CN102286134A - Preparation method for high-performance water reducing agent - Google Patents
Preparation method for high-performance water reducing agent Download PDFInfo
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Abstract
The invention discloses a preparation method for a polycarboxylate high-performance water reducing agent. The water reducing agent is prepared by copolymerization reaction of a macromolecular monomer A (methyl allyl polyoxyethylene ether), a small molecular monomer B (methyl acrylic acid or acrylic acid) and a small molecular monomer C (sodium methyl allyl sulfonate, sodium allylsulfonate or sodium styrene sulfonate) with polymerization activities in water under the protection of an inert gas and the action of an oxidation-reduction initiating system and a chain transfer agent. By adopting the oxidation-reduction initiating system with high activity, the polymerization reaction rate can be improved, the polymerization temperature can be reduced, the reaction time can be shortened, and the polymer has ideal molecular structure. The water reducing agent prepared by the method has excellent properties of high water reducing rate, good dispersibility, no loss in slump, high concrete strength and the like; and meanwhile, because the copolymerization reaction is performed in the water, the method is simple and has the characteristics of environment friendliness, low energy consumption, low cost and the like.
Description
Technical field
The present invention relates to a kind of preparation method of cement water reducing agent, be specifically related to a kind of preparation method of polycarboxylate high performance dehydragent.
Background technology
Water reducer is the admixture most important in the concrete, that usage quantity is maximum.It can improve the performance of freshly mixed concrete greatly, can improve slump retaining, workability and the flowability of concrete mix, can also reduce the water consumption of mixture to increase concrete intensity and weather resistance etc. simultaneously.
Be the first-generation ordinary water-reducing agent of representative and be the s-generation high efficiency water reducing agent of representative with wooden calcium with naphthalene system, trimeric cyanamide, in use have the volume height, water-reducing rate is low, slump-loss is big, concrete strength is low, with the defectives such as bad adaptability of cement and other adulterant; Simultaneously, traditional water reducers such as naphthalene system, trimeric cyanamide are formaldehyde condensation products, in production and application process, formaldehyde is discharged into the atmosphere easily and is caused pollution to environment, the serious harm human health, this type of water reducer can not satisfy develop rapidly of modern high performance concrete and requirements of green environmental protection far away, is replaced by polycarboxylate high performance dehydragent gradually.
What grow up from the eighties is the third generation high-performance water reducing agent of representative with the polycarboxylate, it has long side chain " comb shape " molecular structure, can pass through the relation between polymer molecular structure, molecular arrangement and the performance, realize the designability of molecular structure and performance, develop water reducer product with various specific functions.Polycarboxylate high performance dehydragent has that volume is low, water-reducing rate is high, workability is good, slump retaining is good, concrete strength is high, no chlorion, alkali content are low, with excellent properties such as the adaptability of cement and other adulterant is good, its invention realization and promoted the development of concrete to high performance level.Polycarboxylate high performance dehydragent preparation technology is simple, and is easy to operate, easy to control, preparation process reaches zero release, and environmentally safe is the most desirable at present water reducer product, it will represent cement water reducing agent industry developing direction from now on, become the emphasis of domestic and international research and development and application at present.
At present, the high performance water reducing agent of polyocarboxy acid on the market mainly is divided into polyester type and polyether-type two big classes.Though the polyester type water reducer has higher water-reducing rate, function of slump protection has advantage such as adaptability preferably with cement preferably, but because the synthesis technique of its existence is comparatively complicated, facility investment is big, and the production cycle is long, factors such as prices of raw and semifnished materials height make production cost higher; Monomeric concentration generally was controlled between 20%～30% when the polyester type water reducer was synthetic, monomer concentration is high more, polymerization rate is fast more, the molecular structure of polymkeric substance is rare more to control, the performance of its water reducer is just poor more, so be difficult for producing the product of high density, cause that unit output is low, transportation cost is high; Simultaneously, the long side chain of polyester type water reducer is that ester bond is connected with main chain, at high temperature stores unstable.The existence of these unfavorable factors all will have a strong impact on the promotion and application of polyester type water reducer.
