CN102206060A - Synthetic method for maleic polycarboxylic water reducer - Google Patents
Synthetic method for maleic polycarboxylic water reducer Download PDFInfo
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- CN102206060A CN102206060A CN 201110061090 CN201110061090A CN102206060A CN 102206060 A CN102206060 A CN 102206060A CN 201110061090 CN201110061090 CN 201110061090 CN 201110061090 A CN201110061090 A CN 201110061090A CN 102206060 A CN102206060 A CN 102206060A
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Abstract
The invention discloses a synthetic method for maleic polycarboxylic water reducer. The method is characterized in that: maleic anhydride (MA) and polyethylene glycol (PEG)/methoxy polyethylene glycol (MPEG) are used as the raw materials to synthesize polyethylene glycol maleate monoester (PEG-MA)/methoxy polyethylene glycol maleate monoester (MPEG-MA); and PEG-MA/ MPEG-MA, AA/AANa and methoxy polyethylene glycol metacrylic acid ester (MPEG-MAA) are used as the raw materials to synthesize a maleic polycarboxylic water reducer containing carboxyl and a polyoxyethylene (PEO) side chain structure. According to the invention, the molecular structure of the polycarboxylic water reducer introduces carboxyl and PEO with a long side chain, which enables electrostatic repulsion among cement particles to be increased, dispersibility, i.e. retentivity of dispersion of cement to be improved, and steric hindrance among cement particles is realized, thereby realizing low slump loss. Simultaneously, the preparation method provided in the invention has the advantages of a simple process, mild reaction and wide sources of cheap raw materials.
Description
Technical field
The present invention relates to the synthetic of a kind of water reducer, be specifically related to the synthetic of a kind of toxilic acid class polyocarboxy acid type water reducer.
Background technology
Water reducer is meant under concrete workability and cement consumption permanence condition, can reduce the mixing water amount, improve concrete strength; Or under workability and intensity permanence condition, save a kind of admixture of cement consumption.
Polycarboxylate water-reducer is widely used in the building trade because have characteristics such as low-dosage, high water reducing rate and concrete slump loss are little.Polycarboxylate water-reducer under the situation of low-dosage, the water-reducing rate height of cement, the degree of mobilization of cement is big, concrete intensity height, and long service life.Domestic and international at present adopt vinylformic acid and polyethylene glycol monomethyl ether elder generation's esterification copolymerization are again introduced PEO and carboxyl, or are added other monomer introducing hydroxyl more on molecular structure, make acrylic acid or the like poly carboxylic acid water reducer.The over-all properties of its water reducer is better, but function of slump protection is relatively poor.And toxilic acid is than the easier control of acrylic acid esterification technique, and the carboxyl-content height, helps the raising of function of slump protection.
Summary of the invention
The synthetic method that the purpose of this invention is to provide a kind of toxilic acid class polyocarboxy acid type water reducer.
For reaching above-mentioned purpose, the technical solution used in the present invention is: a kind of toxilic acid class polyocarboxy acid type water reducer is expressed by following formula:
Synthesizing of a kind of toxilic acid class polyocarboxy acid type water reducer, may further comprise the steps:
(1) polyoxyethylene glycol (PEG) that takes by weighing certain mass is put into the single port flask, adds toluene (PEG quality 20%), uses the water pump underpressure distillation, and bath temperature is controlled at 65 ℃, does not have bubble in flask.
(2) under certain bath temperature, maleic anhydride (MA) and the PEG (1000) that handled through the toluene underpressure distillation or methoxy poly (ethylene glycol) (MPEG (1000)) are joined single port flask esterification 4～6h by a certain percentage.Synthetic macromonomer PEG-MA or MPEG-MA are made into the aqueous solution of ρ=50%.
(3) by certain proportioning preparation vinylformic acid (AA), vinylbenzene (ST)/to vinylbenzene benzene sulfonic acid sodium salt (SSS), the water solution A of ρ=50% of methoxy polyethylene glycol methacrylate-styrene polymer (MPEG-MAA), the aqueous solution of the initiator of preparation ρ=50%.
