CN1295184C - Polymer emulsion for cement base material water reducing and its preparing method - Google Patents
Polymer emulsion for cement base material water reducing and its preparing method Download PDFInfo
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- CN1295184C CN1295184C CNB2004100513935A CN200410051393A CN1295184C CN 1295184 C CN1295184 C CN 1295184C CN B2004100513935 A CNB2004100513935 A CN B2004100513935A CN 200410051393 A CN200410051393 A CN 200410051393A CN 1295184 C CN1295184 C CN 1295184C
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Abstract
The present invention relates to a polymer emulsion for water reduction of a cement base material and a preparation method thereof. The polymer emulsion is characterized in that reactive non-ionic emulsifier hydroxyl or alkyl polyalkoxylate glycol (methyl)acryl acrylic ester containing double bonds capable of being polymerized, an ionic emulsifier containing substances of sulfonic groups or sulfuric ester groups or vinyl, (methyl) acrylic acid ester, alkylation styrene or vinyl acetate, and the like are copolymerized in an emulsion way to be synthesized into the polymer emulsion for modification of the stable cement base material. The emulsion has the high water reduction and enhancement effects on the cement base material, and the working performance, the physical and mechanical performance, the water resistance and the durability of the composite cement base material are greatly improved.
Description
Technical field
The present invention relates to a kind of polymer emulsion that is used for the cement-based material diminishing, this emulsion has high diminishing, enhancing and waterproof effect to cement-based material, the invention still further relates to the preparation method of this emulsion.
Background technology
One of material of construction that cement concrete is current application quantity maximum, range of application is the widest, it uses seldom separately, often needs to add organic polymer it is carried out modification.The polymkeric substance that is used for modified cement-concrete comprises water-soluble polymers, polymer emulsion (or dispersion), redispersible polymer powders and liquid polymers.Polymer-modified cement-based matrix material be meant in grout, sand-cement slurry and cement concrete, added be dispersed in the water or can be in water the dispersive polymer materials, this moment, many performances such as the intensity, deformability, adhesive property, water resistance, endurance quality etc. of cement based all can make moderate progress.
High efficiency water reducing agent and polymer emulsion (or dispersion) are the polymkeric substance of the modified cement sill used always.Mixing high efficiency water reducing agent is a kind of important method and the technology of cement concrete modifying, a spot of high efficiency water reducing agent just can significantly improve the serviceability of cement concrete, improve intensity, water-repellancy and the weather resistance of maturing, but it is very little to contributions such as the deformability of cement concrete, adhesive properties, the waterproof water resistance improves not very big, and can not form very thin cement based coating.Polymer emulsion then can significantly improve bonding, water resistance, folding strength and the deformability of cement-based material, and can be used as the cement based coating that waterproof paint uses formation to approach.Polymer-modified cement-based material not only becomes a kind of very important material in the repairing of concrete structure with aspect safeguarding, obtains application more and more widely in new building such as bridge floor, parking lot, harbour, ceramic tile and stone material bonding, buildings waterproof, engineering field such as anticorrosion.
Cement-based polymers emulsion commonly used comprises styrene-butadiene latex (SBR), vinyl acetate emulsion (EVA), benzene emulsion (SA), acrylic ester emulsion (PAE), ethylene-vinyl acetate emulsion (EVA), polychloroprene latex (CR).Styrene-butadiene emulsion contains two keys, and weathering resistance is relatively poor, and the weather resisteant of acrylic polymer is then better.The weathering resistance of benzene emulsion is between styrene-butadiene latex and esters of acrylic acid.Hydrolysis easily takes place in aqueous polyvinyl acetate emulsion under alkaline condition, the water tolerance of the cement concrete of its modification is bad, now seldom uses.The water tolerance of ethylene-vinyl acetate copolymer emulsion improves greatly than the water tolerance of vinyl acetate emulsion, has become a kind of important cement-based material modification polymer.Acrylic polymer has good anti-hydrolytic performance.Metachloroethylene copolymer discharges HCl easy decomposition the under alkaline condition, can not be used for the repairing of erosion resistance occasion such as Steel Concrete.
Except the composition of polymkeric substance itself, other component in the emulsion is all influential to the performance of improving cement concrete.In order to guarantee the stability of emulsion to grout, usually the low molecule emulsifying agent of non-ionic type and Sodium dodecylbenzene sulfonate, the sodium lauryl sulphate (SDS) of the low molecule emulsifying agent of ionic that add more amount as using always, these low molecule emulsifying agents have certain effect to the flowability that increases the modified cement sill, but can reduce the water tolerance of polymer emulsion modified cement-based material, water-intake rate is higher.
