CN111019057A - Viscosity-reducing polycarboxylate superplasticizer and preparation method thereof - Google Patents
Viscosity-reducing polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
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- CN111019057A CN111019057A CN201911238910.2A CN201911238910A CN111019057A CN 111019057 A CN111019057 A CN 111019057A CN 201911238910 A CN201911238910 A CN 201911238910A CN 111019057 A CN111019057 A CN 111019057A
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- polycarboxylate superplasticizer
- reducing
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- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 57
- 239000008030 superplasticizer Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 94
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 49
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 28
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims abstract description 18
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 17
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 15
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 15
- 229920000570 polyether Polymers 0.000 claims abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims description 48
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 30
- 239000000178 monomer Substances 0.000 claims description 17
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- -1 polyoxypropylene Polymers 0.000 claims description 16
- 229920001451 polypropylene glycol Polymers 0.000 claims description 15
- 238000005516 engineering process Methods 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 8
- 230000001502 supplementing effect Effects 0.000 claims description 8
- FAAHFGVRTPKJLH-UHFFFAOYSA-N P1(=O)(OOO1)O.C=C Chemical compound P1(=O)(OOO1)O.C=C FAAHFGVRTPKJLH-UHFFFAOYSA-N 0.000 claims description 7
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 3
- FQCKLAJZOPDQIE-UHFFFAOYSA-N C=C.OP(O)(O)=O.OP(O)(O)=O.O.O.O Chemical compound C=C.OP(O)(O)=O.OP(O)(O)=O.O.O.O FQCKLAJZOPDQIE-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 26
- 239000004568 cement Substances 0.000 abstract description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 5
- 230000002209 hydrophobic effect Effects 0.000 abstract description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 2
- 239000004567 concrete Substances 0.000 description 19
- 230000000694 effects Effects 0.000 description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 238000004873 anchoring Methods 0.000 description 6
- 239000012986 chain transfer agent Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 150000001261 hydroxy acids Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- JBONSOPXRASGCH-UHFFFAOYSA-N C=COOP(=O)(O)O Chemical compound C=COOP(=O)(O)O JBONSOPXRASGCH-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- BZCOSCNPHJNQBP-OWOJBTEDSA-N dihydroxyfumaric acid Chemical class OC(=O)C(\O)=C(/O)C(O)=O BZCOSCNPHJNQBP-OWOJBTEDSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- QVDTXNVYSHVCGW-ONEGZZNKSA-N isopentenol Chemical compound CC(C)\C=C\O QVDTXNVYSHVCGW-ONEGZZNKSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical group CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/243—Phosphorus-containing polymers
- C04B24/246—Phosphorus-containing polymers containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2664—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers
- C04B24/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a viscosity-reducing polycarboxylate superplasticizer and a preparation method thereof, wherein the viscosity-reducing polycarboxylate superplasticizer comprises the following components: 350 parts of 340-one polyether macromonomer, 30-40 parts of maleic anhydride, 4-5 parts of sodium hypophosphite, 4-7 parts of adhesion promoter, 3.0-6.0 parts of potassium persulfate, 0.5-0.8 part of reducing agent and the balance of water, wherein the total mass is 1000 parts, and the solid content is about 40%. According to the invention, acrylic acid which is a raw material for synthesizing a traditional polycarboxylic acid water reducer is replaced by an adhesion promoter, the adhesion promoter is used as a short side chain, and the phosphoric acid and silane structures of the adhesion promoter have strong polarity, so that the molecules of the water reducer are initially and firmly adsorbed on the surfaces of cement particles; free water between molecular chains and cement particles is discharged by a maleic anhydride cyclic structure and a hydrophobic characteristic, the content of the free water in the system is increased, and the viscosity of the system is reduced.
Description
Technical Field
The invention belongs to the technical field of building materials, and relates to a preparation method of a polycarboxylate superplasticizer, in particular to a viscosity-reducing polycarboxylate superplasticizer and a preparation method thereof.
