CN102173638A - Polycarboxylate water reducer and preparation method thereof - Google Patents
Polycarboxylate water reducer and preparation method thereof Download PDFInfo
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- CN102173638A CN102173638A CN 201110008629 CN201110008629A CN102173638A CN 102173638 A CN102173638 A CN 102173638A CN 201110008629 CN201110008629 CN 201110008629 CN 201110008629 A CN201110008629 A CN 201110008629A CN 102173638 A CN102173638 A CN 102173638A
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Abstract
The invention discloses a polycarboxylate water reducer and a preparation method thereof. The molecular weight of the polycarboxylate water reducer is between 20,000 and 60,000, and is prepared by the steps of reacting itaconic acid with methoxy polyethylene glycol to prepare methoxy polyethylene glycol itaconic acid monoester, and then, copolymerizing the methoxy polyethylene glycol itaconic acid monoester with unsaturated carboxylic acid or derivants thereof to synthesize the polycarboxylate water reducer containing carboxyl, an ester group and a side chain of a polyethylene glycol group. In the polycarboxylate water reducer, one carboxyl is introduced into a large polymerization monomer, and the density of the carboxyl is increased so that the water reducing ratio is improved. The polycarboxylate water reducer disclosed by the invention also has the advantage of favorable slump maintenability.
Description
Technical field
The present invention relates to concrete admixture, relate in particular to a kind of polyethers methylene-succinic acid monoesters polycarboxylate dehydragent and preparation method thereof.
Background technology
Concrete is one of contemporary topmost civil engineering material.And concrete admixture is the 5th component except cement, water, sand, stone in the concrete, in high performance concrete in occupation of important status.
The development of water reducer has long history.Nineteen thirty-five U.S. E.W. Si Kelipu builds (Scopture) and at first is developed into the ligninsulfonate water reducer that ligninsulfonate is a main component, is widely used in the C20-C40 concrete, and this series water reducer water-reducing rate is lower, but owing to cheaply still has use now.The sixties in 20th century, Japan has successfully developed the naphthalene sulfonic acidformaldehyde condensation product high efficiency water reducing agent, and Germany has successfully developed sulfonated melamine compound condenses high efficiency water reducing agent, and this two classes water reducer is widely used in the C30-C60 concrete, advantages such as it is lower to have production cost, and water-reducing rate is effective.From the sixties to the beginning of the eighties, it is the developmental stage of high efficiency water reducing agent, this stage water reducer is main representative with naphthalene, principal feature be technical maturity, not bleed, not slow setting, good with cement adaptability, water-reducing rate is higher, but concrete slump loss is very fast, need just can reach different construction requirements by composite, but the water reducer after composite is influential to the development of early age strength of concrete.This product uses formaldehyde, the vitriol oil to synthesize in a large number in addition, and production is seriously polluted to environment.
Japan utilizes alkene and unsaturated carboxylic acid copolymerization in nineteen ninety-five, has successfully developed polycarboxylate high performance water-reducing agent.This kind poly carboxylic acid series water reducer feature is that the connecting key of main chain and side chain is an ester bond.Poly carboxylic acid series water reducer since water-reducing rate up to 30% or more, volume is few, slump retentivity is good, amount of air entrainment is moderate, suitable preparation high workability, self-compacting concrete, and do not use formaldehyde in synthesizing, environmental pollution is little, thereby is subjected to promoting widely.Japan is that research and application poly carboxylic acid series water reducer at most also are the most successful countries, and after nineteen ninety-five, the usage quantity of poly carboxylic acid series water reducer in the Japanese goods concrete surpassed naphthalene water reducer.In Japan, the earliest be the multipolymer of alkene and unsaturated carboxylic acid according to carboxylic acid water reducing agent, breakthrough improvement is all arranged on improved properties and copolymerization technique thereafter, performance is gradually improved.
In recent years, the research of concrete admixture is tending towards high-performance with production day in the world, free of contamination direction develops.The copolymerization polycarboxylic acid series additive is because the water-reducing rate height, and function of slump protection is good, and later strength increases big, and suitable preparation is high-strength, super high strength concrete, high workability and super plasticizing concrete, self-compacting concrete etc., thereby is subjected to extensive concern both domestic and external.
In patent CN101357833A, a kind of a kind of slump retaining polyocarboxy acid superplasticiser that uses methylene-succinic acid as minor comonomer is disclosed, by the big monomer of polyethers, unsaturated monoprotic acid and methylene-succinic acid copolymerization, obtain the poly carboxylic acid slump retaining agent.But the polycarboxylic acid super-plasticizer water-reducing rate of this method preparation is low, is still waiting to improve.
