CN106674531B - A kind of modified cyclodextrin self assembly type polycarboxylate water-reducer and preparation method thereof - Google Patents
A kind of modified cyclodextrin self assembly type polycarboxylate water-reducer and preparation method thereof Download PDFInfo
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- CN106674531B CN106674531B CN201710038165.1A CN201710038165A CN106674531B CN 106674531 B CN106674531 B CN 106674531B CN 201710038165 A CN201710038165 A CN 201710038165A CN 106674531 B CN106674531 B CN 106674531B
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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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
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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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
- 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
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Abstract
The present invention provides a kind of modified cyclodextrin self assembly type polycarboxylate water-reducers and preparation method thereof, modified cyclodextrin is dissolved in deionized water first, the lipophilic minor comonomer containing unsaturated double-bond is added, 1~3h is stirred at room temperature, adds polyethers or polyester macromonomer, is warming up to 40~80 DEG C, the mixed aqueous solution of the aqueous solution of dropwise addition unsaturated carboxylic acid monomer, initiator and chain tra nsfer respectively, time for adding is 2~4h, and 1~2h is kept the temperature after being added dropwise, is then cooled to 30~50 DEG C；It is eventually adding aqueous slkali and adjusts pH value to 6~8, obtain modified cyclodextrin self assembly type polycarboxylate water-reducer.The present invention solves deficiency in the prior art, and the water-reducing agent preparation method is simple, and product can improve the workability of concrete, substantially increases the adaptability with concrete.
Description
Technical field
The present invention relates to technical field of concrete, in particular to a kind of modified cyclodextrin self assembly type polycarboxylate water-reducer and
Preparation method.
Background technique
Polycarboxylate water-reducer is since low with volume, water-reducing rate is high, slump retaining is good, shrinking percentage is low, volume stability is good, work
Skill simple environmentally protective, the advantages that being easily industrialized, it has also become the research hotspot of domestic and international industry.Its molecular structure can
Design is strong, and the potentiality of high performance are big, can prepare the poly- of multifunction by selecting the monomer of different function to be copolymerized
Carboxylic acid water reducer.However, in recent years, large quantities of heavy constructions, Line for Passenger Transportation, the construction of hydraulic and hydroelectric engineering and real estate
The rise of industry causes concrete raw material in short supply, thereby results in the quality such as cement, mineral blend, coarse aggregate, fine aggregate
Problem is serious, and along with China's cement type is various, Engineering Mixed Proportions are varied, often will cause polycarboxylate water-reducer and mixes
Solidifying soil is incompatible, and fresh concrete bleeding easily occurs, isolates, collapses and damage the problems such as too fast.
Cyclodextrin is a series of general name of cyclic oligosaccharides, usually contains 6~12 D- glucopyranose units, each grape
Sugar unit combines cyclization with Isosorbide-5-Nitrae-glycosidic bond, tapers slightly annular shape.Its outer rim is hydrophilic and inner cavity is hydrophobic, can be according to Van der Waals
Power, hydrophobic interaction power, the intermolecular matching effect of Subjective and Objective etc. form inclusion compound with many organic and inorganic molecule and divide
Sub- assembly system.Polycarboxylate water-reducer through cyclodextrin functional modification has the advantages that high-thin arch dam, high water conservation and micro- enhancing, with
Different cement and mineral admixture, sand material inferior etc. have good adaptability, and market application prospect is wide, has caused both at home and abroad
The extensive concern of the numerous scholars of polycarboxylic acids industry.
103819637 A of patent CN is esterified using beta-cyclodextrin and lignin with maleic anhydride, and maleic acid is obtained
Acid anhydride-beta-cyclodextrin-lignin esterification products, and by its with allyl polyglycol, acrylic acid and potassium peroxydisulfate in 60-100
Aqueous free radical polymerization is carried out at a temperature of DEG C, is prepared for a kind of poly carboxylic acid series water reducer containing beta-cyclodextrin and lignin.
