CN106117564B - A kind of preparation method of the highly resistance chamotte mould cement dispersants of graft esterification cationic side chain - Google Patents
A kind of preparation method of the highly resistance chamotte mould cement dispersants of graft esterification cationic side chain Download PDFInfo
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- CN106117564B CN106117564B CN201610563315.6A CN201610563315A CN106117564B CN 106117564 B CN106117564 B CN 106117564B CN 201610563315 A CN201610563315 A CN 201610563315A CN 106117564 B CN106117564 B CN 106117564B
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- acid
- side chain
- esterification
- added
- reaction
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- 239000004568 cement Substances 0.000 title claims abstract description 57
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 53
- 238000005886 esterification reaction Methods 0.000 title claims abstract description 47
- 230000032050 esterification Effects 0.000 title claims abstract description 38
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 27
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 23
- -1 unsaturated cationic quaternary ammonium salt Chemical class 0.000 claims abstract description 21
- 150000000703 Cerium Chemical class 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 239000000376 reactant Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 239000007864 aqueous solution Substances 0.000 claims description 28
- 238000006116 polymerization reaction Methods 0.000 claims description 27
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 23
- 239000000047 product Substances 0.000 claims description 21
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000002202 Polyethylene glycol Substances 0.000 claims description 15
- 238000010792 warming Methods 0.000 claims description 15
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 9
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 7
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- 239000001530 fumaric acid Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N p-toluenesulfonic acid Substances CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 claims description 3
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 3
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 3
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- TZYULTYGSBAILI-UHFFFAOYSA-M trimethyl(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC=C TZYULTYGSBAILI-UHFFFAOYSA-M 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 2
- VNJOVAIIFRNVOK-UHFFFAOYSA-M butyl-dimethyl-(2-prop-2-enoyloxyethyl)azanium;bromide Chemical compound [Br-].CCCC[N+](C)(C)CCOC(=O)C=C VNJOVAIIFRNVOK-UHFFFAOYSA-M 0.000 claims description 2
- MFEOCVXPDXJAAC-UHFFFAOYSA-M dodecyl-dimethyl-(2-prop-2-enoyloxyethyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CCOC(=O)C=C MFEOCVXPDXJAAC-UHFFFAOYSA-M 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid 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
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 claims 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims 2
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims 2
- 150000002191 fatty alcohols Chemical class 0.000 claims 2
- 150000002334 glycols Chemical class 0.000 claims 2
- MSCUNRCIQGLERU-UHFFFAOYSA-N hydroxylium Chemical group [OH+] MSCUNRCIQGLERU-UHFFFAOYSA-N 0.000 claims 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims 2
- UPYPTOCXMIWHSG-UHFFFAOYSA-N 1-dodecylsulfanyldodecane Chemical compound CCCCCCCCCCCCSCCCCCCCCCCCC UPYPTOCXMIWHSG-UHFFFAOYSA-N 0.000 claims 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims 1
- PBCKVROHSSNSDY-UHFFFAOYSA-N 2-methylprop-2-enoic acid;sodium Chemical compound [Na].CC(=C)C(O)=O PBCKVROHSSNSDY-UHFFFAOYSA-N 0.000 claims 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims 1
- 235000011130 ammonium sulphate Nutrition 0.000 claims 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims 1
- ARZADRIAOMWMOJ-UHFFFAOYSA-M dodecyl-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CCOC(=O)C(C)=C ARZADRIAOMWMOJ-UHFFFAOYSA-M 0.000 claims 1
- VFRQEVIIBMUKCQ-UHFFFAOYSA-M ethyl-dimethyl-(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].CC[N+](C)(C)CCOC(=O)C=C VFRQEVIIBMUKCQ-UHFFFAOYSA-M 0.000 claims 1
- ZDWULJNYPFIJBY-UHFFFAOYSA-M hexadecyl-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)CCOC(=O)C(C)=C ZDWULJNYPFIJBY-UHFFFAOYSA-M 0.000 claims 1
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 claims 1
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 claims 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 claims 1
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 claims 1
- OIFLLGNCLZLPAF-UHFFFAOYSA-M trimethyl-(5-methyl-4-oxohex-5-enyl)azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)CCC[N+](C)(C)C OIFLLGNCLZLPAF-UHFFFAOYSA-M 0.000 claims 1
- 150000007513 acids Chemical class 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 22
- 239000000178 monomer Substances 0.000 abstract description 17
- 230000015572 biosynthetic process Effects 0.000 abstract description 16
- 238000003786 synthesis reaction Methods 0.000 abstract description 16
- 239000004927 clay Substances 0.000 abstract description 13
- 230000003467 diminishing effect Effects 0.000 abstract description 13
- 238000013461 design Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 5
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 4
- 229920005646 polycarboxylate Polymers 0.000 abstract description 4
