CN104371071B - Preparation method for hyperbranched polycarboxylic-acid concrete efficient water reducer - Google Patents
Preparation method for hyperbranched polycarboxylic-acid concrete efficient water reducer Download PDFInfo
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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, and in particular to one kind can be used as concrete high-efficiency
Hyperbranched poly carboxylic acid of water reducer and preparation method thereof.
Background technology
Cement dispersants (water reducer) have absorption on cement particle so as to suppress cement particle cohesion, improve concrete
Dispersed effect when in use.
Material as cement peptizaiton has a lot, including lignosulfonates, naphthalene sulfonate/formaldehyde condensation products, benzene
Phenol/p-aminobenzene sulfonic acid/formaldehyde condensation products, melamine sulfonate/formaldehyde condensation products, polycarboxylic acid comb-shaped copolymer etc..
From design feature, preceding several cement dispersants are main with sulfonic group as adsorption group, lack effective offer
The side chain of steric hindrance effect, molecular structure is single, and adjustability is poor, and the peptizaiton to cement is limited, and volume is high and diminishing
Rate is low.
Polycarboxylic acid comb-shaped copolymer has the suction-operated that the main chain rich in carboxyl adsorption group is provided, and with hydrophilic
Property the steric hindrance effect that provides of preferable side chain, the larger peptizaiton that improve to cement.At present, develop both at home and abroad
Polycarboxylic acid super-plasticizer is mostly (methyl) acrylic acid/ester copolymer or alkenyl polyethylene glycol/maleic acid/acrylic copolymer subtracts
Aqua, the molecular structure of this two classes water reducer is in mostly combed, with preparation process is simple, low cost, slump-retaining energy
Good the advantages of, but do not still meet requirement of the modern concrete engineering to high-performance water reducing agent.Therefore, exploitation star knot
The polycarboxylic acid super plasticizer of the new structures such as structure, dissaving structure, lifts its dispersive property, dispersion holding performance, as poly-
One of research direction of carboxylic acid super plasticizer.
On the other hand, the raising of concrete strength mainly realizes that this also results in concrete and glues by reducing water-cement ratio
Degree is larger, triggers a series of construction problems such as concrete-agitating, transport, pumping, largely limits high-strength and superelevation
The popularization of reinforced concrete and application.Current adoptable viscosity reducing process is mainly to be opened in terms of organic admixture and admixture two
Exhibition.The organic admixture of addition is mainly air entraining agent, and the incorporation of air entraining agent makes to form a large amount of small envelopes in concrete mix
Spherical bubble is closed, these microbubbles reduce the frictional resistance between particles of aggregates as ball, so that viscosity is reduced, but
The effect of air entraining agent viscosity reduction is limited, and the bubble of introducing has a negative impact to the intensity of high-strength concrete, on water reducer to coagulation
The native viscosity mechanism of action is still unintelligible, and the research and development of organic thinner do not occur concrete also organic at present still without breakthrough
The Patents of thinner；And also without there is patent or article on concrete thinner in terms of admixture, at present
Mainly improve working performance of concrete by mixing a large amount of flyash, it is commonly known that incorporation flyash can reduce concrete and glue
Degree, but for high-rise, high-strength or super high strength concrete, its viscosity reducing effect is extremely limited.
CN101580353 reports a kind of hyperbranched polycarboxylic acid super-plasticizer and preparation method thereof, by (methyl) acrylic acid
The tert-butyl ester, methylpropene sodium sulfonate, allyl polyethenoxy ether generate copolymer under the effect of initiator azo dicyano valeric acid
Main chain, then hyper branched copolymer is formed by (methyl) acrylic acid and reacting ethylenediamine.The product has that volume is low, water-reducing rate is high,
The advantages of little loss of slump, but preparation technology is complicated, needs aggregated, vacuum distillation, condensation, hydrolysis backflow, separating-purifying
Etc. step, while using various organic solvents, production cost is higher, also easily causes environmental pollution.
CN102504247 reports a kind of dissaving polymer, hyperbranched type polycarboxylic acid super-plasticizer and preparation method thereof,
Intermediate is first obtained by alkenyl amine and 2- acrylamide-2-methyl propane sulfonic sodium addition reactions, then with methoxy poly (ethylene glycol) (first
Base) acrylate, double (methyl) acrylic ester copolymers of polyethylene glycol obtain, with water-reducing rate it is high, slump-retaining can wait well
Advantage.But, organic solvent is still used in its preparation process, environmental pollution is easily caused, while improving production cost.
