CN110003406B - Rosin modified polycarboxylate superplasticizer and preparation method thereof - Google Patents
Rosin modified polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
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- CN110003406B CN110003406B CN201910444069.6A CN201910444069A CN110003406B CN 110003406 B CN110003406 B CN 110003406B CN 201910444069 A CN201910444069 A CN 201910444069A CN 110003406 B CN110003406 B CN 110003406B
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- China
- Prior art keywords
- rosin
- rosin modified
- acid
- parts
- water reducing
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 title claims abstract description 77
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 title claims abstract description 77
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 32
- 239000008030 superplasticizer Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 47
- 239000002253 acid Substances 0.000 claims abstract description 45
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 22
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 150000002148 esters Chemical group 0.000 claims abstract description 12
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 11
- 229920000570 polyether Polymers 0.000 claims description 11
- 239000012986 chain transfer agent Substances 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 8
- -1 Vinyl Dehydroabietate Chemical compound 0.000 claims description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 6
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-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 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 claims description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 4
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 3
- VAPQAGMSICPBKJ-UHFFFAOYSA-N 2-nitroacridine Chemical compound C1=CC=CC2=CC3=CC([N+](=O)[O-])=CC=C3N=C21 VAPQAGMSICPBKJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 229940118785 dehydroabietate Drugs 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- LLLCSBYSPJHDJX-UHFFFAOYSA-M potassium;2-methylprop-2-enoate Chemical compound [K+].CC(=C)C([O-])=O LLLCSBYSPJHDJX-UHFFFAOYSA-M 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 150000003384 small molecules Chemical class 0.000 claims description 3
- 229940047670 sodium acrylate Drugs 0.000 claims description 3
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-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
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 125000004494 ethyl ester group Chemical group 0.000 claims description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 2
- 150000004702 methyl esters Chemical class 0.000 claims description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 230000003472 neutralizing effect Effects 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 239000004568 cement Substances 0.000 abstract description 26
- 239000004567 concrete Substances 0.000 abstract description 19
- 239000000178 monomer Substances 0.000 abstract description 10
- 230000001603 reducing effect Effects 0.000 abstract description 7
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000002794 monomerizing effect Effects 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- FEPCMSPFPMPWJK-OLPJDRRASA-N maleopimaric acid Chemical compound C([C@]12C=C([C@H](C[C@@H]11)[C@H]3C(OC(=O)[C@@H]23)=O)C(C)C)C[C@@H]2[C@]1(C)CCC[C@@]2(C)C(O)=O FEPCMSPFPMPWJK-OLPJDRRASA-N 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- YXHVCZZLWZYHSA-UHFFFAOYSA-N (Z)-6-[8-pentadecenyl]salicylic acid Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1C(O)=O YXHVCZZLWZYHSA-UHFFFAOYSA-N 0.000 description 2
- QUUCYKKMFLJLFS-UHFFFAOYSA-N Dehydroabietan Natural products CC1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 QUUCYKKMFLJLFS-UHFFFAOYSA-N 0.000 description 2
- NFWKVWVWBFBAOV-UHFFFAOYSA-N Dehydroabietic acid Natural products OC(=O)C1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 NFWKVWVWBFBAOV-UHFFFAOYSA-N 0.000 description 2
- YXHVCZZLWZYHSA-FPLPWBNLSA-N Ginkgoic acid Chemical compound CCCCCC\C=C/CCCCCCCC1=CC=CC(O)=C1C(O)=O YXHVCZZLWZYHSA-FPLPWBNLSA-N 0.000 description 2
- 239000011398 Portland cement Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- NFWKVWVWBFBAOV-MISYRCLQSA-N dehydroabietic acid Chemical compound OC(=O)[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 NFWKVWVWBFBAOV-MISYRCLQSA-N 0.000 description 2