Summary of the invention
The purpose of this invention is to provide a kind of polycarboxylate dehydragent and preparation method thereof, this water reducer water-reducing rate height, slump retaining are good.
A kind of polycarboxylate dehydragent provided by the invention, earlier with methylene-succinic acid and the synthetic big monomer of polyethers macromer methoxyl-polyethyleneglycol esterification, synthetic with water miscible unsaturated acid and/or derivative copolymerization under aqueous conditions then, its weight-average molecular weight is 20000～60000, and its structural formula is:
In the formula: R
1Show hydrogen atom or carboxyl
R
2Show hydrogen atom, methyl group or carboxyl
M represents the ether of hydroxyl, amido or C atomicity 1～5
a＝5～60，b＝5～60，n＝10～120。
The preparation method of a kind of polycarboxylate dehydragent provided by the invention comprises the steps:
(1) esterification: with the tosic acid is catalyzer, toluene is the band aqua, by methoxy poly (ethylene glycol) and methylene-succinic acid esterification 6 hours under the refluxing toluene temperature, impurity such as band aqua are removed in underpressure distillation, the mixture of methoxy poly (ethylene glycol) methylene-succinic acid monoesters and residue methylene-succinic acid; Proportioning raw materials: methoxy poly (ethylene glycol): methylene-succinic acid=1: 1.2～1.5 (mol ratio); The tosic acid consumption is 4%～6% of methoxy poly (ethylene glycol) and a methylene-succinic acid total mass, and the consumption of toluene is 50%～80% of methoxy poly (ethylene glycol) and a methylene-succinic acid total mass; Reaction formula is as follows:
In the formula: n=10～120 are preferably 10～50.
(2) copolyreaction: with the persulphate is initiator, the mixture of the methoxy poly (ethylene glycol) methylene-succinic acid monoesters of gained in the step (1) and remaining methylene-succinic acid and water miscible unsaturated acid and/or its derivative at 60～85 ℃ of following copolymerization 3～5h, are obtained polycarboxylate dehydragent; Proportioning raw materials: methoxy poly (ethylene glycol) methylene-succinic acid monoesters and the mixture that remains methylene-succinic acid: water miscible unsaturated acid and/or derivative=1～1.5: 4; Initiator amount is 6%～10% of a polymerization single polymerization monomer total mass; Reaction formula is as follows:
In the formula: R
1Show hydrogen atom or carboxyl
R
2Show hydrogen atom, methyl group or carboxyl
M represents the ether of hydroxyl, amido or C atomicity 1～5
A=5～60, b=5～60; N=10～120, n is preferably 10～50.
The initiator of described free radical copolymerization is ammonium persulphate, Potassium Persulphate or Sodium Persulfate etc.
If when water miscible unsaturated acid polymerization activity was big, polyreaction need add chain-transfer agent, as Thiovanic acid.
Learn through testing repeatedly, the water-reducing rate of polycarboxylate water-reducer and slump hold facility and the absorption of water reducer in cement system are closely related, can change the absorption property of polymkeric substance by the structure that changes polymkeric substance to cement, the polycarboxylate water-reducer initial adsorption of high carboxyl density is many, and high concrete water-reducing ratio can be provided.The present invention has introduced a carboxyl more on the big monomer of polymerization, increased carboxyl density, thereby makes water-reducing rate improve.The present invention also has the slump and keeps good advantage.
Embodiment
Express for simplifying, below show methoxy poly (ethylene glycol) with mpeg table;
Embodiment 1:
In the 250mL there-necked flask of thermometer, agitator, water trap is housed, add MPEG (molecular weight is 1000) 60g, methylene-succinic acid 9.4g, catalyzer tosic acid 2.7g, band aqua toluene 34.7g, heating, stirring dissolves reactant fully, heats up to make toluene continue to reflux, maintain the temperature at 110～120 ℃, after the esterification 6 hours, carry out underpressure distillation, obtain methoxy poly (ethylene glycol) methylene-succinic acid monoesters and remaining methylene-succinic acid mixture except that desolvating.
