CN109096448A - A kind of method that zinc salt catalyzes and synthesizes polycarboxylate water-reducer - Google Patents
A kind of method that zinc salt catalyzes and synthesizes polycarboxylate water-reducer Download PDFInfo
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- CN109096448A CN109096448A CN201810737565.6A CN201810737565A CN109096448A CN 109096448 A CN109096448 A CN 109096448A CN 201810737565 A CN201810737565 A CN 201810737565A CN 109096448 A CN109096448 A CN 109096448A
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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
- 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
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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
- C08F4/00—Polymerisation catalysts
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
- C08F4/10—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of alkaline earth metals, zinc, cadmium, mercury, copper or silver
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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
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
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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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Abstract
The invention discloses a kind of methods that zinc salt catalyzes and synthesizes polycarboxylate water-reducer, it is characterized in that: taking raw material polymeric monomer, minor comonomer, chain-transferring agent, reducing agent, oxidant, catalyst and water；Minor comonomer and chain-transferring agent and water are hybridly prepared into A liquid；Reducing agent and catalyst and water are hybridly prepared into B liquid；Polymeric monomer and water are added in the reactor of thermometer, heat temperature raising simultaneously stirs, when temperature reaches 47~52 DEG C and polymeric monomer is completely dissolved, oxidant is added, mixing, then while be at the uniform velocity added dropwise to A liquid and B liquid, be added dropwise and the total time of insulation reaction be 2~2.5h, reacting rear material is cooled to room temperature, polycarboxylate water-reducer is obtained.Using the present invention, reaction temperature is low, high production efficiency, production cost is low, product dispersion performance and function of slump protection are good, can industrialized production, practical, preparation of the polycarboxylate water-reducer obtained particularly suitable for concrete base building material.
Description
Technical field
The invention belongs to the preparation methods of water-reducing agent, are related to a kind of method that zinc salt catalyzes and synthesizes polycarboxylate water-reducer.This
The polycarboxylate water-reducer of invention preparation is suitable in concrete admixture and construction material.
Background technique
Concrete plays increasingly important role as main construction material, for nation-building and development.Subtract
Key component of the aqua as concrete admixture, it is possible to reduce concrete Water Usage Per Unit Volume promotes ready-mixed concrete
Working performance, the intensity for improving maturing and service life etc..Polycarboxylate water-reducer is a kind of point with comb-type structure
Son has many advantages, such as high water reducing rate, can improve concrete hole structure and compactness.Polycarboxylate water-reducer is as most important mixed
One of solidifying soil additive has the characteristics that green, efficient, high plasticity, deep to be paid attention to by every country, with infrastructure and lives
The increasing of dynamics is built in room, and demand and performance requirement to amount of concrete rise year by year, and the demand to polycarboxylate water-reducer is not yet
It is disconnected to increase.
Currently, the production and application of polycarboxylate water-reducer are wide both at home and abroad, in the prior art, polycarboxylate water-reducer
Production takes redox initiation system to prepare polycarboxylic acids diminishing mainly using polyether macromonomer and all kinds of minor comonomers as primary raw material
Agent.Redox initiation system is generated free radicals by redox reaction, to cause monomer polymerization.Production polycarboxylic acids subtracts
Redox initiation system used in aqua mainly uses the peroxide such as ammonium persulfate and potassium peroxydisulfate as initiator, uses
Heating means synthesize polycarboxylate water-reducer, and polymeric reaction temperature is usually 60~90 DEG C, and higher temperature increases energy consumption, increase
Production cost, to reduce the competitiveness of product in market, dispersion performance, function of slump protection of product etc. also have deficiency.Seek
The striving direction that there is the polycarboxylate water-reducer of superperformance to have become industry for synthesis under lower temperature.
Summary of the invention
The purpose of the present invention is intended to overcome deficiency in the prior art, provides a kind of zinc salt and catalyzes and synthesizes polycarboxylate water-reducer
Method, so that it is good to provide low a kind of low reaction temperature, high production efficiency, production cost, product dispersion performance and function of slump protection
It is good, can industrialized production polycarboxylate water-reducer preparation method.
The contents of the present invention are: a kind of method that zinc salt catalyzes and synthesizes polycarboxylate water-reducer, are steps in place of feature are as follows:
A, ingredient:
Take raw material polymeric monomer, minor comonomer, chain-transferring agent, reducing agent, oxidant, catalyst and water, in which: polymeric monomer: small
The molar ratio of monomer is 3.8:1~4.2:1, and chain-transferring agent is that (monomer gross mass is polymeric monomer and minor comonomer to monomer gross mass
Quality sum, it is rear same) 0.5%~0.7%, reducing agent is the 0.2%~4% of monomer gross mass, and oxidant is that monomer is total
The 0.5%~1.1% of quality, catalyst are the 0.1%~0.2% of monomer gross mass；
Minor comonomer and chain-transferring agent are mixed with water, are configured to A liquid, for use；
Reducing agent and catalyst are mixed with water, are configured to B liquid, for use；
The polymeric monomer is that (abbreviation TPEG, production enterprise and model have isoamyl alcohol polyoxyethylene ether: Liaoning Losec
Chemical limited liability company, OXAA-2400 type TPEG monomer；Liaoning Fine Chemical Industry Co., Ltd., F-54-2400 type
TPEG monomer；ZheJiang HuangMa Science Co., Ltd, HM005-2400 type TPEG monomer etc.), molecular weight is 2000~4000；
(production enterprise and model are preferable are as follows: Liaoning Losec chemistry for the isoamyl alcohol polyoxyethylene ether that preferred molecular weight is 2400
Limited liability company, OXAA-2400 type TPEG monomer)；
The minor comonomer is one in acrylic acid, hydroxy-ethyl acrylate, hydroxypropyl acrylate and methylpropene sodium sulfonate
Kind or two or more mixtures, preferably acrylic acid；
The chain-transferring agent is the mixture of one or both of thioacetic acid, mercaptopropionic acid, preferably thioacetic acid；
The catalyst is the mixture of one or both of zinc chloride, zinc sulfate, preferably sulfuric acid zinc；
The reducing agent is one or both of sodium hypophosphite, sodium hydrogensulfite, sodium sulfite and ascorbic acid
Above mixture, preferably sodium hydrogensulfite；
The oxidant is the mixture of one or more of hydrogen peroxide, potassium peroxydisulfate and ammonium persulfate etc.,
It is preferred that hydrogen peroxide；
B, synthetic reaction:
Polymeric monomer and water are added in the reactor (such as: three-necked flask) of thermometer, (gradually) heat temperature raising is simultaneously
It stirs (dissolution), when temperature reaches 47~52 DEG C and polymeric monomer is completely dissolved, oxidant, mixing (after uniformly) is added, then (use
Constant pressure funnel) be at the uniform velocity added dropwise to A liquid and B liquid simultaneously, be added dropwise and 47~52 DEG C at a temperature of insulation reaction total time be 2~
Reacting rear material is cooled to room temperature by 2.5h, obtains (zinc salt catalyzes and synthesizes) polycarboxylate water-reducer.
