CN104725578A - Preparation method of grafted copolymer and air-entraining and slump-retaining polycarboxylate concrete water reducer - Google Patents
Preparation method of grafted copolymer and air-entraining and slump-retaining polycarboxylate concrete water reducer Download PDFInfo
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Abstract
The invention belongs to the technical field of concrete admixtures in chemical building materials, and particularly relates to a preparation method of a grafted copolymer and an air-entraining and slump-retaining polycarboxylate concrete water reducer. The air-entraining and slump-retaining polycarboxylate air-entrained concrete efficient water reducer is synthesized by the following steps: introducing a double bond in the process of preparing a macromonomer with reaction activity through utilization of polyoxyalkylene ether monomers; copolymerizing a product obtained from the former step and carboxylic acid monomers and allylsulfonate monomers in a solution so as to introduce a long side chain. The preparation technology is very simple; the reaction condition is easy to control; industrial three wastes are not generated in the production process; the solvent can be recycled after being recovered; and the solvent recovery rate reaches 98%-100%, so that the economic benefits are ensured; and the environmental pollution is avoided.
Description
Technical field
The invention belongs to technical field of concrete additives in chemical building material, particularly relate to the preparation method of a kind of graft copolymer and bleed collapse protective poly-carboxylic acid salt cement water reducing agent.
Background technology
Along with developing rapidly of China's economy, the construction of heavy construction gets more and more, concrete technology constantly develops to high strength, high-durability, high workability or special property, admixture has become one of requisite component of concrete, and maximum one applied in concrete admixture by high efficiency water reducing agent.
At present, the cement water reducing agent of domestic use is based on naphthalene water reducer, there is production technique and utilisation technology comparative maturity, higher, the low-cost advantage of water-reducing rate, but exist good not with cement adaptability, Slump Time losing of Large is large and the problem such as consequent poor durability, and containing toxic substances such as formaldehyde in product, very easily cause environmental pollution, be detrimental to health.
By comparison, novel polycarboxylate concrete high efficiency water reducing agent is then owing to having low-dosage, high flowing, protecting plurality of advantages and the study hotspot that becomes international rapidly such as to collapse, cement adaptability is good, molecular structure variable factor is many greatly.Meanwhile, due to the proposition of " high performance concrete " this novel concept, people are seen concrete quality change into by the simple pursuit intensity in past and focus on concrete durability, workability and the adaptability in harsh environment for use simultaneously, this just requires that water reducer has certain bleed and good slump-retaining.Novel polycarboxylate concrete high efficiency water reducing agent prepares the first-selection of low water binder ratio, high-strength, high durability concrete by becoming people.Abroad, especially Japan, the efficient carboxylic acid water reducer of bleed has been widely used in water conservancy, road etc. and has required in the concrete works of high-durability, but the Air Bubble Size that bleed is formed differs stable not, affects concrete strength.
Summary of the invention
The object of the invention is to, overcome the deficiencies in the prior art, provide the preparation method of a kind of graft copolymer and bleed collapse protective poly-carboxylic acid salt cement water reducing agent.With polyalkene glycol acrylates class monomer, carboxylic acid type monomer, allyl sulphonic acid class monomer etc. for bleed collapse protection type water reducer prepared by raw material.Production technique of the present invention is relatively simple, easy control of reaction conditions, require lower to production unit, is a kind of polycarboxylate concrete high efficiency water reducing agent with low-dosage, large diminishing, high-thin arch dam, suitably bleed.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A kind of graft copolymer, the structural formula of described graft copolymer is general formulae IV:
In general formulae IV: the mole ratio of a, b, c is 0 ~ 3:2 ~ 7:1 ~ 5; N represents the mole number of repeating unit, is the integer of 1 ~ 99.
