CN115873182A - Mud-resistant slump-retaining ester type polycarboxylate superplasticizer and preparation method thereof - Google Patents
Mud-resistant slump-retaining ester type polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
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- 150000002148 esters Chemical class 0.000 title claims abstract description 78
- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000008030 superplasticizer Substances 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 110
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 59
- 125000004185 ester group Chemical group 0.000 claims abstract description 57
- 239000002253 acid Substances 0.000 claims abstract description 33
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 97
- 239000004593 Epoxy Substances 0.000 claims description 22
- 239000002202 Polyethylene glycol Substances 0.000 claims description 21
- 229920001223 polyethylene glycol Polymers 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 19
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 claims description 18
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 13
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 claims description 10
- CTDRAOLVEHKAAZ-UHFFFAOYSA-N 4-prop-2-enoxybutan-1-ol Chemical compound OCCCCOCC=C CTDRAOLVEHKAAZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 239000012986 chain transfer agent Substances 0.000 claims description 5
- 239000003995 emulsifying agent Substances 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 4
- HSVCUYGENANRMG-UHFFFAOYSA-N methoxyperoxymethane;2-methylprop-2-enoic acid Chemical compound COOOC.CC(=C)C(O)=O HSVCUYGENANRMG-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- NKVPLYTZHZYULG-UHFFFAOYSA-N methoxyperoxymethane;prop-2-enoic acid Chemical compound COOOC.OC(=O)C=C NKVPLYTZHZYULG-UHFFFAOYSA-N 0.000 claims description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 18
- 230000001603 reducing effect Effects 0.000 abstract description 13
- 230000035945 sensitivity Effects 0.000 abstract description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 30
- 239000000463 material Substances 0.000 description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 18
- 230000036571 hydration Effects 0.000 description 15
- 238000006703 hydration reaction Methods 0.000 description 15
- 238000007334 copolymerization reaction Methods 0.000 description 14
- 238000003756 stirring Methods 0.000 description 12
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 11
- 239000004568 cement Substances 0.000 description 11
- 229920000056 polyoxyethylene ether Polymers 0.000 description 11
- 229940051841 polyoxyethylene ether Drugs 0.000 description 11
- 239000000600 sorbitol Substances 0.000 description 11
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 9
- 229910001424 calcium ion Inorganic materials 0.000 description 9
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 9
- 239000011790 ferrous sulphate Substances 0.000 description 9
- 235000003891 ferrous sulphate Nutrition 0.000 description 9
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 9
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 9
- 229940017219 methyl propionate Drugs 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- QWNBTPQVFKSTLC-UHFFFAOYSA-N bis(ethenyl) pentanedioate Chemical compound C=COC(=O)CCCC(=O)OC=C QWNBTPQVFKSTLC-UHFFFAOYSA-N 0.000 description 7
- 239000004576 sand Substances 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 230000006911 nucleation Effects 0.000 description 5
- 238000010899 nucleation Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical group OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 4
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 4
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 230000000979 retarding effect Effects 0.000 description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 2
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000013074 reference sample Substances 0.000 description 2
- 239000000176 sodium gluconate Substances 0.000 description 2
- 235000012207 sodium gluconate Nutrition 0.000 description 2
- 229940005574 sodium gluconate Drugs 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- JZQAAQZDDMEFGZ-UHFFFAOYSA-N bis(ethenyl) hexanedioate Chemical compound C=COC(=O)CCCCC(=O)OC=C JZQAAQZDDMEFGZ-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- LSGWSXRILNPXKJ-UHFFFAOYSA-N ethyl oxirane-2-carboxylate Chemical compound CCOC(=O)C1CO1 LSGWSXRILNPXKJ-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- -1 lithium aluminum hydride Chemical compound 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention relates to the technical field of concrete admixtures, in particular to a mud-resistant slump loss resistant ester type polycarboxylate water reducing agent and a preparation method thereof. The mud-resistant slump-retaining ester type polycarboxylate superplasticizer is prepared by polymerizing a comonomer; the comonomer comprises an ester macromonomer, polyoxyalkyl ether with an ester group structure, an ester monomer and unsaturated acid. The mud-resistant slump retaining ester type polycarboxylate water reducer provided by the invention has good water reducing performance, can effectively improve the initial dispersing performance of concrete and the strength of the concrete, can reduce the sensitivity of the concrete, and has long-acting slump retaining performance and mud resistant effect.
Description
Technical Field
The invention relates to the technical field of concrete admixtures, in particular to a mud-resistant slump-retaining ester type polycarboxylate superplasticizer and a preparation method thereof
Background
The polycarboxylate superplasticizer has the advantages of high water reducing rate, adjustable molecular structure, environmental friendliness and the like. With the development of the concrete industry, the polycarboxylic acid water reducing agent is widely and rapidly applied to the improvement of various performance requirements of concrete.
With the development of the industry, the performance requirements of the polycarboxylate water reducer not only stay on the water reducing performance, but the market has increasingly increased demand for the polycarboxylate water reducer with multiple functions, such as:
the method has the defects that the market expanses in China are wide, raw materials are different from place to place in different places, and the sensitivity of the polycarboxylate superplasticizer is caused by high mud content (namely stone powder content) in machine-made sand raw materials in some places. The concrete expression is that a large amount of polycarboxylate superplasticizer is needed, so the mud resistance of the polycarboxylate superplasticizer cannot be ignored.
In addition, the concrete conditions in various areas are complex, and fresh concrete is required to maintain the flow performance for a long time. Therefore, the slump-retaining water reducing agent is one of the favorable weapons for coping with complex working conditions.
However, although the existing polycarboxylic acid water reducing agent has good water reducing performance, the slump loss resistance is insufficient, and the capability of improving the early strength of concrete is insufficient; in order to solve the problem of insufficient slump retaining performance, a person skilled in the art can compound a retarder with slump retaining and retarding functions with the existing polycarboxylic acid water reducing agent when using the existing polycarboxylic acid water reducing agent, but the final result is still insufficient to meet the requirements.
