CN103965413A - Low-temperature synthesis technology of polycarboxylic acid high-performance water reducer - Google Patents
Low-temperature synthesis technology of polycarboxylic acid high-performance water reducer Download PDFInfo
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Abstract
The invention discloses a low-temperature synthesis technology of polycarboxylic acid high-performance water reducer. According to the low-temperature synthesis technology, a low-temperature polymerization initiator is used for synthesis of the polycarboxylic acid high-performance water reducer. The synthesis technology comprises the following steps: firstly, dissolving unsaturated polyoxyethylene ether in deionized water and uniformly stirring; then, adding unsaturated monocarboxylic acid or part of unsaturated sulphonate monomer solution to adjust the pH value of the reaction solution to be higher than 3.0, and sequentially adding a reducing agent and a chain transfer agent; dropwise adding an aqueous solution of an oxidizing agent at a temperature of 0-40 DEG C; finally, performing heat preservation for 10-30 minutes, and adjusting the pH value of the solution to be within 6 and 8. According to the invention, the synthesis technology is simple and convenient to operate, the reaction process is easy to control, the generating period is short, the efficiency is improved, and the production cost is reduced; the water reducer, prepared from the low-temperature synthesis technology, is high in water-reducing rate and slump loss resistance and excellent in cement adaptation, and has a higher market prospect.
Description
Technical field:
The invention belongs to building concrete admixture technical field, be specifically related to a kind of low-temperature synthetic method of high performance water reducing agent of polyocarboxy acid.
Background technology:
Along with the development of concrete technology, more next large to the demand of high performance concrete, strong concrete, high-flowing concrete, high-performance water reducing agent has become one of component indispensable in concrete use procedure.
Since poly carboxylic acid series water reducer emerged from the eighties in 20th century, the advantages such as, water-reducing rate high, slump retaining good, can give concrete material various excellent properties, molecular designing strong, environmental protection low with its volume, obtain people's favor, become study hotspot and the direction of water reducer technology in recent years.
Polycarboxylate water-reducer divides two kinds of ester class and ethers.In recent years, TPEG, the production domesticization of HPEG polyethers, ethers polycarboxylic acid water reducing agent is to make large monomer with unsaturated polyether, prepares by the method for one-step polymerization with active minor comonomer.Because this technique is simple, water reducer molecular structure is adjustable, and stable performance is subject to the favor of numerous manufacturers.Ester class polycarboxylate water-reducer is due to processing condition complexity, and synthesis temperature is high, long reaction time, and cost is higher, and unstable properties is progressively replaced by ethers polycarboxylic acid water reducing agent.
At present, in the synthesis technique of ethers polycarboxylic acid water reducing agent, need by steam heating, temperature of reaction is controlled at 60-70 DEG C, and reaction times 4-5 hour, about 6 hours production cycles; Initiator for polymerization has ammonium persulphate, Potassium Persulphate, redox initiation system etc.; Ammonium persulphate kick off temperature at 60-80 DEG C, with the redox initiation system kick off temperature of hydrogen peroxide and xitix composition, at 60 DEG C, the redox initiation system kick off temperature being made up of Potassium Persulphate and sodium bisulfite can be down to 40 DEG C; Common polymerization starter at room temperature initiated polymerization is prepared polycarboxylate water-reducer.
The production unit that polycarboxylate water-reducer synthesis technique relates to has stainless steel cauldron or enamel reaction still, heating boiler, Dropping feeder, cooling water recirculation system, reaction monitoring system etc.; There is the problems such as production unit input is larger, and technique needs strict control, and human input is large, and the production cycle is long, efficiency is low in this technique at present.If can improve polymerization technique, reaction is under low temperature and room temperature (5-35 DEG C), just can save a large amount of production units drops into, it is the input of boiler, reactor, cooling water recirculation system, simplify technique simultaneously, shorten the production cycle, can save a large amount of manpower and materials, reduce production costs, increase economic efficiency.
Summary of the invention:
In order to overcome deficiency of the prior art, the invention provides a kind of low temperature synthesis technique of high performance water reducing agent of polyocarboxy acid, by low temperature polymerization initiator, for the synthesis of high performance water reducing agent of polyocarboxy acid, temperature of reaction, simplifies synthesis technique, enhances productivity.
