CN102060464A - Polycarboxylate water reducing agent by using water as solvent and preparation method thereof - Google Patents
Polycarboxylate water reducing agent by using water as solvent and preparation method thereof Download PDFInfo
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- CN102060464A CN102060464A CN 200910230447 CN200910230447A CN102060464A CN 102060464 A CN102060464 A CN 102060464A CN 200910230447 CN200910230447 CN 200910230447 CN 200910230447 A CN200910230447 A CN 200910230447A CN 102060464 A CN102060464 A CN 102060464A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2641—Polyacrylates; Polymethacrylates
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Abstract
The invention belongs to the technical fields of building materials and chemical synthesis, and particularly relates to a polycarboxylate water reducing agent prepared by a one-step method and a preparation process thereof. The efficient polycarboxylate water reducing agent is obtained by directly dripping monomers a, b, c, d and e and performing polymerization reaction on initiator solution. The water reducing agent can be widely applied in various concrete projects, and has the advantages of high water reducing rate, good slump holding performance and the like. The method is simple, environmentally-friendly and easy to control, and has good social and economic benefits.
Description
Technical field:
The invention belongs to additive for building material and chemosynthesis technical field, be specifically related to a kind of polycarboxylate dehydragent and preparation technology thereof by the single stage method preparation.
Background technology:
Water reducer is a consumption maximum application admixture kind the most widely in the concrete works, and its consumption accounts for more than 80% of the total consumption of admixture.Polycarboxylate dehydragent is little because of its volume, water-reducing rate is high, protect the extensive approval that the advantages such as performance is good of collapsing are received the coagulation pedosphere gradually.Particularly since 2005, be accompanied by railway to the appearance with the admixture regulation of motorway, Line for Passenger Transportation, polycarboxylate dehydragent has all been used in this field, its year usage quantity reach 500,000 tons.In China's other engineering of fundamental construction concrete, also begin to promote the use of polycarboxylate dehydragent at present as water power, highway, concrete civilian, Industrial buildings.Because its excellent performance, market outlook are wide, also become in recent years focus about the research of polycarboxylate dehydragent.Polycarboxylate water-reducer generally all is methoxy poly (ethylene glycol) (methyl) acrylate that obtains to have polymerization activity by methoxy poly (ethylene glycol) and (methyl) vinylformic acid elder generation esterification at present, adopt solution polymerization process and the copolymerization of (methyl) vinylformic acid isoreactivity group to form again, there is complicated process of preparation, influence factor is more, the cost height, shortcomings such as quality instability.Patent CN 101041571A discloses a kind of air entrained collapse-preventing type polycarboxylate concrete high efficiency water reducing agent and preparation thereof, polyalkylene glycol mono body and carboxylic-acid monomer are joined in the reactor that the condensation part flow arrangement is housed, add stopper, catalyzer, solvent, stir, be warming up to 85-125 ℃, reacted 5-15 hour, desolventize and reclaim by the underpressure distillation steaming, promptly get and contain the monomeric polyalkene glycol acrylates class of excess carboxylic acid class monomer, with gained polyalkene glycol acrylates class monomer, carboxylic-acid monomer and the monomeric mixture of allyl sulphonic acid class add water and are made into the aqueous solution, persulphate adds water and is made into initiator solution, adding entry in reactor is dispersion medium, stir, be warmed up to 75-95 ℃, add monomer solution and initiator solution, reacted 4-8 hour, cooling adds alkali with the gained multipolymer and is neutralized to 6.5-8, promptly gets copolymer salt solution.Make in the big monomer process in the first step, add catalyzer, stopper and band aqua, not only increase cost and can bring the impurity complex process into restive; CN 101353397A has introduced a kind of water-soluble grafting polycarboxylic acids dehydragent and preparation method thereof, at first allyl polyethenoxy alcohol ether monomer is added in the reactor, add deionized water and make its dissolving, use the nitrogen purging reactor while stirring to heat up, when being warmed up to 60-120 ℃, while dropwise addition of acrylic acid monomer and monomeric mixed aqueous solution of Hydroxyethyl acrylate and 10% ammonium persulfate aqueous solution, dropwise insulation 1-3 hour, cool to 25-55 ℃, adding alkali accent pH value is that 6.0-7.0 promptly gets described product, the raw materials used cost of this method is higher, and reaction process needs nitrogen purging, the technology relative complex.CN 101215119A discloses a kind of high-performance polycarboxylic acids water reducing agent that adopts the single stage method preparation, in inert atmosphere, in water, the initiation of initiator is reaction down with monomer A and monomers B, the pH value that adopts sodium hydroxide conditioned reaction product then is 4.5-7, get final product target product.Though reaction process is simple, as chain-transfer agent, has unpleasant irritating smell with mercaptoethanol.