The preparation method of graft copolymer of the present invention, it is that 1 ~ 5:2 ~ 7:0 ~ 3 ratio carries out the obtained graft copolymer of copolyreaction in molar ratio by general formula I, general formula I I and general formula III three kinds of monomers,
General formula I is polyalkene glycol acrylates class monomer:
In general formula I: R
1for the alkyl of carbonatoms 1 ~ 5; R
2for the alkyl of OH, H or carbonatoms 1 ~ 10; M is the average addition mole number of oxyalkylene group, is the integer of 1 ~ 99;
General formula I I is carboxylic acid type monomer:
In general formula I I: R
3for the alkyl of H or carbonatoms 1 ~ 5; M
1for H, Na
+or carbonatoms is the alkyl of 1 ~ 4;
General formula III is olefin sulfonic acid class monomer:
In general formula III: R
4for the alkyl of H or carbonatoms 1 ~ 5; M
2for H, Na
+;
Reaction formula is as follows:
In formula: a, b, c represent the mole number of corresponding monomeric unit, a:b:c=0 ~ 3:2 ~ 7:1 ~ 5; N represents the mole number of repeating unit, is the integer of 1 ~ 99.
The preparation method of graft copolymer of the present invention, comprises the following steps:
(1) preparation has the polymeric monomer of reactive behavior: polyalkene glycol acrylates class monomer
Polyalkylene glycol mono body and carboxylic acid type monomer are joined in the reactor that condensation part flow arrangement is housed, add stopper, catalyzer, solvent, stir, be warming up to 80 ~ 125 DEG C, react 5 ~ 15 hours, steam solvent by underpressure distillation and reclaim, obtaining the polyalkene glycol acrylates class monomer containing excess carboxylic acid class monomer;
Wherein, the mol ratio adding polyalkylene glycol mono body and carboxylic acid type monomer is: 1:1.25 ~ 4.0; Add that catalytic amount is added total monomer weight 1 ~ 10%; Adding inhibition dosage is 0.1 ~ 2.5% of total monomer weight; Add that quantity of solvent is grafted monomer gross weight 15 ~ 35%; When adopted solvent is toluene, temperature of reaction is 110 ~ 125 DEG C; When adopted solvent is hexanaphthene, temperature of reaction is 80 ~ 95 DEG C; Solvent recovering rate reaches 98 ~ 100%;
(2) synthesising graft copolymer
the preparation of monomer solution
Added water by the mixture of polyalkene glycol acrylates class monomer, carboxylic acid type monomer and olefin sulfonic acid class monomer and be made into water solution system, the concentration of monomer solution is 20 ~ 70%;
the preparation of initiator solution
Added water by persulphate and be made into initiator solution, the mass concentration of initiator solution is 0.1 ~ 4.0%;
free radical solution polymerization
The water adding total monomer weight 1.0 ~ 2.5 times in reactor is dispersion medium, stirs, is warmed up to 75 ~ 95 DEG C, adds monomer solution and initiator solution, react 4 ~ 8 hours, and cooling, obtains graft copolymer;
Wherein, initiator add-on is 0.1 ~ 5% of total monomer weight, and monomer solution dropped into completely in 0 ~ 5 hour, and initiator solution dropped into completely in 2 ~ 6 hours.
The preparation method of graft copolymer of the present invention, step (1) has polyalkylene glycol mono body described in the polymeric monomer process of reactive behavior in preparation and selects the mixture of a kind of or any mass ratio in the polyoxyethylene glycol of different molecular weight, methoxy poly (ethylene glycol); Described carboxylic acid type monomer selects one or more the mixture in vinylformic acid, methacrylic acid, methyl acrylate, methyl methacrylate.Above-mentioned different molecular weight is conventional on market, and scope is 550 ~ 2000.
The preparation method of graft copolymer of the present invention, step (1) has catalyzer described in the polymeric monomer process of reactive behavior in preparation and selects the mixture of a kind of or any mass ratio in the vitriol oil, tosic acid.
The preparation method of graft copolymer of the present invention, step (1) has stopper described in the polymeric monomer process of reactive behavior in preparation and selects the mixture of a kind of or any mass ratio in thiodiphenylamine, phenol derivatives, preferred thiodiphenylamine.
The preparation method of graft copolymer of the present invention, the mixture of a kind of or any mass ratio in toluene, hexanaphthene selected by solvent described in step (1) graft reaction.