In the contents of the present invention: in ingredient described in step a: polymeric monomer: the molar ratio of minor comonomer be preferably 3.9:1~
4.1:1, chain-transferring agent are preferably monomer gross mass (monomer gross mass is the quality sum of polymeric monomer and minor comonomer, rear same)
0.6%~0.7%, reducing agent is preferably the 0.3%~0.4% of monomer gross mass, and oxidant is preferably the total matter of monomer
The 0.8%~1% of amount, catalyst is preferably the 0.15%~0.2% of monomer gross mass.
In the contents of the present invention: mixing minor comonomer and chain-transferring agent with water described in step a, be configured to A liquid, preferably
Be: by the gross mass of minor comonomer and chain-transferring agent: water is the mass ratio of 1:4.2~4.8 by minor comonomer and chain-transferring agent and water
Mixing, is configured to A liquid.
In the contents of the present invention: mixing reducing agent and catalyst with water described in step a, be configured to B liquid, preferably
Be: by the gross mass of reducing agent and catalyst: water is that the mass ratio of 1:110~200 mixes reducing agent and catalyst with water,
It is configured to B liquid.
In the contents of the present invention: water described in step a preferably distilled water or deionized water.
In the contents of the present invention: polymeric monomer and water being added in the reactor of thermometer described in step b, preferably
Be by polymeric monomer: water is that polymeric monomer and water are added in the reactor of thermometer by the mass ratio of 1:0.5~0.6.
In the contents of the present invention: insulation reaction at 47~52 DEG C of temperature described in step b, preferably 48~50 DEG C of temperature
Lower insulation reaction.
In the contents of the present invention: being at the uniform velocity added dropwise to A liquid and B liquid simultaneously (with constant pressure funnel) again described in step b, drip
The total time of insulation reaction is 2~3h at a temperature of 47~52 DEG C of adduction, preferably: (using constant pressure funnel) simultaneously at the uniform velocity again
A liquid is added dropwise and B liquid, A liquid 1h are dripped off, B liquid 1.5h is dripped off, and after B drop is complete, soaking time is 1h again at 47~52 DEG C of temperature.
In the contents of the present invention: using infrared analysis (FT-IR) to the polycarboxylate water-reducer of preparation；It is tried using cement paste
It tests and carries out performance evaluation with concrete test.
In the contents of the present invention: through infrared spectrum characterization (the analysis data of FT-IR, see Detailed description of the invention), synthesized production
Occurs polycarboxylate water-reducer characteristic group in object.
In the contents of the present invention: in the performance test of polycarboxylate water-reducer obtained, flowing degree of net paste of cement experiment according to
National standard GB/T8077-2000 " concrete admixture homogeneity test method " is tested；Concrete test is according to national standard GB/
T50080-2002 " normal concrete mix performance test standard "；GB/T50081-2002 " normal concrete mechanical property examination
Test method standard " carry out correlation test.
Compared with prior art, the present invention have following features and the utility model has the advantages that
(1) using the present invention, use zinc salt for catalyst for the first time, reduction reaction temperature is to about 47~52 DEG C, redox
More efficient, total reaction time is short, and (zinc salt catalyzes and synthesizes) polycarboxylate water-reducer obtained has good initial dispersion (phase
1~3% is improved with volume water-reducing rate) and function of slump protection (slump-loss reduces within 1 hour)；And synthesis material is cheap and easy to get, closes
It is efficient at simple process, pH can not be adjusted and directly used, it is easy to industrialized production；
(2) using the present invention, in terms of zinc salt mainly has following two to the mechanism of action of free radical polymerization:
On the one hand: zinc ion (Zn is added2+) after, the decomposition rate of hydrogen peroxide can be accelerated, so that hydrogen peroxide
The rate quickening for generating free radical is reacted with sodium hydrogensulfite, is caused monomer and is formed monomer radical, reaction equation is as follows:
When zinc sulfate, sodium hydrogensulfite, hydrogen peroxide are in same reaction system, hydrogen peroxide may be by divalent
Zinc ion (Zn2+:3s23p63d10) three valence states are oxidized to, and the zinc ion of trivalent is in extraordinary valence state (Zn3+:3s23p63d9), and
Oxygen radical is released, oxygen radical has very high reactivity, constantly consumed in the reaction；Sodium hydrogensulfite is made simultaneously
The trivalent zinc in extraordinary valence state can be reduced into divalent zinc for reducing agent, and the divalent zinc regenerated can again and peroxidating
Hydrogen reacts, and continuous circular response releases oxygen radical, until hydrogen peroxide is depleted；Zinc salt promotes free radical
Generating rate improves chain velocity of initiation, and then accelerates rate of polymerization, meanwhile, monomer radical is further generated with monomer reaction
Chain free radical promotes the progress of chain growth, increases the degree of polymerization, so that the polycarboxylate water-reducer molecule amount of synthesis be made to increase；
On the other hand: complex reaction occurs for the oxygen atom in zinc ion and acrylic acid in carboxyl on carbonyl, and then influences carbon
The electrical property of carbon double bond increases monomer radical activity, promotes the generation of chain free radical, makes the polycarboxylate water-reducer molecule amount of synthesis
Increase；
The reaction mechanism is as follows shown in figure:
(4) product of the present invention preparation process is simple, easy to operate, reaction temperature is low, high production efficiency, production cost are low,
Can industrialized production, polycarboxylate water-reducer dispersion performance and function of slump protection obtained are good, particularly useful as concrete admixture
It is practical and in construction material.
