WO2022095232A1 - 一种醚类防腐型聚羧酸减水剂及其制备方法 - Google Patents
一种醚类防腐型聚羧酸减水剂及其制备方法 Download PDFInfo
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- WO2022095232A1 WO2022095232A1 PCT/CN2020/136851 CN2020136851W WO2022095232A1 WO 2022095232 A1 WO2022095232 A1 WO 2022095232A1 CN 2020136851 W CN2020136851 W CN 2020136851W WO 2022095232 A1 WO2022095232 A1 WO 2022095232A1
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- WIPO (PCT)
- Prior art keywords
- ether
- corrosion
- water reducer
- polycarboxylate water
- unsaturated carboxylic
- Prior art date
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000002253 acid Substances 0.000 title abstract description 8
- 238000005260 corrosion Methods 0.000 claims abstract description 47
- 239000000178 monomer Substances 0.000 claims abstract description 32
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 15
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- 230000009471 action Effects 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 69
- 229920005646 polycarboxylate Polymers 0.000 claims description 59
- 239000007864 aqueous solution Substances 0.000 claims description 37
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 19
- 238000007334 copolymerization reaction Methods 0.000 claims description 19
- 239000002202 Polyethylene glycol Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 229920001223 polyethylene glycol Polymers 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 230000002421 anti-septic effect Effects 0.000 claims description 12
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 claims description 12
- NKHAVTQWNUWKEO-NSCUHMNNSA-N monomethyl fumarate Chemical compound COC(=O)\C=C\C(O)=O NKHAVTQWNUWKEO-NSCUHMNNSA-N 0.000 claims description 12
- 229940005650 monomethyl fumarate Drugs 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 10
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 6
- 150000002170 ethers Chemical class 0.000 claims description 6
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 6
- -1 fumaric acid ester Chemical class 0.000 claims description 6
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 6
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 6
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 claims description 5
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 claims description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical group OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 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 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 4
- XLYMOEINVGRTEX-ONEGZZNKSA-N (e)-4-ethoxy-4-oxobut-2-enoic acid Chemical compound CCOC(=O)\C=C\C(O)=O XLYMOEINVGRTEX-ONEGZZNKSA-N 0.000 claims description 3
- ZDMZLTIFXMREFI-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate;phosphoric acid Chemical compound OP(O)(O)=O.OCCOC(=O)C=C ZDMZLTIFXMREFI-UHFFFAOYSA-N 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- FIGQPHJTXZHETQ-UHFFFAOYSA-N CC(C(OC(C(C(C(O)=O)O)O)=O)=O)=C Chemical compound CC(C(OC(C(C(C(O)=O)O)O)=O)=O)=C FIGQPHJTXZHETQ-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical class CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 claims description 2
- GQZXRLWUYONVCP-UHFFFAOYSA-N 3-[1-(dimethylamino)ethyl]phenol Chemical compound CN(C)C(C)C1=CC=CC(O)=C1 GQZXRLWUYONVCP-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 229940074369 monoethyl fumarate Drugs 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 239000012966 redox initiator Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- IGRURXZWJCSNKU-UHFFFAOYSA-N Isopropenylacetic acid Chemical compound CC(=C)CC(O)=O IGRURXZWJCSNKU-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 230000009467 reduction Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 150000003384 small molecules Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 32
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 19
- 239000000243 solution Substances 0.000 description 14
- 239000003755 preservative agent Substances 0.000 description 13
- 229960005070 ascorbic acid Drugs 0.000 description 12
- 235000010323 ascorbic acid Nutrition 0.000 description 12
- 239000011668 ascorbic acid Substances 0.000 description 12
- 230000000844 anti-bacterial effect Effects 0.000 description 9
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 description 8
- 229960004419 dimethyl fumarate Drugs 0.000 description 8
- 239000004567 concrete Substances 0.000 description 5
- 230000002335 preservative effect Effects 0.000 description 5
- 238000013329 compounding Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000008030 superplasticizer Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- AOAGVPIEEAAAOL-RXSVEWSESA-N (2r)-2-[(1s)-1,2-dihydroxyethyl]-3,4-dihydroxy-2h-furan-5-one;hydrogen peroxide Chemical compound OO.OC[C@H](O)[C@H]1OC(=O)C(O)=C1O AOAGVPIEEAAAOL-RXSVEWSESA-N 0.000 description 2
- 101000908015 Homo sapiens Putative inactive carboxylesterase 4 Proteins 0.000 description 2
- 102100023322 Putative inactive carboxylesterase 4 Human genes 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 2
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 description 1
- 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 1
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- KMDBPLUOLGYNMO-UHFFFAOYSA-N 2-hydroxy-4-oxohex-5-ene-1,2,3-tricarboxylic acid Chemical compound OC(=O)CC(O)(C(O)=O)C(C(O)=O)C(=O)C=C KMDBPLUOLGYNMO-UHFFFAOYSA-N 0.000 description 1
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- BUWFOXNJVLKFBR-UHFFFAOYSA-N acetic acid;2-sulfanylacetic acid Chemical compound CC(O)=O.OC(=O)CS BUWFOXNJVLKFBR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 229960000789 guanidine hydrochloride Drugs 0.000 description 1
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940117986 sulfobetaine Drugs 0.000 description 1
- UIERETOOQGIECD-ONEGZZNKSA-N tiglic acid Chemical compound C\C=C(/C)C(O)=O UIERETOOQGIECD-ONEGZZNKSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
Definitions
- the invention relates to the technical field of building materials, in particular to an ether type anti-corrosion polycarboxylate water reducer and a preparation method thereof.
