CN109734849A - A kind of preparation method of comprehensive polycarboxylate water-reducer - Google Patents
A kind of preparation method of comprehensive polycarboxylate water-reducer Download PDFInfo
- Publication number
- CN109734849A CN109734849A CN201811621400.9A CN201811621400A CN109734849A CN 109734849 A CN109734849 A CN 109734849A CN 201811621400 A CN201811621400 A CN 201811621400A CN 109734849 A CN109734849 A CN 109734849A
- Authority
- CN
- China
- Prior art keywords
- solution
- acid
- polycarboxylate water
- reducer
- 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.)
- Pending
Links
Abstract
The invention discloses a kind of preparation method of comprehensive polycarboxylate water-reducer, includes the following steps: 1) to be added in reactor, and polymerization inhibitor and catalyst is added straight chain alcohol, alkenyl acid, carry out esterification, obtain the first mixture；2) the first mixture, the first monomer, alkenyl sulfonate, reducing agent, chain-transferring agent, N,N methylene bis acrylamide and water are mixed to get the first solution；3) initiator and water are mixed to get the second solution；4) second comonomer and water are mixed to get third solution；5) the third solution of 80%~90% the second solution and 70%~90% is instilled into the first solution, obtains the 4th solution；6) the third solution of 10%~20% the second solution and 10%~30% is added in the 4th solution, initiator is added, heating reacts 1~3h, obtains comprehensive polycarboxylate water-reducer.Water-reducing agent of the invention has the function of that high water reduction performance and guarantor are collapsed, and cement adaptability is good.
Description
Technical field
The present invention relates to a kind of comprehensive polycarboxylate water-reducer preparation methods, and it is new to belong to concrete additives in building materials
Type technology field.
Background technique
Common comprehensive polycarboxylate water-reducer is divided into the market: polyesters, polyethers and ester ether are copolymerized three classes.Polyesters
High performance water-reducer technique is first to be esterified to polymerize afterwards, and polymerization methods are to add thermal-initiated polymerization, and monomer is added and is drawn using dropwise addition mode
Send out agent；Polyethers and ester ether copoly type high performance water-reducer technique are one-step polymerization method, and polymerization methods are that heating polymerization and room temperature are poly-
Two ways is closed, monomer and initiator are added using dropwise addition mode.Polyesters high performance water-reducer technique is more complex, to equipment requirement
Higher, combined coefficient is lower, and energy consumption is higher；Polyethers and ester ether copoly type high performance water-reducer technique are relatively easy, and energy consumption is lower,
Efficiency is higher, but conversion ratio is lower, and molecular weight distribution is wider；And existing polycarboxylate water-reducer water-reducing rate is lower, to difference
Kind cement adaptability is bad.
Summary of the invention
It is an object of the present invention to provide a kind of comprehensive polycarboxylate water-reducer preparation methods, to improve polymerisation conversion and reduction
Molecular weight dispersion coefficient improves comprehensive polycarboxylate water-reducer to the adaptability of cement.
In order to achieve the above objectives, the technical solution adopted by the present invention is that:
A kind of preparation method of comprehensive polycarboxylate water-reducer, in which: include the following steps:
1) according to parts by weight, 1~10 part of straight chain alcohol, 5~30 parts of alkenyl acid are added in reactor, and polymerization inhibitor are added
And catalyst, it is maintained at 80~120 DEG C and carries out esterification 3~6 hours, cooling is obtained containing alkenyl acid alcohol after reaction
First mixture of ester；
2) according to parts by weight, by 5~40 part of first mixture, 20~30 part of first monomer, 0.1~0.5 part of alkenyl sulphur
Hydrochlorate, 0.01~0.035 part of reducing agent, 0.01~0.05 part of chain-transferring agent, 0.002 part of N,N methylene bis acrylamide and water
It is mixed to get the first solution；
3) 0.01~0.1 part of initiator and 5~15 parts of water according to parts by weight, are mixed to get the second solution；
4) 3~8 parts of second comonomers and 10~30 parts of water according to parts by weight, are mixed to get third solution；
5) the third solution of 80%~90% the second solution and 70%~90% is instilled into the first solution, controlled at
30~50 DEG C, the 4th solution is obtained after being added dropwise；
6) the third solution of 10%~20% the second solution and 10%~30% is added in the 4th solution, and is added and draws
Agent is sent out, 60~90 DEG C are warming up in 1 hour, and reacts 1~3h at this temperature, is cooled down after reaction, then plus in alkali
With to pH value be 6.5~7.5, the comprehensive polycarboxylate water-reducer can be obtained.