The preparation method of graft copolymer of the present invention, polyalkene glycol acrylates class monomer described in step (2) building-up reactions selects the mixture of a kind of or any mass ratio in the polyethylene glycol monoacrylate of different molecular weight, methoxy poly (ethylene glycol) mono acrylic ester; Described carboxylic acid type monomer select one or more any mass ratioes in vinylformic acid, methacrylic acid, methyl acrylate, methyl methacrylate mixture; Described olefin sulfonic acid class monomer selects the mixture of a kind of or any mass ratio in allylsulfonate, methallyl sulfonate.Above-mentioned different molecular weight is conventional on market, and scope is 600 ~ 2100.
The preparation method of graft copolymer of the present invention, described monomer solution and initiator solution all adopt at the uniform velocity dripping method to add in reactor.
The preparation method of graft copolymer of the present invention, the polyalkene glycol acrylates class monomer selecting different molecular weight simultaneously with carboxylic acid type monomer and allyl sulphonic acid class monomer copolymerization, or only with allyl sulphonic acid class monomer copolymerization, the product of synthesis can separately or with the composite use of arbitrary proportion.
Graft copolymer of the present invention is preparing the application in carboxylate salt cement water reducing agent.
Bleed collapse protective poly-carboxylic acid salt cement water reducing agent, described water reducer is that graft copolymer adds alkali and is neutralized to PH=6.5 ~ 8, the copolymer salt solution obtained.Described alkali select strength of solution be 30% liquid caustic soda or ammoniacal liquor in one or arbitrarily than mixture.
The preparation method of bleed collapse protective poly-carboxylic acid salt cement water reducing agent of the present invention, graft copolymer adds alkali and is neutralized to PH=6.5 ~ 8, and the copolymer salt solution obtained is bleed collapse protective poly-carboxylic acid salt cement water reducing agent.
The synthesis technique of above-mentioned bleed collapse protective poly-carboxylic acid salt concrete high efficiency water reducing agent, the polyalkene glycol acrylates class monomer can selecting different molecular weight respectively or simultaneously with carboxylic acid type monomer and allyl sulphonic acid class monomer copolymerization, the product of synthesis can separately or the composite use of arbitrary proportion.
The invention has the beneficial effects as follows: the synthesis of bleed collapse protective poly-carboxylic acid salt research work of air entrained type concrete high efficiency water reducing agent of the present invention utilizes polyoxyalkylenes ethers monomer, have in the polymeric monomer process of reactive behavior in preparation and introduce double bond, copolymerization is there is in the solution again with carboxylic acid type monomer, allyl sulphonic acid class monomer, introduce long side chain, preparation technology is very simple, reaction conditions is easy to control, production process does not produce three industrial wastes, reusable edible after solvent recuperation, and solvent recovering rate reaches 98 ~ 100%, namely ensure that economic benefit, again non-environmental-pollution.
Bleed collapse protective poly-carboxylic acid salt concrete high efficiency water reducing agent of the present invention, production technique is relatively simple, easy control of reaction conditions, require lower to production unit, is a kind of polycarboxylate concrete high efficiency water reducing agent with low-dosage, large diminishing, high-thin arch dam, suitably bleed.
The solid content adopting the present invention to obtain is the bleed collapse protective poly-carboxylic acid salt concrete high efficiency water reducing agent configuration concrete of 20%, and when water reducer volume is gelling material weight 0.6% ~ 1.0%, water-reducing rate can reach more than 30%; Air content is between 3.0 ~ 6.0%, and agent on crack resistance of concrete freeze thawing ability and weather resistance significantly improve; Concrete strength is high, and slump retaining is good, basic free of losses in concrete slump 2 hours; Workability is good, and without excreting water phenomenon under normal pressure, concrete aid pumpability is good, and education resistance can be good; Alkali content is low, can avoid alkali-aggregate reaction; Chloride ion content is extremely low, to the effect of reinforcing bar non-corroding; Volume stability is good, concrete 28d almost ungauged regions; Product cement adaptability is good, is adapted to the cement of multiple different size, model; Product performance stablize, long storage periods without precipitation, not stratified.
Accompanying drawing explanation
Below with reference to accompanying drawing, the invention will be further described:
Fig. 1 is that bleed collapse protective poly-carboxylic acid salt concrete high efficiency water reducing agent prepares schematic diagram.
