CN101983944A - Polycarboxylic acids water reducing agent containing low molecular weight carbon dioxide copolymer, and preparation method thereof - Google Patents
Polycarboxylic acids water reducing agent containing low molecular weight carbon dioxide copolymer, and preparation method thereof Download PDFInfo
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- CN101983944A CN101983944A CN 201010224108 CN201010224108A CN101983944A CN 101983944 A CN101983944 A CN 101983944A CN 201010224108 CN201010224108 CN 201010224108 CN 201010224108 A CN201010224108 A CN 201010224108A CN 101983944 A CN101983944 A CN 101983944A
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- carbon dioxide
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- weight carbon
- lower molecular
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- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Natural products O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 79
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 79
- 229920001577 copolymer Polymers 0.000 title claims abstract description 77
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 51
- 239000002253 acid Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 150000007513 acids Chemical class 0.000 title abstract 4
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 13
- 150000002148 esters Chemical class 0.000 claims abstract description 11
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 8
- 239000004567 concrete Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000004593 Epoxy Substances 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 43
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 38
- 150000003839 salts Chemical class 0.000 claims description 29
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 24
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 24
- 230000032050 esterification Effects 0.000 claims description 21
- 238000005886 esterification reaction Methods 0.000 claims description 21
- -1 carbon dioxide-epoxy propane-oxyethane Chemical compound 0.000 claims description 15
- 229920000151 polyglycol Polymers 0.000 claims description 15
- 239000010695 polyglycol Substances 0.000 claims description 15
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000004568 cement Substances 0.000 claims description 12
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 9
- 239000004160 Ammonium persulphate Substances 0.000 claims description 8
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 8
- 229920001897 terpolymer Polymers 0.000 claims description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 7
- 150000008065 acid anhydrides Chemical class 0.000 claims description 7
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 7
- 150000003460 sulfonic acids Chemical class 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 6
- 239000011976 maleic acid Substances 0.000 claims description 6
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 5
- 239000004159 Potassium persulphate Substances 0.000 claims description 5
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 5
- 235000011089 carbon dioxide Nutrition 0.000 claims description 5
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 claims description 5
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 235000019394 potassium persulphate Nutrition 0.000 claims description 5
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- 150000003926 acrylamides Chemical class 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000003643 water by type Substances 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 2
- XQPUOQJFHYZPRY-UHFFFAOYSA-N C1C(C2=CC=CC=C2)O1.C1C(C)O1.C(=O)=O Chemical compound C1C(C2=CC=CC=C2)O1.C1C(C)O1.C(=O)=O XQPUOQJFHYZPRY-UHFFFAOYSA-N 0.000 claims description 2
- WSNSMPZJJIYZCV-UHFFFAOYSA-N [Na]C Chemical compound [Na]C WSNSMPZJJIYZCV-UHFFFAOYSA-N 0.000 claims description 2
- 229940048053 acrylate Drugs 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- ZKPLXWZIWFAZNZ-UHFFFAOYSA-N carbon dioxide;2-methyloxirane;7-oxabicyclo[4.1.0]heptane Chemical compound O=C=O.CC1CO1.C1CCCC2OC21 ZKPLXWZIWFAZNZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000005586 carbonic acid group Chemical group 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 229920005990 polystyrene resin Polymers 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000011973 solid acid Substances 0.000 claims description 2
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000013461 design Methods 0.000 abstract description 2
- 239000002202 Polyethylene glycol Substances 0.000 abstract 1
- 230000000903 blocking effect Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 229920001223 polyethylene glycol Polymers 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000004574 high-performance concrete Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 235000019357 lignosulphonate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a polycarboxylic acids water reducing agent containing low molecular weight carbon dioxide copolymer, which is a copolymerization product of unsaturated large monomer, polyethylene glycol monomethyl ether monounsaturated acid ester, cyclic monomer and other unsaturated monomer containing low molecular weight carbon dioxide copolymer, wherein the low molecular weight carbon dioxide copolymer is the copolymer of the carbon dioxide and the epoxy compound. In the invention, the low molecular product generated by the copolymerization reaction of the carbon dioxide and the epoxy compound is used. According to the reasonable design of the molecular structure, the low molecular carbon dioxide copolymer is esterified for blocking to generate the unsaturated large monomer, and then the novel polycarboxylic acids water reducing agent with long/short functional branch is prepared through the copolymerization of the unsaturated large monomer and other functional monomer. The polycarboxylic acids water reducing agent for concrete has stable product quality, and the preparation method has the advantages of short process, simple technology, easily controlled reaction condition, and easy industrial production.
