CN103288376A - Synthesizing and compounding method of polycarboxylate-type high-efficiency water reducing agent - Google Patents
Synthesizing and compounding method of polycarboxylate-type high-efficiency water reducing agent Download PDFInfo
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Abstract
The invention discloses a synthesizing and compounding method of polycarboxylate-type high-efficiency water reducing agent. The synthesizing and compounding method comprises the following steps of: (1), adopting a solution method to prepare an aqueous solution according to a certain molar ratio by using methacrylic acid, acrylic acid and polyethylene glycol as raw materials; adding the aqueous solution to a four-necked flask with a reflux condenser and a mechanical stirrer; adding catalyst and polymerization inhibitor to obtain precursor methoxy polyoxyethylene acrylate macromonomer; (2), heating up to a certain temperature in water bath, dropwise adding a certain concentration of ammonium persulfate aqueous solution within a certain time, continuously reacting for a certain time by keeping the temperature after the dropwise adding is completed; using 30% of NaOH to adjust the pH of the product to 7-8 after cooling to the room temperature to synthesize novel branched polycarboxylate high-performance water reducing agent; (3), obtaining a compounding system of polycarboxylate-type water reducing agent and naphthalene-type water reducing agent by a compounding process.
Description
Technical field
The present invention relates to a kind of synthetic and composite method of polycarboxylic acid series high efficiency water reducing agent.
Background technology
In recent years, building operation not only requires concrete high strength, possesses stable and good workability simultaneously.The consolidating material total amount is big in the high performance concrete on the one hand, thereby water requirement can increase.On the other hand, in order to improve density and intensity, must reduce water cement ratio.The consequence that water cement ratio reduces makes concrete viscosity increase the rheological variation exactly.Solve the effective and the most real approach of above-mentioned contradiction at present and mix water reducer exactly.The effect of ordinary water-reducing agent is: (1) improves workability keeping improving the workability of fresh concrete greatly under the constant situation of water cement ratio, makes it to reach the requirement of pumping; (2) when cement consumption is constant, reduces water consumption, thereby concrete strength is improved; (3) when desired strength is constant, the water consumption diminishing reduces cement consumption thereby water cement ratio is constant, reaches purpose of energy saving.The high water reducing rate of high efficiency water reducing agent further reduces water cement ratio, and concrete intensity further improves, and develops into the high performance concrete stage, has greatly promoted the development of construction industry, is the major progress of modern concrete technology.Simultaneously, high efficiency water reducing agent is by exciting the activity of slag, flyash etc., and high efficiency water reducing agent and the coordinative role between them etc., make these industrial residues partly replace cement to become Additive good in the high performance concrete, have remarkable economical and social benefit, also satisfy the strategy of sustainable development, its development and application level becomes one of important symbol of weighing a national economic development level.On the angle of technical development, entered the stage of high-performance water reducing agent at present.High efficiency water reducing agent is as critical material, except requiring to have the better water-reducing effect, also requirement can better control concrete flow degree through the time loss, solve problems such as concrete bleed, slow setting, bleeding, high workability and high protect plasticity are reached coordinate and unification.At present, widely used naphthalene system, trimeric cyanamide system and amido sulfoacid series high-efficiency water reducer, problem such as the too fast or serious bleeding of concrete ubiquity slump-loss when using separately; And naphthalene system and melamine system water reducer, also there are problems such as cost of material height, scarcity of raw material, especially in process of production to adopt some toxic and harmful substances, have shortcomings such as being unfavorable for Sustainable development, apply thereby partly restricted further.
Poly carboxylic acid series water reducer is novel, the environmental type high efficiency water reducing agent of generally acknowledging both at home and abroad as a kind of novel high-performance water reducing agent, can be used to prepare high performance concrete, is the main flow of 21 century water reducer application.The advantage that polycarboxylic acid series high efficiency water reducing agent is given prominence to is as follows:
1, volume is low, water-reducing rate is high, and its volume is generally 0.05%～0.5% of consolidating material consumption, and water-reducing rate reaches as high as more than 30%;
2, the degree of freedom of Molecular Structure Design is big, and the performance of water reducer can require design according to difference, can effectively control the early hydration of cement in the concrete, is fit to the preparation mass concrete;
3, good with cement, adulterant and other admixture consistency, for using, industrial wastes such as flyash in great mixed amount, slag and slag provide technical guarantee in concrete works;
4, can be used for preparing common, high-strength, high workability, high durability concrete, the concrete of preparation do not emanate, bleeding, slump retention are not good, and the adaptability scope is wide;
5, can use the special concrete of preparing high-strength or superstrength, as the strong mobile concrete of 150MPa superelevation, 200MPa fiber reinforced concrete etc.;
6, formaldehyde is not used in the synthetic production of water reducer, causes the objectionable impurities of environmental pollution few, is conducive to the Sustainable development of architecture engineering material.
