CN104371071A - Preparation method for hyperbranched polycarboxylic-acid concrete efficient water reducer - Google Patents
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Abstract
The invention provides a preparation method for a hyperbranched polycarboxylic-acid concrete efficient water reducer. The hyperbranched polycarboxylic-acid copolymer is prepared from monomers and b through a self-condensation vinyl polymerization reaction. The produced product has the advantages of low doping amount, high water reducing rate, small slump loss, good cement adaptability, viscosity reduction and the like. By employing self-condensation vinyl polymerization, the synthetic method is simple, the technological requirements are low, the production cost is small, solvent recovery is convenient, and environmental pollution is small.
Description
Technical field
The present invention relates to concrete additives in building materials technical field, be specifically related to a kind of hyperbranched poly carboxylic acid that can be used as concrete high efficiency water reducing agent and preparation method thereof.
Background technology
Cement dispersants (water reducer) has the effect being adsorbed on cement particle thus suppressing cement particle cohesion, raising concrete dispersiveness in use.
Material as cement dissemination has a lot, comprises sulfonated lignin, naphthalenesulfonate/formaldehyde condensation products, phenol/Sulphanilic Acid/formaldehyde condensation products, melamine sulfonate/formaldehyde condensation products, polycarboxylic acid comb-shaped copolymer etc.
From constructional feature, front several cement dispersants is mainly adsorption group with sulfonic group, and lack the side chain effectively providing sterically hindered effect, molecular structure is single, and adjustability is poor, limited to the dissemination of cement, and volume is high and water-reducing rate is low.
Polycarboxylic acid comb-shaped copolymer has the adsorption that the main chain that is rich in carboxyl adsorption group provides, and has again the sterically hindered effect that the good side chain of wetting ability provides, the larger dissemination that improve cement.At present, the polycarboxylic acid super-plasticizer of domestic and international exploitation is mostly (methyl) vinylformic acid/ester copolymer or thiazolinyl polyoxyethylene glycol/toxilic acid/acrylic copolymer water reducer, the molecular structure of this two classes water reducer is mostly in combed, there is the advantages such as preparation technology is simple, cost is low, slump retention performance is good, but still can not meet the requirement of modern concrete engineering to high-performance water reducing agent.Therefore, the polycarboxylic acid superplasticizer of novel texture such as exploitation star structure, dissaving structure etc., promotes its dispersing property, dispersion retention, one of research direction becoming polycarboxylic acid super-plasticizer.
On the other hand, the raising of concrete strength realizes mainly through reducing water-cement ratio, it is comparatively large that this result also in concrete viscosity, causes a series of construction problems such as concrete-agitating, transport, pumping, limit the propagation and employment of high-strength shale ceramsite to a great extent.Current adoptable viscosity reducing process is mainly carried out from organic admixture and adulterant two aspect.The organic admixture mainly air entrapment agent added, mixing of air entrapment agent makes to form closed spherical bubble small in a large number in concrete mix, these microbubbles are as ball, reduce the friction resistance between particles of aggregates, thus reduction viscosity, but air entrapment agent viscosity reduction limited use, the intensity of bubble to high-strength concrete introduced has a negative impact, still unintelligible to the concrete viscosity mechanism of action about water reducer, still without breakthrough, also there is not the Patents of the organic viscosity-depression agent of concrete at present in the research and development of organic viscosity-depression agent; And there is not patent about concrete viscosity-depression agent or article equally in adulterant aspect, mainly improve concrete work performance by mixing a large amount of flyash at present, mix flyash as everyone knows and can reduce concrete viscosity, but for high-rise, high-strength or its viscosity reducing effect of super high strength concrete is very limited.