Therefore, it is now known that technology contain some hyperbranched polycarboxylic acid super-plasticizers as cement water reducing agent
Structure and preparation method.But due to raw material, process route etc., its economy and the feature of environmental protection constrain its industrialization
Application.
In sum, there is provided a kind of synthetic method is simple, and technological requirement is low, and production cost is small, convenient solvent reclaiming, environment
The small method for preparing hyperbranched poly carboxylic acid of pollution is very necessary.
The content of the invention
It is contemplated that overcoming existing polycarboxylate water-reducer limited to the dispersion effect of cement, viscosity reducing effect is not enough to ask
A kind of topic, there is provided preparation method of hyperbranched poly polycarboxylic acid concrete high efficiency water reducing agent, the product produced has that volume is low, diminishing
Rate is high, little loss of slump, cement adaptability are good, viscosity reduction the advantages of, and preparation process is simple.
Know-why of the invention：Using Self condensation vinyl polymerization method synthesis of super branched polycarboxylic acids.
, there is self shrinking by monomer a and b in the preparation method of hyperbranched poly polycarboxylic acid concrete's high efficiency water reducing agent that the present invention is provided
Vinyl polymerization reaction is closed, the mol ratio of monomer a and b meets：A/b=1/2~1/10,
1. the molecular structure of wherein monomer a meets formula：
R in formula1It is H or CH3, R2It is H or 1~4 alkyl of carbon atom；X is O, CH2O、CH2CH2O, COO, AO is
The oxyalkylene group of 2~4 carbon atoms or the mixture of two or more this oxyalkylene groups, n are the average addition mole of AO
Number, it is 5~200 integer；When AO is the oxyalkylene group of different carbon numbers in the construction unit of homopolymers molecule, (AO)
N is random copolymerization or block copolymeric structure；
2. the molecular structure of monomer b meets formula：
In formula, Y is Cl or Br, M are H, monovalent metal, (1/2) divalent metal, amino or organic amine, R3ForOr
Described its weight average molecular weight of hyperbranched poly polymers of carboxylic acid is 10,000~100,000.If hyperbranched poly carboxylic
The weight average molecular weight of acid copolymer is too small or too big, and diminishing and function of slump protection can all be deteriorated.
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 and catalyst, part, solvent are sufficiently mixed, N is passed through2By O in solution2Discharge, in N2Under protection
Self condensation vinyl polymerization reaction is carried out, its reaction temperature is 30 DEG C~120 DEG C, and the reaction time is 3h~24h, obtains hyperbranched
Polymer solution, rotary evaporation removes solvent and obtains hyperbranched poly polycarboxylic acid concrete's high efficiency water reducing agent.
The solvent is any one of toluene, methyl alcohol, methyl phenyl ethers anisole, tetrahydrofuran and water or is mixed with arbitrary proportion
Mixture；
The part is any one in bipyridyl, five methyl diethylentriamine, three (2- dimethylaminoethyls) amine；
Its consumption is the 1/50~1/5 of monomer molar amount；
The catalyst is any one in cuprous bromide or stannous chloride；Its consumption is the 1/ of monomer molar amount
100~1/10.
The monomer a that 1. formula of of the present invention represents is at least one in the material with the 1. represented structure of formula,
Mixed with arbitrary proportion.
Monomer b contains at least one in the material that 2. formula represents, when monomer b contains what 2. two or more formulas represented
During material, can be mixed with arbitrary proportion.
The monomer a that 1. formula of of the present invention represents is polyalkylene glycol mono (methyl) acrylate monomer or unsaturated poly-
Alkylene glycol ether monomer.
It is by the poly- Asia of alkoxy when the monomer a that 1. formula represents is polyalkylene glycol mono (methyl) acrylate monomer
Alkyl diol and (methyl) acrylic acid or the lactate synthesis thing with (methyl) acrylic anhydride；Or for (methyl) hydroxyalkyl acrylate with
The addition product of at least one material in oxirane, expoxy propane, epoxy butane.These monomers be used alone or with two kinds with
Upper composition is used with the form of mixtures of arbitrary proportion.When AO is the oxygen of different carbon numbers in the construction unit of homopolymers molecule
When changing alkenyl, (AO) n is random copolymerization or block copolymeric structure.