The PEG-MA/MPEG-AA that (4) will prepare adds in the there-necked flask, adds 10% solution A and 20% initiator solution again.Bath temperature is controlled at 80 ℃, reaction 0.5～1.5h.
(5) A solution and the initiator solution with remainder mixes, and slowly drips 3～4h.
(6) react 1～1.5h again, stopped reaction is cooled to 40 ℃ and adds the NaOH solution, and regulating the pH value is 6.5～7.5, and diluting soln is to ρ=20%, promptly gets solid content and be 20% polycarboxylate water-reducer.
In the technique scheme, described initiator is selected from analytical pure ammonium persulphate (APS).
In the technique scheme, described MA: PEG/MPEG=1: 1～1: 1.5, AA: MPEG-MAA=10: 1～0: 1, MPEG-MAA: PEG-MA/MPEG-MA=1: 1～1: 2.
Because the utilization of technique scheme, the present invention has following characteristics:
This paper selects PEG/MPEG and the esterification of MA elder generation, with esterification products and AA/AANa copolymerization, introduces carboxyl, ester bond, PEO-H/PEO-CH on molecular structure then
3Introduce carboxyl on the molecular structure of polycarboxylate water-reducer, can improve the electrostatic repulsion between the cement granules, thereby the dispersing property that improves cement promptly disperses retentivity; According to sterically hindered theory; introduce long side chain polyoxyethylene groups on the molecular structure of polycarboxylate water-reducer; increase sterically hindered between the cement granules; can improve the dispersing property of cement greatly; main chain can be an ester bond with being connected of Soxylat A 25-7; ehter bond; amido etc.; and ester bond hydrolysis under the cement environment of alkalescence; slowly release carboxyl and Soxylat A 25-7; and contain a plurality of ehter bonds in the molecule; the oxygen of ehter bond and water molecule reaction form powerful hydrogen bond in the aqueous solution; form the wetting ability solid protective membrane; the existing dispersiveness of this protective membrane has dispersion stabilization again. and this has replenished used up carboxyl on the one hand, and Soxylat A 25-7 also has certain sterically hindered on the other hand; reach the purpose of slump retaining, hydroxyl has certain delayed coagulation simultaneously.
Description of drawings
Fig. 1 is the proton magnetic spectrum figure (wherein, A is an esterification products, and B is a copolymerization product) of esterification products and copolymerization product.
Embodiment
Below in conjunction with embodiment the present invention is further described, following examples only are that the present invention will be described but not it are limited.
Embodiment 1: the polyoxyethylene glycol (PEG) that takes by weighing 50g is put into the single port flask, adds toluene (PEG quality 20%), uses the water pump underpressure distillation, and bath temperature is controlled at 65 ℃, does not have bubble in flask.Under certain bath temperature, maleic anhydride (MA) and the PEG (1000) that handled through the toluene underpressure distillation or methoxy poly (ethylene glycol) (MPEG (1000)) are joined single port flask esterification 5h by 1: 1 mol ratio.Synthetic macromonomer PEG-MA or MPEG-MA are made into the aqueous solution of ρ=50%.By 8: 0.02: 1 mol ratio system vinylformic acid (AA), vinylbenzene (ST)/to vinylbenzene benzene sulfonic acid sodium salt (SSS), the water solution A of the ρ of MPEG-MAA=50%, the aqueous solution of the initiator of preparation ρ=50%.The PEG-MA/MPEG-AA that prepared is added in the there-necked flask, add 10% solution A and 20% initiator solution again.Bath temperature is controlled at 80 ℃, reaction 1h.The A solution and the initiator solution of remainder are mixed, slowly drip 4h.React 1h again, stopped reaction is cooled to 40 ℃ and adds the NaOH solution, and regulating the pH value is 7, and diluting soln is to ρ=20%, promptly gets solid content and be 20% polycarboxylate water-reducer.