The present invention solves the technical scheme that its technical problem adopts:
A low-temperature synthetic method for high performance water reducing agent of polyocarboxy acid, is characterized in that, comprises the steps:
(1) unsaturated polyoxy Vinyl Ether is dissolved in deionized water, stirs;
(2) unsaturated monocarboxylic acid or part unsaturated sulfonic acid salt monomer solution are added, regulate reaction solution pH at 3.0-7.0(preferably more than 4.0), reductive agent and chain-transfer agent are added successively;
(3) at 0-40 DEG C of (preferably 5-35 DEG C) lower aqueous solution that drips oxygenant;
(4) insulation 10-30min, the pH to 6-8 of regulator solution, obtains high performance water reducing agent of polyocarboxy acid.
The parts by weight of reaction raw materials are as follows:
Described oxygenant is selected from hydrogen peroxide, tertbutyl peroxide, benzoyl peroxide, ammonium persulphate and Potassium Persulphate.
Described reductive agent is selected from two or more in S-WAT, tartrate, iron protochloride, Mohr's salt, Sodium Pyrosulfite, V-Brite B, Hypophosporous Acid, 50 and sodium hypophosphite.
Unsaturated polyoxy Vinyl Ether described in step (1), its structural formula is as shown in general formula (1):
In general formula (1): R
1, R
2and R
3independently represent separately hydrogen atom or methyl; R
4represent the alkyl of hydrogen atom or carbonatoms 1-10; R represents that carbonatoms is the alkylidene group of 2-5; M represents that the average addition mole number of RO is 1-200; X represents that carbonatoms is the alkylidene group of 1-5.
Described unsaturated monomer is unsaturated monocarboxylic acid, and its general structure is:
Wherein R
5, R
6, R
7independently represent separately hydrogen atom or methyl, M
1represent hydrogen or monovalence metal or ammonium.The preferred vinylformic acid of unsaturated monocarboxylic acid, methacrylic acid.
Described unsaturated monomer is unsaturated sulfonic acid salt monomer, and its general structure is:
Wherein R
8represent the alkyl of hydrogen or carbonatoms 1-3, M
2represent hydrogen or monovalence metal or ammonium.The preferred sodium allyl sulfonate of unsaturated sulfonic acid salt monomer, methylpropene sodium sulfonate.
One or more in described chain-transfer agent selected from mercapto ethanol, Thiovanic acid, 2 mercaptopropionic acid, 3-thiohydracrylic acid and thioglycerin.
The Oxidizing and Reducing Agents that the present invention selects is low temperature polymerization initiator, and with water as solvent, reaction process is without thermal source, and equipment investment is few, and not with an organic solvent, i.e. energy efficient, does not pollute again; Adopt low temperature polymerization initiator, polymeric reaction temperature can be down to below 40 DEG C by original 60 DEG C, and the production cycle is reduced to 1-2 hour, has simplified synthesis technique, and production efficiency is higher, and production cost also has certain reduction.The high performance water reducing agent of polyocarboxy acid of producing has high water reducing rate, the high feature such as collapse, cement adaptability is good of protecting, and is applicable to suitability for industrialized production, has higher market outlook.
Embodiment
Umber in the following example is weight part.
Embodiment 1
By 150 parts of methacrylic Soxylat A 25-7s, 120 parts of deionized waters are put into reaction vessel, stirring and dissolving.15 parts of vinylformic acid are dissolved in 50 parts of water, add in reaction vessel, with sodium hydroxide solution adjusting pH to 5.0; By 1 part of reductive agent (weight ratio of S-WAT and iron protochloride is 1:1), 0.7 part of 2 mercaptopropionic acid adds in reactor successively; 30 part of 2% hydrogen peroxide joined in reactor with 30min, and temperature of reaction rises to 28 DEG C from 10 DEG C, and after dripping off, insulation 30min, is neutralized to pH=7 left and right with sodium hydroxide solution, obtains light yellow transparent liquid, is polycarboxylate water-reducer.
Embodiment 2
By 150 parts of methacrylic Soxylat A 25-7s, 120 parts of deionized waters are put into reaction vessel, stirring and dissolving.17 parts of vinylformic acid are dissolved in 50 parts of water, add in reaction vessel, with sodium hydroxide solution adjusting pH to 5.5; By 1.3 parts of reductive agents (weight ratio of S-WAT, Sodium Pyrosulfite and iron protochloride is 1:1:1), 0.79 part of 2 mercaptopropionic acid adds in reactor successively; 30 part of 2% hydrogen peroxide joined in reactor with 30min, and temperature of reaction rises to 30 DEG C from 15 DEG C, and after dripping off, insulation 20min, is neutralized to pH=7 left and right with sodium hydroxide solution, obtains light yellow transparent liquid, is polycarboxylate water-reducer.