Nineteen thirty-five U.S. E.W. Si Kelipuqie (Scripture) at first is developed into the fluidizer that sulfonated lignin are main component, has opened the prelude of water reducer development.The early stage water reducer that uses has xylogen nitrate, sodium abietate and stearate soap etc.The sixties in 20th century, naphthalene sulfonic acidformaldehyde condensation product sodium A (SNF) and sulfonated melamine compound condenses (SMF), these two kinds of high efficiency water reducing agents are succeeded in developing, and have obtained extensive utilization in concrete works, make the development of concrete technology rise to more high-stage.From the sixties to the beginning of the eighties, it is the developmental stage of high efficiency water reducing agent, the characteristics of this stage water reducer are the water-reducing rate height, but concrete slump loss is very fast, can't satisfy construction requirements such as pumping, can not be for the preparation of the concrete of high-performance and very-high performance, normally method such as compound slow setting component solves in water reducer, but compound slow setting component can be brought new problem, as influences development of early age strength of concrete etc.Late 1980s, Japanology goes out the thionamic acid based water reducer, and it is non-bleed type water soluble resin, water-reducing rate can be up to the essentially no slump-loss of 30%, 90min-120min, but product stability is relatively poor, bleeding easily, thereby influenced its industrial production and application.Japan utilizes alkene and unsaturated carboxylic acid copolymerization in nineteen ninety-five, succeeded in developing polycarboxylate high performance water-reducing agent, poly carboxylic acid series water reducer is because the water-reducing rate height, reach more than 30%, volume is few, and function of slump protection is good, amount of air entrainment and flocculation etc. are comparatively moderate, suitable preparation high workability, the concrete of self-compacting, thus be subjected to the favor of engineering circle.The research to efficient water reducer such as naphthalene system, trimeric cyanamide system abroad is gradually improved, and has obtained widespread use in actual engineering.At present, mainly be the research that turns to poly carboxylic acid series water reducer abroad.Japan is that research and application poly carboxylic acid series water reducer at most also are the most successful countries, a piece of writing surplus the patent aspect poly carboxylic acid series water reducer has ten, and substantially based on vinylformic acid and maleic anhydride, and great majority are synthetic in solvent-based system.The America and Europe also reach ten about the patent of poly carboxylic acid series water reducer surplus a piece of writing, equally also in solvent-based system, finish.Also have the investigator that the modification of multipolymer is studied, carry out modification as the multipolymer to maleic anhydride and styrol copolymer, maleic anhydride and petroleum naphtha in solvent system.In addition, be exactly to obtain modified version poly carboxylic acid series water reducer 18-111 by grafting method, its performance is more superior.At present, there are many investigators also to focus on the research of vinylbenzene, polyoxyethylene and toxilic acid abroad.In application facet, it is reported that poly carboxylic acid series water reducer has surpassed naphthalene water reducer in the usage quantity of Japan after nineteen ninety-five, Japanese polycarboxylic acid series product had accounted for more than 60% of all high-performance AE water reducer product sums in 1998.Till calendar year 2001, oneself has surpassed 80% to the poly carboxylic acid series water reducer consumption in the AE water reducer.The development of U.S.'s high efficiency water reducing agent is more late than Japan, and the U.S. just develops to polycarboxylic acid series high efficiency water reducing agent from naphthalene system, cyanogen ammonia based water reducer at present.At present, abroad more famous producer have Japan colored king, this grease of bamboo, Nippon Paper, rise damp medicine etc., the America and Europe has U.S. MASTE company, GRACE company, Italian MADI company, a Switzerland SIKA company etc.The America and Europe mainly is business promotion and exploitation at present.