The polyether-type water reducer mainly is to be big polymer of monomers with allyl polyethenoxy ether or methacrylic Soxylat A 25-7.Its characteristics are: compare with the polyester type water reducer and need not esterification, can form by the single stage method direct polymerization, technology is simple, and facility investment is little, and is with short production cycle, and energy consumption is low, and cost is low, can produce the high density product.Wherein allyl polyethenoxy ether is because active low, the polyreaction difficulty, and polymkeric substance can not get the ideal molecular structure, and water-reducing rate is low, and concrete slump keeps poor performance, is eliminated gradually.And the methacrylic Soxylat A 25-7 is active high because of it, made water reducer excellent property, the focus that becomes research and development and use.
At present, it is surface-active macromonomer that the methacrylic Soxylat A 25-7 of different grades molecular weight is all adopted in its preparation usually, (methyl) vinylformic acid is minor comonomer, with persulphate (as ammonium persulphate, Sodium Persulfate or Potassium Persulphate) or hydrogen peroxide is initiator, with sulfhydryl compound (as mercaptoethanol, Thiovanic acid, thiohydracrylic acid etc.) is chain-transfer agent, in the aqueous solution, carry out copolymerization, after finishing, reaction neutralizes with alkaline matters such as sodium hydroxide, regulate pH value to 6～7, obtain polycarboxylate high performance dehydragent.The shortcoming that above-mentioned preparation method exists is: the initiating activity of initiator persulphate, hydrogen peroxide is low, temperature of reaction height (70～90 ℃), long reaction time (6～8 hours), polyreaction control difficulty, transformation efficiency is low, polymkeric substance can not get the ideal comb shaped molecular structure, the water reducer poor performance of preparation; Select for use sulfhydryl compound big, the strong impulse smell is arranged, in producing and using, easily cause environmental pollution etc. as chain-transfer agent toxicity.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of polycarboxylate high performance dehydragent, to solve the problems referred to above that exist in the existing technology of preparing.
Realize that the technical scheme that the object of the invention adopted is as follows:
A kind of preparation method of polycarboxylate high performance dehydragent, it is characterized in that: in protection of inert gas with under the effect of oxidation-reduction trigger system, chain-transfer agent, in the aqueous solution, carry out copolyreaction by macromonomer A and small molecule monomer B, C, the back neutralizes with alkali, obtains polycarboxylate high performance dehydragent;
Described macromonomer A is the methacrylic Soxylat A 25-7;
Described small molecule monomer B is methacrylic acid or vinylformic acid;
Described small molecule monomer C is a kind of in methylpropene sodium sulfonate, sodium allylsulfonate or the Sodium styrene sulfonate.
The molecular weight of described macromonomer A methacrylic Soxylat A 25-7 is in polymerization degree n=10～200, and preferable range is n=20～100.
The polymerization single polymerization monomer of copolyreaction comprises macromonomer A and the small molecule monomer B and the C of polymerization activity.Mole proportioning between described macromonomer A, small molecule monomer B and the small molecule monomer C three is 1:1～6:0.1～4, and preferable range is 1:2～5:0.1～3.
Described oxidation-reduction trigger system, wherein oxygenant is a kind of in persulphate, the hydrogen peroxide, consumption is 0.5～4% of a polymerization single polymerization monomer weight; Wherein reductive agent is a kind of in sulphite, the xitix, and consumption is 0.5～3% of a polymerization single polymerization monomer weight.Described persulphate is ammonium persulphate, Sodium Persulfate or Potassium Persulphate, and described sulphite is ammonium sulphite, ammonium bisulfite, S-WAT, sodium bisulfite, potassium sulfite or Potassium hydrogen sulfite.
Described chain-transfer agent is small molecule monomer C, and small molecule monomer C both had been a comonomer, played a part chain-transfer agent again.
Described copolyreaction, its temperature of reaction are 20～65 ℃, and preferable range is 30～60 ℃.
Described copolyreaction, its reaction times is 1～6 hour, preferable range is 2～5 hours.
Described alkali is sodium hydroxide, potassium hydroxide, bicarbonate of ammonia or ammonia, or their aqueous solution.Preferred mass concentration is 30% sodium hydroxide solution, and regulating pH value is 6～7.
Described polycarboxylate high performance dehydragent can add water, and to regulate its solid content be 40～50%.
Advantage of the present invention is:
1. employing oxidation-reduction trigger system, the initiating activity height can reduce the activation energy that generates free radical greatly, improves polymerization rate, reduces polymeric reaction temperature, shortens polymerization reaction time.
