MIKTOARM STAR POLYMER AS CEMENT FLUID ADDITIVES
Provided is Miktoarm star polymers, which are provided either as an aqueous solution or as thin micro-flakes. Also provided is a process of making the star polymers thereof. These polymers bear short polyacrylic segment(s) and long buoyant sulfonated polymer segment(s), which were found to be effective as additives for cement slurry water retention and as a plasticizer.
1 . A miktoarm star polymer comprising: one or more distinct polymer chain(s) bearing one or more of a functional monomeric unit chosen from carboxylic acid, phosphate acid ester, and phosphonate; one or more hydrophilic polymer chain(s) bearing one or more of the functional monomeric unit chosen from sulfonate and sulfate, and combinations thereof.
2 . The miktoarm star polymer according to claim 1 , wherein the one or more distinct polymer chain(s) and one or more hydrophilic polymer chain(s) form a star polymer diverging from a moiety bearing polyfunctional radical transfer functions chosen from thiol or mercaptan functional groups, phosphinic acid, phosphites, and combinations thereof.
3 . The miktoarm star polymer according to claim 1 , further comprising additional monomeric units different from the monomers of the distinct polymer chain(s) and the hydrophilic polymer chain(s).
4 . The miktoarm star polymer according to claim 1 , wherein the one or more distinct polymer chain(s) and the one or more hydrophilic polymer chain(s) are derived from polythiols bearing three or more thiol or mercaptan functional groups.
5 . The miktoarm star according to claim 1 , wherein the polyfunctional radical transfer group is chosen from thiol or mercaptan functional groups, or a combination thereof, and wherein one or more of the thiols or mercaptan functional groups is attached to one or more of the one or more distinct polymers either through stepwise radical transfer polymerization or direct chemical reaction with thiol-bearing substances and the rest of the thiol functional groups from the one or more distinct polymer(s) act as chain transfer agents to grow the hydrophilic polymer chain(s), thus forming the miktoarm star copolymer.
6 . The miktoarm star polymer according to claim 1 , wherein one or more of the one or more distinct polymer chain(s) comprises polyacrylic acid arm(s) having a weight average molecular weight of from about 1000 to about 50000 Daltons and the one or more of the hydrophilic polymer chain(s) comprises sulfonated or sulfated arm(s) having a weight average molecular weight of from about 10000 to about 1,000,000 Daltons.
7 . The miktoarm star polymer according to claim 1 , wherein one or more of the hydrophilic polymer chain(s)s comprises one sulfonic acid-containing monomer or its salt alone or with one or more other monomer.
8 . The miktoarm star polymer according to claim 7 , wherein the sulfonic acid-containing monomer is chosen from 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, methallyl sulfonic acid, allylhydroxypropanesulfoinic acid, or the salts thereof, styrene sulfonate, or allyl polyoxyethylene sulfate ester salt.
9 . The miktoarm star polymer according to claim 2 , wherein the additional monomeric unit is derived from acrylamide, methyacrylamide, N,N-dimethyl(meth)acrylamide, N—N-diethyl(meth)acrylamide, or isopropyl(meth)acrylamide; N-tert-butylacrylamide, or amides of α, β-ethylenically unsaturated mono- or dicarboxylic acids with diamines having one or more primary or secondary amine group; N,N-diallylamines, or N,N-diallyl-N-alkylamines; esters of α, β-ethylenically unsaturated mono- or dicarboxylic acids with C 2-30 alkanediols or their alkoxylates; tetrahydrofurfuryl acrylate; N-vinylcaprolactam, N-vinylpyrolidone, N-vinylacetamide, N-vinylformamide, N-methyl-N-vinylacetamide, N-vinylpiperidone, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam, vinylpyridine, α, β-ethylenically unsaturated ethers of C 2-30 alkanediols or their alkoxylates, or combinations thereof.
10 . A process of producing a miktoarm star polymer comprising:
a) preparing a thiol-bearing telechelic polymer chain by polymerizing a composition comprising monomers bearing carboxylic acids, phosphate acid esters, phosphonates, and combinations thereof; a polythiol or mercaptan-bearing moiety and a radical initiator;
b) preparing a monomer solution comprising one or more monomer(s) bearing sulfonate or sulfate functional groups to form one or more hydrophilic polymer chain(s) or segment(s);
c) combining the thiol-bearing telechelic polymer chain from step a) with the monomer solution containing one or more functional monomers bearing sulfonate or sulfate of step b) and initiating polymerization with radical initiator(s);
d) continuing the polymerization reaction until the thiol concentration is non-detectable by using Ellman assay techniques thereby producing a miktoarm star polymer diverging from a moiety bearing polyfunctional radical transfer functions chosen from thiol or mercaptan functional groups, phosphinic acid, phosphites, and combinations thereof.