Summary of the invention
The object of the present invention is to provide a kind of novel polymer emulsion that is used for the cement-based material diminishing, need not to add other ancillary component, and can improve the work flowability of cement-based material greatly, reduce water consumption, improve the concrete pressure-proof and snap-resistent intensity of hardened cement, adhesive property, waterproof water resistance and endurance quality, solve the above-mentioned variety of issue of prior art; Another object of the present invention is to provide the preparation method of this polymer emulsion.
Utilization of the present invention contains the material that the reactive nonionic emulsifier oh type of polymerizable reaction double key or alkoxylate polyalkylene glycol (methyl) acrylate and ionic emulsifying agent contain sulfonic group or sulfate group and vinyl, can with (methyl) acrylate, alkyl-substituted styrene or vinyl-acetic ester etc. are at the aqueous phase emulsion copolymerization, synthesized a kind of stable cement-based material modification polymer emulsion, this emulsion has high water-reduction and reinforced effects to cement-based material, improve the serviceability of cement-base composite material greatly, physical and mechanical property, the waterproof endurance quality, thus realized purpose of the present invention.
Purpose of the present invention is achieved through the following technical solutions.
The invention provides a kind of polymer emulsion that is used for the cement based diminishing, it is characterized in that, described polymkeric substance is by A, B, the multipolymer that three kinds of structural units of C are formed, wherein A is one or more the monomer in vinylformic acid and the derivative thereof, B is one or more the monomer that contains in the material of sulfonic group or sulfate group and vinyl, but C contains one or more the monomer in the material of copolymerizable vinyl groups for except that the B material other, described polymkeric substance composition is counted A 20%～98% by massfraction, B 2%～20%, C 0～60%, always consists of 100%; Contain one or more the monomer in polyalkene glycol acrylates, polyalkylene glycol methacrylic ester, oxyalkylated polyalkene glycol acrylates, the oxyalkylated polyalkylene glycol methacrylic ester in the described acrylic acid derivative monomer, its content be polymer A structural unit massfraction 5% or more than, and the polymerization degree of its glycol ethers part is 10～500.
Described acrylic acid derivative is acrylate, methacrylic acid and salt thereof, acrylate, acrylamide, N hydroxymethyl acrylamide; Described acrylate is a methyl acrylate, ethyl ester, butyl ester, isobutyl ester, the tert-butyl ester, monooctyl ester, different monooctyl ester and long-chain alkyl groups, methyl methacrylate, ethyl ester, butyl ester, isobutyl ester, the tert-butyl ester, monooctyl ester, different monooctyl ester and long-chain alkyl groups, polyalkene glycol acrylates, the polyalkylene glycol methacrylic ester, oxyalkylated polyalkene glycol acrylates, oxyalkylated polyalkylene glycol methacrylic ester (formula 1), Hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methylacrylate, hydroxypropyl acrylate, fluorine-containing alkyl ester, the acrylate that contains the polyurethane PU group, the methacrylic ester that contains the polyurethane PU group, the acrylate that contains epoxide group contains the methacrylic ester of epoxide group; Described polyalkylene glycol is polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, polypropylene glycol, polytetramethylene glycol, polypropylene glycol polyoxyethylene glycol; Described polyalkylene glycol structure is that the monoalkyl end-blocking (is alkoxylate R`=CH
3, C
2H
5, C
3H
7) or end-blocking (being hydroxyl R`=H) not; Described polyalkene glycol acrylates, polyalkylene glycol methacrylic ester, oxyalkylated polyalkene glycol acrylates, oxyalkylated polyalkylene glycol methacrylic ester are reactive nonionic emulsifier, in the structural unit A of polymkeric substance forms, account for massfraction 5% or more than; They participate in the part in the reaction formation copolymer structure unit, and its glycol ethers part as [CH (R) (CH
2)
mO]
nThe polymerization degree n of R` can from 10 to 500, are the best with 50 to 200 wherein, and end capped alkyl R` can be H, CH
3, C
2H
5, C
3H
7
R＝H，CH
3；m＝1～3；n＝10～500 R`＝H，CH
3，C
2H
5，C
3H
7 R``＝H，CH
3
Formula 1
The described material that contains sulfonic group or sulfuric ester and vinyl, it is the ionic emulsifying agent of polymerizable reaction, comprise styrene sulfonic acid and salt thereof (formula 2), vinyl sulfonic acid and salt thereof (formula 3), allyl sulphonic acid and salt thereof (formula 4), 2-acrylamido-2-methyl propane sulfonic acid (AMPS, formula 5), allyl group-the propenyl derivatives (formula 6～9) that contains sulfonic group or sulfate group, the acrylic acid derivative that contains sulfonic group or sulfate group, the methacrylic acid derivative (formula 10～11) that contains sulfonic group or sulfate group, the propylenedicarboxylic acid derivative (formula 12～13) that contains sulfonic group or sulfate group, contain the maleic acid derivatives (formula 14～15) of sulfonic group or sulfate group etc.