Description
Technical field
The present invention relates to a kind of novel green cement water reducing agent and preparation method thereof, specifically a kind of poly carboxylic acid series water reducer that contains the lower molecular weight carbon dioxide copolymer and preparation method thereof.
Technical background
In concrete industry now, development along with engineerings such as water power, traffic, hundred multiwalled skyscrapers, bridge spanning the sea, airport, high-speed railway, subbottom tunnels, mix high performance water reducer and reduce unit consumption of water, become the industry common recognition thereby improve concrete weather resistance, high strength, high workability effectively.The exploitation of high efficiency water reducing agent and use have become a core technology of high performance concrete.The exploitation of cement water reducing agent and use have been experienced sulfonated lignin, naphthalene system and melamine based water reducer progressively to the evolution of polycarboxylate high performance water-reducing agent.Compare with traditional water reducer, poly carboxylic acid series water reducer by long-chain branch polyoxyethylene groups and short-chain branch suede fixed layer (as-OH ,-SH ,-COR ,-CONH
2,-CN ,-NH
2,-COO
-,-SO
3 -) the super plasticizing of formation distinctive " comb shape " structure, these hydrophilic radicals are by effects such as absorption, electrostatic repulsion, sterically hindered, moistened surfaces, provide dispersed and dispersed to cement granules and keep, improved concrete flowability and flowing property hold facility greatly.
Poly carboxylic acid series water reducer at first is the concrete admixture by Japan's exploitation and application, and has realized suitability for industrialized production in the nineties in 20th century; The research emphasis of states such as America and Europe has also turned to polycarboxylic acid series, and a plurality of launch products are successively arranged.By contrast, the time of domestic research poly carboxylic acid series water reducer is shorter, and the production technique of product, raw-material selection and technology control etc. are all ripe not as good as external.
With carbonic acid gas and epoxy compounds is the technology of utilizing that the carbon dioxide copolymer of representative has been opened novel carbon source, has the industrial prospect of large-scale production.With the carbonic acid gas is raw material synthetic macromolecule amount carbon dioxide copolymer, is expected to be applied at aspects such as degradable medical packaging material, ceramic sizing agent and matrix materials.U.S. Pat P3585168, USP3900424 and USP3953383 adopt the various urethane and the polyethers of zinc alkyl(s)/active hydrogen compounds carbon dioxide copolymer that has been Preparation of Catalyst and different molecular weight.The molecular weight that the catalyzer that Chinese patent application 00136189.9 adopts rare earth compounding/metallorganics/polyol/annular lactone to form, catalysis gained carbon dioxide copolymerization close product surpasses 100,000.Feng Chao in Chinese invention patent CN101220534A with low-molecular-weight carbon dioxide copolymer (M
n=4,000～8,000) prepared a kind of full-biological degradation nonwoven cloth material with high-molecular weight L-poly(lactic acid) or poly butyric ester.Low-molecular-weight carbon dioxide copolymer is used for the synthetic of poly carboxylic acid series water reducer still not to be reported.
Summary of the invention
The object of the present invention is to provide a kind of novel polycarboxylic acid series water reducing agent that contains the lower molecular weight carbon dioxide copolymer and preparation method thereof, make product performance stable, and preparation method's mild condition, technology are simple.
