CN109021180A - A kind of muting sensitive sense shrinkage type polycarboxylate water-reducer and preparation method thereof - Google Patents

A kind of muting sensitive sense shrinkage type polycarboxylate water-reducer and preparation method thereof Download PDF

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CN109021180A
CN109021180A CN201810934459.7A CN201810934459A CN109021180A CN 109021180 A CN109021180 A CN 109021180A CN 201810934459 A CN201810934459 A CN 201810934459A CN 109021180 A CN109021180 A CN 109021180A
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water
carboxylic acid
unsaturated carboxylic
acid
reducer
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CN109021180B (en
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蒋卓君
郭鑫祺
官梦芹
陈晓彬
李祥河
林添兴
郭元强
麻秀星
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FUJIAN KEZIJIE NEW MATERIAL Co Ltd
Kezhijie New Material Group Co Ltd
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FUJIAN KEZIJIE NEW MATERIAL Co Ltd
Kezhijie New Material Group Co Ltd
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    • 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
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2605—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds 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
    • C04B24/2688—Copolymers containing at least three different monomers
    • C04B24/2694—Copolymers containing at least three different monomers 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
    • 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

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  • Ceramic Engineering (AREA)
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  • Health & Medical Sciences (AREA)
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Abstract

The invention discloses a kind of muting sensitive sense shrinkage type polycarboxylate water-reducer and preparation method thereof, the molecular weight of active principle is 10000~150000, and the structural formula of the active principle are as follows:

Description

A kind of muting sensitive sense shrinkage type polycarboxylate water-reducer and preparation method thereof
Technical field
The invention belongs to build additive technical field, and in particular to a kind of muting sensitive sense shrinkage type polycarboxylate water-reducer and its Preparation method.
Background technique
The characteristics of polycarboxylate water-reducer is due to its excellent water-reducing property and easy functionalized design, current China of cost The maximum water-reducing agent product of dosage.
With rapid economic development, also synchronous high-speed develops for market of real estate and infrastructure construction, a large amount of work Cheng Jianshe consumes the cement of flood tide, sandstone, exacerbates the nervous situation of sand and stone resources supply, many areas in the whole nation it is natural Sand, stone resource are increasingly deficient, and supply falls short of demand for sandstone material, cause sandstone material extremely unstable and sandstone clay content is high and unstable Fixed problem also starts to occur water-reducing rate not when polycarboxylate water-reducer is applied to the concrete produced using these materials Enough, guarantor is collapsed bad, to clay content sensitive issue.In addition, the plastic shrinkage of concrete is the master for causing concrete to generate crack Want one of reason, it would be desirable to by adding the wind for having the polycarboxylate water-reducer of Reduce shrinkage effect to reduce concrete plastic cracking Therefore danger develops that a kind of pair of material clay content is insensitive, has certain Reduce shrinkage effect, and water-reducing effect and guarantor are collapsed effect More excellent polycarboxylate water-reducer is significant.
Summary of the invention
The purpose of the present invention is to provide a kind of muting sensitive sense shrinkage type polycarboxylate water-reducers.
Another object of the present invention is to provide the preparation methods of above-mentioned muting sensitive sense shrinkage type polycarboxylate water-reducer.
Technical scheme is as follows:
A kind of muting sensitive sense shrinkage type polycarboxylate water-reducer, the molecular weight of active principle is 10000~150000, and this has Imitate the structural formula of component are as follows:
Wherein, a, b, d, e and n are integer, and a=1~30, b=4~135, d=1~75, e=1~45, n=26 ~90, R1For H or COOM, R2For H or CH3, R3For empty or 1~4 carbon alkyl, R4For empty or 1~4 carbon alkyl, R5ForR6For H or COOM, R7For H or CH3, R8For F or CF3, M H, Na, K or NH4；R3With R4The relationship of opposite place phenyl ring is ortho position, meta or para position.