Formula 2 formulas 3
CH
2＝CR-CH
2-SO
3M
Formula 4 formulas 5
Formula 6 formulas 7
CH
2＝CHCH
2OCH
2CH(OH)CH
2OOCCH(SO
3M)CH
2COOR CH
2＝CHCH
2OOCCH(SO
3M)CH
2COOR
Formula 8 formulas 9
CH
2＝C(R)COO(AO)
nSO
3M CH
2＝C(R)COOCH
2C(R`)(SO
3M)CH
2OOCR``
Formula 10 formulas 11
Formula 12 formulas 13
Formula 14 formulas 15
But described other vinyl material that contains copolymerization except that the B material is vinylbenzene, alkyl-substituted styrene, vinyl acetate, unsaturated monocarboxylic such as butenoic acid and unsaturated dicarboxylic acid such as maleic anhydride, toxilic acid and ester thereof, propylenedicarboxylic acid acid anhydride, propylenedicarboxylic acid, fumaric acid etc., also can be an alkali metal salt, alkaline earth salt, ammonium salt or the quaternary ammonium salt of described unsaturated carboxylic acid; Account for the massfraction 0～60% of multipolymer, polymer emulsion promptly of the present invention can be not contain C-structure unitary pure acrylic acid ester emulsion or contain benzene emulsion, acrylate and vinyl acetate emulsion of C etc.
Polymer emulsion of the present invention is the same with normally used cement matrix water reducer or polymer emulsion, and water content is unrestricted, and by the national standard requirement, pH is 8～9.
The present invention also provides a kind of above-mentioned preparation method who is used for the polymer emulsion of cement-based material diminishing, the step of this method is as follows: is A, B, three kinds of materials of C 20～98: 2～20 by the mass ratio of A: B: C: 0～60 mixes, emulsification in water, then in the presence of radical initiator, copolyreaction takes place, and obtains a kind of polymer emulsion that is used for the cement-based material diminishing of the present invention; Described A material is one or more the material in vinylformic acid and the derivative thereof, described B material is one or more the material that contains in the material of sulfonic group or sulfate group and vinyl, contains one or more material in the material of vinyl of copolymerization but described C material is except that the B material other; Contain one or more the material in polyalkene glycol acrylates, polyalkylene glycol methacrylic ester, oxyalkylated polyalkene glycol acrylates, the oxyalkylated polyalkylene glycol methacrylic ester in the described acrylic acid derivative, its content be described A material mass fractional 5% or more than, and the polymerization degree of its glycol ethers part is 10～500.
Described vinylformic acid and derivative thereof, the described material that contains sulfonic group or sulfate group and vinyl, but described except that the B material other contains the material of the vinyl of copolymerization, all as described above.
Copolyreaction condition in the method for preparing polymer emulsion of the present invention is identical with common copolyreaction condition, and used initiator is water miscible initiator, for example persulphate, hydrogen peroxide and derivative thereof etc.; Its consumption is a reactant quality fractional 0.4%～2%; Can a collection of adding initiator in the reactant, also can add in batches, normally add in two batches; Temperature of reaction can be at 60～90 ℃, preferably 70～80 ℃; After reaction finishes, separate and remove unreacted monomer; The same with common cement-based material water reducer with polymer emulsion, with adjusting PH with base to 8～9.
Polymer emulsion of the present invention is used for cement-based material, and pressure-proof and snap-resistent intensity detects according to GB GB/T17671-1999, and bonding strength detects by 8 type matrix methods, and water-intake rate detects according to the JIS A6203 of Japanese Industrial Standards.The result shows that the present invention compared with prior art has following advantage:
(1) have higher water-reduction, improve the work flowability of cement-based material greatly, reduce water consumption, water-reducing rate can be up to 42%;
(2) improve the concrete pressure-proof and snap-resistent intensity of hardened cement;
(3) improve the concrete adhesive property of hardened cement, improve cohesive strength;
(4) improve concrete waterproof water resistance of hardened cement and endurance quality, make it water-intake rate and greatly reduce.