- 229940118781 dehydroabietic acid Drugs 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011372 high-strength concrete Substances 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- DOBUSJIVSSJEDA-UHFFFAOYSA-L 1,3-dioxa-2$l^{6}-thia-4-mercuracyclobutane 2,2-dioxide Chemical compound [Hg+2].[O-]S([O-])(=O)=O DOBUSJIVSSJEDA-UHFFFAOYSA-L 0.000 description 1
- 244000194101 Ginkgo biloba Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HOOWDPSAHIOHCC-UHFFFAOYSA-N dialuminum tricalcium oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[Al+3].[Al+3].[Ca++].[Ca++].[Ca++] HOOWDPSAHIOHCC-UHFFFAOYSA-N 0.000 description 1
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910000370 mercury sulfate Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000006223 plastic coating Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- YOQNNJXWJAIJIL-UHFFFAOYSA-M potassium 1-oxoprop-2-ene-1-sulfonate Chemical compound C=CC(=O)S(=O)(=O)[O-].[K+] YOQNNJXWJAIJIL-UHFFFAOYSA-M 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- DYFSVSOIHMYPCB-UHFFFAOYSA-M potassium;2-methyl-1-oxoprop-2-ene-1-sulfonate Chemical compound [K+].CC(=C)C(=O)S([O-])(=O)=O DYFSVSOIHMYPCB-UHFFFAOYSA-M 0.000 description 1
- RAJUSMULYYBNSJ-UHFFFAOYSA-N prop-1-ene-1-sulfonic acid Chemical compound CC=CS(O)(=O)=O RAJUSMULYYBNSJ-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000003469 silicate cement Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical group 0.000 description 1
- RHJZKEQBZWBDBV-UHFFFAOYSA-M sodium;1-oxoprop-2-ene-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(=O)C=C RHJZKEQBZWBDBV-UHFFFAOYSA-M 0.000 description 1
- VRAHSRHQTRYBJV-UHFFFAOYSA-M sodium;2-methyl-1-oxoprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)C(=O)S([O-])(=O)=O VRAHSRHQTRYBJV-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 229910021534 tricalcium silicate Inorganic materials 0.000 description 1
- 235000019976 tricalcium silicate Nutrition 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- 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
- 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
- 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
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
-
- 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)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a rosin modified polycarboxylate superplasticizer and a preparation method thereof. Performing ester exchange on carboxyl of a rosin derivative and vinyl acetate to obtain rosin modified vinyl ester containing double bonds as a monomer, and polymerizing the rosin modified vinyl ester and other polycarboxylic acid water reducing agent monomers in an aqueous solution to obtain the rosin modified polycarboxylic acid water reducing agent. The proportion of rosin modified vinyl ester in mixed monomers is optimized, and the prepared polycarboxylic acid water reducing agent has excellent performance and has high water reducing rate at low dosage of 0.12 percent when being used as an additive to be mixed with cement and concrete. Meanwhile, the rosin modified polycarboxylate superplasticizer provided by the invention has greatly improved fluidity and compressive strength on cement and concrete. In the technical scheme provided by the invention, the rosin derivative has the advantages of wide source, low cost, environmental protection, reproducibility and good market popularization value.
Description
Technical Field
The invention relates to the technical field of water reducing agents, and particularly relates to a rosin modified polycarboxylic acid water reducing agent and a preparation method thereof.
Background
After the cement is stirred with water, hydration reaction is produced, and a plurality of flocculent structures appear, which wrap a lot of mixing water, thereby reducing the workability of fresh concrete. In order to maintain the required workability in construction, the amount of mixing water must be increased correspondingly, excessive pores are formed in a cement structure due to the increase of the water amount, so that the physical and mechanical properties of hardened concrete are seriously influenced, and if the wrapped water can be released, the water consumption of the concrete can be greatly reduced. In the process of preparing concrete, a proper amount of water reducing agent is added, so that the effect can be well achieved. Water reduction is an important role that surfactants play in the cement hydration process. The water reducing agent is added to enhance the dispersion effect among cement particles, so that the dosage of mixing water can be reduced under the condition of ensuring the fluidity, and the strength of the concrete is improved.