In the 250ml flask of thermometer, agitator is housed, add the methoxy poly (ethylene glycol) methylene-succinic acid monoesters and the remaining methylene-succinic acid mixture 40g of gained, be warmed up to 50 ℃, after the thing dissolving to be mixed, add 51.9g distilled water successively, maleic anhydride 11.9g stirs, add the 2.0g ammonium persulphate, temperature is controlled at 70～75 ℃, behind the reaction 4h, is cooled to below 40 ℃, add the NaOH aqueous solution and neutralize to such an extent that the pH value is about 7, solid content is 40% yellowish brown transparent liquid.
Embodiment 2:
In the 250mL there-necked flask of thermometer, agitator, water trap is housed, add MPEG (molecular weight is 1200) 60g, methylene-succinic acid 7.8g, catalyzer tosic acid 3.4g, band aqua toluene 33.9g, heating, stirring dissolves reactant fully, heats up to make toluene continue to reflux, maintain the temperature at 110～120 ℃, after the esterification 6 hours, carry out underpressure distillation, obtain methoxy poly (ethylene glycol) methylene-succinic acid monoesters and remaining methylene-succinic acid mixture except that desolvating.
Thermometer is being housed, in the 250mL four-hole boiling flask of agitator, the methoxy poly (ethylene glycol) methylene-succinic acid monoesters and the remaining methylene-succinic acid mixture 40g that add gained, be warmed up to 50 ℃, after the thing dissolving to be mixed, add distilled water 20g successively, chain-transfer agent Thiovanic acid 0.01mL stirs, on one side dropwise addition of acrylic acid 8.8g, drip on one side mass percent and be 6% potassium persulfate solution 34g, the control rate of addition, acrylic acid solution drips 3h, and initiator ammonium persulfate solution drips 3.5h, maintain the temperature at 60～65 ℃, drip back insulation reaction 0.5h, the cooling back adds the NaOH aqueous solution and neutralizes to such an extent that the pH value is about 7, and solid content is 40% yellowish brown transparent liquid.
Embodiment 3:
Identical among the preparation of methoxy poly (ethylene glycol) methylene-succinic acid monoesters and the embodiment 1
In the 250ml flask of thermometer, agitator is housed, add the methoxy poly (ethylene glycol) methylene-succinic acid monoesters and the remaining methylene-succinic acid mixture 40g of gained, be warmed up to 50 ℃, after the thing dissolving to be mixed, add 51.9g distilled water successively, maleic anhydride 6.3g, acrylamide 1.7g, stir, add the 2.8g Sodium Persulfate, temperature is controlled at 70～75 ℃, behind the reaction 4h, be cooled to below 40 ℃, add the NaOH aqueous solution and neutralize to such an extent that the pH value is about 7, solid content is 40% yellowish brown transparent liquid.
Embodiment 4:
Identical among the preparation of methylene-succinic acid monoesters and the embodiment 2.
Thermometer is being housed, in the 250mL four-hole boiling flask of agitator, the methoxy poly (ethylene glycol) methylene-succinic acid monoesters and the remaining methylene-succinic acid mixture 40g that add gained, be warmed up to 50 ℃, after the thing dissolving to be mixed, add distilled water 20g successively, hydroxyethyl methylacrylate 3.3g, chain-transfer agent Thiovanic acid 0.01mL, stir, dropwise addition of acrylic acid 5.5g on one side drips mass percent on one side and is 10% ammonium persulfate solution 32g, controls rate of addition, acrylic acid solution drips 3h, initiator ammonium persulfate solution drips 3.5h, maintains the temperature at 60～65 ℃, drips back insulation reaction 0.5h, the cooling back adds the NaOH aqueous solution and neutralizes to such an extent that the pH value is about 7, and solid content is 40% yellowish brown transparent liquid.
Comparative Examples:
In the 250mL there-necked flask of thermometer, agitator, water trap is housed, add MPEG (molecular weight is 1000) 60g, catalyzer tosic acid 3.1g, band aqua toluene 38.6g, heated and stirred evenly makes reactant dissolve fully, heats up to make toluene continue to reflux, and maintains the temperature at 110～120 ℃, while dropwise addition of acrylic acid 17.3g, 2h drips.After the esterification 6 hours, carry out underpressure distillation, obtain the methoxy poly (ethylene glycol) acrylate except that desolvating.
