CN106008846A - Method for preparation of polycarboxylate high-efficiency water reducing agent with novel acrylic monomer as comonomer - Google Patents
Method for preparation of polycarboxylate high-efficiency water reducing agent with novel acrylic monomer as comonomer Download PDFInfo
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- CN106008846A CN106008846A CN201610277701.9A CN201610277701A CN106008846A CN 106008846 A CN106008846 A CN 106008846A CN 201610277701 A CN201610277701 A CN 201610277701A CN 106008846 A CN106008846 A CN 106008846A
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- water
- reducing agent
- reducer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
Abstract
The invention provides a novel acrylic monomer MPA for preparation of a polycarboxylate high-efficiency water reducing agent; because an unsaturated acid is directly subjected to an esterification reaction with a monomer containing a functional group, the complex problem generated from esterification reaction with use of a polyether macromonomer is avoided, the production cost of the use of the polyether macromonomer is reduced, the polycarboxylate high-efficiency water reducing agent performance is improved, and good economic and social benefits are achieved.
Description
Technical field
The present invention relates to high molecular polymerization and prepare concrete high efficiency water reducing agent field, particularly relate to a kind of novel propylene
The method that acrylic monomer prepares high-efficiency water-reducing agent of poly-carboxylic acid as comonomer.
Background technology
Concrete, as current indispensable construction material, has stepped into commercialization, high performance epoch.Concrete
Commercialization, high performance be dependent on what concrete admixture realized.In additive, most important and most critical kind is to subtract
Water preparation, accounts for more than the 80% of the total consumption of additive.The water reducer applied in the market includes naphthalene system, sulfamate, fat
All multi items such as race and polycarboxylic acids, wherein polycarboxylate water-reducer is that best, the most promising a new generation of current performance subtracts
Water preparation.
Although polycarboxylate water-reducer is developed rapidly in recent years, but due to by the raw materials such as polyether macromonomer and poly-carboxylic
Acid water reducer produces the restriction with application technology, and its consumption is less than 40 % of water reducer total amount.Therefore, polycarboxylate water-reducer tool
Vast potential for future development and the huge market space, exploitation polycarboxylate water-reducer is had to have weight for the development of China's building material industry
Want realistic meaning.Polycarboxylate water-reducer is mainly formed with polyether macromonomer copolymerization by acrylic monomer, due to polycarboxylic acids diminishing
The designability of agent molecule structure, by introducing different functional groups on comonomer, thus can improve the poly-carboxylic of gained
The performance of acid water reducer.
Chinese patent CN102173638A utilizes methoxy poly (ethylene glycol) and itaconic acid esterification to be prepared for the poly-second of methoxyl group two
Alcohol itaconic acid monoesters, and be used for synthesizing polycarboxylate water-reducer, owing to introducing a carboxyl on polymeric monomer, increase carboxyl close
Degree, so that water-reducing rate improves.
Chinese patent CN102206060A utilizes methoxy poly (ethylene glycol) and Polyethylene Glycol to be prepared for maleic anhydride esterification
Methoxy poly (ethylene glycol) and Polyethylene Glycol maleic anhydride monoesters, the water reducer production technology utilizing this type of monomer to synthesize is simple, becomes
This is low, function admirable.
Chinese patent CN102206058A utilizes methoxy poly (ethylene glycol) and acroleic acid esterification to be prepared for the poly-second of methoxyl group two
Alcohol acrylate, it is good that the water reducer using this type of monomer to synthesize in use has cement adaptability, and strength enhancing is fast
Advantage.
Chinese patent CN104725227A utilizes polyoxy alkylidene alcohol and unsaturated carboxylic acid to be prepared for unsaturation by esterification
Dicarboxylic acid monoester, and utilize this type of monomer synthesized polycarboxylate water-reducer make hold thiazolinyl ester bond be not susceptible in alkaline environment
Hydrolytic cleavage, adds the function of slump protection of water reducer.
