CN1636921A - Concrete water reducing agent of polyacrylic acid and its synthesis process - Google Patents
Concrete water reducing agent of polyacrylic acid and its synthesis process Download PDFInfo
- Publication number
- CN1636921A CN1636921A CNA200410061305XA CN200410061305A CN1636921A CN 1636921 A CN1636921 A CN 1636921A CN A200410061305X A CNA200410061305X A CN A200410061305XA CN 200410061305 A CN200410061305 A CN 200410061305A CN 1636921 A CN1636921 A CN 1636921A
- Authority
- CN
- China
- Prior art keywords
- acrylic acid
- reducing agent
- water reducing
- polyethylene glycol
- concrete water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The concrete water reducing agent of polyacrylic acid is prepared through esterification between polyglycol and acrylic acid to obtain esterified product, and the copolymerization of the esterified product with acrylic acid, 2-acrylamide-2-methyl propenyl sodium sulfonate and other sulfonate with unsaturated double bond. The concrete water reducing agent has weight average molecular weight of 20000-60000, concrete water reducing rate over 35 %, concrete compression strength raised by 100-300 % in 3 days, 40-80 % in 28 days and 30-50 % in 90 days, no loss in 2-hr slump of concrete, raised concrete placeability, etc. and is suitable for matching with flyash, slag and other active admixture to prepare high performance concrete.
Description
Technical Field
The present invention belongs to a polyacrylic acid series high-effective water-reducing agent and its synthesis process.
Background
The acrylic water reducing agent is a third-generation water reducing agent, and cement dispersants such as naphthalenesulfonic acid-formaldehyde condensate salt, melamine sulfonic acid-formaldehyde high condensate salt, sulfanilate, water-soluble ethylene copolymer and the like have been used as cement dispersants for improving fluidity in the past. Concrete mixtures of cement dispersants such as naphthalene sulfonic acid formaldehyde condensate salt, melamine sulfonic acid formaldehyde high condensate salt, sulfanilate and the like have the problems of low water reducing rate and large slump loss; although the water-soluble ethylene copolymer cement dispersant has a small slump loss, the setting time is greatly prolonged, resulting in low early strength. At present, the concrete water reducing agent in China mainly takes naphthalene and melamine as main flow products, and polyacrylic acid concrete high-efficiency water reducing agent is not seen yet; the high-efficiency water reducing agent in Japan, America, Italy and other countries is widely applied to concrete engineering with high durability such as water conservancy, roads, high-rise buildings and the like, and the product types are mainly maleic anhydride series and acrylic acid series.
Japanese patent application laid-open No. 9-286648 discloses that polyoxyethylene (ethylene oxide) (33mol), monomethylmonoallyl ether [ compound A]1.524g (1mol), sodium allylsulfonate 144g (1mol), and anhydrous maleic acid 294g (3mol) were weighed in a four-necked flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas inlet tube, dissolved in 1480g of water, and ammonium persulfate 170g (0.75mol) was added as a polymerization initiator, and reacted at 50. + -. 2 ℃ for 12 hours under a nitrogen atmosphere to obtain a copolymer X.
Japanese patent laid-open No. 2000-233956 discloses that a copolymer A is prepared by adding 150g of water to a glass reaction vessel equipped with a thermometer, a stirrer, a nitrogen introducing tube and a reflux condenser, introducing nitrogen while stirring, heating to 80 ℃ and mixing 0.094mol of methoxypolyethylene glycol methacrylate (average addition modulus of ethylene oxide 23), 0.33mol of methacrylic acid, 0.047mol of methyl methacrylate, 6.7g of a 40% aqueous solution of sodium hydroxide, 1.6g of ammonium persulfate and 135.3g of water to prepare a monomer solution, dissolving 1.1g of β -mercaptopropionic acid in 30g of water, dropping the monomer solution into the reaction vessel together at a constant rate of 2 hours, aging at 80 ℃ for 1 hour, cooling the polymer solution, and neutralizing the polymer solution with a 40% aqueous solution of sodium hydroxide.