Thermometer is being housed, in the 250ml flask of agitator, the methoxy poly (ethylene glycol) acrylate 40g that adds gained, be warmed up to 50 ℃, after the thing dissolving to be mixed, add distilled water 20g successively, chain-transfer agent Thiovanic acid 0.01mL stirs, on one side dropwise addition of acrylic acid 13.3g, drip on one side mass percent and be 10% ammonium persulfate solution 32g, the control rate of addition, acrylic acid solution drips 3h, and initiator ammonium persulfate solution drips 3.5h, maintain the temperature at 60～65 ℃, drip back insulation reaction 0.5h, the cooling back adds the NaOH aqueous solution and neutralizes to such an extent that the pH value is about 7, and solid content is 40% yellowish brown transparent liquid.
Water reducer of the present invention is estimated according to the GB8076-2008 standard, and volume is 0.2%, test result as shown in Table 1 and Table 2:
The test of table 1 flowing degree of net paste of cement
The test of table 2 concrete slump
| Embodiment | The initial slump/mm | The 30min slump/mm | The 60min slump/mm |
| 1 | 220 | 195 | 160 |
| 2 | 195 | 170 | 150 |
| 3 | 225 | 215 | 220 |
| 4 | 210 | 205 | 210 |
| Comparative Examples | 195 | 155 | 130 |
Can find out the better performances of water reducer of the present invention from the data of table 1 and table 2.
Claims (4)
1. a polycarboxylate dehydragent is characterized in that, weight-average molecular weight is 20000～60000, and structural formula is:
In the formula: R
1Show hydrogen atom or carboxyl; R
2Show hydrogen atom, methyl group or carboxyl; M represents the ether of hydroxyl, amido or C atomicity 1～5; A=5～60, b=5～60, n=10～120.
2. the preparation method of a kind of polycarboxylate dehydragent as claimed in claim 1 is characterised in that to comprise the steps:
(1) esterification: with the tosic acid is catalyzer, toluene is the band aqua, by methoxy poly (ethylene glycol) and methylene-succinic acid esterification 6 hours under the refluxing toluene temperature, impurity such as band aqua are removed in underpressure distillation, the mixture of methoxy poly (ethylene glycol) methylene-succinic acid monoesters and residue methylene-succinic acid; Proportioning raw materials: methoxy poly (ethylene glycol): methylene-succinic acid=1: 1.2～1.5 (mol ratio); The tosic acid consumption is 4%～6% of methoxy poly (ethylene glycol) and a methylene-succinic acid total mass, and the consumption of toluene is 50%～80% of methoxy poly (ethylene glycol) and a methylene-succinic acid total mass;
(2) copolyreaction: with the persulphate is initiator, the mixture of the methoxy poly (ethylene glycol) methylene-succinic acid monoesters of gained in the step (1) and remaining methylene-succinic acid and water miscible unsaturated acid and/or its derivative at 60～85 ℃ of following copolymerization 3～5h, are obtained polycarboxylate dehydragent; Proportioning raw materials: methoxy poly (ethylene glycol) methylene-succinic acid monoesters and the mixture that remains methylene-succinic acid: water miscible unsaturated acid and/or derivative=1～1.5: 4; Initiator amount is 6%～10% of a polymerization single polymerization monomer total mass.
3. the preparation method of a kind of polycarboxylate dehydragent as claimed in claim 2 is characterised in that the persulphate in the described step (2) is ammonium persulphate, Potassium Persulphate or Sodium Persulfate.
4. the preparation method of a kind of polycarboxylate dehydragent as claimed in claim 2 is characterised in that to add the chain-transfer agent Thiovanic acid in the step (2).