It describes in detail referring to embodiment 5,6.
Embodiment
Following experiment and operational instances are further to explanation of the present invention, should not be used as limitation of the present invention.
Embodiment 1: the preparation of polymer emulsion of the present invention
With methoxylated polyethylene glycol methacrylic ester (number average molecular mass M
n=1000) 5g, methoxylation polypropylene glycol polyethylene glycol methacrylate-styrene polymer (M
n=2000) 5g, polyethylene glycol methacrylate-styrene polymer (M
n=5000) 5g, methyl methacrylate 5g, butyl acrylate 45g, Sodium styrene sulfonate 3g, sodium vinyl sulfonate 2g, vinylbenzene 30g mix, and under agitation drop in the 200g water, and high degree of agitation makes its emulsification.Then 1/5 of emulsion is dropped in the there-necked flask, adding 0.25g ammonium persulfate initiator is warming up to 70～72 ℃, is incubated to material to be blue, and an exothermic peak can appear in this moment, and temperature may rise to more than 80 ℃.Treat to begin to drip remaining emulsion and remaining initiator 0.25g after temperature descends, temperature-stable is at 70～75 ℃, after the monomer emulsion droplet adds in the control bottle, be warming up to 95 ℃, be incubated 0.5 hour, vacuumize again and remove unreacted monomer, cooling at last adds ammoniacal liquor and regulates pH value to 8～9.
Embodiment 2: the preparation of polymer emulsion of the present invention
With polypropylene glycol polyethylene glycol methacrylate-styrene polymer (M
n=2000) 10g, polyethylene glycol acrylate (M
n=4000) 5g, methyl methacrylate 25g, butyl acrylate 47g, Jia Jibingxisuanyizhi 6g, methacrylic acid 2g, trifluoroethyl methacrylate 3g, 2-acrylamido-2-methyl propane sulfonic acid (AMPS) 2g mix, under agitation drop in the 200g water, high degree of agitation makes its emulsification.Then the 80g emulsion is dropped in the there-necked flask, adding 0.35g Potassium Persulphate initiator is warming up to 72～75 ℃, is incubated to material to be blue, and controlled temperature is about 80 ℃ during exothermic heat of reaction.Treat to begin to drip remaining emulsion and remaining initiator 0.35g after temperature descends, temperature-stable is at 70～75 ℃, after the monomer emulsion droplet adds in the control bottle, be warming up to 95 ℃, be incubated 0.5 hour, vacuumize again and remove unreacted monomer, cooling at last adds ammoniacal liquor and regulates pH value to 8～9.
Embodiment 3: the preparation of polymer emulsion of the present invention
With polyethylene glycol acrylate (M
n=4000) 8g, polytetramethylene glycol methacrylic ester (M
n=2000) 4g, methoxylated polyethylene glycol methacrylic ester (M
n=8000) 8g, methyl methacrylate 5g, butyl acrylate 7g, N-methylol acrylic amine 2g, propylenedicarboxylic acid macrogol ester butyl sulfonic acid sodium 5g, methoxylated polyethylene glycol (polymerization degree m=10) maleic acid ester sodium cetanesulfonate 5g, vinyl-acetic ester 55g, propylenedicarboxylic acid 1g mix, under agitation drop in the 200g water, high degree of agitation makes its emulsification.Then the 50g emulsion is dropped in the there-necked flask, add 0.25g Potassium Persulphate initiator, be warming up to 75 ℃ and carry out polymerization.Treating does not have in the condenser when obviously refluxing, and remaining emulsion and remaining initiator 0.6g were dripped off in 2～2.5 hours, is incubated and after 0.5 hour material is cooled to 45 ℃, gets final product discharging, filtration.
