CN101486783A - Preparation of vinyl aromatic polyether grafting concrete superplasticiser - Google Patents
Preparation of vinyl aromatic polyether grafting concrete superplasticiser Download PDFInfo
- Publication number
- CN101486783A CN101486783A CNA2009101110845A CN200910111084A CN101486783A CN 101486783 A CN101486783 A CN 101486783A CN A2009101110845 A CNA2009101110845 A CN A2009101110845A CN 200910111084 A CN200910111084 A CN 200910111084A CN 101486783 A CN101486783 A CN 101486783A
- Authority
- CN
- China
- Prior art keywords
- preparation
- vinyl aromatic
- aromatic polyether
- sulfonation
- weight ratio
- 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
Abstract
The invention discloses a method for preparing vinyl aromatic line polyether graft concrete superplasticizer which is prepared by using the following steps: (1) esterification: catalytic esterification is carried out to chemtura alkyl diol monoalkyl ether and maleic anhydride for obtaining an esterification product; (2) copolymerization: under the action of initiator, the esterification product, vinyl aromatic monomer and vinyl acetate are copolymerized for obtaining a polymerization product; (3) sulfonation reaction: under the action of sulfonation reagent, two sections of sulfonation reaction (low-temperature and high-temperature sulfonation) are carried out to the polymerization product for obtaining a sulfonation product; and (4) neutral reaction: the pH value of the sulfonation product is adjusted to be 7-8, and then diluted by water for obtaining the concrete superplasticizer with certain concentration. The invention can adjust product performance by controlling the product structure, does not use solvent in the process of reaction, is non-toxic and non-polluting, is safe to the environment, and has stable product performance, better security and water reducing property.
Description
Technical field
The present invention relates to a kind of concrete superplasticizer, refer to a kind of preparation method of vinyl aromatic polyether grafting concrete superplasticiser especially.
Background technology
When concrete batching, the amount ratio of water and cement (water cement ratio) is a pair of contradiction.The consolidating material total amount is big in the high performance concrete, thereby water requirement can increase.On the other hand, in order to improve density and intensity, must reduce water cement ratio.The consequence that cement consumption increases and water cement ratio reduces makes concrete viscosity increase the rheological variation exactly.Solve the effective and the most real approach of above-mentioned contradiction at present and mix superplasticizer exactly.It is mobile and not remarkably influenced air content under the situation that water cement ratio remains unchanged, can improve workability that superplasticizer can increase grout; Or same workability, the concrete water amount is reduced, improve concrete strength.
Most of in the market poly carboxylic acid series super plasticizers use big monomer as main synthesis material.Big monomer mainly contains two classes, be respectively methacrylic acid and methoxy polyethylene glycol methacrylate-styrene polymer macromonomer multipolymer and maleic anhydride and allyl alcohol polyethylene glycols macromonomer copolymer, its molecular structure all is a comb type grafting long-chain macromolecule, have intensive hydroxy-acid group on the main chain, have the nonionic polyethylene chain on the side chain.And along with going deep into that poly carboxylic acid is studied, new big monomeric synthetic people's the interest that caused gradually.
Chinese patent publication number CN1792960A, discussed elder generation methoxy poly (ethylene glycol) and maleic anhydride reaction have been generated maleic anhydride methoxy poly (ethylene glycol) ester monomer, utilize synthetic monomer and the copolymerization of 2-acrylamide-2 methyl-propyl sodium sulfonate, the synthetic maleic anhydride series concrete superplasticizer that has carboxyl, sulfonic group and polyoxyethylene chain side chain.Chinese patent publication number CN1948209A, the polyoxyethylene glycol esterified object of maleic anhydride of having discussed gained obtains product with the mixture and vinylformic acid, the methylpropene sodium sulfonate that remain maleic anhydride after 85 ℃ of following copolymerization.Above synthetic method all is earlier by the big monomer of preparation maleic anhydride pol yalkylene glycol monoalkyl ether, after aqueous solution copolymerization obtains product, but need in the reaction process to use cost an arm and a leg, active big unsaturated sulfonic acid thing, the cost height.