The polycarboxylic acid high-performance water reducing agent has a plurality of advantages, the market share is increased year by year, and the polycarboxylic acid high-performance water reducing agent gradually replaces the traditional polycondensation water reducing agent and becomes a mainstream product in the market. The main chain of the polycarboxylate superplasticizer molecule is firmly adsorbed on the surface of cement particles, the hydration reaction can be effectively prevented, the plastic coating performance of the polycarboxylate superplasticizer molecule can be improved, the branched chain surrounds the periphery of the cement particles, the dual functions of steric hindrance and electrostatic repulsion are achieved, the polycarboxylate superplasticizer molecule is different from the traditional superplasticizer molecule in the mechanism of electrostatic repulsion dispersion, the polycarboxylate superplasticizer molecule has better dispersing capacity and water reducing effect, and the comprehensive performance of a concrete product is finally improved. The molecular structure of the polycarboxylate superplasticizer is easy to modify, so that the polycarboxylate superplasticizer can relate to an effective molecular structure according to a cement dispersion action mechanism, and the number of main chain repeating units, the length of side chains and the density of molecules are designed. Due to the designability of the molecular structure and the performance of the polycarboxylic acid high-efficiency water reducing agent, the polycarboxylic acid high-efficiency water reducing agent is a future development direction for further perfecting the serialized and functionalized water reducing agent. CN106883355A discloses a low air entraining and viscosity reducing type polycarboxylate superplasticizer and a preparation method thereof, wherein an alkyl phosphate triester structure containing two double bonds is introduced into a main chain, so that the thickness of an adsorption layer of the polycarboxylate superplasticizer is increased, the aim of reducing the plastic viscosity of concrete is achieved, simultaneously, the defoaming performance is improved, the air entraining property is reduced, but the preparation process is complex, and the fluidity maintaining performance is general. CN107245130B discloses a gingko grafting modified polycarboxylate superplasticizer and a preparation method thereof. Dissolving ginkgolic acid and unsaturated polyether in water, adding unsaturated carboxylic acid, and copolymerizing to obtain the ginkgolic acid graft modified polycarboxylate superplasticizer. But the slump retaining performance is poor, and the mud resistance is still to be improved.
Rosin is a renewable resource with excellent characteristics and is a mixture of various resin acids and fatty acids. The resin acids are the major constituent of rosin, there being a monoacid with 2 double bonds and a tricyclic phenanthrene skeleton. Rosin and its derivatives are widely used in the industries of adhesives, coatings, inks, etc. due to their unique properties. China is a large country for rosin production, the annual output is more than 50 million tons, and how to utilize the rosin which is a renewable natural resource to develop novel fine chemical products so as to meet the needs of various industries is an increasingly important research subject.
Patents CN108503254A, CN108409189A, and CN108623768A disclose a method for preparing a series of water reducing agents from waste rosin. On one hand, the methods need to use a large amount of formaldehyde in the preparation process, and cannot achieve green environmental protection; on the other hand, these methods directly use waste rosin, do not analyze the components thereof, do not understand what the components are reacted therein, and thus cannot obtain a product with a definite composition, and the repeatability may not meet the requirements of industrial production. More importantly, the unmodified rosin is directly used as a raw material due to steric hindrance effect, and the reaction activity is great. And the unmodified rosin has large crystallization tendency, easy oxidation and low softening point. In order to improve or eliminate these defects, it is necessary to modify the rosin structure.
Disclosure of Invention
The invention provides a rosin modified polycarboxylate superplasticizer and a preparation method thereof, aiming at overcoming the defects of the prior art. According to the invention, rosin is modified, double bonds are introduced into a rosin molecular structure through ester exchange reaction, and the modified rosin is used as a hydrophobic modified monomer to be copolymerized with other monomers, so that the polycarboxylic acid water reducing agent with excellent performance is obtained. The rosin structure is introduced into the molecular structure of the polycarboxylate superplasticizer, and is not reported.
