CN102503216A - Method for synthesizing universal polycarboxylic water reducer - Google Patents
Method for synthesizing universal polycarboxylic water reducer Download PDFInfo
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- CN102503216A CN102503216A CN2011103321123A CN201110332112A CN102503216A CN 102503216 A CN102503216 A CN 102503216A CN 2011103321123 A CN2011103321123 A CN 2011103321123A CN 201110332112 A CN201110332112 A CN 201110332112A CN 102503216 A CN102503216 A CN 102503216A
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Abstract
The invention relates to universal polycarboxylic water reducer and preparation method thereof. The universal polycarboxylic water reducer is in liquid state, and the solid content of the universal polycarboxylic water reducer is 40%. The universal polycarboxylic water reducer containing carboxyl, sulfonyl and polyoxyethylene side chains is prepared by aggregation of modified polyoxyethylene ether or polyoxypropylene ether with (methyl) acrylic acid or itaconic acid, sodium methylallyl sulfonate and the like under the action of chain initiator and chain transfer agent. The universal polycarboxylic water reducer prepared by the method is low in alkali content and high in water reducing rate. When the universal polycarboxylic water reducer is added into concrete by the cementing material weight ratio of 0.25-10%, operation of the concrete is laborsaving, and cement mixture has high liquidity, falling protection capacity and workability. The universal polycarboxylic water reducer and the preparation method thereof are simple in process, easy to control and free of environment pollution. The polycarboxylic water reducer which is used as an important component of high-performance concrete is widely applicable to pre-mixed and cast-in-situ concrete for various industrial and civil buildings, and especially has excellent performance in high-strength concrete.
Description
Technical field
The invention belongs to a kind of poly-carboxylic high-performance cement water reducing agent and preparation method thereof.
Background technology
Compare with high efficiency water reducing agents such as naphthalene system, trimeric cyanamide system, sulfamates; Polycarboxylate water-reducer has more excellent performance; Outstanding behaviours is that volume is low, water-reducing rate is high, fresh concrete is mobile and slump retaining is good, lowly shrink, strengthen characteristics such as potentiality are big, environmental friendliness, become in recent years and even the direction of Future Development and application.High performance water reducing agent of polyocarboxy acid has become the representative of concrete admixture last word, and its research and application have obtained domestic and international professional and technical personnel and workmen's great attention.China had obtained fast development in the research and the application facet of high performance water reducing agent of polyocarboxy acid in recent years, used also and shifted to civilian civil engineering work gradually from Important Project, and its consumption will constantly increase.
In recent years; The research and development of domestic high performance water reducing agent of polyocarboxy acid and production application have all obtained large development; Market product is progressively developed to the many kinds of product, performance and the multi-level direction of price by the single relatively situation of original kind just gradually; Application technical research is also abundant inadequately, so the requirement that realistic situation still can not satisfy or help the water reducer variation inadequately and promote.So invented a kind of superior performance, lower-cost universal polycarboxylate water-reducer is very necessary.
Summary of the invention
In order to solve above-mentioned deficiency of the prior art, the present invention has prepared a kind of universal polycarboxylate water-reducer.This universal polycarboxylate water-reducer overcomes water reducer complex manufacturing in the past; The shortcoming of the low or slump retaining difference of water-reducing rate; A kind of universal poly-carboxylic high-performance cement water reducing agent and preparation method are provided; This water reducer performance is high and stable, and synthesis technique is simple, easy control of reaction conditions, is easy to suitability for industrialized production.
A kind of universal polycarboxylate water-reducer is characterized in that comprising following compound, and the molecular weight of said compound is 10000～50000, and structural formula is following:
Wherein M is selected from sodium or ammonium;
R is selected from hydrogen or methyl;
N is the integer of 35-55.
The preparation method of the cement water reducing agent that above-mentioned expression formula is represented; In the Soxylat A 25-7 or the polyethenoxy ether aqueous solution, add acrylic or methacrylic acid and methylpropene sodium sulfonate; As initiator, Thiovanic acid or thiohydracrylic acid carry out polyreaction as chain-transfer agent at 60～80 ℃ with ammonium persulphate or Sodium Persulfate; Described initiator adds at 90～110min; After reaction is accomplished,, obtain 40% polycarboxylate water-reducer solution with sodium hydroxide solution or ethylenediamine solution pH=6～7 that neutralize.
