CN110467705A - A kind of shrinkage type polycarboxylate water-reducer and preparation method thereof - Google Patents
A kind of shrinkage type polycarboxylate water-reducer and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/243—Phosphorus-containing polymers
- C04B24/246—Phosphorus-containing polymers containing polyether side chains
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/335—Polymers modified by chemical after-treatment with organic compounds containing phosphorus
- C08G65/3353—Polymers modified by chemical after-treatment with organic compounds containing phosphorus containing oxygen in addition to phosphorus
- C08G65/3355—Polymers modified by chemical after-treatment with organic compounds containing phosphorus containing oxygen in addition to phosphorus having phosphorus bound to carbon and oxygen
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- 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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- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- General Chemical & Material Sciences (AREA)
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- Structural Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to building additive technical fields, in particular to a kind of shrinkage type polycarboxylate water-reducer and preparation method thereof, wherein, the preparation method of the shrinkage type polycarboxylate water-reducer includes the following steps: for reducing function polymeric monomer to be added in reaction kettle together with water, temperature is controlled at 20~60 DEG C, it is then respectively adding initiator solution, chain-transferring agent aqueous solution and unsaturated acids reactant aqueous solution, obtain reaction product, and pH to 6.0~7.0 is adjusted to get shrinkage type polycarboxylate water-reducer is arrived by alkaline matter.There is hyperbranched reducing function segment, steric hindrance segment and adsorption group segment in shrinkage type polycarboxylate water-reducer molecule structure produced by the present invention, realize that decrement and dispersion performance are unified under low-dosage, and Shrinkage Cracking of Concrete can be prevented, to promote concrete durability.
Description
Technical field
The present invention relates to building additive technical field, in particular to a kind of shrinkage type polycarboxylate water-reducer and its preparation side
Method.
Background technique
The brittleness and contraction problem of concrete are an important factor for influencing its performance, and contraction causes inside concrete generation to be split
Seam, reduces the intensity of concrete, brings adverse effect to its durability, there is that the survey showed that, sets from traffic such as bridge, road surfaces
It is applied to coastal Processing, from civil buildings, commercial building to industrial building, the influence of problem of Cracking is extremely extensive.
Therefore reduce concrete shrinkage, the generation for controlling defect in concrete is most important to the application performance for improving concrete.
The contraction which kind of approach to reduce concrete by has become the emphasis of current engineering circles research.It often adopts both at home and abroad
With addition cement expansive material come the drying shrinkage of compensating concrete.The volume of swelling agent typically constitute from binder total amount 6%~
15%, volume is big and must carry out enough moisture-keeping maintainings to concrete.Economization agent for concrete is by reducing concrete pore
The surface tension of interior water reduces the convergent force of water evaporation process to reduce the contraction of concrete, reduces coagulation soil cracking to reach
The purpose of seam.But economization agent there are problems that influencing concrete strength and price is high, and there is presently no promote the use of a large area.It is poly-
Carboxylic acid series super plasticizer is preferably a kind of concrete admixture of comprehensive performance currently on the market, has that water-reducing rate is high, the slump
The advantages that small is lost, concrete mixture characteristic can be obviously improved, is one of hottest point project of Recent study.There is research
It points out, when water-cement ratio is 0.28, increases in 0.15%~0.23% range with poly carboxylic acid series water reducer volume, high-strength concrete
Initial cracking time delay, plastic shrinkage value are in decreasing trend.Under the conditions of guaranteeing that the mixture slump is consistent, different additives pair
Plastic Shrinkage of Concrete and crack resistance influence are more apparent, and naphthalene system, sulfamate system and fatty family water-reducing agent increase early stage
It shrinks and total contraction mixes the high-strength concrete modeling of polycarboxylate water-reducer compared with naphthalene water reducer and aminosulfonic water-reducing agent
Property shrink it is small, cracking resistance is good, but reduced amplitude is also far from enough, and Reduce shrinkage effect is difficult compared with economization agent.For
Overcome the above-mentioned problem, is very important to the research of shrinkage type poly carboxylic acid series water reducer.
Summary of the invention
To solve the problems in above-mentioned background technique, the present invention provides a kind of preparation side of shrinkage type polycarboxylate water-reducer
Method, comprising the following steps:
Reducing function polymeric monomer is added in reaction kettle together with water, temperature is controlled at 20~60 DEG C, then adds respectively
Enter initiator solution, chain-transferring agent aqueous solution and unsaturated acids reactant aqueous solution, the initiator solution, chain-transferring agent water
The addition of the solution and unsaturated acids aqueous solution preferably mode of dropwise addition is simultaneously added dropwise in completion in 1~4h, after completion of dropwise addition preferably
First carry out 1~3h of heat preservation, and then obtain reaction product, preferably control the reaction product mass concentration be 40%~
50%, and pH to 6.0~7.0 is adjusted to get shrinkage type polycarboxylate water-reducer is arrived by alkaline matter；
The structural formula of the reducing function polymeric monomer are as follows:
Wherein m=50~90, n=2 or 3.