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 4
- 150000001735 carboxylic acids Chemical class 0.000 abstract 1
- 230000005764 inhibitory process Effects 0.000 abstract 1
- 230000003335 steric effect Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 13
- 230000008901 benefit Effects 0.000 description 11
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- 230000000977 initiatory effect Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229910002651 NO3 Inorganic materials 0.000 description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 7
- 238000006392 deoxygenation reaction Methods 0.000 description 7
- 229920002472 Starch Polymers 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 235000019698 starch Nutrition 0.000 description 6
- 239000008107 starch Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 5
- 229920001427 mPEG Polymers 0.000 description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical group O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- JPAOMENBKRZQDR-UHFFFAOYSA-N CC=CC.[Na] Chemical compound CC=CC.[Na] JPAOMENBKRZQDR-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- 229920000881 Modified starch Polymers 0.000 description 2
- 239000004368 Modified starch Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
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- 239000012966 redox initiator Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- LRZBYXVUFNZCPF-UHFFFAOYSA-N 2-bromo-2-methylheptadecane Chemical compound CCCCCCCCCCCCCCCC(C)(C)Br LRZBYXVUFNZCPF-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
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
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- 230000000996 additive effect Effects 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- IUPDXIXTYXNMFR-UHFFFAOYSA-N azane N,N-dimethylmethanamine hydrochloride Chemical compound [Cl-].[NH4+].CN(C)C IUPDXIXTYXNMFR-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- QZHVLXBOWGWDFB-UHFFFAOYSA-N butyl(methyl)azanium bromide Chemical compound [Br-].C(CCC)[NH2+]C QZHVLXBOWGWDFB-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 230000003311 flocculating effect Effects 0.000 description 1
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- SAJCTJNLJMJPDP-UHFFFAOYSA-M hexadecyl-dimethyl-(2-prop-2-enoyloxyethyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)CCOC(=O)C=C SAJCTJNLJMJPDP-UHFFFAOYSA-M 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
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- 238000002955 isolation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- LISZMWMCSIUBEJ-UHFFFAOYSA-N n,n-dimethylbutan-1-amine;hydrobromide Chemical compound [Br-].CCCC[NH+](C)C LISZMWMCSIUBEJ-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
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- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- MLGWTHRHHANFCC-UHFFFAOYSA-N prop-2-en-1-amine;hydrochloride Chemical compound Cl.NCC=C MLGWTHRHHANFCC-UHFFFAOYSA-N 0.000 description 1
- PYNUOAIJIQGACY-UHFFFAOYSA-N propylazanium;chloride Chemical compound Cl.CCCN PYNUOAIJIQGACY-UHFFFAOYSA-N 0.000 description 1
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- 239000004575 stone Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
- C08G81/025—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyether sequences
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- 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
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
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- 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
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
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- C08F126/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F126/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
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- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
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- 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
- C04B2103/48—Foam stabilisers
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Abstract
A kind of preparation method of the highly resistance chamotte mould cement dispersants of graft esterification cationic side chain belongs to dispersing agent field.The present invention is using unsaturated carboxylic acid class monomer as reactant, free radical polymerization, which is carried out, under initiator and chain-transferring agent effect obtains polycarboxylic acids main chain, then using unsaturated cationic quaternary ammonium salt monomer as reactant, free radical polymerization obtains terminal hydroxy group cationic side chain under the oxidation-reduction trigger system of high price cerium salt and alcohol composition, then polycarboxylic acids main chain is passed through graft esterification with terminal hydroxy group cationic side chain, polyethylene glycols compound under the effect of the catalyst and reacts obtained.Process of the present invention is simple and easy to control, low in cost, energy-efficient, environment friendly and pollution-free, pass through the compound side-chain structure of Molecular Design modified synthesis, side chain space steric effect and cationic charge arrangement are realized in success, it shows the diminishing more excellent than common polycarboxylate water-reducer and protects collapse characteristic and inhibition side effect of clay ability, have a vast market foreground and promote and apply potentiality.