Background
As a novel water reducing agent, the polycarboxylic acid water reducing agent has the advantages of low mixing amount, high water reducing rate, good slump retaining performance, good dispersibility, good workability and durability and the like, and gradually occupies the market of the water reducing agent. With the development of the large-scale projects such as the expressway, the bridge project, the expressway in the altitude area and the like in the country in recent years, the use amount and the demand of high-grade concrete are increasing, and many problems also occur. The high-grade concrete needs to control a lower water-cement ratio, and the used mineral admixture promotes the viscosity of the concrete to be increased, the flow rate is slow, the construction is difficult, and the construction progress is influenced. The polycarboxylic acid water reducing agent on the market cannot well solve the problems of viscosity and workability, and the concrete bottom grabbing and segregation are easily caused by increasing the mixing amount. The viscosity regulator well improves the viscosity of concrete, but the viscosity regulator has the problem of compatibility with the polycarboxylic acid water reducer, so that the viscosity reduction type polycarboxylic acid water reducer is urgently needed in the market to solve the construction problem according to the market demand.
At present, the viscosity reduction type polycarboxylate superplasticizer is mainly an ester polycarboxylate superplasticizer, and the water reducer has the problems of long preparation period, high energy consumption, limited conversion rate, difficult control of reaction process, use of toxic and harmful raw materials and the like. The invention provides a preparation method of a viscosity-reducing polycarboxylic acid water reducing agent by taking polyether, maleic anhydride, an adhesion promoter and the like as raw materials and carrying out free radical polymerization, wherein the viscosity-reducing polycarboxylic acid water reducing agent can be prepared at normal temperature, and the reaction condition is mild and controllable.
Patent CN201910343980.8 discloses a viscosity-reducing polycarboxylic acid water-reducing composition and a preparation method thereof, wherein the composition comprises the following components in parts by weight: 200-220 parts of unsaturated polyether macromonomer, 25-35 parts of styrene, 25-35 parts of unsaturated anhydride, 200-250 parts of butyl acetate, 750-800 parts of n-heptane, 2-4 parts of initiator, 1.5-2.2 parts of chain transfer agent and a proper amount of deionized water. According to the invention, the ester viscosity-reducing polycarboxylate superplasticizer is synthesized by using a two-step method, the synthesized intermediate has better reaction activity with MPEG, the conversion rate is high, the process is simpler compared with that of a common ester polycarboxylate superplasticizer, the production efficiency is improved, the cost price is reduced, the energy is saved, the environment is protected, the polycarboxylate superplasticizer is synthesized by using styrene, maleic anhydride and 2000 molecular weight polyethylene glycol monomethyl ether, and the benzene ring and the anhydride are introduced into the side chain of the polycarboxylate superplasticizer to adjust the hydrophilic oleophylic value of the polycarboxylate superplasticizer.
Patent CN201910374955.6 discloses a viscosity-reducing type high-efficiency water-reducing polycarboxylic acid water reducer and a preparation method thereof, wherein the water reducer is prepared by a free radical polymerization reaction of a macromonomer such as an isopentenol polyoxyethylene ether monomer, an unsaturated hydroxy acid monomer or a derivative thereof, or an unsaturated acid with a trans-structure under the action of a reducing agent, an oxidizing agent and a chain transfer agent by adopting an intermittent dropwise adding mode. The anchoring group and the side chain in the water reducing agent are of molecular structures distributed in a block mode, so that electrostatic repulsion and steric hindrance effects can be fully exerted; in addition, the proportion of hydrophilic groups is increased by the hydroxyl, carboxyl and other polar groups introduced by the unsaturated hydroxy acid monomer or the derivative monomer thereof, and the surface tension of the cement pore solution is reduced; in addition, the trans-structure represented by fumaric acid and dihydroxy fumaric acid derivatives has a special structure, namely the rigidity of the monomer and the distribution of two carboxyl groups on the opposite sides of a side chain, so that the monomer is easy to show a tensile structure in space, the possibility of molecular chain entanglement is reduced, the adsorption effect of the polycarboxylic acid water reducing agent on the cement surface is obviously increased, and the viscosity reduction effect of the polycarboxylic acid water reducing agent is improved.
