CN102391435A - Slump-retaining polycarboxylic acid type water reducing agent and preparation method thereof - Google Patents
Slump-retaining polycarboxylic acid type water reducing agent and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of preparation of concrete high-performance water reducing agents, and discloses a slump-retaining polycarboxylic acid type water reducing agent. The water reducing agent is prepared by performing free radical copolymerization reaction on a monomer A, a monomer B and a monomer C in a molar ratio of 1:(2-4.3):(0-0.2) in an aqueous solution under the action of an initiator. The water reducing agent is prepared by the following steps of: 1) dissolving the monomer A, the monomer B and the monomer C in water; 2) adding the initiator solution dropwise into the solution for 1.5 to 2 hours, reacting at the temperature of between 60 and 90 DEG C for 2 to 8 hours and cooling after the reaction is finished; and 3) after cooling to below 50 DEG C, neutralizing the product by using an alkaline compound until the pH value is 5 to 8. The slump-retaining polycarboxylic acid type water reducing agent has high water-reducing rate and low slump loss through time. The production process is pollution-free and simple.
Description
Technical field
The present invention relates to the technical field of preparation concrete high-performance water reducer, be specifically related to a kind of collapse protective poly-carboxylic acid based water reducer and preparation method thereof.
Background technology
Along with the continuous development of building engineering field, the effect of water reducer is more and more important and obvious.Traditional naphthalene system and amido sulfoacid series high-efficiency water reducer are progressively replaced by third generation polycarboxylate high performance water-reducing agent because its slump changes greatly, production technique is polluted inferior positions such as more serious.Polycarboxylate high performance water-reducing agent becomes the cement water reducing agent of at present tool potentiality because water-reducing rate is high, the slump changes characteristics such as little, that production technique is pollution-free.
The synthesis technique of poly carboxylic acid series water reducer mainly contains with methoxy poly (ethylene glycol) ether and is the synthetic water reducer of raw material two-step approach and is the synthetic two kinds of methods of water reducer of raw material single stage method with the unsaturated polyether.Advantages such as wherein single stage method is because simple to operate, and is with short production cycle receive researchist's concern more.
Patent CN 101786824 discloses a kind of preparation method of plastic retaining type polyether assemblage carboxylic acid high-performance water reducing agent; Be under action of evocating; By the copolymerization 2～8 hours in the aqueous solution under 50～80 ℃ of unsaturated polyester oxyalkyl ether monomer (A), unsaturated monocarboxylic acid and derivatives monomer (B) thereof, unsaturated dicarboxylic acid and derivatives monomer (C) thereof and unsaturated sulfonic acid or its salt monomer (D), be cooled to 35～45 ℃ then and be neutralized to pH=5～7 with basic soln and make.This method technology is more loaded down with trivial details, and product initial dispersion rate is relatively poor.
Patent CN 101386490 discloses a kind of preparation method of allyl polyglycol ether type polycarboxylic acid series dehydragent; Be to adopt redox initiation systems by 30～50% unsaturated polyalkylene oxide base ether monomer (A), 5～20% unsaturated monocarboxylic acid and derivatives monomer (B) thereof, three kinds of monomers of unsaturated dicarboxylic acid (C) of 1～20% down at 45～70 ℃, copolymerization forms in the aqueous solution.The operation of this method is trouble, even and product water-reducing rate under the bigger situation of volume not high yet.
Patent CN 101492518 discloses a kind of preparation method of ethers polycarboxylic acid water reducing agent, is to carry out aqueous solution copolymerization by 10～70% allyl polyethenoxy alcohol ether (A), 20～70% vinylformic acid (B), three kinds of monomers of Hydroxyethyl acrylate (C) of 10～30% to form.Because the existence of Hydroxyethyl acrylate makes that the initial water-reducing rate of product is low excessively, the volume that therefore needs is bigger.
Summary of the invention
The objective of the invention is the defective that exists to above technology, an object of the present invention is to provide that a kind of water-reducing rate is high, the slump through the time loss low polyethers poly carboxylic acid series water reducer.Another object of the present invention provides the preparation method of above-mentioned polyethers poly carboxylic acid series water reducer.
