CN102992682A - Universal polycarboxylic acid water reducing agent and preparation method thereof - Google Patents
Universal polycarboxylic acid water reducing agent and preparation method thereof Download PDFInfo
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- CN102992682A CN102992682A CN2012103760303A CN201210376030A CN102992682A CN 102992682 A CN102992682 A CN 102992682A CN 2012103760303 A CN2012103760303 A CN 2012103760303A CN 201210376030 A CN201210376030 A CN 201210376030A CN 102992682 A CN102992682 A CN 102992682A
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Abstract
The invention relates to a universal polycarboxylic acid water reducing agent and a preparation method thereof. The universal polycarboxylic acid water reducing agent is of a liquid state and has the solid content of 40%. The universal polycarboxylic acid water reducing agent is the water reducing agent which is prepared from monomers such as allyl polyether, and maleic anhydride, (meth)acrylic acid or itaconic acid, methyl acrylate and sodium methallyl sulfonate through polymerization under the effects of a molecular weight chain initiator and a chain transfer agent and neutralization; and the water reducing agent contains carboxyl, sulfonic group and an allyl polyether side chain. The universal polycarboxylic acid water reducing agent disclosed by the invention is low in alkali content, high in water-reducing rate, labor-saving in concrete operation, simple in production process, easy in reaction condition control and free of environmental pollution; the cement mixture has high mobility and slump keeping property, and good peaceability; and the universal polycarboxylic acid water reducing agent disclosed by the invention can be used as an important component of high-performance concrete, and can be widely applied to stirred and cast-in-place concrete and ready-mixed concrete for various industrial and civil buildings.
Description
Technical field
The invention belongs to the concrete admixture field, be specifically related to a kind of high performance water reducing agent of polyocarboxy acid and preparation method thereof.
Background technology
Compare with the efficient water reducer such as naphthalene system, melamine series, sulfamate, 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, hangs down characteristics such as shrinking, strengthen potentiality are large, environmental friendliness, therefore 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.
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 relatively single situation of original kind just gradually, it is relatively better that but this area still lacks a kind of performance, the universal polycarboxylic water reducer that cost is relatively low.
Summary of the invention
In order to satisfy the needs of prior art, the invention discloses a kind of universal polycarboxylic water reducer, described universal polycarboxylic water reducer overcomes in the past water reducer complex manufacturing, the shortcoming that slump retaining is poor or cost is higher, excellent performance and stable, its preparation method is simple, and easy control of reaction conditions is easy to suitability for industrialized production.
For achieving the above object, the present invention is achieved through the following technical solutions:
A kind of general polycarboxylate water-reducer, molecular weight are 10000-50000, and chemical structural formula is:
Preferably, the applicant finds that working as general polycarboxylate water-reducer molecular weight is 20000-30000, and R is methyl CH
3, it has best performance as water reducer during n=40-45.
On the basis of the above, the invention discloses the preparation method of described general polycarboxylate water-reducer, comprise following two steps: (1) adds acrylic or methacrylic acid and methylpropene sodium sulfonate and methyl acrylate in allyl polyether and the maleic anhydride aqueous solution, with ammonium persulphate or Sodium Persulfate as initiator, Thiovanic acid or thiohydracrylic acid are as chain-transfer agent, carry out polyreaction at 60～80 ℃, described initiator adds at 90～110min; (2) after reaction is finished, with sodium hydroxide solution or ethylenediamine solution pH=6～7 that neutralize, obtain 40% polycarboxylate water-reducer solution.
Wherein, the usage ratio of each composition can be adjusted according to practical situation, and usually in following ranges: the molar ratio of allyl polyether and maleic anhydride is 1: 1.0～4.5; Methyl acrylate: methylpropene sodium sulfonate: (methyl) acrylic acid molar ratio is 1: 1: 1.0～4.0; Initiator amount is 1%～8% of polymerization single polymerization monomer mole number; Chain-transfer agent is 0.5%～1.5% of polymerization single polymerization monomer consumption.