Japanese patent laid-open No. 2000-185953 describes that methyl polyethylene glycol (n-68) 605g, 2-isocyanate ethyl methacrylate 31g, and dibutyltin dilaurate 0.6g as a catalyst were put in a reaction vessel and subjected to an addition reaction at 75 ℃ for 3 hours with stirring to obtain methoxypolyethylene glycol (n-68) urethane ethyl methacrylate (A-1). 320 parts (0.1mol) of synthesized methoxypolyethylene glycol (n ═ 68) urethane ethyl methacrylate (A-1), 73 parts (0.85mol) of methacrylic acid, 5.5 parts of 2-thiolactol and 400 parts of water are put into a reaction vessel, 57 parts of 30% NaOH aqueous solution is added, the pH of the reaction system is adjusted to 6, after uniform dissolution, nitrogen is introduced into the reaction vessel, then the system temperature is kept at 60 ℃ by a warm water bath, 80 parts of 10% aqueous solution of 4, 4-azo (4-cyanovalericacid) is added dropwise after 3 hours of polymerization, the reaction is continued for 2 hours, and the polymerization reaction is finished. A part of the obtained product was concentrated by a vaporizer, purified with a mixed solvent, and dried to obtain a water-soluble ethylene copolymer.
As can be seen from the three patents, the production process of the water reducing agent is very complex, and the requirement on equipment in the reaction process is very high.
Disclosure of Invention
The invention aims to provide a polyacrylic acid concrete water reducing agent and a synthesis process thereof.
The weight average molecular weight of the polyacrylic acid concrete water reducing agent for achieving the purpose of the invention is 20000-60000, and the expression is as follows:
in the formula: r represents H, CH3Or SO3Na+；
M represents Na+；
a is an integer of 4-23;
m is an integer of 10-60;
n is an integer of 10 to 60.
The synthesis process of the polyacrylic acid concrete water reducing agent comprises the following two steps:
first-step esterification: the method comprises the following steps of (1) carrying out esterification reaction on polyethylene glycol and acrylic acid with the polymerization degree of 5-40 at 80-90 ℃ for 8 +/-0.5 hours by taking p-toluenesulfonic acid or concentrated sulfuric acid as a catalyst, hydroquinone as a polymerization inhibitor and cyclohexane as a water removing agent to generate polyethylene glycol monopropenyl ester, wherein the reaction formula is as follows:
the second step of copolymerization: using water as a solvent, ammonium persulfate as an accelerant and mercaptoethanol as a chain transfer agent, carrying out copolymerization reaction on polyethylene glycol mono-acrylate, acrylic acid and 2-acrylamide-2-sodium methylacrylsulfonate which are reaction products in the first step at the temperature of 85 +/-5 ℃, slowly adding a mixed solution of the polyethylene glycol mono-acrylate, the acrylic acid, the 2-acrylamide-2-sodium methylacrylsulfonate and a mixed solution of the ammonium persulfate and the mercaptoethanol for 2 +/-0.5 hours respectively, continuously reacting for 6 hours, cooling to room temperature, neutralizing with sodium hydroxide or calcium oxide until the pH value is 7, and obtaining the polyacrylic concrete high-efficiency water reducer, wherein the reaction formula is as follows:
R2-(CH＝CH)-COO-(-C2H4O-)n-R1+R2-(CH＝CH)-COOH+CH3CH＝CCOOH→
in the formula: r represents H, CH3Or SO3Na；
R1，R2Representative H, CH3；
M represents Na+；
a is an integer of 4-23;
m is an integer of 10-60;
n is an integer of 10 to 60
In the first-step esterification reaction, the molar ratio of polyethylene glycol to acrylic acid is 1: 1.0-1.5, the dosage of p-toluenesulfonic acid is 1-5 wt% of the dosageof acrylic acid, the dosage of hydroquinone is 0.2-1.0 wt% of the dosage of polyethylene glycol and acrylic acid, and cyclohexane accounts for 50-80 wt% of the total mass of all raw materials; the second step polymerization reaction comprises the following raw materials in percentage by mole: 15-65% of polyethylene glycol monomer; 45-75% of acrylic acid; 5-25% of 2-acrylamide-2-sodium methylacrylsulfonate or sodium allylsulfonate; the using amount of ammonium persulfate is 1-3 wt% of that of acrylic acid; the using amount of the mercaptoethanol serving as the chain transfer agent is 5-15% of that of the acrylic acid.
