CN1109004C - Polycarboxylic acid series water reducing agents for efficient aerocrote - Google Patents
Polycarboxylic acid series water reducing agents for efficient aerocrote Download PDFInfo
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- CN1109004C CN1109004C CN00103594A CN00103594A CN1109004C CN 1109004 C CN1109004 C CN 1109004C CN 00103594 A CN00103594 A CN 00103594A CN 00103594 A CN00103594 A CN 00103594A CN 1109004 C CN1109004 C CN 1109004C
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- China
- Prior art keywords
- water reducing
- methyl
- methacrylic acid
- reducing agents
- concrete
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 32
- 239000002253 acid Substances 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 4
- 238000010189 synthetic method Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 20
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 18
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- -1 polyoxyethylene Polymers 0.000 claims description 10
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 9
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 238000003672 processing method Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims description 2
- 239000004568 cement Substances 0.000 abstract description 7
- 239000012496 blank sample Substances 0.000 abstract description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 abstract 1
- 229940051841 polyoxyethylene ether Drugs 0.000 abstract 1
- 229920000056 polyoxyethylene ether Polymers 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000005809 transesterification reaction Methods 0.000 description 4
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical group ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003487 anti-permeability effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The present invention discloses a method for preparing a high-efficiency polycarboxylic acid series air entraining water reducing agent for concrete. The water reducing agent for concrete is a high-efficiency air entraining water reducing agent for concrete, which is prepared by using methyl polyoxyethylene ether, methyl methacrylate, methacrylic acid, etc. as raw materials through a chemical reaction and has the advantages of simple synthetic methods and easy control of reaction conditions. When the mixed amount of the water reducing agent is 1.5% of the weight of cement, the gas content of prepared concrete is generally from 4 to 7%, the water reducing rate can reach 30%, and the compressive strength in 28 days is 110 to 126% of that of a blank sample.
Description
The present invention relates to prepare the technology category of efficient cement water reducing agent, specifically, relate to the technology category of preparation water reducing agents for efficient aerocrote.
In concrete works, utilize concrete admixture to improve the attention that concrete performance more and more obtains people, particularly in hydro project, road engineering, concrete durability is then had higher requirement, and utilizing cement water reducing agent and air entrapment agent to improve concrete durability has become a kind of important channel of improving concrete performance.The raising concrete durability is mainly reflected in makes concrete have higher freezing and thawing performance, anti-permeability performance reaches lower chloride permeability performance etc.In the cement water reducing agent product, divide normal concrete water reducer, efficient cement water reducing agent, air-entraining concrete water reducer etc.The cement water reducing agent of China is that product is a main flow with naphthalene system and melamine mainly at present, and the bleed high efficiency water reducing agent is not seen as yet, does not have relevant national standard yet.The main drawback of naphthalene system and melamine series concrete water-reducing agent is that bleed is little, produces poor durability.Abroad particularly in Japan, the bleed high efficiency water reducing agent is used widely in water conservancy, road etc. requires the concrete works of high-durability, product type mainly is a maleic anhydride system, promptly utilize chlorallylene or other double bond containing chloric ether and reacting ethylene oxide to insert two keys, react with maleic anhydride again.With Japan is example, the synthetic method of water reducing agents for efficient aerocrote be divided into two the step finish.Concrete steps are as follows:
The first step: behind the nitrogen purge autoclave; under the nitrogen protection condition; make catalyzer with sodium methylate; slowly feed oxyethane in the methyl alcohol in reaction vessel, keep 140 ℃, the reaction down of 0.05～0.5MPa pressure, then; reaction mixture is cooled to room temperature; in reaction vessel, add NaOH, be warming up to 110 ℃, keep the dehydration of 20mmHg pressure.Subsequently, nitrogen pressure is increased to 0.1MPa, slowly in mixture, add a certain amount of chlorallylene and stirring.After 4 hours, when mixture basicity is reduced to a stationary value, can think that reaction stops from the reaction beginning, use the HCl neutralise mixt, the separating by-products salt can obtain allyl ethers, and this is the raw material of next step reaction.
Second the step: with toluene as solvent; under nitrogen protection; in having the reaction vessel of condensation; the allyl ethers that is generated with the first step reaction is a raw material, carries out polyreaction with maleic anhydride, and polymerization temperature is 80 ℃; after stirring makes it to react 4 hours; under 110 ℃, 10mmHg pressure, steam and remove toluene solvant, obtaining transparent viscous liquid is final product.This shows that maleic anhydride series water reducing agents for efficient aerocrote production preparation is very complicated, and reaction process is very high to the requirement of equipment.
Purpose of the present invention is exactly to prepare the water reducing agents for efficient aerocrote that a kind of synthesis technique is simple, reaction conditions is easy to control.