In conclusion, it is a problem addressed by those skilled in the art how to develop a polycarboxylate water reducing agent which has good water reducing performance, can reduce concrete sensitivity and improve initial dispersing performance of concrete, thereby enabling the polycarboxylate water reducing agent to have high slump retaining performance and mud resistance, and can improve strength of concrete.
Disclosure of Invention
In order to solve the defects of the existing polycarboxylic acid water reducing agent mentioned in the background technology. The invention provides a mud-resistant slump-retaining ester type polycarboxylate superplasticizer which has the technical scheme as follows:
the mud-resistant slump-retaining ester type polycarboxylate superplasticizer is prepared by polymerizing a comonomer; the comonomer comprises an ester macromonomer, polyoxyalkyl ether with an ester group structure, an ester monomer and unsaturated acid;
the structural formula of the polyoxyalkyl ether with the ester group structure is as follows:
In some embodiments, the M 1 The structural formula of (A) is as follows:
In some embodiments, the polyoxyalkyl ether with an ester group structure is prepared by ring-opening polymerization of an unsaturated alcohol and an epoxy propionate under the action of a catalyst; the unsaturated alcohol is 1-allyloxypropan-1-ol or 4- (allyloxy) -1-butanol; the epoxy propionate is 2,3-epoxy propionate or 2,3-epoxy propionate.
In some embodiments, the molar ratio of the unsaturated alcohol to the epoxypropionate is 1: (4-18); the ring-opening polymerization reaction temperature is 90-200 ℃, and the reaction pressure is 0.1-0.8 Mpa; wherein, when the reaction pressure is less than 0.2Mpa, the reaction temperature is more than or equal to 100 ℃.
In some embodiments, the ester macromonomer is one or more of polyethylene glycol dimethacrylate, polyethylene glycol monomethyl ether acrylate, polyethylene glycol monomethoxy ether monoacrylate, polyethylene glycol monomethoxy ether monomethacrylate, and has a molecular weight of 2000 to 4000.
In some embodiments, the ester monomer has the following structural formula:
In some embodiments, the unsaturated acid is one or more combinations of acrylic acid, methacrylic acid, itaconic acid.
In some embodiments, the mass ratio of the ester monomer, the ester macromonomer, the polyoxyalkyl ether with an ester group structure and the unsaturated acid is (1.5-6), (10-15) and (3-11).
In some embodiments, the polymerization is carried out at a reaction temperature of 25 ℃ to 35 ℃ for a reaction time of 1h to 2h.
The invention also provides a preparation method of the mud-resistant slump-retaining ester type polycarboxylate superplasticizer, which comprises the following preparation steps: and mixing the ester monomer, the ester macromonomer and the polyoxyalkyl ether with an ester group structure, adding an initiator solution, a chain transfer agent solution, an emulsifier solution and unsaturated acid, and carrying out polymerization reaction at 25-35 ℃ for 1-2 h to prepare the mud-resistant slump-retaining ester type polycarboxylate water reducer.
Compared with the prior art, the mud-resistant slump-retaining ester type polycarboxylate water reducer provided by the invention has the following beneficial effects:
the mud-resistant slump retaining ester type polycarboxylate water reducer provided by the invention has good water reducing performance, can effectively improve the initial dispersing performance of concrete and the strength of the concrete, can reduce the sensitivity of the concrete, and has long-acting slump retaining performance and mud resistant effect.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the following description will clearly and completely describe the embodiments of the present invention, and obviously, the described embodiments are a part of the embodiments of the present invention, but not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The invention provides a preferable embodiment of a preparation method of an anti-mud slump-retaining ester type polycarboxylate superplasticizer, which specifically comprises the following steps:
and mixing the ester monomer, the ester macromonomer and the polyoxyalkyl ether with an ester group structure, dropwise adding an initiator solution, a chain transfer agent solution, an emulsifier solution and unsaturated acid, carrying out polymerization reaction at 25-35 ℃ for 1-2 h, keeping the temperature for a period of time after the reaction is finished, adding liquid alkali to adjust the pH value to 6-7, and thus obtaining the mud-resistant slump-retaining ester type polycarboxylate water reducer.
Wherein the mass ratio of the ester monomer, the ester macromonomer, the polyoxyalkyl ether with an ester group structure and the unsaturated acid is (1.5-6), (10-15) and (3-11).
(1) For the comonomers:
polyoxyalkyl ether having an ester group structure:
the structural formula of the polyoxyalkyl ether with the ester group structure is as follows:
The M is 1 The structural formula of (A) is as follows:
Preferably, the polyoxyalkyl ether with an ester group structure is prepared by ring-opening polymerization reaction of unsaturated alcohol and epoxy propionate under the action of a catalyst; wherein the unsaturated alcohol is 1-allyloxypropan-1-ol or 4- (allyloxy) -1-butanol; the epoxy propionate is 2,3-epoxy methyl propionate or 2,3-epoxy ethyl propionate, and the catalyst is one or a combination of potassium hydroxide, sodium methoxide, potassium hydride, metal sodium and lithium aluminum hydride; the molar ratio of the unsaturated alcohol to the epoxypropionate is 1: (4-18); the ring-opening polymerization reaction temperature is 90-200 ℃, and the reaction pressure is 0.1-0.8 Mpa; wherein, when the reaction pressure is less than 0.2Mpa, the reaction temperature is more than or equal to 100 ℃.
Ester macromonomers, unsaturated acids, ester monomers:
the ester macromonomer is preferably one or a combination of polyethylene glycol dimethacrylate, polyethylene glycol monomethyl ether acrylate, polyethylene glycol monomethoxy ether monoacrylate and polyethylene glycol monomethoxy ether monomethacrylate, and the molecular weight of the ester macromonomer is 2000-4000.