The above is all by the method changing polycarboxylate water-reducer synthesis polymeric monomer used, draws on polyether macromonomer
Enter different functional groups thus improve the performance of polycarboxylate water-reducer.Owing to polyether macromonomer molecular weight makes more greatly in preparation
The polyether macromonomer esterification process with difference in functionality group is complicated, relatively costly, be difficult to preparation.Acrylic acid is synthesis polycarboxylic acids
The indispensable comonomer of water reducer introduces different functional groups by acrylic acid, and synthesis has the acrylic acid of good function
Class monomer, then utilizes novel acrylic monomer to synthesize polycarboxylate water-reducer as comonomer, thus improves gained and gather
The performance of carboxylic acid water reducer.Research shows that introducing phosphate group can be effectively improved poly-carboxylic in the case of sandstone clay content is higher
The anti-mud performance of acid high efficiency water reducing agent, the guarantor that can improve high-efficiency water-reducing agent of poly-carboxylic acid in the case of sandstone clay content is the highest is collapsed
Performance, have not been reported about the work of this respect is domestic.
Summary of the invention
For the deficiencies in the prior art, the present invention provides a kind of novel propylene acids monomer of phosphate group that introduces as altogether
Poly-monomer prepares polycarboxylate water-reducer method.It is from design theory of molecular structure based on the above-mentioned purpose present invention, by insatiable hunger
With the novel propylene acids monomer that acid and 2-HPAA (HPAA) and derivant such as Fig. 1 thereof pass through esterification
MPA is as in figure 2 it is shown, utilize novel propylene acids monomer MPA to prepare the polycarboxylate water-reducer of function admirable.
Wherein, R1 and R2 separately represents hydrogen atom, the alkyl of 1-6 carbon atom or-(CH2)yCOOM, M represent hydrogen
Atom, metal ion, ammonium or the alkyl containing 1-3 carbon atom, y represents the integer of 0-3.
Utilize monomer MPA shown in Fig. 2 for comonomer, can arbitrarily be used for, with existing, the monomer that polycarboxylate water-reducer synthesizes
All kinds of polycarboxylate water-reducer is prepared in copolymerization, includes but not limited to: containing substituted radical or the little molecule insatiable hunger without substituted radical
With alcohol, unsaturated amine, unsaturated carboxylic acid, unsaturated sulfonic acid, unsaturated acid anhydride, unsaturated amides etc., polymerization monomer also includes containing
There is the macromonomer etc. of polymer chain, such as acrylic polyoxyethylene ether, methylpropenyl polyoxyethylene ether, methyl butene polyoxy
Vinyl Ether, vinyl polyoxyethylene ether etc..Kind and the consumption of polymerization monomer can be by those of ordinary skill in the art by poly-carboxylics
Acid water reducer requires to be determined.
The synthesis of the polycarboxylate water-reducer that the present invention provides can use the co-polymeric method of routine to be prepared, the present invention
It is not particularly limited.
Preferably, polymerization process can be: with in water or organic solvent medium, at the additive such as chain-transferring agent, initiator
In the presence of carry out copolymerization and prepare.Wherein, initiator can be the initiator of single kind, as persulfate, azo-compound,
Flower oxides etc., include but not limited to Ammonium persulfate., potassium peroxydisulfate, sodium peroxydisulfate, azodiisobutyronitrile, hydrogen peroxide, peroxide
Changing benzoyl, lauroyl peroxide etc., reducing agent includes but not limited to sodium sulfite, sodium sulfate, ascorbic acid etc..Chain-transferring agent
Can be any kind chain-transferring agent in copolyreaction, such as sulfur alcohol compound, include but not limited to TGA, mercaptopropionic acid
Deng.
The present invention, from design theory of molecular structure, is the innovation again on water reducer direction and breakthrough, for follow-up
Deep level development new varieties polycarboxylate water-reducer has widened thinking and direction.
The novel propylene acids monomer MPA that the present invention provides, due to the unsaturated acids monomer directly and containing functional group
Carry out esterification, it is to avoid utilize the polyether macromonomer to carry out the challenge of esterification generation, reduce and utilize polyethers big
Monomer improves high-efficiency water-reducing agent of poly-carboxylic acid performance production cost.
The novel propylene acids monomer prepared for high-efficiency water-reducing agent of poly-carboxylic acid provided by the present invention can have difference
HPAA monomer and derivant institute band phosphoric acid structure, polycarboxylic acids can be effectively improved in the case of sandstone clay content is higher high
The anti-mud performance of effect water reducer, can improve the slump retaining of high-efficiency water-reducing agent of poly-carboxylic acid in the case of sandstone clay content is the highest
Can, so that the concrete application performance of obtained polycarboxylate water-reducer is significantly improved, there is good economic benefit
And social benefit.