Embodiment 2: the polyoxyethylene glycol (PEG) that takes by weighing 50g is put into the single port flask, adds toluene (PEG quality 20%), uses the water pump underpressure distillation, and bath temperature is controlled at 65 ℃, does not have bubble in flask.Under certain bath temperature, maleic anhydride (MA) and the PEG (1000) that handled through the toluene underpressure distillation or methoxy poly (ethylene glycol) (MPEG (1000)) by joining single port flask esterification 5h at 1: 1.1.Synthetic macromonomer PEG-MA or MPEG-MA are made into the aqueous solution of ρ=50%.By 5: 0.02: 1 mol ratio preparation vinylformic acid (AA), vinylbenzene (ST)/to vinylbenzene benzene sulfonic acid sodium salt (SSS), the water solution A of the ρ of MPEG-MAA=50%, the aqueous solution of the initiator of preparation ρ=50%.The PEG-MA/MPEG-AA that prepared is added in the there-necked flask, add 10% solution A and 20% initiator solution again.Bath temperature is controlled at 80 ℃, reaction 1h.The A solution and the initiator solution of remainder are mixed, slowly drip 4h.React 1h again, stopped reaction is cooled to 40 ℃ and adds the NaOH solution, and regulating the pH value is 7, and diluting soln is to ρ=20%, promptly gets solid content and be 20% polycarboxylate water-reducer.
Embodiment 3: the polyoxyethylene glycol (PEG) that takes by weighing 50g is put into the single port flask, adds toluene (PEG quality 20%), uses the water pump underpressure distillation, and bath temperature is controlled at 65 ℃, does not have bubble in flask.Under certain bath temperature, maleic anhydride (MA) and the PEG (1000) that handled through the toluene underpressure distillation or methoxy poly (ethylene glycol) (MPEG (1000)) by joining single port flask esterification 5h at 1: 1.2.Synthetic macromonomer PEG-MA or MPEG-MA are made into the aqueous solution of ρ=50%.By 3: 0.02: 1 preparation vinylformic acid (AA), vinylbenzene (ST)/to vinylbenzene benzene sulfonic acid sodium salt (SSS), the water solution A of the ρ of MPEG-MAA=50%, the aqueous solution of the initiator of preparation ρ=50%.The PEG-MA/MPEG-AA that prepared is added in the there-necked flask, add 10% solution A and 20% initiator solution again.Bath temperature is controlled at 80 ℃, reaction 1h.The A solution and the initiator solution of remainder are mixed, slowly drip 4h.React 1h again, stopped reaction is cooled to 40 ℃ and adds the NaOH solution, and regulating the pH value is 7, and diluting soln is to ρ=20%, promptly gets solid content and be 20% polycarboxylate water-reducer.
Embodiment 4: the polyoxyethylene glycol (PEG) that takes by weighing 50g is put into the single port flask, adds toluene (PEG quality 20%), uses the water pump underpressure distillation, and bath temperature is controlled at 65 ℃, does not have bubble in flask.Under certain bath temperature, maleic anhydride (MA) and the PEG (1000) that handled through the toluene underpressure distillation or methoxy poly (ethylene glycol) (MPEG (1000)) by joining single port flask esterification 5h at 1: 1.Synthetic macromonomer PEG-MA or MPEG-MA are made into the aqueous solution of ρ=50%.By 1: 0.02: 1 preparation vinylformic acid (AA), vinylbenzene (ST)/to vinylbenzene benzene sulfonic acid sodium salt (SSS), the water solution A of the ρ of MPEG-MAA=50%, the aqueous solution of the initiator of preparation ρ=50%.The PEG-MA/MPEG-AA that prepared is added in the there-necked flask, add 10% solution A and 20% initiator solution again.Bath temperature is controlled at 80 ℃, reaction 1h.The A solution and the initiator solution of remainder are mixed, slowly drip 4h.React 1h again, stopped reaction is cooled to 40 ℃ and adds the NaOH solution, and regulating the pH value is 7, and diluting soln is to ρ=20%, promptly gets solid content and be 20% polycarboxylate water-reducer.