The unsaturated acid is preferably one or more of acrylic acid, methacrylic acid and maleic acid;
the structural formula of the ester monomer is as follows:
Other polymerization starting materials:
preferably, the oxidant is one or more of ammonium persulfate, hydrogen peroxide and tert-butyl hydroperoxide. The reducing agent is preferably one or more of sodium hypophosphite, ascorbic acid, ferrous sulfate and N, N-dimethylaniline. The chain transfer agent is preferably one or more of mercaptoethanol, 2-mercaptopropionic acid, sodium dimethyldithiocarbamate and sodium hypophosphite. The emulsifier is preferably sorbitol polyoxyethylene ether tetraoleate. Among them, it is further preferable that the amount of the oxidizing agent is 0.8 to 3% by mass of the total amount of the polyoxyalkyl ethers having an ester group structure, the amount of the reducing agent is 1 to 3% by mass of the total amount of the polyoxyalkyl ethers having an ester group structure, and the amount of the chain transfer agent is 1 to 3% by mass of the total amount of the polyoxyalkyl ethers having an ester group structure. The dosage of the emulsifier is 1-3% of the total mass of the polyoxyalkyl ether with the ester group structure.
The invention also provides the following examples and comparative examples:
example 1
(1) Preparation of ester group-containing polyoxyalkyl ether: adding 27.9 parts by weight of 4- (allyloxy) -1-butanol and 1.5 parts by weight of potassium hydroxide into a 1.5L stainless steel high-pressure reaction kettle, and uniformly stirring; the reaction kettle was evacuated and replaced with N2 3 times. The reaction kettle is heated to 85 ℃, 131.1 parts of 2,3-epoxy methyl propionate is continuously added into the reaction kettle, the reaction temperature is controlled to be 120 ℃, and the reaction pressure is controlled to be 0.4Mpa. The reaction time is 4-5 h. After the product is cooled, adding a neutralizer, and collecting the product;
(2) And (3) copolymerization reaction: according to parts by weight, firstly, 6 parts of glutaric acid divinyl ester, 10 parts of polyoxyalkyl ether with an ester group structure, 100 parts of polyethylene glycol monomethyl ether acrylate, 1.2 parts of 1% ferrous sulfate solution, 1 part of sorbitol polyoxyethylene ether tetraoleate and 131.5 parts of water are added into a first reaction vessel and uniformly stirred, and 0.8 part of hydrogen peroxide and 20 parts of water are uniformly mixed in a first dripping device; 3 parts of mercaptoethanol and 20 parts of water are uniformly mixed in a second dripping device; uniformly mixing 7 parts of acrylic acid and 120 parts of water in a third dripping device; at normal temperature, sequentially dripping materials in the first dripping device, the second dripping device and the third dripping device into the first reaction container, respectively dripping the materials in the third dripping device, the second dripping device and the first dripping device at 80 min, and reacting for 1h at constant temperature;
(3) And adding 10 parts by weight of 32% sodium hydroxide by mass to obtain the mud-resistant slump-retaining polycarboxylic acid water reducer with the concentration of 40%.
Example 2
(1) Preparation of ester group-containing polyoxyalkyl ether: adding 61.5 parts by weight of 1-allyloxypropanol-1-ol and 1.5 parts by weight of potassium hydroxide into a 1.5L stainless steel high-pressure reaction kettle, and uniformly stirring; the reaction kettle was evacuated and replaced with N2 3 times. The temperature of the reaction kettle is raised to 160 ℃, 737.2 parts of 2,3-epoxypropionic acid ethyl ester is continuously added into the reaction kettle, the reaction temperature is controlled to be 170 ℃, and the reaction pressure is 0.2Mpa. The reaction time is 5-5.5 h. After the product is cooled, adding a neutralizer, and collecting the product;
(2) And (3) copolymerization reaction: according to parts by weight, firstly adding 2 parts of divinyl adipate, 11 parts of polyoxyalkyl ether with an ester group structure, 100 parts of polyethylene glycol monomethoxy ether monomethacrylate, 2.8 parts of sodium hypophosphite, 3 parts of sorbitol polyoxyethylene ether tetraoleate and 130.6 parts of water into a first reaction vessel, uniformly stirring, and uniformly mixing 2.6 parts of tert-butyl hydroperoxide and 20 parts of water in a first dripping device; 2 parts of sodium dimethyldithiocarbamate and 20 parts of water are uniformly mixed in a second dripping device; 5 parts of acrylic acid and 20 parts of water are uniformly mixed in a third dripping device; at normal temperature, sequentially dripping materials in the first dripping device, the second dripping device and the third dripping device into the first reaction container, respectively dripping the materials in the third dripping device, the second dripping device and the first dripping device at 70 min, and reacting for 1h at constant temperature;
(3) And (3) adding 10 parts by weight of 32% sodium hydroxide by mass to obtain the mud-resistant slump-retaining polycarboxylic acid water reducer with the concentration of 40%.
Example 3
(1) Preparation of ester group-containing polyoxyalkyl ether: adding 59.1 parts by weight of 1-allyloxypropanol-1-ol and 1.5 parts by weight of potassium hydroxide into a 1.5L stainless steel high-pressure reaction kettle, and uniformly stirring; the reaction kettle was evacuated and replaced with N2 3 times. Heating the reaction kettle to 90 ℃, continuously adding 934.0 parts of 2,3-epoxy methyl propionate into the reaction kettle, controlling the reaction temperature to be 110 ℃ and the reaction pressure to be 0.5Mpa. The reaction time is 5-6 h. After the product is cooled, adding a neutralizer, and collecting the product;
(2) And (3) copolymerization reaction: according to parts by weight, firstly adding 4.5 parts of glutaric acid divinyl ester, 13 parts of polyoxyalkyl ether with an ester group structure, 100 parts of polyethylene glycol dimethacrylate, 2 parts of sorbitol polyoxyethylene ether tetraoleate and 140.4 parts of water into a first reaction vessel, uniformly stirring, and uniformly mixing 1.5 parts of ammonium sulfate and 20 parts of water in a first dripping device; 1.9 parts of ascorbic acid, 1 part of 2-mercaptopropionic acid and 20 parts of water are uniformly mixed in a second dripping device; uniformly mixing 11 parts of acrylic acid and 20 parts of water in a third dripping device; at normal temperature, sequentially dropwise adding materials in the first dropwise adding device, the second dropwise adding device and the third dropwise adding device into the first reaction vessel, respectively dropwise adding the materials in the third dropwise adding device, the second dropwise adding device and the first dropwise adding device at 100 min, and reacting for 1h at constant temperature;
(3) And adding 10 parts by weight of 32% sodium hydroxide by mass to obtain the mud-resistant slump-retaining polycarboxylic acid water reducer with the concentration of 40%.