CN101580353 reports a kind of hyperbranched polycarboxylic acid super-plasticizer and preparation method thereof, under the effect of initiator azo dicyano valeric acid, generated copolymer chain by (methyl) tert-butyl acrylate, methylpropene sodium sulfonate, allyl polyethenoxy ether, then formed hyper branched copolymer by (methyl) vinylformic acid and reacting ethylenediamine.This product has the advantages such as volume is low, water-reducing rate is high, little loss of slump, but complicated process of preparation, through steps such as polymerization, underpressure distillation, condensation, hydrolysis backflow, separating-purifyings, need use multiple organic solvent simultaneously, production cost is higher, also easily causes environmental pollution.
CN102504247 reports a kind of hyperbranched polymer, hyperbranched type polycarboxylic acid super-plasticizer and preparation method thereof, first obtain intermediate by alkenyl amine and the addition reaction of 2-acrylamide-2-methyl propane sulfonic sodium, obtain with methoxy poly (ethylene glycol) (methyl) acrylate, two (methyl) acrylic ester copolymer of polyoxyethylene glycol again, there is the advantages such as water-reducing rate is high, slump retention performance is good.But, still use organic solvent in its preparation process, easily cause environmental pollution, improve production cost simultaneously.
Therefore, now known technology contains some structures as the hyperbranched polycarboxylic acid super-plasticizer of cement water reducing agent and preparation method.But due to starting material, operational path etc., its economy and the feature of environmental protection constrain its industrialized application.
In sum, provide a kind of synthetic method simple, processing requirement is low, and production cost is little, convenient solvent reclaiming, and the method for what environmental pollution was little prepare hyperbranched poly carboxylic acid is very necessary.
Summary of the invention
It is limited that the present invention is intended to overcome the dispersion effect of existing polycarboxylate water-reducer to cement, the problem of viscosity reducing effect deficiency, a kind of preparation method of hyperbranched poly polycarboxylic acid concrete high efficiency water reducing agent is provided, the product produced has the advantages such as volume is low, water-reducing rate is high, little loss of slump, cement adaptability are good, viscosity reduction, and preparation process is simple.
Know-why of the present invention: adopt Self condensation vinyl polymerization method synthesis of super branched poly carboxylic acid.
, there is Self condensation vinyl polymerization by monomer a and b and react in the preparation method of hyperbranched poly polycarboxylic acid concrete high efficiency water reducing agent provided by the invention, the mol ratio of monomer a and b meets: a/b=1/2 ~ 1/10,
Wherein 1. the molecular structure of monomer a meets general formula:
R in formula
1for H or CH
3, R
2for the alkyl of H or 1 ~ 4 carbon atom; X is O, CH
2o, CH
2cH
2o, COO, AO is the oxyalkylene group of 2 ~ 4 carbon atoms or the mixture of two or more this oxyalkylene groups, and n is the average addition mole number of AO, and it is the integer of 5 ~ 200; When in the structural unit of homopolymer molecule, AO is the oxyalkylene group of different carbonatoms, (AO) n is random copolymerization or block copolymeric structure;
2. the molecular structure of monomer b meets general formula:
In formula, Y is Cl or Br, M is H, monovalent metal, (1/2) divalent metal, amino or organic amine, R
3for
or
Described its weight-average molecular weight of hyperbranched poly polymers of carboxylic acid is 10,000 ~ 100,000.If the weight-average molecular weight of hyperbranched poly polymers of carboxylic acid is too little or too greatly, diminishing and function of slump protection all can deteriorations.
The preparation method of hyperbranched poly polycarboxylic acid concrete high efficiency water reducing agent of the present invention, comprises the steps:
After monomer a, b fully being mixed with catalyzer, part, solvent, pass into N
2by O in solution
2discharge, at N
2carry out Self condensation vinyl polymerization reaction under protection, its temperature of reaction is 30 DEG C ~ 120 DEG C, and the reaction times is 3h ~ 24h, obtains hyperbranched polymer solution, and rotary evaporation is removed solvent and obtained hyperbranched poly polycarboxylic acid concrete high efficiency water reducing agent.