Preferably, the preparation method of the comprehensive polycarboxylate water-reducer, in which: the general formula of the straight chain alcohol
Are as follows: R1(OH)n；The wherein alkane that R1 is 1~12, n are 1~3.
Preferably, the preparation method of the comprehensive polycarboxylate water-reducer, in which: the alkenyl acid is selected from methyl-prop
One of olefin(e) acid, acrylic acid, maleic acid, maleic anhydride or itaconic acid.
Preferably, the preparation method of the comprehensive polycarboxylate water-reducer, in which: the polymerization inhibitor is selected to benzene two
One of phenol, p-hydroxyanisole, phenothiazine；The catalyst is p-methyl benzenesulfonic acid or the concentrated sulfuric acid.
Preferably, the preparation method of the comprehensive polycarboxylate water-reducer, in which: the general formula of first monomer
Are as follows: R3O(R2O)mH；Wherein R3For 3~6 alkenyl, alkenyl is located at the end of the chain；(R2O)mThe oxyalkylene for being 2 selected from carbon atom number
Base, carbon atom number be 3 oxyalkylene group, or combinations thereof, m indicate oxyalkylene group average addition molal quantity；B1Molecular weight is
1000~5000.
Preferably, the preparation method of the comprehensive polycarboxylate water-reducer, in which: the alkenyl sulfonate is selected from first
One of base sodium allylsulfonate, acrylic sodium sulfonate, 2- acrylamide-2-methylpro panesulfonic acid sodium.
Preferably, the preparation method of the comprehensive polycarboxylate water-reducer, in which: it is anti-bad that the reducing agent is selected from L-
One of hematic acid, sodium hydrogensulfite, sodium thiosulfate, sodium formaldehyde sulphoxylate；The chain-transferring agent be selected from thioacetic acid,
One of 3- mercaptopropionic acid, mercaptoethanol, polymerization mercaptan.
Preferably, the preparation method of the comprehensive polycarboxylate water-reducer, in which: the initiator is selected from persulfuric acid
One or more of sodium, potassium peroxydisulfate, ammonium persulfate, hydrogen peroxide；
Preferably, the preparation method of the comprehensive polycarboxylate water-reducer, in which: the second comonomer is selected from methyl
One of acrylic acid, acrylic acid, maleic acid, maleic anhydride or itaconic acid.
Preferably, the preparation method of the comprehensive polycarboxylate water-reducer, in which: in the step 5), be added dropwise the
The time of two solution is 1.5 hours, and the time that third solution is added dropwise is 2 hours.
Reaction mechanism of the invention are as follows: using alkenyl acid and straight chain alcohol as reaction monomers, alkenyl acid alcohol ester is prepared, rear
Double bond copolymerization is opened in the reaction in face, and the also high-molecular compound of the bridging structure of ester bond is added on crosslinking agent formation side chain.
The present invention introduces the ester bond that can slowly hydrolyze under strong basicity environment on side chain, mistake of the key in hydrated cementitious
Cheng Zhong, can slow hydrolytic cleavage so that big molecular breakdown is at multiple relatively small molecules, the small molecule is in cement
Under the action of surface electrical behavior gravitation, it can be adsorbed in the cement granules hydrated product surface, quickly so as to improve the flowing of concrete
Property；Crosslinking agent N is added in the present invention, bridging structure polycarboxylate water-reducer is made, in hydrated cementitious in N- methylene-bisacrylamide
Steric hindrance structure is formed in the process, prevents fast hydration of the water-reducing agent in cement hydration process.