Detailed description of the invention
Fig. 1 is the infrared spectrogram that polycarboxylate water-reducer is prepared in the embodiment of the present invention, and abscissa is wave number (cm-1)、
Ordinate is transmitance (%)；In infrared spectrum, 2888.50cm-1Place is the stretching vibration peak of saturated hydrocarbons c h bond,
1467.53cm-1And 1359.59cm-1For its flexural vibrations peak；1730.19cm-1Place is carboxylic acid C=O stretching vibration peak；
842.54cm-1、963.42cm-1And 1114.61cm-1Place's absorption peak is the characteristic absorption peak of polyoxyethylene ether (- O-).Wherein
1114.61cm-1It is the stretching vibration of C-O in C-O-C structure, 963.42cm-1And 842.54cm-1It is in polyoxyethylene groups respectively
C-C and C-O stretching vibration；Features above peak can show that minor comonomer and polyether macromonomer produce copolymerization in solution, generate
Polycarboxylate water-reducer.
Specific embodiment
The embodiments given below are intended to further illustrate the invention, but is not to be construed as to the scope of the present invention
Limitation, some nonessential improvement and tune that person skilled in art makes the present invention according to the content of aforementioned present invention
It is whole, still fall within protection scope of the present invention.
Embodiment 1:
A kind of method that zinc salt catalyzes and synthesizes polycarboxylate water-reducer, step are as follows: prepare A liquid respectively and (weigh minor comonomer
3.09g, thioacetic acid 0.15g and distilled water 15g mixing) and B liquid (sodium hydrogensulfite 0.12g, zinc sulfate 0.03g and distilled water
20g mixing) for use, polymeric monomer (TPEG) 26.91g and distilled water 15g are added in the three-necked flask for being equipped with thermometer, gradually rises
When temperature reaches 47 DEG C and polymeric monomer is completely dissolved 0.33g hydrogen peroxide is added, after mixing, with perseverance in temperature and stirring and dissolving
A liquid (61min is dripped off) at the uniform velocity is added dropwise simultaneously for pressure dropping funel and B liquid (92min is dripped off), soaking time 1h are cooled to room temperature,
Up to the polycarboxylate water-reducer with good practical performance catalyzed and synthesized by zinc salt.
Embodiment 2:
A kind of method that zinc salt catalyzes and synthesizes polycarboxylate water-reducer, step are as follows: prepare A liquid respectively and (weigh minor comonomer
3.14g, thioacetic acid 0.16g and distilled water 15g mixing) and B liquid (sodium hydrogensulfite 0.10g, zinc sulfate 0.04g and distilled water
20g mixing) for use, polymeric monomer (TPEG) 26.86g and distilled water 15g are added in the three-necked flask for being equipped with thermometer, gradually rises
When temperature reaches 48 DEG C and polymeric monomer is completely dissolved 0.31g hydrogen peroxide is added, after mixing, with perseverance in temperature and stirring and dissolving
A liquid (60min is dripped off) at the uniform velocity is added dropwise simultaneously for pressure dropping funel and B liquid (89min is dripped off), soaking time 1h are cooled to room temperature,
Up to the polycarboxylate water-reducer with good practical performance catalyzed and synthesized by zinc salt.
Embodiment 3:
A kind of method that zinc salt catalyzes and synthesizes polycarboxylate water-reducer, step are as follows: prepare A liquid respectively and (weigh minor comonomer
3.19g, thioacetic acid 0.17g and distilled water 15g mixing) and B liquid (sodium hydrogensulfite 0.08g, zinc sulfate 0.06g and distilled water
20g mixing) for use, polymeric monomer (TPEG) 26.81g and distilled water 15g are added in the three-necked flask for being equipped with thermometer, gradually rises
When temperature reaches 49 DEG C and polymeric monomer is completely dissolved 0.29g hydrogen peroxide is added, after mixing, with perseverance in temperature and stirring and dissolving
A liquid (58min is dripped off) at the uniform velocity is added dropwise simultaneously for pressure dropping funel and B liquid (91min is dripped off), soaking time 1h are cooled to room temperature,
Up to the polycarboxylate water-reducer with good practical performance catalyzed and synthesized by zinc salt.
Embodiment 4:
A kind of method that zinc salt catalyzes and synthesizes polycarboxylate water-reducer, step are as follows: prepare A liquid respectively and (weigh minor comonomer
3.2167g, thioacetic acid 0.2g and distilled water 15g mixing) and B liquid (sodium hydrogensulfite 0.1g, zinc sulfate 0.05g and distilled water
20g mixing) for use, polymeric monomer (TPEG) 26.7833g and distilled water 15g are added in the three-necked flask for being equipped with thermometer, gradually
It heats up and 0.2167g hydrogen peroxide is added when temperature reaches 50 DEG C and polymeric monomer is completely dissolved in stirring and dissolving, after mixing,
A liquid (59min is dripped off) at the uniform velocity is added dropwise simultaneously with constant pressure funnel and B liquid (88min is dripped off), soaking time 1h are cooled to
Room temperature is to get the polycarboxylate water-reducer with superperformance catalyzed and synthesized by zinc salt.
Embodiment 5:
A kind of method that zinc salt catalyzes and synthesizes polycarboxylate water-reducer, step are as follows: prepare A liquid respectively and (weigh minor comonomer
3.26g, thioacetic acid 0.21g and distilled water 15g mixing) and B liquid (sodium hydrogensulfite 0.06g, zinc sulfate 0.04g and distilled water
20g mixing) for use, polymeric monomer (TPEG) 26.74g and distilled water 15g are added in the three-necked flask for being equipped with thermometer, gradually rises
When temperature reaches 51 DEG C and polymeric monomer is completely dissolved 0.15g hydrogen peroxide is added, after mixing, with perseverance in temperature and stirring and dissolving
A liquid (62min is dripped off) at the uniform velocity is added dropwise simultaneously for pressure dropping funel and B liquid (93min is dripped off), soaking time 1h are cooled to room temperature,
Up to the polycarboxylate water-reducer with good practical performance catalyzed and synthesized by zinc salt.