Comparative example 1 (4-hydroxybutyl vinyl ether instead of the unsaturated alcohol of the examples)
(1) Preparation of ester group-containing polyoxyalkyl ether: adding 24.9 parts of 4-hydroxybutyl vinyl ether and 1.5 parts of potassium hydroxide by weight into a 1.5L stainless steel high-pressure reaction kettle, and uniformly stirring; the reaction kettle was evacuated and replaced with N2 3 times. The reaction kettle is heated to 85 ℃, 131.1 parts of 2,3-epoxy methyl propionate is continuously added into the reaction kettle, the reaction temperature is controlled to be 120 ℃, and the reaction pressure is controlled to be 0.4Mpa. The reaction time is 4-5 h. After the product is cooled, adding a neutralizing agent, and collecting the product;
(2) And (3) copolymerization reaction: according to parts by weight, firstly, 6 parts of glutaric acid divinyl ester, 10 parts of polyoxyalkyl ether with an ester group structure, 100 parts of polyethylene glycol monomethyl ether acrylate, 1.2 parts of 1% ferrous sulfate solution, 1 part of sorbitol polyoxyethylene ether tetraoleate and 131.5 parts of water are added into a first reaction vessel and uniformly stirred, and 0.8 part of hydrogen peroxide and 20 parts of water are uniformly mixed in a first dripping device; 3 parts of mercaptoethanol and 20 parts of water are uniformly mixed in a second dripping device; mixing 7 parts of acrylic acid and 120 parts of water uniformly in a third dripping device; at normal temperature, sequentially dripping materials in the first dripping device, the second dripping device and the third dripping device into the first reaction container, respectively dripping the materials in the third dripping device, the second dripping device and the first dripping device at 80 min, and reacting for 1h at constant temperature;
(3) And adding 10 parts by weight of 32% sodium hydroxide by mass to obtain the mud-resistant slump-retaining polycarboxylic acid water reducer with the concentration of 40%.
Comparative example 2 (ethylene glycol monovinyl ether substituted for unsaturated alcohol in example)
(1) Preparation of ester group-containing polyoxyalkyl ether: adding 18.9 parts by weight of ethylene glycol monovinyl ether and 1.5 parts by weight of potassium hydroxide into a 1.5L stainless steel high-pressure reaction kettle, and uniformly stirring; the reaction kettle was evacuated and replaced with N2 3 times. Heating the reaction kettle to 85 ℃, continuously adding 131.1 parts of 2,3-epoxy methyl propionate into the reaction kettle, controlling the reaction temperature to be 120 ℃ and the reaction pressure to be 0.4Mpa. The reaction time is 4-5 h. After the product is cooled, adding a neutralizer, and collecting the product;
(2) And (3) copolymerization reaction: according to parts by weight, firstly, 6 parts of glutaric acid divinyl ester, 10 parts of polyoxyalkyl ether with an ester group structure, 100 parts of polyethylene glycol monomethyl ether acrylate, 1.2 parts of 1% ferrous sulfate solution, 1 part of sorbitol polyoxyethylene ether tetraoleate and 131.5 parts of water are added into a first reaction vessel and uniformly stirred, and 0.8 part of hydrogen peroxide and 20 parts of water are uniformly mixed in a first dripping device; 3 parts of mercaptoethanol and 20 parts of water are uniformly mixed in a second dripping device; mixing 7 parts of acrylic acid and 120 parts of water uniformly in a third dripping device; at normal temperature, sequentially dripping materials in the first dripping device, the second dripping device and the third dripping device into the first reaction container, respectively dripping the materials in the third dripping device, the second dripping device and the first dripping device at 80 min, and reacting for 1h at constant temperature;
(3) And adding 10 parts by weight of 32% sodium hydroxide by mass to obtain the mud-resistant slump-retaining polycarboxylic acid water reducer with the concentration of 40%.
Comparative example 3 (2-methyl-1-buten-4-ol instead of the unsaturated alcohol in the example)
(1) Preparation of ester group-containing polyoxyalkyl ether: adding 18.5 parts of 2-methyl-1-butene-4-ol and 1.5 parts of potassium hydroxide into a 1.5L stainless steel high-pressure reaction kettle, and uniformly stirring; the reaction kettle was evacuated and replaced with N2 3 times. The reaction kettle is heated to 85 ℃, 131.1 parts of 2,3-epoxy methyl propionate is continuously added into the reaction kettle, the reaction temperature is controlled to be 120 ℃, and the reaction pressure is controlled to be 0.4Mpa. The reaction time is 4-5 h. After the product is cooled, adding a neutralizing agent, and collecting the product;
(2) And (3) copolymerization reaction: according to parts by weight, firstly, 6 parts of glutaric acid divinyl ester, 10 parts of polyoxyalkyl ether with an ester group structure, 100 parts of polyethylene glycol monomethyl ether acrylate, 1.2 parts of 1% ferrous sulfate solution, 1 part of sorbitol polyoxyethylene ether tetraoleate and 131.5 parts of water are added into a first reaction vessel and uniformly stirred, and 0.8 part of hydrogen peroxide and 20 parts of water are uniformly mixed in a first dripping device; 3 parts of mercaptoethanol and 20 parts of water are uniformly mixed in a second dripping device; mixing 7 parts of acrylic acid and 120 parts of water uniformly in a third dripping device; at normal temperature, sequentially dripping materials in the first dripping device, the second dripping device and the third dripping device into the first reaction container, respectively dripping the materials in the third dripping device, the second dripping device and the first dripping device at 80 min, and reacting for 1h at constant temperature;
(3) And adding 10 parts by weight of 32% sodium hydroxide by mass to obtain the mud-resistant slump-retaining polycarboxylic acid water reducer with the concentration of 40%.