Realize that the synthetic method of polycarboxylic acid series bleed high efficiency water reducing agent of the present invention carries out in two steps:
The first step is by transesterification reaction, and selecting the EO number for use is that the interior methyl Soxylat A 25-7 of 6～12 scopes is a main raw material, and its molecular structural formula is:
Be catalyzer with the tosic acid, be stopper with the Resorcinol, make methyl methacrylate and methyl Soxylat A 25-7 carry out transesterification reaction to introduce polymerizable double bond.Carry out the second step reaction then, add methacrylic acid, be initiator, be that solvent carries out polyreaction with the butanone with the dibenzoyl peroxide.Make product dissolving wiring solution-forming with sodium hydroxide (or potassium hydroxide) solution after finishing.Its composition of raw materials (being more excellent proportioning in the weight percent, bracket) is:
Methyl Soxylat A 25-7: 39～46.2% (42.03%);
Methyl methacrylate: 8.5～15% (9.77%);
Methacrylic acid: 9～16% (15.44%);
Tosic acid: 3～4% (3.91%);
Resorcinol: 0.08～0.13% (0.12%);
Dibenzoyl peroxide: 1.9～3.5% (2.93%);
Butanone: 19～28% (23.45%);
Sodium hydroxide (or potassium hydroxide): 1.9～3.5% (2.35%).
The first step: use methyl methacrylate and methyl Soxylat A 25-7 generation transesterification reaction to introduce two keys on methyl Soxylat A 25-7 long-chain, reaction formula is as follows:
Concrete processing method is:
Methyl Soxylat A 25-7, Resorcinol, tosic acid are put into reaction vessel, under 85 ± 3 ℃ temperature, after stirring is dissolved Resorcinol and tosic acid fully, in container, drip methyl methacrylate, speed is dripped in control, in 15 ± 5 minutes, drip off, maintain the temperature at then in 85 ± 3 ℃ of scopes, reacted 8 ± 0.5 hours.Reaction generates methacrylic acid methyl polyoxyethylene ether-ester, contains polymerizable double bond in its molecular structure.
Second step: with the butanone is that solvent, dibenzoyl peroxide are initiator, makes the reaction product (being methacrylic acid methyl polyoxyethylene ether-ester) and methacrylic acid polymerization reaction take place of the first step.The reaction formula of this step reaction is as follows:
Concrete processing method is as follows:
At first add the 20-30% of butanone total amount in the first step product (being methacrylic acid methyl polyoxyethylene ether-ester), temperature is controlled at 83 ± 3 ℃, stirs.Drip in methacrylic acid methyl polyoxyethylene ether-ester with remaining butanone dissolving methacrylic acid and dibenzoyl peroxide (BPO) back then, with polymerization reaction take place.Speed is dripped in control, makes it to drip off in 1.5 ± 0.5 hours, and control reaction temperature is in 83 ± 3 ℃ of scopes, reacts 3 ± 0.3 hours.After question response finished substantially, underpressure distillation under 80 ± 5 ℃ of conditions desolventized with steaming, obtained transparent red-brown product, the effective constituent of Here it is this bleed type high efficiency water reducing agent.This product is soluble in alkali lye and is insoluble in water, for ease of using and storing, needs dissolve this polymerisate with sodium hydroxide (or potassium hydroxide) solution, and be 40% solution to be mixed with solid content, this is a polycarboxylic acid series water reducing agents for efficient aerocrote of the present invention.
Polycarboxylic acid series water reducing agents for efficient aerocrote of the present invention is that the bleed high efficiency water reducing agent is compared with maleic anhydride, and is with chlorallylene or other double bond containing chloric ether and the two keys of reacting ethylene oxide access, severe reaction conditions, wayward.And the synthetic of polycarboxylic acid series water reducing agents for efficient aerocrote of the present invention is to utilize the methyl Soxylat A 25-7, adopts transesterification reaction to add two keys, and reaction conditions is easy to control.In addition, adopting maleic anhydride is that the mixed argillous air content of bleed high efficiency water reducing agent preparation is generally 4～5%, ultimate compression strength was generally 100～107% of blank sample in 28 days, and the mixed earth that adopts polycarboxylic acid series water reducing agents for efficient aerocrote of the present invention to prepare, when this water reducer addition content be cement weight 1.5% the time, its air content is generally 4～7%, and it is 110～126% of blank sample that water-reducing rate can reach 30%, 28 day ultimate compression strength.
Claims (2)
1. the synthesis technique of a polycarboxylic acid series water reducing agents for efficient aerocrote, it is characterized in that: synthetic method is carried out in two steps, the first step:
Concrete processing method is: methyl Soxylat A 25-7, Resorcinol, tosic acid are put into reaction vessel, under 85 ± 3 ℃ temperature, stirring makes Resorcinol and tosic acid dissolve the back fully, drips methyl methacrylate in container, speed is dripped in control, in 15 ± 5 minutes, drip off, maintain the temperature at then in 85 ± 3 ℃ of scopes, reacted 8 ± 0.5 hours.Reaction generates methacrylic acid methyl polyoxyethylene ether-ester, contains polymerizable double bond in its molecular structure.