The first step esterification reaction time is 8 plus or minus 0.5 hour.
The second-step copolymerization reaction time is 8 plus or minus 0.5 hour.
The molar ratio of the polyethylene glycol to the acrylic acid in the first esterification reaction is 1: 1.2.
The dosage of the p-toluenesulfonic acid in the first-step esterification reaction is 3 wt% of that of the acrylic acid.
The dosage of the hydroquinone in the first step of esterification reaction is 0.5 wt% of the dosage of the polyethylene glycol and the acrylic acid.
The second step polymerization reaction raw materials have the following mole percentages: 25% of polyethylene glycol monomer, 65% of acrylic acid, and 10% of 2-acrylamide-2-sodium methyl acrylate or sodium propylene sulfonate.
The using amount of ammonium persulfate in the second-step polymerization reaction is 2 wt% of that of acrylic acid.
The using amount of the chain transfer agent mercaptoethanol in the second-step polymerization reaction is 8 wt% of that of the acrylic acid.
Compared with water-soluble ethylene copolymer, maleic anhydride and other acrylic acid high-efficiency water reducing agents, the polyacrylic acid concrete water reducing agent has the advantages that the reaction conditions of the latter are harsh, the water-soluble ethylene copolymer, the maleic anhydride and other acrylic acid high-efficiency water reducing agents are synthesized under the protection of nitrogen, and the raw material addition in the synthesis process is complex and is not easy to control. The polyacrylic acid concrete high-efficiency water reducing agent is synthesized by using polyethylene glycol, adding double bonds by adopting an ester exchange reaction, and then copolymerizing with acrylic acid, 2-acrylamide-2-sodium methylacrylsulfonate or sodium allylsulfonate, so that nitrogen protection is not needed, the reaction temperature is constant, the charging procedure is simple, and the reaction conditions are easy to control. When the mixing amount of the water reducing agent with the concentration of 30 wt% is 0.6% of the weight of cement, the slump of a concrete mixture can reach 18 cm; when the mixing amount is 1.2%, the water reducing rate can reach 30%, the 3-day compressive strength of the concrete is improved by 50-120%, the 28-day compressive strength is improved by 40-80%, and the 90-day compressive strength is improved by 30-50%; the slump loss resistance is high, the slump of the concrete is basically not lost after 2 hours, and the influence of temperature change is hardly caused; the workability is good, the bleeding resistance and the segregation resistance are good, the concrete pumping resistance is small, and the conveying is convenient; the concrete surface has no drainage line, no large air bubbles, small color difference and good appearance quality of the concrete; the alkali content is low; the paint does not contain chloride ions and has no corrosion to the reinforcing steel bars; the freeze thawing resistance and the carbonization resistance are obviously improved compared with common concrete; the 28-day shrinkage of the concrete is reduced by more than 20 percent compared with the naphthalene-based high-efficiency water reducing agent; the product has strong adaptability, is suitable for cement with various specifications and models, and is particularly suitable for preparing high-performance concrete with high strength, high durability, self-compaction and the like by being compatible with active admixtures such as high-quality fly ash, slag and the like; the product has stable performance, no delamination and no precipitation after long-term storage, and no crystallization in winter; the product has the advantages of no toxicity, no pollution, no formaldehyde, safety to the environment and the like.
