CN109053969A - A kind of method that nickel salt catalyzes and synthesizes polycarboxylate water-reducer - Google Patents
A kind of method that nickel salt catalyzes and synthesizes polycarboxylate water-reducer Download PDFInfo
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- CN109053969A CN109053969A CN201810737515.8A CN201810737515A CN109053969A CN 109053969 A CN109053969 A CN 109053969A CN 201810737515 A CN201810737515 A CN 201810737515A CN 109053969 A CN109053969 A CN 109053969A
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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
-
- 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
- C08F4/26—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of manganese, iron group metals or platinum group metals
-
- 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
-
- 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
Abstract
The invention discloses a kind of methods that nickel 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 45~50 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 2~3h, 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 nickel 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 nickel 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 nickel 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 8.2:1~8.5:1, 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) 0.4%~0.8%, reducing agent is the 0.3%~1% of monomer gross mass, and oxidant is that monomer is total
The 0.8%~1% of quality, catalyst are the 0.033%~0.083% 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 six hydration Nickel Chlorides, nickel sulfate hexahydrate, preferably six water
Nickel sulfate；According to the content of nickel in nickel sulfate hexahydrate when nickel salt or seven water nickel sulfates without the crystallization water also can be used, using
Equivalent conversion；
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 45~50 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 45~50 DEG C at a temperature of insulation reaction total time be 2~
Reacting rear material is cooled to room temperature by 3h, obtains (nickel 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 8.3:1~
8.4:1, chain-transferring agent are preferably monomer gross mass (monomer gross mass is the quality sum of polymeric monomer and minor comonomer, rear same)
0.55%~0.75%, reducing agent is preferably the 0.3%~0.45% of monomer gross mass, and oxidant is preferably that monomer is total
The 0.86%~0.9% of quality, catalyst are preferably the 0.033%~0.04% 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 1:4.3~4.8 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 1:90~190 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 is 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 45~50 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 45~50 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 again at 45~50 DEG C of temperature
0.5h。
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 nickel salt for catalyst for the first time, reaction temperature is reduced to 45~50 DEG C, redox effect
Rate is higher, and total reaction time is short, and (nickel salt catalyzes and synthesizes) polycarboxylate water-reducer obtained has good initial dispersion (identical
Volume water-reducing rate improves 1~4%) and function of slump protection (slump-loss reduced in 1 hour), and synthesis material is cheap and easy to get, synthesis
Simple process is efficient, and polycarboxylate water-reducer obtained can not adjust pH and directly use, easy to industrialized production；
(2) using the present invention, in terms of nickel salt mainly has following two to the mechanism of action of free radical polymerization:
On the one hand: (1) nickel ion can be decomposed with catalytic oxidant hydrogen peroxide, promote the redox with sodium hydrogensulfite
Reaction, so that initiator trigger rate is very fast, hydrogen peroxide decomposition primary group of free radicals generating rate is very fast, and it is raw quickly to cause monomer
At monomer radical, accelerate polymerization reaction, shortens polymerization cycle, molecular weight of product is big, and polycarboxylate water-reducer dispersion performance is preferable.
Reaction equation is as follows:
On the other hand: nickel ion can form complex, one negative electrical charge of carboxyl band with carboxylic acid, and there are two can
With the oxygen atom of metallic ion coordination, energy and metal ion-chelant form the stable coordination polymer network bone in electroneutral
Frame.Carboxyl can not only be bonded with a variety of coordination modes with metal ion, can also be combined with metal ion to be formed multi-nuclear metal from
The secondary structure unit of son, and then construct various coordination polymer network structures.Nickel ion is assembled with carboxylic acid group
It is not easy to lose water of coordination when the polymer of position, especially when there is no containing n-donor ligand, is more likely to be bonded with monatomic form with carboxylic acid.
Coordination causes electronic migration, and double bond activity is caused to become larger, so that polymerization is rapider, copolyreaction course is influenced, to influence
Its skeleton structure；Macro manifestations become larger for polymer molecular weight, and polycarboxylate water-reducer water-retaining property improves, so that cement paste 1h is passed through
When fluidity increase.