With reference to accompanying drawing 1, the synthesis technique of bleed collapse protective poly-carboxylic acid salt concrete high efficiency water reducing agent is:
(1) preparation has the polymeric monomer of reactive behavior: polyalkene glycol acrylates class monomer
Polyalkylene glycol mono body and carboxylic acid type monomer are joined in the reactor that condensation part flow arrangement is housed, add stopper, catalyzer, solvent, stir, be warming up to temperature of reaction, react 5 ~ 15 hours, steam solvent by underpressure distillation and reclaim, obtaining the polyalkene glycol acrylates class monomer containing excess carboxylic acid class monomer.
(2) polycarboxylate concrete high efficiency water reducing agent is synthesized
Be warmed up to 75 ~ 95 DEG C, under the condition stirred, adopt at the uniform velocity dripping method to add monomer solution and initiator solution, react 4 ~ 8 hours in reactor, cooling, adds alkali by gained multipolymer and is neutralized to PH=6.5 ~ 8, obtain copolymer salt solution.
embodiment
embodiment 1:
By molecular weight be 600 Liquid Macrogol g and methacrylic acid 45.04g join in the reactor that condensation part flow arrangement is housed, add stopper thiodiphenylamine 0.345g, catalyzer vitriol oil 3.45g, toluene 51.76g, stir, be warming up to 110 DEG C, react 9 hours, steam solvent by underpressure distillation, obtain esterification products 348.83g, be weighed as 51.32g after solvent recuperation, solvent recovering rate is 99.15%; Sodium methallyl sulfonate 47.445g and methacrylic acid 57.57g is added in esterification products, obtain 453.845g monomer, add 543.58g water and be made into the monomer solution that concentration is 50%, be made into the ammonium persulphate 0.544g accounting for total monomer weight 0.1% 21.22g that adds water the initiator solution that concentration is 2.5%; Add water 1250.58g in reactor, stir, be warming up to 75 DEG C, drip monomer solution and initiator solution simultaneously, monomer solution dropwises for 5 hours, initiator solution dropwises for 6 hours, after agent solution to be triggered dropwises, 85 DEG C of insulations 2 hours, cooling, to be cooled to 45 DEG C, adding concentration is that 30% liquid caustic soda is neutralized to PH=6.5, i.e. high-efficiency water-reducing agent of poly-carboxylic acid a.
embodiment 2:
Be the methoxy poly (ethylene glycol) 200g of 600 by molecular weight, tosic acid 5.22g, thiodiphenylamine 0.72g, vinylformic acid 85g, toluene 60g, put into reaction vessel, 115 DEG C of stirring reactions 5 hours, adopt underpressure distillation by whole for toluene go out in order to recycle, obtain 290g esterification products 1, recovery toluene is 59g, and solvent recovering rate is 98.33%; Be the methoxy poly (ethylene glycol) 540g of 2000 by molecular weight, tosic acid 11.9g, Resorcinol 0.525g, vinylformic acid 35g, toluene 150g, put into reaction vessel, 115 DEG C of stirring reactions 8 hours, adopt underpressure distillation by whole for toluene go out in order to recycle, obtain 587g esterification products 2, recovery toluene is 149g, and solvent recovering rate is 99.33%; To get esterification products 1 weight be 290g is that 105g mixes in same container for stirring with esterification products 2 weight, add 700g water and be made into the monomer solution that concentration is 36.07%, get ammonium persulphate 4.42g and add the initiator solution that 300g water is made into 1.45%, 580g water is added in reactor, be warming up to 85 DEG C, drip each 3 hours of monomer, initiator simultaneously, then 90 DEG C of insulations 2.5 hours, add concentration be 30% ammonia neutralization to PH=7.0, obtain high-efficiency water-reducing agent of poly-carboxylic acid b.