11 . The process according to claim 10 , further comprising additional monomeric units different from those in the thiol-bearing telechelic polymer chain(s) and the hydrophilic polymer chain(s), wherein the additional monomer units bears functions other than those in the thiol-bearing telechelic polymer chain(s) and the hydrophilic polymer chain(s).
12 . The process according to claim 10 , wherein the polyfunctional radical transfer function is chosen from thiol or mercaptan functional groups, or a combination thereof, and wherein one or more of the thiols or mercaptan functional groups is attached to one or more of the one or more distinct polymers either through stepwise radical transfer polymerization or direct chemical reaction with thiol-bearing substances and the rest of the thiol functional groups from the one or more distinct polymer chain(s) act as chain transfer agents to grow the hydrophilic polymer chain(s), thus forming the miktoarm star copolymer.
13 . The process according to claim 12 , wherein one or more but not all of the thiol or mercaptan functional groups is attached to the one or more distinct polymer chain(s) and the remaining thiol functional groups on the one or more distinct polymer chain(s) act as chain transfer agents to grow the hydrophilic polymer chain(s).
14 . The process according to claim 10 , wherein the one or more distinct polymer chain(s) comprises a polyacrylic acid arm having a molecular weight of from about 1000 to about 50000 and the one or more hydrophilic polymer chain(s) comprise sulfonated arms having a molecular weight of from about 10000 to about 1,000,000.
15 . The process according to claim 10 , wherein the hydrophilic polymer chain(s) is chosen from 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, methallyl sulfonic acid, allylhydroxypropanesulfoinic acid, or its salts and allyl polyoxyethylene sulfate ester salt alone or with acrylamide, methacrylamide, N,N-dimethyl(meth)acrylamide, N—N-diethyl(meth)acrylamide, isopropyl(meth)acrylamide; N-tert-butylacrylamide, amides of α, β-ethylenically unsaturated mono- or dicarboxylic acids with diamines having one or more primary or secondary amine group; N,N-diallylamines, and N,N-diallyl-N-alkylamines; esters of α, β-ethylenically unsaturated mono- or dicarboxylic acids with C 2-30 alkanediols or their alkoxylates; and tetrahydrofurfuryl acrylate; N-vinylcaprolactam, N-vinylpyrolidone, N-vinylacetamide, N-vinylformamide, N-methyl-N-vinylacetamide, N-vinylpiperidone, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam, and N-vinyl-7-ethyl-2-caprolactam, vinylpyridine, and α, β-ethylenically unsaturated ethers of C 2-30 alkanediols or their alkoxylates.
16 . The process according to claim 10 , wherein the polymerization reaction is continued until the thiol concentration is non-detectable based on Ellman assay techniques.
17 . A method for reducing fluid loss in mortar or concrete processes comprising:
providing a mortar ground or concrete slurry;
adding to the mortar ground or concrete slurry a miktoarm star polymer comprising one or more one or more distinct polymer chain bearing one or more of functional monomeric unit chosen from carboxylic acid, phosphate acid ester, and phosphonate; one or more hydrophilic polymer chain(s) bearing one or more functional monomeric units chosen from sulfonate and sulfate, and combinations thereof.
18 . The method according to claim 17 , wherein the one or more distinct polymer chain(s) and one or more hydrophilic polymer chain(s) form a star polymer diverging from a moiety bearing polyfunctional radical transfer functions chosen from thiol or mercaptan functional groups, phosphinic acid, phosphites, and combinations thereof.
19 . The method according to claim 17 , wherein the polyfunctional radical transfer function is chosen from thiol or mercaptan functional groups, or a combination thereof, and wherein one or more of the thiols or mercaptan functional groups is attached to one or more of the one or more distinct polymers either through stepwise radical transfer polymerization or direct chemical reaction with thiol-bearing substances and the rest of the thiol functional groups from the one or more distinct polymer chain(s) act as chain transfer agents to grow the one or more hydrophilic polymer chain(s), thus forming the miktoarm star polymer.
20 . The method according to any one of claim 17 , wherein the miktoarm star polymer acts as a dispersant or superplasticizer in mortar or concrete processes.