Processing aids and polymer formulations containing the same and method for producing the same
A multi-stage emulsion processing aid polymer comprising one or more functionalized ethylenically unsaturated monomer into the emulsion polymerization reactor, wherein the functionality is selected from the group consisting of β-keto esters, β-keto amides, β-diketones, cyanoacetic esters, malonates, nitroalkanes, β-nitro esters, sulfonazides, thiols, thiol-s-triazines, and amine, where the functionality is incorporated into polymers by polymerizing, ethylenically unsaturated monomers containing these functionalities or by post functionalization of a polymer with additional reactions after polymerization in one of the first or second stages. Foamable halogenated polymers comprising the multi-stage emulsion processing aid polymer is also provided. Also provided are methods for making the multi-stage emulsion processing aid polymer and foamable halogenated polymers.
1. A processing aid polymer powder or pellet comprising:
a multi-stage emulsion processing aid polymer comprising:
(a) from 25 to 75 percent by weight of a first stage polymer which comprises units derived from non-functionalized ethylenically unsaturated monomer and no units derived from functionalized monomers; and
(b) from 25 to 75 percent by weight of a second stage polymer which comprises;
(i) from 10 to 90 mole % units derived from one or more non-functionalized ethylenically unsaturated monomer(s), and
(ii) from 10 to 90 mole % units derived from one or more functionalized ethylenically unsaturated monomer(s), wherein the functionality of said one or more functionalized ethylenically unsaturated monomer(s) is selected from the group consisting of β-keto esters, β-keto amides, β-diketones, cyanoacetic esters, malonates, nitroalkanes, β-nitro esters, sulfonazides, thiols, thiol-s-triazines, and amine; and
wherein the multi-stage emulsion processing aid polymer of said processing aid polymer powder or pellet has a Mw equal to or greater than 700,000, and a mean particle diameter size in the range of from 50 to 500 microns.
2. The processing aid polymer powder or pellet according to claim 1 , wherein the functionalized ethylenically unsaturated monomer is selected from the group of β-keto esters and amides, β-diketones, cyanoacetic esters, malonates, nitroalkanes and β-nitro esters.
3. The processing aid polymer powder or pellet according to claim 1 , wherein the functionalized ethylenically unsaturated monomer is selected from the group of acetoacetoxyethyl(meth)acrylate, acetoacetoxypropyl(meth)acrylate, acetoacetoxybutyl(meth)acrylate, 2,3-di(acetoacetoxy)propyl(meth)acrylate, acetoacetoxyethyl(meth)acrylamide, 2-cyanoacetoxyethyl(meth)acrylate, 2-cyanoacetoxyethyl(meth)acrylamide, N-cyanoacetyl-N-metylaminoethyl(meth)acrylate, N-(2 propionylacetoxybutyl)(meth)acrylamide.
4. The processing aid polymer powder or pellet according to claim 1 , wherein the functionalized ethylenically unsaturated monomer is acetoacetoxyethyl(meth)acrylate, wherein the processing aid polymer has a Tg between 10° C. and 150° C.
5. The processing aid polymer powder or pellet according to claim 4 , wherein the functionalized ethylenically unsaturated monomer is acetoacetoxyethyl(meth)acrylate, wherein the processing aid polymer has a Tg is between 55° C. and 150° C.
6. The processing aid polymer powder or pellet according to claim 1 , wherein the functionalized ethylenically unsaturated monomer is acetoacetoxyethyl(meth)acrylate, wherein the processing aid polymer has a Mw equal to or greater than 1.6 million.
7. A formulation comprising (a) from 20 to 99% by weight of one or more halogenated polymers (A) selected from homopolymers or copolymers comprising at least 80% by weight of the halogenated polymer of one or more monomers selected from vinyl chloride, vinyl fluoride, vinylidene chloride, and vinylidene fluoride, and chlorinated polyvinyl chloride, and chlorinated polyethylene; and (b) from 0.5 to 20% by weight of one or more multi-stage processing aid polymers according to claim 1 wherein the one or more the processing aid polymers is used at a level in the formulation to provide 0.00040 to 0.0056 moles of functionalized monomer repeat units per 100 g of halogenated polymers.