embodiment 3:
By molecular weight be 750 methoxy poly (ethylene glycol) 375g and methyl methacrylate 150g join in the reactor that condensation part flow arrangement is housed, add stopper thiodiphenylamine 13.125g, catalyzer tosic acid 52.5g, solvent hexanaphthene 131.25g, stir, be warming up to 82 DEG C, react 12 hours, steam solvent by underpressure distillation and reclaim, obtaining esterification products 574.2g, be weighed as 129g after solvent recuperation, solvent recovering rate is 98.29%; In esterification products, add 1000g water be made into the monomer solution that concentration is 36.48%, be made into the Sodium Persulfate 10.36g 410g that adds water the initiator solution that concentration is 2.46%; Add water 960g in reactor, stir, disposable input monomer solution, is then warming up to 85 DEG C, initiator solution adopts dripping method at a slow speed, within 2 hours, dropwise, after initiator dropwises, 95 DEG C of insulations 2 hours, cooling, to be cooled to 45 DEG C, adding concentration is that 30% liquid caustic soda is neutralized to PH=7.5, and namely high-efficiency water-reducing agent of poly-carboxylic acid c(performance is in table 1 and table 2).
embodiment 4:
By molecular weight be 2000 methoxy poly (ethylene glycol) 1000g and methyl acrylate 172g join in the reactor that condensation part flow arrangement is housed, add stopper thiodiphenylamine 5.86g, catalyzer vitriol oil 46.88g, solvent hexanaphthene 410.2g, stir, be warming up to 95 DEG C, react 15 hours, steam solvent by underpressure distillation and reclaim, obtaining esterification products 1208.2g, be weighed as 403.6g after solvent recuperation, solvent recovering rate is 98.39%; In esterification products, add 216.225g sodium allyl sulfonate and 86.09g methacrylic acid, add 2265g water and be made into the monomer solution that concentration is 40%, be made into the ammonium persulphate 7.92g 730g that adds water the initiator solution that concentration is 1.08%; Add water 3000g in reactor, drip monomer solution and initiator solution while stirring at 95 DEG C simultaneously, monomer solution dropwises for 3 hours, initiator solution dropwises for 3.5 hours, after initiator dropwises, 95 DEG C of insulations 0.5 hour, then lower the temperature, to be cooled to 45 DEG C, add concentration be the ammonia neutralization of 30% to PH=8, namely high-efficiency water-reducing agent of poly-carboxylic acid d(performance is in table 1 and table 2).
embodiment 5:
Be the methoxy poly (ethylene glycol) 700g of 1000 by molecular weight, vinylformic acid 200g, joins in the reactor that condensation part flow arrangement is housed, and adds stopper thiodiphenylamine 45g, catalyzer vitriol oil 18g, solvent toluene 300g, 110 DEG C of stirring reactions 8 hours, after completion of the reaction, underpressure distillation mode is adopted to steam solvent and reclaim, obtain esterification products 950g, reclaiming toluene amount is 294g, and solvent recovering rate is 98%; Esterification products is added 1000g water and be made into the monomer solution that concentration is 48.72%, take ammonium persulphate 20g, add the initiator solution that 1000g water dissolution obtains 1.96%, add water 1800g in reactor, stir, be warming up to 90 DEG C and drip monomer solution and initiator solution simultaneously, within 4 hours, dropwise, 95 DEG C of insulations 1.5 hours, cooling, to be cooled to 45 DEG C, adding concentration is that 30% liquid caustic soda is neutralized to PH=7.0, obtains high-efficiency water-reducing agent of poly-carboxylic acid e(performance in table 1 and table 2).
The concrete performance index of high efficiency water reducing agent prepared by the present invention and naphthalene water reducer mixed by table 1
The concrete performance mixing high efficiency water reducing agent prepared by the present invention and naphthalene water reducer is detected according to " concrete admixture " (GB/T8076 ~ 2008) and " concrete pump-feed agent " (JC473 ~ 2001).
The homogeneity index of high efficiency water reducing agent prepared by table 2 the present invention and naphthalene water reducer
Note: synthesizing water used is tap water; To survey naphthalene series high-efficiency water-reducing agent be that FDN(height is dense) commercially available prod.
The high efficiency water reducing agent prepared according to " Methods for testing uniformity of concrete admixture " (GB/T8077 ~ 2012) detection the present invention and the homogeneity index of naphthalene water reducer.