Preferably, the molar ratio of described allyl polyether and maleic anhydride is 1: 3.0; Methyl acrylate: methylpropene sodium sulfonate: (methyl) acrylic acid molar ratio is 1: 1: 2.0.
Preferably, described initiator amount is 5.6% of polymerization single polymerization monomer mole number; Described chain-transfer agent is 0.75% of polymerization single polymerization monomer consumption.
It should be noted that the applicant has used (methyl) acrylic acid phraseology herein, be used for the expression following meanings: vinylformic acid and/or methacrylic acid.
Compare with other preparation method; the synthetic of polycarboxylic acid concrete water reducer of the present invention is to utilize to add acrylic or methacrylic acid and methyl acrylate and methylpropene sodium sulfonate copolymerization in allyl polyether and the maleic anhydride aqueous solution; need not nitrogen protection; temperature of reaction is constant; reinforced program is simple, and reaction conditions is easy to control.
Polyacrylic acid series concrete water-reducing agent of the present invention is used for concrete batching, when this water reducer volume of 20wt% concentration be cement weight 1% the time, the concrete mix slump can reach more than the 18cm; When volume was 1%, water-reducing rate can reach 27%; Chloride ion-containing not is to the reinforcing bar non-corrosiveness; 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 (especially southern cement) of plurality of specifications, model, and product performance are stable, and long storage is not stratified, the nothing precipitation, and winter is without crystallization; The advantages such as the product nontoxic pollution-free does not contain formaldehyde, and is environmentally safe.
The applicant found through experiments, and in more excellent situation, namely molecular weight is 20000-30000, and R is methyl CH
3, during n=40-45, described polyacrylic acid series concrete water-reducing agent is used for concrete batching, when this water reducer volume of 20wt% concentration be cement weight 1% the time, the concrete mix slump can reach more than the 25cm; When volume was 1%, water-reducing rate can reach 35%; Concrete 28d shrinking percentage is that analog high efficiency water reducing agent reduces more than 40% than naphthalene.
Embodiment
In the following embodiments, the proportioning of each reactant is as follows; Allyl polyether and maleic anhydride are 1: 3.0; Methyl acrylate: methylpropene sodium sulfonate: (methyl) acrylic acid molar ratio is 1: 1: 2.0; Initiator amount is 1%～8% of polymerization minor comonomer mole number, and optimum amount is 5.6%; Chain-transfer agent is 0.5%～1.5% of polymerization single polymerization monomer consumption, and optimum amount is 0.75%;
Following embodiment only is used for the subsidiary book those skilled in the art and understands better invention essence of the present invention, but not is construed as limiting.The change that those skilled in the art carry out on this basis, replacement still belong to protection scope of the present invention.
Embodiment 1: best proportioning
Be that 2000 allyl polyether, 15 parts of maleic anhydrides and water are some with 100.00 parts of molecular weight, put into reaction vessel, heat up, under 70 ± 5 ℃ of temperature, stirring is dissolved reactant fully, drip again the aqueous solution that is dissolved with 10.80 parts of vinylformic acid, 4.74 parts of methylpropene sodium sulfonates, 2.13 parts of methyl acrylates and 40 parts of deionized waters and 24.00 part of 5% ammonium persulfate solution and 10.00 parts of mass percents in the container and be 10% the thin basic ethanol of solution, the control rate of addition, dripped off at 100 ± 10 minutes, maintain the temperature at 70 ± 5 ℃, continue reaction 4 hours.Add again 2.53 part of 40% sodium hydroxide solution after the cooling and regulate PH=6.5 ± 0.5, obtain poly-carboxylic high-performance cement water reducing agent of the present invention.