Embodiment 4: the preparation of polymer emulsion of the present invention
With methoxylated polyethylene glycol methacrylic ester (number average molecular mass M
n=1000) 20g, methacrylic acid polyethylene glycol (polymerization degree n=20) sodium sulfate 10g, methoxylated polyethylene glycol (polymerization degree m=20) maleic acid ester sodium cetanesulfonate 10g, vinyl-acetic ester 58g, maleic anhydride 2g mix, under agitation drop in the 200g water, high degree of agitation makes its emulsification.Then the 60g emulsion is dropped in the there-necked flask, add the 0.50g ammonium persulfate initiator, be warming up to 75 ℃ and carry out polymerization.Treating does not have in the condenser when obviously refluxing, and remaining emulsion and remaining initiator 1.5g were dripped off in 2～2.5 hours, is incubated and after 1 hour material is cooled to 45 ℃, gets final product discharging, filtration.
Embodiment 5: polymer emulsion of the present invention is used for the test of cement paste modification
The polymer emulsion of embodiment 1 preparation is used for the test of cement paste modification.Cement is the 42.5R ordinary Portland cement, and pressure-proof and snap-resistent intensity detects according to GB GB/T17671-1999, and bonding strength detects by 8 type matrix methods, and water-intake rate detects according to the JIS A6203 of Japanese Industrial Standards.Make performance relatively with FDN (naphthalene sulfonic acidformaldehyde condensation product series high-efficiency water-reducing agent), benzene emulsion (SDS does not have traditional cinnamic acrylic ester emulsion of the low molecule emulsifying agent of chemical reactivity with sodium lauryl sulphate SDS and OP class), the results are shown in Table 1.
Table 1: polymer emulsion modified cement paste (blank cement paste water cement ratio is 0.4)
| Polymkeric substance | Polymer cement ratio % | Water-reducing rate % | Ultimate compression strength MPa | Water-intake rate % | |
| 3 days | 28 days | ||||
| Blank FDN high efficiency water reducing agent benzene emulsion (SDS) | 0 0.75 5 | 0 35 8 | 40.8 60.3 38.6 | 65.3 85.4 68.9 | 9.86 6.15 5.21 |
| Polymer emulsion of the present invention | 2.5 5 10 15 | 18 29 38 42 | 48.4 54.7 42.9 36.8 | 75.8 83.2 80.5 73.6 | 3.82 2.48 1.35 0.83 |
By table 1 as seen, after mixing and stirring, polymer emulsion of the present invention and cement has higher diminishing and enhancement, water-reducing rate and polymkeric substance volume (are polymer cement ratio, the per-cent of polymkeric substance and cement) closely related, polymer cement ratio be 2.5% o'clock water-reducing rate be 18% and polymer cement ratio be 5% o'clock 29%, water-reducing rate is the highest can be up to 42% (be higher than FDN high efficiency water reducing agent volume commonly used be 0.75% o'clock water-reducing rate 35%), and traditional benzene emulsion volume that also to be higher than with the low molecule of SDS be emulsifying agent is 5% o'clock a water-reducing rate 8%.Polymer emulsion of the present invention is greatly improved to strength of cement, and volume is that 5%: 28 day ultimate compression strength reaches 83.2MPa, far above blank strength of cement 65.3MPa; Though its volume is very big to the early strength influence of cement, increases with consumption, delayed coagulation strengthens to some extent, still has higher early strength; The SDS benzene emulsion then increases with consumption, and intensity significantly descends.The waterproof water resistance of the cement that the present invention simultaneously is emulsion modified has improved greatly, 24 hours water-intake rates after emulsion modified hardening of cement greatly reduce, water-intake rate is relevant with the polymkeric substance volume, volume increases, water-intake rate descends, 2.48% of 3.82% during from polymer cement ratio 2.5% and 5% o'clock, 0.83% when dropping to polymer cement ratio 15%, during all far below 9.86% and FDN 0.75% of blank cement 6.15%, 5.21% when also being lower than traditional benzene emulsion polymer cement ratio 5%.
Embodiment 6: polymer emulsion of the present invention is used for the test of sand-cement slurry modification
The polymer emulsion of embodiment 1 preparation is used for the test of sand-cement slurry modification.Cement is the 42.5R ordinary Portland cement, and sand is standard sand, and pressure-proof and snap-resistent intensity detects according to GB GB/T17671-1999, and bonding strength detects by 8 type matrix methods, and water-intake rate detects according to the JIS A6203 of Japanese Industrial Standards.Make performance relatively with FDN (naphthalene sulfonic acidformaldehyde condensation product series high-efficiency water-reducing agent), benzene emulsion (SDS does not have traditional cinnamic acrylic ester emulsion of the low molecule emulsifying agent of chemical reactivity with sodium lauryl sulphate SDS and 0P class), the results are shown in Table 2.