2. small molecule monomer C is that not only polymkeric substance introduces sulfonic acid group, and plays chain transfer again, prevents from quick-friedly to take place according to phenomenon in polyreaction, regulates molecular weight automatically, makes the water reducer of preparation have better molecular structure, and concrete performance is more excellent.
3. the polycarboxylate dehydragent water-reducing rate height of the inventive method preparation is dispersed strong, and the slump keeps performance excellent, 2 hours no slump-loss.
4. the consistency and the adaptability of the polycarboxylate dehydragent of the inventive method preparation and cement and other adulterant are good.
5. the inventive method technology is simple, and is easy to operate, easy to control, the feed stock conversion height, and energy consumption is low, and cost is low.
6. avoid in the inventive method polyreaction using toxicity big, have the sulfhydryl compound of intense stimulus smell to be chain-transfer agent, made water reducer environmentally safe, environmental protection.
The present invention will be described in detail below in conjunction with specific embodiment.
Embodiment
Preparation method according to polycarboxylate high performance dehydragent of the present invention, by active macromonomer A methacrylic Soxylat A 25-7 and small molecule monomer B(methyl) vinylformic acid, small molecule monomer C methylpropene sodium sulfonate, sodium allylsulfonate or Sodium styrene sulfonate carry out copolyreaction in the aqueous solution, neutralize with alkali at last, obtain polycarboxylate high performance dehydragent.Copolyreaction is carried out under the nitrogen protection condition, and initiator adopts oxidation-reduction trigger system.
Implement the inventive method, copolyreaction can be undertaken by following dual mode:
(1), before the copolymerization, earlier each comonomer, initiator and chain-transfer agent and water are mixed in reactor, temperature of reaction system is risen to the copolyreaction temperature, constant temperature carried out copolyreaction in 2～5 hours under agitation condition again.
(2), before the copolyreaction, the aqueous solution that adds the partial reaction thing in the reactor earlier, and be warming up to the copolyreaction temperature, under agitation condition, the aqueous solution of other comonomer, initiator or chain-transfer agent is added drop-wise in the reactor then, dropwise continuation constant temperature and carry out copolymerization, dropping and constant temperature time 2～5 hours.Usually preferentially select the 2nd kind of mode for use.
Press the relevant regulations of GB8076-2008 " concrete admixture " carries out about concrete water-reducing ratio and slump consistancy test method.
Implement the present invention and be not limited to following specific embodiment, such as for concrete material, reaction conditions or the mode etc. that are adopted in following examples, those skilled in the art can be equal to or the replacement or the variation of equivalence.Described embodiment helps the understanding of the present invention and enforcement, is not to be construed as limiting the invention.Protection scope of the present invention is not exceeded with embodiment, but is limited by claim.
Embodiment 1
In the 1000ml flask of agitator, thermometer, dropping funnel and condenser is housed, add 300g methacrylic Soxylat A 25-7 (n=25), 20g methylpropene sodium sulfonate, 2g S-WAT and 160g deionized water.Stir and also to feed nitrogen protection, treat that temperature rises to 50 ℃, begin to drip the aqueous solution that the aqueous solution be made up of 55g vinylformic acid and 37g deionized water and 4.5g Sodium Persulfate and 85g deionized water are formed.Acrylic acid aqueous solution dripped off in 2.5 hours, and sodium persulfate aqueous solution dripped off in 3 hours.Dropwise and continued insulation reaction 1 hour, cooling then, the sodium hydroxide solution with 30% is neutralized to pH value 6～7, and adding water adjustment solid content simultaneously is 45%, promptly gets little yellow thickness aqueous solution purpose product.The test-results of its concrete water-reducing ratio and the slump sees Table 1.
Embodiment 2
In the 1000ml flask of agitator, thermometer, dropping funnel and condenser is housed, add 300g methacrylic Soxylat A 25-7 (n=50), 10.5g methylpropene sodium sulfonate, 2g S-WAT and 160g deionized water.Stir and also to feed nitrogen protection, treat that temperature rises to 30 ℃, begin to drip the aqueous solution that the aqueous solution be made up of 30g vinylformic acid and 20g deionized water and 4.5g Sodium Persulfate and 85g deionized water are formed.Acrylic acid aqueous solution dripped off in 2.5 hours, and sodium persulfate aqueous solution dripped off in 3 hours.Dropwise and continued insulation reaction 1 hour, cooling then, the sodium hydroxide solution with 30% is neutralized to pH value 6～7, and adding water adjustment solid content simultaneously is 45%, promptly gets little yellow thickness aqueous solution purpose product.The test-results of its concrete water-reducing ratio and the slump sees Table 1.