The styrene group and the strong polar anhydride group of low-pole are arranged in the Zelan 338 molecular structure, be linear alternate copolymer.The regular styrene group that distributing on the main chain, thus can be easy to be sulfonated the introducing sulfonic acid group; A large amount of anhydride groups can be converted into hydroxy-acid group.Graft modification to Zelan 338 prepares high-performance water reducing agent, has also caused people's interest.
Chinese patent publication number CN1712381A has discussed 1, prepares Zelan 338 in the 2-ethylene dichloride, and after sulfonation and graft polyether side chain obtain superplasticizer; Chinese patent publication number CN101104696A has discussed polystyrene-maleic anhydride and methoxy poly (ethylene glycol) have been carried out esterification earlier in solvent, then obtains product through aftertreatment.Above synthetic method all is earlier by the preparation Zelan 338, graft polyether side chain then, but in preparation process, need to use solvent, on environmental protection and economy, exist not enough.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of vinyl aromatic polyether grafting concrete superplasticiser, this preparation method is in reaction process, in molecular structure, introduce vi-ny l aromatic monomers with anhydride group and polyethers long-chain, utilize two sections sulfonation to prepare the superplasticizer of high sulfonic acid group, its main process is under condition of no solvent, prepare maleic anhydride pol yalkylene glycol monoalkyl ether esterification products by esterification, back esterification products and vi-ny l aromatic monomers, vinyl acetate carries out copolyreaction, prepares vinyl aromatic polyether grafting concrete superplasticiser by two sections sulfonation reactions at last.
For solving the problems of the technologies described above, technical solution of the present invention is:
A kind of preparation method of aromatic vinyl polyether-type polycarboxylic acid super-plasticizer may further comprise the steps:
(1) esterification: under the nitrogen protection, pol yalkylene glycol monoalkyl ether, maleic anhydride, stopper are placed reactor, stirring heating heats up; Wherein the weight ratio of pol yalkylene glycol monoalkyl ether and maleic anhydride is 2:1～6:1, prescribes a time limit when this ratio is higher than, and maleic anhydride is more than needed, and cost rises, and when being lower than down in limited time, esterification yield can descend; The weight ratio of maleic anhydride and stopper is 200:1～100:1; Be warming up to 50～70 ℃, allow pol yalkylene glycol monoalkyl ether and maleic anhydride melt, add catalyzer, the weight ratio of catalyzer and pol yalkylene glycol monoalkyl ether is 3:100～3:50; Be warming up to 80～110 ℃, react after 1～3 hour, obtain esterification products.
Described pol yalkylene glycol monoalkyl ether is a kind of in poly glycol monomethyl ether, polyethyleneglycol ether, polypropylene glycol monomethyl ether, the polypropylene glycol list ether.
Described stopper is a kind of in 2,6 ditertiary butyl p cresol, the Ursol D.
Described catalyzer is a kind of in sulfuric acid, phosphoric acid, the tosic acid.
(2) copolyreaction: in the reactor that contains esterification products, add vi-ny l aromatic monomers, vinyl acetate and initiator, stir and obtain three's mixture, the weight ratio of maleic anhydride is 1:1～3:1 in vi-ny l aromatic monomers and the step (1), the weight ratio of vinyl acetate and vi-ny l aromatic monomers is 1:10～1:30, and the weight ratio of initiator and vi-ny l aromatic monomers is 1:25～1:10; Maintain the temperature at 80～110 ℃, react after 2～4 hours, obtain copolymerization product.
Described vi-ny l aromatic monomers is vinylbenzene, alpha-methyl styrene, 1,1, and a kind of in 2-diphenylethlene, 2-vinyl naphthalene, the 9-vinyl anthracene.
Described initiator is a kind of in the special butyl ester of dibenzoyl peroxide, peroxidation phenylformic acid, the di-isopropyl peroxydicarbonate.