The patent CN201910727235.3 discloses a viscosity-reducing polycarboxylic acid water reducer and a preparation method thereof, wherein the water reducer is a copolymer polymerized by an unsaturated polyether macromonomer, acrylic acid, an unsaturated polyether phosphate macromonomer, acrylamide, an alkenyl-terminated ester structure double-tail polyoxyethylene ether macromonomer, an initiator and a chain transfer agent through free radical copolymerization, and the preparation method comprises the step of carrying out copolymerization on the unsaturated polyether phosphate macromonomer, isopentenyl polyoxyethylene ether, the alkenyl-terminated ester structure double-tail polyoxyethylene ether macromonomer, acrylic acid, acrylamide, the initiator and the chain transfer agent with water at 40-60 ℃ for 3-5 hours to obtain a copolymer solution. The viscosity reduction type polycarboxylate superplasticizer disclosed by the invention is novel in structure, reasonable in design, and high in fluidity and low in viscosity.
Different from the patents, the synthesized polycarboxylate superplasticizer disclosed by the invention does not use acrylic acid in raw materials, maleic anhydride with higher dosage is used as a polymerization monomer, an epoxy structure of the maleic anhydride has stronger hydrophobic property, water molecules wrapped by short side chain layers of a polymer main chain are discharged, the free water content in a concrete system is increased, the slurry viscosity is reduced, and the fluidity is increased; maleic anhydride is used for replacing acrylic acid, the density of carboxyl groups on the main chain of the polycarboxylate superplasticizer is low, a part of adhesion promoters are doped in the synthetic raw materials, and strong polar groups such as phosphoric acid and silane groups ensure that the molecular main chain of the polycarboxylate superplasticizer is adsorbed on cement particles at the dependent point. The maleic anhydride is gradually hydrolyzed into dicarboxyl in an alkaline environment, the durability of the concrete slump is longer due to the characteristic of delaying the release of the carboxyl, and the loss of a concrete system is reduced.
Disclosure of Invention
The invention aims to provide a viscosity-reducing polycarboxylate superplasticizer and a preparation method thereof, and solves the problem of compatibility of a viscosity regulator and the polycarboxylate superplasticizer in the prior art.
The viscosity-reducing polycarboxylate superplasticizer prepared by the invention is prepared by replacing acrylic acid with maleic anhydride, and carrying out free radical polymerization on the maleic anhydride, a polyether macromonomer, an initiator, a chain transfer agent and a reducing agent under the condition of modifying an adhesion promoter at normal temperature; the polycarboxylate water reducer has extremely low carboxyl density, strong polar groups such as phosphate groups and the like provide anchoring capability and are adsorbed on the surfaces of cement particles, water molecules wrapped by a solvent layer are discharged through epoxy structure side chains connected to the main chain of the water reducer, the free water content of a concrete system is increased, and the purposes of reducing the viscosity of the concrete system and improving the slump are achieved.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the preparation method of the viscosity-reducing polycarboxylate superplasticizer is characterized by comprising the following steps:
step one, putting 340 parts of polyether macromonomer, 30-40 parts of maleic anhydride and 350 parts of water in a reaction kettle bottom material, and stirring at normal temperature until the monomers are completely dissolved;
step two: simultaneously dripping A, B materials, wherein the material A is dripped for 1.5-2.5h, and the material B is dripped for 2-3 h; wherein the material A is a mixed solution of 3-6 parts of potassium persulfate and 60 parts of water, and the material B is a mixed solution of 4-7 parts of adhesion promoter, 4-5 parts of sodium hypophosphite, 0.5-0.8 part of reducing agent and 100 parts of water. And (4) preserving heat and curing for 1h after the dropwise addition is finished, and supplementing 90 parts of water to obtain the viscosity-reducing polycarboxylate superplasticizer.
Further, the polyether macromonomer is allyl polyoxypropylene ether with 1600-2200 molecular weight.
Furthermore, the adhesion promoter is any one or more of r-methyl acrylic propyl group trimethoxy silane, vinyl triethoxy silane, vinyl trimethoxy silane, vinyl tri (b-methoxy ethoxy) silane and ethylene oxygen phosphate.