Reaction mechanism figure is as follows:
(3) 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, 2882.17cm-1Place is the stretching vibration peak of saturated hydrocarbons c h bond,
1467.35cm-1And 1345.02cm-1For its flexural vibrations peak；1726.76cm-1Place is carboxyl C=O stretching vibration peak；
842.69cm-1、951.55cm-1And 1113.46cm-1The absorption peak at place is the characteristic absorption peak of long side chain polyoxyethylene groups, wherein
1113.46cm-1It is the stretching vibration of ehter bond C-O-C, 951.55cm-1For C-O stretching vibration peak and 842.69cm-1It is stretched for C-C
Contracting vibration peak；Features above peak can show that minor comonomer and polyether macromonomer produce copolymerization in solution, generates polycarboxylic acids and subtracts
Aqua.
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 nickel salt catalyzes and synthesizes polycarboxylate water-reducer, step are as follows: prepare A liquid respectively and (weigh minor comonomer
3.17g, thioacetic acid 0.12g and distilled water 15g mixing) and B liquid (sodium hydrogensulfite 0.15g, nickel sulfate hexahydrate 0.015g and steaming
Distilled water 20g mixing) for use, polymeric monomer (TPEG) 26.83g and distilled water 15g are added in the three-necked flask for being equipped with thermometer, by
Edge up temperature and stirring and dissolving, and when temperature reaches 46 DEG C and polymeric monomer is completely dissolved, 0.2774g hydrogen peroxide is added, is uniformly mixed
Afterwards, A liquid (62min is dripped off) and B liquid (91min is dripped off) are at the uniform velocity added dropwise simultaneously with constant pressure funnel, soaking time 0.5h is cold
But to room temperature to get the polycarboxylate water-reducer with superperformance catalyzed and synthesized by nickel salt.
Embodiment 2:
A kind of method that nickel salt catalyzes and synthesizes polycarboxylate water-reducer, step are as follows: prepare A liquid respectively and (weigh minor comonomer
3.10g, thioacetic acid 0.15g and distilled water 15g mixing) and B liquid (sodium hydrogensulfite 0.18g, nickel sulfate hexahydrate 0.01g and steaming
Distilled water 20g mixing) for use, polymeric monomer (TPEG) 26.9g and distilled water 15g are added in the three-necked flask for being equipped with thermometer, by
Edge up temperature and stirring and dissolving, and when temperature reaches 48 DEG C and polymeric monomer is completely dissolved, 0.2864g hydrogen peroxide is added, is uniformly mixed
Afterwards, A liquid (58min is dripped off) and B liquid (87min is dripped off) are at the uniform velocity added dropwise simultaneously with constant pressure funnel, soaking time 0.5h is cold
But to room temperature to get the polycarboxylate water-reducer with good practical performance catalyzed and synthesized by nickel salt.
Embodiment 3:
A kind of method that nickel salt catalyzes and synthesizes polycarboxylate water-reducer, step are as follows: prepare A liquid respectively and (weigh minor comonomer
3.217g, thioacetic acid 0.17g and distilled water 15g mixing) and B liquid (sodium hydrogensulfite 0.2g, nickel sulfate hexahydrate 0.02g and steaming
Distilled water 20g mixing) for use, polymeric monomer (TPEG) 26.783g and distilled water 15g are added in the three-necked flask for being equipped with thermometer,
It is gradually warmed up and 0.2928g hydrogen peroxide is added when temperature reaches 50 DEG C and polymeric monomer is completely dissolved in stirring and dissolving, mixing is equal
After even, A liquid (60min is dripped off) and B liquid (94min is dripped off) are at the uniform velocity added dropwise simultaneously with constant pressure funnel, soaking time 0.5h,
It is cooled to room temperature to get the polycarboxylate water-reducer with good practical performance catalyzed and synthesized by nickel salt.
Embodiment 4:
A kind of method that nickel salt catalyzes and synthesizes polycarboxylate water-reducer, step are as follows: prepare A liquid respectively and (weigh minor comonomer
3.2167g, thioacetic acid 0.12g and distilled water 15g mixing) and B liquid (sodium hydrogensulfite 0.1g, nickel sulfate hexahydrate 0.01g and steaming
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,
It is gradually warmed up and 0.2167g hydrogen peroxide is added when temperature reaches 48 DEG C and polymeric monomer is completely dissolved in stirring and dissolving, mixing is equal
After even, A liquid (56min is dripped off) and B liquid (88min is dripped off) are at the uniform velocity added dropwise simultaneously with constant pressure funnel, soaking time 0.5h,
It is cooled to room temperature to get the polycarboxylate water-reducer with good practical performance catalyzed and synthesized by nickel salt.