Summary of the invention:
The objective of the invention is problem, a kind of polycarboxylate dehydragent and method preparation technology simple, with low cost of excellent performance is provided at existing water reducer technology of preparing existence.
For achieving the above object, the present invention is by the following technical solutions:
Polycarboxylate dehydragent of the present invention is characterized in that: by following a, b, c, d, five kinds of monomers of e according to a certain ratio under the initiator effect copolyreaction make:
The a maleic anhydride:
The b acrylic monomer:
R wherein
1Expression hydrogen atom or methyl.
C allyl ether series monomer
R3 represents hydrogen atom or C
1-3Alkyl, n represents number of repeat unit, its value is for 10-80;
The d aminated compounds
R
4Expression hydrogen atom or C
1-3Alkane; R
5Expression hydrogen atom or C
1-3Alkyl or C
1-8Alkylsulphonic acid;
E olefin sulfonic acid class monomer
R
6Expression hydrogen atom or C
1-3Alkyl, M represents hydrogen atom or alkali metal cation;
Above-mentioned monomer molar proportioning: a: b: c: d: e is 1: 0.5-2.0: 0.3-2.0: 0.3-1.5: 0.1-0.5.
The preparation method of polycarboxylate dehydragent of the present invention is as follows:
(1) in four-hole boiling flask, adds monomer a, e and a part of monomer c, add a certain amount of deionized water and make its dissolving and be heated to 50-100 ℃.
(2) drip monomer b, c, d solution and the initiator solution for preparing in advance respectively in four-hole boiling flask, 2-6h drips off, insulation 1-5h.
(3) be cooled to 25-45 ℃, add alkali and be neutralized to PH=7.0 ± 0.5, both described polycarboxylate dehydragent.
Described initiator is an inorganic peroxy class initiator, initiator system of ammonium persulfate, and consumption is the 1-8% of monomer total amount.The monomer solution concentration of preparation is 30-80%, and initiator solution concentration is 1-20%.
Polycarboxylate dehydragent of the present invention, it at the solid volume of folding 0.2% o'clock of gelling material, concrete water-reducing ratio can reach more than 30%, 28d ultimate compression strength can be brought up to more than 140, the product cement adaptability is good, be applicable to the cement of multiple different manufacturers, specification, model, stable performance, long storage does not have precipitation, not stratified.
Polycarboxylate dehydragent preparation technology of the present invention is very simple, and reaction conditions is easy to control, and production process does not produce three industrial wastes, and directly water is as solvent, and cost is low, energy consumption is low, has both guaranteed economic benefit, again non-environmental-pollution.
Embodiment:
Embodiment 1
In four-hole boiling flask, add 19.61g maleic anhydride, 100g molecular weight and be 2000 allyl polyglycol ether and the sodium allyl sulfonate of 5.76g, add deionized water dissolving.Heat to 75 ℃, drip respectively by the 100g molecular weight is the monomer solution of 2000 allyl polyglycol ether, 17.22g methacrylic acid and 14.2g acrylamide and deionized water preparation, with initiator solution by 3g ammonium persulphate and deionized water preparation, dropwised in 3 hours, be incubated after 2 hours, cool to 30 ℃,, promptly get polycarboxylate dehydragent PC-1 with the 30% sodium hydroxide solution Ph=7.0 that neutralizes.
Embodiment 2
In four-hole boiling flask, add 19.61g maleic anhydride, 100g molecular weight and be 2000 allyl polyglycol ether and the sodium allyl sulfonate of 14.4g, add deionized water dissolving.Heat to 85 ℃, drip respectively by the 100g molecular weight is the monomer solution of 2000 allyl polyglycol ether, 14.4g vinylformic acid and 20.07g2-acrylamido-2-methyl propane sulfonic acid and deionized water preparation, with initiator solution by 5g ammonium persulphate and deionized water preparation, dropwised in 3 hours, be incubated after 2 hours, cool to 30 ℃,, promptly get polycarboxylate dehydragent PC-2 with the 40% sodium hydroxide solution Ph=7.0 that neutralizes.
