CN106496441A - 一种低价态变价阳离子改性聚羧酸减水剂母料及其低温制备方法 - Google Patents
一种低价态变价阳离子改性聚羧酸减水剂母料及其低温制备方法 Download PDFInfo
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- CN106496441A CN106496441A CN201610955558.4A CN201610955558A CN106496441A CN 106496441 A CN106496441 A CN 106496441A CN 201610955558 A CN201610955558 A CN 201610955558A CN 106496441 A CN106496441 A CN 106496441A
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- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 50
- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 17
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 239000007800 oxidant agent Substances 0.000 claims abstract description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 13
- 229920000570 polyether Polymers 0.000 claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010413 mother solution Substances 0.000 claims abstract description 8
- 150000001767 cationic compounds Chemical class 0.000 claims abstract description 7
- 239000003381 stabilizer Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 34
- 239000003999 initiator Substances 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 15
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 13
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 13
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000000498 cooling water Substances 0.000 claims description 10
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 8
- 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 claims description 8
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 8
- 230000003467 diminishing effect Effects 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 235000010323 ascorbic acid Nutrition 0.000 claims description 6
- 239000011668 ascorbic acid Substances 0.000 claims description 6
- 229960005070 ascorbic acid Drugs 0.000 claims description 6
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- SPFMQWBKVUQXJV-BTVCFUMJSA-N (2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanal;hydrate Chemical compound O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O SPFMQWBKVUQXJV-BTVCFUMJSA-N 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 5
- -1 Cobaltous sulfates Chemical class 0.000 claims description 5