Detailed description of the invention
Below in conjunction with comparative example and embodiment, the invention will be further described, but is not limited to this.
Embodiment 1
It is that the methyl allyl polyoxyethylene ether (TPEG) of 2400,173.5 parts of water put into four mouthfuls by 70 parts of polyoxyethylene degree of polymerization
In flask, stirring in water bath, it is heated to 55 ° of C, 10.1 parts of acrylic acid, 5.04 parts of sodium allylsulfonates is dissolved in 23.3 parts of water, makes
It fully dissolves and is prepared as mixed monomer solution.3.97 parts of Ammonium persulfate .s are dissolved in 52.7 parts of water that to make mass fraction be 7%
Solution.Every 10min, 61.7 parts of MPA are joined four-hole boiling flask, constant temperature 10min.After be warming up to 70 ° of C, drip list the most respectively
Body mixed solution and ammonium persulfate solution 1.5h, isothermal reaction 3h, it is cooled to 50 ° of C, adds 40%KOH solution 9.7 parts, regulate pH
=8.Prepared concentration is the water reducer product 1 of 40%.
Embodiment 2
It is that the methyl allyl polyoxyethylene ether (TPEG) of 2400,82.5 parts of water put into four mouthfuls of burnings by 70 parts of polyoxyethylene degree of polymerization
In Ping, stirring in water bath, it is heated to 50 ° of C, 6.56 parts of sodium p styrene sulfonates, 22.9 parts of acrylic acid, 34.26 parts of MPA are dissolved in
In 100 parts of water, it is prepared as mixed monomer solution.7.23 parts of Ammonium persulfate .s are dissolved in 28.9 parts of water and make the solution of 20%.Rear intensification
To 70 ° of C, dropping mixed monomer solution and ammonium persulfate solution 3h, isothermal reaction 1h, it is cooled to 45 ° of C, adds 40%KOH solution
8.2 parts, regulate pH=8.Prepared concentration is the water reducer product 2 of 40%.
Comparative example 1
It is that the methyl allyl polyoxyethylene ether (TPEG) of 2400,173.5 parts of water put into four mouthfuls by 70 parts of polyoxyethylene degree of polymerization
In flask, stirring in water bath, it is heated to 55 ° of C, 10.1 parts of acrylic acid, 5.04 parts of sodium allylsulfonates is dissolved in 23.3 parts of water, makes
It fully dissolves and is prepared as mixed monomer solution.3.97 parts of Ammonium persulfate .s are dissolved in 52.7 parts of water that to make mass fraction be 7%
Solution.Every 10min, 39.2 parts of methyl-maleic acid acid anhydrides, 22.5 parts of acrylic acid methyl ester .s are joined four-hole boiling flask, constant temperature
10min.After be warming up to 70 ° of C, dropping monomer mixture solution and ammonium persulfate solution 1.5h, isothermal reaction 3h the most respectively, cooling
To 50 ° of C, add 40%KOH solution 9.7 parts, regulate pH=8.Prepared concentration is the water reducer product 3 of 40%.
Comparative example 2
It is that the methyl allyl polyoxyethylene ether (TPEG) of 2400,82.5 parts of water put into four mouthfuls of burnings by 70 parts of polyoxyethylene degree of polymerization
In Ping, stirring in water bath, it is heated to 50 ° of C, by 6.56 parts of sodium p styrene sulfonates, 22.9 parts of acrylic acid, 34.26 parts of acrylic acid first
Ester is dissolved in 100 parts of water, is prepared as mixed monomer solution.7.23 parts of Ammonium persulfate .s are dissolved in 28.9 parts of water and make the solution of 20%.
After be warming up to 70 ° of C, dropping mixed monomer solution and ammonium persulfate solution 3h, isothermal reaction 1h, be cooled to 45 ° of C, add 40%
KOH solution 8.2 parts, regulates pH=8.Prepared concentration is the water reducer product 4 of 40%.
Implementation result:
1. flowing degree of net paste of cement
For investigating the polycarboxylate water-reducer of the present invention synthesis mobility action effect to different cement, measuring
Each embodiment paste flowing degree to different cement types under identical volume.Test presses GB/T8077-2012 " outside concrete
Add agent homogeneity test method " carry out, W/C=0.29, volume is the solid volume of folding.Result of the test is shown in Table 1.