In order to realize first above-mentioned technical purpose, its technical scheme is following:
A kind of collapse protective poly-carboxylic acid based water reducer, this water reducer are carried out free radicals copolymerization reaction and are formed by monomer A, monomers B and the monomer C mol ratio according to 1:2～4.3:0～0.2 in the aqueous solution under action of evocating, wherein:
1) monomer A: be methyl butene polyoxyethylenated alcohol monomer, general formula is:
In the general formula, n is the integer between 5～100;
2) monomers B: be unsaturated monocarboxylic acid and derivatives monomer thereof, general formula is:
In the general formula, R
1Be hydrogen or methyl, R
2Be hydrogen or methyl, R
3Be hydrogen or methyl, R
4Be hydrogen or methyl or ethyl or amido;
3) monomer C: be unsaturated sulfonic acid and salt monomer thereof, general formula is:
In the general formula, R5 is hydrogen or methyl, and M is hydrogen or alkalimetal ion.
As preferably, described monomer A can be that molecular weight is any monomer between 1200～2400.
As preferably, described monomers B can be any one or a few in vinylformic acid, methyl acrylate, acrylic amide, methylacrylic acid, TEB 3K, the USAF RH-1.
As preferably, described monomer C can be any one or a few in allyl sulphonic acid or its salt, methallyl sulfonic acid or its salt.
In order to realize second above-mentioned technical purpose, its technical scheme is following:
A kind of preparation method who prepares a kind of collapse protective poly-carboxylic acid based water reducer as claimed in claim 1 is characterized in that, this method may further comprise the steps:
1) monomer A, monomers B and monomer C is soluble in water;
2) initiator solution is added dropwise to above solution, the time that drips initiator solution is 1.5～2 hours, and temperature of reaction is 60～90 ℃, and the reaction times is 2～8 hours, and reaction finishes the back cooling;
When 3) being cooled to below 50 ℃, using basic cpd that product is neutralized to pH is 5～8, promptly gets title product.
As preferably, described initiator be in Sodium Persulfate, Potassium Persulphate, the ammonium persulphate any one or multiple, its consumption is 0.8% of monomer A, monomers B and a monomer C gross weight.
As preferably, described temperature of reaction is 75 ~ 82 ℃, and the time of insulation reaction is 2 ~ 4 hours.
As preferably, described basic cpd is any one or a few in sodium hydroxide, Pottasium Hydroxide, quadrol, the trolamine.
Not only water-reducing rate is high in the present invention, the slump through the time loss low, and production technique is pollution-free and technology is simple.
Embodiment
Embodiment below in conjunction with concrete is described in further detail the present invention.
Embodiment 1
In the four-hole boiling flask that disposes whisking appliance, TM, Dropping feeder, reflux cooler, add 200g deionized water, 150g methyl butene polyoxyethylenated alcohol (molecular weight is 1200), 30.92g vinylformic acid, 8.84g sodium allyl sulfonate; Stirring is warming up to 80 ℃; The 4g Sodium Persulfate is dissolved in the initiator solution that is mixed with 5% concentration in the 80g deionized water; In above-mentioned four-hole boiling flask, slowly dripping this initiator solution under 80 ℃, dropwised 80 ℃ of following isothermal reactions 2 hours in about 1.5 hours; Reaction finishes below the postcooling to 50 ℃; Adding 32% aqueous sodium hydroxide solution adjusting pH value is 7, obtains the collapse protective poly-carboxylic acid series high-performance dehydragent of the embodiment of the invention, and code name is PC (I).
Embodiment 2
In the four-hole boiling flask that disposes whisking appliance, TM, Dropping feeder, reflux cooler, add 150g deionized water, 135g methyl butene polyoxyethylenated alcohol (molecular weight is 2200), 15.46g vinylformic acid, 4.85g methylpropene sodium sulfonate; Stirring is warming up to 80 ℃; The 2g Potassium Persulphate is dissolved in the initiator solution that is mixed with 5% concentration in the 40g deionized water; In above-mentioned four-hole boiling flask, slowly dripping this initiator solution under 80 ℃, dropwised 80 ℃ of following isothermal reactions 4 hours in about 2 hours; Reaction finishes below the postcooling to 50 ℃; Adding 32% aqueous sodium hydroxide solution adjusting pH value is 7, obtains the collapse protective poly-carboxylic acid series high-performance dehydragent of the embodiment of the invention, and code name is PC (IV).
