 5 weight acrylic acid or methacrylic acid or sodium 4-vinylbenzenesulfonate or 2-acrylamido-2-methyl propanesulfonic acid or a salt thereof or a combination thereof; and d) less than 0.5 weight percent of a phosphorus acid monomer. 6. The method of claim 5 wherein the monomers have the same monomer profile as the second seed polymer particles. 7. The method of claim 1 wherein the aqueous dispersions of the first and second seed polymer particles are mixed together at a first-to-second seed polymer particles weight-to-weight ratio of from 1:2 to 10:1, wherein the monomer emulsion comprises less than 0.1 weight of a phosphorus acid monomer based on the weight of the monomer emulsion. 8. The method of claim 7 wherein the ratio of volume average particle size of the protuberating core polymer particles to the non-protuberating core polymer particle is from 1.45:1 to 0.9:1. 9. The method of claim 8 wherein the volume average particle size of the protuberating core polymer particles is in the range of from 110 to 160 nm, and the volume average particle size of the non-protuberating core polymer particles is in the range of from 70 to 140 nm. 10. The method of claim 9 wherein the ratio of volume average particle size of the protuberating core polymer particles to the non-protuberating core polymer particle is from 1.42:1 to 1.2:1; the volume average particle size of the protuberating core polymer particles is in the range of 110 to 150 nm, and the volume average particle size of the non-protuberating core polymer particles is in the range of 80 to 130 nm. 11. The method of claim 10 wherein weight-to-weight ratio of particles with the protuberating phosphorus acid functionalized core to particles without a protuberating core is in the range of 50:50 to 68:32. 12. The method of claim 1 which comprises the further step of combining the bimorphological aqueous dispersion of polymer particles with TiO 2 particles to form a dispersion polymer particles that are adsorbed and not adsorbed to TiO 2 .
Methyl esters {, e.g. methyl (meth)acrylate} · CPC title
Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer (C08F295/00, C08F297/00 take precedence) · CPC title
{Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond} in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00 · CPC title
Homopolymers or copolymers of acrylic acid esters · CPC title
Emulsion polymerisation · CPC title
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