(3) sulfonation reaction: (purpose that adds dewatering agent is in order to make the sulfonation better effects if to add dewatering agent in copolymerization product, can improve sulphonation rate, if do not add dewatering agent, then the sulfonation time can be longer, and use the consumption of sulphonating agent to increase), stir after 10～20 minutes, begin to drip sulphonating agent, carry out low-temperature sulfonation, the weight ratio of vi-ny l aromatic monomers is 1:50 in dewatering agent and the step (2), and the weight ratio of vi-ny l aromatic monomers is 1:1 in sulphonating agent and the step (2); React after 1～4 hour, be warming up to 120～160 ℃ (temperature is also unsuitable too high, too high then can carbonization) herein, add sulphonating agent, carry out the high temperature sulfonation, the weight ratio of the middle vi-ny l aromatic monomers of sulphonating agent and step (2) is 2:1～4:1; Continue reaction 2～6 hours, stopped reaction is cooled to room temperature, obtains sulfonated products.
Described dewatering agent is a kind of in Vanadium Pentoxide in FLAKES, the boron trioxide.
Described sulphonating agent is a kind of in the vitriol oil, sulphur trioxide, chlorsulfonic acid, acetylsulfuric acid salt, hexanoyl vitriol, the lauroyl vitriol.
Ending to this step, just obtained the concrete superplasticizer, but the shelf time is shorter, probably is about a week, that is to say that the concrete superplasticizer by the above-mentioned steps preparation needs to use within a week.
In order to improve the shelf time, also need increase step (4) neutralization reaction: regulate pH to 7～8 with alkali lye, thin up obtains vinyl aromatic polyether grafting concrete superplasticiser.
Described alkali lye is a kind of in sodium hydroxide, potassium hydroxide, the calcium hydroxide.
After adopting such scheme, the present invention has following advantage:
1, can control the final product structure by the condition of each step reaction of control, be beneficial to regulate product performance.
2, it is stable to be made into behind the aqueous solution product performance, not stratified during storage, do not precipitate.
3, in the preparation superplasticizer process, do not use solvent, nontoxic pollution-free, advantage such as environmentally safe.
4, adopt maleic anhydride as raw material, in the superplasticizer molecular structure, introduce the carboxylic acid anhydride group, slump retaining is preferably arranged; And maleic anhydride is cheap, helps reducing the cost of superplasticizer, realizes suitability for industrialized production easily.
5, adopt low-temperature sulfonation and two sections sulfonation methods of high temperature sulfonation bonded, sulfonation is thorough, can introduce more sulfonate group on the aromatic ring in the superplasticizer molecular structure, and the anhydride bond after the sulfonation kept, and water reducing ability is preferably arranged.
Embodiment
The invention will be further described below in conjunction with specific embodiment.
Embodiment 1
Under the nitrogen protection, be 600 poly glycol monomethyl ether 60.00g with molecular weight, maleic anhydride 10.00g, 2,6 ditertiary butyl p cresol 0.05g join in the reactor, and stirring heating when being warming up to 60 ℃, adds sulfuric acid 1.80g.Continue to be warming up to 80 ℃, behind reaction 2h under this temperature, obtain esterification products.In containing the reactor of esterification products, add vinylbenzene 10.00g, vinyl acetate 0.50g, initiator dibenzoyl peroxide 0.40g.Behind the reaction 4h, obtain copolymerization product under 80 ℃.
Add dewatering agent Vanadium Pentoxide in FLAKES 0.20g in the copolymerization product, stir and dewatering agent was uniformly dispersed in 15 minutes.Under 80 ℃, drip vitriol oil 10.00g.React after two hours, be warming up to 120 ℃, add acetylsulfuric acid salt 40.00g.After continuing reaction 2h, stopped reaction is cooled to room temperature, obtains sulfonated products.With mass concentration is that 30% sodium hydroxide solution is regulated pH to 7～8, and thin up to massfraction is 20%, promptly gets vinyl aromatic polyether grafting concrete superplasticiser.