Embodiment 3
In the 1000ml flask of agitator, thermometer, dropping funnel and condenser is housed, add 300g methacrylic Soxylat A 25-7 (n=75), 7g methylpropene sodium sulfonate, 2g S-WAT and 160g deionized water.Stir and also to feed nitrogen protection, treat that temperature rises to 60 ℃, begin to drip the aqueous solution that the aqueous solution be made up of 20g vinylformic acid and 13g deionized water and 4.5g Sodium Persulfate and 85g deionized water are formed.Acrylic acid aqueous solution dripped off in 2.5 hours, and sodium persulfate aqueous solution dripped off in 3 hours.Dropwise and continued insulation reaction 1 hour, cooling then, the sodium hydroxide solution with 30% is neutralized to pH value 6～7, and adding water adjustment solid content simultaneously is 45%, promptly gets little yellow thickness aqueous solution purpose product.The test-results of its concrete water-reducing ratio and the slump sees Table 1.
Comparative example 1
In the 1000ml flask of agitator, thermometer, dropping funnel and condenser is housed, add 300g methacrylic Soxylat A 25-7 (n=25) and 160g deionized water.Stir and the feeding nitrogen protection, treat that temperature rises to 80 ℃, begin to drip the aqueous solution of forming by 55g vinylformic acid, 1.5g mercaptoethanol and 40g deionized water and the aqueous solution of forming by 4.5g Sodium Persulfate and 50g deionized water.Vinylformic acid, the mercaptoethanol aqueous solution dripped off in 3 hours, and sodium persulfate aqueous solution dripped off in 3.5 hours.Dropwise and continued insulation reaction 3 hours, cooling then, the sodium hydroxide solution with 30% is neutralized to pH value 6～7, and adding water adjustment solid content simultaneously is 40%, promptly gets the purpose product.The test-results of its concrete water-reducing ratio and the slump sees Table 1.
Comparative example 2
In the 1000ml flask of agitator, thermometer, dropping funnel and condenser is housed, add 300g methacrylic Soxylat A 25-7 (n=50) and 160g deionized water.Stir and the feeding nitrogen protection, treat that temperature rises to 80 ℃, begin to drip the aqueous solution of forming by 30g vinylformic acid, 1.5g mercaptoethanol and 40g deionized water and the aqueous solution of forming by 4.5g Sodium Persulfate and 50g deionized water.Vinylformic acid, the mercaptoethanol aqueous solution dripped off in 3 hours, and sodium persulfate aqueous solution dripped off in 3.5 hours.Dropwise and continued insulation reaction 3 hours, cooling then, the sodium hydroxide solution with 30% is neutralized to pH value 6～7, and adding water adjustment solid content simultaneously is 40%, promptly gets the purpose product.The test-results of its concrete water-reducing ratio and the slump sees Table 1.
Comparative example 3
In the 1000ml flask of agitator, thermometer, dropping funnel and condenser is housed, add 300g methacrylic Soxylat A 25-7 (n=75) and 160g deionized water.Stir and the feeding nitrogen protection, treat that temperature rises to 80 ℃, begin to drip the aqueous solution of forming by 20g vinylformic acid, 1.5g mercaptoethanol and 40g deionized water and the aqueous solution of forming by 4.5g Sodium Persulfate and 50g deionized water.Vinylformic acid, the mercaptoethanol aqueous solution dripped off in 3 hours, and sodium persulfate aqueous solution dripped off in 3.5 hours.Dropwise and continued insulation reaction 3 hours, cooling then, the sodium hydroxide solution with 30% is neutralized to pH value 6～7, and adding water adjustment solid content simultaneously is 40%, promptly gets the purpose product.The test-results of its concrete water-reducing ratio and the slump sees Table 1.
Embodiment 5
Substantially the same manner as Example 1, difference is that vinylformic acid replaces with methacrylic acid.
Embodiment 6
Substantially the same manner as Example 1, difference is that methylpropene sodium sulfonate replaces with sodium allylsulfonate.
Embodiment 7
Substantially the same manner as Example 1, difference is that methylpropene sodium sulfonate replaces with Sodium styrene sulfonate.