The utility model has the advantages that
Due to the above technical solutions, the present invention has the following advantages over the prior art:
(1) molecular structure of the comprehensive polycarboxylate water-reducer of the present invention is bridging structure, and molecular weight dispersion coefficient is smaller, point
Son amount narrow distribution；The present invention, as reaction monomers, prepares alkenyl acid alcohol ester, in reaction below using alkenyl acid and straight chain alcohol
The also high-molecular compound of the bridging structure of ester bond is added on crosslinking agent formation side chain in middle opening double bond copolymerization；The present invention exists
The ester bond that can slowly hydrolyze under strong basicity environment is introduced on side chain, which, being capable of slow water during hydrated cementitious
Solution fracture, so that big molecular breakdown is at multiple relatively small molecules, the small molecule is in cement surface electrical property gravitation
Under effect, it can be adsorbed in the cement granules hydrated product surface, quickly so as to improve the mobility of concrete；It is added in the present invention
Bridging structure polycarboxylate water-reducer is made in crosslinking agent, and steric hindrance structure is formed in cement hydration process, and water-reducing agent is prevented to exist
Fast hydration in cement hydration process.
(2) it is of the invention comprehensive polycarboxylate water-reducer reactive mode be esterification-copolymerization formula successive reaction, water-reducing agent turn
Rate is higher, and molecular weight polydispersity coefficient PDI is smaller.
(3) comprehensive polycarboxylate water-reducer of the invention had not only had high water reduction performance, but also had guarantor to collapse function, and to water
Mud adaptability is preferable.
Specific embodiment
The present invention will be further described below with reference to examples:
Embodiment 1:
A kind of preparation method of comprehensive polycarboxylate water-reducer, includes the following steps:
(1) 2 parts of 15 parts of ethyl alcohol monomer of methacrylic acid is added in dry reaction vessel, is added a certain amount of
Hydroquinone and p-methyl benzenesulfonic acid are esterified at a temperature of 110~115 DEG C as catalyst, keep reaction 4 hours, end of reaction
After cooling, the first mixture containing methacrylic acid ethyl alcohol ester is obtained；
(2) by 17 part of first mixture, 25 parts of allyl polyethenoxy ethers 1200 (APEG-1200), 0.1 part of metering system
Sodium sulfonate, 0.01 part of L-AA, 0.01 part of thioacetic acid, 0.002 part of crosslinking agent N, N- methylene-bisacrylamide are added
45 parts of water is fitted into reaction vessel, is stirred and the first solution is made；
(3) 0.02 part of hydrogen peroxide and 10 parts of water are made into the second solution, it is spare is packed into dropping funel；
(4) 3 parts of acrylic acid and 15 parts of water are made into third solution, it is spare is packed into dropping funel；
(5) the third solution of 80% the second solution and 90% is instilled into the first solution, material rises automatically during dropwise addition
Temperature, reaction temperature let nature take its course control at 30~50 DEG C；
(6) it is added at one time remaining 20% the second solution and 10% third solution after completion of dropwise addition, adds 0.01 part of mistake
Then ammonium sulfate is warming up to 65 ± 2 DEG C in 1 hour, and constant temperature 1.5h at this temperature；Then plus alkali cool down after constant temperature,
Being neutralized to pH value is 6.5~7.5, and comprehensive polycarboxylate water-reducer PC1 can be obtained.