The technical problem to be solved by the invention is solved by the following technical scheme:
the first purpose of the invention is to provide a rosin modified polycarboxylic acid water reducing agent, which is prepared from the following raw materials in parts by mole:
20-50 parts of micromolecule unsaturated carboxylic acid, 3-10 parts of salt of the micromolecule unsaturated acid, 15-30 parts of unsaturated polyether macromonomer, 5-20 parts of rosin modified vinyl ester, 0.2-2 parts of initiator and 0.2-2 parts of chain transfer agent.
In a preferred technical scheme of the invention, the rosin modified polycarboxylic acid water reducing agent is prepared from the following raw materials in parts by mole:
35-50 parts of micromolecule unsaturated carboxylic acid, 5-8 parts of micromolecule unsaturated acid salt, 20-25 parts of unsaturated polyether macromonomer, 8-12 parts of rosin modified vinyl ester, 0.5-1 part of initiator and 0.5-0.8 part of chain transfer agent.
Further, the small molecule unsaturated carboxylic acid is selected from at least one of acrylic acid and methacrylic acid. The unsaturated carboxylic acid may also contain ester in certain proportion, the ester forming group is at least one of methyl ester, ethyl ester, propyl ester and butyl ester, and the amount of the unsaturated carboxylic acid ester is not more than 10% of the unsaturated carboxylic acid.
Further, the salt of the small molecular unsaturated acid is a salt of an unsaturated carboxylic acid or a propenyl sulfonate, and the salt is a sodium salt or a potassium salt; preferably at least one selected from the group consisting of sodium acrylate, potassium acrylate, sodium methacrylate, potassium methacrylate, sodium acryl sulfonate, potassium acryl sulfonate, sodium methacryl sulfonate and potassium methacryl sulfonate.
Further, the unsaturated polyether macromonomer is selected from at least one of Allyl Polyoxyethylene Ether (APEG), isoamyl alcohol polyoxyethylene ether (TPEG) and methallyl alcohol polyoxyethylene ether (HPEG); the number average molecular weight of the unsaturated polyether macromonomer is 500-4000, preferably 1500-3000.
Further, the rosin-modified vinyl ester is at least one of Vinyl Tetrahydroabietate (VTA), Vinyl Dehydroabietate (VDA), and vinyl maleopimaric acid (VMPA).
Further, the initiator is selected from at least one of dibenzoyl peroxide (BPO), Azobisisobutyronitrile (AIBN), ammonium persulfate and potassium persulfate.
Further, the chain transfer agent is selected from at least one of mercaptopropionic acid, thioglycolic acid, mercaptoethanol, and isopropanol.
The rosin modified vinyl ester adopted by the invention is prepared by using carboxyl in rosin molecules and carrying out ester exchange reaction of vinyl acetate. Specific examples are Vinyl Tetrahydroabietate (VTA), Vinyl Dehydroabietate (VDA) and vinyl maleopimaric acid (VMPA).
Tetrahydrovinyl Abietate (VTA) is obtained by transesterification of perhydrogenated rosin with vinyl acetate. Specific methods refer to Lierpin R, et al.j.polym.sci.a, 1966, 4 (8): 2003. the dehydroabietic acid vinyl ester (VDA) is prepared by using dehydroabietic acid as a raw material and mercury sulfate as an initiator to perform ester exchange reaction with vinyl acetate. Specific methods refer to Fukuda W, et al.j polym.sci a.1968, 6 (4): 1050. the maleopimaric acid vinyl ester (VMPA) is prepared by carrying out ester exchange reaction on maleopimaric acid (MPA) and vinyl acetate, and the structure of the maleopimaric acid vinyl ester (VMPA) contains acid anhydride, and the specific method refers to Lewis JB, et al.J.org.chem.1960, 25 (7): 1206.