Furthermore, one end of the ethylene oxy phosphate is a double bond, R is an alkyl chain, and the molecular structural formula is as follows:
further, the reducing agent is a chemical technology product FF6M and/or TP132 of Shanghai Enlossa.
The viscosity reduction type polycarboxylate superplasticizer is characterized by comprising the following components in parts by weight: prepared by any one of the methods. The main components for preparing the viscosity-reducing polycarboxylate superplasticizer provided by the invention are as follows:
340 portion of 350 portions of polyether macromonomer
30-40 parts of maleic anhydride
4-5 parts of sodium hypophosphite
4-7 parts of adhesion promoter
3-6 parts of potassium persulfate
0.5-0.8 parts of reducing agent
The balance of water, the total mass is 1000 parts, and the solid content is about 40%.
The invention has the beneficial effects that:
according to the invention, acrylic acid which is a raw material for synthesizing the traditional polycarboxylic acid water reducing agent is replaced by maleic anhydride, free water between a molecular chain and cement particles is discharged by using a maleic anhydride annular structure and a hydrophobic characteristic, the content of the free water in a system is increased, and the viscosity of the system is reduced; the adhesion promoter is used as a short side chain, the phosphoric acid and silane structures have strong polarity, so that the water reducer molecules are initially and firmly adsorbed on the surface of cement particles, and the concrete beneficial effects are as follows:
1. the viscosity-reduction polycarboxylate superplasticizer provided by the invention abandons the conventional polycarboxylate superplasticizer synthesis common raw material of acrylic acid, and is replaced by an adhesion promoter, and the strong-polarity phosphoric acid and silane structures enable the water reducer molecules to be initially and firmly adsorbed on the surfaces of cement particles, so that fewer anchoring points can achieve the anchoring effect of higher carboxyl density. The maleic anhydride increases the hydrophobic viscosity reduction components on the main chain of the polycarboxylate water reducer, the stronger hydrophobic capacity of the epoxy structure can discharge water molecules wrapped by the side chain on the main chain of the polycarboxylate water reducer, and the free water content in the system is increased, so that the viscosity of the concrete system is improved.
2. The viscosity-reducing polycarboxylate superplasticizer disclosed by the invention has the advantages that the raw materials for synthesizing the viscosity-reducing polycarboxylate superplasticizer do not contain acrylic acid, the hydrolysis of maleic anhydride needs a certain time, the density of carboxyl groups on the main chain of the superplasticizer is extremely low, and the strong anchoring groups needed by the early adsorption of the viscosity-reducing polycarboxylate superplasticizer are as follows: the phosphate group of the end of the adhesion promoter containing phosphate group has stronger anchoring capability than carboxyl; according to the invention, potassium persulfate is used as an initiator instead of a hydrogen peroxide system, sodium hypophosphite is used as a chain transfer agent, and the potassium persulfate is grafted to the end group of the main chain during polymerization reaction, so that hydrophilic groups on the main chain are increased, and the adsorption effect of the main chain of the water reducing agent is increased.
3. The reducing agent adopts Shanghai Enlossa chemical technology products FF6M and TP1328, and the novel reducing agent has the advantages of high activity and high performance, longer activity durability, wide pH adaptation range, adaptability to various oxidants, low-temperature polymerization, reduction of the content of polymerization residual monomers and the like.
4. According to the invention, the allyl polyoxypropylene ether is used as a polymeric macromonomer, and compared with allyl polyoxyethylene ether, the long-chain branch contains more methyl groups, so that water molecules wrapped in the polyether long-chain branch are easily discharged to form free water, and the viscosity of slurry is effectively reduced; the molecular weight of the polyether monomer is selected between 1600-2200, and the steric hindrance provided by the conventional 1200 molecular weight polyether branched chain provided by Oker corporation is smaller, and the dispersing ability is weaker.
Detailed Description
Example 1
The preparation method of the viscosity-reducing polycarboxylate superplasticizer comprises the following steps of preparing 1000 parts of raw materials by mass, wherein the mass fraction of the raw materials is about 40%, and the raw materials mainly comprise the following components:
340 parts of 1600 molecular weight allyl polyoxypropylene ether
40 parts of maleic anhydride
5 parts of sodium hypophosphite
7 parts of ethylene oxy phosphate (R is methyl)
6 parts of potassium persulfate
0.6 part of Shanghai Enlosha chemical technology product FF6M
The balance of water.