Embodiment 2
Be 2000 Soxylat A 25-7,15 parts of maleic anhydrides and 100.00 parts of water with 100.00 parts of molecular weight, put into reaction vessel, heat up, under 70 ± 5 ℃ of temperature, stirring is dissolved reactant fully, drip again the aqueous solution that is dissolved with 10.80 parts of vinylformic acid, 4.74 parts of methylpropene sodium sulfonates, 2.13 parts of methyl acrylates and 52 parts of deionized waters and 12.00 part of 5% ammonium persulfate solution and 10.00 parts of mass percents in the container and be 10% the thin basic ethanol of solution, the control rate of addition, dripped off at 100 ± 10 minutes, maintain the temperature at 70 ± 5 ℃, continue reaction 4 hours.Add again 2.53 part of 40% sodium hydroxide solution after the cooling and regulate PH=6.5 ± 0.5, obtain poly-carboxylic high-performance cement water reducing agent of the present invention.
Embodiment 3
Be 2000 Soxylat A 25-7,15 parts of maleic anhydrides and 100.00 parts of water with 100.00 parts of molecular weight, put into reaction vessel, heat up, under 80 ± 5 ℃ of temperature, stirring is dissolved reactant fully, drip again the aqueous solution that is dissolved with 10.80 parts of vinylformic acid, 4.74 parts of methylpropene sodium sulfonates, 2.13 parts of methyl acrylates and 47 parts of deionized waters and 12.00 part of 5% ammonium persulfate solution and 15.00 parts of mass percents in the container and be 10% the thin basic ethanol of solution, the control rate of addition, dripped off at 100 ± 10 minutes, maintain the temperature at 80 ± 5 ℃, continue reaction 4 hours.Add again 2.53 part of 40% sodium hydroxide solution after the cooling and regulate PH=6.5 ± 0.5, obtain poly-carboxylic high-performance cement water reducing agent of the present invention.
Embodiment 4
It is 2000 Soxylat A 25-7 with 100.00 parts of molecular weight, 15 parts of maleic anhydrides and 100.00 parts of deionized waters, put into reaction vessel, heat up, under 80 ± 5 ℃ of temperature, stirring is dissolved reactant fully, drip in the container again and be dissolved with 10.80 parts of vinylformic acid, 4.74 part methylpropene sodium sulfonate, 2.13 the aqueous solution of part methyl acrylate and 35 parts of deionized waters and 24.00 part of 5% ammonium persulfate solution and 15.00 parts of mass percents are 10% thin basic ethanolic soln, the control rate of addition, dripped off at 100 ± 10 minutes, maintain the temperature at 80 ± 5 ℃, continue reaction 4 hours.Add again 2.53 part of 40% sodium hydroxide solution after the cooling and regulate PH=6.5 ± 0.5, obtain poly-carboxylic high-performance cement water reducing agent of the present invention.
The above-mentioned general polycarboxylate water-reducer that the present invention provides, test (GB/T8077-2000) according to clean slurry degree of mobilization: adopt reference cement, according to GB/T8077-87 test flowing degree of net paste of cement, detected result is as shown in table 1 below:
Table 1: performance test results
The concrete slump retaining situation is as a result shown in the following table 2:
Table 2 is protected the situation experimental result of collapsing
Claims (9)
1. a general polycarboxylate water-reducer is characterized in that, molecular weight 10000～50000, and chemical structural formula is
2. general polycarboxylate water-reducer according to claim 1 is characterized in that, molecular weight is 20000-30000, and R is methyl CH
3, n=40-45.
3. the preparation method of a general polycarboxylate water-reducer, it is characterized in that, comprise the steps: that (1) adds acrylic or methacrylic acid and methylpropene sodium sulfonate and methyl acrylate in allyl polyether and the maleic anhydride aqueous solution, with ammonium persulphate or Sodium Persulfate as initiator, Thiovanic acid or thiohydracrylic acid are as chain-transfer agent, carry out polyreaction at 60～80 ℃, described initiator adds at 90～110min; (2) after reaction is finished, with sodium hydroxide solution or ethylenediamine solution pH=6～7 that neutralize, obtain 40% polycarboxylate water-reducer solution.
4. preparation method according to claim 3 is characterized in that, the molar ratio of allyl polyether and maleic anhydride is 1: 1.0～4.5; Methyl acrylate: methylpropene sodium sulfonate: (methyl) acrylic acid molar ratio is 1: 1: 1.0～4.0; Initiator amount is 1%～8% of polymerization single polymerization monomer mole number; Chain-transfer agent is 0.5%～1.5% of polymerization single polymerization monomer consumption.