the second purpose of the invention is to provide a preparation method of the rosin modified polycarboxylate superplasticizer, which comprises the following steps:
(S1) preparing the reactants into aqueous solution according to the mixture ratio;
(S2) adding an unsaturated polyether macromonomer into a reaction container, heating to 40-80 ℃, slowly adding a small molecular unsaturated carboxylic acid, a small molecular unsaturated carboxylic acid salt, rosin modified vinyl ester, an initiator and a chain transfer agent aqueous solution, and reacting at 40-80 ℃ for 2-6 hours after the addition is finished;
(S3) cooling, and using liquid caustic soda to adjust the pH value of the system to 6-7, thereby obtaining the rosin modified polycarboxylic acid water reducing agent.
Further, the aqueous solution in which the small molecular unsaturated carboxylic acid, the salt of the small molecular unsaturated carboxylic acid, the rosin-modified vinyl ester, the initiator and the chain transfer agent are slowly added is dropwise added.
Further, the aqueous solutions of the respective raw materials may be dropped into the reaction vessel simultaneously, or a mixed solution of the aqueous solutions of the respective raw materials may be dropped into the reaction vessel.
Further, the dripping time is 2-4 h.
The third purpose of the invention is to apply the rosin modified polycarboxylate superplasticizer to cement engineering construction.
The rosin modified polycarboxylate superplasticizer provided by the invention is used as an additive in cement and concrete construction, so that the workability of cement is effectively improved, and the compressive strength is also improved to a greater extent. The water reducer provided by the invention is proved to have excellent comprehensive performance, convenient manufacture and low cost, is a novel green and environment-friendly water reducer and has good market popularization value.
The polycarboxylic acid water reducing agent containing the rosin molecular structure is prepared by carrying out simple ester exchange reaction on rosin derivatives to obtain a rosin modified vinyl ester monomer containing active double-structure, and copolymerizing the vinyl ester monomer with other monomers. The tricyclic phenanthrene skeleton in the rosin molecular structure performs hydrophobic modification on water reducing agent molecules, the hydrophobic chain segment enhances the resistance among concrete particles attached with the water reducing agent molecules, the steric hindrance effect of the water reducing agent molecules is enhanced, the adaptability of polycarboxylic acid to concrete is enhanced, and the fluidity of slurry is improved, so that the comprehensive performance of the water reducing agent is improved. In a cement dispersion system, a common polycarboxylic acid water reducing agent is adsorbed on the surface of cement particles through a polar group with negative electricity on a main chain, such as carboxyl, sulfonic group and the like, and meanwhile, hydrophilic side chain polyethylene oxide extends in an aqueous solution to play a certain steric hindrance role. The rosin modified polycarboxylate superplasticizer provided by the invention introduces a molecular structure of rosin into a molecular main chain structure. Due to the hydrophobic effect of the rosin, the rosin can not interact with water molecules to generate hydrogen bonds, can not move to a gas-water interface, and can only be adsorbed to a solid-liquid interface of cement particles and water, so that the adsorption capacity of the rosin is higher than that of a common polycarboxylic acid water reducing agent.
Compared with the prior art, the invention has the following beneficial effects:
the polycarboxylate superplasticizer prepared by the invention can reach a high water-reducing rate of more than 32% at a low mixing amount, provides more strength-rich space for actual production, and simultaneously enables the production of high-strength concrete easy to pump.
Secondly, a certain amount of tiny and homogeneous air bubbles are introduced into the concrete by the special structure of the rosin, and redundant free water forms 'balls', so that the fluidity of the concrete is improved, and the brittleness of the concrete is reduced.
And thirdly, under the condition of meeting the requirement of high water reducing rate, the raw material proportion is optimized, and under the condition of not changing the cement consumption, the blended concrete has high reinforcement.
Detailed Description
The invention is further illustrated by the following specific examples, which should not be construed as limiting the invention.