Table 1: the concrete water-reducing ratio and the slump
| Water reducer | Cement | Volume (folding is the weight percent of cement admittedly) | Water-reducing rate | The initial slump (mm) | 1 hour slump (mm) | 2 hours slumps (mm) |
| Embodiment 1 | Jin Feng (P.O42.5) | 0.2% | 31% | 210 | 212 | 210 |
| Embodiment 2 | Jin Feng (P.O42.5) | 0.2% | 32.5% | 210 | 213 | 211 |
| Embodiment 3 | Jin Feng (P.O42.5) | 0.2% | 31.5% | 210 | 211 | 210 |
| Comparative example 1 | Jin Feng (P.O42.5) | 0.2% | 24% | 210 | 185 | 155 |
| Comparative example 2 | Jin Feng (P.O42.5) | 0.2% | 26% | 210 | 190 | 163 |
| Comparative example 3 | Jin Feng (P.O42.5) | 0.2% | 25% | 210 | 188 | 160 |
Claims (10)
1. the preparation method of a polycarboxylate high performance dehydragent, it is characterized in that: in protection of inert gas with under the effect of oxidation-reduction trigger system, chain-transfer agent, in the aqueous solution, carry out copolyreaction by macromonomer A and small molecule monomer B, C, the back neutralizes with alkali, obtains polycarboxylate high performance dehydragent;
Described macromonomer A is the methacrylic Soxylat A 25-7;
Described small molecule monomer B is methacrylic acid or vinylformic acid;
Described small molecule monomer C is a kind of in methylpropene sodium sulfonate, sodium allylsulfonate or the Sodium styrene sulfonate.
2. the preparation method of polycarboxylate high performance dehydragent according to claim 1, the molecular weight that it is characterized in that described macromonomer A methacrylic Soxylat A 25-7 is in polymerization degree n=10～200.
3. the preparation method of polycarboxylate high performance dehydragent according to claim 1 is characterized in that the mole proportioning between described macromonomer A, small molecule monomer B and the small molecule monomer C three is 1:1～6:0.1～4.
4. the preparation method of polycarboxylate high performance dehydragent according to claim 1 is characterized in that described oxidation-reduction trigger system, and wherein oxygenant is a kind of in persulphate or the hydrogen peroxide, and consumption is 0.5～4% of a polymerization single polymerization monomer weight; Wherein reductive agent is a kind of in sulphite or the xitix, and consumption is 0.5～3% of a polymerization single polymerization monomer weight.
5. the preparation method of polycarboxylate high performance dehydragent according to claim 1 is characterized in that described chain-transfer agent is small molecule monomer C.
6. the preparation method of polycarboxylate high performance dehydragent according to claim 1 is characterized in that described copolyreaction, and its temperature of reaction is 20～65 ℃.
7. the preparation method of polycarboxylate high performance dehydragent according to claim 1 is characterized in that described copolyreaction, and its reaction times is 1～6 hour.
8. the preparation method of polycarboxylate high performance dehydragent according to claim 1 is characterized in that described alkali is sodium hydroxide, potassium hydroxide, bicarbonate of ammonia or ammonia, or their aqueous solution.
9. the preparation method of polycarboxylate high performance dehydragent according to claim 1 is characterized in that neutralizing with alkali, and regulating pH value is 6～7.
10. the preparation method of polycarboxylate high performance dehydragent according to claim 1 is characterized in that it is 40～50% that described polycarboxylate high performance dehydragent is regulated its solid content.
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| CN115678624A (en) * | 2021-07-23 | 2023-02-03 | 中国科学院宁波材料技术与工程研究所 | Modified sulfonate polycondensate dispersant, and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101974135A (en) * | 2010-10-15 | 2011-02-16 | 北京工业大学 | Normal-temperature synthesis method for polycarboxylic acid water-reducing agent |
-
2011
- 2011-06-09 CN CN 201110153873 patent/CN102286134A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101974135A (en) * | 2010-10-15 | 2011-02-16 | 北京工业大学 | Normal-temperature synthesis method for polycarboxylic acid water-reducing agent |
Non-Patent Citations (1)
| Title |
|---|
| 《中国博士学位论文全文数据库 工程科技II辑》 20110215 张荣国 "聚丙烯酸高效减水剂的合成及其结构与性能的关系研究" 68 1-10 , 第02期 * |
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