Embodiment 3
In four-hole boiling flask, add 19.61g maleic anhydride, 120g molecular weight and be 2400 allyl polyglycol ether and the methylpropene sodium sulfonate of 12.6g, add deionized water dissolving.Heat to 70 ℃, drip respectively by the 120g molecular weight is the monomer solution of 2400 allyl polyglycol ether, 17.29g vinylformic acid and 5.68g acrylamide and deionized water preparation, with initiator solution by 8g ammonium persulphate and deionized water preparation, dropwised in 2 hours, be incubated after 2 hours, cool to 30 ℃,, promptly get polycarboxylate dehydragent PC-3 with the 40% sodium hydroxide solution Ph=7.0 that neutralizes.
Embodiment 4
In four-hole boiling flask, add 19.61g maleic anhydride, 72g molecular weight and be 2400 allyl polyglycol ether and the methylpropene sodium sulfonate of 9.49g, add deionized water dissolving.Heat to 90 ℃, drip respectively by the 72g molecular weight is the monomer solution of 2400 allyl polyglycol ether, 25.8g methacrylic acid and 7.1g acrylamide and deionized water preparation, with initiator solution by 10g ammonium persulphate and deionized water preparation, dropwised in 3 hours, be incubated after 1 hour, cool to 30 ℃,, promptly get polycarboxylate dehydragent PC-4 with the 40% sodium hydroxide solution Ph=7.0 that neutralizes.
Embodiment 5
In four-hole boiling flask, add 19.61g maleic anhydride, 144g molecular weight and be 4800 allyl polyglycol ether and the methylpropene sodium sulfonate of 9.49g, add deionized water dissolving.Heat to 95 ℃, drip respectively by the 144g molecular weight is the monomer solution of 4800 allyl polyglycol ether, 25.8g methacrylic acid and 7.1g acrylamide and deionized water preparation, with initiator solution by 10g ammonium persulphate and deionized water preparation, dropwised in 3 hours, be incubated after 1 hour, cool to 30 ℃,, promptly get polycarboxylate dehydragent PC-5 with the 40% sodium hydroxide solution Ph=7.0 that neutralizes.
Experimental example 1
Water reducer PC-1, the PC-2 that the present invention is made, PC-3, PC-4, PC-5 and two kinds of commercially available water reducer SS-1, SS-2 measure indexs such as their clean slurry degree of mobilization, mortar water-reducing rate, concrete water-reducing ratio respectively, flowing degree of net paste of cement is with reference to GB/T8077-2000 " Methods for testing uniformity of concrete admixture ", water reducer volume (by solid content) is a cement total amount 0.2%, water 87g (comprising the institute of water reducer water content own).The mortar water-reducing rate is controlled mortar degree of mobilization (180 ± 5) mm with reference to GB/T8077-2000 " Methods for testing uniformity of concrete admixture ", and water reducer volume (by solid content) is a cement total amount 0.2%.Concrete test is with reference to GB8076-1997 " concrete admixture " standard detection.Every side's cement consumption is 330kg/m
3Concrete mix is: m (cement): m (sand): m (stone)=1: 2.34: 3.50, and sand coarse aggregate ratio 40%, water reducer volume (by solid content) is a cement total amount 0.2%.Test-results such as following table 1 and table 2.
The different water reducers of table 1 are to the influence of flowing degree of net paste of cement and mortar water-reducing rate
| The water reducer model | Clean slurry degree of mobilization/mm | Mortar water-reducing rate/% |
| PC-1 | 260 | 19.86 |
| PC-2 | 265 | 20.04 |
| PC-3 | 240 | 18.54 |
| PC-4 | 255 | 18.60 |
| PC-5 | 268 | 20.70 |
| SS-1 | 235 | 18.60 |
| SS-2 | 255 | 17.83 |
Table 2 concrete test result
Test shows, adopt the polycarboxylate dehydragent of preparation in example 1 of the present invention and the example 4, starch degree of mobilization and mortar water-reducing rate only and all be higher than commercially available two kinds of products, the concrete amount of air entrainment is lower, water-reducing rate and each phase intensity are all higher, say that totally performance is better than commercially available water reducer SS-1, SS-2.