Embodiment 2
Under the nitrogen protection, be 1200 polypropylene glycol list ether 120.00g with molecular weight, maleic anhydride 60.00g, Ursol D 0.30g joins in the reactor, and stirring heating when being warming up to 60 ℃, adds sulfuric acid 6.00g.Continue to be warming up to 90 ℃, obtaining esterification products behind the reaction 2h under this temperature.In containing the reactor of esterification products, add 9-vinyl anthracene 60.00g, vinyl acetate 2.0g, initiator dibenzoyl peroxide 5.40g.Behind the reaction 3h, obtain copolymerization product under 90 ℃.
Add dewatering agent Vanadium Pentoxide in FLAKES 1.20g in the copolymerization product, stir and dewatering agent was uniformly dispersed in 15 minutes.Under 80 ℃, drip chlorsulfonic acid 60.0g.React after two hours, be warming up to 160 ℃, add lauroyl vitriol 120.00g.After continuing reaction 3h, stopped reaction is cooled to room temperature, obtains sulfonated products.With mass concentration is that 30% potassium hydroxide solution is regulated pH to 7～8, and thin up to massfraction is 20%, promptly gets vinyl aromatic polyether grafting concrete superplasticiser.
Embodiment 3
Under the nitrogen protection, be 1000 polyethyleneglycol ether 100.00g with molecular weight, maleic anhydride 20.00g, 2,6 ditertiary butyl p cresol 0.20g adds. and in reactor, stirring heating when being warming up to 60 ℃, adds phosphatase 24 .00g.Continue to be warming up to 80 ℃, behind reaction 3h under this temperature, obtain esterification products.In containing the reactor of esterification products, add alpha-methyl styrene 40.00g, vinyl acetate 4.00g, the special butyl ester 2.40g of initiator peroxidation phenylformic acid.Behind the reaction 2h, obtain copolymerization product under 80 ℃.
Add dewatering agent boron trioxide 0.80g in the copolymerization product, stir and dewatering agent was uniformly dispersed in 15 minutes.Under 80 ℃, drip sulphur trioxide 40.00g.React after two hours, be warming up to 130 ℃, add hexanoyl vitriol 80.00g.After continuing reaction 6h, stopped reaction is cooled to room temperature, obtains sulfonated products.With mass concentration is that 30% sodium hydroxide solution is regulated pH to 7～8, and thin up to massfraction is 20%, promptly gets vinyl aromatic polyether grafting concrete superplasticiser.
Embodiment 4
Under the nitrogen protection, be 1000 polypropylene glycol monomethyl ether 100.00g with molecular weight, maleic anhydride 25.00g, Ursol D 0.25g joins in the reactor, and stirring heating when being warming up to 60 ℃, adds tosic acid 3.00g.Continue to be warming up to 100 ℃, behind reaction 2h under this temperature, obtain esterification products.In containing the reactor of esterification products, add 1,2-diphenylethlene 75.00g, vinyl acetate 5.00g, initiator di-isopropyl peroxydicarbonate 7.50g.Behind the reaction 3h, obtain copolymerization product under 100 ℃.
Add dewatering agent boron trioxide 1.50g in the copolymerization product, stir and dewatering agent was uniformly dispersed in 15 minutes.Under 80 ℃, drip chlorsulfonic acid 75.00g.React after two hours, be warming up to 120 ℃, add hexanoyl vitriol 150.00g.After continuing reaction 5h, stopped reaction is cooled to room temperature, obtains sulfonated products.With mass concentration is that 30% aqua calcis is regulated pH to 7～8, and thin up to massfraction is 20%, promptly gets vinyl aromatic polyether grafting concrete superplasticiser.