104817663 A of patent CN provides a kind of functional monomer containing beta-cyclodextrin, with beta-cyclodextrin, to first
Base benzene sulfonyl chloride, hydramine and ethylene oxidic ester are raw material, by selective sulfonylation, hydramine substitution reaction and epoxy addition
Reaction, has synthesized a kind of modified beta-cyclodextrin function monomer, has utilized the monomer and acrylic acid, methylpropene sodium sulfonate and isobutene
Alcohol polyoxyethylene ether etc. carries out Raolical polymerizable using redox initiation system, is prepared for a kind of side chain and contains β-ring
The polycarboxylate water-reducer of dextrin.
105778023 A of patent CN is esterified by the sulfonated products of alpha-cyclodextrin or beta-cyclodextrin and maleic anhydride,
Obtain sulfated cyclodextrins maleate, and by itself and polyethylene glycol monomethyl ethermethacrylic acid esters, 2- methallyl alcohol polyoxy second
Alkene ether, acrylic acid and ammonium persulfate react at a temperature of 85~95 DEG C, are prepared for a kind of sulfated cyclodextrins polycarboxylate water-reducer.
Although being successfully prepared the polycarboxylate water-reducer that side chain contains cyclodextrin by the studies above, preparation method compared with
For complexity, comprising: esterification, sulfonylation, hydramine replaces and the chemical reaction of the Various Complexes such as epoxy addition and free radical polymerization, it is difficult to
Meet safety in production and energy-saving and environment-friendly requirement, product quality is also difficult to ensure, and economic cost is high.
Summary of the invention
The present invention provides a kind of modified cyclodextrin self assembly type polycarboxylate water-reducers, solve in above-mentioned background technique
Deficiency, the water-reducing agent preparation method is simple, improves the workability of concrete, substantially increases the adaptability with concrete.
Realize technical solution used by above-mentioned purpose of the present invention are as follows:
A kind of modified cyclodextrin self assembly type polycarboxylate water-reducer, general structure are as follows:
Wherein: R1For-H ,-COOH or-CH2COOH；R2For-H or-CH3；R3For-H or-CH3；R4For/(i.e. C atom is direct
With R5It is connected) or-COO-；R5For phenyl ,-CH2CH2CH3、-(CH2)3CH3Or-(CH2)4CH3；R6For ethoxy or hydroxypropyl；R7
For-H or-CH3；R8For-CH2-、-CH2CH2Or-CO-；R9For-H or-CH3；X, Y, Z and n are positive integer, X=50~150,
Y=5~20, Z=10~50, n=45~76.
The present invention additionally provides the method for preparing above-mentioned modified cyclodextrin self assembly type polycarboxylate water-reducer simultaneously, including with
Lower step: modified cyclodextrin is dissolved in deionized water, and the lipophilic minor comonomer containing unsaturated double-bond is added, stirs at room temperature
Mix 1~3h, add polyethers or polyester macromonomer, be warming up to 40~80 DEG C, respectively be added dropwise unsaturated carboxylic acid monomer aqueous solution,
The mixed aqueous solution of initiator and chain tra nsfer, time for adding are 2~4h, and 1~2h is kept the temperature after being added dropwise, then it is cooled to 30~
50℃；It is eventually adding aqueous slkali and adjusts pH value to 6~8, obtain modified cyclodextrin self assembly type polycarboxylate water-reducer；
The wherein modified cyclodextrin, lipophilic minor comonomer, polyethers or polyester macromonomer, unsaturated carboxylic acid monomer, initiation
The molar ratio of agent and chain-transferring agent is (0.1~0.7): (0.1~0.7): 1:(3.5~7): (0.05~0.35): (0.05~
0.25)。
Preferably, the modified cyclodextrin is one of hydroxyethyl-β-cyclodextrin or hydroxypropyl-β-cyclodextrin.
Preferably, the lipophilic minor comonomer is styrene, n-propyl, n-butyl acrylate, acrylic acid positive penta
One of ester, n propyl methacrylate, n-BMA, n-amylmethacrylate.
Preferably, the polyethers or polyester macromonomer are allyl polyethenoxy base of the molecular weight between 2000~3500
Ether, methacrylic polyoxyethylene ether, prenol polyoxyethylene ether, polyalkylene glycol acrylate monomethyl ether ester, methyl-prop
One of olefin(e) acid poly glycol monomethyl ether ester.
Preferably, the unsaturated carboxylic acid monomer is acrylic acid, methacrylic acid, maleic anhydride, fumaric acid and itaconic acid
One or more of.