- ether-based polycarboxylate water-reducing agent because it has a higher water-reducing effect than ester-based polycarboxylate water-reducing agent, it also has advantages in price and outstanding cost performance, so it has become the most popular on the market.
- Mainstream polycarboxylate admixture As for ether-based polycarboxylate water-reducing agent, because it has a higher water-reducing effect than ester-based polycarboxylate water-reducing agent, it also has advantages in price and outstanding cost performance, so it has become the most popular on the market. Mainstream polycarboxylate admixture.
- the method of compounding and adding preservatives is the most widely used method at present, but the compounded preservatives generally have a small molecular weight. On the one hand, there may be the problem of uneven dispersion of the preservatives in the polycarboxylate At present, the commonly used compound preservatives still have the problem of decomposition and failure in the environment higher than 50 °C, which limits their application to a certain extent.
- CN110642996A published on January 3, 2020, discloses a self-ether type anti-corrosion type polycarboxylate water reducer and a preparation method thereof, but the monomer with anti-corrosion properties used in it is polymethacrylate acyloxyethene trimethylammonium chloride, poly[2-(acryloyloxy)ethyl]trimethylammonium bromide, polybenzylethyltrimethylammonium chloride, polyallyltrimethylammonium chloride, Any one or more of poly(3-acrylamidopropyl)trimethylammonium bromide.
- these substances are already polymers and have no polymerization activity, so they cannot be incorporated into the molecular structure of the superplasticizer, so in essence, this method is also a method for compounding preservatives.
- CN110128048A published on August 16, 2019, discloses a summer antiseptic slump-preserving polycarboxylate water reducer and a preparation method thereof, which is also a method of compounding a fungicide (polyhexamethyleneguanidine phosphate) achieve anti-corrosion properties.
- CN110015857A published on July 16, 2019, discloses a preparation method and application of a straw-starch-based mixed-modified composite polycarboxylate water-reducing agent, using dimethyl fumarate as a preservative to directly It is compounded into the patented product, but the water solubility of dimethyl fumarate is not very good.
- polycarboxylate water reducer a large amount of water is generally required to be compounded, and the water content often exceeds 90%. , so the effect of directly compounding and adding dimethyl fumarate is not ideal.
- CN109796561A published on May 24, 2019, discloses an aromatic ring polycarboxylate water-reducing agent mother liquor and its preparation method and application, using aryl conjugated unsaturated carboxylic acid as an anti-corrosion monomer to prepare a Polycarboxylate water reducing agent with anti-corrosion effect, but there are problems of large steric hindrance and unsatisfactory polymerization effect during the polymerization of aryl conjugated unsaturated carboxylic acid, which will eventually affect the performance of the product.
- CN109400819A published on March 1, 2019, discloses a viscosity-reducing antibacterial amphoteric polycarboxylate superplasticizer and a preparation method thereof, using guanidine hydrochloride and an alkyl compound with amine groups at both ends to prepare antibacterial The monomer is then used in the synthesis of the polycarboxylate water reducing agent. The synthesis process is complicated and the energy consumption is high.
- CN108373526A discloses an antifouling and antibacterial polycarboxylate water reducer and a preparation method thereof.
- (meth)acrylic acid sulfobetaine and methacrylic acid By adding (meth)acrylic acid sulfobetaine and methacrylic acid during polymerization Acyloxyethyltrimethylammonium chloride can achieve antibacterial effect, but the cost of these two monomers is relatively high.
- CN107698721A published on February 16, 2018, discloses a branched-chain antibacterial polycarboxylate water reducer, its preparation method and application, but the preparation process is too complicated and the production efficiency is low.
- CN107265907A published on October 20, 2017, discloses an amphoteric antibacterial polycarboxylic acid-based superplasticizer and a preparation method thereof.
- CN105621927A discloses a preparation method of an antibacterial preservative for polycarboxylate superplasticizers, and introduces antibacterial and antibacterial preservatives into polyoxyethylene ether with a similar structure to polycarboxylate superplasticizers.
- the functional betaine and dimethyl fumarate monomers undergo free radical copolymerization, which makes the molecular structure of the preservative and the polycarboxylic acid water reducer similar and compatible.
- the product of this patent only has anti-corrosion effect and does not have the effect of water reduction, and the direct polymerization of dimethyl fumarate monomer and unsaturated monomer in the system has poor water solubility and phase separation during the polymerization process. problem, making the polymerization efficiency low.