Description
Technical field
The present invention relates to a kind of cement concrete technical fields of highly resistance chamotte mould dispersing agent, are related specifically to a kind of use
Unsaturated carboxylic acid monomer first polymerize polycarboxylic acids main chain polymerizing cationically side chain then main side chain graft esterification synthesis highly resistance chamotte mould again
The specific preparation method of cement dispersants.
Background technique
With the fast development of concrete science and engineering technology, workability of concrete, durability etc. can be obviously improved
The cement concrete chemical admixture of performance is increasingly taken seriously and favors, however, concrete raw material is to chemical admixture
Application performance have an important influence, especially admixture aggregate when a small amount of clay for being brought into can mobility to concrete, strong
Degree, impermeability etc. have negative effect, this, which has become, restricts keeping in check for cement concrete chemical admixture popularization and application.
Due to the continuous increase serious in short supply and carrying capacity of environment of high-quality aggregate resources, it is mixed to develop a kind of highly resistance chamotte mould cement
Solidifying soil dispersing agent has been the task of top priority.The great advantage of high-molecular type dispersing agent be can by exchange polymerized monomer type,
Change the product that the methods of monomer match ratio and regulatory molecule structure functional group design different molecular structures and performance, thus
It is the dispersing agent kind that a kind of structure flexible design degree is big, performance regulation space is big.Therefore, cement concrete dispersing agent is ground
Study carefully and apply it is more and more extensive, towards efficiency is more significant, feature is distincter, functionality is stronger, the wider array of direction of adaptation range not
Disconnected development.
Molecular Design method is introduced into the synthesis field of cement concrete dispersing agent, development can inhibit clay pair
The highly resistance chamotte mould dispersing agent of effect not only has the excellent working performance of traditional dispersing agent, while also having and resisting clay pair work
Peculiar advantage feature can sufficiently alleviate the imbalance between supply and demand of high-quality aggregate, realize ecological environmental protection and natural resources section
It can lower consumption, show good application prospect.
Patent CN 104402292A (publication date: on March 11st, 2015) reports a kind of preparation of modified starch water-reducing agent
Method.The patent is to carry out degradation modification using starch as primary raw material with oxidant and sodium carbonate, monomer and initiation is then added
Agent carries out graft polymerization and prepares modified starch dispersing agent, and water-reducing rate is 3-4 hours up to 26-28%, retarding time, can be effective
Ground prevents phenomena such as bleeding, isolation.The advantages of invention is using safety and environmental protection and native starch from a wealth of sources is former as reaction
Material, realizes the purpose for reducing cost, simultaneously as it is partially modified in structure, therefore water can also be improved to a certain extent
The workability of cement concrete and adaptability containing argillaceous sand stone.But the invention product still need in net slurry mortar concrete
The additives such as polycarboxylate water-reducer are used cooperatively, and are not able to achieve the anti-mud multifunctional all of diminishing, do not have on structural level
The unique advantage of standby complex function type, the progress and innovation in structure that can not inherently realize.