Can be as monomer a for the specific example of polyalkylene glycol mono (methyl) acrylate monomer includes：Poly- second two
Alcohol list (methyl) acrylate, polypropylene glycol list (methyl) acrylate, polytetramethylene glycol list (methyl) acrylate, polyethylene glycol
Polypropylene glycol list (methyl) acrylate, polyethylene glycol polytetramethylene glycol list (methyl) acrylate, polypropylene glycol polytetramethylene glycol list
(methyl) acrylate, polyethylene glycol polypropylene glycol polytetramethylene glycol list (methyl) acrylate, methoxy poly (ethylene glycol) list (first
Base) acrylate, methoxyl group polypropylene glycol list (methyl) acrylate, methoxyl group polytetramethylene glycol list (methyl) acrylate, first
Epoxide polyethylene 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, ethyoxyl polyethyleneglycol (methyl) acrylate, ethyoxyl polypropylene glycol list (methyl) acrylate, ethyoxyl
Polytetramethylene glycol list (methyl) acrylate, ethyoxyl polyethylene glycol polypropylene glycol list (methyl) acrylate, the poly- second two of ethyoxyl
Alcohol polytetramethylene glycol list (methyl) acrylate, ethyoxyl polypropylene glycol polytetramethylene glycol list (methyl) acrylate, the poly- second of ethyoxyl
Glycol polypropylene glycol polytetramethylene glycol list (methyl) acrylate, propoxyl group polyethyleneglycol (methyl) acrylate, propoxyl group gather
Propane diols list (methyl) acrylate, propoxyl group polytetramethylene glycol list (methyl) acrylate, propoxyl group polyethylene glycol polypropylene glycol
Single (methyl) acrylate, propoxyl group polyethylene glycol polytetramethylene glycol list (methyl) acrylate, propoxyl group polypropylene glycol polybutadiene
Alcohol list (methyl) acrylate, propoxyl group polyethylene glycol polypropylene glycol polytetramethylene glycol list (methyl) acrylate, the poly- second of butoxy
Glycol list (methyl) acrylate, butoxypolypropylene glycol list (methyl) acrylate, ethyoxyl polytetramethylene glycol list (methyl) third
Olefin(e) acid ester, butoxy polyethylene glycol polypropylene glycol list (methyl) acrylate, butoxy polyethylene glycol polytetramethylene glycol list (methyl)
Acrylate, butoxypolypropylene glycol polytetramethylene glycol list (methyl) acrylate, butoxy polyethylene glycol polypropylene glycol polybutadiene
Alcohol list (methyl) acrylate.
It is by unsaturated alcohol when the monomer a that 1. formula of of the present invention represents is unsaturated polyalkylene glycol ethers class monomer
With the addition product of at least one material in oxirane, expoxy propane, epoxy butane.These monomers are used alone or with two kinds
Or two or more compositions are used with the form of mixtures of arbitrary proportion.
Can be as polyalkylene glycol mono (methyl) acrylate monomer of monomer a or unsaturated polyalkylene glycol ethers
Monomer, as long as meeting formula structural requirement 1., the different performance shadows to prepared acid amides/acid imide polycarboxylic acids of its species
Ring very little.
The application process of hyperbranched high-efficiency water-reducing agent of poly-carboxylic acid of the present invention：Its volume is total Binder Materials weight
0.05%~0.5%,
Its application process of hyperbranched high-efficiency water-reducing agent of poly-carboxylic acid of the present invention is identical with existing water reducer, and simply volume is slightly
There is difference.The art those skilled in the art generally know that specific volume and the species of the water reducer for being used have necessarily
Relation.
Used 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 mistake
Low, then the dispersion effect to cement is unsatisfactory；Volume is too high, causes waste economically, and dispersion effect does not enter
One step increases.
Hyperbranched high-efficiency water-reducing agent of poly-carboxylic acid of the present invention can also be selected from ammonia known in the state of the art with least one
Base sulfonic acid based water reducer, Lignins ordinary water-reducing agent and existing polycarboxylate dehydragent are mixed and used.In addition, except above
The known cement water reducing agent for proposing, wherein air entraining agent, swelling agent, retarder, early strength agent, tackifier, decrement can also be added
Agent and defoamer etc..
The present invention has advantages below compared with prior art：
(1) have synthetic method simple using the method for the present invention, technological requirement is low, and production cost is small, solvent recovery side
Just, the small advantage of environmental pollution.
(2) polycarboxylate water-reducer prepared using the method for the present invention has that volume is low, water-reducing rate is high, slump-loss
Small, cement adaptability is good, viscosity reduction the advantages of.