The preparation method of above-mentioned muting sensitive sense shrinkage type polycarboxylate water-reducer, includes the following steps:
(1) esterification: molecular weight is mixed for 1200~4000 methoxy poly (ethylene glycol) and the first compound, in nitrogen Under gas shielded, it is warming up to 110~140 DEG C, is added the first catalyst, after 1.0~3.0h of insulation reaction, is cooled to 70~90 DEG C, Unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides, polymerization inhibitor and the second catalyst is added, continues 1.0~3.0h of insulation reaction, during which uses It vacuumizes or leads to method of the nitrogen with water and remove water, be down to room temperature after reaction, obtain containing esterification products and unreacted First mixture of unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides；The structural formula of above-mentioned first compound is
Above-mentioned first catalyst is the concentrated sulfuric acid, at least one of benzene sulfonic acid, p-methyl benzenesulfonic acid and ethylsulfonic acid, above-mentioned unsaturation Carboxylic acid or unsaturated carboxylic acid anhydrides are at least one of acrylic acid, methacrylic acid, maleic acid and maleic anhydride, above-mentioned polymerization inhibitor For 4- hydroxyl -2,2,6,6- tetramethyl piperidine -1- oxygen radicals (No. CAS is 2226-96-2) and/or 2, (the 4- t-octyl of 2- bis- Phenyl) -1- hardship diazanyl free radical (No. CAS is 84077-81-6), above-mentioned second catalyst is by mellitic acid and p-methyl benzenesulfonic acid It is composed by 0.8~1.2: 0.8~1.2 mass ratio；
(2) monomer blend: by the first mixture made from step (1) and fluorine-containing unsaturated carboxylic acid with 200: 1~8 quality Than mixing, and water is added and makes its dissolution, obtains copolymerized monomer mixture solution；Above-mentioned fluorine-containing unsaturated carboxylic acid is 2- (trifluoro Methyl) acrylic acid and/or 2- perfluoroalkyl acrylate；
(3) copolyreaction: by above-mentioned copolymerized monomer mixture solution, initiator solution and molecular weight regulator aqueous solution Instill water in reacted, reaction temperature be 10~60 DEG C, time for adding be 0.5~4.0h, after being added dropwise keep the temperature 0~ 1.0h obtains copolymerization product；
(4) neutralization reaction: copolymerization product alkali made from step (3) is adjusted into pH to 5~7 and is subtracted to get the muting sensitive sense Miniature polycarboxylate water-reducer.
In a preferred embodiment of the invention, in the step (1), the methoxy poly (ethylene glycol), first change The molar ratio for closing object and unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides is 1: 2~4: 5~10.
It is further preferred that the dosage of first catalyst is methoxy poly (ethylene glycol) and the first compound gross mass 0.3~3.0%；The polymerization inhibitor dosage is unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides 0.2~3.0%；Second catalyst Dosage be the 0.2~2.0% of unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides quality.
In a preferred embodiment of the invention, the total amount of water used in the step (2) and step (3) makes described The mass concentration of copolymerization product is 20~70%.
It is further preferred that the dosage of the initiator is the gross mass of solute in the copolymerized monomer mixture solution 0.5~3.0%, the dosage of the molecular weight regulator is 0.2 of the gross mass of solute in the copolymerized monomer mixture solution ~2.0%.
In a preferred embodiment of the invention, the initiator is that water soluble, redox causes system or water-soluble Property azo initiator.
In a preferred embodiment of the invention, the molecular weight regulator is thioacetic acid, mercaptopropionic acid, sulfydryl At least one of ethyl alcohol, isopropanol, sodium hypophosphite and tertiary sodium phosphate.
The beneficial effects of the present invention are:
1, muting sensitive sense shrinkage type polycarboxylate water-reducer of the invention is rigid due to introducing in branch and main chain junction Benzene ring structure, so that the conformation of muting sensitive sense shrinkage type polycarboxylate water-reducer in the solution is more unfolded, molecular dimension is larger, no The poly- carboxylic of muting sensitive sense shrinkage type that its water-reducing property is easily weakened by the clay adsorption with layer structure to interlayer, therefore is obtained Sour water-reducing agent has the characteristic low to clay content sensibility.