Patent CN 104311743A (publication date: on January 28th, 2015) reports a kind of low cost for wastewater treatment
The preparation method of modified flocculant.The invention is caused based on hydroxymethyl starch by the way that ammonium ceric nitrate is added as initiator
Acrylamide monomer reacts to obtain modified flocculant with formaldehyde and dimethylamine again in hydroxymethyl starch surface grafting polymerization, product.
The advantages of invention be using the extensive hydroxymethyl starch in source as key reaction raw material, it is low in cost, the pH value scope of application is wide,
Flocculating property is excellent, and the ammonium ceric nitrate initiator used can also effectively utilize the advantage of the initiation system.But it should
Invention product neither has the ability of diminishing dispersion as excellent flocculant, does not also have highly resistance mud effect, therefore although utilize
The initiation system of ammonium ceric nitrate, still can not be applied to cement concrete anti-mud water-reducing agent field.
Patent CN104446101A (publication date: on March 25th, 2015) reports the cation-modified polycarboxylic acids of one kind and subtracts
Aqua is by isoamyl alcohol polyoxyethylene ether monomer, unitary unsaturated carboxylic acid and its derivatives monomer, cationic monomer and two
Combined polymerization under the action of initiator and chain-transferring agent of first unsaturated carboxylic acid and its derivatives monomer forms.The invention product is added
When into concrete, it can be adsorbed on positively charged and negatively charged cement minerals surface simultaneously, embody and be superior to anion
The characteristics of type polycarboxylate water-reducer, moreover, product strand in cement slurry alkaline environment extends, absorption shape is more
Unfold, water-reducing rate is more excellent.But the invention product is only to introduce cationic monomer in the main chain of molecular structure, is mentioned
High diminishing dispersion effect centainly, and be not implemented while diminishing dispersion and show highly resistance mud performance etc. using feature,
Fail to achieve the purpose that Molecular Design method realizes chemical admixture functionalization.
Cement concrete described in most patents has been provided with the works such as good mobility, dispersibility with diminishing dispersing agent
Make performance.However, the product that above-mentioned synthetic method obtains has a degree of shortcoming, researcher focuses mostly on to be subtracted in realization
Water dispersion, anti-mud, flocculation a certain item performance therein, and seldom pass through the cationic that is graft-polymerized under high price cerium salt initiation system
The method of side chain realizes that integrating diminishing-guarantor is collapsed-disperses-complex function type chemical admixture of the application performances such as anti-mud.Only
It is only limited in water reducer of cement concrete field by simple backbone modification or synthetic starch base diminishing dispersant material
Popularization and application, warp facts proved that synthesis have multiple action complex function group type molecular structure can significantly improve polymer
Application performance effect.Therefore, this requires the cement concrete dispersing agents of synthesis to realize the innovation of molecular structure, not only to have
Standby diminishing protects the-compound working performance of anti-mud of collapsing, while also can guarantee convenient and fast technological operation, cheap preparation cost, letter
The reaction raw materials being singly easy to get, are conducive to industrialized production and popularization and application, and related this respect work has not been reported both at home and abroad.
Summary of the invention
The object of the present invention is to provide a kind of synthesis works of the highly resistance chamotte mould cement dispersants of graft esterification cationic side chain
Skill carries out free radical polymerization by unsaturated carboxylic acid class monomer and obtains polycarboxylic acids main chain, then forms high price cerium salt and alcohols
Oxidation-reduction trigger system, which causes, to be polymerize unsaturated cationic quaternary ammonium salt monomer and obtains terminal hydroxy group cationic side chain, then by poly- carboxylic
The highly resistance chamotte mould cement that sour main chain and terminal hydroxy group cationic side chain, polyethylene glycols compound graft esterification are had excellent performance is mixed
Solidifying soil dispersing agent.The present invention is to increase from design theory of molecular structure using high price cerium salt -ol as Redox Initiator
The step of polymeric cationic side chain and successfully graft esterification is realized under system, and polycarboxylic acids main chain is connected to cationic side chain
It is formed together the new polycarboxylic acid water reducer with the multiple actions such as high water reduction and highly resistance mud, realizes and passes through molecular side chain
The modified purpose for improving its work efficiency, enriches polymer architecture-performance study answering in concrete chemical admixture field
With.There is compound side-chain structure using the cement concrete diminishing dispersing agent of this method synthesis, subtract different from conventional polycarboxylic acids
The side chain of aqua forms, and polyether lateral chain can be acted on by steric hindrance realizes that excellent diminishing protects effect of collapsing, cation
Side-chain structure can also change charge electrical property in the concrete system of high clay content, and polyether lateral chain is further prevented to be adsorbed
Into clay interlayer, the adverse effect that can effectively inhibit clay to generate dispersion flows performance is shown than common polycarboxylic acids
The more excellent working characteristics of water-reducing agent and function and effect.