- the present invention provides an ether-type anti-corrosion polycarboxylate water-reducing agent, which is composed of a small anti-corrosion functional monomer and a non-corrosive agent.
- Saturated ether macromonomers, unsaturated carboxylic acids and/or unsaturated carboxylic acid anhydrides, and workability-modified small monomers are polymerized under the action of initiators and molecular weight regulators, and the main chain of the resulting molecules has a small anti-corrosion function.
- Monomer ether type anti-corrosion polycarboxylate water reducer is composed of a small anti-corrosion functional monomer and a non-corrosive agent.
- the anti-corrosion functional small monomer is fumarate and/or maleate.
- the mass ratio range of unsaturated macromonomer, anticorrosion functional small monomer, unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride, and workability modified small monomer is 180: (1 to 15): (5 to 30): (1 to 5).
- the dosage of the initiator is 0.5-3.0% of the total mass of the reactant; the dosage of the molecular weight regulator is 0.2-3.0% of the total mass of the reactant.
- the initiator aqueous solution, the molecular weight regulator aqueous solution, the unsaturated carboxylic acid and/or the unsaturated carboxylic acid anhydride aqueous solution are added dropwise within 2 to 6 h, and the reaction temperature is 20 ⁇ 90°C, keep the temperature for 0 ⁇ 3h after the dropwise addition is completed, and add alkali to adjust the pH value of the product to 5 ⁇ 7.
- the initiator includes a water-soluble redox initiation system or a water-soluble peroxide initiation system reagent; specifically, hydrogen peroxide-ascorbic acid, hydrogen peroxide-ascorbic acid, and ammonium persulfate can be used;
- the molecular weight regulator includes at least one of thioglycolic acid, mercaptoethanol, mercaptopropionic acid, sulfonated mercaptopropionic acid, and sodium hypophosphite.
- the fumaric acid ester includes monomethyl fumarate and monoethyl fumarate.
- the maleic acid ester includes diethyl maleate, dimethyl maleate and dipropyl maleate.
- the molecular weight of the unsaturated macromonomer is 600-6000.
- the unsaturated ether macromonomers are allyl polyethylene glycol, 3-methyl-3-butene-1-polyethylene glycol, 2-methyl At least one of allyl polyethylene glycol.
- the unsaturated carboxylic acid and/or the unsaturated carboxylic anhydride is at least one of acrylic acid, methacrylic acid and maleic anhydride.
- the workability-modified small monomers are: acrylamide, methyl methacrylate, hydroxyethyl acrylate phosphate, methacryloyl tartrate, acryloyl citric acid at least one of glycerides.
- the present invention also provides a preparation method of the ether type anti-corrosion type polycarboxylate water reducing agent as described above, comprising the following steps:
- alkali is added to adjust the pH value of the product to 5-7, that is, ether type anticorrosive polycarboxylate water reducing agent is obtained.
- the ether anti-corrosion type polycarboxylate water reducer provided by the present invention is copolymerized by unsaturated macromonomer, anti-corrosion functional small monomer, unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride, and workability modified small monomer At least one monomer unit of fumarate and maleate is introduced into the molecular structure of the product to obtain an ether-type anti-corrosion polycarboxylate water-reducing agent with anti-corrosion properties.
- the final product formed is a stable polymer structure, which can withstand high temperatures above 50 °C, and has better high-temperature anti-corrosion performance. Excellent.
- the ether type anti-corrosion polycarboxylate water reducer provided by the invention is suitable for the application occasions where the polycarboxylate water reducer has high cost performance and high anti-corrosion requirements.
- the cost is more in line with the application requirements of polycarboxylate superplasticizers, and has important practical application value.
- the present invention also provides the following preparation examples of the ether antiseptic polycarboxylate water reducer:
- step (2) adding 10g of sodium hydroxide aqueous solution with a concentration of 32% to the copolymerization product obtained in step (1) to obtain the ether type anti-corrosion polycarboxylate water reducer KZJ-4.
- ascorbic acid aqueous solution wherein, ascorbic acid 0.40, water 20.00g), the reaction temperature is 40 °C, and the dropping time is 3.0h, after the dropping is completed, the insulation is kept for 0.5h to obtain the copolymerization product;
- PCE-1 and monomethyl fumarate were compounded according to the mass ratio of 183:1 to obtain a comparative sample, which was recorded as PCE-2.
- the ether anti-corrosion type polycarboxylate water reducer prepared in Examples 1 to 5 and the polycarboxylate prepared in Comparative Example 1, Comparative Example 2, Comparative Example 3, Comparative Example 4, and Comparative Example 5 were used.
- the water agent is diluted to a concentration of 15%, and 1% white sugar and 2% sodium gluconate are added to obtain the final product of the water reducing agent.
- the specific test results are shown in Table 2.