8. The formulation according to claim 7 wherein the functionalized ethylenically unsaturated monomer is selected from the group of β-keto esters and amides, β-diketones, cyanoacetic esters, malonates, nitroalkanes and β-nitro esters.
9. The formulation according to claim 7 wherein the functionalized ethylenically unsaturated monomer is selected from the group of acetoacetoxyethyl(meth)acrylate, acetoacetoxypropyl(meth)acrylate, acetoacetoxybutyl(meth)acrylate, 2,3-di(acetoacetoxy)propyl(meth)acrylate, acetoacetoxyethyl(meth)acrylamide, 2-cyanoacetoxyethyl(meth)acrylate, 2-cyanoacetoxyethyl(meth)acrylamide, N-cyanoacetyl-N-metylaminoethyl(meth)acrylate, N-(2 propionylacetoxybutyl)(meth)acrylamide.
10. A multi-stage emulsion polymerization process comprising:
feeding water, at least one non-functionalized ethylenically unsaturated monomer and no functionalized monomers, and surfactant into an emulsion polymerization reactor, thereby forming a first stage polymer of a multi-stage emulsion polymerization process, wherein the first stage polymer comprises from 25% to 75% by weight of the total weight of the multistage emulsion polymer;
feeding one or more functionalized ethylenically unsaturated monomer into the emulsion polymerization reactor to form a second stage polymer, in the presence of the first stage polymer, wherein the functionality of said one or more functionalized ethylenically unsaturated monomer(s) is selected from the group consisting of β-keto esters, β-keto amides, β-diketones, cyanoacetic esters, malonates, nitroalkanes, β-nitro esters, sulfonazides, thiols, thiol-s-triazines, and amine, and wherein the second stage polymer comprises from 25% to 75% by weight of the total weight of the multistage emulsion polymer, and wherein said second stage polymer which comprises (i) from 10 to 90 mole % units derived from one or more non-functionalized ethylenically unsaturated monomer(s), and (ii) from 10 to 90 mole % units derived from one or more functionalized ethylenically unsaturated monomer(s) into the emulsion polymerization reactor; and
drying or allowing to dry, the multistage emulsion polymer thereby forming a multi-stage emulsion polymer processing aid powder or pellet having a mean particle diameter size in the range of from 50 to 500 microns.
11. A process for producing a foamable halogenated polymer formulation comprising:
blending (a) from 20 to 99% by weight of one or more halogenated polymers (A) selected from homopolymers or copolymers comprising at least 80% by weight of the halogenated polymer of one or more monomers selected from vinyl chloride, vinyl fluoride, vinylidene chloride, and vinylidene fluoride, and chlorinated polyvinyl chloride, and chlorinated polyethylene; with (b) one or more multi-stage emulsion processing aid polymer produced according to the process of claim 1 wherein the one or more the processing aid polymers is used at a level in the formulation to provide 0.00040 to 0.0056 moles of monomer repeat units of one or more functionalities per 100 g of halogenated polymers.
12. A process for producing a foamable halogenated polymer formulation comprising:
blending (a) from 20 to 99% by weight of one or more halogenated polymers (A) selected from homopolymers or copolymers comprising at least 80% by weight of the halogenated polymer of one or more monomers selected from vinyl chloride, vinyl fluoride, vinylidene chloride, and vinylidene fluoride, and chlorinated polyvinyl chloride, and chlorinated polyethylene; with (b) one or more multistage emulsion processing aid polymer produced according to the process of claim 10 wherein the one or more the processing aid polymers is used at a level in the formulation to provide 0.00040 to 0.0056 moles of monomer repeat units of one or more functionalities per 100 g of halogenated polymers.