Described solvent be toluene, methyl alcohol, methyl-phenoxide, tetrahydrofuran (THF) and water any one or with arbitrary proportion mixing mixture;
Described part is any one in dipyridyl, five methyl diethylentriamine, three (2-dimethylaminoethyl) amine; Its consumption is 1/50 ~ 1/5 of monomer molar amount;
Described catalyzer is any one in cuprous bromide or cuprous chloride; Its consumption is 1/100 ~ 1/10 of monomer molar amount.
The monomer a that 1. formula of of the present invention represents has at least one in the material of the 1. represented structure of general formula, mixes with arbitrary proportion.
Monomer b contains at least one in the material that 2. general formula represent, when monomer b contains the material that 2. two or more general formula represent, can mix with arbitrary proportion.
The monomer a that 1. formula of of the present invention represents is polyalkylene glycol mono (methyl) acrylate monomer or unsaturated polyester alkylene glycol ether monomer.
When the monomer a that 1. general formula represents is polyalkylene glycol mono (methyl) acrylate monomer, be by alkoxy polyalkyleneglycol and (methyl) vinylformic acid or the lactate synthesis thing with (methyl) acrylic anhydride; Or be the affixture of at least one material in (methyl) hydroxyalkyl acrylate and oxyethane, propylene oxide, butylene oxide ring.These monomers are used alone or use with the form of mixtures of arbitrary proportion with two or more composition.When in the structural unit of homopolymer molecule, AO is the oxyalkylene group of different carbonatoms, (AO) n is random copolymerization or block copolymeric structure.
The object lesson that can be polyalkylene glycol mono (methyl) acrylate monomer as monomer a comprises: polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, polytetramethylene glycol list (methyl) acrylate, polyoxyethylene glycol polypropylene glycol list (methyl) acrylate, polyoxyethylene glycol polytetramethylene glycol list (methyl) acrylate, polypropylene glycol polytetramethylene glycol list (methyl) acrylate, polyoxyethylene glycol polypropylene glycol polytetramethylene glycol list (methyl) acrylate, methoxy poly (ethylene glycol) list (methyl) acrylate, methoxyl group polypropylene glycol list (methyl) acrylate, methoxyl group polytetramethylene glycol list (methyl) acrylate, methoxy poly (ethylene glycol) polypropylene glycol list (methyl) acrylate, methoxy poly (ethylene glycol) polytetramethylene glycol list (methyl) acrylate, methoxyl group polypropylene glycol polytetramethylene glycol list (methyl) acrylate, methoxy poly (ethylene glycol) polypropylene glycol polytetramethylene glycol list (methyl) acrylate, oxyethyl group polyethyleneglycol (methyl) acrylate, oxyethyl group polypropylene glycol list (methyl) acrylate, oxyethyl group polytetramethylene glycol list (methyl) acrylate, oxyethyl group polyoxyethylene glycol polypropylene glycol list (methyl) acrylate, oxyethyl group polyoxyethylene glycol polytetramethylene glycol list (methyl) acrylate, oxyethyl group polypropylene glycol polytetramethylene glycol list (methyl) acrylate, oxyethyl group polyoxyethylene glycol polypropylene glycol polytetramethylene glycol list (methyl) acrylate, propoxy-polyethyleneglycol (methyl) acrylate, propoxy-polypropylene glycol list (methyl) acrylate, propoxy-polytetramethylene glycol list (methyl) acrylate, propoxy-polyoxyethylene glycol polypropylene glycol list (methyl) acrylate, propoxy-polyoxyethylene glycol polytetramethylene glycol list (methyl) acrylate, propoxy-polypropylene glycol polytetramethylene glycol list (methyl) acrylate, propoxy-polyoxyethylene glycol polypropylene glycol polytetramethylene glycol list (methyl) acrylate, butoxy polyethyleneglycol (methyl) acrylate, butoxypolypropylene glycol list (methyl) acrylate, oxyethyl group polytetramethylene glycol list (methyl) acrylate, butoxy polyoxyethylene glycol polypropylene glycol list (methyl) acrylate, butoxy polyoxyethylene glycol polytetramethylene glycol list (methyl) acrylate, butoxypolypropylene glycol polytetramethylene glycol list (methyl) acrylate, butoxy polyoxyethylene glycol polypropylene glycol polytetramethylene glycol list (methyl) acrylate.