Drawings
FIG. 1 is a flow chart of the synthetic process of the polyacrylic acid concrete water reducer of the present invention.
The figure shows that: in the presence of p-toluenesulfonic acid, polyethylene glycol reacts with acrylic acid to generate polyethylene glycol monoacrylate, the mixture of the polyethylene glycol monoacrylate and the acrylic acid with 2-acrylamide-2-sodium methylacrylsulfonate, ammonium persulfate and mercaptoethanol are respectively and slowly added to carry out polymerization reaction, and then sodium hydroxide or calcium oxide is used for neutralization to prepare the polyacrylic acid concrete water reducer with the concentration of 30 wt%.
Detailed Description
The proportions of the reactants in the following examples are as follows:
the raw material formula in the esterification reaction is as follows:
the molar ratio of the polyethylene glycol to the acrylic acid is 1: 1.0-1.5, preferably 1: 1.2,
the dosage of the p-toluenesulfonic acid is 1-5 wt% of that of the acrylic acid, and the optimal dosage is 3 wt%
The dosage of the hydroquinone is 0.2 to 1.0wt percent of the total amount, and the optimal dosage is 0.5wt percent;
the cyclohexane accounts for 50-80 wt% of the total mass of all the raw materials; most preferably 80 wt%;
the raw materials in the polymerization reaction are in mole percentage:
15-45% of polyethylene glycol monomer, preferably 25%;
50-75% of acrylic acid, and preferably 65%;
5-25% of 2-acrylamide-2-sodium methylacrylsulfonate or sodium allylsulfonate, preferably 10%;
the using amount of ammonium persulfate is 1-3 wt% of that of acrylic acid, and the best is 2 wt%;
the using amount of the mercaptoethanol is 3-15 wt% of that of the acrylic acid, and the best is 8 wt%
Example 1: taking the best proportion
Putting 40.00g of polyethylene glycol with the molecular weight of 400, 8.4g of acrylic acid, 0.25g of hydroquinone, 1.5g of p-toluenesulfonic acid and 200g of cyclohexane into a reaction container, stirring at the temperature of 60 ℃, keeping the temperature at 80-90 ℃ for reacting for 8 hours after the hydroquinone and the p-toluenesulfonic acid are completely dissolved, filtering, and vacuumizing to remove the cyclohexane to obtain polyethylene glycol monoacrylate; 54.41g of water is added into a three-neck flask, the temperature is controlled at 85 +/-5 ℃, then 46.80g of the esterification product of the first step, 14g of acrylic acid and 9.16g of sodium 2-acrylamide-2-methylacrylsulfonate are added into 54.41g of water to be dissolved and mixed for dripping, 1.19g of ammonium persulfate and 1.62gof mercaptoethanol are dissolved into 54.41g of water, the three are respectively dripped into the three-neck flask at a controlled speed, the dripping is finished within 2 +/-0.5 hours, and the reaction is continued for 6 hours. After the reaction is finished, cooling to room temperature, and neutralizing by using sodium hydroxide until the pH value is 7 to obtain the polyacrylic acid concrete high-efficiency water reducing agent.
Example 2:
putting 40.00g of polyethylene glycol with the molecular weight of 400, 10.5g of acrylic acid, 0.26g of hydroquinone, 2.65g of p-toluenesulfonic acid and 210g of cyclohexane into a reaction container, stirring at the temperature of 60 ℃, keeping the temperature at 80-90 ℃ for reacting for 8 hours after the hydroquinone and the p-toluenesulfonic acid are completely dissolved, filtering, and vacuumizing to remove the cyclohexane to obtain polyethylene glycol monoacrylate; 55.84g of water is added into a three-neck flask, the temperature is controlled at 85 +/-5 ℃, then 46.80g of the esterification product in the first step, 14g of acrylic acid and 10.99g of sodium 2-acrylamide-2-methylacrylsulfonate are added into 55.84g of water to be dissolved and mixed for dripping, 1.19g of ammonium persulfate and 1.62g of mercaptoethanol are dissolved into 55.84g of water, the three are respectively dripped into the three-neck flask at a controlled speed, the dripping is finished within 2 +/-0.5 hours, and the reaction is continued for 6 hours. After the reaction is finished, cooling to room temperature, and neutralizing by using sodium hydroxide until the pH value is 7 to obtain the polyacrylic acid concrete high-efficiency water reducing agent.