With reference to embodiment, technical scheme is described in further detail.
Specific embodiment
For a better understanding of the present invention, with reference to case study on implementation, the invention will be further described.
In the embodiment of the present invention, the weight average molecular weight Mw of polymer is given birth to using Wyatt technology corporation
MiniDAWN Tristar aqueous gels permeation chromatograph (GPC) of product is measured；Experiment condition is as follows：Post：TSK-GELSW
(TOSOH companies), elutriant：0.1M NaNO3, flowing velocity：0.8ml/min, injection：The 20 μ l0.1% aqueous solution (show poor folding
Photodetector).
Embodiment 1
By in 48g polyethylene glycol acrylates (Mn=480g/mol), 49.5g alkali and cross 2- bromomethyls acrylic acid with
After 2.87g cuprous bromides, 6.25g bipyridyls, 73g methyl alcohol and 73g water are sufficiently mixed, N is passed through2By O in solution2Discharge, in N2Protect
Self condensation vinyl polymerization reaction is carried out under shield, its reaction temperature is 40 DEG C, and the reaction time is 8h, obtains dissaving polymer molten
Liquid, rotary evaporation removes solvent and obtains dissaving polymer, and molecular weight is 17476.
Embodiment 2
By in 240g monomer methylallyls polyglycol ether (Mn=2400g/mol), 120.5g alkali and cross 2- (4-
(bromomethyl) phenyl) acrylic acid and 5.74g cuprous bromides, 10.97g tri- (2- dimethylaminoethyls) amine, 240g toluene fully mixes
After conjunction, N is passed through2By O in solution2Discharge, in N2Self condensation vinyl polymerization reaction is carried out under protection, its reaction temperature is 100
DEG C, the reaction time is 16h, obtains dissaving polymer solution, and rotary evaporation removes solvent and obtains dissaving polymer, molecular weight
It is 35114.
Embodiment 3
By in 95g monomer methoxypolyethylene glycols methacrylate (Mn=950g/mol), 71.6g alkali and cross 3- it is bromo-
2- methylene butyric acids are fully mixed with 1.02g cuprous bromides, 2.48g five methyl diethylentriamines, 155.5g methyl alcohol and 233g water
After conjunction, N is passed through2By O in solution2Discharge, in N2Self condensation vinyl polymerization reaction is carried out under protection, its reaction temperature is 30 DEG C,
Reaction time is 10h, obtains dissaving polymer solution, and rotary evaporation removes solvent and obtains dissaving polymer, and molecular weight is
59877。
Embodiment 4
By 100g first in cyclobutenyl polyglycol ether (Mn=1000g/mol), 126.3g alkali and cross 2- (4- (1- chlorine
Ethyl) phenyl) after acrylic acid and 6.93g stannous chlorides, 21.87g bipyridyls, 64g tetrahydrofurans be sufficiently mixed, it is passed through N2Will be molten
O in liquid2Discharge, in N2Self condensation vinyl polymerization reaction is carried out under protection, its reaction temperature is 55 DEG C, and the reaction time is 22h,
Dissaving polymer solution is obtained, rotary evaporation removes solvent and obtains dissaving polymer, and molecular weight is 83096.
Application Example：
In Application Example, the cement for being used is small wild field 52.5PII, and sand is the middle sand of modulus of fineness M=2.6, stone
Son is rubble that particle diameter is 5~20mm continuous gradings.
Contrast Application Example is PCA (I) polycarboxylate water-reducer produced using Jiangsu Botexin Materials Co., Ltd.
Water-reducing rate, bleeding rate, air content, setting time test method are with reference to GB8077-2000 in application example《Concrete
Additive homogeneity test method》Relevant regulations perform.
Application Example 1
Water reducer of the present invention is evaluated according to GB8077-2000 standards, and the ratio of mud is 0.35, its paste flowing degree result
Such as table 1.
Influence of the different carboxylic acids class hyper branched copolymer of table 1 to paste flowing degree
When the fixed ratio of mud is 0.35, hyperbranched poly carboxylic acid volume is 0.12%, and the volume of comparative example is 0.15%, described
Volume is the ratio that solid water reducer accounts for cement, and mixing the cement after hyperbranched poly carboxylic acid has preferable mobility and fluidity to keep
Ability, and better than comparative example.In other words, relative to traditional polycarboxylic acids, hyperbranched poly carboxylic acid disperses the excellent performance of cement.