Embodiment 6:
A kind of method that zinc salt catalyzes and synthesizes polycarboxylate water-reducer, step are as follows: prepare A liquid respectively and (weigh minor comonomer
3.31g, thioacetic acid 0.19g and distilled water 15g mixing) and B liquid (sodium hydrogensulfite 0.11g, zinc sulfate 0.05g and distilled water
20g mixing) for use, polymeric monomer (TPEG) 26.69g and distilled water 15g are added in the three-necked flask for being equipped with thermometer, gradually rises
0.2816g hydrogen peroxide is added when temperature reaches 52 DEG C and polymeric monomer is completely dissolved in temperature and stirring and dissolving, after mixing, uses
A liquid (59min is dripped off) at the uniform velocity is added dropwise simultaneously for constant pressure funnel and B liquid (88min is dripped off), soaking time 1h are cooled to room
Temperature is to get the polycarboxylate water-reducer with good practical performance catalyzed and synthesized by zinc salt.
Embodiment 7:
A kind of method that zinc salt catalyzes and synthesizes polycarboxylate water-reducer, step are as follows: prepare A liquid respectively and (weigh minor comonomer
3.36g, thioacetic acid 0.17g and distilled water 15g mixing) and B liquid (sodium hydrogensulfite 0.09g, zinc sulfate 0.03g and distilled water
20g mixing) for use, polymeric monomer (TPEG) 26.64g and distilled water 15g are added in the three-necked flask for being equipped with thermometer, gradually rises
0.256g hydrogen peroxide is added when temperature reaches 48 DEG C and polymeric monomer is completely dissolved in temperature and stirring and dissolving, after mixing, uses
A liquid (61min is dripped off) at the uniform velocity is added dropwise simultaneously for constant pressure funnel and B liquid (90min is dripped off), soaking time 1h are cooled to room
Temperature is to get the polycarboxylate water-reducer with good practical performance catalyzed and synthesized by zinc salt.
Embodiment 8:
A kind of method that zinc salt catalyzes and synthesizes polycarboxylate water-reducer, step are as follows: prepare A liquid respectively and (weigh minor comonomer
3.26g, thioacetic acid 0.16g and distilled water 15g mixing) and B liquid (sodium hydrogensulfite 0.07g, zinc sulfate 0.06g and distilled water
20g mixing) for use, polymeric monomer (TPEG) 26.74g and distilled water 15g are added in the three-necked flask for being equipped with thermometer, gradually rises
When temperature reaches 49 DEG C and polymeric monomer is completely dissolved 0.19g hydrogen peroxide is added, after mixing, with perseverance in temperature and stirring and dissolving
A liquid (61min is dripped off) at the uniform velocity is added dropwise simultaneously for pressure dropping funel and B liquid (92min is dripped off), soaking time 1h are cooled to room temperature,
Up to the polycarboxylate water-reducer with good practical performance catalyzed and synthesized by zinc salt.
Embodiment 9:
A kind of method that zinc salt catalyzes and synthesizes polycarboxylate water-reducer, step are as follows: prepare A liquid respectively and (weigh minor comonomer
3.16g, thioacetic acid 0.15g and distilled water 15g mixing) and B liquid (sodium hydrogensulfite 0.12g, zinc sulfate 0.05g and distilled water
20g mixing) for use, polymeric monomer (TPEG) 26.84g and distilled water 15g are added in the three-necked flask for being equipped with thermometer, gradually rises
0.2677g hydrogen peroxide is added when temperature reaches 47 DEG C and polymeric monomer is completely dissolved in temperature and stirring and dissolving, after mixing, uses
A liquid (62min is dripped off) at the uniform velocity is added dropwise simultaneously for constant pressure funnel and B liquid (94min is dripped off), soaking time 1h are cooled to room
Temperature is to get the polycarboxylate water-reducer with good practical performance catalyzed and synthesized by zinc salt.
Embodiment 10:
A kind of method that zinc salt catalyzes and synthesizes polycarboxylate water-reducer, step are as follows: prepare A liquid respectively and (weigh minor comonomer
3.06g, thioacetic acid 0.2g and distilled water 15g mixing) and B liquid (sodium hydrogensulfite 0.1g, zinc sulfate 0.04g and distilled water 20g
Mixing) for use, polymeric monomer (TPEG) 26.94g and distilled water 15g are added in the three-necked flask for being equipped with thermometer, is gradually warmed up
And when temperature reaches 50 DEG C and polymeric monomer is completely dissolved 0.2617g hydrogen peroxide is added, after mixing, with perseverance in stirring and dissolving
A liquid (60min is dripped off) at the uniform velocity is added dropwise simultaneously for pressure dropping funel and B liquid (89min is dripped off), soaking time 1h are cooled to room temperature,
Up to the polycarboxylate water-reducer with good practical performance catalyzed and synthesized by zinc salt.
Application Example:
Cement paste experiment, concrete test are carried out to the polycarboxylate water-reducer of synthesis.The performance of polycarboxylate water-reducer refers to
Mark is according to professional standard JG/T223-2007 " polycarboxylate high performance water-reducing agent "；Flowing degree of net paste of cement is tested according to national standard
GB/T8077-2000 " concrete admixture homogeneity test method " is tested, and it is 0.12% that water-reducing agent, which rolls over solid volume, test
The results are shown in Table 1；Concrete test according to national standard GB/T50080-2002 " normal concrete mix performance test standard ",
It is 0.15% that water-reducing agent, which rolls over solid volume,；GB-T50081-2002 " standard for test methods of mechanical properties of ordinary concrete " carries out related
Test.
Table 1: application performance test result:
Illustrate: polycarboxylate water-reducer rolls over solid volume 0.12%, middle P.O 42.5R cement (China's joint Cement Group north
Chuan Zhonglian Cement Co., Ltd production).W/C is water/cement (mass ratio).
