CN104371074A - Low-temperature high-concentration polycarboxylic acid water reducing agent and preparation method thereof - Google Patents

Low-temperature high-concentration polycarboxylic acid water reducing agent and preparation method thereof Download PDF

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CN104371074A
CN104371074A CN201410624218.4A CN201410624218A CN104371074A CN 104371074 A CN104371074 A CN 104371074A CN 201410624218 A CN201410624218 A CN 201410624218A CN 104371074 A CN104371074 A CN 104371074A
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concentration
water reducing
preparation
water
reducing agent
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黄海
汪志勇
腾茂茁
李双
秦洋
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China Tiesiju Civil Engineering Group Co Ltd CTCE Group
China Railway Group Ltd CREC
Anjui Engineering Material Technology Co Ltd of CTCE Group
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China Tiesiju Civil Engineering Group Co Ltd CTCE Group
China Railway Group Ltd CREC
Anjui Engineering Material Technology Co Ltd of CTCE Group
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Abstract

The invention discloses a preparation method of a low-temperature high-concentration polycarboxylic acid water reducing agent. The low-temperature high-concentration polycarboxylic acid water reducing agent is prepared by copolymerizing 80-90 wt% of methylalkenyl polyoxyethylene and polyoxypropylene ether and 10-20 wt% of acrylic acid at 0-15 DEG C by a single-tank sectional dropwise addition process under the action of an ammonium persulfate-ferrous sulfate redox initiation system. The product concentration is up to 65%. The method has the advantages of simple production technique and low raw material cost, and is suitable for producing the high-concentration polycarboxylic acid water reducing agent under the condition of zero heat source in winter in northern China; and the concentration of up to 65% greatly lowers the transportation cost of the water reducing agent mother solution, and thus, the method has obvious economic benefit and social benefit. The polycarboxylic acid water reducing agent prepared by the method has the advantages of high water reducing rate, favorable slump holding capacity of the prepared concrete, and high environment adaptability.