Example 3:
putting 40.00g of polyethylene glycol with the molecular weight of 400, 8.4g of acrylic acid, 0.25g of hydroquinone, 1.51g of p-toluenesulfonic acid and 200g of cyclohexane into a reaction container, stirring at the temperature of 60 ℃, keeping the temperature at 110-115 ℃ for 8 +/-0.5 hours after the hydroquinone and the p-toluenesulfonic acid are completely dissolved, filtering, and vacuumizing to remove the cyclohexane to obtain polyethylene glycol monomethacrylate; 60.92g of water is added into a three-neck flask, the temperature is controlled to be 85 +/-5 ℃, then 46.80g of esterification product in the first step, 22.36g of acrylic acid and 9.16g of sodium 2-acrylamide-2-methyl-propenesulfonate are added with 60.92g of water to be dissolved and mixed, 60.92g of water is used to dissolve 1.19g of ammonium persulfate and 1.62g of mercaptoethanol, the three are respectively dripped into the three-neck flask at a controlled speed, the three are dripped within 2 +/-0.5 hours, and the reaction is continued for 6 hours. After the reaction is finished, cooling to room temperature, and neutralizing by using sodium hydroxide until the pH value is 7 to obtain the polyacrylic acid concrete high-efficiency water reducing agent.
Claims (11)
1. The utility model provides a polyacrylic acid concrete water reducing agent, characterized by weight average molecular weight is 20000 ~ 60000, and the expression is:
in the formula: r represents H, CH3Or SO3Na+；
M represents Na+；
a is an integer of 4-23;
m is an integer of 10-60;
n is an integer of 10 to 60.
2. The synthesis process of the polyacrylic acid series concrete water reducing agent according to claim 1, characterized in that the synthesis method comprises two steps:
first-step esterification: the method comprises the following steps of carrying out esterification reaction at 80-90 ℃ by using p-toluenesulfonic acid or concentrated sulfuric acid as a catalyst, hydroquinone as a polymerization inhibitor and cyclohexane as a water removing agent and using polyethylene glycol with the polymerization degree of 5-40 and acrylic acid to generate polyethylene glycol monopropylene ester, wherein the reaction formula is as follows:
the second step of copolymerization: using water as a solvent, ammonium persulfate as an accelerator and mercaptoethanol as a chain transfer agent, carrying out copolymerization reaction on polyethylene glycol monoallyl ester, acrylic acid, 2-acrylamide-2-sodium methylacrylsulfonate or sodium allylsulfonate at 85 +/-5 ℃, finishing the addition of the polyethylene glycol monoallyl ester, the acrylic acid, the 2-acrylamide-2-sodium methylacrylsulfonate, the ammonium persulfate and the mercaptoethanol in 2 +/-0.5 hours respectively, cooling to room temperature, and neutralizing with sodium hydroxide or calcium oxide until the pH value is 7 to obtain the polyacrylic acid concrete water reducer, wherein the reaction formula is as follows:
in the formula: r represents H, CH3Or SO3Na+；
R1，R2Representative H, CH3；
M represents Na+；
a is an integer of 4-23;
m is an integer of 10-60;
n is an integer of 10 to 60.