Described polyoxy second (third) alkene ether is 1: 1.0～4.5 with (methyl) acrylic acid molar ratio; Methylpropene sodium sulfonate: (methyl) acrylic acid molar ratio is 1: 2.0～9.0; Initiator amount is 1%～6% of a polymerization single polymerization monomer mole number; Chain-transfer agent is 1%～3% of a polymerization single polymerization monomer consumption;
Described initiator optimum amount is 2.9% of a polymerization single polymerization monomer mole number;
Described chain-transfer agent optimum amount is 1.9% of a polymerization single polymerization monomer consumption;
The synthetic of polycarboxylic acid concrete water reducer of the present invention is to utilize to add acrylic or methacrylic acid and methylpropene sodium sulfonate copolymerization in polyoxy second (third) the alkene ether aqueous solution; Need not nitrogen protection; Temperature of reaction is constant, and reinforced program is simple, and reaction conditions is easy to control.Adopt the concrete of ROHM series concrete water-reducing agent of the present invention preparation, when this water reducer volume of 20wt% concentration be cement weight 1% the time, the concrete mix slump can reach 19cm; When volume was 1%, water-reducing rate can reach 27%, and concrete 1d ultimate compression strength improves 80～120%, and 3d ultimate compression strength improves 80～100%, had time of coagulation comparatively obviously and shortened; Concrete surface does not have bleeding line, no air pocket, aberration is little, Surface Quality of Concrete good; Alkali content is low; Chloride ion-containing not is to the reinforcing bar non-corrosiveness; Freeze-thaw-ability and anti-carbonization ability significantly improve than normal concrete; Concrete 28d shrinking percentage is that analog high efficiency water reducing agent reduces more than 20% than naphthalene; The adaptation of product is strong, is adapted to the cement of plurality of specifications, model, and product performance are stable, and long storage is not stratified, the nothing deposition, does not have crystallization winter; Advantages such as the product nontoxic pollution-free does not contain formaldehyde, and is environmentally safe.
Embodiment
The proportioning of each reactant is following among the following embodiment; Polyoxy second (third) alkene ether is 1: 4.0 with (methyl) acrylic acid molar ratio; Methylpropene sodium sulfonate: (methyl) acrylic acid molar ratio is 1: 5.0; Initiator amount is 1%～6% of a polymerization minor comonomer mole number, and optimum amount is 2.9%; Chain-transfer agent is 1%～3% of a polymerization single polymerization monomer consumption, and optimum amount is 1.9%.
Embodiment 1:
Best proportioning
With molecular weight is 120.00 parts of 2400 Soxylat A 25-7s and 97.05 parts in water, puts into reaction vessel, heats up; Under 65 ± 5 ℃ of temperature, stir reactant is dissolved fully, in container, drip 60.00 parts of the aqueous solution that is dissolved with 40 parts in 6.3 parts+water of 14.4 parts+methylpropene sodium sulfonate of vinylformic acid and 5% ammonium persulfate solutions and mass percent again and be 10.00 parts of 10% the thin basic propionic acid of solution; The control rate of addition; Dripped off at 100 ± 10 minutes, maintain the temperature at 65 ± 5 ℃, continue reaction 4 hours.Add about 4 part of 40% sodium hydroxide solution after the cooling again and regulate PH=6.5 ± 0.5, obtain 40% poly-carboxylic high-performance cement water reducing agent of the present invention.