In order to reach above-mentioned purpose, solution of the present invention is:
A kind of poly carboxylic acid series water reducer that contains the lower molecular weight carbon dioxide copolymer is characterized in that this water reducer is the copolymerization product that contains lower molecular weight carbon dioxide copolymer, poly glycol monomethyl ether list unsaturated acid ester, cyclic monomer and other unsaturated monomers.Wherein, described lower molecular weight carbon dioxide copolymer is the multipolymer of carbonic acid gas and epoxy compounds, its molecular formula W
1Represent by formula (a):
R
1＝OH，H；
x＝0.05-0.8；
N is an integer, between 1 to 20;
The lower molecular weight carbon dioxide copolymer is carbonic acid gas-ethylene oxide copolymer, carbon dioxide-epoxy propane copolymer, carbon dioxide-cyclohexene oxide copolymer, carbonic acid gas-Styrene oxide 98min. multipolymer, carbon dioxide-epoxy propane-oxyethane terpolymer, carbonic acid gas-oxyethane-cyclohexene oxide terpolymer, a kind of in carbon dioxide-epoxy propane-cyclohexene oxide terpolymer or carbon dioxide-epoxy propane-Styrene oxide 98min. terpolymer, two or three mixes.
The molecular formula W of described poly glycol monomethyl ether list unsaturated acid ester
2Represent by formula (b):
Formula (b)
M is the integer between 5-200.
Described cyclic monomer and other unsaturated monomers comprise: the mixture of a kind of, two or more components in oxyethane, propylene oxide, cyclohexene oxide, Styrene oxide 98min., (methyl) vinylformic acid, unsaturated sulfonic acid or its salt, unsaturated amides, (methyl) acrylate or its salt, unsaturated dicarboxylic acid (salt) and the acid anhydrides thereof, wherein:
(1) unsaturated sulfonic acid or its salt comprise: the mixture of a kind of, two or three component in vinyl sulfonic acid or its salt, α-sodium olefin sulfonate, (methyl) sodium allyl sulfonate, styrene sulfonic acid or its salt;
(2) unsaturated amides comprises: the mixture of one or both in acrylamide, the 2-Methacrylamide;
(3) (methyl) acrylate (salt) comprising: the mixture of a kind of, two or more components in (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate and (methyl) sodium acrylate (ammonium) salt;
(4) unsaturated dicarboxylic acid (salt) and acid anhydrides thereof comprise: the mixture of a kind of, two or more components in maleic acid (salt), fumaric acid (salt), MALEIC ANHYDRIDE, the fumaric acid anhydride.
The number-average molecular weight of described lower molecular weight carbon dioxide copolymer is 350～2800.
The described preparation method who contains the poly carboxylic acid series water reducer of lower molecular weight carbon dioxide copolymer comprises following reactions steps:
The first step, the esterification end capping: with the acidifying sulphonated polystyrene resin is catalyzer, with lower molecular weight carbon dioxide copolymer and MALEIC ANHYDRIDE, perhaps lower molecular weight carbon dioxide copolymer and (methyl) vinylformic acid, perhaps lower molecular weight carbon dioxide copolymer and MALEIC ANHYDRIDE and (methyl) acrylic acid mixture, at 60～90 ℃, esterification is 3～6 hours under the reduced pressure, remove solid acid, obtain end capped lower molecular weight carbon dioxide copolymer of MALEIC ANHYDRIDE and the mixture that remains MALEIC ANHYDRIDE, perhaps end capped lower molecular weight carbon dioxide copolymer of (methyl) vinylformic acid and the acrylic acid mixture of residue (methyl), the perhaps mixture of end capped lower molecular weight carbon dioxide copolymer of (methyl) vinylformic acid and MALEIC ANHYDRIDE mixture and residue (methyl) vinylformic acid and residue MALEIC ANHYDRIDE;
Second step, copolymerization: with in ammonium persulphate, Sodium Persulfate, the Potassium Persulphate one or both is initiator, with the resulting mixture of esterification end capping in the first step, deionized water, poly glycol monomethyl ether list unsaturated acid ester, cyclic monomer and other unsaturated monomers are introduced in the reactor, at 60～95 ℃ copolymerization takes place down, the reaction times is 3～8 hours; After polyreaction finishes, cooling, regulating pH with alkali lye is 7～8, obtains red-brown or brown yellow transparent liquid, is the poly carboxylic acid series water reducer that the present invention contains the lower molecular weight carbon dioxide copolymer.