3. The process for synthesizing the polyacrylic acid series concrete water reducing agent according to claim 2, wherein in the first step of esterification reaction, the molar ratio of polyethylene glycol to acrylic acid is 1: 1.0-1.5, the dosage of p-toluenesulfonic acid is 1-5 wt% of the dosage of polyethylene glycol and acrylic acid, the dosage of hydroquinone is 0.2-1.0 wt% of the dosage of polyethylene glycol and acrylic acid, and cyclohexane accounts for 50-80 wt% of the total mass of all raw materials; the second step is that the mole percentage of the raw materials of the polymerization reaction is 15-65% of polyethylene glycol monomer; 45-75% of acrylic acid; 5-25% of 2-acrylamide-2-sodium methylacrylsulfonate or sodium allylsulfonate; the using amount of ammonium persulfate is 1-3 wt% of that of acrylic acid; the amount of the mercaptoethanol is 5-15 wt% of that of the acrylic acid.
4. The process for synthesizing a polyacrylic acid series concrete water reducing agent according to claim 2, wherein the esterification reaction time of the first step is 8 ± 0.5 hours.
5. The process for synthesizing a polyacrylic acid series concrete water reducing agent according to claim 2, wherein the time of the second step copolymerization reaction is 8 ± 0.5 hours.
6. The process for synthesizing a polyacrylic acid series concrete water reducing agent according to claim 3, wherein the molar ratio of the polyethylene glycol to the acrylic acid in the first esterification reaction is 1: 1.2.
7. The process for synthesizing a polyacrylic acid series concrete water reducing agent according to claim 3, wherein the amount of p-toluenesulfonic acid used in the first esterification reaction is 3 wt% of the amount of acrylic acid.
8. The process for synthesizing the polyacrylic acid series concrete water reducing agent according to claim 3, wherein the amount of hydroquinone in the first esterification reaction is 0.5 wt% of the amount of the polyethylene glycol and the acrylic acid.
9. The process for synthesizing the polyacrylic acid series concrete water reducing agent according to claim 3, wherein the mole percentage of the raw materials in the second step of polymerization reaction is as follows: 25% of polyethylene glycol monomer, 65% of acrylic acid, and 10% of 2-acrylamide-2-sodium methyl acrylate or sodium propylene sulfonate.
10. The process for synthesizing polyacrylic acid series concrete water reducing agent according to claim 3, wherein the amount of ammonium persulfate in the second polymerization step is 2 wt% of the amount of acrylic acid.
11. The process for synthesizing polyacrylic acid series concrete water reducing agent according to claim 3, wherein the amount of mercaptoethanol used in the second polymerization step is 8 wt% of the amount of acrylic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410061305XA CN100360455C (en) | 2004-12-09 | 2004-12-09 | Concrete water reducing agent of polyacrylic acid and its synthesis process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410061305XA CN100360455C (en) | 2004-12-09 | 2004-12-09 | Concrete water reducing agent of polyacrylic acid and its synthesis process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1636921A true CN1636921A (en) | 2005-07-13 |
| CN100360455C CN100360455C (en) | 2008-01-09 |
Family
ID=34846317
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200410061305XA Expired - Fee Related CN100360455C (en) | 2004-12-09 | 2004-12-09 | Concrete water reducing agent of polyacrylic acid and its synthesis process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100360455C (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100432116C (en) * | 2007-04-24 | 2008-11-12 | 陕西科技大学 | Method for preparing pumping agent of environmental protective vinyl class in polymer type |