Application Example 2
Evaluate the carboxylic acids dissaving polymer synthesized by embodiment and influence of the comparative example to fresh concrete, fixed water
Gray scale, adjustment polycarboxylic acids solid volume makes the initial slump of fresh concrete be 21cm ± 2cm, and experimental result is shown in Table 2.
Influence of the different carboxylic acids class hyper branched copolymer of table 2 to fresh mixing concrete property
The comb shape polycarboxylic acids of comparative example is 0.15% in volume, and the slump during ratio of mud 0.44 is 20cm, the warp of 0.5h
When loss be 17cm, divergence is 41.5cm, and the gradual loss of 0.5h is 37.5cm.The ratio of mud is fixed as 0.44, in embodiment
Synthesized hyperbranched poly carboxylic acid is in volume for cement consumption 0.12%, and the slump and divergence of concrete are most of all
Good compared with comparative example, such as embodiment 3, initial slump is 22cm, and the gradual loss of 0.5h is 20cm, and divergence is 45cm, 0.5h
Gradual loss be 42cm.Accordingly, with respect to traditional polycarboxylic acids, hyperbranched poly carboxylic acid disperses the excellent performance of cement, and not
Change air content.
Application Example 3
Evaluation comparison example and the mortar rheological property of embodiment 3, adjusting admixture dosage makes the initial extension of fresh mortar
It is 300mm ± 5mm to spend, and experimental result is shown in Table 3.
Influence of the different carboxylic acids analog copolymer of table 3 to mortar rheological property
In the case of the identical ratio of mud, identical divergence is reached, hyperbranched poly carboxylic acid volume is low compared with combed polycarboxylic acids
0.06%, illustrate that hyperbranched poly carboxylic acid diminishing is big compared with combed polycarboxylic acids, and mortar workability is good, with shearing force and low
Plastic viscosity.
Claims (6)
1. a kind of preparation method of hyperbranched poly polycarboxylic acid concrete high efficiency water reducing agent, it is characterised in that：It is occurred by monomer a and b
Self condensation vinyl polymerization reaction is obtained hyperbranched poly polymers of carboxylic acid, as polycarboxylic acid concrete high efficiency water reducing agent；Monomer a with
The mol ratio of b meets：A/b=1/2~1/10；
1. the molecular structure of wherein monomer a meets formula：
R in formula1It is H or CH3, R2It is H or 1~4 alkyl of carbon atom；X is O, CH2O、CH2CH2O, COO, AO are 2~4
The mixture of the oxyalkylene group of individual carbon atom or two or more this oxyalkylene groups, n is the average addition molal quantity of AO, its
It is 5~200 integer；
2. the molecular structure of monomer b meets formula：
In formula, Y is Cl or Br, M are H, monovalent metal, (1/2) divalent metal, amino or organic amine, R3ForOr
Described its weight average molecular weight of hyperbranched poly polymers of carboxylic acid is 10,000~100,000.
2. method according to claim 1, it is characterised in that：Specifically include following step：
After monomer a, b and catalyst, part, solvent are sufficiently mixed, N is passed through2By O in solution2Discharge, in N2Carried out under protection
Self condensation vinyl polymerization reacts, and its reaction temperature is 30 DEG C~120 DEG C, and the reaction time is 3h~24h, obtains hyperbranched polymerization
Thing solution, rotary evaporation removes solvent and obtains hyperbranched poly polymers of carboxylic acid；
The solvent for toluene, methyl alcohol, methyl phenyl ethers anisole, tetrahydrofuran and water any one or with arbitrary proportion mix mixing
Thing；
The part is any one in bipyridyl, five methyl diethylentriamine, three (2- dimethylaminoethyls) amine；It is used
Measure is the 1/50~1/5 of monomer molar amount；
The catalyst is any one in cuprous bromide or stannous chloride；Its consumption for monomer molar amount 1/100~
1/10。
3. method according to claim 1 and 2, it is characterised in that：The monomer a that 1. formula represents is polyalkylene two
Alcohol list (methyl) acrylate monomer or unsaturated polyalkylene glycol ethers monomer.
4. method according to claim 3, it is characterised in that：The monomer a that 1. formula represents is polyalkylene glycol mono (first
Base) acrylate monomer when, be the ester by alkoxy polyalkyleneglycol and (methyl) acrylic acid or with (methyl) acrylic anhydride
It is combined to thing；Or be at least one material in (methyl) hydroxyalkyl acrylate and oxirane, expoxy propane, epoxy butane
Addition product；These monomers are used alone or are used with the form of mixtures of arbitrary proportion with two or more compositions；When homopolymers point
When AO is the oxyalkylene group of different carbon numbers in the construction unit of son, (AO) n is random copolymerization or block copolymeric structure.