- 229930091371 Fructose Natural products 0.000 claims description 5
- 239000005715 Fructose Substances 0.000 claims description 5
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 5
- 229960000673 dextrose monohydrate Drugs 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 230000005070 ripening Effects 0.000 claims description 5
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 4
- VYGBQXDNOUHIBZ-UHFFFAOYSA-L sodium formaldehyde sulphoxylate Chemical compound [Na+].[Na+].O=C.[O-]S[O-] VYGBQXDNOUHIBZ-UHFFFAOYSA-L 0.000 claims description 4
- 235000010265 sodium sulphite Nutrition 0.000 claims description 4
- 150000003460 sulfonic acids Chemical class 0.000 claims description 4
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 3
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 3
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- MPPQGYCZBNURDG-UHFFFAOYSA-N 2-propionyl-6-dimethylaminonaphthalene Chemical compound C1=C(N(C)C)C=CC2=CC(C(=O)CC)=CC=C21 MPPQGYCZBNURDG-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 2
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 claims description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 claims description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 2
- 229940045872 sodium percarbonate Drugs 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- 125000001033 ether group Chemical group 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract 2
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 239000012452 mother liquor Substances 0.000 abstract 1
- 230000003020 moisturizing effect Effects 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 8
- 230000004913 activation Effects 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 239000004568 cement Substances 0.000 description 4
- 229960002163 hydrogen peroxide Drugs 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- FPNCFEPWJLGURZ-UHFFFAOYSA-L iron(2+);sulfite Chemical class [Fe+2].[O-]S([O-])=O FPNCFEPWJLGURZ-UHFFFAOYSA-L 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
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- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
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- 239000000047 product Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 2