Example 1
(S1) mixing the following raw materials in parts by mole: preparing an aqueous solution from 38 parts of methacrylic acid, 5 parts of sodium methallylsulfonate, 9 parts of VTA, 0.5 part of ammonium persulfate and 0.6 part of mercaptopropionic acid;
(S2), adding 21 molar parts of TPEG (number average molecular weight 2200) into a reaction vessel, heating to 60 ℃, then respectively and simultaneously dropwise adding the aqueous solution of the raw materials into the reaction vessel for 3 hours, and reacting for 5 hours at 60-80 ℃ after dropwise adding;
(S3) cooling, and using liquid caustic soda to adjust the pH value of the system to 6-7, thereby obtaining the rosin modified polycarboxylic acid water reducing agent.
Example 2
(S1) mixing the following raw materials in parts by mole: 42 parts of methacrylic acid, 7 parts of sodium methallylsulfonate, 10 parts of VTA, 0.8 part of potassium persulfate and 0.7 part of mercaptopropionic acid are prepared into an aqueous solution;
(S2), adding 25 molar parts of HPEG (number average molecular weight 2400) into a reaction container, heating to 70 ℃, dropwise adding a mixed solution of the water solution of the raw materials for 2 hours, and reacting for 4 hours at 60-80 ℃ after dropwise adding;
(S3) cooling, and using liquid caustic soda to adjust the pH value of the system to 6-7, thereby obtaining the rosin modified polycarboxylic acid water reducing agent.
Universal preparation method of rosin modified polycarboxylic acid water reducing agent
(S1) preparing the reactants into aqueous solution according to the mixture ratio;
(S2) adding unsaturated polyether macromonomer into a reaction container, heating to 40-80 ℃, then respectively and slowly adding micromolecule unsaturated carboxylic acid, micromolecule unsaturated acid salt, rosin modified vinyl ester, initiator and aqueous solution of chain transfer agent, and reacting for 2-6 h at 40-80 ℃ after the addition is finished;
(S3) cooling, and using liquid caustic soda to adjust the pH value of the system to 6-7, thereby obtaining the rosin modified polycarboxylic acid water reducing agent.
According to the general preparation method, different raw materials and proportions are selected to prepare a series of rosin modified polycarboxylic acid water reducing agents (no rosin modified vinyl ester monomer is added in a comparative example). The skilled person can select suitable reaction conditions, such as reaction temperature and reaction time, according to actual needs. The slow addition mode is dropwise addition, and the mixture of the raw material aqueous solutions can be respectively and simultaneously dropwise added or directly dropwise added, wherein the dropwise addition time is 2-4 h. The polycarboxylic acid water reducing agents of examples 3 to 8 and comparative examples 1 and 2 were prepared according to the raw materials and the compounding ratios shown in table 1.
TABLE 1
Characterization of rosin-modified polycarboxylic acid water reducing agent
1. Gel chromatography analysis
The water phase gel chromatography analysis uses an instrument of a United states Waters gel permeation chromatograph to test the molecular weight and the distribution of the obtained rosin modified polycarboxylate superplasticizer. When the polycarboxylic acid water reducing agent passes through the chromatographic column at the flow rate of 1.0L/min, molecules with different sizes pass through the chromatographic column at different speeds to be separated, the temperature of the chromatographic column is controlled at 40 ℃, and the eluent is 0.1mol/LNa2SO4Aqueous solutions, calibration standard curves were calibrated with different molecular weight monodisperse polyethylene glycols.
2. Clear paste test and coagulation test
The performance of the rosin modified polycarboxylate superplasticizer prepared by the invention is tested. The cement paste fluidity test is carried out according to the relevant standards specified in GB/T8077-. The folding solid content of the polycarboxylic acid water reducing agent is 0.12 percent. The concrete compression strength test is carried out according to GB/T50081-2002 Standard of mechanical property test method of common concrete, the test block size is 100mm multiplied by 100mm, and the test block is converted into the standard test block strength according to the standard requirement.