2, muting sensitive sense shrinkage type polycarboxylate water-reducer of the invention in main chain due to introducing the side with benzene ring structure Base, steric hindrance is larger, so that the muting sensitive sense shrinkage type polycarboxylate water-reducer has excellent water-reducing effect.
3, muting sensitive sense shrinkage type polycarboxylate water-reducer of the invention can be in concrete alkalinity due to having in molecular structure Under the conditions of hydrolysis release the ester group structure of the carboxylic acid group with water-reducing effect so that the muting sensitive sense shrinkage type polycarboxylic acids diminishing Agent protects effect of collapsing with outstanding.
4, muting sensitive sense shrinkage type polycarboxylate water-reducer of the invention due to introducing fluorine carbon structure in the molecular structure, by it When applied to concrete, more conventional carbon carbon structure, the effect for reducing solution surface tension is become apparent from, so that the muting sensitive sense is reduced Type polycarboxylate water-reducer has the effect of significantly reducing concrete shrinkage.
Specific embodiment
Technical solution of the present invention is further explained and described below by way of specific embodiment.
The molecular weight of the effective component of muting sensitive sense shrinkage type polycarboxylate water-reducer obtained by following embodiments be 10000~ 150000, and the structural formula of the effective component is as follows:
Wherein, a, b, d, e and n are integer, and a=1~30, b=4~135, d=1~75, e=1~45, n=26 ~90, R1For H or COOM, R2For H or CH3, R3For empty or 1~4 carbon alkyl, R4For empty or 1~4 carbon alkyl, R5ForR6For H or COOM, R7For H or CH3, R8For F or CF3, M H, Na, K or NH4；R3With R4The relationship of opposite place phenyl ring is ortho position, meta or para position.
Embodiment 1
(1) esterification: the methoxy poly (ethylene glycol) and 27.00g P-hydroxybenzoic acid for being 1200 by 120.00g molecular weight Mixing is warming up to 110 DEG C under nitrogen protection, and 1.60g p-methyl benzenesulfonic acid is added, and insulation reaction 1.0h is cooled to 70 DEG C, adds Enter 60.00g acrylic acid, 1.25g4- hydroxyl -2,2, the second catalyst of 6,6- tetramethyl piperidine -1- oxygen radicals and 0.50g is protected Temperature reaction 2.0h, during which removes water with the method with water of vacuumizing, is down to room temperature after reaction, obtain containing esterification products with First mixture of unreacted acrylic acid；
(2) monomer blend: by the first mixture made from 200.00g step (1) and 2.00g2- (trifluoromethyl) acrylic acid Mixing, and 100.00g water is added and makes its dissolution, obtain copolymerized monomer mixture solution；
(3) copolyreaction: by above-mentioned copolymerized monomer mixture solution, aqueous hydrogen peroxide solution (wherein hydrogen peroxide 0.90g, water 20.00g), aqueous ascorbic acid (wherein 0.30g, water 20.00g) and thioacetic acid aqueous solution (wherein thioacetic acid 0.70g, Water 20.00g) it instills in 140.00g water and is reacted, reaction temperature is 55 DEG C, and time for adding 2.5h is kept the temperature after being added dropwise 0.5h obtains copolymerization product；
(4) alkali of copolymerization product made from step (3) neutralization reaction: is adjusted into pH to 5~7 to get a kind of muting sensitive Feel shrinkage type polycarboxylate water-reducer PCE-1.