The method comprises the following steps: putting 340 parts of 1600-molecular-weight allyl polyoxypropylene ether, 40 parts of maleic anhydride and 350 parts of water into a reaction kettle bottom material, and stirring at normal temperature until all monomers are dissolved;
step two: simultaneously dripping A, B materials, wherein the material A is dripped for 1.5h, and the material B is dripped for 2 h; wherein the material A is a mixed solution of 6 parts of potassium persulfate and 60 parts of water, and the material B is a mixed solution of 7 parts of ethylene oxy phosphate (R is methyl), 5 parts of sodium hypophosphite, 0.5 part of Shanghai Enlossa chemical technology product FF6M and 100 parts of water. And (4) preserving heat and curing for 1h after the dropwise addition is finished, and supplementing 90 parts of water to obtain the viscosity-reducing polycarboxylate superplasticizer.
Example 2
The preparation method of the viscosity-reducing polycarboxylate superplasticizer comprises the following steps of preparing 1000 parts of raw materials by mass, wherein the mass fraction of the raw materials is about 40%, and the raw materials mainly comprise the following components:
342 parts of 1800 parts of allyl polyoxypropylene ether
38 parts of maleic anhydride
4.8 parts of sodium hypophosphite
6.2 parts of r-methyl acrylic propyl ester group trimethoxy silane
3 parts of potassium persulfate
0.6 part of Shanghai Yingluosha chemical technology product TP1328
The balance of water.
The method comprises the following steps: putting 342 parts of 1800 molecular weight allyl polyoxypropylene ether, 38 parts of maleic anhydride and 350 parts of water into a reaction kettle bottom material, and stirring at normal temperature until all monomers are dissolved;
step two: simultaneously dripping A, B materials, wherein the material A is dripped for 2 hours, and the material B is dripped for 2.5 hours; wherein the material A is a mixed solution of 3 parts of potassium persulfate and 60 parts of water, and the material B is a mixed solution of 6.2 parts of r-methyl acrylic propyl trimethoxy silane, 4.8 parts of sodium hypophosphite, 0.6 part of Shanghai Enlosa chemical engineering product TP1328 and 100 parts of water. And (4) preserving heat and curing for 1h after the dropwise addition is finished, and supplementing 90 parts of water to obtain the viscosity-reducing polycarboxylate superplasticizer.
Example 3
The preparation method of the viscosity-reducing polycarboxylate superplasticizer comprises the following steps of preparing 1000 parts of raw materials by mass, wherein the mass fraction of the raw materials is about 40%, and the raw materials mainly comprise the following components:
344 parts of 2000 molecular weight allyl polyoxypropylene ether
36 parts of maleic anhydride
4.6 parts of sodium hypophosphite
5.7 parts of a composition of vinyltris (b-methoxyethoxy) silane and vinyloxy phosphate (R is methyl) in a mass ratio of 1:1
5.5 parts of potassium persulfate
0.7 part of Shanghai Enlosha chemical technology product FF6M
The balance of water.
The method comprises the following steps: putting 344 parts of 2000-molecular-weight allyl polyoxypropylene ether, 36 parts of maleic anhydride and 350 parts of water into a reaction kettle bottom material, and stirring at normal temperature until all monomers are dissolved;
step two: simultaneously dripping A, B materials, wherein the material A is dripped for 2.5 hours, and the material B is dripped for 3 hours; the material A is a mixed solution of 5.5 parts of potassium persulfate and 60 parts of water, and the material B is a mixed solution of 5.7 parts of a composition of vinyl tri (B-methoxyethoxy) silane and ethylene oxy phosphate (R is methyl) with the mass ratio of 1:1, 4.6 parts of sodium hypophosphite, 0.7 part of Shanghai Enlosa chemical technology product FF6M and 100 parts of water. And (4) preserving heat and curing for 1h after the dropwise addition is finished, and supplementing 90 parts of water to obtain the viscosity-reducing polycarboxylate superplasticizer.