5. preparation method according to claim 4 is characterized in that, the molar ratio of allyl polyether and maleic anhydride is 1: 3.0.
6. preparation method according to claim 4 is characterized in that, methyl acrylate: methylpropene sodium sulfonate: (methyl) acrylic acid molar ratio is 1: 1: 2.0.
7. preparation method according to claim 4 is characterized in that, initiator amount is 5.6% of polymerization single polymerization monomer mole number.
8. preparation method according to claim 4 is characterized in that, chain-transfer agent is 0.75% of polymerization single polymerization monomer consumption.
9. preparation method according to claim 3 is characterized in that, polymerization reaction time is 6 ± 0.5h.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103396031A (en) * | 2013-07-19 | 2013-11-20 | 北京东方雨虹防水技术股份有限公司 | Carboxylate water reducing agent and preparation method thereof |
| CN104496253A (en) * | 2014-12-23 | 2015-04-08 | 岳阳东方雨虹防水技术有限责任公司 | Special early-strength polycarboxylate superplasticizer for prefabricated parts and preparation method of special early-strength polycarboxylate superplasticizer |
| CN105153375A (en) * | 2015-09-21 | 2015-12-16 | 华南理工大学 | Method for synthesizing polycarboxylate superplasticizer through RAFT method |
| CN105778011A (en) * | 2016-03-08 | 2016-07-20 | 济南世纪华新实业有限公司 | Water-reduction and plasticity-maintaining polycarboxylate-type water reducing agent and preparing method thereof |
| CN108752538A (en) * | 2018-06-28 | 2018-11-06 | 江苏百瑞吉新材料有限公司 | A kind of high overlength of system containing mud guarantor is collapsed concrete tailored version poly carboxylic acid series water reducer |
| CN110818375A (en) * | 2019-11-22 | 2020-02-21 | 甘昌成 | Aerated concrete and preparation method thereof |
| CN116178617A (en) * | 2022-10-25 | 2023-05-30 | 江苏超力建材科技有限公司 | Star-shaped high-performance polycarboxylate superplasticizer and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103396031A (en) * | 2013-07-19 | 2013-11-20 | 北京东方雨虹防水技术股份有限公司 | Carboxylate water reducing agent and preparation method thereof |
| CN104496253A (en) * | 2014-12-23 | 2015-04-08 | 岳阳东方雨虹防水技术有限责任公司 | Special early-strength polycarboxylate superplasticizer for prefabricated parts and preparation method of special early-strength polycarboxylate superplasticizer |
| CN105153375A (en) * | 2015-09-21 | 2015-12-16 | 华南理工大学 | Method for synthesizing polycarboxylate superplasticizer through RAFT method |
| CN105778011A (en) * | 2016-03-08 | 2016-07-20 | 济南世纪华新实业有限公司 | Water-reduction and plasticity-maintaining polycarboxylate-type water reducing agent and preparing method thereof |
| CN108752538A (en) * | 2018-06-28 | 2018-11-06 | 江苏百瑞吉新材料有限公司 | A kind of high overlength of system containing mud guarantor is collapsed concrete tailored version poly carboxylic acid series water reducer |
| CN110818375A (en) * | 2019-11-22 | 2020-02-21 | 甘昌成 | Aerated concrete and preparation method thereof |
| CN116178617A (en) * | 2022-10-25 | 2023-05-30 | 江苏超力建材科技有限公司 | Star-shaped high-performance polycarboxylate superplasticizer and preparation method thereof |
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Effective date of registration: 20170407 Address after: 414009 Industrial Park, Yunxi District, Hunan, Yueyang Patentee after: Yueyang Oriental Yuhong Waterproof Technology Co., Ltd. Patentee after: Beijing Oriental Yuhong Waterproof Technology Co., Ltd. Address before: 100123 Beijing, Gaobeidian, Kang Kang home district, building 4, building No. Patentee before: Beijing Oriental Yuhong Waterproof Technology Co., Ltd. |
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