Embodiment 3
In the four-hole boiling flask that disposes whisking appliance, TM, Dropping feeder, reflux cooler, add 200g deionized water, 150g methyl butene polyoxyethylenated alcohol (molecular weight is 2400), 17.41g methylacrylic acid, 4.42g sodium allyl sulfonate, 4.42g acrylic amide; Stirring is warming up to 80 ℃; The 2g Sodium Persulfate is dissolved in the initiator solution that is mixed with 5% concentration in the 40g deionized water; In above-mentioned four-hole boiling flask, slowly dripping this initiator solution under 80 ℃, dropwised 80 ℃ of following isothermal reactions 2 hours in about 1.5 hours; Reaction finishes below the postcooling to 50 ℃; Adding 32% aqueous sodium hydroxide solution adjusting pH value is 7, obtains the collapse protective poly-carboxylic acid series high-performance dehydragent of the embodiment of the invention, and code name is PC (V).
Comparative example
In the four-hole boiling flask that disposes whisking appliance, TM, Dropping feeder, reflux cooler, add 150g deionized water, 135g allyl polyethenoxy ether (molecular weight is 2200), 15.46g vinylformic acid and 1.24g Thiovanic acid; Stirring is warming up to 80 ℃; The 2g ammonium persulphate is dissolved in the initiator solution that is mixed with % concentration in the 30g deionized water; In above-mentioned four-hole boiling flask, slowly dripping this initiator solution under 80 ℃, dropwised 80 ℃ of following isothermal reactions 2 hours in about 1.5 hours; Reaction finishes below the postcooling to 50 ℃; Adding 32% aqueous sodium hydroxide solution adjusting pH value is 7, obtains the collapse protective poly-carboxylic acid series high-performance dehydragent of the embodiment of the invention, and code name is PC (A).
In this comparative example, do not use monomer (C), and only used the vinylformic acid in the monomer (B).This example has vital role with monobasic olefinically unsaturated carboxylic acid derivatives in the monomer (B) of explanation the present invention design and the material in the monomer (C) to product property.
Implementation result
Through corresponding experiment, the water reducer PC (A) that obtains in the water reducer PC (I) that obtains in the foregoing description 1 to 5 ~ PC (V) and the comparative example is compared below, the water reducer performance for preparing in the embodiment of the invention is done further to set forth.
(1) mortar test:
Table 1: mortar test-results
| Poly carboxylic acid series water reducer | Volume (%) | Initial flow degree (mm) | 1h degree of mobilization (mm) | Water-reducing rate (%) |
| PC(A) | 0.2 | 200 | 160 | 23 |
| PC(Ⅰ) | 0.2 | 215 | 185 | 26 |
| PC(Ⅱ) | 0.2 | 210 | 190 | 25 |
| PC(Ⅲ) | 0.2 | 215 | 195 | 26 |
Can know from the result of table 1, compare, adopt the concrete water-reducing ratio of PC (I) ~ PC (V) preparation higher, and the degree of mobilization hold facility be better behind the 1h with comparative example PC (A).
(2) C35 concrete test:
Adopt ordinary Portland cement, medium sand, rubble (particle diameter 5 ~ 25mm, grade continuously), concrete mix is seen table 2, under above-mentioned condition, mixes and stirs concrete and measures its slump, air content, slump retention value etc., its result sees table 3.