Embodiment 2
(1) esterification: by 200.00g molecular weight be 2000 methoxy poly (ethylene glycol) and 35.00g to methylol benzene first Acid-mixed is closed, and under nitrogen protection, is warming up to 120 DEG C, and 2.80g benzene sulfonic acid is added, and insulation reaction 1.5h is cooled to 80 DEG C, is added 60.00g methacrylic acid, 0.90g 2,2- bis- (4- t-octyl phenyl) second catalyst of -1- hardship diazanyl free radical and 0.8g are protected Temperature reaction 3.0h, during which the method with logical nitrogen with water removes water, is down to room temperature after reaction, obtain containing esterification products with First mixture of unreacted methacrylic acid；
(2) monomer blend: the first mixture made from 200.00g step (1) and 3.00g2- perfluoroalkyl acrylate are mixed, and 100.00g water is added and makes its dissolution, obtains copolymerized monomer mixture solution；
(3) copolyreaction: (wherein by above-mentioned copolymerized monomer mixture solution, azo diisobutyl amidine hydrochloric acid saline solution Azo diisobutyl amidine hydrochloride 2.20g, water 30.00g) and sodium hypophosphite aqueous solution (wherein sodium hypophosphite 1.80g, water It 30.00g) instills in 40.00g water and is reacted, reaction temperature is 45 DEG C, and time for adding 2.0h is kept the temperature after being added dropwise 0.5h obtains copolymerization product；
(4) neutralization reaction: copolymerization product alkali made from step (4) is adjusted into pH to 5~7 and is subtracted to get the muting sensitive sense Miniature polycarboxylate water-reducer PCE-2.
Embodiment 3
(1) esterification: the methoxy poly (ethylene glycol) and 40.00g p-hydroxybenzenyl sulfonate for being 2400 by 240.00g molecular weight Mixing is warming up to 125 DEG C under nitrogen protection, and 6.80g p-methyl benzenesulfonic acid is added, and insulation reaction 2.0h is cooled to 75 DEG C, adds Enter 35.00g maleic acid, 25.00g acrylic acid, 0.60g4- hydroxyl -2,2,6,6- tetramethyl piperidine -1- oxygen radicals and 1.00g Second catalyst, insulation reaction 1.5h are down to room temperature after reaction, obtain during which with the method removing water vacuumized with water The first mixture containing esterification products and unreacted maleic acid and unreacted acrylic acid；
(2) monomer blend: by the first mixture made from 200.00g step (1) and 4.00g2- (trifluoromethyl) acrylic acid Mixing, and 100.00g water is added and makes its dissolution, obtain copolymerized monomer mixture solution；
(3) copolyreaction: by above-mentioned copolymerized monomer mixture solution, azo dicyano valeric acid aqueous solution (wherein azo two Cyanopentanoic acid 2.20g, water 30.00g) and trisodium phosphate aqueous solution (wherein tertiary sodium phosphate 3.20g, water 30.00g) instillation It is reacted in 140.00g water, reaction temperature is 50 DEG C, and time for adding 1.5h keeps the temperature 1.0h after being added dropwise, and must be copolymerized production Object；
(4) neutralization reaction: copolymerization product alkali made from step (4) is adjusted into pH to 5~7 and is subtracted to get the muting sensitive sense Miniature polycarboxylate water-reducer PCE-3.
Embodiment 4
(1) esterification: the methoxy poly (ethylene glycol) and 45.00g p-hydroxyphenylaceticacid for being 3000 by 300.00g molecular weight Mixing is warming up to 130 DEG C under nitrogen protection, and 6.00g ethylsulfonic acid is added, and insulation reaction 2.5h is cooled to 85 DEG C, is added 30.00g maleic anhydride, 30.00g acrylic acid, 0.90g 2, (4- t-octyl the phenyl) -1- hardship diazanyl free radical of 2- bis- and 0.70g During which second catalyst, insulation reaction 2.5h remove water with logical method of the nitrogen with water, are down to room temperature after reaction, obtain The first mixture containing esterification products and unreacted maleic anhydride and unreacted acrylic acid；
(2) monomer blend: by the first mixture made from 200.00g step (1), 2.00g2- (trifluoromethyl) acrylic acid It is mixed with 2.00g2- perfluoroalkyl acrylate, and 100.00g water is added and makes its dissolution, obtain copolymerized monomer mixture solution；
(3) copolyreaction: by above-mentioned copolymerized monomer mixture solution, aqueous hydrogen peroxide solution (wherein, hydrogen peroxide 2.00g, water 20.00g), trisodium phosphate aqueous solution (wherein, tertiary sodium phosphate 1.00g, water 20.00g), aqueous ascorbic acid are (wherein, anti-bad Hematic acid 0.20, water 20.00g) it instills in 240.00g water and is reacted, reaction temperature is 35 DEG C, time for adding 2.0h, is added dropwise After keep the temperature 1.0h, obtain copolymerization product；
(4) neutralization reaction: copolymerization product alkali made from step (4) is adjusted into pH to 5~7 and is subtracted to get the muting sensitive sense Miniature polycarboxylate water-reducer PCE-4.