Example 4
The preparation method of the viscosity-reducing polycarboxylate superplasticizer comprises the following steps of preparing 1000 parts of raw materials by mass, wherein the mass fraction of the raw materials is about 40%, and the raw materials mainly comprise the following components:
346 parts of 2200 molecular weight allyl polyoxypropylene ether
34 parts of maleic anhydride
4.4 parts of sodium hypophosphite
5 parts of vinyl tri (b-methoxyethoxy) silane and vinyl triethoxysilane in a mass ratio of 2:1
4 parts of potassium persulfate
0.8 part of Shanghai Enlosha chemical technology product FF6M
The balance of water.
The method comprises the following steps: 346 parts of 2200 parts of molecular weight allyl polyoxypropylene ether, 34 parts of maleic anhydride and 350 parts of water are placed in a reaction kettle bottom material and stirred at normal temperature until all monomers are dissolved;
step two: simultaneously dripping A, B materials, wherein the material A is dripped for 2 hours, and the material B is dripped for 2.5 hours; the material A is a mixed solution of 4 parts of potassium persulfate and 60 parts of water, and the material B is a mixed solution of 5 parts of vinyl tri (B-methoxyethoxy) silane and vinyl triethoxysilane, 4.4 parts of sodium hypophosphite, 0.8 part of Shanghai Enlosa chemical technology product FF6M and 100 parts of water in a mass ratio of 2: 1. And (4) preserving heat and curing for 1h after the dropwise addition is finished, and supplementing 90 parts of water to obtain the viscosity-reducing polycarboxylate superplasticizer.
Example 5
The preparation method of the viscosity-reducing polycarboxylate superplasticizer comprises the following steps of preparing 1000 parts of raw materials by mass, wherein the mass fraction of the raw materials is about 40%, and the raw materials mainly comprise the following components:
348 parts of 1600 molecular weight allyl polyoxypropylene ether
32 parts of maleic anhydride
4.2 parts of sodium hypophosphite
4 parts of vinyltrimethoxysilane
5 parts of potassium persulfate
0.7 part of Shanghai Yingluosha chemical technology product TP1328
The balance of water.
The method comprises the following steps: putting 348 parts of 1600-molecular-weight allyl polyoxypropylene ether, 32 parts of maleic anhydride and 350 parts of water into a reaction kettle bottom material, and stirring at normal temperature until all monomers are dissolved;
step two: simultaneously dripping A, B materials, wherein the material A is dripped for 1.5h, and the material B is dripped for 2 h; wherein the material A is a mixed solution of 5 parts of potassium persulfate and 60 parts of water, and the material B is a mixed solution of 4 parts of vinyl trimethoxy silane, 4.2 parts of sodium hypophosphite, 0.7 part of Shanghai Enlosa chemical technology product TP1328 and 100 parts of water. And (4) preserving heat and curing for 1h after the dropwise addition is finished, and supplementing 90 parts of water to obtain the viscosity-reducing polycarboxylate superplasticizer.
Example 6
The preparation method of the viscosity-reducing polycarboxylate superplasticizer comprises the following steps of preparing 1000 parts of raw materials by mass, wherein the mass fraction of the raw materials is about 40%, and the raw materials mainly comprise the following components:
350 parts of 2200 parts of molecular weight allyl polyoxypropylene ether
30 parts of maleic anhydride
4 parts of sodium hypophosphite
6 parts of composition of vinyl tri (b-methoxyethoxy) silane and ethylene oxy phosphate (R is methyl) with the mass ratio of 1:1
4.5 parts of potassium persulfate
0.5 part of Shanghai Yingluosha chemical technology product TP1328
The balance of water.