Embodiment 2
With molecular weight is 120.00 parts of 2400 Soxylat A 25-7s and 81.85 parts in water, puts into reaction vessel, heats up; Under 65 ± 5 ℃ of temperature, stir reactant is dissolved fully, in container, drip 60.00 parts of the aqueous solution that is dissolved with 40 parts in 6.3 parts+water of 3.6 parts+methylpropene sodium sulfonate of vinylformic acid and 5% ammonium persulfate solutions and mass percent again and be 10.00 parts of 10% the thin basic propionic acid of solution; The control rate of addition; Dripped off at 100 ± 10 minutes, maintain the temperature at 65 ± 5 ℃, continue reaction 4 hours.Add about 4 part of 40% sodium hydroxide solution after the cooling again and regulate PH=6.5 ± 0.5, obtain 40% poly-carboxylic high-performance cement water reducing agent of the present invention.
Embodiment 3
With molecular weight is 120.00 parts of 2400 Soxylat A 25-7s and 102.45 parts in water, puts into reaction vessel, heats up; Under 65 ± 5 ℃ of temperature, stir reactant is dissolved fully, in container, drip 60.00 parts of the aqueous solution that is dissolved with 40 parts in 6.3 parts+water of 18 parts+methylpropene sodium sulfonate of vinylformic acid and 5% ammonium persulfate solutions and mass percent again and be 10.00 parts of 10% the thin basic propionic acid of solution; The control rate of addition; Dripped off at 100 ± 10 minutes, maintain the temperature at 65 ± 5 ℃, continue reaction 4 hours.Add about 4 part of 40% sodium hydroxide solution after the cooling again and regulate PH=6.5 ± 0.5, obtain 40% poly-carboxylic high-performance cement water reducing agent of the present invention.
Embodiment 4
With molecular weight is 120.00 parts of 2400 Soxylat A 25-7s and 91.05 parts in water, puts into reaction vessel, heats up; Under 65 ± 5 ℃ of temperature, stir reactant is dissolved fully, in container, drip 60.00 parts of the aqueous solution that is dissolved with 40 parts in 2.3 parts+water of 14.4 parts+methylpropene sodium sulfonate of vinylformic acid and 5% ammonium persulfate solutions and mass percent again and be 10.00 parts of 10% the thin basic propionic acid of solution; The control rate of addition; Dripped off at 100 ± 10 minutes, maintain the temperature at 65 ± 5 ℃, continue reaction 4 hours.Add about 4 part of 40% sodium hydroxide solution after the cooling again and regulate PH=6.5 ± 0.5, obtain 40% poly-carboxylic high-performance cement water reducing agent of the present invention.
Embodiment 5
With molecular weight is 120.00 parts of 2400 Soxylat A 25-7s and 104.5 parts in water, puts into reaction vessel, heats up; Under 65 ± 5 ℃ of temperature, stir reactant is dissolved fully, in container, drip 60.00 parts of the aqueous solution that is dissolved with 40 parts in 11.3 parts+water of 14.4 parts+methylpropene sodium sulfonate of vinylformic acid and 5% ammonium persulfate solutions and mass percent again and be 10.00 parts of 10% the thin basic propionic acid of solution; The control rate of addition; Dripped off at 100 ± 10 minutes, maintain the temperature at 65 ± 5 ℃, continue reaction 4 hours.Add about 4 part of 40% sodium hydroxide solution after the cooling again and regulate PH=6.5 ± 0.5, obtain 40% poly-carboxylic high-performance cement water reducing agent of the present invention.
Embodiment 6
With molecular weight is 120.00 parts of 2400 Soxylat A 25-7s and 136.05 parts in water, puts into reaction vessel, heats up; Under 65 ± 5 ℃ of temperature, stir reactant is dissolved fully, in container, drip 21.00 parts of the aqueous solution that is dissolved with 40 parts in 6.3 parts+water of 14.4 parts+methylpropene sodium sulfonate of vinylformic acid and 5% ammonium persulfate solutions and mass percent again and be 10.00 parts of 10% the thin basic propionic acid of solution; The control rate of addition; Dripped off at 100 ± 10 minutes, maintain the temperature at 65 ± 5 ℃, continue reaction 4 hours.Add about 4 part of 40% sodium hydroxide solution after the cooling again and regulate PH=6.5 ± 0.5, obtain 40% poly-carboxylic high-performance cement water reducing agent of the present invention.