- PCE-1 has begun to have odor and mildew at 30 days, and the antiseptic effect of PCE-2 directly compounded with monomethyl fumarate is slightly better than that of PCE-1, but it is also less effective at 60 days. Odor and mildew appeared, compound BI The PCE-3 of K350 preservative and the amount of monomethyl fumarate in the synthesis are replaced by dimethyl fumarate.
- the ether-based anti-corrosion polycarboxylate water reducers prepared in Examples 1 to 5 of the present invention have significantly better anti-corrosion effects than the Comparative Examples under the environment of 50 ° C, indicating that the specific raw materials and Proportion matching, the monomethyl fumarate and/or unsaturated carboxylic acid anhydride are introduced into the molecular structure of the product by means of polymerization, so that the prepared ether type anti-corrosion polycarboxylate water reducer has a highly stable structure and is resistant to Under the high temperature above 50 °C, the high temperature anti-corrosion performance is more excellent.
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Abstract
一种醚类防腐型聚羧酸减水剂及其制备方法,该醚类防腐型聚羧酸减水剂由防腐功能小单体与不饱和醚类大单体、不饱和羧酸和/或不饱和羧酸酐、和易性改性小单体在引发剂和分子量调节剂作用下进行聚合反应,生成分子主链上链接有防腐功能小单体的醚类防腐型聚羧酸减水剂,防腐功能小单体为富马酸酯和/或马来酸酯。所述醚类防腐型聚羧酸减水剂为自带防腐效果的醚类减水剂,防腐、减水效果优良,得到的醚类防腐型聚羧酸减水剂产物为稳定的高分子结构,能够耐受高于50℃以上的高温,高温防腐性能更加优异,所用的原材料来源广泛,价格较低,制备工艺简单。
Description
本发明涉及建筑材料技术领域,特别涉及一种醚类防腐型聚羧酸减水剂及其制备方法。
随着现代科技的发展与进步,基础性工程建设规模日益扩大,现代建设工程向高层、超高层、大跨度框架工程发展,对混凝土的需求越来越大,对混凝土的泵送、抗离析等性能要求越来越高。
在混凝土材料中,常会用到外加剂,如减水剂。目前聚羧酸减水剂在应用过程中常出现发霉、发臭的问题,虽然对其混凝土应用性能影响不大,但是却给应用单位带来了使用不便的问题,目前常规的解决聚羧酸减水剂发霉、发臭问题的方法为复配防腐剂,也有部分人员研究了防腐型聚羧酸减水剂。
而对于醚类聚羧酸减水剂,由于其具有相较于酯类聚羧酸减水剂更高的减水效果,价格方面也比较有优势,性价比突出,因此已经成为了目前市面上的主流聚羧酸外加剂。
复配加入防腐剂的方法是目前实际应用最广的方法,但是复配的防腐剂一般分子量较小,一方面可能存在防腐剂在聚羧酸减水剂中分散不均的问题,另一方面目前常规使用的复配用防腐剂在高于50℃的环境下还会存在分解失效的问题,在一定程度上限制了其的应用。
CN110642996A,公开时间为2020年01月03日,公开了一种自醚类防腐型聚羧酸减水剂及其制备方法,但是其使用的具有防腐性能的单体为聚甲 基丙烯酸酰氧乙基三甲基氯化铵、聚[2-(丙烯酰基氧基)乙基]三甲基溴化铵、聚苄乙基三甲基氯化铵、聚烯丙基三甲基氯化铵、聚(3-丙烯酰胺丙基)三甲基溴化铵中的任意一种或几种。但是这些物质已经是聚合物了,并无聚合活性,无法接到减水剂分子结构中,因此实质上该方法也是复配防腐剂的方法。