Table 2: concrete mix
Table 3: concrete test result
| Poly carboxylic acid series water reducer | Volume (%) | The initial slump (mm) | Initial extension degree (mm) | The 1h slump (mm) | 1h divergence (mm) | Air content (%) |
| PC(A) | 0.2 | 205 | 510 | 140 | 380 | 5.9 |
| PC(Ⅰ) | 0.2 | 230 | 550 | 200 | 460 | 5.2 |
| PC(Ⅱ) | 0.2 | 235 | 560 | 200 | 460 | 4.9 |
| PC(Ⅲ) | 0.2 | 235 | 540 | 205 | 470 | 5.9 |
Result by table 3 can know; Compare with comparative example PC (A); Under low-dosage (0.2%); Adopt the concrete of PC (I) ~ PC (V) preparation to have the higher initial slump and divergence, and the slump of 60min is also less with the divergence loss, explain and adopt the water reducer for preparing in the embodiment of the invention to have higher water-reducing rate and better slump hold facility.
Claims (8)
1. collapse protective poly-carboxylic acid based water reducer, it is characterized in that: this water reducer is carried out free radicals copolymerization reaction and is formed by monomer A, monomers B and the monomer C mol ratio according to 1:2～4.3:0～0.2 in the aqueous solution under action of evocating, wherein:
1) monomer A: be methyl butene polyoxyethylenated alcohol monomer, general formula is:
In the general formula, n is the addition quantity of oxyethane, is the integer between 5～100;
2) monomers B: be unsaturated monocarboxylic acid and derivatives monomer thereof, general formula is:
In the general formula, R
1, R
2, R
3Represent hydrogen or methyl, R
4Represent hydrogen or methyl or ethyl or amido;
3) monomer C: be unsaturated sulfonic acid and salt monomer thereof, general formula is:
In the general formula, R5 represents hydrogen or methyl, and M represents hydrogen or alkalimetal ion.
2. a kind of collapse protective poly-carboxylic acid based water reducer as claimed in claim 1 is characterized in that, described monomer A can be that molecular weight is any monomer between 1200～2400.
3. a kind of collapse protective poly-carboxylic acid based water reducer as claimed in claim 1; It is characterized in that described monomers B can be any one or a few in vinylformic acid, methyl acrylate, acrylic amide, methylacrylic acid, TEB 3K, the USAF RH-1.
4. a kind of collapse protective poly-carboxylic acid based water reducer as claimed in claim 1 is characterized in that, described monomer C can be any one or a few in allyl sulphonic acid or its salt, methallyl sulfonic acid or its salt.
5. a preparation method who prepares a kind of collapse protective poly-carboxylic acid based water reducer as claimed in claim 1 is characterized in that, this method may further comprise the steps:
1) monomer A, monomers B and monomer C is soluble in water;
2) initiator solution is added dropwise to above solution, the time that drips initiator solution is 1.5～2 hours, and temperature of reaction is 60～90 ℃, and the reaction times is 2～8 hours, and reaction finishes the back cooling;
When 3) being cooled to below 50 ℃, using basic cpd that product is neutralized to pH is 5～8, promptly gets title product.
6. the preparation method of a kind of collapse protective poly-carboxylic acid based water reducer as claimed in claim 5; It is characterized in that; Described initiator be in Sodium Persulfate, Potassium Persulphate, the ammonium persulphate any one or multiple, its consumption is 0.8% of monomer A, monomers B and a monomer C gross weight.
7. the preparation method of a kind of collapse protective poly-carboxylic acid based water reducer as claimed in claim 5 is characterized in that, described temperature of reaction is 75 ~ 82 ℃, and the time of insulation reaction is 2 ~ 4 hours.
8. the preparation method of a kind of collapse protective poly-carboxylic acid based water reducer as claimed in claim 5 is characterized in that, described basic cpd is any one or a few in sodium hydroxide, Pottasium Hydroxide, quadrol, the trolamine.
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| CN106699988A (en) * | 2016-12-21 | 2017-05-24 | 河南省科学院高新技术研究中心 | Polycarboxylate-type macromolecular water reducer and preparation method thereof |
| CN106699988B (en) * | 2016-12-21 | 2018-09-28 | 河南省科学院高新技术研究中心 | A kind of polycarboxylic-acid polymeric superplasticizer and preparation method thereof |
| CN110386773A (en) * | 2019-06-28 | 2019-10-29 | 浙江老虎山建材有限公司 | A kind of concrete subtracts the preparation method of jelly |
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