Embodiment 3
By 150 parts of methacrylic Soxylat A 25-7s, 120 parts of deionized waters are put into reaction vessel, stirring and dissolving.By 10 parts of vinylformic acid, 5 parts of methylpropene sodium sulfonates are dissolved in 50 parts of water, add in reaction vessel, with sodium hydroxide solution adjusting pH to 5.0; By 1 part of reductive agent (weight ratio of S-WAT and Mohr's salt is 1:1), 0.7 part of 3-thiohydracrylic acid adds in reactor successively; 30 part of 2% hydrogen peroxide joined in reactor with 30min, and temperature of reaction rises to 28 DEG C from 10 DEG C, and after dripping off, insulation 30min, is neutralized to pH=7 left and right with sodium hydroxide solution, obtains light yellow transparent liquid, is polycarboxylate water-reducer.
Embodiment 4
By 150 parts of methacrylic Soxylat A 25-7s, 120 parts of deionized waters are put into reaction vessel, stirring and dissolving.By 15 parts of vinylformic acid, 2 parts of methylpropene sodium sulfonates are dissolved in 50 parts of water, add in reaction vessel, with sodium hydroxide solution adjusting pH to 5.0; By 1 part of reductive agent (S-WAT, the weight ratio of tartrate and Mohr's salt is 1:1), 0.7 part of 3-thiohydracrylic acid adds in reactor successively; 30 part of 2% hydrogen peroxide joined in reactor with 10min, and temperature of reaction rises to 25 DEG C from 5 DEG C, and after dripping off, insulation 10min, is neutralized to pH=7 left and right with sodium hydroxide solution, obtains light yellow transparent liquid, is polycarboxylate water-reducer.
Embodiment 5
By 150 parts of methacrylic Soxylat A 25-7s, 120 parts of deionized waters are put into reaction vessel, stirring and dissolving.By 15 parts of vinylformic acid, 1 part of methylpropene sodium sulfonate is dissolved in 50 parts of water, adds in reaction vessel, with sodium hydroxide solution adjusting pH to 5.0; By 1 part of reductive agent (weight ratio of S-WAT, V-Brite B and Mohr's salt is 1:1:1), 0.7 part of 3-thiohydracrylic acid adds in reactor successively; 30 part of 2% hydrogen peroxide joined in reactor with 30min, and temperature of reaction rises to 30 DEG C from 20 DEG C, and after dripping off, insulation 30min, is neutralized to pH=7 left and right with sodium hydroxide solution, obtains light yellow transparent liquid, is polycarboxylate water-reducer.
Embodiment 6
By 150 parts of methacrylic Soxylat A 25-7s, 120 parts of deionized waters are put into reaction vessel, stirring and dissolving.15 parts of vinylformic acid are dissolved in 50 parts of water, add in reaction vessel, with sodium hydroxide solution adjusting pH to 5.0; By 1 part of reductive agent (weight ratio of S-WAT, V-Brite B and Mohr's salt is 1:1:1), 0.7 part of 3-thiohydracrylic acid adds in reactor successively; 30 part of 2% hydrogen peroxide joined in reactor with 30min, and temperature of reaction rises to 33 DEG C from 27 DEG C, and after dripping off, insulation 10min, is neutralized to pH=7 left and right with sodium hydroxide solution, obtains light yellow transparent liquid, is polycarboxylate water-reducer.
Embodiment 7
By 150 parts of methacrylic Soxylat A 25-7s, 120 parts of deionized waters are put into reaction vessel, stirring and dissolving.By 15 parts of vinylformic acid, 5 parts of methylpropene sodium sulfonates are dissolved in 50 parts of water, add in reaction vessel, with sodium hydroxide solution adjusting pH to 5.0; By 1 part of reductive agent (weight ratio of S-WAT, sodium hypophosphite and Mohr's salt is 1:1:1), 0.7 part of 3-thiohydracrylic acid adds in reactor successively; 30 part of 2% hydrogen peroxide joined in reactor with 30min, and temperature of reaction rises to 35 DEG C from 30 DEG C, and after dripping off, insulation 30min, is neutralized to pH=7 left and right with sodium hydroxide solution, obtains light yellow transparent liquid, is polycarboxylate water-reducer.
Comparative example
Below according to the synthetic polycarboxylate water-reducer of traditional synthetic method, to contrast with the synthetic water reducer of the present invention.
Comparative example 1
Add 150 parts of polyethers and 120 parts of deionized waters to being equipped with in the reactor of thermometer, agitator, Dropping feeder, nitrogen ingress pipe and reflux exchanger.Under agitation inside reactor is carried out to nitrogen replacement.Be warming up to 60 DEG C, 1 part of 30% hydrogen peroxide added; With the solution that drips 15 parts of vinylformic acid and 50 parts of water compositions for 3 hours; Simultaneously with the aqueous solution that drips 0.9 part of thiohydracrylic acid, 0.5 part of xitix and 30 parts of water compositions for 3.5 hours.After dripping, thereby insulation completes polyreaction for 1 hour.Cooling, adds finite concentration sodium hydroxide solution to be neutralized to pH=5-7, obtains yellow transparent liquid, is polycarboxylate water-reducer.