When the monomer a that 1. formula of of the present invention represents is unsaturated polyester aklylene glycol ethers monomer, be by the affixture of at least one material in unsaturated alcohol and oxyethane, propylene oxide, butylene oxide ring.These monomers are used alone or use with the form of mixtures of arbitrary proportion with two or more composition.
Can as the polyalkylene glycol mono of monomer a (methyl) acrylate monomer or unsaturated polyester alkylene glycol ether monomer, as long as meet general formula structural requirement 1., the performance impact of difference to prepared acid amides/imide poly carboxylic acid of its kind is very little.
The application method of hyperbranched high-efficiency water-reducing agent of poly-carboxylic acid of the present invention: its volume is 0.05% ~ 0.5% of total gelling material weight,
Its application method of hyperbranched high-efficiency water-reducing agent of poly-carboxylic acid of the present invention is identical with existing water reducer, and just volume is slightly different.The art those skilled in the art generally know that concrete volume has certain relation with the kind of the water reducer adopted.
As improvement, the volume of hyperbranched high-efficiency water-reducing agent of poly-carboxylic acid of the present invention is 0.08% ~ 0.3%.Volume is too low, then can not be satisfactory to the dispersion effect of cement; Volume is too high, cause waste economically, and dispersion effect does not increase further.
Hyperbranched high-efficiency water-reducing agent of poly-carboxylic acid of the present invention also can be selected from aminosulfonic water-reducing agent known in the state of the art, Lignins ordinary water-reducing agent and existing polycarboxylate dehydragent mutually used in combination with at least one.In addition, except known cement water reducing agent presented above, wherein also air entrapment agent, swelling agent, retardant, hardening accelerator, tackifier, economization agent and defoamer etc. can be added.
The present invention compared with prior art has the following advantages:
(1) adopt method of the present invention to have synthetic method simple, processing requirement is low, and production cost is little, convenient solvent reclaiming, the advantage that environmental pollution is little.
(2) polycarboxylate water-reducer adopting method of the present invention to prepare has the advantages such as volume is low, water-reducing rate is high, little loss of slump, cement adaptability are good, viscosity reduction.
Below in conjunction with embodiment, technical scheme of the present invention is described in further detail.
Embodiment
In order to understand the present invention better, below in conjunction with case study on implementation, the invention will be further described.
In the embodiment of the present invention, miniDAWN Tristar aqueous gel permeation chromatograph (GPC) that the weight-average molecular weight Mw of polymkeric substance adopts Wyatt technology corporation to produce measures; Experiment condition is as follows: post: TSK-GELSW (TOSOH company), eluant: 0.1M NaNO
3, velocity of flow: 0.8ml/min, injection: the 20 μ l0.1% aqueous solution (differential refraction detector).
Embodiment 1
By in 48g polyethylene glycol acrylate (Mn=480g/mol), 49.5g alkali and cross 2-brooethyl vinylformic acid fully mix with 2.87g cuprous bromide, 6.25g dipyridyl, 73g methyl alcohol and 73g water after, pass into N
2by O in solution
2discharge, at N
2carry out Self condensation vinyl polymerization reaction under protection, its temperature of reaction is 40 DEG C, and the reaction times is 8h, and obtain hyperbranched polymer solution, rotary evaporation is removed solvent and obtained hyperbranched polymer, and molecular weight is 17476.