The method comprises the following steps: putting 350 parts of 2200 molecular weight allyl polyoxypropylene ether, 30 parts of maleic anhydride and 350 parts of water into a reaction kettle bottom material, and stirring at normal temperature until the monomers are completely dissolved;
step two: simultaneously dripping A, B materials, wherein the material A is dripped for 2.5 hours, and the material B is dripped for 3 hours; the material A is a mixed solution of 6.2 parts of potassium persulfate and 60 parts of water, and the material B is a mixed solution of 6 parts of a composition of vinyl tri (B-methoxyethoxy) silane and ethylene oxy phosphate (R is methyl) in a mass ratio of 1:1, 4 parts of sodium hypophosphite, 0.6 part of Shanghai Enlosa chemical technology product TP1328 and 100 parts of water. And (4) preserving heat and curing for 1h after the dropwise addition is finished, and supplementing 90 parts of water to obtain the viscosity-reducing polycarboxylate superplasticizer.
The polycarboxylate superplasticizer prepared by the above example and a common polycarboxylate superplasticizer are prepared into the water reducers with the same concentration, and the influence of different water reducers with different formulations with the same concentration on the concrete performance under the same condition is respectively tested. The cement used in the experiment is Huaxin 42.5 ordinary silica cement, and the test standard GB/8076-.
TABLE 1 Effect of different Water reducing Agents on concrete Properties
According to the influence table of different water reducing agents on the concrete performance, the compression strength and slump/expansion degree of different water reducing agents are obviously reflected, the concrete effects of examples 1-6 are softer than those of common water reducing agent samples, and the concrete mixing force is relatively light; the initial and time-dependent losses of examples 1-6 are also better. The strength of the polycarboxylate water reducer in 3d and 7d is higher than that of the common polycarboxylate water reducer in corresponding age period, the strength of the polycarboxylate water reducer in 28d is relatively slowly improved, the analysis reason is that the molecular weight of the synthesized polycarboxylate water reducer is large due to insufficient consumption of a reducing agent, loss is accelerated along with cement hydration, water loss is fast, and the strength of the polycarboxylate water reducer in 3d and 7d is obviously improved; where example 3 is best in strength and slump/spread and strength has an early strength effect, the formulation and preparation process of example 3 is most preferred. The workability indexes of the examples 1-6 are better on the whole, and the concrete hydration product migration and development are facilitated, so that the concrete strength is amplified to a certain extent.
Claims (6)
1. The preparation method of the viscosity-reducing polycarboxylate superplasticizer is characterized by comprising the following steps:
step one, putting 340 parts of polyether macromonomer, 30-40 parts of maleic anhydride and 350 parts of water in a reaction kettle bottom material, and stirring at normal temperature until the monomers are completely dissolved;
step two: simultaneously dripping A, B materials, wherein the material A is dripped for 1.5-2.5h, and the material B is dripped for 2-3 h; wherein the material A is a mixed solution of 3-6 parts of potassium persulfate and 60 parts of water, and the material B is a mixed solution of 4-7 parts of adhesion promoter, 4-5 parts of sodium hypophosphite, 0.5-0.8 part of reducing agent and 100 parts of water. And (4) preserving heat and curing for 1-2h after the dropwise addition is finished, and supplementing 90 parts of water to obtain the viscosity-reducing polycarboxylic acid water reducer.
2. The preparation method of the viscosity-reducing polycarboxylate superplasticizer according to claim 1, which is characterized by comprising the following steps: the polyether macromonomer is allyl polyoxypropylene ether with 1600-2200 molecular weight.
3. The preparation method of the viscosity-reducing polycarboxylate superplasticizer according to claim 1, which is characterized by comprising the following steps: the adhesion promoter is one or more of r-methyl acrylic propyl group trimethoxy silane, vinyl triethoxy silane, vinyl trimethoxy silane, vinyl tri (b-methoxy ethoxy) silane and ethylene oxygen phosphate.
4. The preparation method of the viscosity-reducing polycarboxylate superplasticizer according to claim 3, comprising the following steps: one end of the ethylene oxy phosphate is a double bond, R is an alkyl chain, and the molecular structural formula is as follows:
5. the preparation method of the viscosity-reducing polycarboxylate superplasticizer according to claim 1, which is characterized by comprising the following steps: the reducing agent is a Shanghai Engelsa chemical technology product FF6M and/or TP 1328.
6. The viscosity reduction type polycarboxylate superplasticizer is characterized by comprising the following components in parts by weight: prepared by the process of any one of claims 1 to 5.
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