Embodiment 5
Under the nitrogen protection, be 1200 poly glycol monomethyl ether 120.00g with molecular weight, maleic anhydride 30.00g, 2,6 ditertiary butyl p cresol 0.23g join in the reactor, and stirring heating when being warming up to 60 ℃, adds tosic acid 7.20g.Continue to be warming up to 110 ℃, behind reaction 1h under this temperature, obtain esterification products.In containing the reactor of esterification products, add 2-vinyl naphthalene 60.00g, vinyl acetate 2.00g, initiator di-isopropyl peroxydicarbonate 3.00g.Behind the reaction 2h, obtain copolymerization product under 110 ℃.
Add dewatering agent Vanadium Pentoxide in FLAKES 1.20g in the copolymerization product, stir and dewatering agent was uniformly dispersed in 15 minutes.Under 80 ℃, drip sulphur trioxide 60.00g.React after two hours, be warming up to 160 ℃, add lauroyl vitriol 180.00g.After continuing reaction 4h, stopped reaction is cooled to room temperature, obtains sulfonated products.With mass concentration is that 30% sodium hydroxide solution is regulated pH to 7～8, and thin up to massfraction is 20%, promptly gets vinyl aromatic polyether grafting concrete superplasticiser.
Embodiment 6
Under the nitrogen protection, be 1000 poly glycol monomethyl ether 100.00g with molecular weight, maleic anhydride 20.00g, 2,6 ditertiary butyl p cresol 0.10g join in the reactor, and stirring heating when being warming up to 60 ℃, adds sulfuric acid 3.00g.Continue to be warming up to 80 ℃, behind reaction 3h under this temperature, obtain esterification products.In containing the reactor of esterification products, add vinylbenzene 20.00g, vinyl acetate 2.00g, initiator dibenzoyl peroxide 2.00g.Behind the reaction 4h, obtain copolymerization product under 80 ℃.
Add dewatering agent boron trioxide 0.40g in the copolymerization product, stir and dewatering agent was uniformly dispersed in 15 minutes.Under 80 ℃, drip vitriol oil 20.00g.React after two hours, be warming up to 120 ℃, add acetylsulfuric acid salt 80.00g.After continuing reaction 6h, stopped reaction is cooled to room temperature, obtains sulfonated products.With mass concentration is that 30% potassium hydroxide solution is regulated pH to 7～8, and thin up to massfraction is 20%, promptly gets vinyl aromatic polyether grafting concrete superplasticiser.
Tested by embodiment 1 to embodiment 6 prepared vinyl aromatic polyether grafting concrete superplasticiser, used cement is three moral PO, 42.5 silicate cements.According to GB/T8077-2000 the superplasticizer of gained is carried out the flowing degree of net paste of cement test, when volume is 0.3wt% (with respect to cement consumption), starch degree of mobilization only, loss hardly in 1 hour greater than 250mm; According to GB/T8076-1997 the superplasticizer of gained is carried out the concrete water-reducing ratio test, when volume is 0.6wt% (with respect to cement consumption), water-reducing rate is higher than 30%.The 3 days ultimate compression strength of concrete test block that is mixed with superplasticizer of the present invention improves greater than 28%, 28 day ultimate compression strength and improves greater than 50%.
Claims (11)
1, a kind of preparation method of vinyl aromatic polyether grafting concrete superplasticiser is characterized in that may further comprise the steps:
(1) esterification: under the nitrogen protection, pol yalkylene glycol monoalkyl ether, maleic anhydride, stopper are placed reactor, stirring heating heats up, wherein the weight ratio of pol yalkylene glycol monoalkyl ether and maleic anhydride is 2:1～6:1, and the weight ratio of maleic anhydride and stopper is 200:1～100:1; Be warming up to 50～70 ℃, add catalyzer, the weight ratio of catalyzer and pol yalkylene glycol monoalkyl ether is 3:100～3:50; Be warming up to 80～110 ℃, react after 1～3 hour, obtain esterification products;
(2) copolyreaction: in the reactor that contains esterification products, add vi-ny l aromatic monomers, vinyl acetate and initiator, stir and obtain three's mixture, the weight ratio of maleic anhydride is 1:1～3:1 in vi-ny l aromatic monomers and the step (1), the weight ratio of vinyl acetate and vi-ny l aromatic monomers is 1:10～1:30, and the weight ratio of initiator and vi-ny l aromatic monomers is 1:25～1:10; Maintain the temperature at 80～110 ℃, react after 2～4 hours, obtain copolymerization product;
(3) sulfonation reaction: drip sulphonating agent in copolymerization product, carry out low-temperature sulfonation, the weight ratio of vi-ny l aromatic monomers is 1:1 in sulphonating agent and the step (2); React after 1～4 hour, be warming up to 120～160 ℃, add sulphonating agent, carry out the high temperature sulfonation, the weight ratio of vi-ny l aromatic monomers is 2:1～4:1 in sulphonating agent and the step (2); Continue reaction 2～6 hours, stopped reaction is cooled to room temperature, obtains sulfonated products.