Claims (10)
1. a graft copolymer, is characterized in that: the structural formula of described graft copolymer is general formulae IV:
In general formulae IV: the mole ratio of a, b, c is 0 ~ 3:2 ~ 7:1 ~ 5; N represents the mole number of repeating unit, is the integer of 1 ~ 99.
2. the preparation method of graft copolymer as claimed in claim 1, is characterized in that: it carries out the obtained graft copolymer of copolyreaction by general formula I, general formula I I and general formula III three kinds of monomers,
General formula I is polyalkene glycol acrylates class monomer:
In general formula I: R
1for the alkyl of carbonatoms 1 ~ 5; R
2for the alkyl of OH, H or carbonatoms 1 ~ 10; M is the average addition mole number of oxyalkylene group, is the integer of 1 ~ 99;
General formula I I is carboxylic acid type monomer:
In general formula I I: R
3for the alkyl of H or carbonatoms 1 ~ 5; M
1for H, Na
+or carbonatoms is the alkyl of 1 ~ 4;
General formula III is olefin sulfonic acid class monomer:
In general formula III: R
4for the alkyl of H or carbonatoms 1 ~ 5; M
2for H, Na
+;
Reaction formula is as follows:
In formula: a, b, c represent the mole number of corresponding monomeric unit, a:b:c=0 ~ 3:2 ~ 7:1 ~ 5; N represents the mole number of repeating unit, is the integer of 1 ~ 99.
3. the preparation method of graft copolymer as claimed in claim 2, is characterized in that: comprise the following steps:
(1) preparation has the polymeric monomer of reactive behavior: polyalkene glycol acrylates class monomer
Polyalkylene glycol mono body and carboxylic acid type monomer are joined in the reactor that condensation part flow arrangement is housed, add stopper, catalyzer, solvent, stir, be warming up to 80 ~ 125 DEG C, react 5 ~ 15 hours, steam solvent by underpressure distillation and reclaim, obtaining the polyalkene glycol acrylates class monomer containing excess carboxylic acid class monomer;
Wherein, the mol ratio adding polyalkylene glycol mono body and carboxylic acid type monomer is: 1:1.25 ~ 4.0; Add that catalytic amount is added total monomer weight 1 ~ 10%; Adding inhibition dosage is 0.1 ~ 2.5% of total monomer weight; Add that quantity of solvent is grafted monomer gross weight 15 ~ 35%; When adopted solvent is toluene, temperature of reaction is 110 ~ 125 DEG C; When adopted solvent is hexanaphthene, temperature of reaction is 80 ~ 95 DEG C; Solvent recovering rate reaches 98 ~ 100%;
(2) synthesising graft copolymer
The preparation of monomer solution
Added water by the mixture of polyalkene glycol acrylates class monomer, carboxylic acid type monomer and olefin sulfonic acid class monomer and be made into water solution system, the concentration of monomer solution is 20 ~ 70%;
the preparation of initiator solution
Added water by persulphate and be made into initiator solution, the mass concentration of initiator solution is 0.1 ~ 4.0%;
Free radical solution polymerization
The water adding total monomer weight 1.0 ~ 2.5 times in reactor is dispersion medium, stirs, is warmed up to 75 ~ 95 DEG C, adds monomer solution and initiator solution, react 4 ~ 8 hours, and cooling, obtains graft copolymer;
Wherein, initiator add-on is 0.1 ~ 5% of total monomer weight, and monomer solution dropped into completely in 0 ~ 5 hour, and initiator solution dropped into completely in 2 ~ 6 hours.
4. the preparation method of graft copolymer according to claim 3, is characterized in that: step (1) has polyalkylene glycol mono body described in the polymeric monomer process of reactive behavior in preparation and selects the mixture of a kind of or any mass ratio in the polyoxyethylene glycol of different molecular weight, methoxy poly (ethylene glycol); Described carboxylic acid type monomer selects one or more the mixture in vinylformic acid, methacrylic acid, methyl acrylate, methyl methacrylate; The mixture of a kind of or any mass ratio in the vitriol oil, tosic acid selected by described catalyzer; The mixture of a kind of or any mass ratio in thiodiphenylamine, phenol derivatives selected by described stopper, preferred thiodiphenylamine; The mixture of a kind of or any mass ratio in toluene, hexanaphthene selected by solvent described in step (1) graft reaction.