The described poly carboxylic acid series water reducer that contains the lower molecular weight carbon dioxide copolymer in massfraction by all or part of being polymerized in the following raw materials according:
10～150 parts of one or more of the resulting mixture of the first step esterification end capping,
30～150 parts of poly glycol monomethyl ether list unsaturated acid esters,
5～35 parts of unsaturated sulfonic acid or its salt,
3～35 parts of acrylamides,
3～30 parts in (methyl) vinylformic acid,
3～35 parts of (methyl) acrylate or its salt
5～80 parts of oxyethane, propylene oxide, cyclohexene oxide or Styrene oxide 98min.s,
5～60 parts on unsaturated dicarboxylic acid (salt) and acid anhydrides thereof,
0.05～15 part of ammonium persulphate, Sodium Persulfate or Potassium Persulphate,
260～900 parts of deionized waters.
In the described esterification end capping process, the mixture of (methyl) vinylformic acid, MALEIC ANHYDRIDE or (methyl) vinylformic acid and maleic acid and the mol ratio n of lower molecular weight carbon dioxide copolymer are in the scope of 5: 1≤n≤1: 1, and excessive (methyl) vinylformic acid, MALEIC ANHYDRIDE or (methyl) vinylformic acid need not separate with the mixture of maleic acid and is directly used in polyreaction after the esterification.
The existence form of described lower molecular weight carbon dioxide copolymer in the gained poly carboxylic acid series water reducer has following two kinds:
(1) the lower molecular weight carbon dioxide copolymer becomes a kind of long-chain branch in polymkeric substance, its general molecular formula W
3Represent by formula (c);
R
1，R
2，R
3＝H，CH
3；
M
1＝H，Na，NH
4；
M
2=H, Na, NH
4, or CH
3, C
2H
5, C
4H
7
M
3＝H，CH
3，Na，NH
4；
Wherein, a, b, c, d, e, f are the molar fractions of each component, and a+b+c+d+e+f=1.0;
(2) or the lower molecular weight carbon dioxide copolymer in polymkeric substance, form cross-linking set, the general structure W of its crosslinking structure multipolymer
4(d) is expressed as by formula:
Or:
Or:
The present invention utilizes the lower molecular weight carbon dioxide copolymer, pass through reasonable molecular structural design, earlier with lower molecular weight carbon dioxide copolymer esterification end-blocking, and then with poly glycol monomethyl ether list unsaturated acid ester, cyclic monomer and other unsaturated monomer copolymerizations, prepare the novel poly carboxylic acid series water reducer that has the functional side chain of length/weak point, thereby realized purpose of the present invention.
Compared with prior art, advantage of the present invention:
One, provides a kind of method of utilizing greenhouse gases carbonic acid gas synthetic macromolecule fine chemical product, and can fully utilize the low molecular weight product that produces in the high molecular carbon dioxide copolymer production of resins process, cheap and have a good social benefit;
Two, remove easily and regenerate at lower molecular weight carbon dioxide copolymer esterification end capping rear catalyst, the mixture that esterification obtains can directly use in copolymerization;
In a word, the preparation method who contains the novel poly carboxylic acid series water reducer of lower molecular weight carbon dioxide copolymer provided by the invention has that flow process is short, technology is simple, reaction conditions is easily controlled, be easy to advantages such as industrialization production.