The work of domestic research water reducer starts from the fifties in last century, and what research was used at that time is some ordinary water-reducing agents, as molasses, and humic acids and salt water reducer, paper pulp tankage lignosulfonic acid salt etc.The beginning of the seventies, the NNO diffusant that dyeing industry uses is introduced concrete as water reducer, its performance obviously is better than calcium lignin sulphonate, and this breakthrough major progress indicates that the application of China's concrete admixture and research have entered more high-stage.At the beginning of 1981, concrete product studying and designing institute in Suzhou has succeeded in developing trimeric cyanamide formal sulfonate.At the beginning of the eighties, 330 Engineering Bureau once studied the water-reducing property of bean curd water and dropped in the engineering and use.Be under 0.1% situation in the blending amount, can save cement 8%, concrete strength increases by 100, have simultaneously protect mould, effects such as plasticising, slow setting.At the beginning of 1986, the relevant technologies of the series high-performance admixture of Austria and Britain is introduced in China Changzhou, Beijing first, has further promoted research, development and the application of domestic admixture.From the beginning of the eighties so far, kind and the level of high efficiency water reducing agent have had develop rapidly, the high efficiency water reducing agent that modified lignin resin sodium sulfonate system and trimeric cyanamide are etc. has all arrived good Application and Development.But the overwhelming majority is still naphthalene water reducer in the high efficiency water reducing agent, accounts for more than 90% of high efficiency water reducing agent total amount, and other kind product application degree relative mistake is a little.So needing research especially is the more superior polycarboxylic acid series high efficiency water reducing agent of performance.At present, the degree of China's research poly carboxylic acid series water reducer still is in the starting stage.But synthetic progress and the policy with utilisation technology of the development of concrete technology and admixture is helped, for preparation function high-performance water reducing agent provides condition.From the document of retrieval, can find out and mainly concentrate on universities and colleges and partly build scientific research institutions, the maleic anhydride that carries out as Tsing-Hua University's Li Yongde etc. and the AE water reducer development of oleic series, the water reducer research that the Zhang Guanlun of Tongji University etc. carries out, the carboxylate salt that the just auspicious grade of the king of Shandong Building Material College is carried out, the development of acrylamide series water reducer, the development of the oleic series water reducer that the Sichuan Liu De of light industry institute honor etc. is carried out, Wuhan University of Technology Materials Academy week the novel poly-hydroxy polycarboxylic acid concrete vulcanizing agent that carries out in vain of shield the research of synthetic and sulfuration mechanism, architecture science research institute Bian Rong soldier in Jiangsu etc.s carries out the development of the serial water reducer of toxilic acid f that the development of maleic anhydride series water reducer and the Liu Tong of Building Material Science Inst., Tianjin etc. carry out.Li Zhili etc. are by the new and effective water reducer of ACS of the radical solution copolymerization preparation of vinyl monomer, Shen Ru etc. utilize and improve molecular structure, the unit kind, functional group's ratio and to methods such as functional group modification, developed ZS.ZSF serial reaction high-performance water reducing agent, Li Chongzhi, Li Yongdes etc. are by test, poly carboxylic acid series water reducer structure and property relationship have been analyzed, and by the orthogonal experiment analytical method, study the polymerization degree of the ratio of reaction monomers and polyoxyethylene chain to the poly carboxylic acid series water reducer Effect on Performance, proposed a kind of optimum formula of synthesizing polycarboxylic acid dehydragent.Ran Gan equality is by macromolecular material principle of design and macromonomer technology of preparing, utilize the achievement in research in defoamer field, designed and synthesized a kind of macromonomer of their defoaming function that can polymerization, adopt aqueous solution copolymerization technology, synthesized a kind of low bleed that has, the efficient poly carboxylic acid series water reducer of high function of slump protection, it is main raw material that Bao Zhijun etc. have synthesized with vinylformic acid and poly glycol monomethyl ether, by the exploration to synthesis technologic parameter, every performance index of synthetic PC1 high efficiency water reducing agent all can reach even be better than the relevant high efficiency water reducing agent primary standard with industry of country.But concrete is development imbalances at home, has influenced the development of polycarboxylic acid series high efficiency water reducing agent.The research and development polycarboxylate high performance water-reducing agent is the inevitable requirement of technology of high performance concrete development.Poly carboxylic acid series water reducer is high-strength high-flowing concrete, high volume fly ash concrete most important component, so its application prospect is more and more wide.
Summary of the invention
The object of the present invention is to provide a kind of water-reducing rate height, slump retentivity is good, technology is simple, the cycle is short, technology is reasonable, the process controllability is good, perfect quality control method is arranged, the polycarboxylate high performance water-reducing agent that cost is relatively low, be easy to be converted into actual productivity, and production process three-waste free discharge, guaranteed, the save energy of raw material meet the strategic requirement of national sustainable development.