The present invention provides a kind of preparation methods of the highly resistance chamotte mould cement dispersants of graft esterification cationic side chain, pass through
First backbone polymerization again cationic side chain polymerization then graft esterification method synthesize highly resistance chamotte mould cement dispersants material, including with
Lower condition and step:
(1) backbone polymerization: sequentially added into reactor (methyl) acrylic acid or its mixture with unsaturated carboxylic acid,
Water, molecular weight regulator, the initiator persulfate aqueous solution that mass fraction is 1-30%, and when each feeding interval stirring
Between 5-20 minutes, be warming up at 55-90 DEG C and carry out polymerization reaction, react 1.5-8 hours to get polycarboxylic acids main chain aqueous solution；
(2) cationic side chain polymerize: monomer unsaturation cation quaternary ammonium salt and reducing agent lower aliphatic alcohols being added another
In reactor, adds water and be configured to the aqueous solution that mass concentration is 2-10%, reactor inflated with nitrogen 3-5 deoxygenation 10- repeatedly
It is sealed after 30 minutes, oxidant high price cerium salt is added, be uniformly mixed within stirring 10-30 minutes, be continuously heating at 10-60 DEG C to it
Polymerization reaction is carried out, reacts 6-16 hours to get terminal hydroxy group cationic side chain aqueous solution；
(3) graft esterification: by step (1) products therefrom polycarboxylic acids main chain aqueous solution and step (2) products therefrom terminal hydroxy group
Cationic side chain aqueous solution mixes, and adds polyethylene glycols compound, is warming up to 50-70 DEG C, to polyethylene glycols chemical combination
Object is in a liquid state, and vacuumizes moisture in removing system, and catalyst is added, and stirs 5-20 minutes, temperature is increased to add at 80-100 DEG C
Enter water entrainer, be continuously heating to carry out esterification at 100-150 DEG C, separates reaction gained water while reaction, instead
Water entrainer is sloughed by vacuumizing after answering 2-10 hours, esterification reaction product is obtained, is cooled to 25-40 DEG C, it is dilute to be eventually adding water
Release needed for concentration graft esterification cationic side chain cement dispersants solution.
Unsaturated carboxylic acid described in above-mentioned steps (1) is one of itaconic acid, maleic acid (acid anhydride), fumaric acid or several
Kind, the molar ratio of (methyl) acrylic acid being added in dosage and step (1) is 0.1-5:1；Addition water described in step (1)
Quality be in step (1) (methyl) acrylic acid or its mixture quality with unsaturated carboxylic acid and 80-200%；In step (1)
The molecular weight regulator is thioacetic acid, mercaptopropionic acid, methylpropene sodium sulfonate, Sodium Allyl Sulfonate or dodecyl
The molar ratio of mercaptan, (methyl) acrylic acid that dosage and step (1) are added or itself and the mixture of unsaturated carboxylic acid is 0.01-
0.15:1；Initiator persulfate described in step (1) is ammonium persulfate, potassium peroxydisulfate or sodium peroxydisulfate, dosage and step
(1) molar ratio of (methyl) acrylic acid or itself and the mixture of unsaturated carboxylic acid that are added is 0.01-0.1:1.