Embodiment
Embodiment of the present invention provides a kind of novel poly carboxylic acid series water reducer that contains the lower molecular weight carbon dioxide copolymer and preparation method thereof, this water reducer is all or part of employing ammonium persulphate initiator system by following each component, and copolymerization generates distinctive " comb shape " super plasticizing structure in water solvent.Weight fraction according to reactant composition is:
End capped lower molecular weight carbon dioxide copolymer of MALEIC ANHYDRIDE and the mixture that remains MALEIC ANHYDRIDE, perhaps, end capped lower molecular weight carbon dioxide copolymer of (methyl) vinylformic acid and residue, (methyl) acrylic acid mixture, perhaps, end capped lower molecular weight carbon dioxide copolymer of (methyl) vinylformic acid and MALEIC ANHYDRIDE mixture and residue, the mixture of (methyl) vinylformic acid and residue MALEIC ANHYDRIDE, (a) 10～150 parts
30～150 parts of poly glycol monomethyl ether list unsaturated acid esters,
5～35 parts of unsaturated sulfonic acid or its salt,
3～35 parts of acrylamides,
3～30 parts in (methyl) vinylformic acid,
3～35 parts of (methyl) acrylate or its salt
5～80 parts of oxyethane, propylene oxide, cyclohexene oxide or Styrene oxide 98min.s,
5～60 parts on unsaturated dicarboxylic acid (salt) and acid anhydrides thereof,
0.05～15 part of ammonium persulphate, Sodium Persulfate or Potassium Persulphate,
260～900 parts of deionized waters.
In polymerization process, according to mass ratio each component is fed intake, and under 50～98 ℃ temperature, adopting the persulphate initiator system, red-brown that obtains after the polymerization in aqueous phase solution or pale brown look homogeneous liquid are the novel poly carboxylic acid series water reducer that contains the lower molecular weight carbon dioxide copolymer.
The present invention is further illustrated below by specific embodiment:
Embodiment 1:
With number-average molecular weight 350～2400 lower molecular weight carbon dioxide copolymer 48.7g, MALEIC ANHYDRIDE 5g, sulfonated polystyrene 8g adds in the reactor, after stirring, heating also maintains the temperature at 80 ± 5 ℃ of reaction 4h down, obtains end capped lower molecular weight carbon dioxide copolymer of MALEIC ANHYDRIDE and the mixture that remains MALEIC ANHYDRIDE.
Then, in the reactor of being furnished with agitator, thermometer, Dropping feeder, reflux exchanger, add 540g deionized water, 20g sodium vinyl sulfonate, after being warming up to 75 ℃, in 5h, in aforesaid reaction vessel, introduce the mixture, 6g propylene oxide, 125g poly glycol monomethyl ether monomethacrylates, 22g vinylformic acid, 15g butyl methacrylate of 48g lower molecular weight carbon dioxide copolymer-MALEIC ANHYDRIDE esterification end-blocking product and residue MALEIC ANHYDRIDE, 2.5% ammonium persulfate solution 80g, temperature of reaction is controlled at 75 ± 5 ℃, and polyreaction is finished.The cooling back adds the sodium hydroxide neutralization in polymerization system, regulate pH=7～8, obtains polycarboxylic acid series high-performance cement water reducing agent of the present invention, with this water reducer called after mx-1.
Embodiment 2:
With number-average molecular weight 350～2400 lower molecular weight carbon dioxide copolymer 48.7g, MALEIC ANHYDRIDE 5g, sulfonated polystyrene 8g adds in the reactor, after stirring, heating also maintains the temperature at 80 ± 5 ℃ of reaction 4h down, obtains end capped lower molecular weight carbon dioxide copolymer of MALEIC ANHYDRIDE and the mixture that remains MALEIC ANHYDRIDE.