These embodiment only are used to the present invention is described and should not limit the scope of this invention.In addition, after having read content of the present invention, those skilled in the art make the change or the modification of the various equivalent form of values to the present invention, and these equivalent form of values belong to claims institute restricted portion of the application equally.
Claims (5)
1. toxilic acid class polyocarboxy acid type water reducer, express by following formula:
2. toxilic acid class polyocarboxy acid type water reducer is characterized in that: mainly comprised for 2 steps:
(1) polyethylene glycol methacrylate-styrene polymer (PEG-MA)/methoxy polyethylene glycol methacrylate-styrene polymer (MPEG-MA) is synthetic
(2) water reducer is synthetic
3. the preparation method of a toxilic acid class polyocarboxy acid type water reducer is characterized in that: specifically may further comprise the steps:
(1) polyoxyethylene glycol (PEG) that takes by weighing certain mass is put into the single port flask, adds toluene (PEG quality 20%), uses the water pump underpressure distillation, and bath temperature is controlled at 65 ℃, does not have bubble in flask.
(2) under certain bath temperature, maleic anhydride (MA) and the PEG (1000) that handled through the toluene underpressure distillation or methoxy poly (ethylene glycol) (MPEG (1000)) are joined single port flask esterification 4～6h by a certain percentage.Synthetic macromonomer PEG-MA or MPEG-MA are made into the aqueous solution of ρ=50%.
(3) by certain proportioning preparation vinylformic acid (AA), vinylbenzene (ST)/to vinylbenzene benzene sulfonic acid sodium salt (SSS), the water solution A of ρ=50% of methoxy polyethylene glycol methacrylate-styrene polymer (MPEG-MAA), the aqueous solution of the initiator of preparation ρ=50%.
The PEG-MA/MPEG-AA that (4) will prepare adds in the there-necked flask, adds 10% solution A and 20% initiator solution again.Bath temperature is controlled at 80 ℃, reaction 0.5～1.5h.
(5) A solution and the initiator solution with remainder mixes, and slowly drips 3～4h.
(6) react 1～1.5h again, stopped reaction is cooled to 40 ℃ and adds the NaOH solution, and regulating the pH value is 6.5～7.5, and diluting soln is to ρ=20%, promptly gets solid content and be 20% polycarboxylate water-reducer.
4. the preparation method of a toxilic acid class polyocarboxy acid type water reducer, it is characterized in that: described initiator is selected from analytical pure ammonium persulphate (APS).
5. the preparation method of a toxilic acid class polyocarboxy acid type water reducer is characterized in that: described MA: PEG/MPEG=1: 1～1: 1.5, and AA: MPEG-MAA=10: 1～0: 1, MPEG-MAA: PEG-MA/MPEG-MA=1: 1～1: 2.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103183794A (en) * | 2011-12-27 | 2013-07-03 | 山西黄腾化工有限公司 | Method for preparing polycarboxylic acid type water reducer by solid acid esterification |
| CN104418965A (en) * | 2013-08-27 | 2015-03-18 | 中国石油化工股份有限公司 | Preparation method of self-healing agent for oil well cement, well cementation self-healing cement slurry and application |
| CN106749969A (en) * | 2016-12-06 | 2017-05-31 | 上海建工材料工程有限公司 | A kind of polycarboxylic acids building additive and its synthetic method containing phenyl structure |
| CN108003305A (en) * | 2018-01-25 | 2018-05-08 | 北京砼帮汇科技有限公司 | A kind of synthetic method of polycarboxylate water-reducer |
| CN108948284A (en) * | 2018-06-11 | 2018-12-07 | 清远市德诚化工科技有限公司 | A kind of polyether ester modified polyether water-reducing agent and preparation method thereof |