Table 2: polymer emulsion modified sand-cement slurry (blank sand-cement slurry water cement ratio is 0.5)
| Polymkeric substance | Polymer cement ratio % | Water-reducing rate % | Resistance to compression [anti-folding] intensity MPa | Bonding strength MPa | Water-intake rate % | |
| 3 days | 28 days | |||||
| Blank FDN benzene emulsion (SDS) | 0 1 5 | 0 20 5 | 37.1 41.3 36.8 | 52.5[6.8] 60.1[7.3] 54.7[7.0] | 0.9 0.9 1.4 | 6.23 5.31 4.65 |
| Polymer emulsion of the present invention | 2.5 5 10 15 20 | 8.5 18 24 28 32 | 40.1 38.2 35.4 31.8 28.6 | 58.2[7.5] 54.6[8.3] 51.5[11.0] 47.1[12.5] 41.5[10.8] | 1.2 1.5 2.5 2.3 1.7 | 4.88 3.75 1.26 0.69 0.33 |
Can see equally from table 2, emulsion of the present invention has high diminishing and enhancement to sand-cement slurry, to the water-reducing rate of the sand-cement slurry of 1: 3 standard sand up to 32% (FDN only is 20%), polymer cement ratio is that 5% o'clock water-reducing rate reaches 18%, and the water-reducing rate of the benzene emulsion that traditional SDS produces under the same polymer cement ratio is 5%.Emulsion of the present invention is also not obvious to the delayed coagulation of sand-cement slurry, along with the increase of polymer cement ratio, delayed coagulation strengthens gradually, still has higher early strength and 28 days intensity when polymer cement ratio 20%, the SDS benzene emulsion then increases with consumption, and intensity significantly descends.FDN high efficiency water reducing agent consumption increases to a certain degree then water-reducing rate and increases and increase to some extent with consumption, and this water miscible polyalcohol water reducing agent consumption can not be excessive, crosses conference water-reducing rate is descended, and also can reduce the water resistance of mortar.Emulsion modified sand-cement slurry of the present invention, when polymer cement ratio 10%, have higher compression 51.5MPa, anti-folding 12.5MPa and bonding strength 2.5MPa, afterwards both also are higher than 7.3MPa, the 0.9MPa of FDN and 7.0MPa, the 1.4MPa of SDS benzene emulsion far above barren 6.8MPa, 0.9MPa.The water-intake rate of emulsion modified sand-cement slurry simultaneously of the present invention reduces greatly, water-intake rate is 3.75% during polymer cement ratio 5%, polymer cement ratio increases to 10% o'clock water-intake rate and reduces to 1.26%, water-intake rate was low to moderate 0.33% in 20% o'clock, far below 6.23% and FDN of blank sand-cement slurry 5.31%, SDS benzene emulsion volume be 5% 4.65%.The water tolerance of the sand-cement slurry that high diminishing of the present invention is emulsion modified has improved greatly.
Claims (10)
1. polymer emulsion that is used for the cement based diminishing, it is characterized in that, described polymkeric substance is by A, B, the multipolymer that three kinds of structural units of C are formed, wherein A is one or more the monomer in vinylformic acid and the derivative thereof, B is one or more the monomer that contains in the material of sulfonic group or sulfate group and vinyl, but C contains one or more the monomer in the material of copolymerizable vinyl groups for except that the B material other, described polymkeric substance composition is counted A 20%～98% by massfraction, B 2%～20%, C 0～60%, always consists of 100%; Contain polyalkene glycol acrylates in the described acrylic acid derivative monomer, the polyalkylene glycol methacrylic ester, oxyalkylated polyalkene glycol acrylates, the monomer of one or more in the oxyalkylated polyalkylene glycol methacrylic ester, its content be polymer A structural unit massfraction 5% or more than, and the polymerization degree of its glycol ethers part is 10～500, described polyalkylene glycol is a polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol or polypropylene glycol polyoxyethylene glycol, described alkoxylate is methoxylation, ethoxylation or propoxylation.
2. a kind of polymer emulsion that is used for the cement based diminishing according to claim 1 is characterized in that described acrylic acid derivative is acrylate, methacrylic acid and salt thereof, N hydroxymethyl acrylamide; The described material that contains sulfonic group or sulfuric ester and vinyl, be styrene sulfonic acid and salt thereof, vinyl sulfonic acid and salt thereof, allyl sulphonic acid and salt thereof, 2-acrylamido-2-methyl propane sulfonic acid, polyalkylene glycol acrylate sulfuric acid, methacrylic acid polyethylene glycol sulfuric acid, propylenedicarboxylic acid macrogol ester butyl sulfosalt, methoxylated polyethylene glycol maleic acid ester hexadecyl sulfonate; But described other vinyl material that contains copolymerization except that the B material is vinylbenzene, vinyl acetate, unsaturated dicarboxylic acid and an alkali metal salt thereof, alkaline earth salt, ammonium salt or quaternary ammonium salt.