Embodiment 5:
A kind of method that nickel salt catalyzes and synthesizes polycarboxylate water-reducer, step are as follows: prepare A liquid respectively and (weigh minor comonomer
3.233g, thioacetic acid 0.2g and distilled water 15g mixing) and B liquid (sodium hydrogensulfite 0.16g, nickel sulfate hexahydrate 0.01g and steaming
Distilled water 20g mixing) for use, polymeric monomer (TPEG) 26.767g and distilled water 15g are added in the three-necked flask for being equipped with thermometer,
It is gradually warmed up and 0.2782g hydrogen peroxide is added when temperature reaches 46 DEG C and polymeric monomer is completely dissolved in stirring and dissolving, mixing is equal
After even, A liquid (63min is dripped off) and B liquid (92min is dripped off) are at the uniform velocity added dropwise simultaneously with constant pressure funnel, soaking time 0.5h,
It is cooled to room temperature to get the polycarboxylate water-reducer with superperformance catalyzed and synthesized by nickel salt.
Embodiment 6:
A kind of method that nickel salt catalyzes and synthesizes polycarboxylate water-reducer, step are as follows: prepare A liquid respectively and (weigh minor comonomer
3.304g, thioacetic acid 0.17g and distilled water 15g mixing) and B liquid (sodium hydrogensulfite 0.1g, nickel sulfate hexahydrate 0.012g and steaming
Distilled water 20g mixing) for use, polymeric monomer (TPEG) 26.696g and distilled water 15g are added in the three-necked flask for being equipped with thermometer,
It is gradually warmed up and 0.2614g hydrogen peroxide is added when temperature reaches 50 DEG C and polymeric monomer is completely dissolved in stirring and dissolving, mixing is equal
After even, A liquid (59min is dripped off) and B liquid (89min is dripped off) are at the uniform velocity added dropwise simultaneously with constant pressure funnel, soaking time 0.5h,
It is cooled to room temperature to get the polycarboxylate water-reducer with good practical performance catalyzed and synthesized by nickel salt.
Embodiment 7:
A kind of method that nickel salt catalyzes and synthesizes polycarboxylate water-reducer, step are as follows: prepare A liquid respectively and (weigh minor comonomer
3.257g, thioacetic acid 0.2g and distilled water 15g mixing) and B liquid (sodium hydrogensulfite 0.14g, nickel sulfate hexahydrate 0.01g and steaming
Distilled water 20g mixing) for use, polymeric monomer (TPEG) 26.743g and distilled water 15g are added in the three-necked flask for being equipped with thermometer,
It is gradually warmed up and 0.266g hydrogen peroxide is added when temperature reaches 48 DEG C and polymeric monomer is completely dissolved in stirring and dissolving, be uniformly mixed
Afterwards, A liquid (63min is dripped off) and B liquid (90min is dripped off) are at the uniform velocity added dropwise simultaneously with constant pressure funnel, soaking time 0.5h is cold
But to room temperature to get the polycarboxylate water-reducer with good practical performance catalyzed and synthesized by nickel salt.
Embodiment 8:
A kind of method that nickel salt catalyzes and synthesizes polycarboxylate water-reducer, step are as follows: prepare A liquid respectively and (weigh minor comonomer
3.208g, thioacetic acid 0.14g and distilled water 15g mixing) and B liquid (sodium hydrogensulfite 0.18g, nickel sulfate hexahydrate 0.016g and
Distilled water 20g mixing) for use, polymeric monomer (TPEG) 26.872g and distilled water are added in the three-necked flask for being equipped with thermometer
15g, is gradually warmed up and 0.2905g hydrogen peroxide is added when temperature reaches 49 DEG C and polymeric monomer is completely dissolved in stirring and dissolving, mixes
After closing uniformly, A liquid (61min is dripped off) at the uniform velocity is added dropwise simultaneously with constant pressure funnel and B liquid (94min is dripped off), soaking time are
0.5h is cooled to room temperature to get the polycarboxylate water-reducer with good practical performance catalyzed and synthesized by nickel salt.