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical class [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
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- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011790 ferrous sulphate Chemical group 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 229920000344 molecularly imprinted polymer Polymers 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical group [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 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
- 229940117958 vinyl acetate Drugs 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
- C04B24/2605—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
-
- 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
- C04B2103/302—Water reducers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Polymerization Catalysts (AREA)
Abstract
本发明公开了一种低价态变价阳离子改性聚羧酸减水剂母料及其低温制备方法,此改性母液针对无加热生产条件或区域气候偏寒的外加剂企业,以母液质量百分比40%为限定,合成原材料总质量为1000份,其用量比例为:聚醚大单体用量为340~360,丙烯酸用量为32.0~50.0,链转移剂用量为1.3~3.0,氧化剂用量为3.0~5.0,还原剂用量为0.55~3.50,低价态变价阳离子化合物用量为0.020~0.070,稳定剂用量为0.1~0.5,液碱用量为10~15,其余为水。本发明合成的聚羧酸减水剂在低温下即可聚合,侧链分布均匀,分子量分布范围较宽,产品表现出减水率高,适应性广的特点。
Description
技术领域
本发明涉及一种水泥基胶凝材料用聚羧酸减水剂,适应于无加热生产条件或区域气候偏寒的环境,具体涉及一种低价态变价阳离子改性聚羧酸减水剂母料极其低温制备方法。
背景技术
随国家绿色建材战略的提出,聚羧酸减水剂常温合成技术已趋向于成熟,摒弃合成加热工艺的过氧化物作为引发剂,常温合成多采用氧化-还原体系来降低分解活化能,常温的概念通常指的是15~25℃。当温度低于15℃,常见氧化-还原体系不足以确保引发效果,此时,多采用与水接触能放出大量热的吊白粉、保险粉类强还原剂,但该氧化剂-强还原剂体系在短时间内会释放大量自由基,聚合速率、链增长速率显著大于链终止速率,上述三者的不匹配易导致减水剂分子形成紊乱结构,减水剂分子主链合成前期偏长,主链因合成中后期强还原剂半衰期较短和前期丙烯酸消耗较大而偏短,支链嫁接混乱无序,减水剂效果变差。
氧化剂-还原剂体系活化能通常在100~250kJ/mol,Fe2+、Co2+可作为助还原剂或氧化-还原体系的催化剂,氧化剂-还原剂-低价态变价阳离子引发体系的活化能可降低到40~60kJ/mol,在5℃即可引发聚合,保持较高的聚合速率。此外,若低价态变价阳离子用量不足,协助作用不明显;弱低价态变价阳离子用量过大,聚合速度太快而使分子量增加且容易失控;控制低价态变价阳离子的用量是减水剂低温合成及性能优异的关键所在。
CN 103159899 A公开了一种聚羧酸系减水剂的制备方法,以重量百分比配制的原料,由去离子水30-55%、聚氧乙烯醚35-50%、羧酸衍生物单体5-10%、催化剂0.0005-0.002%、引发剂1.5-4.5%、链转移剂0.2-0.8%、结构改性剂1.0-2.5%、碱液4.5-8.5%组成;在20-35℃下,将去离子水与聚氧乙烯醚置于反应釜中溶解,待完全溶解后,依次加入羧酸衍生物单体、催化剂、引发剂、链转移剂、结构改性剂,搅拌28-32分钟后,在室温下静置4-6小时,在搅拌状态下加碱液,调pH值为6.0-7.5,即得产品。
CN 105036596 A公开了一种低温合成聚羧酸减水剂及其制备方法,包括如下重量份的组分:不饱和聚醚150~250重量份、不饱和羟基酯2~30重量份、乙烯基醚1~2重量份、丙烯酸10~30重量份、质量浓度30~35%的氢氧化钾溶液2~10重量份、链转移剂0.5~2重量份、低温还原剂0.2~0.8重量份、甲醛合次硫酸氢钠0.1~0.5重量份、抗坏血酸0.1~0.5重量份、质量浓度30~35%的过氧化氢溶液1~5重量份、七水合硫酸亚铁0.01~0.1重量份、质量浓度30~35%的氢氧化钠溶液12~20重量份和去离子水240~340重量份。