Embodiment 7
With molecular weight is 120.00 parts of 2400 Soxylat A 25-7s and 31.05 parts in water, puts into reaction vessel, heats up; Under 65 ± 5 ℃ of temperature, stir reactant is dissolved fully, in container, drip 126.0 parts of the aqueous solution that is dissolved with 40 parts in 6.3 parts+water of 14.4 parts+methylpropene sodium sulfonate of vinylformic acid and 5% ammonium persulfate solutions and mass percent again and be 10.00 parts of 10% the thin basic propionic acid of solution; The control rate of addition; Dripped off at 100 ± 10 minutes, maintain the temperature at 65 ± 5 ℃, continue reaction 4 hours.Add about 4 part of 40% sodium hydroxide solution after the cooling again and regulate PH=6.5 ± 0.5, obtain 40% poly-carboxylic high-performance cement water reducing agent of the present invention.
Embodiment 8
With molecular weight is 120.00 parts of 2400 Soxylat A 25-7s and 101.79 parts in water, puts into reaction vessel, heats up; Under 65 ± 5 ℃ of temperature, stir reactant is dissolved fully, in container, drip 60.00 parts of the aqueous solution that is dissolved with 40 parts in 6.3 parts+water of 14.4 parts+methylpropene sodium sulfonate of vinylformic acid and 5% ammonium persulfate solutions and mass percent again and be 5.26 parts of 10% the thin basic propionic acid of solution; The control rate of addition; Dripped off at 100 ± 10 minutes, maintain the temperature at 65 ± 5 ℃, continue reaction 4 hours.Add about 4 part of 40% sodium hydroxide solution after the cooling again and regulate PH=6.5 ± 0.5, obtain 40% poly-carboxylic high-performance cement water reducing agent of the present invention.
Embodiment 9
With molecular weight is 120.00 parts of 2400 Soxylat A 25-7s and 91.26 parts in water, puts into reaction vessel, heats up; Under 65 ± 5 ℃ of temperature, stir reactant is dissolved fully, in container, drip 60.00 parts of the aqueous solution that is dissolved with 40 parts in 6.3 parts+water of 14.4 parts+methylpropene sodium sulfonate of vinylformic acid and 5% ammonium persulfate solutions and mass percent again and be 15.79 parts of 10% the thin basic propionic acid of solution; The control rate of addition; Dripped off at 100 ± 10 minutes, maintain the temperature at 65 ± 5 ℃, continue reaction 4 hours.Add about 4 part of 40% sodium hydroxide solution after the cooling again and regulate PH=6.5 ± 0.5, obtain 40% poly-carboxylic high-performance cement water reducing agent of the present invention.
Above-mentioned this general polycarboxylate water-reducer that the present invention provides, example detection result is following:
Clean slurry degree of mobilization test (GB/T8077-2000): adopt reference cement, according to GB/T8077-87 test cement paste degree of mobilization.The result sees table 1.
Table 1
Concrete slump retaining situation result such as table 2
Claims (8)
1. a universal polycarboxylate water-reducer is characterized in that comprising following compound, and the molecular weight of said compound is 10000～50000, and structural formula is following:
Wherein M is selected from sodium or ammonium;
R is selected from hydrogen or methyl;
N is the integer of 35-55.
2. according to the preparation method of the represented polycarboxylate water-reducer of expression formula in the claim 1; It comprises following process step: in the aqueous solution of Soxylat A 25-7 or polyethenoxy ether, add acrylic or methacrylic acid and methylpropene sodium sulfonate; As initiator, Thiovanic acid or thiohydracrylic acid carry out polyreaction as chain-transfer agent at 60～80 ℃ with ammonium persulphate or Sodium Persulfate; Described initiator added at 90～110 minutes; After reaction is accomplished,, obtain 40% polycarboxylate water-reducer solution with sodium hydroxide solution or ethylenediamine solution pH=6～7 that neutralize.