Description

A kind of low temperature and high concentration polycarboxylate water-reducer and preparation method thereof
Technical field
The present invention relates to concrete admixture field, be specifically related to a kind of preparation method of low temperature and high concentration polycarboxylate water-reducer and obtained polycarboxylate water-reducer.
Background technology
In recent years, along with the construction of China's whole nation significant enginnnring, higher to the technology of material of construction, environmental protection and resistance to performance requriements of waiting so long.Polycarboxylate high performance water-reducing agent is the hightech architecture product that domestic fast development is in recent years got up, and is the product that various countries develop at building materials field primary study, becomes the development mark of building field state of the art and building operation level to a certain extent.The One-step production that the development trend of the industrialized producing technology of polycarboxylate high performance water-reducing agent is produced to ethers by the two-step approach of ester class develops, and is developed by the ordinary temperature production of the high temperature production of 40 ~ 80 DEG C to 15 ~ 30 DEG C.Because north of china in winter water temperature is all lower than 15 DEG C, when utilizing existing technique to carry out suitability for industrialized production, still need heating installation.So research and development low-temperature industrial production technique, can production unit be simplified, energy-conserving and environment-protective, more meet the standard of modernization green production.In addition, found by market study, the concentration of domestic common polycarboxylate superplasticizer mother liquor is mostly about 40%, and this is for the admixture producer only having compounding capacity, and the transportation cost of mother liquor is higher becomes the important factor restricting this kind of enterprise development.Therefore, the high density polycarboxylate superplasticizer mother liquor developing excellent property has significant economic benefit and social benefit.
In order to reduce the temperature of reaction of polycarboxylate high performance water-reducing agent, improve mother liquid concentration, domestic and international related researcher does a lot of work, and common way adopts ammonium persulphate-vitamins C or H 2o 2-vitamins Cs etc. are as initiator system.But being only applicable to temperature of reaction during this method suitability for industrialized production is 15 ~ 30 DEG C, and mother liquid concentration is the situation of 40 ~ 50%.
Current domestic poly carboxylic acid series water reducer high concentration produces main employing high temperature production technique, and normal temperature suitability for industrialized production is only applicable to the normal concentration at 15 ~ 30 DEG C.A kind of polyethers polycarboxylate water-reducer low-temperature synthetic method is disclosed in patent CN102964079A, under redox system by the minor comonomer component of unsaturated Soxylat A 25-7 and monocarboxylic acid or part unsaturated sulfonic acid and salt monomer thereof be reaction raw materials in aqueous copolymerization form, at cooling stages, add the active slow setting component of multi-hydroxy carboxy acid's salt or borate family and prepare polycarboxylate water-reducer.This kind of production method is carried out stage by stage, and preparation reaction monomers is complicated, need be heated to 30 ~ 50 DEG C, inadequate energy-conserving and environment-protective.A kind of preparation method of concrete polycarboxylate water-reducer at normal temperature is disclosed in patent CN101775107A.Although reaction process is without the need to heating, during suitability for industrialized production, when initial reaction temperature lower than 15 DEG C or reaction density more than 60%, be easy to produce the problem that cannot react.Adopt the water reducer of this method synthesis, be only applicable to the production of normal temperature normal concentration polycarboxylate water-reducer, for the production of low temperature and high concentration polycarboxylate water-reducer, still cannot meet production requirement.
Summary of the invention
The object of the invention is the defect existed for above-mentioned technology, provide that a kind of water-reducing rate is high, function of slump protection good, be applicable to the production method of low temperature and high concentration polycarboxylate water-reducer suitability for industrialized production, this production technique is simple, and cost is low.
For realizing foregoing invention, the present invention adopts following technical scheme:
A kind of preparation method of low temperature and high concentration polycarboxylate water-reducer, it is characterized in that: its by methyl thiazolinyl Soxylat A 25-7, vinylformic acid two kinds of water-soluble monomers at 0 ~ 15 DEG C, adopt single tank segmentation dripping method, utilize " ammonium persulphate-ferrous sulfate " redox initiation system copolymerization to form, the mass percent of described two kinds of monomers is: monomer methyl thiazolinyl Soxylat A 25-7 80 ~ 90%, monomeric acrylic 10 ~ 20%.