Embodiment 9:
A kind of method that nickel salt catalyzes and synthesizes polycarboxylate water-reducer, step are as follows: prepare A liquid respectively and (weigh minor comonomer
3.275g, thioacetic acid 0.16g and distilled water 15g mixing) and B liquid (sodium hydrogensulfite 0.12g, nickel sulfate hexahydrate 0.015g and
Distilled water 20g mixing) for use, polymeric monomer (TPEG) 26.725g and distilled water are added in the three-necked flask for being equipped with thermometer
15g, is gradually warmed up and 0.2677g hydrogen peroxide is added when temperature reaches 45 DEG C and polymeric monomer is completely dissolved in stirring and dissolving, mixes
After closing uniformly, A liquid (60min is dripped off) at the uniform velocity is added dropwise simultaneously with constant pressure funnel and B liquid (94min is dripped off), soaking time are
0.5h is cooled to room temperature to get the polycarboxylate water-reducer with good practical performance catalyzed and synthesized by nickel salt.
Embodiment 10:
A kind of method that nickel 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 0.15g, nickel sulfate hexahydrate 0.01g and steaming
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,
It is gradually warmed up and 0.2754g hydrogen peroxide is added when temperature reaches 48 DEG C and polymeric monomer is completely dissolved in stirring and dissolving, mixing is equal
After even, A liquid (61min is dripped off) and B liquid (92min is dripped off) are at the uniform velocity added dropwise simultaneously with constant pressure funnel, soaking time 0.5h,
It is cooled to room temperature to get the polycarboxylate water-reducer with good practical performance catalyzed and synthesized by nickel 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 nickel 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 8.2:1, chain-transferring agent be monomer gross mass (monomer gross mass be polymeric monomer and minor comonomer quality it
With it is rear same) 0.4%, reducing agent is the 0.3% of monomer gross mass, and oxidant is the 0.8% of monomer gross mass, and catalyst is
The 0.033% 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 45 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 45 DEG C at a temperature of total time of insulation reaction be 3h, after reaction
Material is cooled to room temperature, and obtains (nickel salt catalyzes and synthesizes) polycarboxylate water-reducer.
Embodiment 12:
A kind of method that nickel 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 8.5:1, chain-transferring agent be monomer gross mass (monomer gross mass be polymeric monomer and minor comonomer quality it
With it is rear same) 0.8%, reducing agent is the 1% of monomer gross mass, and oxidant is the 1% of monomer gross mass, and catalyst is monomer
The 0.083% of 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 2h, after reaction
Material is cooled to room temperature, and obtains (nickel salt catalyzes and synthesizes) polycarboxylate water-reducer.
Embodiment 13:
A kind of method that nickel 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 8.35:1, and chain-transferring agent is that (monomer gross mass is the quality of polymeric monomer and minor comonomer to monomer gross mass
The sum of, it is rear same) 0.6%, reducing agent is the 0.65% of monomer gross mass, and oxidant is the 0.9% of monomer gross mass, catalyst
It is the 0.058% 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 48 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 48 DEG C at a temperature of total time of insulation reaction be 2.5h, will react
Material is cooled to room temperature afterwards, obtains (nickel salt catalyzes and synthesizes) polycarboxylate water-reducer.
Embodiment 14:
A kind of method that nickel 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 8.3:1, 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 0.5% of monomer gross mass, and oxidant is the 0.9% of monomer gross mass, and catalyst is
The 0.045% 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 45~50 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 45~50 DEG C at a temperature of total time of insulation reaction be
2.5h reacting rear material is cooled to room temperature, (nickel salt catalyzes and synthesizes) polycarboxylate water-reducer is obtained.
Embodiment 15:
A kind of method that nickel 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 8.4:1, chain-transferring agent be monomer gross mass (monomer gross mass be polymeric monomer and minor comonomer quality it
With it is rear same) 0.7%, reducing agent is the 0.7% of monomer gross mass, and oxidant is the 0.9% of monomer gross mass, and catalyst is
The 0.063% 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 45~50 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 45~50 DEG C at a temperature of total time of insulation reaction be
Reacting rear material is cooled to room temperature by 2.5h, obtains (nickel salt catalyzes and synthesizes) polycarboxylate water-reducer.