5. method according to claim 4, it is characterised in that：The monomer a is polyalkylene glycol mono (methyl) propylene
The specific example of acid ester monomer includes：Polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, poly- fourth
Glycol list (methyl) acrylate, polyethylene glycol polypropylene glycol list (methyl) acrylate, polyethylene glycol polytetramethylene glycol list (first
Base) acrylate, polypropylene glycol polytetramethylene glycol list (methyl) acrylate, polyethylene 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, the poly- second two of methoxyl group
Alcohol polytetramethylene glycol list (methyl) acrylate, methoxyl group polypropylene glycol polytetramethylene glycol list (methyl) acrylate, the poly- second of methoxyl group
Glycol polypropylene glycol polytetramethylene glycol list (methyl) acrylate, ethyoxyl polyethyleneglycol (methyl) acrylate, ethyoxyl gather
Propane diols list (methyl) acrylate, ethyoxyl polytetramethylene glycol list (methyl) acrylate, ethyoxyl polyethylene glycol polypropylene glycol
Single (methyl) acrylate, ethyoxyl polyethylene glycol polytetramethylene glycol list (methyl) acrylate, ethyoxyl polypropylene glycol polybutadiene
Alcohol list (methyl) acrylate, ethyoxyl polyethylene glycol polypropylene glycol polytetramethylene glycol list (methyl) acrylate, the poly- second of propoxyl group
Glycol list (methyl) acrylate, propoxyl group polypropylene glycol list (methyl) acrylate, propoxyl group polytetramethylene glycol list (methyl) third
Olefin(e) acid ester, propoxyl group polyethylene glycol polypropylene glycol list (methyl) acrylate, propoxyl group polyethylene glycol polytetramethylene glycol list (methyl)
Acrylate, propoxyl group polypropylene glycol polytetramethylene glycol list (methyl) acrylate, propoxyl group polyethylene glycol polypropylene glycol polybutadiene
Alcohol list (methyl) acrylate, butoxy polyethyleneglycol (methyl) acrylate, butoxypolypropylene glycol list (methyl) propylene
Acid esters, ethyoxyl polytetramethylene glycol list (methyl) acrylate, butoxy polyethylene glycol polypropylene glycol list (methyl) acrylate, fourth
Epoxide polyethylene glycol polytetramethylene glycol list (methyl) acrylate, butoxypolypropylene glycol polytetramethylene glycol list (methyl) acrylate,
Butoxy polyethylene glycol polypropylene glycol polytetramethylene glycol list (methyl) acrylate.
6. method according to claim 3, it is characterised in that the monomer a that 1. formula represents is unsaturated polyalkylene
It is by the addition of at least one material in unsaturated alcohol and oxirane, expoxy propane, epoxy butane during glycol ethers monomer
Thing；These monomers are used alone or are used with the form of mixtures of arbitrary proportion with two or more composition.
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| CN105367721B (en) * | 2015-11-30 | 2018-02-23 | 江苏苏博特新材料股份有限公司 | The preparation method and application of viscosity reduction type polycarboxylic acid super-plasticizer |
| CN105712650B (en) * | 2015-12-11 | 2018-06-26 | 江苏苏博特新材料股份有限公司 | A kind of preparation method of strong adaptability polycarboxylate water-reducer |
| 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 |
| JP2019059815A (en) * | 2017-09-25 | 2019-04-18 | 第一工業製薬株式会社 | Copolymer, dispersant, and dispersion composition |
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| CN101580353A (en) * | 2009-06-01 | 2009-11-18 | 济南大学 | Hyper-branched polycarboxylate high-efficiency water reducing agent and preparation method thereof |
| CN102002134A (en) * | 2010-11-05 | 2011-04-06 | 济南大学 | Hyperbranched polymer, hyperbranched type water reducing agent of polycarboxylic acid series and preparation method and application thereof |
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| CN101580353A (en) * | 2009-06-01 | 2009-11-18 | 济南大学 | Hyper-branched polycarboxylate high-efficiency water reducing agent and preparation method thereof |
| CN102002134A (en) * | 2010-11-05 | 2011-04-06 | 济南大学 | Hyperbranched polymer, hyperbranched type water reducing agent of polycarboxylic acid series and preparation method and application thereof |
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