Preferably, the initiator is hydrogen peroxide-ascorbic acid, hydrogen peroxide-sodium formaldehyde sulfoxylate, hydrogen peroxide-sodium hypophosphite, mistake
One of ammonium sulfate-ascorbic acid, ammonium persulfate-sodium sulfite, ammonium persulfate-sodium bisulfite.
Preferably, the chain-transferring agent is thioacetic acid, mercaptopropionic acid, mercaptoethanol, n- dodecyl mereaptan, metering system sulphur
One of sour sodium.
Compared with prior art, beneficial effects of the present invention are as follows:
(1) the modification beta-cyclodextrin structure having on polycarboxylate water-reducer molecule side chain provided by the invention is modified β-ring
What the hydrophobic internal cavities of dextrin and the straight chained alkyl in lipophilicity minor comonomer or phenyl were formed by hydrophobic interaction self assembly,
It is more simple and easy to get compared to the maleic anhydride esterification method of cyclodextrin or other chemic modified methods.
(2) the modified beta-cyclodextrin structure of the self assembly type on polycarboxylate water-reducer molecule side chain disclosed by the invention is different from
The structure of chemical bonding, the structure have environment-responsive, can slough different proportion in the environment of different type concrete
Modified beta-cyclodextrin molecule, and lipophilic group is released, the hydrophilic lipophilic balance of polycarboxylate water-reducer is voluntarily adjusted, is changed
The workability of kind concrete, substantially increases the adaptability with concrete.
(3) ester group in polycarboxylate water-reducer molecule side chain disclosed by the invention can be sent out under the strong alkali environment of concrete
Unboiled water solution, releases carboxyl, continues to play the role of absorption, dispersion, and the modification beta-cyclodextrin molecule released in addition has
Certain water retention, the guarantor for greatly improving the polycarboxylate water-reducer are collapsed ability.
(4) preparation method of polycarboxylate water-reducer disclosed by the invention uses numerator self-assembly technique, solves oleophylic
Property minor comonomer can not participate in the problem of aqueous free radical polymerization, and compared with the preparation method of similar product, the technique is more
It is safe and simple, environmentally protective, low energy consumption, at low cost, be suitble to industrial scale production.
Specific embodiment
Below with reference to specific embodiment, the present invention will be further described.
Embodiment 1
0.15mol hydroxypropyl-β-cyclodextrin is dissolved in deionized water, 0.15mol n-butyl acrylate is added, in room temperature
Lower stirring 1.0h is added the methacrylic polyoxyethylene ether that 1.0mol molecular weight is 2000, is warming up to 40 DEG C, is added
The aqueous solution, ascorbic acid containing 0.016mol and 0.056mol mercapto of the acrylic acid containing 3.7mol is added dropwise in 0.055mol hydrogen peroxide respectively
The mixed aqueous solution of guanidine-acetic acid, time for adding are respectively 2h and 2.5h, and 1.0h is kept the temperature after being added dropwise, is then cooled to 30 DEG C,
The liquid alkaline and water of mass fraction 30% is added, adjusting pH value is 6~8, obtains the modification ring paste that product is mass fraction 40%
Smart self assembly type polycarboxylate water-reducer PC-Z1.
Embodiment 2
0.15mol hydroxyethyl-β-cyclodextrin is dissolved in deionized water, 0.15mol n-propyl is added, in room temperature
Lower stirring 1.0h is added the polyalkylene glycol acrylate monomethyl ether ester that 1.0mol molecular weight is 2000, is warming up to 60 DEG C, is added
The aqueous solution of acrylic acid containing 2.5mol and 1.2mol methacrylic acid is added dropwise respectively, hangs containing 0.015mol for 0.069mol hydrogen peroxide
The mixed aqueous solution of white piece and 0.07mol mercaptopropionic acid, time for adding is respectively 2.5h and 3.0h, is kept the temperature after being added dropwise
Then 1.0h is cooled to 50 DEG C, the liquid alkaline and water of mass fraction 30% is added, and adjusting pH value is 6~8, and obtaining product is matter
Measure the modified cyclodextrin self assembly type polycarboxylate water-reducer PC-Z2 of score 40%.