2, the preparation method of a kind of vinyl aromatic polyether grafting concrete superplasticiser according to claim 1 is characterized in that: also comprise step (4) neutralization reaction afterwards in step (3): regulate pH to 7～8, thin up with alkali lye.
3, the preparation method of a kind of vinyl aromatic polyether grafting concrete superplasticiser according to claim 1 and 2, it is characterized in that: in the step (3), before beginning to drip sulphonating agent, in copolymerization product, add earlier dewatering agent, stirred 10～20 minutes, the weight ratio of vi-ny l aromatic monomers is 1:50 in dewatering agent and the step (2).
4, the preparation method of a kind of vinyl aromatic polyether grafting concrete superplasticiser according to claim 1 is characterized in that: the pol yalkylene glycol monoalkyl ether described in the step (1) is a kind of in poly glycol monomethyl ether, polyethyleneglycol ether, polypropylene glycol monomethyl ether, the polypropylene glycol list ether.
5, the preparation method of a kind of vinyl aromatic polyether grafting concrete superplasticiser according to claim 1 is characterized in that: the stopper described in the step (1) is a kind of in 2,6 ditertiary butyl p cresol, the Ursol D.
6, the preparation method of a kind of vinyl aromatic polyether grafting concrete superplasticiser according to claim 1 is characterized in that: the catalyzer described in the step (1) is a kind of in sulfuric acid, phosphoric acid, the tosic acid.
7, the preparation method of a kind of vinyl aromatic polyether grafting concrete superplasticiser according to claim 1, it is characterized in that: the vi-ny l aromatic monomers described in the step (2) is vinylbenzene, alpha-methyl styrene, 1, the 1-diphenylethlene, 1, a kind of in 2-diphenylethlene, 2-vinyl naphthalene, the 9-vinyl anthracene.
8, the preparation method of a kind of vinyl aromatic polyether grafting concrete superplasticiser according to claim 1 is characterized in that: the initiator described in the step (2) is a kind of in the special butyl ester of dibenzoyl peroxide, peroxidation phenylformic acid, the di-isopropyl peroxydicarbonate.
9, the preparation method of a kind of vinyl aromatic polyether grafting concrete superplasticiser according to claim 1 is characterized in that: the dewatering agent described in the step (3) is a kind of in Vanadium Pentoxide in FLAKES, the boron trioxide.
10, the preparation method of a kind of vinyl aromatic polyether grafting concrete superplasticiser according to claim 1 is characterized in that: the sulphonating agent described in the step (3) is a kind of in the vitriol oil, sulphur trioxide, chlorsulfonic acid, acetylsulfuric acid salt, hexanoyl vitriol, the lauroyl vitriol.