Claims (7)
1. polycarboxylate dehydragent that adopts single stage method preparation is characterized in that: by following a, b, c, d, five kinds of monomers of e according to a certain ratio under the initiator effect copolyreaction make:
The a maleic anhydride:
The b acrylic monomer:
R wherein
1Expression hydrogen atom or C
1-3Alkyl, R
2Expression hydrogen atom, alkali metal cation, ammonium or C
1-4Aliphatic alkyl;
C allyl ether series monomer
R3 represents hydrogen atom or C
1-3Alkyl, n represents number of repeat unit, its value is for 10-80;
The d aminated compounds
R
4Expression hydrogen atom or C
1-3Alkane; R
5Expression hydrogen atom or C
1-3Alkyl or C
1-8Alkylsulphonic acid;
E olefin sulfonic acid class monomer
R
6Expression hydrogen atom or C
1-3Alkyl, M represents hydrogen atom or alkali metal cation;
Above-mentioned monomer molar proportioning: a: b: c: d: e is 1: 0.5-2.0: 0.3-2.0: 0.3-1.5: 0.1-0.5.
2. polycarboxylate dehydragent according to claim 1 is characterized in that, described monomer b is acrylic or methacrylic acid.
3. polycarboxylate dehydragent according to claim 1 is characterized in that, the molecular weight of described monomer c is 1000-5000.
4. the preparation method of polycarboxylate dehydragent according to claim 1 is characterized in that, may further comprise the steps:
(1) in four-hole boiling flask, adds monomer a, e and a part of monomer c, add a certain amount of deionized water and make its dissolving and be heated to 50-100 ℃.
(2) drip monomer b, c, d solution and the initiator solution for preparing in advance respectively in four-hole boiling flask, 2-6h drips off, insulation 1-5h.
(3) be cooled to 25-45 ℃, add alkali and be neutralized to PH=7.0 ± 0.5, both described polycarboxylate dehydragent.
5. the preparation method of polycarboxylate dehydragent according to claim 4 is characterized in that, the amount of the monomer c of the first step adding four-hole boiling flask accounts for the 10-80% of total amount.
6. the preparation method of polycarboxylate dehydragent according to claim 4 is characterized in that, described initiator is an inorganic peroxy class initiator, initiator system of ammonium persulfate.
7. the preparation method of polycarboxylate dehydragent according to claim 4 is characterized in that, described initiator amount is the 1-8% of monomer total amount.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250295A (en) * | 2011-05-24 | 2011-11-23 | 中建商品混凝土天津有限公司 | Concrete super plasticizer for machine-made sand and preparation method thereof |
| CN102675557A (en) * | 2011-12-16 | 2012-09-19 | 天津冶建特种材料有限公司 | Slow-release type concrete slump retaining agent and preparation method thereof |
| CN110003403A (en) * | 2019-04-23 | 2019-07-12 | 长沙加美乐素化工有限公司 | A kind of anti-mud early-strength water-reducing agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6166112A (en) * | 1997-03-10 | 2000-12-26 | Nippon Shokubai Co., Ltd. | Cement admixture and cement composition |
| WO2006129883A1 (en) * | 2005-06-01 | 2006-12-07 | Nippon Shokubai Co., Ltd. | Powdery cement dispersant |
| CN101538134B (en) * | 2009-04-14 | 2012-02-22 | 大连建科北方化学有限公司 | Polyether class polycarboxylic acid high-efficiency water reducing agent and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250295A (en) * | 2011-05-24 | 2011-11-23 | 中建商品混凝土天津有限公司 | Concrete super plasticizer for machine-made sand and preparation method thereof |
| CN102675557A (en) * | 2011-12-16 | 2012-09-19 | 天津冶建特种材料有限公司 | Slow-release type concrete slump retaining agent and preparation method thereof |
| CN110003403A (en) * | 2019-04-23 | 2019-07-12 | 长沙加美乐素化工有限公司 | A kind of anti-mud early-strength water-reducing agent and preparation method thereof |
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Denomination of invention: Polycarboxylate water reducing agent by using water as solvent and preparation method thereof Effective date of registration: 20140527 Granted publication date: 20130828 Pledgee: Shandong UnionPay Company limited by guarantee Pledgor: SHANDONG HONGYI TECHNOLOGY Co.,Ltd. Registration number: 2014370000004 |
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Address after: 241000 room 208, building 1, No.9, Wanjiang Avenue, Jiangbei industrial concentration area, Jiujiang District, Wuhu City, Anhui Province Patentee after: Anhui Conch Material Technology Co.,Ltd. Address before: Room 208, No. 1 Building, No. 9 Wanjiang Avenue, Jiangbei Industrial Concentration Area, Wuhu City, Anhui Province Patentee before: Anhui Conch New Materials Technology Co.,Ltd. |
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