The technical scheme that the present invention takes for the technical problem that exists in the solution known technology is:
Adopt solution method, be raw material with methacrylic acid, vinylformic acid and polyoxyethylene glycol, be mixed with aqueous solution adding by certain mol proportion and be equipped with in the four-hole boiling flask of reflux exchanger and mechanical stirrer, add catalyzer and stopper, made the big monomer of thing methoxy polyoxyethylene acrylate in early stage; Heating in water bath drips certain density ammonium persulfate aqueous solution within a certain period of time to certain temperature, after dropwising, continue the insulation reaction certain hour, cool to room temperature, regulate product pH to 7-8 with 30%NaOH, synthesized the novel dendritic high performance water reducing agent of polyocarboxy acid; The poly carboxylic acid series water reducer that has obtained by complex process and the compound system of naphthalene water reducer.The best proportioning of big each component of monomer of thing methoxy polyoxyethylene acrylate in early stage: the mol ratio of methacrylic acid and polyoxyethylene glycol is 2: 1, temperature of reaction is 100 ℃, catalyst consumption is 4% of methacrylic acid and polyoxyethylene glycol total amount, and the consumption of stopper is 0.3% of methacrylic acid quality; The optimum process condition of novel dendritic high performance water reducing agent of polyocarboxy acid: determine that the reaction times is 6h, the temperature of reaction is 95 ℃; The optimum compound proportion of poly carboxylic acid series water reducer and naphthalene water reducer, obtaining rational proportion is 1: 2.
The high performance water reducing agent of polyocarboxy acid performance index:
Flowing degree of net paste of cement/ram: 〉=240; Chlorion massfraction/% :≤0.2; Sodium sulfate quality mark/% :≤10.0; Alkali massfraction (Na2O+0.658K2O)/% :≤10.0; Concrete water-reducing ratio/%: 〉=20; Air content/%: 〉=4.5; Slump retention value: 30min 〉=180; 60min 〉=150; Normal pressure bleeding rate ratio/% :≤20; Pressure bleeding rate ratio/% :≤90; Ultimate compression strength %:3d 〉=130175 are qualified; 7d 〉=125150 are qualified; Qualified shrinkage ratio/the % in 28d 〉=120130 :≤135; Relative weather resistance/% (200 times): 〉=80
Embodiment
Below will be described in detail the preferred embodiments of the present invention; Should be appreciated that preferred embodiment only for the present invention is described, rather than in order to limit protection scope of the present invention.
Adopt solution method, be raw material with methacrylic acid, vinylformic acid and polyoxyethylene glycol, being mixed with aqueous solution adding by certain mol proportion is equipped with in the four-hole boiling flask of reflux exchanger and mechanical stirrer, add catalyzer and stopper, drawn and made the big monomer of thing methoxy polyoxyethylene acrylate in early stage; Heating in water bath drips certain density ammonium persulfate aqueous solution within a certain period of time to certain temperature, after dropwising, continue the insulation reaction certain hour, cool to room temperature, regulate product pH to 7-8 with 30%NaOH, synthesized the novel dendritic high performance water reducing agent of polyocarboxy acid; The poly carboxylic acid series water reducer that has obtained by complex process and the compound system of naphthalene water reducer.The best proportioning of big each component of monomer of thing methoxy polyoxyethylene acrylate in early stage: the mol ratio of methacrylic acid and polyoxyethylene glycol is 2: 1, temperature of reaction is 100 ℃, catalyst consumption is 4% of methacrylic acid and polyoxyethylene glycol total amount, and the consumption of stopper is 0.3% of methacrylic acid quality; The optimum process condition of novel dendritic high performance water reducing agent of polyocarboxy acid: determine that the reaction times is 6h, the temperature of reaction is 95 ℃; The optimum compound proportion of poly carboxylic acid series water reducer and naphthalene water reducer, obtaining rational proportion is 1: 2.
By synthetic big monomer and water reducer are carried out the infrared spectrum analysis: by synthetic big monomer and water reducer are carried out the infrared spectrum analysis, there is not absorption peak in poly glycol monomethyl ether at 1720cm-1 and 1636cm-1, illustrate esterification has taken place, in addition in the poly glycol monomethyl ether-OH do not have obvious characteristics to absorb in the drawings at the 350cm-1 place this peak obviously weakens, illustrate that esterification is more thorough; Acrylic acid characteristic peak weakens in the water reducer molecule, illustrates that the grafting process is comparatively complete;
Press the determination of test method ultimate compression strength of regulation among the GB8076-1997 " concrete admixture ", 3 days strength ratios of cement reach 174%, 7 days strength ratios reach 171%, 28 day strength ratio and reach 146%, and this illustrates that homemade water reducer has certain early strength function and the later strength development is good;
Press the test method of regulation among the GB8076-1997 " concrete admixture ", when volume reached 0.4%, water-reducing rate reached 33.8%;
Adopt different conditions of mixture ratios, the flowing degree of net paste of cement maximum reaches 277mm.