In the examples, the test cement is a standard cement special for testing concrete admixture, and is 42.5 strength grade P.I type portland cement formed by grinding portland cement clinker with the following quality indexes and dihydrate gypsum together. The standard cement not only meets the technical requirements of silicate cement with 42.5 strength grade, but also contains 6-8% of composite tricalcium aluminate, 50-55% of tricalcium silicate, no more than 1.2% of free calcium oxide and alkali (Na)2O+0.658K2O) content is not more than 1.0 percent, and the specific surface area of the cement is 320 +/-20 m2In terms of/kg. The operation conditions are that the water cement ratio is 0.35, and the curing time of the cement cured sample is 28 days.
The characterization data and the performance detection results of the rosin modified polycarboxylate superplasticizer prepared by the invention are shown in the following table 2:
TABLE 2
TABLE 2
As can be seen from the data in Table 2, M is the ratio of the rosin modified polycarboxylic acid water reducer provided by the invention to the polycarboxylic acid synthesized by the traditional methodnAnd MwAnd PDI are relatively close, which indicates that the molecular structure of the polycarboxylic acid is not influenced by the addition of the rosin modified vinyl ester monomer. But the static slurry fluidity of the rosin modified polycarboxylate superplasticizer is obviously improved, the loss with time is small, and the rosin modified polycarboxylate superplasticizer has obvious advantages. At 0.12%Under the condition of low mixing amount, the water reducing agent provided by the invention has higher water reducing rate, and the production of high-strength concrete easy to pump becomes possible. In addition, the cement compressive property of the blending water reducer is tested, and the compressive strength of the polycarboxylate water reducer is greatly improved after the polycarboxylate water reducer is modified by rosin. The hydrophobic rosin molecular structure influences the hydration process of cement particles, so that the strength of the cement particles is improved.
The above embodiments are merely illustrative of the present disclosure and do not represent a limitation of the present disclosure. Other variations of the specific structure of the invention will occur to those skilled in the art.
Claims (10)
1. A rosin modified polycarboxylate superplasticizer is prepared from the following raw materials in parts by mole:
20-50 parts of micromolecule unsaturated carboxylic acid, 3-10 parts of salt of the micromolecule unsaturated acid, 15-30 parts of unsaturated polyether macromonomer, 5-20 parts of rosin modified vinyl ester, 0.2-2 parts of initiator and 0.2-2 parts of chain transfer agent; the rosin modified vinyl ester is a product of ester exchange between carboxyl on the rosin derivative and vinyl acetate.
2. The rosin modified polycarboxylate superplasticizer according to claim 1, which is prepared from the following raw materials in parts by mole:
35-50 parts of micromolecule unsaturated carboxylic acid, 5-8 parts of micromolecule unsaturated acid salt, 20-25 parts of unsaturated polyether macromonomer, 8-12 parts of rosin modified vinyl ester, 0.5-1 part of initiator and 0.5-0.8 part of chain transfer agent.
3. The rosin modified polycarboxylic acid water reducing agent according to claim 1, wherein the small molecule unsaturated carboxylic acid is selected from at least one of acrylic acid and methacrylic acid; the small molecular unsaturated carboxylic acid contains ester of unsaturated carboxylic acid in a certain proportion, the ester forming group is at least one of methyl ester, ethyl ester, propyl ester and butyl ester, and the ester of unsaturated carboxylic acid is not more than 10 mol% of the unsaturated carboxylic acid.
4. The rosin modified polycarboxylic acid water reducing agent according to claim 1, characterized in that the salt of the small molecule unsaturated acid is at least one selected from the group consisting of sodium acrylate, potassium acrylate, sodium acrylate sulfonate, potassium acrylate sulfonate, sodium methacrylate, potassium methacrylate, sodium methacrylate and potassium methacrylate sulfonate.
5. The rosin modified polycarboxylic acid water reducing agent according to claim 4, characterized in that the salt of the small molecular unsaturated acid is selected from at least one of sodium methallylsulfonate and potassium methallylsulfonate.