Comparative example 4 (polyether macromonomer substituted for ester macromonomer in example)
(1) Preparation of ester group-containing polyoxyalkyl ether: adding 27.9 parts by weight of 4- (allyloxy) -1-butanol and 1.5 parts by weight of potassium hydroxide into a 1.5L stainless steel high-pressure reaction kettle, and uniformly stirring; the reaction kettle was evacuated and replaced with N2 3 times. The reaction kettle is heated to 85 ℃, 131.1 parts of 2,3-epoxy methyl propionate is continuously added into the reaction kettle, the reaction temperature is controlled to be 120 ℃, and the reaction pressure is controlled to be 0.4Mpa. The reaction time is 4-5 h. After the product is cooled, adding a neutralizer, and collecting the product;
(2) And (3) copolymerization reaction: according to parts by weight, firstly, 6 parts of glutaric acid divinyl ester, 10 parts of polyoxyalkyl ether with an ester group structure, 100 parts of EPEG polyether, 1.2 parts of ferrous sulfate 1% solution, 1 part of sorbitol polyoxyethylene ether tetraoleate and 131.5 parts of water are added into a first reaction container and uniformly stirred, and 0.8 part of hydrogen peroxide and 20 parts of water are uniformly mixed in a first dripping device; 3 parts of mercaptoethanol and 20 parts of water are uniformly mixed in a second dripping device; uniformly mixing 7 parts of acrylic acid and 120 parts of water in a third dripping device; at normal temperature, sequentially dropwise adding materials in the first dropwise adding device, the second dropwise adding device and the third dropwise adding device into the first reaction vessel, respectively dropwise adding the materials in the third dropwise adding device, the second dropwise adding device and the first dropwise adding device at 80 min, and reacting for 1h at constant temperature;
(3) And adding 10 parts by weight of 32% sodium hydroxide by mass to obtain the mud-resistant slump-retaining polycarboxylic acid water reducer with the concentration of 40%.
Comparative example 5 (polyoxyalkyl ether having no ester group Structure participating in copolymerization reaction)
(1) And (3) copolymerization reaction: according to parts by weight, firstly, 6 parts of glutaric acid divinyl ester, 100 parts of polyethylene glycol monomethyl ether acrylate, 1.2 parts of ferrous sulfate 1% solution, 1 part of sorbitol polyoxyethylene ether tetraoleate and 116.5 parts of water are added into a first reaction vessel and uniformly stirred, and 0.8 part of hydrogen peroxide and 20 parts of water are uniformly mixed in a first dripping device; 3 parts of mercaptoethanol and 20 parts of water are uniformly mixed in a second dripping device; mixing 7 parts of acrylic acid and 120 parts of water uniformly in a third dripping device; at normal temperature, sequentially dripping materials in the first dripping device, the second dripping device and the third dripping device into the first reaction container, respectively dripping the materials in the third dripping device, the second dripping device and the first dripping device at 80 min, and reacting for 1h at constant temperature;
(2) And adding 10 parts by weight of 32% sodium hydroxide by mass to obtain the mud-resistant slump-retaining polycarboxylic acid water reducer with the concentration of 40%.
Comparative example 6
And (3) selecting commercially available Poi nt-TS8 type polycarboxylate superplasticizer mother liquor and sodium gluconate, wherein the use amounts of the mother liquor and the sodium gluconate are respectively 0.2% and 0.03% of the mass of the cementing material, and compounding to carry out concrete verification.
Comparative example 7 (copolymerization without ester monomer)
(1) Preparation of ester group-containing polyoxyalkyl ether: adding 27.9 parts by weight of 4- (allyloxy) -1-butanol and 1.5 parts by weight of potassium hydroxide into a 1.5L stainless steel high-pressure reaction kettle, and uniformly stirring; the reaction kettle was evacuated and replaced with N2 3 times. Heating the reaction kettle to 85 ℃, continuously adding 131.1 parts of 2,3-epoxy methyl propionate into the reaction kettle, controlling the reaction temperature to be 120 ℃ and the reaction pressure to be 0.4Mpa. The reaction time is 4-5 h. After the product is cooled, adding a neutralizer, and collecting the product;
(2) And (3) copolymerization reaction: according to parts by weight, firstly, adding 10 parts of polyoxyalkyl ether with an ester group structure, 100 parts of polyethylene glycol monomethyl ether acrylate, 1.2 parts of ferrous sulfate 1% solution, 1 part of sorbitol polyoxyethylene ether tetraoleate and 125.8 parts of water into a first reaction vessel, uniformly stirring, and uniformly mixing 0.8 part of hydrogen peroxide and 20 parts of water in a first dripping device; 3 parts of mercaptoethanol and 20 parts of water are uniformly mixed in a second dripping device; uniformly mixing 7 parts of acrylic acid and 120 parts of water in a third dripping device; at normal temperature, sequentially dropwise adding materials in the first dropwise adding device, the second dropwise adding device and the third dropwise adding device into the first reaction vessel, respectively dropwise adding the materials in the third dropwise adding device, the second dropwise adding device and the first dropwise adding device at 80 min, and reacting for 1h at constant temperature;
(3) And (3) adding 10 parts by weight of 32% sodium hydroxide by mass to obtain the mud-resistant slump-retaining polycarboxylic acid water reducer with the concentration of 40%.