Embodiment 3
0.15mol hydroxyethyl-β-cyclodextrin is dissolved in deionized water, 0.15mol n propyl methacrylate is added,
1.0h is stirred at room temperature, and the Methylacrylic acid polyethylene glycol single armor ether ester that 1.0mol molecular weight is 2000 is added, is warming up to 65 DEG C,
0.08mol hydrogen peroxide is added, be added dropwise respectively the aqueous solution of the methacrylic acid containing 3.7mol, sodium hypophosphite containing 0.015mol and
The mixed aqueous solution of 0.085mol mercaptoethanol, time for adding are respectively 3.0h and 3.0h, 1.5h are kept the temperature after being added dropwise, then
50 DEG C are cooled to, the liquid alkaline and water of mass fraction 30% is added, adjusting pH value is 6~8, and obtaining product is mass fraction 40%
Modified cyclodextrin self assembly type polycarboxylate water-reducer PC-Z3.
Embodiment 4
0.225mol hydroxyethyl-β-cyclodextrin is dissolved in deionized water, the parent of 0.225mol n-butyl acrylate is added
1.5h is stirred at room temperature in oiliness minor comonomer, and the allyl polyethenoxy base ether that 1.0mol molecular weight is 2400 is added, is warming up to
65 DEG C, 0.115mol ammonium persulfate is added, aqueous solution, the ascorbic acid containing 0.018mol of the maleic anhydride containing 4.5mol are added dropwise respectively
And the mixed aqueous solution of 0.11mol n- dodecyl mereaptan, time for adding are respectively 3.0h and 3.0h, keep the temperature 1.5h after being added dropwise,
Then 50 DEG C are cooled to, the liquid alkaline and water of mass fraction 30% is added, adjusting pH value is 6~8, and obtaining product is mass fraction
40% modified cyclodextrin self assembly type polycarboxylate water-reducer PC-Z4.
Embodiment 5
0.225mol hydroxypropyl-β-cyclodextrin is dissolved in deionized water, 0.225mol n-BMA is added,
1.5h is stirred at room temperature, the methacrylic polyoxyethylene ether that 1.0mol molecular weight is 2400 is added, is warming up to 40 DEG C, adds
Enter 0.146mol ammonium persulfate, the mixed aqueous solution of acrylic acid containing 2.0mol and 2.5mol maleic anhydride is added dropwise respectively, contains
The mixed aqueous solution of 0.019mol sodium sulfite and 0.11mol methylpropene sodium sulfonate, time for adding are respectively 3.0h and 3.5h,
2.0h is kept the temperature after being added dropwise, is then cooled to 30 DEG C, and the liquid alkaline and water of mass fraction 30% is added, adjusting pH value is 6~8,
Obtain the modified cyclodextrin self assembly type polycarboxylate water-reducer PC-Z5 that product is mass fraction 40%.
Embodiment 6
0.225mol hydroxypropyl-β-cyclodextrin is dissolved in deionized water, 0.225mol styrene is added, stirs at room temperature
1.5h is mixed, the isoamyl alcohol polyoxyethylene ether that 1.0mol molecular weight is 2400 is added, is warming up to 45 DEG C, 0.172mol over cure is added
Sour ammonium, be added dropwise respectively the mixed aqueous solution of acrylic acid containing 1.5mol and 3.0mol fumaric acid, sodium hydrogensulfite containing 0.02mol and
The mixed aqueous solution of 0.121mol thioacetic acid, time for adding are respectively 3.0h and 3.5h, 1.5h are kept the temperature after being added dropwise, then
35 DEG C are cooled to, the liquid alkaline and water of mass fraction 30% is added, adjusting pH value is 6~8, and obtaining product is mass fraction 40%
Modified cyclodextrin self assembly type polycarboxylate water-reducer PC-Z6.