3. a kind of polymer emulsion that is used for the cement based diminishing according to claim 2, it is characterized in that, described acrylate is a methyl acrylate, ethyl ester, butyl ester, isobutyl ester, the tert-butyl ester, methyl methacrylate, ethyl ester, butyl ester, isobutyl ester, the tert-butyl ester, polyalkene glycol acrylates, the polyalkylene glycol methacrylic ester, oxyalkylated polyalkene glycol acrylates, oxyalkylated polyalkylene glycol methacrylic ester, the fluorine-containing alkyl ester of methacrylic acid, described polyalkylene glycol is a polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol or polypropylene glycol polyoxyethylene glycol, described alkoxylate is methoxylation, ethoxylation or propoxylation.
4. a kind of polymer emulsion that is used for the cement based diminishing according to claim 3 is characterized in that, described polyalkylene glycol structure is the not end-blocking of oxyalkylated monoalkyl end-blocking or oh type.
5. a kind of polymer emulsion that is used for the cement based diminishing according to claim 2 is characterized in that, described unsaturated dicarboxylic acid is maleic anhydride, toxilic acid and ester thereof, propylenedicarboxylic acid acid anhydride, propylenedicarboxylic acid.
6. preparation method who is used for the polymer emulsion of cement-based material diminishing, the step of this method is as follows: is A, B, three kinds of materials of C 20～98: 2～20 by the mass ratio of A: B: C: 0～60 mixes, emulsification in water, then in the presence of radical initiator, copolyreaction takes place, and obtains a kind of polymer emulsion that is used for the cement-based material diminishing of the present invention; Described A material is one or more the material in vinylformic acid and the derivative thereof, described B material is one or more the material that contains in the material of sulfonic group or sulfate group and vinyl, contains one or more material in the material of vinyl of copolymerization but described C material is except that the B material other; Contain polyalkene glycol acrylates in the described acrylic acid derivative, the polyalkylene glycol methacrylic ester, oxyalkylated polyalkene glycol acrylates, the material of one or more in the oxyalkylated polyalkylene glycol methacrylic ester, its content be described A material mass fractional 5% or more than, and the polymerization degree of its glycol ethers part is 10～500, described polyalkylene glycol is a polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol or polypropylene glycol polyoxyethylene glycol, described alkoxylate is methoxylation, ethoxylation or propoxylation.
7. a kind of preparation method who is used for the polymer emulsion of cement-based material diminishing according to claim 6 is characterized in that described acrylic acid derivative is acrylate, methacrylic acid and salt thereof, N hydroxymethyl acrylamide; The described material that contains sulfonic group or sulfuric ester and vinyl, be styrene sulfonic acid and salt thereof, vinyl sulfonic acid and salt thereof, allyl sulphonic acid and salt thereof, 2-acrylamido-2-methyl propane sulfonic acid, polyalkylene glycol acrylate sulfuric acid, methacrylic acid polyethylene glycol sulfuric acid, propylenedicarboxylic acid macrogol ester butyl sulfosalt, methoxylated polyethylene glycol maleic acid ester hexadecyl sulfonate; But described other vinyl material that contains copolymerization except that the B material is vinylbenzene, vinyl acetate, unsaturated dicarboxylic acid and an alkali metal salt thereof, alkaline earth salt, ammonium salt or quaternary ammonium salt.
8. a kind of preparation method who is used for the polymer emulsion of cement-based material diminishing according to claim 7, it is characterized in that, described acrylate is a methyl acrylate, ethyl ester, butyl ester, isobutyl ester, the tert-butyl ester, methyl methacrylate, ethyl ester, butyl ester, isobutyl ester, the tert-butyl ester, polyalkene glycol acrylates, the polyalkylene glycol methacrylic ester, oxyalkylated polyalkene glycol acrylates, oxyalkylated polyalkylene glycol methacrylic ester, the fluorine-containing alkyl ester of methacrylic acid, described polyalkylene glycol is a polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol or polypropylene glycol polyoxyethylene glycol, described alkoxylate is methoxylation, ethoxylation or propoxylation.