Comparative example 8 hydroxyethyl acrylate instead of the ester monomer of the example
(1) Preparation of ester group-containing polyoxyalkyl ether: adding 27.9 parts by weight of 4- (allyloxy) -1-butanol and 1.5 parts by weight of potassium hydroxide into a 1.5L stainless steel high-pressure reaction kettle, and uniformly stirring; the reaction kettle was evacuated and replaced with N2 3 times. The reaction kettle is heated to 85 ℃, 131.1 parts of 2,3-epoxy methyl propionate is continuously added into the reaction kettle, the reaction temperature is controlled to be 120 ℃, and the reaction pressure is controlled to be 0.4Mpa. The reaction time is 4-5 h. After the product is cooled, adding a neutralizer, and collecting the product;
(2) And (3) copolymerization reaction: according to parts by weight, firstly, 6 parts of hydroxyethyl acrylate, 10 parts of polyoxyalkyl ether with an ester group structure, 100 parts of polyethylene glycol monomethyl ether acrylate, 1.2 parts of 1% ferrous sulfate solution, 1 part of sorbitol polyoxyethylene ether tetraoleate and 131.5 parts of water are added into a first reaction vessel and uniformly stirred, and 0.8 part of hydrogen peroxide and 20 parts of water are uniformly mixed in a first dripping device; 3 parts of mercaptoethanol and 20 parts of water are uniformly mixed in a second dripping device; mixing 7 parts of acrylic acid and 120 parts of water uniformly in a third dripping device; at normal temperature, sequentially dropwise adding materials in the first dropwise adding device, the second dropwise adding device and the third dropwise adding device into the first reaction vessel, respectively dropwise adding the materials in the third dropwise adding device, the second dropwise adding device and the first dropwise adding device at 80 min, and reacting for 1h at constant temperature;
(3) And adding 10 parts by weight of 32% sodium hydroxide by mass to obtain the mud-resistant slump-retaining polycarboxylic acid water reducer with the concentration of 40%.
Performance testing of the products of the examples and comparative examples:
comparing the water reducing agent products synthesized in examples 1-3 with those synthesized in comparative examples 1-8 with machine-made sand concrete: the red lion PO42.5R cement is used as a raw material, and the concrete is prepared from the following raw materials in percentage by weight: cement 287kg/m 3 123kg/m of fly ash 3 Machine-made sand 827kg/m 3 1011kg/m stone 3 Wherein the content of the machine-made sandstone powder is 1 percent; wherein, the mixing amount of the water reducing agent in the examples 1 to 3 is 0.2 percent (folded solid part) of the mass of the cementing material, the mixing amount of the water reducing agent in the comparative examples 1 to 5 and the comparative examples 7 to 8 is 0.2 percent (folded solid part) of the mass of the cementing material, the mixing amount of the admixture in the comparative example 6 refers to a specific compound formula, and the reference sample is not added with the admixture; the concrete samples of examples 1 to 3 and comparative examples 1 to 8 were subjected to slump, expansion and other property tests in accordance with GB 8076-2008 "concrete admixture", and the concrete test results are shown in Table 1;
the products synthesized in examples 1 to 3 and comparative examples 7 to 8 were subjected to the mud resistance test in accordance with the above admixture blending amounts: with the above reference mix ratio, the difference is only: wherein the content of the machine-made sand powder is adjusted to be 5 percent, and the rest conditions are unchanged; the slump, the expansion and other performance tests are tested according to GB 8076-2008 concrete admixture, and the results of the mud resistance performance test are shown in Table 2.
Table 1 concrete performance test data
Table 2 mud resistance test data
As can be seen from the results of tables 1-2:
the performances of the examples 1 to 3 are all better than those of the reference sample and the comparative examples 1 to 7, and the results of the examples 1 to 3 show that after the mud-resistant slump-retaining ester type polycarboxylate water reducer provided by the embodiment of the invention is added, the initial dispersing performance and slump-retaining performance of concrete can be effectively improved, the strength of the concrete is improved, and the sensitivity of the concrete can be reduced when the content of the produced sand powder is higher, so that the mud-resistant slump-retaining ester type polycarboxylate water reducer provided by the embodiment of the invention has obvious slump-retaining and mud-resistant effects.
Comparing the results of the comparative example and the examples shows that:
comparative example 1 used 4-hydroxybutyl vinyl ether instead of the unsaturated alcohol of the examples, comparative example 2 used ethylene glycol monovinyl ether instead of the unsaturated alcohol of the examples, and comparative example 3 used 2-methyl-1-buten-4-ol instead of the unsaturated alcohol of the examples. As can be seen from the test results of example 1 and comparative examples 1 to 3, the examples of the present invention using unsaturated alcohols have a greater improvement in initial water-reducing performance of concrete than the case of preparing polyoxyalkyl ethers having an ester group structure using 4-hydroxybutyl vinyl ether, ethylene glycol monovinyl ether, 2-methyl-1-buten-4-ol as a starter.
Compared with the comparative example 4, the test results of the example 1 and the comparative example 4 show that the ester macromonomer adopted in the embodiment of the invention participates in polymerization, the initial concrete water reducing performance is slightly reduced, but the slump retaining performance is improved, the embodiment of the invention has the long-acting slump retaining effect, and the overall performance is better.
Comparative example 5 does not use polyoxyalkyl ether having an ester group structure to participate in the copolymerization reaction, and it can be seen from the test results of example 1 and comparative example 5 that the slump retaining ability of concrete is lowered and the strength of concrete is slightly lowered when the polyoxyalkyl ether having an ester group structure is not used in comparative example 5.
Comparative example 6 adopts the existing water reducing agent and retarder with slump retaining and retarding effects to compound; as can be seen from the test results of the embodiment 1 and the comparative example 6, compared with the mode of compounding the retarder by using the existing water reducing agent, the mud-resistant slump-retaining ester type polycarboxylate water reducing agent provided by the embodiment of the invention has better water reducing performance, greatly improves the slump-retaining performance, and simultaneously improves the early strength of concrete.
Compared with the scheme of not adding the ester monomer or using other existing types of ester monomers, the polycarboxylic acid water reducer prepared by the embodiment of the invention has better slump retaining performance and can improve the strength effect of concrete by adopting the specific ester monomer. Meanwhile, the concrete has a better anti-mud effect on machine-made sand with higher stone powder content, which is particularly shown in that the concrete of the embodiment of the invention still has flowing performance within 2 hours (see the data of the expansion degree of 2 hours in the table 2 in detail), while the concrete of the comparative examples 6-7 has no flowing performance.