CN110128048A,公开时间为2019年08月16日,公开了一种夏季用防腐保坍聚羧酸减水剂及其制备方法,也是通过复配杀菌剂(聚六亚甲基胍磷酸盐)的方法实现防腐性能。
CN110015857A,公开时间为2019年07月16日,公开了一种秸秆-淀粉基混合改性的复合型聚羧酸减水剂的制备方法及其应用,将富马酸二甲酯作为防腐剂直接复配到专利产品中,但是富马酸二甲酯的水溶性并不是很好,聚羧酸减水剂的实际使用过程中一般需要复配加入大量的水,水的含量常常超过了90%,因此直接复配加入富马酸二甲酯的效果并不理想。
CN109796561A,公开时间为2019年05月24日,公开了一种芳环类聚羧酸减水剂母液及其制备方法和应用,使用芳基共轭不饱和羧酸作为防腐型单体制备具有自防腐效果的聚羧酸减水剂,但是芳基共轭不饱和羧酸聚合时存在位阻大,聚合效果不理想的问题,最终也将影响产品的性能。
CN109400819A,公开时间为2019年03月01日,公开了一种集降粘抗菌两性型聚羧酸系高效减水剂及其制备方法,使用盐酸胍和两端为胺基的烷基化合物制备抗菌单体,再用于聚羧酸减水剂的合成,合成过程复杂,且能耗高。
CN108373526A,公开时间为2018年08月07日,公开了一种防污抗菌型聚羧酸减水剂及其制备方法,通过在聚合时加入(甲基)丙烯酸磺酸基甜菜碱、甲基丙烯酰氧乙基三甲基氯化铵,实现抗菌效果,但是这两种单体成本 均较高。
CN107698721A,公开时间为2018年02月16日,公开了一种支链型抗菌聚羧酸减水剂、其制备方法及应用,但是制备过程过于复杂,生产效率低。
CN107265907A,公开时间为2017年10月20日,公开了一种两性型抗菌聚羧酸系高效减水剂及其制备方法,通过先共聚再与不饱和聚酯大单体、端卤素基聚醚依次反应,过程较为复杂,且由于是大分子量与大分子的反应,产品转化率会受到限制,影响产品性能。
CN105621927A,公开时间为2016年06月01日,公开了用于聚羧酸系减水剂的抗菌防腐剂的制备方法,在聚羧酸系减水剂相似的结构聚氧乙烯醚中引入含有抗菌功能的甜菜碱及富马酸二甲脂单体进行自由基共聚反应,使防腐剂与聚竣酸系减水剂分子结构相似相容。但是该专利的产品只具有防腐效果,并不具备减水的效果,且将富马酸二甲脂单体与不饱和单体的体系中直接聚合,存在水溶性差,在聚合过程中存在相分离的问题,使得聚合效率低。
发明内容
为解决上述背景技术中提到的如何提供一种防腐效果优异且稳定的醚类聚羧酸减水剂,本发明提供醚类防腐型聚羧酸减水剂,由防腐功能小单体与不饱和醚类大单体、不饱和羧酸和/或不饱和羧酸酐、和易性改性小单体在引发剂和分子量调节剂作用下进行聚合反应,生成分子主链上链接有防腐功能小单体的醚类防腐型聚羧酸减水剂;
所述防腐功能小单体为富马酸酯和/或马来酸酯。
在上述技术方案的基础上,进一步地,不饱和大单体、防腐功能小单体、不饱和羧酸和/或不饱和羧酸酐、和易性改性小单体的质量比范围是180:(1~ 15):(5~30):(1~5)。
在上述技术方案的基础上,进一步地,所述引发剂的用量为所述反应物总质量的0.5~3.0%;所述分子量调节剂的用量为所述反应物总质量的0.2~3.0%。
在上述技术方案的基础上,进一步地,在聚合反应过程中,在2~6h内滴加引发剂水溶液、分子量调节剂水溶液、不饱和羧酸和/或不饱和羧酸酐水溶液,反应温度为20~90℃,滴加完毕后保温0~3h,加入碱调节产物pH值至5~7。
在上述技术方案的基础上,进一步地,所述引发剂包括水溶性氧化还原引发体系或水溶性过氧化物引发体系试剂;具体可以采用双氧水-抗坏血酸、双氧水-吊白块、过硫酸铵;
所述分子量调节剂包括巯基乙酸、巯基乙醇、巯基丙酸、磺化巯基丙酸、次磷酸钠中的至少一种。
在上述技术方案的基础上,进一步地,所述富马酸酯包括富马酸单甲酯、富马酸单乙酯。
在上述技术方案的基础上,进一步地,所述马来酸酯包括马来酸二乙酯、马来酸二甲酯、马来酸二丙酯。
在上述技术方案的基础上,进一步地,所述不饱和大单体分子量为600~6000。
在上述技术方案的基础上,进一步地,所述不饱和醚类大单体为烯丙基聚乙二醇、3-甲基-3-丁烯-1-聚乙二醇、2-甲基烯丙基聚乙二醇中的至少一种。
在上述技术方案的基础上,进一步地,所述不饱和羧酸和/或不饱和羧酸酐为丙烯酸、甲基丙烯酸、马来酸酐中的至少一种。
在上述技术方案的基础上,进一步地,所述和易性改性小单体为:丙烯酰胺、甲基丙烯酸甲酯、丙烯酸羟乙酯磷酸酯、甲基丙烯基酒石酸酯、丙烯基柠檬酸甘油酯中的至少一种。