9. a kind of preparation method who is used for the polymer emulsion of cement-based material diminishing according to claim 8 is characterized in that, described polyalkylene glycol structure is the not end-blocking of oxyalkylated monoalkyl end-blocking or oh type.
10. a kind of preparation method who is used for the polymer emulsion of cement-based material diminishing according to claim 7 is characterized in that, described unsaturated dicarboxylic acid is maleic anhydride, toxilic acid and ester thereof, propylenedicarboxylic acid acid anhydride, propylenedicarboxylic acid.
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| CNB2004100513935A CN1295184C (en) | 2004-09-09 | 2004-09-09 | Polymer emulsion for cement base material water reducing and its preparing method |
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| CN1295184C true CN1295184C (en) | 2007-01-17 |
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| CN103819629B (en) * | 2014-03-04 | 2016-03-30 | 南京瑞迪高新技术有限公司 | A kind of preparation method of bleed controllable type ethers poly carboxylic acid series water reducer |
| CN105153378A (en) * | 2015-08-25 | 2015-12-16 | 哈尔滨强石混凝土技术开发股份有限公司 | High-efficient polycarboxylate retarding and water reducing agent for mass concrete |
| CN106478890B (en) * | 2016-09-22 | 2019-02-12 | 佛山市顺德区巴德富实业有限公司 | A kind of polyurethane/polyvinyl acetate hybridisation emulsion and preparation method thereof |
| CN106543985A (en) * | 2016-09-30 | 2017-03-29 | 中国石油集团川庆钻探工程有限公司长庆固井公司 | A kind of emulsion-type oil-well cement filtrate reducer and preparation method thereof |
| CN106632886B (en) * | 2016-11-14 | 2020-04-24 | 北京水木佳维科技有限公司 | Polymer and preparation method and application thereof |
| CN109111548A (en) * | 2017-11-16 | 2019-01-01 | 邯郸市瑞斯达化工科技有限公司 | Methylacrylic higher alcohols ester and the formula of conventional emulsion polymerization and preparation method thereof |
| CN115353351B (en) * | 2022-08-29 | 2023-04-14 | 新疆科能新材料技术股份有限公司 | Thin-spraying high-performance polymer mortar for tunnel rock protection |
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| CN1052472A (en) * | 1989-12-16 | 1991-06-26 | 湖南省建筑材料研究设计院 | The composition of high-strength cement mortar and goods and manufacture method |
| CN1052471A (en) * | 1989-12-14 | 1991-06-26 | 罗姆和哈斯公司 | Has the cement that improves chemical resistance by polymer modification |
| CN1073323A (en) * | 1991-12-05 | 1993-06-23 | 雷恩自动机株式会社 | Supply with the method and apparatus of an even strip bread mass |
| CN1109033A (en) * | 1993-11-22 | 1995-09-27 | 罗姆和哈斯公司 | Redispersible dry polymers for flexible cementitious products |
| CN1261599A (en) * | 1998-12-28 | 2000-08-02 | 株式会社日本触媒 | Cement additire, cement composition and polycarboxylic acid polymer |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1052471A (en) * | 1989-12-14 | 1991-06-26 | 罗姆和哈斯公司 | Has the cement that improves chemical resistance by polymer modification |
| CN1052472A (en) * | 1989-12-16 | 1991-06-26 | 湖南省建筑材料研究设计院 | The composition of high-strength cement mortar and goods and manufacture method |
| CN1073323A (en) * | 1991-12-05 | 1993-06-23 | 雷恩自动机株式会社 | Supply with the method and apparatus of an even strip bread mass |
| CN1109033A (en) * | 1993-11-22 | 1995-09-27 | 罗姆和哈斯公司 | Redispersible dry polymers for flexible cementitious products |
| CN1261599A (en) * | 1998-12-28 | 2000-08-02 | 株式会社日本触媒 | Cement additire, cement composition and polycarboxylic acid polymer |
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Assignee: Shenzhen Wushan Building Industrial Co.,Ltd. Assignor: Guangzhou Inst. of Chemistry, Chinese Academy of Sciences Contract fulfillment period: 2007.11.20 to 2012.11.19 contract change Contract record no.: 2009440001449 Denomination of invention: Polymer emulsion for cement base material water reducing and its preparing method Granted publication date: 20070117 License type: Exclusive license Record date: 2009.9.24 |
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