Comprehensive polycarboxylate water-reducer PC1 molecular structural formula
Embodiment 2:
A kind of preparation method of comprehensive polycarboxylate water-reducer, includes the following steps:
(1) by 4 parts of propyl alcohol monomer, 14.7 parts of maleic anhydride is added in dry reaction vessel, is added a certain amount of
The concentrated sulfuric acid is esterified at a temperature of 85 DEG C~90 DEG C as catalyst, after keeping reaction 5 hours, end of reaction cooling, is contained
First mixture of maleic acid propyl alcohol ester；
(2) by 18.7 part of first mixture, 30 parts of methyl allyl polyoxyethylene ethers 2400 (HPEG-2400), 0.3 part of 2-
Acrylamide-2-methylpro panesulfonic acid sodium, 0.02 part of L-AA and 0.01 part of sodium hydrogensulfite, 0.03 part of mercaptopropionic acid,
0.002 part of crosslinking agent N, N- methylene-bisacrylamide is added 45 parts of water and is fitted into reaction vessel, is stirred and is made first
Solution；
(3) 0.02 part of hydrogen peroxide and 0.01 part of ammonium persulfate and 10 parts of water are made into the second solution, it is standby is packed into dropping funel
With；
(4) by 3 parts of methacrylic acids and 15 parts of water wiring solution-forming E1, it is spare to be packed into dropping funel；
(5) the third solution of 85% the second solution and 80% is instilled into the first solution, material rises automatically during dropwise addition
Temperature, reaction temperature let nature take its course control at 30~50 DEG C；
(6) it is added at one time remaining 15% the second solution and 20% third solution after completion of dropwise addition, adds 0.02 part of mistake
Then sodium sulphate is warming up to 80 ± 2 DEG C in 1 hour, and constant temperature 2h at this temperature；Cool down after constant temperature, then plus in alkali
With to pH value be 6.5~7.5, comprehensive polycarboxylate water-reducer PC2 can be obtained.
Comprehensive polycarboxylate water-reducer PC2 molecular structural formula
Embodiment 3:
A kind of preparation method of comprehensive polycarboxylate water-reducer, includes the following steps:
(1) by 10 parts of sec-n-octyl alcohol monomer, 16.6 parts of acrylic acid is added in dry reaction vessel, is added a certain amount of
Polymerization inhibitor phenothiazine and a certain amount of concentrated sulfuric acid as catalyst, be esterified at a temperature of 115 DEG C~120 DEG C, keep reaction 5 small
When, after end of reaction is cooling, obtain the first mixture containing acrylic acid sec-n-octyl alcohol ester；
(2) by 26.6 parts of said mixture A1, 20 parts of isopentene group polyoxyethylene ether 3000 (TPEG-3000), 0.5 part third
Alkene sodium sulfonate, 0.03 part of sodium hydrogensulfite, 0.01 part of polymerization mercaptan, 0.002 part of crosslinking agent N, N- methylene-bisacrylamide add
Enter 45 parts of water to be fitted into reaction vessel, is stirred and the first solution is made；
(3) 0.05 part of hydrogen peroxide and 0.02 part of sodium peroxydisulfate and 10 parts of water are made into the second solution, it is standby is packed into dropping funel
With；
(4) 5 parts of itaconic acids and 15 parts of water are made into third solution, it is spare is packed into dropping funel；
(5) the third solution of 90% the second solution and 70% is instilled into the first solution, material rises automatically during dropwise addition
Temperature, reaction temperature let nature take its course control at 30~50 DEG C；
(6) it is added at one time remaining 10% the second solution and 30% third solution after completion of dropwise addition, adds 0.05 part of mistake
Then potassium sulfate is warming up to 87 ± 2 DEG C in 1 hour, and constant temperature 1h at this temperature；Cool down after constant temperature, then plus in alkali
With to pH value be 6.5~7.5, comprehensive polycarboxylate water-reducer PC3 can be obtained.
Comprehensive polycarboxylate water-reducer PC3 molecular structural formula
The conversion ratio of 40% polycarboxylate water-reducer FOX-5H of our company sample as a comparison, Examples 1 to 3 and comparative sample and more
Test result is as follows by coefficient of dispersion PDI shown in table:
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative sample | |
| Conversion ratio | 91.5% | 91.8% | 92.3% | 90% |
| Polydisperse system PDI | 1.83 | 1.73 | 1.60 | 2.10 |
The comprehensive polycarboxylate water-reducer conversion ratio of Examples 1 to 3 preparation is higher, and molecular weight polydispersity coefficient PDI is smaller.