Synthetic polycarboxylate water-reducer has been carried out termination process, efficiently solve with the naphthalene water reducer blend in the different composite gelation problems that produce that compare.
Optimize the optimum process condition that has obtained poly carboxylic acid series water reducer, reach even partly surpass the performance index of expection on the performance.
The present invention adopts one still process to carry out, and after reaction finished, the solid content of product was near 100%, and whole process has realized the unification of high-performance and economy and the feature of environmental protection, is conducive to apply.Simultaneously, adopt composite having reached of poly carboxylic acid series water reducer and naphthalene water reducer to reduce the cost, operation easily is easy to through engineering approaches in implementation process.Certainly, in the synthetic water reducer macromole process of preparation, also found the problem that remains to be furtherd investigate that some are new, as containing surface active ingredient in the synthetic poly carboxylic acid series water reducer of project preparation, can introduce a little unnecessary bubbles after adding concrete, be necessary to research and develop a kind of suitable defoamer or suds suppressor, stop the generation of harmful bubble, do not influence concrete other performance simultaneously again.In addition, research and develop multi-functional poly carboxylic acid series water reducer, to increase the use range of poly carboxylic acid series water reducer, solve its functional single problem.
The above, it only is preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, though the present invention with preferred embodiment openly as above, yet, be not in order to limit the present invention, any those skilled in the art, in not breaking away from the technical solution of the present invention scope, certainly can utilize the technology contents of announcement to make a little change or modification, become the equivalent embodiment of equivalent variations, be the content that does not break away from technical solution of the present invention in every case, any simple modification that foundation technical spirit of the present invention is done above embodiment, equivalent variations and modification all belong in the scope of technical solution of the present invention.
Claims (2)
1. synthesizing and composite method of a polycarboxylic acid series high efficiency water reducing agent, may further comprise the steps:
1) adopts solution method, be raw material with methacrylic acid, vinylformic acid and polyoxyethylene glycol, be mixed with aqueous solution adding by certain mol proportion and be equipped with in the four-hole boiling flask of reflux exchanger and mechanical stirrer, add catalyzer and stopper, made the big monomer of thing methoxy polyoxyethylene acrylate in early stage;
2) heating in water bath drips certain density ammonium persulfate aqueous solution within a certain period of time to certain temperature, after dropwising, continue the insulation reaction certain hour, cool to room temperature, regulate product pH to 7-8 with 30%NaOH, synthesized the novel dendritic high performance water reducing agent of polyocarboxy acid;
3) poly carboxylic acid series water reducer that has obtained by complex process and the compound system of naphthalene water reducer.
2. the synthetic and composite method of polycarboxylic acid series high efficiency water reducing agent according to claim 1, it is characterized in that, the best proportioning of big each component of monomer of thing methoxy polyoxyethylene acrylate in early stage: the mol ratio of methacrylic acid and polyoxyethylene glycol is 2: 1, temperature of reaction is 100 ℃, catalyst consumption is 4% of methacrylic acid and polyoxyethylene glycol total amount, and the consumption of stopper is 0.3% of methacrylic acid quality; The optimum process condition of novel dendritic high performance water reducing agent of polyocarboxy acid: determine that the reaction times is 6h, the temperature of reaction is 95 ℃; The optimum compound proportion of poly carboxylic acid series water reducer and naphthalene water reducer is 1: 2.
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Cited By (3)
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| CN105778111A (en) * | 2016-03-08 | 2016-07-20 | 苏州珍展科技材料有限公司 | Preparation method and application of novel laminar composite |
| CN108101402A (en) * | 2017-12-19 | 2018-06-01 | 萧县沃德化工科技有限公司 | A kind of polycarboxylate water-reducer and preparation method thereof |
| CN109881288A (en) * | 2019-02-27 | 2019-06-14 | 圣华盾防护科技股份有限公司 | Alkali-resistant glass fiber, protective garment and protective garment fabric |
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| CN109881288A (en) * | 2019-02-27 | 2019-06-14 | 圣华盾防护科技股份有限公司 | Alkali-resistant glass fiber, protective garment and protective garment fabric |
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Application publication date: 20130911 |