Embodiment 5
(1) esterification: by 400.00g molecular weight be 4000 methoxy poly (ethylene glycol) and 50.00g to methylol benzene sulphur Acid-mixed is closed, and under nitrogen protection, is warming up to 140 DEG C, and the 9.00g concentrated sulfuric acid is added, and insulation reaction 3.0h is cooled to 90 DEG C, is added 60.00g acrylic acid, 0.90g4- hydroxyl -2,2, the second catalyst of 6,6- tetramethyl piperidine -1- oxygen radicals and 1.10g, heat preservation 1.0h is reacted, during which water is removed with the method with water of vacuumizing, is down to room temperature after reaction, is obtained containing esterification products and not First mixture of the acrylic acid of reaction；
(2) monomer blend: by the first mixture made from 200.00g step (1) and 6.00g2- (trifluoromethyl) acrylic acid Mixing, and 100.00g water is added and makes its dissolution, obtain copolymerized monomer mixture solution；
(3) copolyreaction: by above-mentioned copolymerized monomer mixture solution, azo dicyano valeric acid aqueous solution (wherein, azo two Cyanopentanoic acid 3.80g, water 30.00g), sodium hypophosphite aqueous solution (wherein, sodium hypophosphite 2.20g, water 30.00g) instill 40.00g It is reacted in water, reaction temperature is 40 DEG C, and time for adding 3.0h keeps the temperature 0.5h after being added dropwise, obtains copolymerization product；
(4) neutralization reaction: copolymerization product alkali made from step (4) is adjusted into pH to 5~7 and is subtracted to get the muting sensitive sense Miniature polycarboxylate water-reducer PCE-5.
According to GB/T8076-2008 to embodiment 1 to muting sensitive sense shrinkage type polycarboxylate water-reducer obtained by embodiment 5 into Row test is rolled over when solid volume is 0.20% (relative to cement consumption), and it is big that water-reducing rate is above 40%, 28d compressive strength rate 90% is respectively less than in 150%, 28d shrinkage ratio.
Using 42.5 ordinary portland cement of Fujian good fortune P.O, concrete mix are as follows: cement 300kg/m3, flyash 100kg/m3, miberal powder 100kg/m3, sand 690kg/m3, stone 1050kg/m3, water 160kg/m3, and add 4.0% (phase of bentonite For cement consumption), to muting sensitive sense shrinkage type polycarboxylate water-reducer and commercially available high water reduction obtained by embodiment 1 to embodiment 5 Polycarboxylate water-reducer (PCE) is tested for the property according to solid volume 0.16% is rolled over.Test concrete initial slump and divergence, The test result of the 2h slump and divergence, different additives is as shown in table 1.
The different additive test results of table 1
As it can be seen from table 1 it is poly- that the embodiment that the present invention synthesizes compares commercially available high water reduction to mixed with bentonitic material Carboxylic acid water reducer (PCE), water-reducing rate is bigger, and function of slump protection is more preferable, it can be seen that the poly- carboxylic of muting sensitive sense shrinkage type prepared by the present invention Sour water-reducing agent is relatively low to the material sensitivity that clay content is high.
Those of ordinary skill in the art still are able to it is found that when technical solution of the present invention changes in following ranges To same as the previously described embodiments or similar technical effect, protection scope of the present invention is still fallen within:
A kind of muting sensitive sense shrinkage type polycarboxylate water-reducer, the molecular weight of active principle is 10000~150000, and this has Imitate the structural formula of component are as follows:
Wherein, a, b, d, e and n are integer, and a=1~30, b=4~135, d=1~75, e=1~45, n=26 ~90, R1For H or COOM, R2For H or CH3, R3For empty or 1~4 carbon alkyl, R4For empty or 1~4 carbon alkyl, R5ForR6For H or COOM, R7For H or CH3, R8For F or CF3, M H, Na, K or NH4；R3With R4The relationship of opposite place phenyl ring is ortho position, meta or para position.