| CN100457796C (en) * | 2006-10-11 | 2009-02-04 | 重庆大学 | Poly carboxylic acid series super plasticizer and its preparing method |
| CN100463872C (en) * | 2006-11-23 | 2009-02-25 | 苏州夏诺高分子技术有限公司 | Preparation method of polycarboxylate water reducing agent |
| CN101475664B (en) * | 2009-01-16 | 2010-09-22 | 北京工业大学 | Preparation of polycarboxylic acid water reducing agent for prefabricated part |
| CN101906209A (en) * | 2010-07-30 | 2010-12-08 | 武汉科技大学 | Method for synthesizing polyethylene glycol monomethacrylate from solid superacid by catalytic esterification |
| CN1919924B (en) * | 2005-08-26 | 2012-02-22 | 建筑技术研究有限公司 | Powdery polymer composition based on polyether carboxylate |
| CN101787137B (en) * | 2010-01-28 | 2012-02-29 | 同济大学 | Polycarboxylic water reducer having reducing function, synthesis method and application method thereof |
| CN102976654A (en) * | 2012-12-04 | 2013-03-20 | 江苏苏博特新材料股份有限公司 | Polycarboxylic superplasticizer and application thereof |
| CN104108896A (en) * | 2013-04-17 | 2014-10-22 | 湖南德兆建材科技有限公司 | Polycarboxylic acid ceramic plasticizer and preparation method thereof |
| CN105060761A (en) * | 2015-07-26 | 2015-11-18 | 尹红 | Water reducing agent for concrete |
| CN109400821A (en) * | 2018-11-02 | 2019-03-01 | 四川同舟化工科技有限公司 | A kind of agent on crack resistance of concrete bleeding inhibitor and preparation method thereof with diminishing function |
| CN111117632A (en) * | 2019-12-24 | 2020-05-08 | 陈红喜 | Preparation method of salt-tolerant water-retaining agent |
| CN112110670A (en) * | 2020-09-23 | 2020-12-22 | 四川鼎德商品混凝土有限公司 | Preparation method of segregation-resisting agent for concrete and product thereof |
| CN114805824A (en) * | 2022-05-06 | 2022-07-29 | 苏光伟 | Multifunctional concrete additive and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1109004C (en) * | 2000-04-04 | 2003-05-21 | 北京市建筑材料科学研究院 | Polycarboxylic acid series water reducing agents for efficient aerocrote |
| CN1093095C (en) * | 2000-11-07 | 2002-10-23 | 复旦大学 | Efficient carboxilic acid grafting water-reducing agent and its synthesis |
-
2004
- 2004-12-09 CN CNB200410061305XA patent/CN100360455C/en not_active Expired - Fee Related
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1919924B (en) * | 2005-08-26 | 2012-02-22 | 建筑技术研究有限公司 | Powdery polymer composition based on polyether carboxylate |
| CN100457796C (en) * | 2006-10-11 | 2009-02-04 | 重庆大学 | Poly carboxylic acid series super plasticizer and its preparing method |
| CN100463872C (en) * | 2006-11-23 | 2009-02-25 | 苏州夏诺高分子技术有限公司 | Preparation method of polycarboxylate water reducing agent |
| CN100432116C (en) * | 2007-04-24 | 2008-11-12 | 陕西科技大学 | Method for preparing pumping agent of environmental protective vinyl class in polymer type |
| CN101475664B (en) * | 2009-01-16 | 2010-09-22 | 北京工业大学 | Preparation of polycarboxylic acid water reducing agent for prefabricated part |
| CN101787137B (en) * | 2010-01-28 | 2012-02-29 | 同济大学 | Polycarboxylic water reducer having reducing function, synthesis method and application method thereof |
| CN101906209A (en) * | 2010-07-30 | 2010-12-08 | 武汉科技大学 | Method for synthesizing polyethylene glycol monomethacrylate from solid superacid by catalytic esterification |
| CN101906209B (en) * | 2010-07-30 | 2012-05-30 | 武汉科技大学 | Method for synthesizing polyethylene glycol monomethacrylate from solid superacid by catalytic esterification |
| CN102976654A (en) * | 2012-12-04 | 2013-03-20 | 江苏苏博特新材料股份有限公司 | Polycarboxylic superplasticizer and application thereof |
| CN102976654B (en) * | 2012-12-04 | 2014-12-10 | 江苏苏博特新材料股份有限公司 | Polycarboxylic superplasticizer and application thereof |
| CN104108896A (en) * | 2013-04-17 | 2014-10-22 | 湖南德兆建材科技有限公司 | Polycarboxylic acid ceramic plasticizer and preparation method thereof |