On the basis of above scheme, it is preferable that the reducing function polymeric monomer the preparation method comprises the following steps:
Poly glycol monomethyl ether, maleic anhydride, polyphosphate, catalyst and polymerization inhibitor are added in reaction kettle, protected
It protects under conditions of gas, the protective gas is preferably nitrogen, and isothermal reaction, the isothermal reaction are carried out at 40~100 DEG C
Time is preferably 4~6h to get to reducing function polymeric monomer；
The structural formula of the polyphosphate are as follows:
Wherein n=2 or 3.
On the basis of above scheme, it is preferable that the catalyst is FeCl3·6H2O、SnCl2·2H2O、NaHSO4·
H2O、CuSO4·5H2One of O.
On the basis of above scheme, it is preferable that the polymerization inhibitor is o-tert-butylphenol or phenthazine.
On the basis of above scheme, it is preferable that the molecular weight of the poly glycol monomethyl ether is 2400~4000；It is described
Catalyst amount is the 0.3%~1.5% of poly glycol monomethyl ether quality；The polymerization inhibitor dosage is poly glycol monomethyl ether matter
The 0.3%~1.2% of amount；The molar ratio of the poly glycol monomethyl ether, polyphosphate and maleic anhydride is 1:(1~2): 1.
On the basis of above scheme, it is preferable that the polyphosphate the preparation method comprises the following steps:
Under conditions of protective gas, the protective gas is preferably nitrogen, and trimethylolpropane is added into reaction kettle,
Cooling in ice-water bath, the cooling time is preferably 0.5~1h, and triethylamine is added, adds the dichloro of dichloro etherophosphoric acid
After dichloromethane, it is warming up to 40~50 DEG C and reacts, the reaction time is preferably 12~for 24 hours；After reaction, it stands and filters again,
The time of repose is preferably 12h, collects filtrate, solvent is distilled off, obtains polyphosphate.
On the basis of above scheme, it is preferable that the trimethylolpropane is 1:1 with dichloro etherophosphoric acid molar ratio.
On the basis of above scheme, it is preferable that the initiator is redox system, including oxidant and reduction
Agent, the oxidant are one of ammonium persulfate, potassium peroxydisulfate, hydrogen peroxide, and the reducing agent is ascorbic acid, formaldehyde conjunction time
One of sodium bisulfate, Mohr's salt, sodium hypophosphite, Br ü ggolit FF6.
On the basis of above scheme, it is preferable that the unsaturated acids is acrylic acid, methacrylic acid, itaconic acid and alkene
At least one of propyl succinic acid.
On the basis of above scheme, it is preferable that the chain-transferring agent is thioacetic acid, isopropanol, sodium formate, 3- sulfydryl
The different monooctyl ester of propionic acid, lauryl mercaptan or 3- mercaptopropionic acid.
On the basis of above scheme, it is preferable that the alkaline matter is sodium hydroxide, calcium hydroxide, potassium hydroxide, oxygen
Change at least one of calcium, ammonium hydroxide and triethanolamine.
On the basis of above scheme, it is preferable that the dosage of the unsaturated acids is the 5% of reducing function polymeric monomer quality
~10%, the dosage of initiator is the 1.0%~5.0% of reducing function polymeric monomer quality, and the dosage of chain-transferring agent is decrement function
The 0.5%~1.0% of energy polymeric monomer quality.
The present invention also provides subtract prepared by the preparation method of a kind of as above any shrinkage type polycarboxylate water-reducer
Miniature polycarboxylate water-reducer.
Preparation method of the invention and use shrinkage type polycarboxylate water-reducer prepared by preparation method of the present invention have with
Lower technical principle and the utility model has the advantages that
1, the homemade reducing function polymeric monomer of the present invention has dissaving structure, has not only contained ethyoxyl but also has contained alkyl chain,
Have the function of reducing function and steric hindrance, also contains phosphate adsorption group；
2, reducing function polymeric monomer is largely introduced into polycarboxylic acids molecular structure by the present invention by copolymerization, so that polycarboxylic acids
Molecular structure has reducing function segment, steric hindrance segment and adsorption group segment, and dissaving structure overcomes straight chain economization agent easy
By the problem of concrete Adsorption Effect decrement performance, while dissaving structure has biggish steric hindrance, applies in concrete
In there is preferable dispersion performance, the phosphate adsorption group contained can further improve the dispersion performance of concrete, solves simultaneously
Certainly economization agent reduces the problem of concrete strength.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In technical solution be clearly and completely described, it is clear that described embodiments are some of the embodiments of the present invention, without
It is whole embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not before making creative work
Every other embodiment obtained is put, shall fall within the protection scope of the present invention.