The preparation method of described polycarboxylate water-reducer, is characterized in that, specifically comprises the steps:
(1) joined in reactor by methyl thiazolinyl Soxylat A 25-7, then add a certain amount of softening water, stir, the add-on of described softening water is (45 ~ 50) % of above-mentioned monomer mass;
(2) be that the aqueous solution of ammonium persulphate of (20 ~ 40) % joins in reactor by concentration, stir, reactor temperature is 0 ~ 15 DEG C, and the add-on of ammonium persulfate aqueous solution is (1.5 ~ 3) % of methyl thiazolinyl Soxylat A 25-7 and vinylformic acid two kinds of monomer total masses;
(3) in concentration be (55 ~ 65) % Acrylic Acid Monomer the aqueous solution in add thiohydracrylic acid and ferrous sulfate, stir, form and drip solution, adopt single tank segmentation dripping method, dropping solution is added drop-wise in reactor, continuous stirring, require that the time for adding dripping solution controls at 3 ~ 3.2h, front 1h drips the dropping solution of half quality, drip the dropping solution of second half quality remaining time, drip solution and dropwise follow-up continuation of insurance temperature 1h, the add-on of thiohydracrylic acid is (0.6 ~ 1.0) % of methyl thiazolinyl Soxylat A 25-7 quality, the add-on of ferrous sulfate is (0.4 ~ 0.6) % of methyl thiazolinyl Soxylat A 25-7 and vinylformic acid two kinds of monomer total masses,
(4) pH value regulating product is 6 ~ 7, can obtain target product.
The preparation method of described low temperature and high concentration polycarboxylate water-reducer, it is characterized in that: described methyl thiazolinyl Soxylat A 25-7 is block structure, outward appearance is that white is to light yellow sheet, degree of unsaturation >=0.3, hydroxyl value is 23.4 ~ 26.7mgKOH/g, the pH value of the 1% methyl thiazolinyl Soxylat A 25-7 aqueous solution is 5.0 ~ 7.0, double bond retention rate >=85.0%, and its chemical structural formula is as follows:
Molecular weight is 2000 ~ 3000, and wherein m value is the arbitrary integer in 32 ~ 68, and n value is the arbitrary integer in 0 ~ 10.
The preparation method of described low temperature and high concentration polycarboxylate water-reducer, it is characterized in that: described single tank segmentation dripping method refers to all dropping monomers all in same dropping tank, polymerization drips monomer dropping speed soon early stage, and it is slow that the polymerization later stage drips monomer dropping speed.
The polycarboxylate water-reducer that the inventive method is obtained.
Product concentration obtained by the inventive method is up to 65%, and production technique is simple, and low in raw material price, is applicable to the production of north of china in winter zero thermal source high density poly carboxylic acid series water reducer; Concentration up to 65% greatly reduces the transportation cost of water reducer mother liquor, has significant economic benefit and social benefit.
The following beneficial effect that the present invention compared with prior art has:
(1) the present invention adopts the low-temperature oxidation reduction initiating system of ammonium persulphate-ferrous sulfate, even if temperature of reaction is low to moderate 0 ~ 5 DEG C, adopts the suitability for industrialized production of this initiator system also without the need to heating, polyreaction can be made normally to carry out.Therefore the production technique scope of application of the water reducer of patent of the present invention is wider, is particularly suitable for the production of north of china in winter zero thermal source high density polycarboxylate water-reducer.
(2) because initiator system is active large, the concentration improving polymeric mother liquid also can make reaction carry out smoothly, utilize the present invention can produce mother liquid concentration up to 65% polycarboxylate water-reducer, for the concrete admixture producer only having compounding capacity, can greatly reduce mother liquor transportation cost, reduce the wasting of resources, there is significant economic benefit and social benefit.
(3) the present invention adopts single tank to drip, and simplifies production equipment and process.Reaction monomers kind used is few, and Easy dosing, very easily operates and implement.
(4) the present invention creatively adopts the method that segmentation drips, and early stage, monomer dropping speed was fast, made up the polymerization mechanism that free radical causes slowly, and late monomer rate of addition is slow, because free radical increases and the speed of termination is fast.The polycarboxylate water-reducer structure utilizing this dropping method to produce is more even, the excellent propertys such as water-reducing rate, flowing retentivity.
(5) production technique of the present invention compares patent CN102964079A, does not need heating.Compare patent CN101775107A and Patents, production technique is easier, and use range is wider.