Embodiment 7
0.44mol hydroxypropyl-β-cyclodextrin is dissolved in deionized water, 0.44mol acrylic acid n-pentyl ester is added, in room temperature
Lower stirring 2.5h is added the methacrylic polyoxyethylene ether that 1.0mol molecular weight is 2700, is warming up to 50 DEG C, is added
0.235mol hydrogen peroxide, be added dropwise respectively acrylic acid containing 4mol and 1.5mol itaconic acid mixed aqueous solution, containing 0.025mol it is anti-bad
The mixed aqueous solution of hematic acid and 0.163mol mercaptopropionic acid, time for adding are respectively 3.5h and 4.0h, are kept the temperature after being added dropwise
Then 2.0h is cooled to 40 DEG C, the liquid alkaline and water of mass fraction 30% is added, and adjusting pH value is 6~8, and obtaining product is matter
Measure the modified cyclodextrin self assembly type polycarboxylate water-reducer PC-Z7 of score 40%.
Embodiment 8
0.65mol hydroxypropyl-β-cyclodextrin is dissolved in deionized water, 0.65mol n-amylmethacrylate is added,
3.0h is stirred at room temperature, and the methacrylic polyoxyethylene ether that 1.0mol molecular weight is 3500 is added, is warming up to 60 DEG C, is added
The mixed aqueous solution of acrylic acid containing 5mol and 1.5mol itaconic acid is added dropwise respectively, resists containing 0.029mol for 0.308mol ammonium persulfate
The mixed aqueous solution of bad hematic acid and 0.21mol mercaptoethanol, time for adding are respectively 3.5h and 4.0h, are kept the temperature after being added dropwise
Then 2.0h is cooled to 50 DEG C, the liquid alkaline and water of mass fraction 30% is added, and adjusting pH value is 6~8, and obtaining product is matter
Measure the modified cyclodextrin self assembly type polycarboxylate water-reducer PC-Z8 of score 40%.
Comparative example 1
0.15mol beta-cyclodextrin maleate is dissolved in deionized water, the methyl that 1.0mol molecular weight is 2000 is added
Allyl polyethenoxy base ether is warming up to 40 DEG C, and 0.055mol hydrogen peroxide is added, the water-soluble of the acrylic acid containing 3.7mol is added dropwise respectively
The mixed aqueous solution of liquid, ascorbic acid containing 0.016mol and 0.056mol thioacetic acid, time for adding are respectively 2h and 2.5h, drop
1.0h is kept the temperature after adding, is then cooled to 30 DEG C, the liquid alkaline and water of mass fraction 30% is added, and adjusting pH value is 6~8, is obtained
It is the polycarboxylate water-reducer of the side chain containing cyclodextrin of mass fraction 40% to product.
Implementation result verifying:
Polycarboxylate water-reducer of the present invention is according to GB/T 8077-2012 " concrete admixture homogeneity test method " to net
Slurry fluidity is measured, and cement is benchmark cement.Experimental result is shown in Table 1.
1 flowing degree of net paste of cement test result of table
Wherein, comparative example 1 is the polycarboxylate water-reducer of beta-cyclodextrin maleate preparation, and comparative example 2 is commercially available polycarboxylic acids
Water-reducing agent.
As seen from the results in Table 1, comparative example 1,2 is compared, Examples 1 to 8 is flowed in initial flow degree and 60min, 120min
Both be substantially better than in terms of degree gradual loss.It can be seen that the introducing of modified cyclodextrin self assembly side chain improves polycarboxylic acids and subtracts
The water-reducing rate and slump retaining of aqua have superior dispersibility and fluidity retentivity compared with commercial product.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited to this,
Without departing from the technical solutions of the present invention, made to the above embodiment according to the technical essence of the invention any simply to repair
Change, equivalent variations and modification, all of which are still within the scope of the technical scheme of the invention.