In conclusion, the mud-resistant slump-retaining ester type polycarboxylate water reducer provided by the invention has good water reducing performance, can effectively improve the initial dispersing performance of concrete and the strength of the concrete, can reduce the sensitivity of the concrete, and has long-acting slump-retaining performance and mud-resistant effect.
The mud-resistant slump retaining ester type polycarboxylate superplasticizer and the preparation method thereof provided by the invention at least comprise the following design concepts, action mechanisms and beneficial effects:
1. the invention introduces polyoxyalkyl ether with an ester group structure into a comonomer, wherein the polyoxyalkyl ether with the ester group structure is prepared by ring-opening polymerization reaction of unsaturated alcohol, such as 1-allyloxypropyl-1-ol (the carbon structure is 3+3) and 4- (allyloxy) -1-butanol (the carbon structure is 3+4) and epoxy propionate. The polyoxyalkyl ether with the ester structure is introduced with a plurality of sections of ester groups, and a large number of carboxyl groups are introduced after hydrolysis, so that not only a complex is formed with calcium ions on the surface of cement particles, but also a chain segment extends into a pore solution and also forms a complex with the calcium ions in the solution, the concentration of the calcium ions in the pore solution is greatly reduced, and a large number of hydroxyl groups are introduced to form a cement particle covering net, thereby hindering the material exchange of the calcium ions and hydration products, delaying the nucleation rate of the hydration products on the surface of the cement particles, playing the role of slump protection, and simultaneously delaying the nucleation rate of the hydration products in the solution. Therefore, the polyoxyalkyl ether with the ester group structure is used as a comonomer and introduced into the polycarboxylic acid water reducing agent, and can play roles in retarding and slump retaining.
2. The mud-resistant slump-retaining ester type polycarboxylate water reducer provided by the invention not only introduces the polyoxyalkyl ether comonomer with an ester group structure, but also introduces the ester monomer with double alkenyl to form a cross-linking structure, so that the structure of the mud-resistant slump-retaining ester type polycarboxylate water reducer is slightly cross-linked. Under the alkaline condition of cement, the hydrolysis of the crosslinking structure is slower than that of the water reducing agent obtained by copolymerization of monomers containing ester groups, acid anhydrides and other groups, and the carboxylic acid groups contributing to the water reducing effect are continuously released by gradual hydrolysis along with the prolonging of time, so that the lost water reducing rate is compensated, and the effect of maintaining slump is achieved. The ester group releases carboxylate radicals during hydrolysis to adsorb calcium ions and the surfaces of cement particles or hydration products, further reduces the concentration of the calcium ions in the solution, covers the nucleation points of the hydration products, prolongs the nucleation time of the hydration products, inhibits the growth of Ca (OH) 2 and AFt crystal nuclei, slows down the hydration speed, prolongs the hydration induction period of cement, thereby playing a role in improving the dispersion retentivity and having excellent slump retaining effect. Meanwhile, products released after hydrolysis still have a large amount of carboxylate radicals, and can be freely dispersed to negative electricity regions of cement particles or complex calcium ions, so that nucleation sites of hydration products are further filled, and the generation of the hydration products is further hindered. The released carboxylic acid and hydroxyl complex calcium ions have strong capability, the adsorption capability of the water reducing agent is enhanced, the calcium ions released during cement hydration can be continuously combined, and the hydration of hydrated minerals and the growth of hydration products are inhibited, so that the cement hydration process is greatly delayed, free water is further released, the later hydration degree of concrete is higher, and the compressive strength of the concrete at the same age is improved. And the released micromolecular carboxyl can enter the intercalation of the mud powder, so that the adsorption of the mud powder to the water reducing agent is reduced, and the mud-resisting effect of the polycarboxylic acid water reducing agent is improved.
3. The invention introduces the ester macromonomer, and can effectively improve the long-acting slump retaining effect of the polycarboxylate superplasticizer.
4. In the preparation process of the existing 4-carbon or 5-carbon water reducing agent, the reaction temperature is up to 60 ℃, and heating equipment is needed. The existing 2+2 or 2+4 type water reducing agent is accepted by the current market due to short reaction time, excellent water reducing rate and slump retaining performance, but the macromonomer has high reaction activity and needs low-temperature equipment; the existing two have higher production cost.
According to the water reducer provided by the invention, the unsaturated alcohol in the polyoxyalkyl ether with the ester group structure preferably adopts 1-allyloxypropyl-1-ol (the carbon structure is 3+3) or 4- (allyloxy) -1-butanol (the carbon structure is 3+4), and the reaction temperature can be controlled at room temperature (namely 25-35 ℃) in the process of preparing the anti-mud slump retaining ester type polycarboxylate water reducer by using the polyoxyalkyl ether with the ester group structure as a comonomer by adopting the terminal alkene initiator (namely the unsaturated alcohol) with the 3+3 carbon structure and the 3+4 carbon structure. Compared with 2+2 or 2+4 carbon structure initiator, the carbon structure initiator has lower reaction activity, does not need to react under the low-temperature condition, has the effects of energy conservation and environmental protection, and caters for the emission reduction of double carbon. Compared with 4-carbon and 5-carbon polycarboxylic acid water reducing agents, the water reducing agent does not need to be heated for reaction, and energy is saved.
5. The preparation process of the mud-resistant slump-retaining ester type polycarboxylate water reducer provided by the invention is simple in technological operation, mild in reaction conditions, easy for large-scale production, safe and pollution-free in production process, and belongs to an environment-friendly product.
In conclusion, the mud-resistant slump-retaining ester type polycarboxylate water reducer and the preparation method thereof can reduce the production cost, and the polycarboxylate water reducer introduces a polyether structure with ester groups on the side chains, and the ester groups are used as slow-release groups, so that a more three-dimensional adsorption effect is provided; ester macromonomer is introduced, the ester side chain of the ester macromonomer slowly releases adsorption groups to provide long-acting slump retaining effect, meanwhile, ester groups of the ester monomer on the main chain are hydrolyzed to release micromolecule carboxylic acid, and the micromolecule carboxylic acid enters mud powder intercalation to improve the mud-resistant effect.