11, the preparation method of a kind of vinyl aromatic polyether grafting concrete superplasticiser according to claim 2 is characterized in that: the alkali lye described in the step (4) is a kind of in sodium hydroxide, potassium hydroxide, the calcium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101110845A CN101486783B (en) | 2009-02-18 | 2009-02-18 | Preparation of vinyl aromatic polyether grafting concrete superplasticiser |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101110845A CN101486783B (en) | 2009-02-18 | 2009-02-18 | Preparation of vinyl aromatic polyether grafting concrete superplasticiser |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101486783A true CN101486783A (en) | 2009-07-22 |
| CN101486783B CN101486783B (en) | 2011-12-21 |
Family
ID=40889855
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009101110845A Active CN101486783B (en) | 2009-02-18 | 2009-02-18 | Preparation of vinyl aromatic polyether grafting concrete superplasticiser |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101486783B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012012923A1 (en) | 2010-07-27 | 2012-02-02 | 上海台界化工有限公司 | Synthesis method of polycarboxylic acid water-reducing agent |
| CN102504140A (en) * | 2011-11-30 | 2012-06-20 | 上海东大化学有限公司 | Polycarboxylic acid water reducing agent prepared from poly(ethylene glycol) ethyl ether, and preparation method and using method for polycarboxylic acid water reducing agent |
| CN103384651A (en) * | 2010-12-24 | 2013-11-06 | Sika技术股份公司 | Polymer made from maleic acid, allyl ether, and vinyl acetate, production of said polymer, and use of said polymer |
| CN103588969A (en) * | 2013-10-24 | 2014-02-19 | 中科院广州化学有限公司 | Polyethylene glycol methyl ether maleate, and preparation method and application thereof |
| CN103665274A (en) * | 2013-12-03 | 2014-03-26 | 沈阳化工大学 | Method for preparing sulfonated polycarboxylate water reducer grafted with glucose |
| CN103951308A (en) * | 2014-04-17 | 2014-07-30 | 山东卓星化工有限公司 | Sulfonyl modified polyoxyethylene ether super plasticizer and preparation method thereof |
| CN108218278A (en) * | 2017-12-28 | 2018-06-29 | 科之杰新材料集团有限公司 | A kind of preparation method of esters high dispersive high-slump-retentionpolycarboxylate polycarboxylate water reducer |
| CN109061120A (en) * | 2018-09-30 | 2018-12-21 | 福建科之杰新材料有限公司 | Produce the test evaluation method of precast concrete lining segment concrete |
-
2009
- 2009-02-18 CN CN2009101110845A patent/CN101486783B/en active Active
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012012923A1 (en) | 2010-07-27 | 2012-02-02 | 上海台界化工有限公司 | Synthesis method of polycarboxylic acid water-reducing agent |
| CN103384651A (en) * | 2010-12-24 | 2013-11-06 | Sika技术股份公司 | Polymer made from maleic acid, allyl ether, and vinyl acetate, production of said polymer, and use of said polymer |
| CN102504140A (en) * | 2011-11-30 | 2012-06-20 | 上海东大化学有限公司 | Polycarboxylic acid water reducing agent prepared from poly(ethylene glycol) ethyl ether, and preparation method and using method for polycarboxylic acid water reducing agent |
| CN102504140B (en) * | 2011-11-30 | 2013-09-25 | 上海东大化学有限公司 | Polycarboxylic acid water reducing agent prepared from poly(ethylene glycol) ethyl ether, and preparation method and using method for polycarboxylic acid water reducing agent |
| CN103588969A (en) * | 2013-10-24 | 2014-02-19 | 中科院广州化学有限公司 | Polyethylene glycol methyl ether maleate, and preparation method and application thereof |
| CN103665274A (en) * | 2013-12-03 | 2014-03-26 | 沈阳化工大学 | Method for preparing sulfonated polycarboxylate water reducer grafted with glucose |
| CN103951308A (en) * | 2014-04-17 | 2014-07-30 | 山东卓星化工有限公司 | Sulfonyl modified polyoxyethylene ether super plasticizer and preparation method thereof |
| CN108218278A (en) * | 2017-12-28 | 2018-06-29 | 科之杰新材料集团有限公司 | A kind of preparation method of esters high dispersive high-slump-retentionpolycarboxylate polycarboxylate water reducer |