Table 2:C30Concrete test result:
Illustrate: test polycarboxylate water-reducer rolls over solid volume 0.15%, and P.O 42.5R cement, middle sand (mechanism are joined in
Sand), 5~25 continuous size fraction rubbles, every 360 ㎏ of side's dosage of cement, sand coarse aggregate ratio 45%.
Embodiment 11:
A kind of method that zinc salt catalyzes and synthesizes polycarboxylate water-reducer, step are as follows:
A, ingredient:
Take raw material polymeric monomer, minor comonomer, chain-transferring agent, reducing agent, oxidant, catalyst and water, in which: polymeric monomer: small
The molar ratio of monomer is 3.8:1, chain-transferring agent be monomer gross mass (monomer gross mass be polymeric monomer and minor comonomer quality it
With it is rear same) 0.5%, reducing agent is the 0.2% of monomer gross mass, and oxidant is the 0.5% of monomer gross mass, and catalyst is
The 0.1% of monomer gross mass；
Minor comonomer and chain-transferring agent are mixed with water, are configured to A liquid, for use；
Reducing agent and catalyst are mixed with water, are configured to B liquid, for use；
B, synthetic reaction:
Polymeric monomer and water are added in the reactor (such as: three-necked flask) of thermometer, (gradually) heat temperature raising is simultaneously
It stirs (dissolution), when temperature reaches 47 DEG C and polymeric monomer is completely dissolved, oxidant, mixing (after uniformly) is added, then (use constant pressure
Dropping funel) be at the uniform velocity added dropwise to A liquid and B liquid simultaneously, be added dropwise and 47 DEG C at a temperature of total time of insulation reaction be 2.5h, will react
Material is cooled to room temperature afterwards, obtains (zinc salt catalyzes and synthesizes) polycarboxylate water-reducer.
Embodiment 12:
A kind of method that zinc salt catalyzes and synthesizes polycarboxylate water-reducer, step are as follows:
A, ingredient:
Take raw material polymeric monomer, minor comonomer, chain-transferring agent, reducing agent, oxidant, catalyst and water, in which: polymeric monomer: small
The molar ratio of monomer is 4.2:1, chain-transferring agent be monomer gross mass (monomer gross mass be polymeric monomer and minor comonomer quality it
With it is rear same) 0.7%, reducing agent is the 4% of monomer gross mass, and oxidant is the 1.1% of monomer gross mass, and catalyst is single
The 0.2% of body gross mass；
Minor comonomer and chain-transferring agent are mixed with water, are configured to A liquid, for use；
Reducing agent and catalyst are mixed with water, are configured to B liquid, for use；
B, synthetic reaction:
Polymeric monomer and water are added in the reactor (such as: three-necked flask) of thermometer, (gradually) heat temperature raising is simultaneously
It stirs (dissolution), when temperature reaches 52 DEG C and polymeric monomer is completely dissolved, oxidant, mixing (after uniformly) is added, then (use constant pressure
Dropping funel) be at the uniform velocity added dropwise to A liquid and B liquid simultaneously, be added dropwise and 52 DEG C at a temperature of total time of insulation reaction be 2h, after reaction
Material is cooled to room temperature, and obtains (zinc salt catalyzes and synthesizes) polycarboxylate water-reducer.
Embodiment 13:
A kind of method that zinc salt catalyzes and synthesizes polycarboxylate water-reducer, step are as follows:
A, ingredient:
Take raw material polymeric monomer, minor comonomer, chain-transferring agent, reducing agent, oxidant, catalyst and water, in which: polymeric monomer: small
The molar ratio of monomer is 4:1, chain-transferring agent be monomer gross mass (monomer gross mass be polymeric monomer and minor comonomer quality it
With it is rear same) 0.6%, reducing agent is the 2.1% of monomer gross mass, and oxidant is the 0.8% of monomer gross mass, and catalyst is
The 0.15% of monomer gross mass；
Minor comonomer and chain-transferring agent are mixed with water, are configured to A liquid, for use；
Reducing agent and catalyst are mixed with water, are configured to B liquid, for use；
B, synthetic reaction:
Polymeric monomer and water are added in the reactor (such as: three-necked flask) of thermometer, (gradually) heat temperature raising is simultaneously
It stirs (dissolution), when temperature reaches 50 DEG C and polymeric monomer is completely dissolved, oxidant, mixing (after uniformly) is added, then (use constant pressure
Dropping funel) be at the uniform velocity added dropwise to A liquid and B liquid simultaneously, be added dropwise and 50 DEG C at a temperature of total time of insulation reaction be 2.5h, will react
Material is cooled to room temperature afterwards, obtains (zinc salt catalyzes and synthesizes) polycarboxylate water-reducer.
Embodiment 14:
A kind of method that zinc salt catalyzes and synthesizes polycarboxylate water-reducer, step are as follows:
A, ingredient:
Take raw material polymeric monomer, minor comonomer, chain-transferring agent, reducing agent, oxidant, catalyst and water, in which: polymeric monomer: small
The molar ratio of monomer is 3.9:1, chain-transferring agent be monomer gross mass (monomer gross mass be polymeric monomer and minor comonomer quality it
With it is rear same) 0.6%, reducing agent is the 0.9% of monomer gross mass, and oxidant is the 0.7% of monomer gross mass, and catalyst is
The 0.13% of monomer gross mass；
Minor comonomer and chain-transferring agent are mixed with water, are configured to A liquid, for use；
Reducing agent and catalyst are mixed with water, are configured to B liquid, for use；
B, synthetic reaction:
Polymeric monomer and water are added in the reactor (such as: three-necked flask) of thermometer, (gradually) heat temperature raising is simultaneously
It stirs (dissolution), when temperature reaches 49 DEG C and polymeric monomer is completely dissolved, oxidant, mixing (after uniformly) is added, then (use constant pressure
Dropping funel) be at the uniform velocity added dropwise to A liquid and B liquid simultaneously, be added dropwise and 49 DEG C at a temperature of total time of insulation reaction be 2.2h, will react
Material is cooled to room temperature afterwards, obtains (zinc salt catalyzes and synthesizes) polycarboxylate water-reducer.