Unsaturated cation quaternary ammonium salt described in above-mentioned steps (2) is trimethylallylammonium chloride, dimethyl diene
Propyl ammonium chloride, tetra allyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, methylacryoyloxyethyl trimethyl ammonia chloride
Ammonium, methacryl hydroxypropyltrimonium chloride, acryloxyethyldimethyl butylammonium bromide, methylacryoyloxyethyl two
Methyl butyl ammonium bromide, acryloxyethyldimethyl dodecyl ammonium bromide, methylacryoyloxyethyl dimethyl dodecyl
Base ammonium bromide, acryloxyethyldimethyl cetyl ammonium bromide, methylacryoyloxyethyl dimethyl hexadecyl bromide
One or more of ammonium, the molar ratio of high price cerium salt described in dosage and step (2) are 10-1000:1；Institute in step (2)
The lower aliphatic alcohols stated are normal propyl alcohol, isopropanol, n-butanol, isobutanol, n-amyl alcohol, 2-methyl-1-butene alcohol, 3- methyl-1-fourth
Alcohol, 2,2- dimethyl -1- propyl alcohol or cyclohexanol, (methyl) acrylic acid that dosage and step (1) are added or itself and unsaturated carboxylic acid
Mixture molar ratio be 0.1-0.25:1；High price cerium salt described in step (2) is ammonium ceric nitrate or Cericammoniumsulfate, dosage
Molar ratio with lower aliphatic alcohols described in step (2) is 0.03-1:1.
Polyethylene glycols compound described in above-mentioned steps (3) be polyethylene glycol or methoxy poly (ethylene glycol), dosage with
The molar ratio of (methyl) acrylic acid or itself and the mixture of unsaturated carboxylic acid that step (1) is added is 0.15-0.25:1；Step
(3) catalyst described in is p-methyl benzenesulfonic acid, phosphoric acid or sulfamic acid, and dosage is polyethylene glycols compound in step (3)
The 2.5-20% of quality；Water entrainer described in step (3) is hexamethylene, benzene or toluene, and dosage is reactant in esterification
The 8-30% of gross mass, signified reactant are products therefrom polycarboxylic acids main chain in step (1), products therefrom end in step (2)
Polyethylene glycols compound in hydroxyl cationic side chain and step (3).
The number-average molecular weight of polyethylene glycols compound in the method for the present invention is 500-3000.
The method of the present invention has the advantages that compared with prior art
1. the present invention is from design theory of molecular structure, using unsaturated cationic quaternary ammonium salt monomer as reactant, in height
Free radical polymerization obtains cationic side chain under the oxidation-reduction trigger system of valence cerium salt and alcohol composition, this is from conventional polyethers
The unique design that side chain develops to diversification, the compound side chain of multifunction, is on comb shape diminishing dispersant molecule structure direction
Innovation and breakthrough, change of the dispersing agent in terms of application performance not only may be implemented in novel special structure, but also advantageous
In expanding Polymer supported catalyst-structure-performance intension of theory, other new types of Cernent point are developed to a deeper level to be subsequent
Powder has widened Research Thinking and developing direction.
2. being different from other inventive methods being only to be copolymerized a small amount of cationic structural in molecular backbone, the method for the present invention
The highly resistance chamotte mould cement dispersants of the graft esterification cationic side chain of synthesis have a large amount of quaternary ammonium salt cationic polymerization macromolecule chains,
Electrostatic adsorption can be generated with the interlayer of electronegative clay particle and surface, be conducive to be adsorbed on clay interlayer, meanwhile,
The interlamination region volume of clay is not infinity, can be to avoid other polyethers sides after having adsorbed a large amount of cationic side chain
Chain enters clay interlayer, does not lose so that the diminishing of the cement dispersants be protected to protect effect of collapsing, to show high water reduction, highly resistance
The function and effect of mud.The product can also diversification expanded application in the fields such as fine chemistry industry and surfactant, be a kind of tool
There is the cement concrete dispersing agent of peculiar advantage and distinguishing feature, has a good application prospect and the market competitiveness.