The preparation method of above-mentioned muting sensitive sense shrinkage type polycarboxylate water-reducer, includes the following steps:
(1) esterification: molecular weight is mixed for 1200~4000 methoxy poly (ethylene glycol) and the first compound, in nitrogen Under gas shielded, it is warming up to 110~140 DEG C, is added the first catalyst, after 1.0~3.0h of insulation reaction, is cooled to 70~90 DEG C, Unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides, polymerization inhibitor and the second catalyst is added, continues 1.0~3.0h of insulation reaction, during which uses It vacuumizes or leads to method of the nitrogen with water and remove water, be down to room temperature after reaction, obtain containing esterification products and unreacted First mixture of unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides；The structural formula of above-mentioned first compound the following is
Above-mentioned first catalyst is the concentrated sulfuric acid, at least one of benzene sulfonic acid, p-methyl benzenesulfonic acid and ethylsulfonic acid, above-mentioned unsaturation Carboxylic acid or unsaturated carboxylic acid anhydrides are at least one of acrylic acid, methacrylic acid, maleic acid and maleic anhydride, above-mentioned polymerization inhibitor For 4- hydroxyl -2,2,6,6- tetramethyl piperidine -1- oxygen radicals and/or 2, (4- t-octyl the phenyl) -1- hardship of 2- bis- diazanyl freedom Base, above-mentioned second catalyst are composed of mellitic acid and p-methyl benzenesulfonic acid by 0.8~1.2: 0.8~1.2 mass ratio；
(2) monomer blend: by the first mixture made from step (1) and fluorine-containing unsaturated carboxylic acid with 200: 1~8 quality Than mixing, and water is added and makes its dissolution, obtains copolymerized monomer mixture solution；Above-mentioned fluorine-containing unsaturated carboxylic acid is 2- (trifluoro Methyl) acrylic acid and/or 2- perfluoroalkyl acrylate；
(3) copolyreaction: by above-mentioned copolymerized monomer mixture solution, initiator solution and molecular weight regulator aqueous solution Instill water in reacted, reaction temperature be 10~60 DEG C, time for adding be 0.5~4.0h, after being added dropwise keep the temperature 0~ 1.0h obtains copolymerization product；
(4) neutralization reaction: copolymerization product alkali made from step (3) is adjusted into pH to 5~7 and is subtracted to get the muting sensitive sense Miniature polycarboxylate water-reducer.
In the step (1), the methoxy poly (ethylene glycol), the first compound and unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides Molar ratio be 1: 2~4: 5~10.The dosage of first catalyst is methoxy poly (ethylene glycol) and the first compound gross mass 0.3~3.0%；The polymerization inhibitor dosage is unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides 0.2~3.0%；Second catalysis The dosage of agent is the 0.2~2.0% of unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides quality.
The total amount of water used in the step (2) and step (3) makes the mass concentration of the copolymerization product be 20~70%. The dosage of the initiator is 0.5~3.0% of the gross mass of solute in the copolymerized monomer mixture solution, the molecular weight The dosage of regulator is 0.2~2.0% of the gross mass of solute in the copolymerized monomer mixture solution.
The initiator is that water soluble, redox causes system or water-soluble azo initiator.The molecular weight regulator For at least one of thioacetic acid, mercaptopropionic acid, mercaptoethanol, isopropanol, sodium hypophosphite and tertiary sodium phosphate.
The foregoing is only a preferred embodiment of the present invention, the range that the present invention that therefore, it cannot be limited according to is implemented, i.e., Equivalent changes and modifications made in accordance with the scope of the invention and the contents of the specification should still be within the scope of the present invention.

Claims (8)

1. a kind of muting sensitive sense shrinkage type polycarboxylate water-reducer, it is characterised in that: the molecular weight of its active principle be 10000~ 150000, and the structural formula of the active principle are as follows:
Wherein, a, b, d, e and n are integer, and a=1~30, b=4~135, d=1~75, e=1~45, n=26~90, R1For H or COOM, R2For H or CH3, R3For empty or 1~4 carbon alkyl, R4For empty or 1~4 carbon alkyl, R5ForR6For H or COOM, R7For H or CH3, R8For F or CF3, M H, Na, K or NH4；R3With R4The relationship of opposite place phenyl ring is ortho position, meta or para position.