As it can be seen from table 1 the polycarboxylate water-reducer solution of the inventive method synthesis, the ratio of mud and the folding of 0.2% 0.29 are solid
Under volume, all can show dispersive property and the cement adaptability of excellence.Utilize polycarboxylic acids prepared by novel propylene acids monomer
High efficiency water reducing agent embodiment starches the efficient diminishing of polycarboxylic acids that retentivity is better than commonly not utilizing novel acrylic class monomer to prepare only
Agent comparative example.
2. concrete slump and divergence
First, water reducer sample is blended by JGJ55 with certain proportioning with cement, sand, stone, water etc..Test material
And specification is shown in Table 2, concrete mix is shown in Table 3.
Table 2 tests material and specification
| Material | Specification |
| Sand | Medium sand (fluvial sand) |
| Stone | Particle diameter (16-31.5mm) |
| Reference cement | Special PI.42.5 checked by concrete admixture |
Table 3 concrete mix
In table 3, " ratio of mud " refers to the mass ratio of cement and water in concrete: " sand coarse aggregate ratio " refer in concrete sand and sand and
The mass ratio of stone summation；After " water reducer volume " refers to that polycarboxylate water-reducer folding is solid, add the use of cement quality 0.2%
Amount.
The slump and divergence test data are as shown in table 4.
Table 4 water reducer Evaluation results
From table 4, it can be seen that the polycarboxylate water-reducer solution of the inventive method synthesis all can show excellent in concrete system
Different divergence and the holding capacity of the slump.Utilize high-efficiency water-reducing agent of poly-carboxylic acid embodiment prepared by novel propylene acids monomer
Concrete slump retaining is better than the high-efficiency water-reducing agent of poly-carboxylic acid comparative example commonly not utilizing novel acrylic class monomer to prepare.
Claims (1)
1. novel propylene acids monomer prepares a high-efficiency water-reducing agent of poly-carboxylic acid method as comonomer, it is characterized in that: with not
Saturated acid and 2-hydroxyl phosphoryl acetic acid and derivant thereof prepare novel propylene acids monomer by esterification, utilize preparation
Novel monomeric synthesizes polycarboxylate water-reducer further.
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|---|---|---|---|
| CN201610277701.9A CN106008846B (en) | 2016-04-29 | 2016-04-29 | A kind of acrylic monomer prepares high-efficiency water-reducing agent of poly-carboxylic acid method as comonomer |
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|---|---|---|---|
| CN201610277701.9A CN106008846B (en) | 2016-04-29 | 2016-04-29 | A kind of acrylic monomer prepares high-efficiency water-reducing agent of poly-carboxylic acid method as comonomer |
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| CN106008846A true CN106008846A (en) | 2016-10-12 |
| CN106008846B CN106008846B (en) | 2018-10-09 |
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| CN201610277701.9A Expired - Fee Related CN106008846B (en) | 2016-04-29 | 2016-04-29 | A kind of acrylic monomer prepares high-efficiency water-reducing agent of poly-carboxylic acid method as comonomer |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015041678A1 (en) * | 2013-09-20 | 2015-03-26 | Halliburton Energy Services, Inc. | Methods for etching fractures and microfractures in shale formations |
| US20150175752A1 (en) * | 2012-09-07 | 2015-06-25 | Chryso | Copolymers having gem-acetophone groups |
| CN105254825A (en) * | 2015-11-18 | 2016-01-20 | 科之杰新材料集团有限公司 | Preparation method of esters retarding polycarboxylic acid slump retaining agent |
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2016
- 2016-04-29 CN CN201610277701.9A patent/CN106008846B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150175752A1 (en) * | 2012-09-07 | 2015-06-25 | Chryso | Copolymers having gem-acetophone groups |
| WO2015041678A1 (en) * | 2013-09-20 | 2015-03-26 | Halliburton Energy Services, Inc. | Methods for etching fractures and microfractures in shale formations |
| CN105254825A (en) * | 2015-11-18 | 2016-01-20 | 科之杰新材料集团有限公司 | Preparation method of esters retarding polycarboxylic acid slump retaining agent |
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