The present invention also provides embodiments as follows:
Embodiment 1
(1) preparation of polyphosphate: under nitrogen protection, 10mol trimethylolpropane being added into the first reaction unit,
The cooling 1h in ice-water bath, is added 500ml triethylamine, and quickly the lower methylene chloride for instilling 100ml dichloro etherophosphoric acid of stirring is molten
Liquid (solution concentration 100mol/L), time for adding 1h are to slowly warm up to 45 DEG C of reactions for 24 hours after being added dropwise.After standing 12h
It filters, collects filtrate, solvent is distilled off, obtains polyphosphate.
(2) prepared by reducing function polymeric monomer: poly glycol monomethyl ether, 4.1g maleic acid by 100g molecular weight for 2400
Polyphosphate, 0.5g SnCl prepared by acid anhydride, 19g step (1)2·2H2O and 0.6g o-tert-butylphenol is added to the second reaction dress
In setting, under nitrogen protection, at 90 DEG C isothermal reaction 5h to get arrive reducing function polymeric monomer.
(3) preparation of shrinkage type polycarboxylate water-reducer: by reducing function polymeric monomer made from 100g step (2), 1g dioxygen
Water is added in reaction kettle together with water, controls temperature at 40 DEG C, then respectively at dropwise addition sodium formaldehyde sulphoxylate water in 3h
Solution, thioacetic acid aqueous solution and acrylic acid aqueous solution, keep the temperature 1h after completion of dropwise addition, obtain reaction product, and controlled concentration is
50%；
Reaction product sodium hydroxide adjusts pH to 6.0~7.0 to get shrinkage type polycarboxylate water-reducer is arrived.Wherein formaldehyde
Closing bisulphite sodium water solution is that 0.5g sodium formaldehyde sulphoxylate is dissolved in 150g water, and thioacetic acid aqueous solution is 0.5g mercapto
Guanidine-acetic acid is dissolved in 150g water, and acrylic acid aqueous solution is that 5g acrylic acid solution is dissolved in 180g water.
Embodiment 2
(1) preparation of polyphosphate: under nitrogen protection, 10mol trimethylolpropane being added into the first reaction unit,
The cooling 1h in ice-water bath, is added 500ml triethylamine, and quickly the lower methylene chloride for instilling 100ml dichloro etherophosphoric acid of stirring is molten
Liquid (solution concentration 100mol/L), time for adding 1h are to slowly warm up to 45 DEG C of reactions for 24 hours after being added dropwise.After standing 12h
It filters, collects filtrate, solvent is distilled off, obtains polyphosphate.
(2) prepared by reducing function polymeric monomer: poly glycol monomethyl ether, 3.3g maleic acid by 100g molecular weight for 3000
Polyphosphate, 1g NaHSO prepared by acid anhydride, 25g step (1)4·H2O and 0.8g phenthazine is added in the second reaction unit, In
Under nitrogen protection, at 100 DEG C isothermal reaction 6h to get arrive reducing function polymeric monomer.
(3) preparation of shrinkage type polycarboxylate water-reducer: by reducing function polymeric monomer made from 100g step (2), 1.5g mistake
Ammonium sulfate is added in reaction kettle together with water, control temperature at 50 DEG C, then respectively in 2h be added dropwise aqueous ascorbic acid,
3- isooctyl mercaptopropionate aqueous solution and itaconic acid aqueous solution, keep the temperature 1.5h after completion of dropwise addition, obtain reaction product, and control dense
Degree is 50%；
Reaction product potassium hydroxide adjusts pH to 6.0~7.0 to get shrinkage type polycarboxylate water-reducer is arrived.It is wherein anti-bad
Hematic acid aqueous solution is 0.4g dissolution of ascorbic acid in 150g water, and 3- isooctyl mercaptopropionate aqueous solution is 0.8g 3- sulfydryl third
The different monooctyl ester of acid is dissolved in 150g water, and itaconic acid aqueous solution is that 8g itaconic acid is dissolved in 180g water.