5. the preparation method of graft copolymer according to claim 3, is characterized in that: polyalkene glycol acrylates class monomer described in step (2) building-up reactions selects the mixture of a kind of or any mass ratio in the polyethylene glycol monoacrylate of different molecular weight, methoxy poly (ethylene glycol) mono acrylic ester; Described carboxylic acid type monomer select one or more any mass ratioes in vinylformic acid, methacrylic acid, methyl acrylate, methyl methacrylate mixture; Described olefin sulfonic acid class monomer selects the mixture of a kind of or any mass ratio in allylsulfonate, methallyl sulfonate.
6. the preparation method of graft copolymer according to claim 3, is characterized in that: described monomer solution and initiator solution all adopt at the uniform velocity dripping method to add in reactor.
7. the preparation method of graft copolymer according to claim 3, it is characterized in that: the polyalkene glycol acrylates class monomer selecting different molecular weight simultaneously with carboxylic acid type monomer and allyl sulphonic acid class monomer copolymerization, or only with allyl sulphonic acid class monomer copolymerization, the product of synthesis can separately or with the composite use of arbitrary proportion.
8. graft copolymer as claimed in claim 1 is preparing the application in carboxylate salt cement water reducing agent.
9. bleed collapse protective poly-carboxylic acid salt cement water reducing agent, is characterized in that: described water reducer is that graft copolymer adds alkali and is neutralized to PH=6.5 ~ 8, the copolymer salt solution obtained.
10. the preparation method of bleed collapse protective poly-carboxylic acid salt cement water reducing agent according to claim 9, it is characterized in that: graft copolymer adds alkali and is neutralized to PH=6.5 ~ 8, the copolymer salt solution obtained is bleed collapse protective poly-carboxylic acid salt cement water reducing agent.
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| CN106749963A (en) * | 2016-11-29 | 2017-05-31 | 中建商品混凝土（福建）有限公司 | A kind of bleed controllable type poly carboxylic acid series water reducer for pure machine-made sand concrete and preparation method thereof |
| CN106749926A (en) * | 2016-11-30 | 2017-05-31 | 东北林业大学 | Improve the additive and its preparation and application of cement mortar bending and compressive strength |
| CN109134245A (en) * | 2018-10-22 | 2019-01-04 | 南京晓庄学院 | A kind of method of ester-interchange method production hydroxyethyl methacrylate |
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| CN101244907A (en) * | 2007-02-13 | 2008-08-20 | 上海申立建材有限公司 | Polycarboxylic acids series concrete high efficiency water reducing agent and synthesizing process |
| CN102173638A (en) * | 2011-01-11 | 2011-09-07 | 山西大学 | Polycarboxylate water reducer and preparation method thereof |
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| CN101244907A (en) * | 2007-02-13 | 2008-08-20 | 上海申立建材有限公司 | Polycarboxylic acids series concrete high efficiency water reducing agent and synthesizing process |
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| CN106749963A (en) * | 2016-11-29 | 2017-05-31 | 中建商品混凝土（福建）有限公司 | A kind of bleed controllable type poly carboxylic acid series water reducer for pure machine-made sand concrete and preparation method thereof |
| CN106749963B (en) * | 2016-11-29 | 2019-11-26 | 中建商品混凝土（福建）有限公司 | A kind of bleed controllable type poly carboxylic acid series water reducer and preparation method thereof for pure machine-made sand concrete |
| CN106749926A (en) * | 2016-11-30 | 2017-05-31 | 东北林业大学 | Improve the additive and its preparation and application of cement mortar bending and compressive strength |
| CN106749926B (en) * | 2016-11-30 | 2018-09-14 | 东北林业大学 | Improve the additive and its preparation and application of cement mortar bending and compressive strength |
| CN109134245A (en) * | 2018-10-22 | 2019-01-04 | 南京晓庄学院 | A kind of method of ester-interchange method production hydroxyethyl methacrylate |
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Application publication date: 20150624 |