本发明还提供一种如上任意所述醚类防腐型聚羧酸减水剂的制备方法,包括以下步骤:
将不饱和醚类大单体、防腐功能小单体、和易性改性小单体和水加入到反应器中搅拌,待物料混合均匀后,滴加不饱和羧酸和/或不饱和羧酸酐、引发剂、分子量调节剂,滴加时间为0.5~6h,反应温度为10~90℃;滴加完毕后保温0~3h,得共聚产物;
在得到的共聚产物中,加入碱调节产物pH值至5~7,即获得醚类防腐型聚羧酸减水剂。
本发明提供的醚类防腐型聚羧酸减水剂通过不饱和大单体、防腐功能小单体、不饱和羧酸和/或不饱和羧酸酐、和易性改性小单体共聚的方式在产物分子结构中引入富马酸酯、马来酸酯中的至少一种单体单元,得到自身具有防腐性能的醚类防腐型聚羧酸减水剂,无需再复配小分子防腐剂,不存在防腐剂和聚羧酸减水剂相容性不好导致的分布不均问题,且形成的最终产物为稳定的高分子结构,能够耐受高于50℃以上的高温,高温防腐性能更加优异。
本发明提供的醚类防腐型聚羧酸减水剂适用于对聚羧酸减水剂性价比、防腐性要求较高应用场合,所用的原材料来源广泛,价格较低,制备工艺简单,使得项目产品的成本更符合聚羧酸减水剂的应用要求,具有重要的实际应用价值。
为使本发明实施例的目的、技术方案和优点更加清楚,下面将结合本发 明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
本发明还提供如下所示醚类防腐型聚羧酸减水剂的制备实施例:
实施例1
(1)将180.00g分子量为2400的3-甲基-3-丁烯-1-聚乙二醇、2.40g富马酸单甲酯、2.00g丙烯酰胺和145.00g水加入到反应器中,开启搅拌器和控温装置,待物料混合均匀,开始滴加丙烯酸水溶液(其中,丙烯酸20.00g,水20.00g)、双氧水水溶液(其中,双氧水1.50g,水20.00g)、巯基丙酸水溶液(其中,巯基丙酸0.80g,水20.00g)、抗坏血酸水溶液(其中,抗坏血酸0.40,水20.00g),反应温度为40℃,滴加时间为3.0h,滴加完毕后保温0.5h,得共聚产物;
(2)在步骤(1)制得的共聚产物中加入11g 32%浓度的氢氧化钠水溶液,即得所述醚类防腐型聚羧酸减水剂,记为KZJ-1。
实施例2
(1)将180.00g分子量为2400的2-甲基烯丙基聚乙二醇、2.50g马来酸二乙酯、3.00g甲基丙烯基酒石酸酯和145.00g水加入到反应器中,开启搅拌器和控温装置,待物料混合均匀,开始滴加丙烯酸水溶液(其中,丙烯酸22.00g,水20.00g)、双氧水水溶液(其中,双氧水1.70g,水20.00g)、巯基乙酸水溶液(其中,巯基乙酸0.90g,水20.00g)、抗坏血酸水溶液(其中,抗坏血酸0.40,水20.00g),反应温度为40℃,滴加时间为2.5h,滴加完毕后保温1h,得共聚产物;
(2)在步骤(1)制得的共聚产物中加入11g 32%浓度的氢氧化钠水溶液,即得所述醚类防腐型聚羧酸减水剂,记为KZJ-2。
实施例3:
(1)将60.00g分子量为2400的3-甲基-3-丁烯-1-聚乙二醇、120.00g分子量为2400的2-甲基烯丙基聚乙二醇、3.00g富马酸单乙酯、1.50g甲基丙烯酸甲酯和145.00g水加入到反应器中,开启搅拌器和控温装置,待物料混合均匀,开始滴加丙烯酸和马来酸酐混合水溶液(其中,丙烯酸15.00g,马来酸酐5.00g,水20.00g)、双氧水水溶液(其中,双氧水1.70g,水20.00g)、巯基乙醇水溶液(其中,巯基乙醇0.70g,水20.00g)、吊白块水溶液(其中,吊白块0.50,水20.00g),反应温度为45℃,滴加时间为2.0h,滴加完毕后保温1h,得共聚产物;
(2)在步骤(1)制得的共聚产物中加入12g32%浓度的氢氧化钠水溶液,即得所述醚类防腐型聚羧酸减水剂KZJ-3。
实施例4:
(1)将180.00g分子量为2400的3-甲基-3-丁烯-1-聚乙二醇、0.50g富马酸单甲酯、1.50g马来酸二乙酯、2.00g次磷酸钠、2.00g丙烯基柠檬酸甘油酯和150.00g水加入到反应器中,开启搅拌器和控温装置,待物料混合均匀,开始滴加丙烯酸和甲基丙烯酸混合水溶液(其中,丙烯酸17.00g,甲基丙烯酸5.00g,水20.00g)、双氧水水溶液(其中,双氧水1.70g,水20.00g)、巯基乙醇水溶液(其中,巯基乙醇0.70g,水20.00g)、抗坏血酸水溶液(其中,抗坏血酸0.20,水20.00g),反应温度为45℃,滴加时间为3.0h,滴加完毕后保温1h,得共聚产物;
(2)在步骤(1)制得的共聚产物中加入10g 32%浓度的氢氧化钠水溶液,即得所述醚类防腐型聚羧酸减水剂KZJ-4。