Then, disposing agitator, thermometer, Dropping feeder, add the 536g deionized water in the reactor of reflux exchanger, the 20g sodium vinyl sulfonate, 24g poly glycol monomethyl ether monomethacrylates, after being warming up to 75 ℃, in 3h, in aforesaid reaction vessel, introduce 48g lower molecular weight carbon dioxide copolymer-MALEIC ANHYDRIDE esterification end-blocking product and the mixture that remains MALEIC ANHYDRIDE, the 6g propylene oxide, 100g poly glycol monomethyl ether monomethacrylates, 22g vinylformic acid, the 15g butyl methacrylate, the 15g acrylamide, 2.5% ammonium persulfate solution 80g, temperature of reaction is controlled at 75 ± 5 ℃, and polyreaction is finished.The cooling back adds the sodium hydroxide neutralization, regulates pH=7～8, obtains polycarboxylic acid series high-performance cement water reducing agent of the present invention, with this water reducer called after mx-2.
Embodiment 3:
With number-average molecular weight 350～2400 lower molecular weight carbon dioxide copolymer 48.7g, MALEIC ANHYDRIDE 5g, sulfonated polystyrene 8g adds in the reactor, after stirring, heating also maintains the temperature at 80 ± 5 ℃ of reaction 4h down, obtains lower molecular weight carbon dioxide copolymer-MALEIC ANHYDRIDE esterification end-blocking product and the mixture that remains MALEIC ANHYDRIDE.
Then, in the reactor that disposes agitator, thermometer, Dropping feeder, reflux exchanger, add 616g deionized water, 2.0g ammonium persulphate, after being warming up to 75 ℃, in 5h, in aforesaid reaction vessel, introduce 24g lower molecular weight carbon dioxide copolymer-MALEIC ANHYDRIDE esterification products and the mixture, 10g sodium vinyl sulfonate, 124g poly glycol monomethyl ether monomethacrylates, the 20g vinylformic acid that remain MALEIC ANHYDRIDE, temperature of reaction is controlled at 85 ± 5 ℃, after dropwising, under this temperature, continue reaction 1h.The cooling back adds the sodium hydroxide neutralization, regulates pH=7～8, obtains polycarboxylic acid series high-performance cement water reducing agent of the present invention, with this water reducer called after mx-3.
Embodiment 4:
With number-average molecular weight 350～2400 lower molecular weight carbon dioxide copolymer 97.4g, MALEIC ANHYDRIDE 10g, sulfonated polystyrene 16g adds in the reactor, after stirring, heating also maintains the temperature at 80 ± 5 ℃ of reaction 4h down, obtains lower molecular weight carbon dioxide copolymer-MALEIC ANHYDRIDE esterification products and the mixture that remains MALEIC ANHYDRIDE.
Then, in the reactor that disposes agitator, thermometer, Dropping feeder, reflux exchanger, add 783.0g deionized water, 3.0g ammonium persulphate, after being warming up to 75 ℃, in 3h, in aforesaid reaction vessel, drip by mixture, 10.5g sodium vinyl sulfonate, 182.0g poly glycol monomethyl ether monomethacrylates, the 30.0g vinylformic acid of 70g lower molecular weight carbon dioxide copolymer-MALEIC ANHYDRIDE esterification products with the residue MALEIC ANHYDRIDE, temperature of reaction is controlled at 75 ± 5 ℃, after dropwising, under this temperature, continue reaction 1h.The cooling back adds the sodium hydroxide neutralization, regulates pH=7～8, obtains polycarboxylic acid series high-performance cement water reducing agent of the present invention, with this water reducer called after mx-4.
The water reducer that obtains in the foregoing description 1 to 4 is used for the clean slurry fluidity testing of standard cement, the serviceability of the water reducer for preparing in the embodiment of the invention is set forth.Adopt standard cement, the clean slurry degree of mobilization according to GB/T8077-2000 test cement the results are shown in Table 1.