Embodiment 3
(1) preparation of polyphosphate: under nitrogen protection, 10mol trimethylolpropane being added into the first reaction unit,
The cooling 1h in ice-water bath, is added 500ml triethylamine, and quickly the lower methylene chloride for instilling 100ml dichloro etherophosphoric acid of stirring is molten
Liquid (solution concentration 100mol/L), time for adding 1h are to slowly warm up to 45 DEG C of reactions for 24 hours after being added dropwise.After standing 12h
It filters, collects filtrate, solvent is distilled off, obtains polyphosphate.
(2) prepared by reducing function polymeric monomer: poly glycol monomethyl ether, 2.45g maleic acid by 100g molecular weight for 4000
Polyphosphate, 1.2g FeCl prepared by acid anhydride, 15g step (1)3·6H2O and 1.0g phenthazine is added in the second reaction unit,
Under nitrogen protection, at 80 DEG C isothermal reaction 4h to get arrive reducing function polymeric monomer.
(3) preparation of shrinkage type polycarboxylate water-reducer: by reducing function polymeric monomer made from 100g step (2), 1.8g mistake
Potassium sulfate is added in reaction kettle together with water, and control temperature is then water-soluble respectively at sodium hypophosphite is added dropwise in 2.5h at 45 DEG C
Liquid, lauryl mercaptan aqueous solution and allyl succinic aqueous acid, keep the temperature 3h after completion of dropwise addition, obtain reaction product, and control
Concentration processed is 50%；
Reaction product triethanolamine adjusts pH to 6.0~7.0 to get shrinkage type polycarboxylate water-reducer is arrived.Wherein secondary phosphorus
Acid sodium aqueous solution is that 0.6g sodium hypophosphite is dissolved in 150g water, and lauryl mercaptan aqueous solution is that 0.7g lauryl mercaptan is molten
For solution in 150g water, allyl succinic aqueous acid is that 10g allyl succinic acid is dissolved in 180g water.
Comparative example
(1) prepared by polymeric monomer: poly glycol monomethyl ether, 2.45g maleic anhydride, 1.2g by 100g molecular weight for 4000
FeCl3·6H2O and 1.0g phenthazine is added in the second reaction unit, under nitrogen protection, the isothermal reaction 4h at 80 DEG C, i.e., and
Obtain reducing function polymeric monomer.
(2) preparation of polycarboxylate water-reducer: by polymeric monomer made from 100g step (1), 1.8g potassium peroxydisulfate is together with water
It is added in reaction kettle, controls temperature at 45 DEG C, then respectively at dropwise addition sodium hypophosphite aqueous solution, lauryl mercaptan in 2.5h
Aqueous solution and allyl succinic aqueous acid, keep the temperature 3h after completion of dropwise addition, obtain the reaction product that concentration is 50%；
Reaction product triethanolamine adjusts pH to 6.0~7.0 to get polycarboxylate water-reducer.Wherein sodium hypophosphite is water-soluble
Liquid is that 0.6g sodium hypophosphite is dissolved in 150g water, and lauryl mercaptan aqueous solution is that 0.7g lauryl mercaptan is dissolved in 150g
In water, allyl succinic aqueous acid is that 10g allyl succinic acid is dissolved in 180g water.
It should be noted that design parameter or some common agents in above-described embodiment, are the tool under present inventive concept
Body embodiment or preferred embodiment, rather than its limitations；Those skilled in the art, can be in present inventive concept and protection scope
It is adaptively adjusted.
By polycarboxylate water-reducer obtained by commercially available BHY-2A type economization agent for concrete, embodiment 1-3 and comparative example, using standard
Cement surveys concrete contraction percentage when other performances according to GB 8076-2008 " concrete admixture ".Acquired results such as table 1
It is shown.
1 embodiment performance comparison of table
Test result explanation, compared with comparative example, reducing function polymeric monomer is introduced polycarboxylic acids point by copolymerization by the present invention
In minor structure, so that polycarboxylic acids molecular structure has reducing function segment, steric hindrance segment and adsorption group segment, hyperbranched knot
The reducing function segment of structure declines concrete contraction percentage, while improving the dispersion performance of concrete, and the phosphate contained is inhaled
Attached group further increases the dispersion performance of concrete.Commercially available BHY-2A type economization agent for concrete can improve the decrement of concrete
Performance, but the intensity of concrete is influenced, the reducing function segment of dissaving structure of the present invention overcomes straight chain economization agent easily by coagulation
The problem of native Adsorption Effect decrement performance, further improves the decrement performance of concrete, while phosphate adsorption group can be into
One step improves concrete dispersion performance, and on concrete strength without influence.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (13)
1. a kind of preparation method of shrinkage type polycarboxylate water-reducer, which comprises the following steps:
Reducing function polymeric monomer is added in reaction kettle together with water, temperature is controlled at 20~60 DEG C, is then respectively adding and draws
Agent aqueous solution, chain-transferring agent aqueous solution and unsaturated acids reactant aqueous solution are sent out, obtains reaction product, and adjust by alkaline matter
PH to 6.0~7.0 to get arrive shrinkage type polycarboxylate water-reducer；
The structural formula of the reducing function polymeric monomer are as follows:
Wherein m=50~90, n=2 or 3.