Second step:
Concrete processing method is as follows: at first add the 20-30% of butanone total amount in the first step product (being methacrylic acid methyl polyoxyethylene ether-ester), temperature is controlled at 83 ± 3 ℃, stirs.Drip in methacrylic acid methyl polyoxyethylene ether-ester with remaining butanone dissolving methacrylic acid and dibenzoyl peroxide (BPO) back then, with polymerization reaction take place.Speed is dripped in control, makes it to drip off in 1.5 ± 0.5 hours, and control reaction temperature is in 83 ± 3 ℃ of scopes, reacts 3 ± 0.3 hours.After question response finished substantially, underpressure distillation under 80 ± 5 ℃ of conditions desolventized with steaming, obtains polycarboxylic acid series water reducing agents for efficient aerocrote of the present invention.
Composition of raw materials (weight ratio) is:
Methyl Soxylat A 25-7: 39～46.2%;
Methyl methacrylate: 8.5～15%;
Methacrylic acid: 9～16%;
Tosic acid: 3～4%;
Resorcinol: 0.08～0.13%;
Dibenzoyl peroxide: 1.9～3.5%;
Butanone: 19～28%;
Sodium hydroxide (or potassium hydroxide): 1.9～3.5%.
2. the synthesis technique of polycarboxylic acid series water reducing agents for efficient aerocrote according to claim 1, it is characterized in that: composition of raw materials (weight ratio) is:
Methyl Soxylat A 25-7: 42.03%;
Methyl methacrylate: 9.77%;
Methacrylic acid: 15.44%;
Tosic acid: 3.91%;
Resorcinol: 0.12%;
Dibenzoyl peroxide: 2.93%;
Butanone: 23.45%
Sodium hydroxide (or potassium hydroxide): 2.35%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00103594A CN1109004C (en) | 2000-04-04 | 2000-04-04 | Polycarboxylic acid series water reducing agents for efficient aerocrote |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00103594A CN1109004C (en) | 2000-04-04 | 2000-04-04 | Polycarboxylic acid series water reducing agents for efficient aerocrote |
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| Publication Number | Publication Date |
|---|---|
| CN1316398A CN1316398A (en) | 2001-10-10 |
| CN1109004C true CN1109004C (en) | 2003-05-21 |
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| CN00103594A Expired - Fee Related CN1109004C (en) | 2000-04-04 | 2000-04-04 | Polycarboxylic acid series water reducing agents for efficient aerocrote |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250040B (en) * | 2006-03-22 | 2010-12-08 | 西安建筑科技大学 | Concrete used for steel-concrete composite structures with a strength grade of C100 |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102004005434A1 (en) * | 2004-02-04 | 2005-08-25 | Construction Research & Technology Gmbh | Copolymers based on unsaturated mono- or dicarboxylic acid derivatives and oxyalkylene glycol-alkenyl ethers, process for their preparation and their use |
| CN100360455C (en) * | 2004-12-09 | 2008-01-09 | 武汉科技大学 | Polyacrylic acid concrete water reducer and its synthesis process |
| CN1314614C (en) * | 2004-12-10 | 2007-05-09 | 武汉理工大学 | Polycarboxylate concrete water reducer and preparation method thereof |
| CN100358825C (en) * | 2006-01-17 | 2008-01-02 | 武汉理工大学 | Acrylic multi-polymer copolymer high-efficiency water reducer and its synthesis method |
| CN101205128B (en) * | 2007-11-21 | 2010-06-09 | 厦门市建筑科学研究院集团股份有限公司 | Early strength type polycarboxylic acid series high-performance water reducing agent and method for manufacturing same |
| CN101624270B (en) * | 2009-08-03 | 2012-01-04 | 常州汇迪建材有限公司 | High-efficiency polycarboxylic acid series water reducing agent and preparation method thereof |
| CN101792527B (en) * | 2010-01-29 | 2011-11-09 | 辽宁奥克化学股份有限公司 | Polyoxyethylene ether-ester type monomer, synthesis thereof and application in synthesis of water reducing agent |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1035485A (en) * | 1988-01-20 | 1989-09-13 | 山道士有限公司 | Additives for ultra-dry concrete |
| CN1135207A (en) * | 1993-09-29 | 1996-11-06 | 格雷斯公司 | Modified cement additive product with improved rheology and preparation method thereof |
| CN1189473A (en) * | 1996-12-26 | 1998-08-05 | 株式会社日本触媒 | Cement dispersant, method for producing polycarboxylic acid for cement dispersant and cement composition |
-
2000
- 2000-04-04 CN CN00103594A patent/CN1109004C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1035485A (en) * | 1988-01-20 | 1989-09-13 | 山道士有限公司 | Additives for ultra-dry concrete |
| CN1135207A (en) * | 1993-09-29 | 1996-11-06 | 格雷斯公司 | Modified cement additive product with improved rheology and preparation method thereof |
| CN1189473A (en) * | 1996-12-26 | 1998-08-05 | 株式会社日本触媒 | Cement dispersant, method for producing polycarboxylic acid for cement dispersant and cement composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250040B (en) * | 2006-03-22 | 2010-12-08 | 西安建筑科技大学 | Concrete used for steel-concrete composite structures with a strength grade of C100 |
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| CN1316398A (en) | 2001-10-10 |
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