The experiment of the clean slurry of table 1 degree of mobilization
| Water reducer of cement concrete | The solid volume, % | Clean slurry is mobile, mm |
| mx-1 | 0.21 | 280 |
| mx-2 | 0.18 | 285 |
| mx-3 | 0.13 | 308 |
| mx-4 | 0.16 | 310 |
Claims (8)
1. poly carboxylic acid series water reducer that contains the lower molecular weight carbon dioxide copolymer, it is characterized in that, this water reducer is the copolymerization product that contains lower molecular weight carbon dioxide copolymer, poly glycol monomethyl ether list unsaturated acid ester, cyclic monomer and other unsaturated monomers, wherein, described lower molecular weight carbon dioxide copolymer is the multipolymer of carbonic acid gas and epoxy compounds, its molecular formula W
1Represent by formula (a):
R
1＝OH，H；
x＝0.05-0.8；
N is an integer, between 1 to 20;
The lower molecular weight carbon dioxide copolymer is carbonic acid gas-ethylene oxide copolymer, carbon dioxide-epoxy propane copolymer, carbon dioxide-cyclohexene oxide copolymer, carbonic acid gas-Styrene oxide 98min. multipolymer, carbon dioxide-epoxy propane-oxyethane terpolymer, carbonic acid gas-oxyethane-cyclohexene oxide terpolymer, a kind of in carbon dioxide-epoxy propane-cyclohexene oxide terpolymer or carbon dioxide-epoxy propane-Styrene oxide 98min. terpolymer, two or three mixes.
2. a kind of poly carboxylic acid series water reducer that contains the lower molecular weight carbon dioxide copolymer as claimed in claim 1 is characterized in that, the monomeric molecular formula W of described poly glycol monomethyl ether list unsaturated acid ester
2Represent by formula (b):
M is the integer between 5-200.
3. a kind of poly carboxylic acid series water reducer that contains the lower molecular weight carbon dioxide copolymer as claimed in claim 1, it is characterized in that, described cyclic monomer and other unsaturated monomers comprise: the mixture of a kind of, two or more components in oxyethane, propylene oxide, cyclohexene oxide, Styrene oxide 98min., (methyl) vinylformic acid, unsaturated sulfonic acid or its salt, unsaturated amides, (methyl) acrylate or its salt, unsaturated dicarboxylic acid (salt) and the acid anhydrides thereof, wherein:
(1) unsaturated sulfonic acid or its salt comprise: the mixture of a kind of, two or three component in vinyl sulfonic acid or its salt, α-sodium olefin sulfonate, (methyl) sodium allyl sulfonate, styrene sulfonic acid or its salt;
(2) unsaturated amides comprises: the mixture of one or both in acrylamide, the 2-Methacrylamide;
(3) (methyl) acrylate (salt) comprising: the mixture of a kind of, two or more components in (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate and (methyl) sodium acrylate (ammonium) salt;
(4) unsaturated dicarboxylic acid (salt) and acid anhydrides thereof comprise: the mixture of a kind of, two or more components in maleic acid (salt), fumaric acid (salt), MALEIC ANHYDRIDE, the fumaric acid anhydride.
4. a kind of poly carboxylic acid series water reducer that contains the lower molecular weight carbon dioxide copolymer as claimed in claim 1 is characterized in that the number-average molecular weight of described lower molecular weight carbon dioxide copolymer is 350～2800.
5. the preparation method who contains the poly carboxylic acid series water reducer of lower molecular weight carbon dioxide copolymer as claimed in claim 1 is characterized in that comprising following reactions steps:
The first step, the esterification end capping: with the acidifying sulphonated polystyrene resin is catalyzer, with lower molecular weight carbon dioxide copolymer and MALEIC ANHYDRIDE, perhaps lower molecular weight carbon dioxide copolymer and (methyl) vinylformic acid, perhaps lower molecular weight carbon dioxide copolymer and MALEIC ANHYDRIDE and (methyl) acrylic acid mixture, at 60～120 ℃, esterification is 3～6 hours under the reduced pressure, remove solid acid, obtain end capped lower molecular weight carbon dioxide copolymer of MALEIC ANHYDRIDE and the mixture that remains MALEIC ANHYDRIDE, perhaps end capped lower molecular weight carbon dioxide copolymer of (methyl) vinylformic acid and the acrylic acid mixture of residue (methyl), the perhaps mixture of end capped lower molecular weight carbon dioxide copolymer of (methyl) vinylformic acid and MALEIC ANHYDRIDE mixture and residue (methyl) vinylformic acid and residue MALEIC ANHYDRIDE;
Second step, copolymerization: with in ammonium persulphate, Sodium Persulfate, the Potassium Persulphate one or both is initiator, with the resulting mixture of esterification end capping in the first step, deionized water, poly glycol monomethyl ether list unsaturated acid ester, cyclic monomer and other unsaturated monomers are introduced in the reactor, at 60～95 ℃ copolymerization takes place down, the reaction times is 3～8 hours; After polyreaction finishes, cooling, regulating pH with alkali lye is 7～8, obtains red-brown or brown yellow transparent liquid, is the poly carboxylic acid series water reducer that the present invention contains the lower molecular weight carbon dioxide copolymer.