Embodiment 16:
A kind of method that nickel 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 8.2:1~8.5:1, chain-transferring agent be monomer gross mass (monomer gross mass be polymeric monomer with
It is the quality sum of minor comonomer, rear same) 0.4%~0.8% in it is any, reducing agent is to appoint in the 0.3%~1% of monomer gross mass
One, oxidant be monomer gross mass 0.8%~1% in it is any, catalyst be monomer gross mass 0.033%~0.083%
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 45~50 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 45~50 DEG C at a temperature of insulation reaction total time be 2~
It is any in 3h, reacting rear material is cooled to room temperature, (nickel salt catalyzes and synthesizes) polycarboxylate water-reducer is obtained.
Embodiment 17:
A kind of method that nickel salt catalyzes and synthesizes polycarboxylate water-reducer, in ingredient described in step a: polymeric monomer: minor comonomer rubs
, than being 8.3:1, chain-transferring agent is monomer gross mass for you (monomer gross mass is the quality sum of polymeric monomer and minor comonomer, rear same)
0.55%, reducing agent be monomer gross mass 0.3%, oxidant be monomer gross mass 0.86%, catalyst be monomer it is total
The 0.033% of quality；It is any in the other the same as in Example 1 1~16, it omits.
Embodiment 18:
A kind of method that nickel salt catalyzes and synthesizes polycarboxylate water-reducer, in ingredient described in step a: polymeric monomer: minor comonomer rubs
, than being 8.4:1, chain-transferring agent is monomer gross mass for you (monomer gross mass is the quality sum of polymeric monomer and minor comonomer, rear same)
0.75%, reducing agent be monomer gross mass 0.45%, oxidant be monomer gross mass 0.9%, catalyst be monomer it is total
The 0.04% of quality；It is any in the other the same as in Example 1 1~16, it omits.
Embodiment 19:
A kind of method that nickel salt catalyzes and synthesizes polycarboxylate water-reducer, in ingredient described in step a: polymeric monomer: minor comonomer rubs
, than being 8.3:1, 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 be monomer gross mass 0.38%, oxidant be monomer gross mass 0.88%, catalyst be monomer it is total
The 0.037% of quality；It is any in the other the same as in Example 1 1~16, it omits.
Embodiment 20:
A kind of method that nickel salt catalyzes and synthesizes polycarboxylate water-reducer,
Minor comonomer and chain-transferring agent are mixed with water described in step a, are configured to A liquid, preferably: pressing minor comonomer and chain
The gross mass of transfer agent: water is that the mass ratio of 1:4.3 mixes minor comonomer and chain-transferring agent with water, is configured to A liquid；
Reducing agent and catalyst are mixed with water described in step a, are configured to B liquid, preferably: pressing reducing agent and catalysis
The gross mass of agent: water is that the mass ratio of 1:90 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, preferably by polymeric monomer: water is
Polymeric monomer and water are added in the reactor of thermometer by the mass ratio of 1:0.5；
It is the same as any in embodiment 11~19, omission.
Embodiment 21:
A kind of method that nickel salt catalyzes and synthesizes polycarboxylate water-reducer,
Minor comonomer and chain-transferring agent are mixed with water described in step a, are configured to A liquid, preferably: pressing minor comonomer and chain
The gross mass of transfer agent: water is that the mass ratio of 1:4.8 mixes minor comonomer and chain-transferring agent with water, is configured to A liquid；
Reducing agent and catalyst are mixed with water described in step a, are configured to B liquid, preferably: pressing reducing agent and catalysis
The gross mass of agent: water is that the mass ratio of 1:190 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, preferably by polymeric monomer: water is
Polymeric monomer and water are added in the reactor of thermometer by the mass ratio of 1:0.6；
It is the same as any in embodiment 11~19, omission.
Embodiment 22:
A kind of method that nickel salt catalyzes and synthesizes polycarboxylate water-reducer,
Minor comonomer and chain-transferring agent are mixed with water described in step a, are configured to A liquid, preferably: pressing minor comonomer and chain
The gross mass of transfer agent: water is that the mass ratio of 1:4.6 mixes minor comonomer and chain-transferring agent with water, is configured to A liquid；
Reducing agent and catalyst are mixed with water described in step a, are configured to B liquid, preferably: pressing reducing agent and catalysis
The gross mass of agent: 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, preferably by polymeric monomer: water is
Polymeric monomer and water are added in the reactor of thermometer by the mass ratio of 1:0.56；
It is the same as any in embodiment 11~19, omission.