(6) the present invention is directed to low temperature and high concentration polycarboxylate water-reducer and invent, also be applicable to the production of normal temperature and normal concentration polycarboxylate water-reducer simultaneously, the production technique of polycarboxylate water-reducer has been enriched in its preparation and invention, for the production of north of china in winter zero thermal source high density poly carboxylic acid series water reducer provides technical guarantee.
The method of concrete enforcement
Example 1
By molecular weight be 2400 methyl thiazolinyl Soxylat A 25-7 4000kg add in reactor, then add 2000kg softening water make it dissolve, add the ammonium persulfate aqueous solution 67kg of 40% until completely dissolved.After stirring, at temperature is 0 ~ 5 DEG C, the mixing dripping vinylformic acid, thiohydracrylic acid, ferrous sulfate and water drips solution 953.2kg, and in this dropping liquid, vinylformic acid is 533.2kg, and thiohydracrylic acid is 33.4kg, and ferrous sulfate is 20kg, and water is 400kg.The time for adding of this dropping liquid controls at 3-3.2h, and front 1h drips the dropping liquid of half quality, and drip the dropping liquid of second half quality remaining time, dropping liquid dropwises follow-up continuation of insurance temperature 1h.Adopt 30%NaOH solution to regulate the pH value of product to be 7, obtained product is the high density poly carboxylic acid series water reducer of temperature production, and water reducer concentration is up to 65%.
Example 2
By molecular weight be 2200 methyl thiazolinyl Soxylat A 25-7 6000kg add in reactor, then add 3000kg softening water make it dissolve, add the ammonium persulfate aqueous solution 100kg of 40% until completely dissolved.After stirring, at temperature is 0 ~ 15 DEG C, the mixing dripping vinylformic acid, thiohydracrylic acid, ferrous sulfate and water drips solution 1942.8kg, and in this dropping liquid, vinylformic acid is 1058.8kg, and thiohydracrylic acid is 52kg, and ferrous sulfate is 32kg, and water is 800kg.The time for adding of this dropping liquid controls at 3-3.2h, and front 1h drips the dropping liquid of half quality, and drip the dropping liquid of second half quality remaining time, dropping liquid dropwises follow-up continuation of insurance temperature 1h.Adopt 30%NaOH solution to regulate the pH value of product to be 7, obtained product is the ultrahigh concentration poly carboxylic acid series water reducer that very low temperature is produced, and water reducer concentration is up to 64.5%.
Comparative example 3 (embodiment 3 in patent CN101775107A)
When 20 DEG C, in the four-hole boiling flask that thermometer, agitator are housed, add isopentene Soxylat A 25-7 60 parts, 60 parts, water, constantly stir to make its uniform dissolution in water; Then 3.5 parts, vinylformic acid is added, cis-butenedioic anhydride 1 part, vinyl-acetic ester 1.2 parts, potassium permanganate 0.5; Get oxalic acid 0.3 part, be dissolved in 10 parts of water, in 2 ~ 3 hours, add uniformly in four-hole boiling flask, add rear continuation stirring 20 minutes, add the sodium hydroxide solution 7 parts of 40%, make temperature rise.When temperature no longer rises, continue stirring and namely obtain contrast product in 30 minutes.
Specific embodiment
According to Duan Baili wind district, Lan-xing Railway Xinjiang to the requirement of high performance concrete, preparation C30 grade concrete.Wherein cement is Tianshan Mountains low alkali cement PO 42.5, flyash is II grade of ash, sand to be fineness modulus be 2.8 medium sand (silt content 3.5%), stone is the continuous grading (silt content 1.5%) of 5-25mm, water reducer volume is 1.0% of gel material content, relative air humidity 20%.Test by following proportioning: cement: flyash: sand: stone: water: admixture=269:145:709:1020:160:4.14 (unit: Kg); To concrete basic demand: go out the machine slump 220 ± 20mm, 2h gradual loss is no more than 15%, concrete is not emanated, not bleeding.Carry out concrete examination by above-mentioned requirements to join, it the results are shown in Table shown in 1.
Table 1 testing concrete performance result
In table 1, comparative example water reducer concentration is 46.3%, and embodiment 1 and 2 water reducer concentration is up to 65%.From table 1 test result, the product adopting its performance of polycarboxylate water-reducer synthesized by the present invention and comparative example to synthesize is suitable.Therefore, the present invention can at lower temperatures, and the poly carboxylic acid series water reducer product of synthesis greater concn, synthesized product can meet Duan Baili wind district, Lan-xing Railway Xinjiang completely to the requirement of high performance concrete.
In addition to the implementation, the present invention can also have other embodiments, and as the dropping monomer adopting front 1.5h to drip 2/3rds quality, rear 1.5h drips the dropping monomer of 1/3rd quality; Adopt the methyl thiazolinyl polyoxyethylene, polyethenoxy ether etc. of other molecular weight.All employings are equal to the technical scheme of replacement or equivalent transformation formation, are the protection domain of application claims.