2. the preparation method of muting sensitive sense shrinkage type polycarboxylate water-reducer described in claim 1, it is characterised in that: including walking as follows It is rapid:
(1) esterification: molecular weight is mixed for 1200~4000 methoxy poly (ethylene glycol) and the first compound, is protected in nitrogen Under shield, it is warming up to 110~140 DEG C, is added the first catalyst, after 1.0~3.0h of insulation reaction, is cooled to 70~90 DEG C, is added Unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides, polymerization inhibitor and the second catalyst continue 1.0~3.0h of insulation reaction, during which true with taking out Method of the empty or logical nitrogen with water removes water, is down to room temperature after reaction, obtains containing esterification products and unreacted insatiable hunger With the first mixture of carboxylic acid or unsaturated carboxylic acid anhydrides；The structural formula of above-mentioned first compound isAbove-mentioned first catalyst is the concentrated sulfuric acid, benzene sulfonic acid, p-methyl benzenesulfonic acid At least one of with ethylsulfonic acid, above-mentioned unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides are acrylic acid, methacrylic acid, maleic acid At least one of with maleic anhydride, above-mentioned polymerization inhibitor is 4- hydroxyl -2,2,6,6- tetramethyl piperidine -1- oxygen radicals and/or 2,2- bis- (4- t-octyl phenyl) -1- hardship diazanyl free radicals, above-mentioned second catalyst press 0.8 by mellitic acid and p-methyl benzenesulfonic acid ~1.2: 0.8~1.2 mass ratio is composed；
(2) monomer blend: the first mixture made from step (1) and fluorine-containing unsaturated carboxylic acid is mixed with 200: 1~8 mass ratio It closes, and water is added and makes its dissolution, obtain copolymerized monomer mixture solution；Above-mentioned fluorine-containing unsaturated carboxylic acid is 2- (trifluoromethyl) Acrylic acid and/or 2- perfluoroalkyl acrylate；
(3) copolyreaction: above-mentioned copolymerized monomer mixture solution, initiator solution and molecular weight regulator aqueous solution are instilled It is reacted in water, reaction temperature is 10~60 DEG C, and time for adding is 0.5~4.0h, and 0~1.0h is kept the temperature after being added dropwise, is obtained Copolymerization product；
(4) alkali of copolymerization product made from step (3) neutralization reaction: is adjusted into pH to 5~7 to get the muting sensitive sense shrinkage type Polycarboxylate water-reducer.
3. preparation method as claimed in claim 2, it is characterised in that: in the step (1), the methoxy poly (ethylene glycol), The molar ratio of first compound and unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides is 1: 2~4: 5~10.
4. preparation method as claimed in claim 3, it is characterised in that: the dosage of first catalyst is the poly- second two of methoxyl group The 0.3~3.0% of pure and mild first compound gross mass；The polymerization inhibitor dosage is unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides 0.2 ~3.0%；The dosage of second catalyst is the 0.2~2.0% of unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides quality.
5. preparation method as claimed in claim 2, it is characterised in that: the total amount of water used in the step (2) and step (3) makes The mass concentration for obtaining the copolymerization product is 20~70%.
6. preparation method as claimed in claim 5, it is characterised in that: the dosage of the initiator is comonomer mixing The 0.5~3.0% of the gross mass of solute in object solution, the dosage of the molecular weight regulator are that the copolymerized monomer mixture is molten The 0.2~2.0% of the gross mass of solute in liquid.
7. the preparation method as described in any claim in claim 2 to 6, it is characterised in that: the initiator is water-soluble Property redox initiation system or water-soluble azo initiator.
8. the preparation method as described in any claim in claim 2 to 6, it is characterised in that: the molecular weight regulator For at least one of thioacetic acid, mercaptopropionic acid, mercaptoethanol, isopropanol, sodium hypophosphite and tertiary sodium phosphate.
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