Application Example 1: comprehensive polycarboxylate water-reducer carries out C30 concrete experiments using reference cement
The comprehensive polycarboxylate water-reducer as obtained by embodiment one to three uses reference water by GB8076-2008 standard
Mud carries out C30 concrete experiments, and each embodiment and comparative sample (40% polycarboxylate water-reducer FOX-5H of our company) are in identical diminishing
Agent volume (folding is the 0.2% of cement admittedly), concrete performance is as follows:
| Benchmark | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative sample | |
| Water-reducing rate, % | ? | 29 | 31 | 32 | 27 |
| Initial slump, mm | 200 | 220 | 220 | 225 | 210 |
| The slump after 1h, mm | 80 | 195 | 210 | 220 | 170 |
| 3d compressive strength rate, % | 100 | 185 | 175 | 181 | 164 |
Application Example 2: comprehensive polycarboxylate water-reducer carries out C30 concrete experiments using conch cement
The comprehensive polycarboxylate water-reducer as obtained by embodiment one to three is made by GB8076-2008 standard using conch
Cement carries out C30 concrete experiments, and each embodiment and comparative sample (40% polycarboxylate water-reducer FOX-5H of our company) subtract identical
Aqua volume (folding is the 0.2% of cement admittedly), concrete performance is as follows:
| Benchmark | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative sample | |
| Water-reducing rate, % | ? | 30 | 31 | 31 | 28 |
| Initial slump, mm | 200 | 220 | 215 | 215 | 210 |
| The slump after 1h, mm | 70 | 205 | 210 | 215 | 165 |
| 3d compressive strength rate, % | 100 | 182 | 187 | 179 | 170 |
Application Example 3: comprehensive polycarboxylate water-reducer carries out C30 concrete experiments using golden cutting edge of a knife or a sword cement
The comprehensive polycarboxylate water-reducer as obtained by embodiment one to three uses Jin Fengshui by GB8076-2008 standard
Mud carries out C30 concrete experiments, and each embodiment and comparative sample (40% polycarboxylate water-reducer FOX-5H of our company) are in identical diminishing
Agent volume (folding is the 0.2% of cement admittedly), concrete performance is as follows:
| Benchmark | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative sample | |
| Water-reducing rate, % | ? | 31 | 32 | 33 | 29 |
| Initial slump, mm | 210 | 215 | 210 | 215 | 210 |
| Slump mm after 1h | 100 | 225 | 230 | 225 | 190 |
| 3d compressive strength rate, % | 100 | 182 | 175 | 178 | 166 |
As can be seen from the table, three embodiment water-reducing rates of the invention are higher, and function of slump protection is preferable, suitable to cement not of the same race
Answering property is preferable, excellent combination property.
Claims (10)
1. a kind of preparation method of comprehensive polycarboxylate water-reducer, characterized by the following steps:
1) according to parts by weight, 1~10 part of straight chain alcohol, 5~30 parts of alkenyl acid are added in reactor, and polymerization inhibitor are added and urges
Agent is maintained at 80~120 DEG C and carries out esterification 3~6 hours, and cooling is obtained containing alkenyl acid alcohol ester after reaction
First mixture；
2) according to parts by weight, by 5~40 part of first mixture, 20~30 part of first monomer, 0.1~0.5 part of alkenyl sulfonate,
0.01~0.035 part of reducing agent, 0.01~0.05 part of chain-transferring agent, 0.002 part of N,N methylene bis acrylamide and water mixing
Obtain the first solution；
3) 0.01~0.1 part of initiator and 5~15 parts of water according to parts by weight, are mixed to get the second solution；
4) 3~8 parts of second comonomers and 10~30 parts of water according to parts by weight, are mixed to get third solution；
5) the third solution of 80%~90% the second solution and 70%~90% is instilled into the first solution, controlled at 30~
50 DEG C, the 4th solution is obtained after being added dropwise；
6) the third solution of 10%~20% the second solution and 10%~30% is added in the 4th solution, and initiation is added
Then plus alkali neutralization agent is warming up to 60~90 DEG C in 1 hour, and reacts 1~3h at this temperature, cools down after reaction,
It is 6.5~7.5 to pH value, the comprehensive polycarboxylate water-reducer can be obtained.