Comparative example 2
Add 150 parts of polyethers and 120 parts of deionized waters to being equipped with in the reactor of thermometer, agitator, Dropping feeder, nitrogen ingress pipe and reflux exchanger.Under agitation inside reactor is carried out to nitrogen replacement.Be warming up to 60 DEG C, 1 part of 30% hydrogen peroxide added; With 10 parts of vinylformic acid of dropping in 3 hours, the solution of 5 parts of methylpropene sodium sulfonates and 50 parts of water compositions; Simultaneously with the aqueous solution that drips 0.5 part of thiohydracrylic acid, 0.5 part of xitix and 30 parts of water compositions for 3.5 hours.After dripping, thereby insulation completes polyreaction for 1 hour.Cooling, adds finite concentration sodium hydroxide solution to be neutralized to pH=5-7, obtains yellow transparent liquid, is polycarboxylate water-reducer.
Effect assessment
1. clean slurry degree of mobilization evaluation
Test determination the clean slurry degree of mobilization of sample under identical volume.Test is carried out according to GB/T8077-2000 " Methods for testing uniformity of concrete admixture ", W/C=0.29, and the solid volume of admixture folding is 0.15%.
The clean slurry of table 1 slump test
Embodiment and comparative example adopt identical polyethers, different polymerization techniques.Embodiment has adopted low temperature polymerization technique, and comparative example adopts traditional heated polymerizable technique.Under identical volume, both clean slurry degree of mobilization and through time degree of mobilization substantially always, illustrate that polycarboxylate water-reducer performance prepared by low temperature polymerization technique is equal to traditional polycarboxylate water-reducer.
2. concrete evaluation
Test method is with reference to GB8076-2008 " concrete admixture ".The solid volume of folding of admixture is 0.2%.It is 200 ± 20mm that adjustment water consumption makes the initial slump of fresh concrete.Test-results is in table 2.
Table 2 concrete test
Water reducer prepared by embodiment and the comparative example water-reducing rate in concrete is suitable, and the concrete function of slump protection of 1 hour is basically identical, illustrates that the performance of two kinds of water reducers is suitable.
Above specific embodiments of the invention be have been described in detail, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and alternative also all among category of the present invention.Therefore, lower equalization conversion and the amendment of doing, all should contain within the scope of the invention without departing from the spirit and scope of the present invention.
Claims (10)
1. a low-temperature synthetic method for high performance water reducing agent of polyocarboxy acid, is characterized in that, comprises the steps:
(1) unsaturated polyoxy Vinyl Ether is dissolved in deionized water, stirs;
(2) unsaturated monocarboxylic acid or part unsaturated sulfonic acid salt monomer solution are added, regulate reaction solution pH at 3.0-7.0, reductive agent and chain-transfer agent are added successively;
(3) at 0-40 DEG C, drip the aqueous solution of oxygenant;
(4) insulation 10-30min, the pH to 6-8 of regulator solution, obtains high performance water reducing agent of polyocarboxy acid.
2. method according to claim 1, is characterized in that, the parts by weight of reaction raw materials are as follows:
3. method according to claim 1, is characterized in that, described oxygenant is selected from hydrogen peroxide, tertbutyl peroxide, benzoyl peroxide, ammonium persulphate and Potassium Persulphate.
4. method according to claim 1, is characterized in that, described reductive agent is selected from two or more in S-WAT, tartrate, iron protochloride, Mohr's salt, Sodium Pyrosulfite, V-Brite B, Hypophosporous Acid, 50 and sodium hypophosphite.
5. method according to claim 1, is characterized in that, the unsaturated polyoxy Vinyl Ether described in step (1), and its structural formula is as shown in general formula (1):
In general formula (1): R
1, R
2and R
3independently represent separately hydrogen atom or methyl; R
4represent the alkyl of hydrogen atom or carbonatoms 1-10; R represents that carbonatoms is the alkylidene group of 2-5; M represents that the average addition mole number of RO is 1-200; X represents that carbonatoms is the alkylidene group of 1-5.
6. method according to claim 1, is characterized in that, described unsaturated monomer is unsaturated monocarboxylic acid, and its general structure is:
Wherein R
5, R
6, R
7independently represent separately hydrogen atom or methyl, M
1represent hydrogen or monovalence metal or ammonium.