6. The rosin modified polycarboxylate superplasticizer according to claim 1, wherein said unsaturated polyether macromonomer is at least one selected from Allyl Polyoxyethylene Ether (APEG), prenyl polyoxyethylene ether (TPEG) and methallyl alcohol polyoxyethylene ether (HPEG) having a molecular weight of 500-3000.
7. The rosin-modified polycarboxylic acid water reducing agent according to claim 1, wherein the rosin-modified vinyl ester is at least one of Vinyl Tetrahydroabietate (VTA), Vinyl Dehydroabietate (VDA) and vinyl maleopimaric acid (VMPA).
8. The rosin-modified polycarboxylic acid water reducing agent according to claim 1, wherein said initiator is selected from at least one of dibenzoyl peroxide (BPO), Azobisisobutyronitrile (AIBN), ammonium persulfate, potassium persulfate; the chain transfer agent is selected from at least one of mercaptopropionic acid, thioglycolic acid, mercaptoethanol, and isopropanol.
9. The preparation method of the rosin modified polycarboxylate superplasticizer according to claim 1, comprising the following steps:
(S1) preparing the reactants into aqueous solution according to the mixture ratio;
(S2) adding an unsaturated polyether macromonomer into a reaction container, heating to 40-80 ℃, slowly adding a small molecular unsaturated carboxylic acid, a small molecular unsaturated acid salt, rosin modified vinyl ester, an initiator and a chain transfer agent aqueous solution, and reacting at 40-80 ℃ for 2-6 hours after the addition is finished;
(S3) cooling, and neutralizing the system with liquid alkali until the pH value is 6-7 to obtain the rosin modified polycarboxylic acid water reducing agent.
10. The preparation method of claim 9, wherein the slow addition is performed in a dropwise manner, and the dropwise addition time is 2-4 hours; the dropwise addition is to drop the aqueous solution of each raw material into the reaction vessel at the same time, or to drop the mixed solution of the aqueous solutions of each raw material into the reaction vessel.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3206440A (en) * | 1961-06-29 | 1965-09-14 | Glen W Hedrick | Vinyl esters of maleic anhydride adducts |
| JPS58135168A (en) * | 1982-02-03 | 1983-08-11 | 花王株式会社 | cement additives |
| CN102585103A (en) * | 2011-11-18 | 2012-07-18 | 重庆建研科之杰新材料有限公司 | Preparation method for low-bleeding water aliphatic high-efficiency water reducing agent |
| CN108101407A (en) * | 2016-11-24 | 2018-06-01 | 温州威力助剂有限公司 | Polycarboxylic-acid composite water-reducing agent and preparation method thereof |
| CN108328960A (en) * | 2018-03-22 | 2018-07-27 | 长沙小新新能源科技有限公司 | A kind of concrete poly carboxylic acid series water reducer and preparation method thereof |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3206440A (en) * | 1961-06-29 | 1965-09-14 | Glen W Hedrick | Vinyl esters of maleic anhydride adducts |
| JPS58135168A (en) * | 1982-02-03 | 1983-08-11 | 花王株式会社 | cement additives |
| CN102585103A (en) * | 2011-11-18 | 2012-07-18 | 重庆建研科之杰新材料有限公司 | Preparation method for low-bleeding water aliphatic high-efficiency water reducing agent |
| CN108101407A (en) * | 2016-11-24 | 2018-06-01 | 温州威力助剂有限公司 | Polycarboxylic-acid composite water-reducing agent and preparation method thereof |
| CN108328960A (en) * | 2018-03-22 | 2018-07-27 | 长沙小新新能源科技有限公司 | A kind of concrete poly carboxylic acid series water reducer and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Polymers from vinyl Esters of perhydrogenated rosin;R.Liepins等;《Journal of Polymer Science: Part A-1：Polymer Chemistry》;19660831;第4卷(第8期);第2003-2014页 * |
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