Claims (7)
1. a kind of method for preparing modified cyclodextrin self assembly type polycarboxylate water-reducer, the poly- carboxylic of modified cyclodextrin self assembly type
The general structure of sour water-reducing agent are as follows:
Wherein: R1For-H ,-COOH or-CH2COOH；R2For-H or-CH3；R3For-H or-CH3；R4For/or-COO-；R5For benzene
Base ,-CH2CH2CH3、-(CH2)3CH3Or-(CH2)4CH3；R6For ethoxy or hydroxypropyl；R7For-H or-CH3；R8For-CH2-、-
CH2CH2Or-CO-；R9For-H or-CH3；X, Y, Z and n are positive integer, X=50~150, Y=5~20, Z=10~50, n
=45~76；
It is characterized in that the preparation method comprises the following steps: modified cyclodextrin being dissolved in deionized water, is added containing not
It is saturated the lipophilic minor comonomer of double bond, 1~3h is stirred at room temperature, adds polyethers or polyester macromonomer, is warming up to 40~80
DEG C, the mixed aqueous solution of the aqueous solution of dropwise addition unsaturated carboxylic acid monomer, initiator and chain tra nsfer, time for adding are 2~4h respectively,
1~2h is kept the temperature after being added dropwise, and is then cooled to 30~50 DEG C；It is eventually adding aqueous slkali and adjusts pH value to 6~8, obtain and change
Property cyclodextrin self assembly type polycarboxylate water-reducer；
Wherein the modified cyclodextrin, lipophilic minor comonomer, polyethers or polyester macromonomer, unsaturated carboxylic acid monomer, initiator and
The molar ratio of chain-transferring agent is (0.1~0.7): (0.1~0.7): 1:(3.5~7): (0.05~0.35): (0.05~0.25).
2. preparation method according to claim 1, it is characterised in that: the modified cyclodextrin is hydroxyethyl-β-cyclodextrin
Or one of hydroxypropyl-β-cyclodextrin.
3. preparation method according to claim 1, it is characterised in that: the lipophilicity minor comonomer is styrene, acrylic acid
N-propyl, n-butyl acrylate, acrylic acid n-pentyl ester, n propyl methacrylate, n-BMA, methacrylic acid
One of n-pentyl ester.
4. preparation method according to claim 1, it is characterised in that: the polyethers or polyester macromonomer exist for molecular weight
Allyl polyethenoxy base ether between 2000~3500, methacrylic polyoxyethylene ether, prenol polyoxyethylene groups
One of ether, polyalkylene glycol acrylate monomethyl ether ester, Methylacrylic acid polyethylene glycol single armor ether ester.
5. preparation method according to claim 1, it is characterised in that: the unsaturated carboxylic acid monomer is acrylic acid, methyl
One or more of acrylic acid, maleic anhydride, fumaric acid and itaconic acid.
6. preparation method according to claim 1, it is characterised in that: the initiator is hydrogen peroxide-ascorbic acid, dioxygen
Water-sodium formaldehyde sulfoxylate, hydrogen peroxide-sodium hypophosphite, ammonium persulfate-ascorbic acid, ammonium persulfate-sodium sulfite, ammonium persulfate-sulfurous
One of sour hydrogen sodium.
7. preparation method according to claim 1, it is characterised in that: the chain-transferring agent be thioacetic acid, mercaptopropionic acid,
One of mercaptoethanol, n- dodecyl mereaptan, methylpropene sodium sulfonate.
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| CN107312132B (en) * | 2017-07-19 | 2019-10-15 | 中交二航武汉港湾新材料有限公司 | The polycarboxylate water-reducer and preparation method thereof of modified sugars side-chain structure |
| CN108373522B (en) * | 2018-02-12 | 2020-07-03 | 中交二航武汉港湾新材料有限公司 | Polycarboxylate superplasticizer with modified cyclodextrin side chain structure and preparation method thereof |
| CN109734841B (en) * | 2019-01-22 | 2021-02-05 | 武汉优城科技有限公司 | Star-topology-structure-reinforced polycarboxylate superplasticizer and preparation method thereof |
| CN110218022B (en) * | 2019-06-20 | 2021-10-29 | 中交二航武汉港湾新材料有限公司 | Chitosan oligosaccharide graft modified polycarboxylate superplasticizer and preparation method thereof |
| CN114901727A (en) * | 2019-12-27 | 2022-08-12 | 国立大学法人大阪大学 | Resin composition, polymer, method for producing polymer, binder for electrochemical device, electrode mixture, electrode, electrochemical device, and secondary battery |
| CN114014992B (en) * | 2021-11-12 | 2023-06-23 | 中交第四航务工程局有限公司 | Mutually exclusive/associative polycarboxylate superplasticizer and preparation method and application thereof |
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| CN105060759A (en) * | 2015-08-14 | 2015-11-18 | 中建材中岩科技有限公司 | Preparation method of slow-release polycarboxylate superplasticizer |
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