Embodiment 2
By in 240g monomer methylallyl polyglycol ether (Mn=2400g/mol), 120.5g alkali and cross 2-(4-(brooethyl) phenyl) vinylformic acid fully mix with 5.74g cuprous bromide, 10.97g tri-(2-dimethylaminoethyl) amine, 240g toluene after, pass into N
2by O in solution
2discharge, at N
2carry out Self condensation vinyl polymerization reaction under protection, its temperature of reaction is 100 DEG C, and the reaction times is 16h, and obtain hyperbranched polymer solution, rotary evaporation is removed solvent and obtained hyperbranched polymer, and molecular weight is 35114.
Embodiment 3
By in 95g monomer methoxypolyethylene glycol methacrylic ester (Mn=950g/mol), 71.6g alkali and cross the bromo-2-methylene butyric acid of 3-fully mix with 1.02g cuprous bromide, 2.48g five methyl diethylentriamine, 155.5g methyl alcohol and 233g water after, pass into N
2by O in solution
2discharge, at N
2carry out Self condensation vinyl polymerization reaction under protection, its temperature of reaction is 30 DEG C, and the reaction times is 10h, and obtain hyperbranched polymer solution, rotary evaporation is removed solvent and obtained hyperbranched polymer, and molecular weight is 59877.
Embodiment 4
By 100g first in butenyl polyglycol ether (Mn=1000g/mol), 126.3g alkali and cross 2-(4-(1-chloroethyl) phenyl) vinylformic acid fully mix with 6.93g cuprous chloride, 21.87g dipyridyl, 64g tetrahydrofuran (THF) after, pass into N
2by O in solution
2discharge, at N
2carry out Self condensation vinyl polymerization reaction under protection, its temperature of reaction is 55 DEG C, and the reaction times is 22h, and obtain hyperbranched polymer solution, rotary evaporation is removed solvent and obtained hyperbranched polymer, and molecular weight is 83096.
Application Example:
In Application Example, the cement adopted is little wild field 52.5PII, and sand is the medium sand of fineness modulus M=2.6, the rubble of stone to be particle diameter be 5 ~ 20mm continuous grading.
Contrast Application Example is PCA (I) polycarboxylate water-reducer using Jiangsu Botexin Materials Co., Ltd to produce.
In application example, water-reducing rate, bleeding rate, air content, the relevant regulations of test method reference GB8077-2000 time of coagulation " Methods for testing uniformity of concrete admixture " perform.
Application Example 1
Water reducer of the present invention is evaluated according to GB8077-2000 standard, and water cement ratio is 0.35, and its paste flowing degree result is as table 1.
Table 1 different carboxylic acids class hyper branched copolymer is on the impact of paste flowing degree
When fixing water cement ratio is 0.35, hyperbranched poly carboxylic acid volume is 0.12%, and the volume of comparative example is 0.15%, and described volume is the ratio that solid water reducer accounts for cement, the cement mixed after hyperbranched poly carboxylic acid has good mobility and degree of mobilization hold facility, and is better than comparative example.In other words, relative to traditional poly carboxylic acid, the excellent performance of hyperbranched poly carboxylic acid dispersion cement.
Application Example 2
Carboxylic-acid hyperbranched polymer synthesized by Evaluation operation example and comparative example are on the impact of fresh concrete, and fixing water cement ratio, adjustment poly carboxylic acid solid volume makes the initial slump of fresh concrete be 21cm ± 2cm, and experimental result is in table 2.
Table 2 different carboxylic acids class hyper branched copolymer is on the impact of fresh mixing concrete property
The comb shape poly carboxylic acid of comparative example is 0.15% at volume, and slump during water cement ratio 0.44 is the gradual loss of 20cm, 0.5h is 17cm, and divergence is the gradual loss of 41.5cm, 0.5h is 37.5cm.Water cement ratio is fixed as 0.44, hyperbranched poly carboxylic acid synthesized in embodiment is when volume is 0.12% of cement consumption, the concrete slump and divergence major part all comparatively comparative example are good, as embodiment 3, initial slump is 22cm, the gradual loss of 0.5h is 20cm, and divergence is the gradual loss of 45cm, 0.5h is 42cm.Therefore, relative to traditional poly carboxylic acid, the excellent performance of hyperbranched poly carboxylic acid dispersion cement, and do not change air content.