| CN105060761A (en) * | 2015-07-26 | 2015-11-18 | 尹红 | Water reducing agent for concrete |
| CN106396464A (en) * | 2015-07-26 | 2017-02-15 | 常熟市谷雷特机械产品设计有限公司 | Water reducing agent used for concrete |
| CN105060761B (en) * | 2015-07-26 | 2017-03-22 | 大田县伊鑫新型材料有限公司 | Water reducing agent for concrete |
| CN106396464B (en) * | 2015-07-26 | 2018-05-15 | 江苏中砼新材料科技有限公司 | A kind of concrete water-reducing agent |
| CN109400821A (en) * | 2018-11-02 | 2019-03-01 | 四川同舟化工科技有限公司 | A kind of agent on crack resistance of concrete bleeding inhibitor and preparation method thereof with diminishing function |
| CN111117632A (en) * | 2019-12-24 | 2020-05-08 | 陈红喜 | Preparation method of salt-tolerant water-retaining agent |
| CN112110670A (en) * | 2020-09-23 | 2020-12-22 | 四川鼎德商品混凝土有限公司 | Preparation method of segregation-resisting agent for concrete and product thereof |
| CN114805824A (en) * | 2022-05-06 | 2022-07-29 | 苏光伟 | Multifunctional concrete additive and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100360455C (en) | 2008-01-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1308257C (en) | Water reducing agent of poly carboxylic acid series concrete and its preparation process | |
| CN1330600C (en) | Maleic acid anhydride series concrete water-reducing agent and preparation process thereof | |
| CN1636921A (en) | Concrete water reducing agent of polyacrylic acid and its synthesis process | |
| CN111592619B (en) | Starch-based polycarboxylate superplasticizer mate, and preparation method and application method thereof | |
| CN110642993B (en) | Preparation method of retarding ether polycarboxylate superplasticizer | |
| CN1300198C (en) | Polyacrylic acid salts shrinkage-reducing-agent and method for making same | |
| CN101538134A (en) | Polyether class polycarboxylic acid high-efficiency water reducing agent and preparation method thereof | |
| CN111234095B (en) | Method for preparing polycarboxylate superplasticizer by using C6 monomer | |
| CN101244907A (en) | Polycarboxylic acids series concrete high efficiency water reducing agent and synthesizing process | |
| CN114195421A (en) | Preparation method of polycarboxylic acid admixture for machine-made sand concrete | |
| CN100457796C (en) | Poly carboxylic acid series super plasticizer and its preparing method | |
| CN107337769B (en) | Slump-retaining type polycarboxylate superplasticizer and preparation method thereof | |
| CN106084147B (en) | Preparation method of shrinkage reducing agent with water reducing performance | |
| CN101056897A (en) | Anion polymers | |
| JP3327809B2 (en) | Cement dispersant, method for dispersing cement and cement composition | |
| CN102718427B (en) | Sulfonyl modified carboxylic acid water-reducing agent and preparation method thereof | |
| US20060254469A1 (en) | Additive for hydraulic material and concrete composition | |
| CN1314614C (en) | Concrete water reducing agent of polycarboxylic acid and its prepn process | |
| CN1948209A (en) | Method of preparing poly carboxylic acid series water reducer using maleic anhydride | |
| CN102731730A (en) | Hydrogen peroxide auxiliarily-initiated carboxylic acid water reducer and its preparation method | |
| CN111592264A (en) | Dicarboxyl sulfonic acid group polycarboxylic acid water reducing agent and preparation method thereof | |
| CN114656600A (en) | Preparation method of high-solid-content early-strength polycarboxylate superplasticizer | |
| CN109503774B (en) | A kind of polycarboxylate water-reducer that temperature sensitivity is small | |
| CN114478939B (en) | Slow-release polycarboxylate superplasticizer and preparation method thereof | |
| CN1800076A (en) | Acrylic acid series multiple copolymer analog high efficiency water reducing agent and its synthesis method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080109 Termination date: 20101209 |