实施例5:
(1)将180.00g分子量为2400的3-甲基-3-丁烯-1-聚乙二醇、2.00g富马酸单甲酯、1.50g马来酸二乙酯、3.00g次磷酸钠、3.00g丙烯酸羟乙酯 磷酸酯和150.00g水加入到反应器中,开启搅拌器和控温装置,待物料混合均匀,开始滴加丙烯酸混合水溶液(其中,丙烯酸22.00g,水20.00g)、过硫酸铵水溶液(其中,过硫酸铵1.20g,水20.00g),反应温度为60℃,滴加时间为3.0h,滴加完毕后保温1h,得共聚产物;
(2)在步骤(1)制得的共聚产物中加入11g32%浓度的氢氧化钠水溶液,即得所述醚类防腐型聚羧酸减水剂KZJ-5。
对比例1:
(1)将180.00g分子量为2400的3-甲基-3-丁烯-1-聚乙二醇、2.00g丙烯酰胺和145.00g水加入到反应器中,开启搅拌器和控温装置,待物料混合均匀,开始滴加丙烯酸水溶液(其中,丙烯酸20.00g,水20.00g)、双氧水水溶液(其中,双氧水1.50g,水20.00g)、巯基丙酸水溶液(其中,巯基丙酸0.80g,水20.00g)、抗坏血酸水溶液(其中,抗坏血酸0.40,水20.00g),反应温度为40℃,滴加时间为3.0h,滴加完毕后保温0.5h,得共聚产物;
(2)在步骤(1)制得的共聚产物中加入11g 32%浓度的氢氧化钠水溶液,即得对比样品,记为PCE-1。
对比例2:
将PCE-1和富马酸单甲酯按照质量比为183:1进行复配,即得对比样品,记为PCE-2。
对比例3:
对比例4:
(1)将180.00g分子量为2400的3-甲基-3-丁烯-1-聚乙二醇、2.66g富马酸二甲酯、2.00g丙烯酰胺和145.00g水加入到反应器中,开启搅拌器和 控温装置,待物料混合均匀,开始滴加丙烯酸水溶液(其中,丙烯酸20.00g,水20.00g)、双氧水水溶液(其中,双氧水1.50g,水20.00g)、巯基丙酸水溶液(其中,巯基丙酸0.80g,水20.00g)、抗坏血酸水溶液(其中,抗坏血酸0.40,水20.00g),反应温度为40℃,滴加时间为3.0h,滴加完毕后保温0.5h,得共聚产物;
(2)在步骤(1)制得的共聚产物中加入11g 32%浓度的氢氧化钠水溶液,即得所述醚类防腐型聚羧酸减水剂,记为PCE-4。
对比例5:
(1)将180.00g分子量为2400的3-甲基-3-丁烯-1-聚乙二醇、2.40g富马酸单甲酯和145.00g水加入到反应器中,开启搅拌器和控温装置,待物料混合均匀,开始滴加丙烯酸水溶液(其中,丙烯酸20.00g,水20.00g)、双氧水水溶液(其中,双氧水1.50g,水20.00g)、巯基丙酸水溶液(其中,巯基丙酸0.80g,水20.00g)、抗坏血酸水溶液(其中,抗坏血酸0.40,水20.00g),反应温度为40℃,滴加时间为3.0h,滴加完毕后保温0.5h,得共聚产物;
(2)在步骤(1)制得的共聚产物中加入11g 32%浓度的氢氧化钠水溶液,即得所述醚类防腐型聚羧酸减水剂,记为PCE-5。
性能检测:
1、混凝土性能测试
按照GB/T8076-2008对实施例1到实施例5所制得的醚类防腐型聚羧酸减水剂和对比例1、对比例2、对比例3、对比例4、对比例5所制得的聚羧酸减水剂按照折固掺量为0.20%进行性能测试,测试结果如表1所示:
表1 混凝土测试结果
如表1所示,PCE-1与KZJ-1对比的结果显示,将KZJ-1中的富马酸单甲酯去掉后,对产物的减水率和3d、7d、28d抗压强度比基本没有影响,PCE-4和KZJ-1对比的结果显示,将KZJ-1中的富马酸单甲酯等物质的量换成富马酸二甲酯后产品减水率和3d、7d、28d抗压强度比均略有下降,PCE-5和KZJ-1对比的结果显示,将KZJ-1中的丙烯酰胺去掉后,产物的减水率和3d、7d、28d抗压强度比略有下降,混凝土和易性变差,按本专利技术方案合成的产品均具有较高的减水率和3d、7d、28d抗压强度比。
2、防腐性能测试
将实施例1到实施例5所制得的醚类防腐型聚羧酸减水剂和对比例1、对比例2、对比例3、对比例4、对比例5所制得的聚羧酸减水剂稀释成浓度15%,外加1%白糖和2%葡糖糖酸钠复配得到最终减水剂成品,将这些成品样品各300g置于相同的容积为500ml的敞口玻璃容器中,先加热到50℃恒温12小时后,置于30℃恒温箱中,放置15天(d)、30d、60d、90d、120d,并在相应的时间观察样品的状态(是否有异味、浑浊或长霉),以比较几个样品的防腐性能,具体测试结果见表2。
表2 防腐性能测试结果
从表2可以看出,PCE-1在30天时已经开始出现异味和长霉现象,直接复配富马酸单甲酯的PCE-2的防腐效果较PCE-1稍好,但是在60天时也出现了异味和长霉现象,复配BI