The mud-resistant slump retaining ester type polycarboxylate water reducer provided by the invention has good water reducing performance, can effectively improve the initial dispersing performance of concrete and the strength of the concrete, and has long-acting slump retaining performance and mud resistant effect.
The specific parameters or some common reagents or raw materials in the above embodiments are specific embodiments or preferred embodiments of the inventive concept, and are not limited thereto; those skilled in the art can adapt the same within the spirit and scope of the present invention.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the spirit of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The mud-resistant slump-retaining ester type polycarboxylate superplasticizer is characterized by being prepared by polymerizing a comonomer; the comonomer comprises an ester macromonomer, polyoxyalkyl ether with an ester group structure, an ester monomer and unsaturated acid;
the structural formula of the polyoxyalkyl ether with the ester group structure is as follows:
H 2 C＝CH-CH 2 -C-O-R 1 -O-M 1 -R 2 ，
wherein R is 1 Is an alkylene group having 3 or 4 carbon atoms; r 2 Is H or CH 3 ；M 1 Is an epoxyalkyl group with an ester group structure.
2. The mud-resistant slump-retaining ester type polycarboxylate superplasticizer according to claim 1, wherein M is 1 The structural formula of (A) is as follows:
wherein n is 4 to 18.
3. The mud-resistant slump retaining ester type polycarboxylate superplasticizer according to claim 1, wherein the polyoxyalkyl ether with an ester group structure is prepared by ring-opening polymerization of unsaturated alcohol and epoxy propionate under the action of a catalyst;
the unsaturated alcohol is 1-allyloxypropan-1-ol or 4- (allyloxy) -1-butanol; the epoxy propionate is 2,3-epoxy propionate or 2,3-epoxy propionate.
4. The mud-resistant slump retaining ester type polycarboxylate water reducer as claimed in claim 3, wherein the molar ratio of the unsaturated alcohol to the epoxy propionate is 1: (4-18);
the ring-opening polymerization reaction temperature is 90-200 ℃, and the reaction pressure is 0.1-0.8 Mpa; wherein, when the reaction pressure is less than 0.2Mpa, the reaction temperature is more than or equal to 100 ℃.
5. The mud-resistant slump retaining ester type polycarboxylate superplasticizer according to claim 1, wherein the ester type macromonomer is one or more of polyethylene glycol dimethacrylate, polyethylene glycol monomethyl ether acrylate, polyethylene glycol monomethoxy ether monoacrylate and polyethylene glycol monomethoxy ether monomethacrylate, and the molecular weight of the ester type macromonomer is 2000-4000.
6. The mud-resistant slump retaining ester type polycarboxylate superplasticizer according to claim 1, wherein the structural formula of the ester monomer is as follows:
wherein R is 3 Is an alkylene group having 1 to 5 carbon atoms.
7. The mud-resistant slump retaining ester type polycarboxylate superplasticizer according to claim 1, wherein the unsaturated acid is one or more of acrylic acid, methacrylic acid and itaconic acid.
8. The mud-resistant slump retaining ester type polycarboxylate superplasticizer according to claim 1, wherein the mass ratio of the ester monomer, the ester macromonomer, the polyoxyalkyl ether with an ester group structure and the unsaturated acid is (1.5-6) to 100 (10-15) to (3-11).
9. The anti-mud slump loss resistant ester type polycarboxylate water reducer according to claim 1, wherein the reaction temperature of the polymerization is 25-35 ℃, and the reaction time is 1-2 h.
10. The preparation method of the mud-resistant slump-retaining ester type polycarboxylate water reducer as claimed in any one of claims 1 to 9, characterized by comprising the following preparation steps:
and mixing the ester monomer, the ester macromonomer and the polyoxyalkyl ether with the ester group structure, adding an initiator solution, a chain transfer agent solution, an emulsifier solution and unsaturated acid, and carrying out polymerization reaction at 25-35 ℃ for 1-2 h to obtain the mud-resistant slump-retaining ester type polycarboxylic acid water reducer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211643276.2A CN115873182A (en) | 2022-12-20 | 2022-12-20 | Mud-resistant slump-retaining ester type polycarboxylate superplasticizer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2024131610A1 (en) * | 2022-12-20 | 2024-06-27 | 科之杰新材料集团有限公司 | Polyoxyalkyl ether with ester group structure, and ether polycarboxylic acid water reducing agent and preparation method therefor |
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| JP2004067934A (en) * | 2002-08-08 | 2004-03-04 | Nippon Shokubai Co Ltd | Copolymer for cement additive |
| JP2015054787A (en) * | 2013-09-10 | 2015-03-23 | 花王株式会社 | Method for producing cement dispersant |
| CN109400822A (en) * | 2018-11-09 | 2019-03-01 | 湖北鑫统领万象科技有限公司 | A kind of preparation method of collapse protective poly-carboxylic acid water reducing agent mother liquor |
| CN109485323A (en) * | 2018-12-26 | 2019-03-19 | 广东红墙新材料股份有限公司 | Early strong viscosity reduction type polycarboxylate water-reducer is preparing the purposes in prefabricated components concrete |
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| JP2004067934A (en) * | 2002-08-08 | 2004-03-04 | Nippon Shokubai Co Ltd | Copolymer for cement additive |
| JP2015054787A (en) * | 2013-09-10 | 2015-03-23 | 花王株式会社 | Method for producing cement dispersant |
| CN109400822A (en) * | 2018-11-09 | 2019-03-01 | 湖北鑫统领万象科技有限公司 | A kind of preparation method of collapse protective poly-carboxylic acid water reducing agent mother liquor |
| CN109485323A (en) * | 2018-12-26 | 2019-03-19 | 广东红墙新材料股份有限公司 | Early strong viscosity reduction type polycarboxylate water-reducer is preparing the purposes in prefabricated components concrete |
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| WO2024131610A1 (en) * | 2022-12-20 | 2024-06-27 | 科之杰新材料集团有限公司 | Polyoxyalkyl ether with ester group structure, and ether polycarboxylic acid water reducing agent and preparation method therefor |
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