6. the preparation method who contains the poly carboxylic acid series water reducer of lower molecular weight carbon dioxide copolymer as claimed in claim 5 is characterized in that, the water reducer of cement concrete in described second step is made up of all or part of of following listed raw material in massfraction:
10～150 parts of one or more of the resulting mixture of the first step esterification end capping,
30～150 parts of poly glycol monomethyl ether list unsaturated acid esters,
5～35 parts of unsaturated sulfonic acid or its salt,
3～35 parts of acrylamides,
3～30 parts in (methyl) vinylformic acid,
3～35 parts of (methyl) acrylate or its salt
5～80 parts of oxyethane, propylene oxide, cyclohexene oxide or Styrene oxide 98min.s,
5～60 parts on unsaturated dicarboxylic acid (salt) and acid anhydrides thereof,
0.05～15 part of ammonium persulphate, Sodium Persulfate or Potassium Persulphate,
260～900 parts of deionized waters.
7. the preparation method who contains the poly carboxylic acid series water reducer of lower molecular weight carbon dioxide copolymer as claimed in claim 5, it is characterized in that: in the described esterification end capping process, the mixture of (methyl) vinylformic acid, MALEIC ANHYDRIDE or (methyl) vinylformic acid and maleic acid and the mol ratio n of lower molecular weight carbon dioxide copolymer are in the scope of 5: 1≤n≤1: 1, and excessive (methyl) vinylformic acid, MALEIC ANHYDRIDE or (methyl) vinylformic acid need not separate with the mixture of maleic acid and is directly used in polyreaction after the esterification.
8. the preparation method who contains the poly carboxylic acid series water reducer of lower molecular weight carbon dioxide copolymer as claimed in claim 7 is characterized in that: the existence form of described lower molecular weight carbon dioxide copolymer in polymkeric substance has following two kinds:
(1) the lower molecular weight carbon dioxide copolymer becomes a kind of long-chain branch in polymkeric substance, its general molecular formula W
3Represent by formula (c):
Formula (c)
R
1，R
2，R
3＝H，CH
3；
M
1＝H，Na，NH
4；
M
2=H, Na, NH
4, or CH
3, C
2H
5, C
4H
7
M
3＝H，CH
3，Na，NH
4；
Wherein, a, b, c, d, e, f are the molar fractions of each component, and a+b+c+d+e+f=1.0;
(2) or the lower molecular weight carbon dioxide copolymer in polymkeric substance, form cross-linking set, the general structure W of its crosslinking structure multipolymer
4(d) is expressed as by formula:
Or:
Or:
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| CN104193215A (en) * | 2014-09-02 | 2014-12-10 | 武汉理工大学 | Ternary block macromonomer graft copolymerization high-property polycarboxylic acid water-reducing agent and preparation method thereof |
| CN106046272A (en) * | 2016-07-18 | 2016-10-26 | 江苏中铁奥莱特新材料股份有限公司 | Method for preparing polycarboxylate superplasticizer by use of carbon dioxide |
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| CN107828027B (en) * | 2017-11-17 | 2020-12-29 | 江苏苏博特新材料股份有限公司 | Concrete workability regulator with water reducing function and preparation method thereof |
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