| CN109694446A (en) * | 2018-12-14 | 2019-04-30 | 上海台界化工有限公司 | A kind of synthetic method of solid polycarboxylic acid water reducing agent |
| CN112608424A (en) * | 2019-12-28 | 2021-04-06 | 科之杰新材料集团浙江有限公司 | Ester ether copolymerization low-bleeding type polycarboxylate superplasticizer and preparation method thereof |
| CN113772989A (en) * | 2021-09-16 | 2021-12-10 | 重庆富普新材料有限公司 | Preparation method of special additive mother liquor for limestone-based wet-mixed mortar |
| CN114702273A (en) * | 2019-12-24 | 2022-07-05 | 科之杰新材料集团福建有限公司 | Polycarboxylate superplasticizer for reinforcing steel bar sleeve grouting material for prefabricated part and grouting material thereof |
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- 2011-03-15 CN CN 201110061090 patent/CN102206060A/en active Pending
Non-Patent Citations (1)
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| 《化学与生物工程》 20100725 张超灿等 "马来酸类聚羧酸减水剂的合成及其对水泥净浆流动性的影响研究" 46-50 1-5 第27卷, 第7期 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103183794B (en) * | 2011-12-27 | 2015-04-29 | 山西黄腾化工有限公司 | Method for preparing polycarboxylic acid type water reducer by solid acid esterification |
| CN103183794A (en) * | 2011-12-27 | 2013-07-03 | 山西黄腾化工有限公司 | Method for preparing polycarboxylic acid type water reducer by solid acid esterification |
| CN104418965A (en) * | 2013-08-27 | 2015-03-18 | 中国石油化工股份有限公司 | Preparation method of self-healing agent for oil well cement, well cementation self-healing cement slurry and application |
| CN104418965B (en) * | 2013-08-27 | 2018-02-23 | 中国石油化工股份有限公司 | Preparation method, well cementation self-healing cement mortar and the application of oil-well cement self-healing mixture |
| CN106749969A (en) * | 2016-12-06 | 2017-05-31 | 上海建工材料工程有限公司 | A kind of polycarboxylic acids building additive and its synthetic method containing phenyl structure |
| CN108003305B (en) * | 2018-01-25 | 2020-11-03 | 北京砼帮汇科技有限公司 | Synthetic method of polycarboxylate superplasticizer |
| CN108003305A (en) * | 2018-01-25 | 2018-05-08 | 北京砼帮汇科技有限公司 | A kind of synthetic method of polycarboxylate water-reducer |
| CN108948284A (en) * | 2018-06-11 | 2018-12-07 | 清远市德诚化工科技有限公司 | A kind of polyether ester modified polyether water-reducing agent and preparation method thereof |
| CN108948284B (en) * | 2018-06-11 | 2020-11-20 | 清远市德诚化工科技有限公司 | Polyether ester modified polyether water reducer and preparation method thereof |
| CN109694446A (en) * | 2018-12-14 | 2019-04-30 | 上海台界化工有限公司 | A kind of synthetic method of solid polycarboxylic acid water reducing agent |
| CN109694446B (en) * | 2018-12-14 | 2021-03-30 | 上海台界化工有限公司 | Synthesis method of solid polycarboxylate superplasticizer |
| CN114702273A (en) * | 2019-12-24 | 2022-07-05 | 科之杰新材料集团福建有限公司 | Polycarboxylate superplasticizer for reinforcing steel bar sleeve grouting material for prefabricated part and grouting material thereof |
| CN112608424A (en) * | 2019-12-28 | 2021-04-06 | 科之杰新材料集团浙江有限公司 | Ester ether copolymerization low-bleeding type polycarboxylate superplasticizer and preparation method thereof |
| CN112608424B (en) * | 2019-12-28 | 2022-08-16 | 科之杰新材料集团浙江有限公司 | Ester ether copolymerization low-bleeding type polycarboxylate superplasticizer and preparation method thereof |
| CN113772989A (en) * | 2021-09-16 | 2021-12-10 | 重庆富普新材料有限公司 | Preparation method of special additive mother liquor for limestone-based wet-mixed mortar |
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Application publication date: 20111005 |