K350防腐剂的PCE-3和将合成中的富马酸单甲酯等物质的量换成富马酸二甲酯PCE-4的防腐效果和PCE-2相当,PCE-5的防腐效果和KZJ-1相当,而本发明实施例1到实施例5所制得的醚类防腐型聚羧酸减水剂在50℃的环境下较对比例防腐效果明显更好,说明了通过特定的原料和比例配合,将富马酸单甲酯和/或不饱和羧酸酐通过聚合的方式产物分子结构中引入,使制得的醚类防腐型聚羧酸减水剂,具有高度稳定的结构,能够耐受高于50℃以上的高温,高温防腐性能更加优异。
最后应说明的是:以上各实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述各实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修 改,或者对其中部分或者全部技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。
Claims (12)
- 一种醚类防腐型聚羧酸减水剂,其特征在于:由防腐功能小单体与不饱和醚类大单体、不饱和羧酸和/或不饱和羧酸酐、和易性改性小单体在引发剂和分子量调节剂作用下进行聚合反应,生成分子主链上链接有防腐功能小单体的醚类防腐型聚羧酸减水剂;所述防腐功能小单体为富马酸酯和/或马来酸酯。
- 根据权利要求1所述的醚类防腐型聚羧酸减水剂,其特征在于:不饱和大单体、防腐功能小单体、不饱和羧酸和/或不饱和羧酸酐、和易性改性小单体的质量比范围是180:(1~15):(5~30):(1~5)。
- 根据权利要求1所述的醚类防腐型聚羧酸减水剂,其特征在于:所述引发剂的用量为所述反应物总质量的0.5~3.0%;所述分子量调节剂的用量为所述反应物总质量的0.2~3.0%。
- 根据权利要求1所述的醚类防腐型聚羧酸减水剂,其特征在于:在聚合反应过程中,在2~6h内滴加引发剂水溶液、分子量调节剂水溶液、不饱和羧酸和/或不饱和羧酸酐水溶液,反应温度为20~90℃,滴加完毕后保温0~3h,加入碱调节产物pH值至5~7。
- 根据权利要求4所述的醚类防腐型聚羧酸减水剂,其特征在于:所述引发剂包括水溶性氧化还原引发体系或水溶性过氧化物引发体系试剂;所述分子量调节剂包括巯基乙酸、巯基乙醇、巯基丙酸、磺化巯基丙酸、次磷酸钠中的至少一种。
- 根据权利要求1所述的醚类防腐型聚羧酸减水剂,其特征在于:所述富马酸酯包括富马酸单甲酯、富马酸单乙酯。
- 根据权利要求1所述的醚类防腐型聚羧酸减水剂,其特征在于:所述马来酸酯包括马来酸二乙酯、马来酸二甲酯、马来酸二丙酯。
- 根据权利要求1所述的醚类防腐型聚羧酸减水剂,其特征在于:所述 不饱和大单体分子量为600~6000。
- 根据权利要求1所述的醚类防腐型聚羧酸减水剂,其特征在于:所述不饱和醚类大单体为烯丙基聚乙二醇、3-甲基-3-丁烯-1-聚乙二醇、2-甲基烯丙基聚乙二醇中的至少一种。
- 根据权利要求1所述的醚类防腐型聚羧酸减水剂,其特征在于:所述不饱和羧酸和/或不饱和羧酸酐为丙烯酸、甲基丙烯酸、马来酸酐中的至少一种。
- 根据权利要求1所述的醚类防腐型聚羧酸减水剂,其特征在于:所述和易性改性小单体为:丙烯酰胺、甲基丙烯酸甲酯、丙烯酸羟乙酯磷酸酯、甲基丙烯基酒石酸酯、丙烯基柠檬酸甘油酯中的至少一种。
- 一种根据权利要求1~11任一项所述醚类防腐型聚羧酸减水剂的制备方法,其特征在于,包括以下步骤:将不饱和醚类大单体、防腐功能小单体、和易性改性小单体和水加入到反应器中搅拌,待物料混合均匀后,滴加不饱和羧酸和/或不饱和羧酸酐、引发剂、分子量调节剂,滴加时间为0.5~6h,反应温度为10~90℃;滴加完毕后保温0~3h,得共聚产物;在得到的共聚产物中,加入碱调节产物pH值至5~7,即获得醚类防腐型聚羧酸减水剂。
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CN117402297B (zh) * | 2023-12-15 | 2024-03-05 | 四川省晋川建材有限公司 | 聚羧酸减水剂及其制备方法 |
CN117430760A (zh) * | 2023-12-20 | 2024-01-23 | 四川省晋川建材有限公司 | 抗泥型聚羧酸减水剂及其制备方法 |
CN117430760B (zh) * | 2023-12-20 | 2024-03-08 | 四川省晋川建材有限公司 | 抗泥型聚羧酸减水剂及其制备方法 |
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