Application Example 3
The mortar rheological property of evaluation comparison example and embodiment 3, adjustment admixture dosage makes the initial extension degree of fresh mortar be 300mm ± 5mm, and experimental result is in table 3.
Table 3 different carboxylic acids analog copolymer is on the impact of mortar rheological property
When identical water cement ratio, reach identical divergence, hyperbranched poly carboxylic acid volume comparatively combed poly carboxylic acid is low by 0.06%, illustrate that hyperbranched poly carboxylic acid diminishing is large compared with combed poly carboxylic acid, and mortar workability is good, has shearing force and low plastic viscosity.
Claims (6)
1. a preparation method for hyperbranched poly polycarboxylic acid concrete high efficiency water reducing agent, is characterized in that: be by monomer a and b, Self condensation vinyl polymerization occurs to react obtained hyperbranched poly polymers of carboxylic acid, be polycarboxylic acid concrete high efficiency water reducing agent; The mol ratio of monomer a and b meets: a/b=1/2 ~ 1/10;
Wherein 1. the molecular structure of monomer a meets general formula:
R in formula
1for H or CH
3, R
2for the alkyl of H or 1 ~ 4 carbon atom; X is O, CH
2o, CH
2cH
2o, COO, AO is the oxyalkylene group of 2 ~ 4 carbon atoms or the mixture of two or more this oxyalkylene groups, and n is the average addition mole number of AO, and it is the integer of 5 ~ 200;
2. the molecular structure of monomer b meets general formula:
In formula, Y is Cl or Br, M is H, monovalent metal, (1/2) divalent metal, amino or organic amine, R
3for
or
Described its weight-average molecular weight of hyperbranched poly polymers of carboxylic acid is 10,000 ~ 100,000.If the weight-average molecular weight of hyperbranched poly polymers of carboxylic acid is too little or too greatly, diminishing and function of slump protection all can deteriorations.
2. method according to claim 1, is characterized in that: specifically comprise the steps:
After monomer a, b fully being mixed with catalyzer, part, solvent, pass into N
2by O in solution
2discharge, at N
2carry out Self condensation vinyl polymerization reaction under protection, its temperature of reaction is 30 DEG C ~ 120 DEG C, and the reaction times is 3h ~ 24h, obtains hyperbranched polymer solution, and rotary evaporation is removed solvent and obtained hyperbranched poly polymers of carboxylic acid;
Described solvent be toluene, methyl alcohol, methyl-phenoxide, tetrahydrofuran (THF) and water any one or with arbitrary proportion mixing mixture;
Described part is any one in dipyridyl, five methyl diethylentriamine, three (2-dimethylaminoethyl) amine; Its consumption is 1/50 ~ 1/5 of monomer molar amount;
Described catalyzer is any one in cuprous bromide or cuprous chloride; Its consumption is 1/100 ~ 1/10 of monomer molar amount.
3. method according to claim 1 and 2, is characterized in that: the monomer a that 1. described general formula represents is polyalkylene glycol mono (methyl) acrylate monomer or unsaturated polyester alkylene glycol ether monomer.
4. method according to claim 3, it is characterized in that: when the monomer a that 1. general formula represents is polyalkylene glycol mono (methyl) acrylate monomer, is by alkoxy polyalkyleneglycol and (methyl) vinylformic acid or the lactate synthesis thing with (methyl) acrylic anhydride; Or be the affixture of at least one material in (methyl) hydroxyalkyl acrylate and oxyethane, propylene oxide, butylene oxide ring; These monomers are used alone or use with the form of mixtures of arbitrary proportion with two or more composition; When in the structural unit of homopolymer molecule, AO is the oxyalkylene group of different carbonatoms, (AO) n is random copolymerization or block copolymeric structure.