CN 103508696 A公开了一种聚羧酸抗含泥减水剂,它由以下组分制成:烯丙基类聚氧乙烯聚氧丙烯醚、组分R、R1、R2、链转移剂、引发剂R3和水,组分R为马来酸酐、甲基丙烯磺酸钠、醋酸乙烯酯、衣康酸、衣康酸酐、富马酸中的一种或几种;R1为丙烯酸、甲基丙烯酸中的一种或者两种的混合物;R2为抗坏血酸、吊白块、硫酸亚铁、硫酸亚锡、次磷酸钠、亚硫酸氢钠、草酸中的一种或几种;还公开了其制备方法。
发明内容
本专利思路在于降低氧化剂-还原剂引发体系的分解活化能,但不提高引发体系单位时间自由基的释放量或速率。整个减水剂合成过程温度控制在15~30℃,减水剂分子主链和侧链构建有序,主链长度规整,最终得到能满足特殊需求的含有理想分子结构的聚羧酸主链、侧链,并使其具有一定电荷密度及分子构象的减水剂分子聚合物。
本发明所要解决的技术问题是提供一种低价态变价阳离子改性聚羧酸减水剂母料及其低温制备方法。
本发明的低价态变价阳离子改性聚羧酸减水剂母料,由下述各组分聚合而成,原料总质量份为1000,各组分包括:
聚醚大单体:340~360;
丙烯酸:32.0~50.0;
链转移剂:1.3~3.0;
氧化剂:3.0~5.0;
还原剂:0.55~3.50;
低价态变价阳离子化合物:0.020~0.070;
稳定剂:0.1~0.5;
液碱:10~15;
水:其余。
所述的聚醚大单体为烯丙基聚氧乙烯醚、甲基烯丙基聚氧乙烯醚、异戊烯醇聚氧乙烯醚、乙烯基丁基醚聚氧乙烯醚的一种或几种组成;所述聚醚大单体从低温反应活性的角度上判断,优选为异戊烯醇聚氧乙烯醚、乙烯基丁基醚聚氧乙烯醚的一种或两种组成;所述聚醚大单体从减水剂设计理念的角度上判断,优选为2400分子量的乙烯基丁基醚聚氧乙烯醚。
所述的氧化剂为过氧化氢、过氧乙酸、重铬酸钠、铬酸、硝酸、高锰酸钾、过硫酸铵、过硫酸钾、过碳酸钠、过硼酸钠、过硼酸钾的一种或几种组成;所述的氧化剂优选为摩尔质量小的氧化剂,即过氧化氢、过氧乙酸的一种或两种组成。
所述的低价态变价阳离子化合物为七水硫酸亚铁、七水硫酸亚钴一种或两种组成。
所述的引发剂为链转移剂和还原剂的水溶液混合物。
所述的链转移剂为巯基乙酸、巯基丙酸、巯基乙醇、甲基丙烯酸磺酸钠、次磷酸钠的一种或几种组成;所述的链转移剂为液体类链转移剂,即巯基乙酸、巯基丙酸、巯基乙醇时,用量为1.3~2.0;所述的链转移剂为固体类链转移剂,即甲基丙烯酸磺酸钠、次磷酸钠时,用量为2.0~3.0。
所述的还原剂为连二亚硫酸钠、甲醛合次硫酸氢钠、抗坏血酸、亚硫酸氢钠、焦亚硫酸钠、一水葡萄糖、果糖的一种或几种组成;所述的还原剂为中强类还原剂,即连二亚硫酸钠、甲醛合次硫酸氢钠、抗坏血酸的一种或几种组成时,用量为0.55~1.00;所述的还原剂为弱还原剂,即亚硫酸氢钠、焦亚硫酸钠、一水葡萄糖、果糖的一种或几种组成时,用量为1.00~3.50;所述的还原剂优选为有机类弱还原剂,即一水葡萄糖、果糖的一种或两种组成,用量为2.00~3.50。
所述的稳定剂为氟硅酸钠、氟硅酸锌、氟硅酸镁的一种或几种。
所述液碱为质量比30~32%的工业级NaOH。
本发明的低价态变价阳离子改性聚羧酸减水剂母料的低温制备方法,包括如下过程:
将聚醚大单体置于反应容器中,持续搅拌,直至溶液无明显块状或片状物料;
将氧化剂置于已溶解完全的聚醚大单体溶液中,滴加引发剂;引发剂滴加5min后,一次性加入低价态变价阳离子化合物;再5min后,开始滴加小单体溶液;小单体溶液滴加时间为3~4h,小单体溶液优先于引发剂滴加完,引发剂滞后于小单体溶液10~20min后滴加完;调整冷却水阀门开度,确保滴加过程中的反应温度控制在20~30℃;
滴加完毕后,关闭冷却水阀门,自动熟化1~2h;当反应液温度降到25℃下,加液碱中和,搅拌10min后,停止搅拌,母液静置于反应釜中10~15h后即可放出。
所述的小单体溶液为丙烯酸的水溶液。
本发明的有益效果是:
1.氧化剂-还原剂-低价态变价阳离子引发体系可确保初始低温5~15℃下的有效引发,整个合成反应控制在20~30℃,低于40℃的合成环境会塑造较为均一的减水剂分子结构;此外,采用乙烯基丁基醚聚氧乙烯醚较其他聚醚大单体有更高的聚合活性,且侧链分布更均匀;乙烯基丁基醚聚氧乙烯醚高温稳定性差,易降解,但相对切合低温合成工艺。
2.该发明对氧化剂-还原剂引发体系中还原剂做出具体限定,选取半衰期较长的有机类弱还原剂,匹配低价态变价阳离子,确保减水剂分子结构的均一性,并改善减水剂对混凝土的和易性;减水剂合成后,低价态变价阳离子会水解为絮状或沉淀状导致成品变浑,氟硅酸类稳定剂会促使阳离子以可溶性盐形式存在。
具体实施方式
下面通过实例对本发明进行进一步的阐述,下述说明仅为了解释本发明,并不对内容进行限定。
实施例1
一种低价态变价阳离子改性聚羧酸减水剂母料,由按质量百分比的下述各组分聚合而成,原料总质量为1000份,各组分及工艺参数如下:
底料:2400分子量的异戊烯醇聚氧乙烯醚:352,水:200;
氧化剂溶液:过氢化氢:5,水:5;
底料的温度:10℃;
氧化剂溶液加入后10min内依次滴加引发剂、小单体溶液,引发剂滴加5min后,一次性加入七水亚硫酸铁;再5min后,开始滴加小单体溶液;
七水硫酸铁:0.035;