| CN108218278B (en) * | 2017-12-28 | 2020-06-05 | 科之杰新材料集团有限公司 | Preparation method of ester high-dispersion high-slump-retaining polycarboxylate superplasticizer |
| CN109061120A (en) * | 2018-09-30 | 2018-12-21 | 福建科之杰新材料有限公司 | Produce the test evaluation method of precast concrete lining segment concrete |
| CN109061120B (en) * | 2018-09-30 | 2021-05-04 | 科之杰新材料集团福建有限公司 | Test evaluation method for concrete for producing precast concrete lining segment |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101486783B (en) | 2011-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101486783B (en) | Preparation of vinyl aromatic polyether grafting concrete superplasticiser | |
| CN105669912B (en) | A kind of method for preparing star-like poly carboxylic acid series water reducer | |
| CN102504238B (en) | Unsaturated polyether monomer, comb-like branched copolymer cement dispersant prepared by the same, and preparation method thereof | |
| CN103265201B (en) | Sorbitol modified polycarboxylate-type water reducing agent and synthetic method thereof | |
| CN101735411B (en) | Method for preparing sustained-release polycarboxylic water reducer | |
| CN104140503A (en) | Method for synthesizing high-water-reduction high-slump-retaining high-performance polycarboxylate water reducer at normal temperature | |
| CN106543382A (en) | A kind of solid lamellar polycarboxylate water-reducer and its polymerization process for preparing | |
| CN102432776B (en) | Method for preparing early strength type polycarboxylic acid water-reducing agent | |
| CN101475664B (en) | Preparation of polycarboxylic acid water reducing agent for prefabricated part | |
| CN102532435B (en) | Polycarboxylene high-performance water reducing agent and preparation method thereof | |
| CN101838122B (en) | Compound additive of unshaped refractory material system, preparation method and application | |
| CN104861122A (en) | Heat-source-free early strength polycarboxylate water reducer and preparation method thereof | |
| CN106749970B (en) | A kind of sheet polycarboxylic acid slump retaining agent and preparation method thereof admittedly | |
| CN101575403B (en) | Polymerization method for preparing polycarboxylic high-efficiency water-reducing agent | |
| CN106277899A (en) | A kind of polycarboxylate water-reducer and preparation method thereof | |
| CN103965416B (en) | Component high-early strength type polycarboxylic acids dehydragent and preparation method thereof | |
| CN100463872C (en) | Preparation method of polycarboxylate water reducing agent | |
| CN105601843A (en) | Early-strength ethers polycarboxylic acid water reducing agent and preparation method thereof | |
| CN101885888A (en) | Preparation method of slow-release type unshaped refractory additive | |
| CN105906753A (en) | Preparation method of polycarboxylate superplasticizer | |
| CN102010487B (en) | Method for preparing polycarboxylate water reducing agent | |
| CN102101906A (en) | Method for preparing amide/imide type high-concentration polycarboxylic acid high-performance water reducer | |
| CN114634602B (en) | Preparation method of hyperbranched solid polycarboxylate superplasticizer | |
| CN101234866A (en) | Method for preparing polycarboxylic acids series high-efficiency water-reducing agent | |
| CN112851889A (en) | Preparation method of graphene oxide modified TPEG type polycarboxylate superplasticizer |
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 | ||
| C56 | Change in the name or address of the patentee |
Owner name: KEZHIJIE NEW MATERIALS GROUP CO., LTD. Free format text: FORMER NAME: FUJIAN KEZIJIE NEW MATERIAL CO., LTD. |
|
| CP01 | Change in the name or title of a patent holder |
Address after: 361100 Xiamen Xiangan high tech industrial base in Fujian District Patentee after: Kezhijie New Material Group Co., Ltd. Patentee after: Xiamen Building Science Research Institute Group Co., Ltd. Address before: 361100 Xiamen Xiangan high tech industrial base in Fujian District Patentee before: Fujian Kezijie New Material Co., Ltd. Patentee before: Xiamen Building Science Research Institute Group Co., Ltd. |