2. the preparation method of comprehensive polycarboxylate water-reducer according to claim 1, it is characterised in that: the straight chain alcohol
General formula are as follows: R1(OH)n；The wherein alkane that R1 is 1~12, n are 1~3.
3. the preparation method of comprehensive polycarboxylate water-reducer according to claim 1, it is characterised in that: the alkenyl acid choosing
From one of methacrylic acid, acrylic acid, maleic acid, maleic anhydride, itaconic acid.
4. the preparation method of comprehensive polycarboxylate water-reducer according to claim 1, it is characterised in that: the polymerization inhibitor choosing
From one of hydroquinone, p-hydroxyanisole, phenothiazine；The catalyst is p-methyl benzenesulfonic acid or the concentrated sulfuric acid.
5. the preparation method of comprehensive polycarboxylate water-reducer according to claim 1, it is characterised in that: first monomer
General formula are as follows: R3O(R2O)mH；Wherein R3For 3~6 alkenyl, alkenyl is located at the end of the chain；(R2O)mThe oxygen for being 2 selected from carbon atom number
Change alkenyl, carbon atom number be 3 oxyalkylene group, or combinations thereof, m indicate oxyalkylene group average addition molal quantity；B1Molecular weight
It is 1000~5000.
6. the preparation method of comprehensive polycarboxylate water-reducer according to claim 1, it is characterised in that: the olefin sulfonic acid
Salt is selected from one of methylpropene sodium sulfonate, acrylic sodium sulfonate, 2- acrylamide-2-methylpro panesulfonic acid sodium.
7. the preparation method of comprehensive polycarboxylate water-reducer according to claim 1, it is characterised in that: the reducing agent choosing
From one of L-AA, sodium hydrogensulfite, sodium thiosulfate, sodium formaldehyde sulphoxylate；The chain-transferring agent is selected from
One of thioacetic acid, 3- mercaptopropionic acid, mercaptoethanol, polymerization mercaptan.
8. the preparation method of comprehensive polycarboxylate water-reducer according to claim 1, it is characterised in that: the initiator choosing
From one or more of sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate, hydrogen peroxide.
9. the preparation method of comprehensive polycarboxylate water-reducer according to claim 1, it is characterised in that: the second comonomer
Selected from one of methacrylic acid, acrylic acid, maleic acid, maleic anhydride, itaconic acid.
10. the preparation method of comprehensive polycarboxylate water-reducer according to claim 1, it is characterised in that: the step 5)
In, the time that the second solution is added dropwise is 1.5 hours, and the time that third solution is added dropwise is 2 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811621400.9A CN109734849A (en) | 2018-12-28 | 2018-12-28 | A kind of preparation method of comprehensive polycarboxylate water-reducer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811621400.9A CN109734849A (en) | 2018-12-28 | 2018-12-28 | A kind of preparation method of comprehensive polycarboxylate water-reducer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109734849A true CN109734849A (en) | 2019-05-10 |
Family
ID=66361724
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811621400.9A Pending CN109734849A (en) | 2018-12-28 | 2018-12-28 | A kind of preparation method of comprehensive polycarboxylate water-reducer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109734849A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06256054A (en) * | 1993-03-01 | 1994-09-13 | Denki Kagaku Kogyo Kk | Cement dispersant |
| US5985989A (en) * | 1997-07-09 | 1999-11-16 | Arco Chemical Technology, Lp | Method of making a water reducing additive for cement |
| CN102093519A (en) * | 2010-12-06 | 2011-06-15 | 江苏汇迪建材有限公司 | Preparation method of mud-resistant type polycarboxylate superplasticizer |
| CN103333297A (en) * | 2013-06-24 | 2013-10-02 | 北京工业大学 | Preparation method of reduced polycarboxylate-type high-performance water reducing agent |
| CN107602762A (en) * | 2017-09-29 | 2018-01-19 | 济南大学 | For one kind with N, N methylene-bisacrylamides are micro- cross-linked polycarboxylic's high efficiency water reducing agent of cross-linking monomer and preparation method thereof |