Claims (5)

1. the preparation method of a low temperature and high concentration polycarboxylate water-reducer, it is characterized in that: its by methyl thiazolinyl Soxylat A 25-7, vinylformic acid two kinds of water-soluble monomers at 0 ~ 15 DEG C, adopt single tank segmentation dripping method, utilize " ammonium persulphate-ferrous sulfate " redox initiation system copolymerization to form, the mass percent of described two kinds of monomers is: monomer methyl thiazolinyl Soxylat A 25-7 80 ~ 90%, monomeric acrylic 10 ~ 20%.
2. the preparation method of polycarboxylate water-reducer according to claim 1, is characterized in that, specifically comprises the steps:
(1) joined in reactor by methyl thiazolinyl Soxylat A 25-7, then add a certain amount of softening water, stir, the add-on of described softening water is (45 ~ 50) % of above-mentioned monomer mass;
(2) be that the aqueous solution of ammonium persulphate of (20 ~ 40) % joins in reactor by concentration, stir, reactor temperature is 0 ~ 15 DEG C, and the add-on of ammonium persulfate aqueous solution is (1.5 ~ 3) % of methyl thiazolinyl Soxylat A 25-7 and vinylformic acid two kinds of monomer total masses;
(3) in concentration be (55 ~ 65) % Acrylic Acid Monomer the aqueous solution in add thiohydracrylic acid and ferrous sulfate, stir, form and drip solution, adopt single tank segmentation dripping method, dropping solution is added drop-wise in reactor, continuous stirring, require that the time for adding dripping solution controls at 3 ~ 3.2h, front 1h drips the dropping solution of half quality, drip the dropping solution of second half quality remaining time, drip solution and dropwise follow-up continuation of insurance temperature 1h, the add-on of thiohydracrylic acid is (0.6 ~ 1.0) % of methyl thiazolinyl Soxylat A 25-7 quality, the add-on of ferrous sulfate is (0.4 ~ 0.6) % of methyl thiazolinyl Soxylat A 25-7 and vinylformic acid two kinds of monomer total masses,
(4) pH value regulating product is 6 ~ 7, can obtain target product.
3. the preparation method of low temperature and high concentration polycarboxylate water-reducer according to claim 1 and 2, it is characterized in that: described methyl thiazolinyl Soxylat A 25-7 is block structure, outward appearance is that white is to light yellow sheet, degree of unsaturation >=0.3, hydroxyl value is 23.4 ~ 26.7mgKOH/g, the pH value of the 1% methyl thiazolinyl Soxylat A 25-7 aqueous solution is 5.0 ~ 7.0, double bond retention rate >=85.0%, and its chemical structural formula is as follows:
Molecular weight is 2000 ~ 3000, and wherein m value is the arbitrary integer in 32 ~ 68, and n value is the arbitrary integer in 0 ~ 10.
4. the preparation method of low temperature and high concentration polycarboxylate water-reducer according to claim 1 and 2, it is characterized in that: described single tank segmentation dripping method refers to all dropping monomers all in same dropping tank, polymerization drips monomer dropping speed soon early stage, and it is slow that the polymerization later stage drips monomer dropping speed.
5. the polycarboxylate water-reducer that obtains of the preparation method of a low temperature and high concentration polycarboxylate water-reducer according to claim 1.
CN201410624218.4A 2014-11-06 2014-11-06 Low-temperature high-concentration polycarboxylic acid water reducing agent and preparation method thereof Pending CN104371074A (en)

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Cited By (7)