5. method according to claim 4, is characterized in that: described monomer a is that the object lesson of polyalkylene glycol mono (methyl) acrylate monomer comprises: polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, polytetramethylene glycol list (methyl) acrylate, polyoxyethylene glycol polypropylene glycol list (methyl) acrylate, polyoxyethylene glycol polytetramethylene glycol list (methyl) acrylate, polypropylene glycol polytetramethylene glycol list (methyl) acrylate, polyoxyethylene glycol polypropylene glycol polytetramethylene glycol list (methyl) acrylate, methoxy poly (ethylene glycol) list (methyl) acrylate, methoxyl group polypropylene glycol list (methyl) acrylate, methoxyl group polytetramethylene glycol list (methyl) acrylate, methoxy poly (ethylene glycol) polypropylene glycol list (methyl) acrylate, methoxy poly (ethylene glycol) polytetramethylene glycol list (methyl) acrylate, methoxyl group polypropylene glycol polytetramethylene glycol list (methyl) acrylate, methoxy poly (ethylene glycol) polypropylene glycol polytetramethylene glycol list (methyl) acrylate, oxyethyl group polyethyleneglycol (methyl) acrylate, oxyethyl group polypropylene glycol list (methyl) acrylate, oxyethyl group polytetramethylene glycol list (methyl) acrylate, oxyethyl group polyoxyethylene glycol polypropylene glycol list (methyl) acrylate, oxyethyl group polyoxyethylene glycol polytetramethylene glycol list (methyl) acrylate, oxyethyl group polypropylene glycol polytetramethylene glycol list (methyl) acrylate, oxyethyl group polyoxyethylene glycol polypropylene glycol polytetramethylene glycol list (methyl) acrylate, propoxy-polyethyleneglycol (methyl) acrylate, propoxy-polypropylene glycol list (methyl) acrylate, propoxy-polytetramethylene glycol list (methyl) acrylate, propoxy-polyoxyethylene glycol polypropylene glycol list (methyl) acrylate, propoxy-polyoxyethylene glycol polytetramethylene glycol list (methyl) acrylate, propoxy-polypropylene glycol polytetramethylene glycol list (methyl) acrylate, propoxy-polyoxyethylene glycol polypropylene glycol polytetramethylene glycol list (methyl) acrylate, butoxy polyethyleneglycol (methyl) acrylate, butoxypolypropylene glycol list (methyl) acrylate, oxyethyl group polytetramethylene glycol list (methyl) acrylate, butoxy polyoxyethylene glycol polypropylene glycol list (methyl) acrylate, butoxy polyoxyethylene glycol polytetramethylene glycol list (methyl) acrylate, butoxypolypropylene glycol polytetramethylene glycol list (methyl) acrylate, butoxy polyoxyethylene glycol polypropylene glycol polytetramethylene glycol list (methyl) acrylate.
6. method according to claim 3, when it is characterized in that the monomer a that 1. described general formula represents is unsaturated polyester aklylene glycol ethers monomer, is by the affixture of at least one material in unsaturated alcohol and oxyethane, propylene oxide, butylene oxide ring; These monomers are used alone or use with the form of mixtures of arbitrary proportion with two or more composition.
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| CN105367721A (en) * | 2015-11-30 | 2016-03-02 | 江苏苏博特新材料股份有限公司 | Method for preparing viscosity-reduction-type polycarboxylic acid superplasticizer and application of viscosity-reduction-type polycarboxylic acid superplasticizer |
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| CN105669913A (en) * | 2016-03-03 | 2016-06-15 | 江苏中铁奥莱特新材料有限公司 | Preparation method of star polycarboxylate water reducing agent with controllable molecular structure |
| CN105669913B (en) * | 2016-03-03 | 2018-03-13 | 江苏中铁奥莱特新材料股份有限公司 | A kind of preparation method of the controllable star-like poly carboxylic acid series water reducer of molecular structure |
| CN111065661A (en) * | 2017-09-25 | 2020-04-24 | 第一工业制药株式会社 | Copolymer, dispersant, and dispersion composition |
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