3. the preparation method of universal polycarboxylate water-reducer according to claim 2 is characterized in that: polyoxy second (third) alkene ether is 1: 1.0～4.5 with (methyl) acrylic acid molar ratio; Methylpropene sodium sulfonate: (methyl) acrylic acid molar ratio is 1: 2.0～9.0; Initiator amount is 1%～6% of a polymerization single polymerization monomer mole number; Chain-transfer agent is 1%～3% of a polymerization single polymerization monomer mol ratio consumption.
4. the preparation method of universal polycarboxylate water-reducer according to claim 2 is characterized in that: polyoxy second (third) alkene ether is 1: 4.0 with (methyl) acrylic acid optimum molar ratio.
5. methylpropene sodium sulfonate: (methyl) acrylic acid optimum molar ratio is 1: 5.0.
6. the preparation method of universal polycarboxylate water-reducer according to claim 2, it is characterized in that: the optimum amount of initiator is 2.9% of a polymerization single polymerization monomer mole number.
7. the preparation method of universal polycarboxylate water-reducer according to claim 2, it is characterized in that: the optimum amount of chain-transfer agent is 1.9% of a polymerization single polymerization monomer consumption.
8. the preparation method of universal polycarboxylate water-reducer according to claim 2, it is characterized in that: polymerization reaction time is 6 ± 0.5 hours.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731009A (en) * | 2012-06-21 | 2012-10-17 | 马清浩 | Sulfo group-containing polyester carboxylic acid water reducer and its preparation method |
| CN103214206A (en) * | 2013-04-17 | 2013-07-24 | 岳阳东方雨虹防水技术有限责任公司 | Slow release type polycarboxylate water reducer and preparation method thereof |
| CN104530325A (en) * | 2014-12-26 | 2015-04-22 | 深圳中大新材科技有限公司 | Method for preparing high-performance poly-carboxylic water reducer |
| CN106397683A (en) * | 2016-08-30 | 2017-02-15 | 北京东方雨虹防水技术股份有限公司 | Polycarboxylate superplasticizer for reducing viscosity of high-grade concrete and preparation method thereof |
| CN107446091A (en) * | 2017-09-16 | 2017-12-08 | 芜湖市立泰建筑新材料有限公司 | A kind of polycarboxylate water-reducer and preparation method thereof |
| CN108659179A (en) * | 2018-06-15 | 2018-10-16 | 山西中铁铁诚建材科技有限公司 | A kind of polycarboxylate water-reducer and its synthetic method |
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| CN101200355A (en) * | 2007-12-21 | 2008-06-18 | 四川师范大学 | Polycarboxylic acids series water reducer and method for making same |
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- 2011-10-27 CN CN2011103321123A patent/CN102503216A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101200355A (en) * | 2007-12-21 | 2008-06-18 | 四川师范大学 | Polycarboxylic acids series water reducer and method for making same |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731009A (en) * | 2012-06-21 | 2012-10-17 | 马清浩 | Sulfo group-containing polyester carboxylic acid water reducer and its preparation method |
| CN103214206A (en) * | 2013-04-17 | 2013-07-24 | 岳阳东方雨虹防水技术有限责任公司 | Slow release type polycarboxylate water reducer and preparation method thereof |
| CN103214206B (en) * | 2013-04-17 | 2016-04-06 | 岳阳东方雨虹防水技术有限责任公司 | A kind of sustained-release polycarboxylic water reducer and preparation method thereof |
| CN104530325A (en) * | 2014-12-26 | 2015-04-22 | 深圳中大新材科技有限公司 | Method for preparing high-performance poly-carboxylic water reducer |
| CN106397683A (en) * | 2016-08-30 | 2017-02-15 | 北京东方雨虹防水技术股份有限公司 | Polycarboxylate superplasticizer for reducing viscosity of high-grade concrete and preparation method thereof |
| CN107446091A (en) * | 2017-09-16 | 2017-12-08 | 芜湖市立泰建筑新材料有限公司 | A kind of polycarboxylate water-reducer and preparation method thereof |
| CN108659179A (en) * | 2018-06-15 | 2018-10-16 | 山西中铁铁诚建材科技有限公司 | A kind of polycarboxylate water-reducer and its synthetic method |
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