7. method according to claim 1, is characterized in that, described unsaturated monomer is unsaturated sulfonic acid salt monomer, and its general structure is:
Wherein R
8represent the alkyl of hydrogen or carbonatoms 1-3, M
2represent hydrogen or monovalence metal or ammonium.
8. method according to claim 1, is characterized in that, described reaction solution pH is more than 4.0.
9. method according to claim 1, is characterized in that, one or more in described chain-transfer agent selected from mercapto ethanol, Thiovanic acid, 2 mercaptopropionic acid, 3-thiohydracrylic acid and thioglycerin.
10. method according to claim 1, is characterized in that, described temperature of reaction is at 5-35 DEG C.
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| CN104558435A (en) * | 2015-01-05 | 2015-04-29 | 江苏中凯新材料有限公司 | Low-temperature synthetic method of multi-branched polycarboxylate superplasticizer |
| CN104692701A (en) * | 2015-03-04 | 2015-06-10 | 河南新汉材料科技有限公司 | Room-temperature synthetic type polycarboxylic high performance water-reducing agent and preparation method thereof |
| CN105293981A (en) * | 2015-10-29 | 2016-02-03 | 中国建筑材料科学研究总院 | Slump retention agent and preparation method thereof |
| WO2016026346A1 (en) * | 2014-08-22 | 2016-02-25 | 科之杰新材料集团有限公司 | Low-temperature method for preparing high-adaptability ether polycarboxylic acid water reducer |
| CN105837762A (en) * | 2016-05-30 | 2016-08-10 | 江苏名和集团有限公司 | Polycarboxylate superplasticizer synthesized at normal temperature and preparation method thereof |
| CN109180874A (en) * | 2018-07-13 | 2019-01-11 | 成都宏基建材股份有限公司 | A kind of polycarboxylate water-reducer and preparation method thereof |
| CN109593156A (en) * | 2018-12-14 | 2019-04-09 | 长沙加美乐素化工有限公司 | A kind of technique synthesizing comprehensive water-reducing agent using six carbon monomers |
| CN111154045A (en) * | 2019-12-30 | 2020-05-15 | 四川恒泽建材有限公司 | Ultralow-temperature polycarboxylate superplasticizer and synthesis method thereof |
| CN111925490A (en) * | 2020-08-19 | 2020-11-13 | 嘉善华豪建材有限公司 | Production process of water-reducing slump-retaining polycarboxylic acid |
| CN115466363A (en) * | 2022-10-31 | 2022-12-13 | 中建材中岩科技有限公司 | Polycarboxylate superplasticizer prepared at ultralow temperature and preparation method thereof |
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| CN104558435A (en) * | 2015-01-05 | 2015-04-29 | 江苏中凯新材料有限公司 | Low-temperature synthetic method of multi-branched polycarboxylate superplasticizer |
| CN104558435B (en) * | 2015-01-05 | 2018-02-02 | 江苏中凯新材料有限公司 | A kind of low-temperature synthetic method of multi-branched polycarboxylic water reducer |
| CN104692701A (en) * | 2015-03-04 | 2015-06-10 | 河南新汉材料科技有限公司 | Room-temperature synthetic type polycarboxylic high performance water-reducing agent and preparation method thereof |
| CN105293981A (en) * | 2015-10-29 | 2016-02-03 | 中国建筑材料科学研究总院 | Slump retention agent and preparation method thereof |
| CN105837762A (en) * | 2016-05-30 | 2016-08-10 | 江苏名和集团有限公司 | Polycarboxylate superplasticizer synthesized at normal temperature and preparation method thereof |
| CN109180874A (en) * | 2018-07-13 | 2019-01-11 | 成都宏基建材股份有限公司 | A kind of polycarboxylate water-reducer and preparation method thereof |
| CN109593156A (en) * | 2018-12-14 | 2019-04-09 | 长沙加美乐素化工有限公司 | A kind of technique synthesizing comprehensive water-reducing agent using six carbon monomers |
| CN111154045A (en) * | 2019-12-30 | 2020-05-15 | 四川恒泽建材有限公司 | Ultralow-temperature polycarboxylate superplasticizer and synthesis method thereof |
| CN111925490A (en) * | 2020-08-19 | 2020-11-13 | 嘉善华豪建材有限公司 | Production process of water-reducing slump-retaining polycarboxylic acid |
| CN115466363A (en) * | 2022-10-31 | 2022-12-13 | 中建材中岩科技有限公司 | Polycarboxylate superplasticizer prepared at ultralow temperature and preparation method thereof |
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