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Publication number Priority date Publication date Assignee Title
CN104926183A (en) * 2015-05-27 2015-09-23 中交四航工程研究院有限公司 High-adaptability and high-performance polycarboxylic water-reducing agent and preparation method for same
CN105254819A (en) * 2015-10-15 2016-01-20 中铁四局集团有限公司 Room-temperature preparation method of early strength type polycarboxylate superplasticizer
CN105601824A (en) * 2015-12-24 2016-05-25 江苏苏博特新材料股份有限公司 Preparation method of concrete water reducing agent with ultrahigh water reducing capacity
CN106496441A (en) * 2016-10-27 2017-03-15 湖北工业大学 A kind of lower valency appraises at the current rate cation-modified polycarboxylate water-reducer masterbatch and its low temperature preparation method
CN107777907A (en) * 2017-09-28 2018-03-09 长沙加美乐素化工有限公司 The Early-strength polycarboxylate superplasticizer used for undervulcanization cement and Machine-made Sand concrete
CN109535347A (en) * 2018-12-24 2019-03-29 科之杰新材料集团有限公司 A kind of preparation method of block water-retaining type concrete admixture
CN115466363A (en) * 2022-10-31 2022-12-13 中建材中岩科技有限公司 Polycarboxylate superplasticizer prepared at ultralow temperature and preparation method thereof

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CN101775107A (en) * 2010-02-03 2010-07-14 北京冶建特种材料有限公司 Preparation method of concrete polycarboxylate water-reducer at normal temperature
CN103483505A (en) * 2013-09-25 2014-01-01 山东省水利科学研究院 Polycarboxylate superplasticizer catalyzing production technology without high temperature
CN103804610A (en) * 2014-02-13 2014-05-21 贵州科之杰新材料有限公司 Method for preparing high-performance polycarboxylate superplasticizer via heat resource-free process

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CN101538134A (en) * 2009-04-14 2009-09-23 大连市建筑科学研究设计院股份有限公司 Polyether class polycarboxylic acid high-efficiency water reducing agent and preparation method thereof
CN101775107A (en) * 2010-02-03 2010-07-14 北京冶建特种材料有限公司 Preparation method of concrete polycarboxylate water-reducer at normal temperature
CN103483505A (en) * 2013-09-25 2014-01-01 山东省水利科学研究院 Polycarboxylate superplasticizer catalyzing production technology without high temperature
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Cited By (10)

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Publication number Priority date Publication date Assignee Title
CN104926183A (en) * 2015-05-27 2015-09-23 中交四航工程研究院有限公司 High-adaptability and high-performance polycarboxylic water-reducing agent and preparation method for same
CN105254819A (en) * 2015-10-15 2016-01-20 中铁四局集团有限公司 Room-temperature preparation method of early strength type polycarboxylate superplasticizer
CN105601824A (en) * 2015-12-24 2016-05-25 江苏苏博特新材料股份有限公司 Preparation method of concrete water reducing agent with ultrahigh water reducing capacity
CN105601824B (en) * 2015-12-24 2017-11-24 江苏苏博特新材料股份有限公司 A kind of preparation method of the cement water reducing agent of superelevation diminishing
CN106496441A (en) * 2016-10-27 2017-03-15 湖北工业大学 A kind of lower valency appraises at the current rate cation-modified polycarboxylate water-reducer masterbatch and its low temperature preparation method
CN106496441B (en) * 2016-10-27 2018-11-13 湖北工业大学 A kind of lower valency appraises at the current rate cation-modified polycarboxylate water-reducer masterbatch and its low temperature preparation method
CN107777907A (en) * 2017-09-28 2018-03-09 长沙加美乐素化工有限公司 The Early-strength polycarboxylate superplasticizer used for undervulcanization cement and Machine-made Sand concrete
CN109535347A (en) * 2018-12-24 2019-03-29 科之杰新材料集团有限公司 A kind of preparation method of block water-retaining type concrete admixture
CN109535347B (en) * 2018-12-24 2021-01-22 科之杰新材料集团有限公司 Preparation method of block water-retaining concrete admixture
CN115466363A (en) * 2022-10-31 2022-12-13 中建材中岩科技有限公司 Polycarboxylate superplasticizer prepared at ultralow temperature and preparation method thereof

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