-
2018
- 2018-12-28 CN CN201811621400.9A patent/CN109734849A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06256054A (en) * | 1993-03-01 | 1994-09-13 | Denki Kagaku Kogyo Kk | Cement dispersant |
| US5985989A (en) * | 1997-07-09 | 1999-11-16 | Arco Chemical Technology, Lp | Method of making a water reducing additive for cement |
| CN102093519A (en) * | 2010-12-06 | 2011-06-15 | 江苏汇迪建材有限公司 | Preparation method of mud-resistant type polycarboxylate superplasticizer |
| CN103333297A (en) * | 2013-06-24 | 2013-10-02 | 北京工业大学 | Preparation method of reduced polycarboxylate-type high-performance water reducing agent |
| CN107602762A (en) * | 2017-09-29 | 2018-01-19 | 济南大学 | For one kind with N, N methylene-bisacrylamides are micro- cross-linked polycarboxylic's high efficiency water reducing agent of cross-linking monomer and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105367720B (en) | A kind of diminishing collapse protective poly-carboxylic acid water reducing agent and preparation method thereof | |
| CN102976655B (en) | Slump retaining polycarboxylic acid superplasticizer | |
| WO2014085996A1 (en) | Slump retaining polycarboxylic acid superplasticizer | |
| CN112724329A (en) | Viscosity-reducing polycarboxylic acid concrete water reducer and preparation method thereof | |
| CN101056897B (en) | Anion polymers | |
| CN108794700A (en) | A kind of carboxylic acid group polymer and preparation method thereof and sustained-release polycarboxylic water reducer | |
| CN108948288B (en) | Preparation method of crosslinking type polycarboxylate superplasticizer by adopting carboxyl functional monomer | |
| CN109608593A (en) | A kind of preparation method of polyethers synthesis water reducing type polycarboxylate water-reducer | |
| CN106800622A (en) | A kind of slow release slump retaining polycarboxylate water reducer and preparation method thereof | |
| CN105461866B (en) | A kind of viscosity reduction type polycarboxylate water-reducer and preparation method thereof | |
| CN109970922A (en) | A kind of shrinkage type Early-strength polycarboxylate superplasticizer mother liquor and preparation process | |
| CN107501482A (en) | A kind of preparation method of low responsive type polycarboxylate water-reducer | |
| CN101735541A (en) | Environmental-friendly type emulsion for heat insulating material and preparation method thereof | |
| CN106749963B (en) | A kind of bleed controllable type poly carboxylic acid series water reducer and preparation method thereof for pure machine-made sand concrete | |
| CN111349199B (en) | Steady-state polycarboxylic acid superplasticizer with core-shell structure and preparation method thereof | |
| CN108276533A (en) | A kind of high ecad polycarboxylate water-reducer and preparation method thereof | |
| CN106519137A (en) | Cross-star-shaped slow-release slump-retaining type polycarboxylic-acid water-reducing agent and preparation method thereof | |
| CN105949409A (en) | Polycarboxylate-series concrete water reducing agent containing chitosan, and preparation method thereof | |
| CN107936190A (en) | Four dripping method preparation methods of high diminishing collapse protective poly-carboxylic acid water reducing agent | |
| CN104496253B (en) | Special early-strength polycarboxylate superplasticizer for prefabricated parts and preparation method of special early-strength polycarboxylate superplasticizer | |
| CN101386489B (en) | Polycarboxylate dehydragent and preparation method thereof | |
| CN110643003B (en) | Preparation method of retarding type ester polycarboxylate superplasticizer | |
| CN106916292A (en) | A kind of polyoxyalkyl ether and preparation method thereof, the polycarboxylate water-reducer as obtained by it and preparation method | |
| CN108586672A (en) | A kind of cross-linking type polycarboxylic acid super-plasticizer and its preparation method and application | |
| CN105085821A (en) | Heat-energy-free novel integrated efficient polycarboxylic acid water reducer and preparation method therefor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190510 |
|
| RJ01 | Rejection of invention patent application after publication |