2. the preparation method of shrinkage type polycarboxylate water-reducer according to claim 1, which is characterized in that the reducing function
Polymeric monomer the preparation method comprises the following steps:
Poly glycol monomethyl ether, maleic anhydride, polyphosphate, catalyst and polymerization inhibitor are added in reaction kettle, in protection gas
Under conditions of body, isothermal reaction is carried out at 40~100 DEG C to get reducing function polymeric monomer is arrived；
The structural formula of the polyphosphate are as follows:
Wherein n=2 or 3.
3. the preparation method of shrinkage type polycarboxylate water-reducer according to claim 2, it is characterised in that: the catalyst is
FeCl3·6H2O、SnCl2·2H2O、NaHSO4·H2O、CuSO4·5H2One of O.
4. the preparation method of shrinkage type polycarboxylate water-reducer according to claim 2, it is characterised in that: the polymerization inhibitor is
O-tert-butylphenol or phenthazine.
5. the preparation method of shrinkage type polycarboxylate water-reducer according to claim 2, it is characterised in that: the polyethylene glycol
The molecular weight of monomethyl ether is 2400~4000；The catalyst amount is the 0.3%~1.5% of poly glycol monomethyl ether quality；
The polymerization inhibitor dosage is the 0.3%~1.2% of poly glycol monomethyl ether quality；The poly glycol monomethyl ether, polyphosphate
Molar ratio with maleic anhydride is 1:(1~2): 1.
6. the preparation method of shrinkage type polycarboxylate water-reducer according to claim 2, which is characterized in that the polyphosphate
The preparation method comprises the following steps:
Under conditions of protective gas, trimethylolpropane is added into reaction kettle, it is cooling in ice-water bath, triethylamine is added,
After adding the dichloromethane solution of dichloro etherophosphoric acid, it is warming up to 40~50 DEG C and reacts；After reaction, it stands and takes out again
Filter collects filtrate, solvent is distilled off, obtains polyphosphate.
7. the preparation method of shrinkage type polycarboxylate water-reducer according to claim 6, it is characterised in that: the trihydroxy methyl
Propane and dichloro etherophosphoric acid molar ratio are 1:1.
8. the preparation method of shrinkage type polycarboxylate water-reducer according to claim 1, it is characterised in that: the initiator is
Redox system, including Oxidizing and Reducing Agents, the oxidant be one of ammonium persulfate, potassium peroxydisulfate, hydrogen peroxide,
The reducing agent is one of ascorbic acid, sodium formaldehyde sulphoxylate, Mohr's salt, sodium hypophosphite, Br ü ggolit FF6.
9. the preparation method of shrinkage type polycarboxylate water-reducer according to claim 1, it is characterised in that: the unsaturated acids
For at least one of acrylic acid, methacrylic acid, itaconic acid and allyl succinic acid.
10. the preparation method of shrinkage type polycarboxylate water-reducer according to claim 1, it is characterised in that: the chain tra nsfer
Agent is thioacetic acid, isopropanol, sodium formate, 3- isooctyl mercaptopropionate, lauryl mercaptan or 3- mercaptopropionic acid.
11. the preparation method of shrinkage type polycarboxylate water-reducer according to claim 1, it is characterised in that: the basic species
Matter is at least one of sodium hydroxide, calcium hydroxide, potassium hydroxide, calcium oxide, ammonium hydroxide and triethanolamine.
12. the preparation method of shrinkage type polycarboxylate water-reducer according to claim 1, it is characterised in that: the unsaturation
The dosage of acid is the 5%~10% of reducing function polymeric monomer quality, and the dosage of initiator is reducing function polymeric monomer quality
1.0%~5.0%, the dosage of chain-transferring agent is the 0.5%~1.0% of reducing function polymeric monomer quality.
13. prepared by a kind of preparation method of shrinkage type polycarboxylate water-reducers described in any item according to claim 1~12
Shrinkage type polycarboxylate water-reducer.
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