Embodiment 15:
A kind of method that zinc salt catalyzes and synthesizes polycarboxylate water-reducer, step are as follows:
A, ingredient:
Take raw material polymeric monomer, minor comonomer, chain-transferring agent, reducing agent, oxidant, catalyst and water, in which: polymeric monomer: small
The molar ratio of monomer is 4.1:1, chain-transferring agent be monomer gross mass (monomer gross mass be polymeric monomer and minor comonomer quality it
With it is rear same) 0.65%, reducing agent is the 3% of monomer gross mass, and oxidant is the 0.9% of monomer gross mass, and catalyst is single
The 0.17% of body gross mass；
Minor comonomer and chain-transferring agent are mixed with water, are configured to A liquid, for use；
Reducing agent and catalyst are mixed with water, are configured to B liquid, for use；
B, synthetic reaction:
Polymeric monomer and water are added in the reactor (such as: three-necked flask) of thermometer, (gradually) heat temperature raising is simultaneously
It stirs (dissolution), when temperature reaches 51 DEG C and polymeric monomer is completely dissolved, oxidant, mixing (after uniformly) is added, then (use constant pressure
Dropping funel) be at the uniform velocity added dropwise to A liquid and B liquid simultaneously, be added dropwise and 51 DEG C at a temperature of total time of insulation reaction be 2~2.5h, will
Reacting rear material is cooled to room temperature, and obtains (zinc salt catalyzes and synthesizes) polycarboxylate water-reducer.
Embodiment 16:
A kind of method that zinc salt catalyzes and synthesizes polycarboxylate water-reducer, step are as follows:
A, ingredient:
Take raw material polymeric monomer, minor comonomer, chain-transferring agent, reducing agent, oxidant, catalyst and water, in which: polymeric monomer: small
The molar ratio of monomer be it is any in 3.8:1~4.2:1, chain-transferring agent be monomer gross mass (monomer gross mass be polymeric monomer with
It is the quality sum of minor comonomer, rear same) 0.5%~0.7% in it is any, reducing agent is to appoint in the 0.2%~4% of monomer gross mass
One, oxidant be monomer gross mass 0.5%~1.1% in it is any, catalyst be monomer gross mass 0.1%~0.2% in
It is any；
Minor comonomer and chain-transferring agent are mixed with water, are configured to A liquid, for use；
Reducing agent and catalyst are mixed with water, are configured to B liquid, for use；
B, synthetic reaction:
Polymeric monomer and water are added in the reactor (such as: three-necked flask) of thermometer, (gradually) heat temperature raising is simultaneously
It stirs (dissolution), when temperature reaches 47~52 DEG C and polymeric monomer is completely dissolved, oxidant, mixing (after uniformly) is added, then (use
Constant pressure funnel) be at the uniform velocity added dropwise to A liquid and B liquid simultaneously, be added dropwise and 47~52 DEG C at a temperature of insulation reaction total time be 2~
Reacting rear material is cooled to room temperature by 2.5h, obtains (zinc salt catalyzes and synthesizes) polycarboxylate water-reducer.
Embodiment 17:
A kind of method that zinc salt catalyzes and synthesizes polycarboxylate water-reducer, step are as follows:
A, ingredient:
Take raw material polymeric monomer, minor comonomer, chain-transferring agent, reducing agent, oxidant, catalyst and water, in which: polymeric monomer: small
The molar ratio of monomer is 4:1, chain-transferring agent be monomer gross mass (monomer gross mass be polymeric monomer and minor comonomer quality it
With it is rear same) 0.6%, reducing agent is the 2% of monomer gross mass, and oxidant is the 0.8% of monomer gross mass, and catalyst is single
The 0.15% of body gross mass；
Minor comonomer and chain-transferring agent are mixed with water, are configured to A liquid, for use；
Reducing agent and catalyst are mixed with water, are configured to B liquid, for use；
B, synthetic reaction:
Polymeric monomer and water are added in the reactor (such as: three-necked flask) of thermometer, (gradually) heat temperature raising is simultaneously
It stirs (dissolution), when temperature reaches 47~52 DEG C and polymeric monomer is completely dissolved, oxidant, mixing (after uniformly) is added, then (use
Constant pressure funnel) A liquid and B liquid, A liquid 1h be at the uniform velocity added dropwise simultaneously drip off, B liquid 1.5h is dripped off, after B drop is complete, temperature 47~
Soaking time is 1h again at 52 DEG C, and reacting rear material is cooled to room temperature, (zinc salt catalyzes and synthesizes) polycarboxylate water-reducer is obtained.
Embodiment 18:
A kind of method that zinc salt catalyzes and synthesizes polycarboxylate water-reducer, in ingredient described in step a: polymeric monomer: minor comonomer rubs
You are relatively good for 3.9:1, chain-transferring agent be monomer gross mass (monomer gross mass be polymeric monomer and minor comonomer quality it
With it is rear same) 0.6%, reducing agent is the 0.3% of monomer gross mass, and oxidant is the 0.8% of monomer gross mass, and catalyst is
The 0.15% of monomer gross mass；It is any in the other the same as in Example 1 1~17, it omits.
Embodiment 19:
A kind of method that zinc salt catalyzes and synthesizes polycarboxylate water-reducer, in ingredient described in step a: polymeric monomer: minor comonomer rubs
, than being 4.1:1, chain-transferring agent is monomer gross mass for you (monomer gross mass is the quality sum of polymeric monomer and minor comonomer, rear same)
0.7%, reducing agent be monomer gross mass 0.4%, oxidant be monomer gross mass 1%, catalyst is monomer gross mass
0.2%；It is any in the other the same as in Example 1 1~17, it omits.
Embodiment 20:
A kind of method that zinc salt catalyzes and synthesizes polycarboxylate water-reducer, in ingredient described in step a: polymeric monomer: minor comonomer rubs
, than being 4:1, chain-transferring agent is monomer gross mass for you (monomer gross mass is the quality sum of polymeric monomer and minor comonomer, rear same)
0.65%, reducing agent is the 0.35% of monomer gross mass, and oxidant is the 0.9% of monomer gross mass, and catalyst is the total matter of monomer
The 0.18% of amount；It is any in the other the same as in Example 1 1~17, it omits.