引发剂:巯基乙酸:1.5,抗坏血酸:0.85,水:120;
小单体溶液:丙烯酸:39.5,水:50;
引发剂滴加时间:3.5h;
小单体溶液滴加时间:3.0h;
调整冷却水阀门开度,确保滴加过程中的反应温度控制在20~30℃;
滴加完毕后,关闭冷却水阀门,自动熟化1h;当反应温度降到25℃下,加液碱中和,补水;
液碱:10;
补水:216.115;
补水后,搅拌10min,母液静置于反应釜中15h后即可放出。
实施例2
底料:2400分子量的乙烯基丁基醚聚氧乙烯醚:355,水:220;
氧化剂溶液:过氧乙酸:5.0,水:10;
底料的温度:7℃;
氧化剂溶液加入后10min内依次滴加引发剂、小单体溶液,引发剂滴加5min后,一次性加入七水亚硫酸铁;再5min后,开始滴加小单体溶液;
七水硫酸铁:0.057;
引发剂:甲基丙烯酸磺酸钠:2.7,一水葡萄糖:3.5,水:120;
小单体溶液:丙烯酸:36.2,水:50;
引发剂滴加时间:4.0h;
小单体溶液滴加时间3.5h;
调整冷却水阀门开度,确保滴加过程中的反应温度控制在20~30℃;
滴加完毕后,关闭冷却水阀门,自动熟化1.5h;当反应温度降到25℃下,加液碱中和,补水;
液碱:12;
补水:185.543;
补水后,搅拌10min,母液静置于反应釜中12h后即可放出。
实施例3
底料:2400分子量的乙烯基丁基醚聚氧乙烯醚:342,水:250;
氧化剂溶液:过氧化氢:4.5,水:15;
底料的温度:13℃;
氧化剂溶液加入后10min内依次滴加引发剂、小单体溶液,引发剂滴加5min后,一次性加入七水亚硫酸铁;再5min后,开始滴加小单体溶液;
七水硫酸钴:0.065;
引发剂:次磷酸钠:3.0,亚硫酸氢钠:1.5,果糖:1.5,水:120;
小单体溶液:丙烯酸:48.5,水:50;
引发剂滴加时间:3.5h;
小单体溶液滴加时间3.0h;
调整冷却水阀门开度,确保滴加过程中的反应温度控制在20~30℃;
滴加完毕后,关闭冷却水阀门,自动熟化2.0h;当反应温度降到25℃下,加液碱中和,补水;
液碱:15;
补水:148.935;
补水后,搅拌10min,母液静置于反应釜中10h后即可放出。
分别测试上述实例低价态变价阳离子改性聚羧酸减水剂母料与普通聚羧酸减水剂母液同等浓度下的水泥净浆初始流动性和经时流动性。实验所用水泥为华新42.5普硅水泥,参考GB/8076-2008《混凝土外加剂》测试标准。
不同减水剂对水泥净浆流动影响
根据上述初始及经时净浆流动性比较,低价态变价阳离子改性聚羧酸减水剂母料实例1、2、3的初始流动性均较普通减水剂母液的较大些或等同,但经时流动性较初始流动性更佳。由上所述,低价态变价阳离子改性聚羧酸减水剂具有均一的减水剂分子结构,尤其表现为侧链结构的均质化,该均质化的支链体系尤其表现为保坍性能的显著提高,同时也有利于提高初始分散性。
Claims (6)
1.一种低价态变价阳离子改性聚羧酸减水剂母料,由下述各组分聚合而成,原料总质量份为1000,各组分包括:
聚醚大单体:340~360;
丙烯酸:32.0~50.0;
链转移剂:1.3~3.0;
氧化剂:3.0~5.0;
还原剂:0.55~3.50;
低价态变价阳离子化合物:0.020~0.070;
稳定剂:0.1~0.5;
液碱:10~15;
水:其余;
所述的聚醚大单体为烯丙基聚氧乙烯醚、甲基烯丙基聚氧乙烯醚、异戊烯醇聚氧乙烯醚、乙烯基丁基醚聚氧乙烯醚的一种或几种组成;
所述的低价态变价阳离子化合物为七水硫酸亚铁、七水硫酸亚钴一种或两种组成;
所述的引发剂为链转移剂和还原剂的水溶液混合物;
所述的稳定剂为氟硅酸钠、氟硅酸锌、氟硅酸镁的一种或几种。
2.根据权利要求1所述的改性聚羧酸减水剂母料,其特征在于,所述的氧化剂为过氧化氢、过氧乙酸、重铬酸钠、铬酸、硝酸、高锰酸钾、过硫酸铵、过硫酸钾、过碳酸钠、过硼酸钠、过硼酸钾的一种或几种组成。
3.根据权利要求1所述的改性聚羧酸减水剂母料,其特征在于,所述的链转移剂为巯基乙酸、巯基丙酸、巯基乙醇、甲基丙烯酸磺酸钠、次磷酸钠的一种或几种组成。
4.根据权利要求1所述的改性聚羧酸减水剂母料,其特征在于,所述的还原剂为连二亚硫酸钠、甲醛合次硫酸氢钠、抗坏血酸、亚硫酸氢钠、焦亚硫酸钠、一水葡萄糖、果糖的一种或几种组成。
5.根据权利要求1所述的改性聚羧酸减水剂母料,其特征在于,所述液碱为质量比30~32%的工业级NaOH。
6.权利要求1所述的低价态变价阳离子改性聚羧酸减水剂母料的低温制备方法,其特征在于,包括如下过程:
将聚醚大单体置于反应容器中,持续搅拌,直至溶液无明显块状或片状物料;
将氧化剂置于已溶解完全的聚醚大单体溶液中,滴加引发剂;引发剂滴加5min后,一次性加入低价态变价阳离子化合物;再5min后,开始滴加小单体溶液;小单体溶液滴加时间为3~4h,引发剂滞后于小单体溶液10~20min后滴加完,所述的小单体溶液为丙烯酸的水溶液;调整冷却水阀门开度,确保滴加过程中的反应温度控制在20~30℃;
滴加完毕后,关闭冷却水阀门,自动熟化1~2h;当反应液温度降到25℃下,加液碱中和,搅拌10min后,停止搅拌,母液静置于反应釜中10~15h后即可放出。
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