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382272A (en) * | 2011-09-17 | 2012-03-21 | 深圳市五山建材实业有限公司 | Method for preparing polycarboxylic acid water reducer by itaconic acid |
| CN104725578A (en) * | 2015-03-18 | 2015-06-24 | 东阿东昌天汇科技有限公司 | Preparation method of grafted copolymer and air-entraining and slump-retaining polycarboxylate concrete water reducer |
| CN104725227A (en) * | 2013-12-18 | 2015-06-24 | 辽宁奥克化学股份有限公司 | Unsaturated carboxylate monoester, preparation method and application thereof, and polycarboxylate water reducer obtained by taking unsaturated carboxylate monoester as polymeric monomer |
| CN106277899A (en) * | 2016-08-22 | 2017-01-04 | 山西大学 | A kind of polycarboxylate water-reducer and preparation method thereof |
| CN106478893A (en) * | 2016-09-30 | 2017-03-08 | 安徽瑞和新材料有限公司 | A kind of preparation method of concrete viscous regulator |
| CN109678383A (en) * | 2019-01-19 | 2019-04-26 | 浙江吉盛化学建材有限公司 | A kind of macromolecular monoesters water-reducing agent preparation process |
| CN113683736A (en) * | 2021-08-10 | 2021-11-23 | 安徽海螺新材料科技有限公司 | Viscosity reduction type polycarboxylate superplasticizer for high-strength concrete and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101041570A (en) * | 2007-04-27 | 2007-09-26 | 北京工业大学 | Preparation method of graft copolymerization carboxylate high-performance dehydragent |
| CN101234866A (en) * | 2007-12-21 | 2008-08-06 | 王伟松 | Preparation method of polycarboxylic acid series high-efficiency water reducing agent |
| CN101289292A (en) * | 2008-06-13 | 2008-10-22 | 北京工业大学 | Early strength polycarboxylic acid high performance dehydragent and method for preparing same |
| CN101792282A (en) * | 2010-03-26 | 2010-08-04 | 山西大学 | Polycarboxylate water reducing agent and preparation method thereof |
-
2011
- 2011-01-11 CN CN 201110008629 patent/CN102173638A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101041570A (en) * | 2007-04-27 | 2007-09-26 | 北京工业大学 | Preparation method of graft copolymerization carboxylate high-performance dehydragent |
| CN101234866A (en) * | 2007-12-21 | 2008-08-06 | 王伟松 | Preparation method of polycarboxylic acid series high-efficiency water reducing agent |
| CN101289292A (en) * | 2008-06-13 | 2008-10-22 | 北京工业大学 | Early strength polycarboxylic acid high performance dehydragent and method for preparing same |
| CN101792282A (en) * | 2010-03-26 | 2010-08-04 | 山西大学 | Polycarboxylate water reducing agent and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| 《建设工程混凝土应用新技术(会议录)》 20091231 黄波 高保塑聚羧酸混凝土高效减水剂的研制 全文 1-4 , 2 * |
| 《新型建筑材料》 20101231 王玲等 衣康酸类聚羧酸系减水剂的合成及其性能研究 全文 1-4 , 第12期 2 * |
| 《混凝土》 20100228 唐林生等 新型聚乙二醇接枝聚羧酸减水剂的制备 第75-76页 1-4 , 第2期 2 * |
| 《清华大学学报(自然科学版)》 20091231 孔祥明等 聚羧酸系减水剂的合成及应用性能 全文 1-4 第49卷, 第12期 2 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382272A (en) * | 2011-09-17 | 2012-03-21 | 深圳市五山建材实业有限公司 | Method for preparing polycarboxylic acid water reducer by itaconic acid |
| CN104725227A (en) * | 2013-12-18 | 2015-06-24 | 辽宁奥克化学股份有限公司 | Unsaturated carboxylate monoester, preparation method and application thereof, and polycarboxylate water reducer obtained by taking unsaturated carboxylate monoester as polymeric monomer |
| CN104725227B (en) * | 2013-12-18 | 2017-03-01 | 辽宁奥克化学股份有限公司 | A kind of unsaturated carboxylic acid monoesters, its preparation method and application and its polycarboxylate water-reducer as polymerized monomer gained |
| CN104725578A (en) * | 2015-03-18 | 2015-06-24 | 东阿东昌天汇科技有限公司 | Preparation method of grafted copolymer and air-entraining and slump-retaining polycarboxylate concrete water reducer |
| CN106277899A (en) * | 2016-08-22 | 2017-01-04 | 山西大学 | A kind of polycarboxylate water-reducer and preparation method thereof |
| CN106478893A (en) * | 2016-09-30 | 2017-03-08 | 安徽瑞和新材料有限公司 | A kind of preparation method of concrete viscous regulator |
| CN106478893B (en) * | 2016-09-30 | 2018-11-23 | 安徽瑞和新材料有限公司 | A kind of preparation method of concrete viscous regulator |
| CN109678383A (en) * | 2019-01-19 | 2019-04-26 | 浙江吉盛化学建材有限公司 | A kind of macromolecular monoesters water-reducing agent preparation process |
| CN113683736A (en) * | 2021-08-10 | 2021-11-23 | 安徽海螺新材料科技有限公司 | Viscosity reduction type polycarboxylate superplasticizer for high-strength concrete and preparation method thereof |
| CN113683736B (en) * | 2021-08-10 | 2024-05-07 | 安徽海螺材料科技股份有限公司 | Viscosity-reducing polycarboxylate superplasticizer for high-strength concrete and preparation method thereof |
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Application publication date: 20110907 |