Embodiment 23:
A kind of method that nickel salt catalyzes and synthesizes polycarboxylate water-reducer,
Minor comonomer and chain-transferring agent are mixed with water described in step a, are configured to A liquid, preferably: pressing minor comonomer and chain
The gross mass of transfer agent: water is that mass ratio any in 1:4.3~4.8 mixes minor comonomer and chain-transferring agent with water, is prepared
At A liquid；
Reducing agent and catalyst are mixed with water described in step a, are configured to B liquid, preferably: pressing reducing agent and catalysis
The gross mass of agent: water is that mass ratio any in 1:90~190 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, preferably by polymeric monomer: water is
Polymeric monomer and water are added in the reactor of thermometer by any mass ratio in 1:0.5~0.6；
It is the same as any in embodiment 11~19, omission.
Embodiment 24:
In above-described embodiment 14: 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, replacement at a temperature of 45~50 DEG C of adduction are as follows: is at the uniform velocity dripped simultaneously (with constant pressure funnel) again
Add A liquid and B liquid, A liquid 1h is dripped off, and B liquid 1.5h is dripped off, and after B drop is complete, soaking time is 0.5h again at 45~50 DEG C of temperature.
Embodiment 25:
In above-described embodiment 15: 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, replacement at a temperature of 45~50 DEG C of adduction are as follows: is at the uniform velocity dripped simultaneously (with constant pressure funnel) again
Add A liquid and B liquid, A liquid 1h is dripped off, and B liquid 1.5h is dripped off, and after B drop is complete, soaking time is 0.5h again at 45~50 DEG C of temperature.
In above-described embodiment:
The water is distilled water or deionized water.
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.
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 six hydration Nickel Chlorides, nickel sulfate hexahydrate, preferably six water
Nickel sulfate；According to the content of nickel in nickel sulfate hexahydrate when nickel salt or seven water nickel sulfates without the crystallization water also can be used, using
Equivalent conversion；
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 14~16 and 24~25: insulation reaction at 45~50 DEG C of temperature described in step b, preferably
Insulation reaction at 48~50 DEG C of temperature.
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.
In above-described embodiment: technological parameter (temperature, time etc.) and dosage of each component numerical value in each step etc. are range
, 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 nickel 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 8.2:1~8.5:1, chain-transferring agent is the 0.4%~0.8% of monomer gross mass, and reducing agent is monomer gross mass
0.3%~1%, oxidant is the 0.8%~1% of monomer gross mass, and catalyst is the 0.033%~0.083% 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 six hydration Nickel Chlorides, nickel sulfate hexahydrate；
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 45~50 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 45~50 DEG C of temperature
The total time of lower insulation reaction is 2~3h, and reacting rear material is cooled to room temperature, polycarboxylate water-reducer is obtained.
2. by the method that nickel 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 8.3:1~8.4:1, and chain-transferring agent is the 0.55%~0.75% of monomer gross mass, reducing agent
It is the 0.3%~0.45% of monomer gross mass, oxidant is the 0.86%~0.9% of monomer gross mass, and catalyst is monomer gross mass
0.033%~0.04%.
3. by the method that nickel 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 1:4.3~
4.8 mass ratio mixes minor comonomer and chain-transferring agent with water, is configured to A liquid.
4. by the method that nickel 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 1:90~190
Mass ratio mixes reducing agent and catalyst with water, is configured to B liquid.
5. by the method that nickel 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 nickel 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 nickel 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 45~50 DEG C of degree, is insulation reaction at 48~50 DEG C of temperature.
8. by the method that nickel 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 45~50 DEG C at a temperature of total time of insulation reaction be 2~3h, preferably:
A liquid is added dropwise again while at the uniform velocity and B liquid, A liquid 1h are dripped off, B liquid 1.5h is dripped off, and after B drop is complete, is kept the temperature again at 45~50 DEG C of temperature
Time is 0.5h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
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| CN105693948A (en) * | 2016-03-22 | 2016-06-22 | 广东乐尔康生物科技股份有限公司 | Preparation method of green and environment-friendly, and high-stability polycarboxylic acid water reducing agent mother liquid |
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