Embodiment 21:
A kind of method that zinc salt catalyzes and synthesizes polycarboxylate water-reducer,
Minor comonomer and chain-transferring agent are mixed with water described in step a, A liquid is configured to, is: by minor comonomer and chain-transferring agent
Gross mass: water be 1:4.2 mass ratio minor comonomer and chain-transferring agent are mixed with water, be configured to A liquid.
Reducing agent and catalyst are mixed with water described in step a, B liquid is configured to, is: by the total of reducing agent and catalyst
Quality: water is that the mass ratio of 1:110 mixes reducing agent and catalyst with water, is configured to B liquid.
Polymeric monomer and water are added in the reactor of thermometer described in step b, are: by polymeric monomer: water 1:0.5
Mass ratio polymeric monomer and water are added in the reactor of thermometer.
It is any in the other the same as in Example 1 1~20, it omits.
Embodiment 22:
A kind of method that zinc salt catalyzes and synthesizes polycarboxylate water-reducer,
Minor comonomer and chain-transferring agent are mixed with water described in step a, A liquid is configured to, is: by minor comonomer and chain-transferring agent
Gross mass: water be 1:4.8 mass ratio minor comonomer and chain-transferring agent are mixed with water, be configured to A liquid.
Reducing agent and catalyst are mixed with water described in step a, B liquid is configured to, is: by the total of reducing agent and catalyst
Quality: water is that the mass ratio of 1:200 mixes reducing agent and catalyst with water, is configured to B liquid.
Polymeric monomer and water are added in the reactor of thermometer described in step b, are: by polymeric monomer: water 1:0.6
Mass ratio polymeric monomer and water are added in the reactor of thermometer.
It is any in the other the same as in Example 1 1~20, it omits.
Embodiment 23:
A kind of method that zinc salt catalyzes and synthesizes polycarboxylate water-reducer,
Minor comonomer and chain-transferring agent are mixed with water described in step a, A liquid is configured to, is: by minor comonomer and chain-transferring agent
Gross mass: water be 1:4.5 mass ratio minor comonomer and chain-transferring agent are mixed with water, be configured to A liquid.
Reducing agent and catalyst are mixed with water described in step a, B liquid is configured to, is: by the total of reducing agent and catalyst
Quality: water is that the mass ratio of 1:150 mixes reducing agent and catalyst with water, is configured to B liquid.
Polymeric monomer and water are added in the reactor of thermometer described in step b, are: by polymeric monomer: water 1:
Polymeric monomer and water are added in the reactor of thermometer by 0.56 mass ratio.
It is any in the other the same as in Example 1 1~20, it omits.
Embodiment 24:
A kind of method that zinc salt catalyzes and synthesizes polycarboxylate water-reducer,
Minor comonomer and chain-transferring agent are mixed with water described in step a, A liquid is configured to, is: by minor comonomer and chain-transferring agent
Gross mass: water be 1:4.3 mass ratio minor comonomer and chain-transferring agent are mixed with water, be configured to A liquid.
Reducing agent and catalyst are mixed with water described in step a, B liquid is configured to, is: by the total of reducing agent and catalyst
Quality: water is that the mass ratio of 1:170 mixes reducing agent and catalyst with water, is configured to B liquid.
Polymeric monomer and water are added in the reactor of thermometer described in step b, are: by polymeric monomer: water 1:
Polymeric monomer and water are added in the reactor of thermometer by 0.55 mass ratio.
It is any in the other the same as in Example 1 1~20, it omits.
Embodiment 25:
A kind of method that zinc salt catalyzes and synthesizes polycarboxylate water-reducer,
Minor comonomer and chain-transferring agent are mixed with water described in step a, A liquid is configured to, is: by minor comonomer and chain-transferring agent
Gross mass: water is that any mass ratio mixes minor comonomer and chain-transferring agent with water in 1:4.2~4.8, is configured to A liquid.
Reducing agent and catalyst are mixed with water described in step a, B liquid is configured to, is: by the total of reducing agent and catalyst
Quality: water is that mass ratio any in 1:110~200 mixes reducing agent and catalyst with water, is configured to B liquid.
Polymeric monomer and water are added in the reactor of thermometer described in step b, are: by polymeric monomer: water 1:0.5
Polymeric monomer and water are added in the reactor of thermometer by any mass ratio in~0.6.
It is any in the other the same as in Example 1 1~20, it omits.
In above-described embodiment:
The minor comonomer is one in acrylic acid, hydroxy-ethyl acrylate, hydroxypropyl acrylate and methylpropene sodium sulfonate
Kind or two or more mixtures, preferably acrylic acid；
The water is distilled water or deionized water.
In above-described embodiment 11~25:
The polymeric monomer is that (abbreviation TPEG, production enterprise and model have isoamyl alcohol polyoxyethylene ether: Liaoning Losec
Chemical limited liability company, OXAA-2400 type TPEG monomer；Liaoning Fine Chemical Industry Co., Ltd., F-54-2400 type
TPEG monomer；ZheJiang HuangMa Science Co., Ltd, HM005-2400 type TPEG monomer etc.), molecular weight is 2000~4000；
(production enterprise and model are preferable are as follows: Liaoning Losec chemistry for the isoamyl alcohol polyoxyethylene ether that preferred molecular weight is 2400
Limited liability company, OXAA-2400 type TPEG monomer)；
The chain-transferring agent is the mixture of one or both of thioacetic acid, mercaptopropionic acid, preferably thioacetic acid；
The catalyst is the mixture of one or both of zinc chloride, zinc sulfate, preferably sulfuric acid zinc；
The reducing agent is one or both of sodium hypophosphite, sodium hydrogensulfite, sodium sulfite and ascorbic acid
Above mixture, preferably sodium hydrogensulfite；
The oxidant is the mixture of one or more of hydrogen peroxide, potassium peroxydisulfate and ammonium persulfate etc.,
It is preferred that hydrogen peroxide；
In above-described embodiment 16~17: insulation reaction at 47~52 DEG C of temperature described in step b, preferably temperature 48~
Insulation reaction at 50 DEG C.
In above-described embodiment: used each raw material is commercial product.
In above-described embodiment: it is not specifically specified in used percentage, be quality (weight) percentage or
Well known to a person skilled in the art percentages；Described quality (weight) part can be gram or kilogram.Technique in each step
Parameter (temperature, time etc.) and dosage of each component numerical value etc. are range, and any point is applicable.
The technology contents being not specifically delineated in the content of present invention and above-described embodiment are compared with technology.
The present invention is not limited to the above embodiments, can be implemented described in the content of present invention and has the good result.
Claims (8)
1. a kind of method that zinc salt catalyzes and synthesizes polycarboxylate water-reducer, it is characterized in that step are as follows:
A, ingredient:
Take raw material polymeric monomer, minor comonomer, chain-transferring agent, reducing agent, oxidant, catalyst and water, in which: polymeric monomer: minor comonomer
Molar ratio be 3.8:1~4.2:1, chain-transferring agent is the 0.5%~0.7% of monomer gross mass, and reducing agent is monomer gross mass
0.2%~4%, oxidant is the 0.5%~1.1% of monomer gross mass, and catalyst is the 0.1%~0.2% of monomer gross mass；
Minor comonomer and chain-transferring agent are mixed with water, are configured to A liquid, for use；
Reducing agent and catalyst are mixed with water, are configured to B liquid, for use；
The polymeric monomer is isoamyl alcohol polyoxyethylene ether, and molecular weight is 2000~4000；
The minor comonomer be one of acrylic acid, hydroxy-ethyl acrylate, hydroxypropyl acrylate and methylpropene sodium sulfonate or
Two or more mixtures；
The chain-transferring agent is the mixture of one or both of thioacetic acid, mercaptopropionic acid；
The catalyst is the mixture of one or both of zinc chloride, zinc sulfate；
The reducing agent is one or more of sodium hypophosphite, sodium hydrogensulfite, sodium sulfite and ascorbic acid
Mixture；
The oxidant is the mixture of one or more of hydrogen peroxide, potassium peroxydisulfate and ammonium persulfate etc.；
B, synthetic reaction:
Polymeric monomer and water are added in the reactor of thermometer, heat temperature raising simultaneously stirs, to temperature reach 47~52 DEG C and
When polymeric monomer is completely dissolved, oxidant, mixing is added, then while being at the uniform velocity added dropwise to A liquid and B liquid, dropwise addition and 47~52 DEG C of temperature
The total time of lower insulation reaction is 2~2.5h, and reacting rear material is cooled to room temperature, polycarboxylate water-reducer is obtained.
2. by the method that zinc salt described in claim 1 catalyzes and synthesizes polycarboxylate water-reducer, it is characterized in that: in ingredient described in step a:
Polymeric monomer: the molar ratio of minor comonomer is preferably 3.9:1~4.1:1, chain-transferring agent be preferably monomer gross mass 0.6%~
0.7%, reducing agent is preferably the 0.3%~0.4% of monomer gross mass, and oxidant is preferably the 0.8%~1% of monomer gross mass,
Catalyst is preferably the 0.15%~0.2% of monomer gross mass.
3. by the method that zinc salt as claimed in claim 1 or 2 catalyzes and synthesizes polycarboxylate water-reducer, it is characterized in that: will described in step a
Minor comonomer and chain-transferring agent are mixed with water, are configured to A liquid, are: by the gross mass of minor comonomer and chain-transferring agent: water be 1:4.2~
4.8 mass ratio mixes minor comonomer and chain-transferring agent with water, is configured to A liquid.
4. by the method that zinc salt as claimed in claim 1 or 2 catalyzes and synthesizes polycarboxylate water-reducer, it is characterized in that: will described in step a
Reducing agent and catalyst are mixed with water, are configured to B liquid, are: by the gross mass of reducing agent and catalyst: water is 1:110~200
Mass ratio mixes reducing agent and catalyst with water, is configured to B liquid.
5. by the method that zinc salt as claimed in claim 1 or 2 catalyzes and synthesizes polycarboxylate water-reducer, it is characterized in that: water described in step a
It is distilled water or deionized water.
6. by the method that zinc salt as claimed in claim 1 or 2 catalyzes and synthesizes polycarboxylate water-reducer, it is characterized in that: will described in step b
Polymeric monomer and water are added in the reactor of thermometer, are by polymeric monomer: water is that the mass ratio of 1:0.5~0.6 will be single greatly
Body and water are added in the reactor of thermometer.
7. by the method that zinc salt as claimed in claim 1 or 2 catalyzes and synthesizes polycarboxylate water-reducer, it is characterized in that: temperature described in step b
Insulation reaction at 47~52 DEG C of degree, is insulation reaction at 48~50 DEG C of temperature.
8. by the method that zinc salt as claimed in claim 1 or 2 catalyzes and synthesizes polycarboxylate water-reducer, it is characterized in that: described in step b again
At the uniform velocity be added dropwise to A liquid and B liquid simultaneously, be added dropwise and 47~52 DEG C at a temperature of total time of insulation reaction be 2~3h, be: again simultaneously
A liquid at the uniform velocity is added dropwise and B liquid, A liquid 1h are dripped off, B liquid 1.5h is dripped off, and after B drop is complete, soaking time is again at 47~52 DEG C of temperature
1h。
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| CN113372508A (en) * | 2021-06-09 | 2021-09-10 | 西南科技大学 | Method for synthesizing polycarboxylate superplasticizer through manganese oxide heterogeneous catalysis quaternary copolymerization of 6C polyether macromonomer |
| CN115449023A (en) * | 2021-06-09 | 2022-12-09 | 西南科技大学 | Method for synthesizing polycarboxylate superplasticizer through zinc oxide heterogeneous catalytic ternary copolymerization of 6C polyether macromonomer |
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| CN104231183A (en) * | 2014-09-23 | 2014-12-24 | 江苏奥莱特新材料有限公司 | Preparation method for polycarboxylate-type water reducer |
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| CN103159899A (en) * | 2012-12-21 | 2013-06-19 | 新疆德蓝股份有限公司 | Preparing method for polycarboxylate water reducing agent |
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| CN115449023A (en) * | 2021-06-09 | 2022-12-09 | 西南科技大学 | Method for synthesizing polycarboxylate superplasticizer through zinc oxide heterogeneous catalytic ternary copolymerization of 6C polyether macromonomer |
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