3. synthetic method of the present invention is compared with the traditional method, raw materials required for the reaction is common to be easy to get, and entire synthesis process is simple
Controllably, esterification used and polymerization procedure are also normal operations technique, without special operation or expensive auxiliary agent, enrich synthesis
The preparation method of cement concrete chemical admixture has the characteristics that apparent efficient and convenient, it is easy to accomplish industrialized production.
The synthesis process, without particular/special requirement, and remains with the functional group of high water reduction contained by tradition and high-thin arch dam effect to equipment, and
Have many advantages, such as that molecule can designed capacity be strong, molecular weight is controllable, narrow molecular weight distribution, the degree of polymerization are high, have promote well it is latent
Power and application value.
4. the method for the present invention innovatively uses the redox initiation system of high price cerium salt -ol class, high price cerium salt is utilized
Strong oxidizing property and the characteristic for having the free free radical of initiation organic matter generation, have abandoned traditional one-component hot initiator system, list
The initiation system of one high price cerium salt, oxidation-reduction trigger system such as hydrogen peroxide-VC system etc., the polymerization under the initiation system is anti-
Process is answered mildly to stablize, side reaction is few, and can substantially reduce the activation energy in polymerization process, it has a extensive future,
A kind of method of new initiation polymerization is provided with dispersing agent for cement concrete.
5. low energy consumption for a synthesis process, mild condition, safety and environmental protection, solvent-free murder by poisoning, cleanliness without any pollution, water entrainer used
It can also continue to be recycled after liquid separation-standing-separation, greatly reduce wastage of material, saved production cost.Water entrainer
It is condensed back the temperature plateau that can also keep reaction system, and the viscosity of reaction system can be reduced, makes to be stirred more
It is even abundant, improve the esterification yield and reaction rate of system.Meanwhile the unsaturated carboxylic acid class monomer used and unsaturated cationic season
The suitable molecular weight range of ammonium salt monomer raw material is wide, is conducive to the large-scale popularization and application of Diversified Products, increases highly resistance chamotte mould
The market share occupancy volume of cement concrete dispersing agent.
6. the highly resistance chamotte mould cement dispersing agent according to the method for the present invention synthesis has more than common polycarboxylate water-reducer
Excellent workability, diminishing guarantor are collapsed ability and anti-mud effect, remain to show preferable mobility and holding in high clay content
Ability, and very strong adaptability is shown to the cement of different cultivars.In addition, the cement dispersants Product Status is stablized, it is high
It is not stratified after being stood under concentration, it is not crystallized after being stored under low temperature and performance is unaffected.The synthetic method is simple direct
Meanwhile products obtained therefrom still has excellent performance indexes, is conducive to industrial application, therefore has warp well
Benefit of helping and social benefit.
Specific embodiment
The present invention is described in further detail below with reference to embodiment, but implementation of the invention is without being limited thereto.
Embodiment 1
The ammonium persulfate for being first 18% by 7.21g acrylic acid, 8.65g water, 0.91g thioacetic acid and 5.1g mass fraction
It is added in reactor, each feeding interval 9 minutes is warming up at 75 DEG C and carries out polymerization reaction, reacts 7 hours to get polycarboxylic acids
Main chain aqueous solution；Then successively into another reactor be added 12.89g trimethylallylammonium chloride, 1.41g n-butanol and
700.41g water, 4 deoxygenations seal reactor inflated with nitrogen after 15 minutes repeatedly, be added 0.52g ammonium ceric nitrate, stirring 25 minutes to
It is uniformly mixed, and is continuously heating to carry out polymerization reaction at 35 DEG C, and reaction 12 hours water-soluble to get terminal hydroxy group cationic side chain
Liquid, then be separately added into reactor gained polycarboxylic acids main chain aqueous solution and 50.4g methoxy poly (ethylene glycol) (molecular weight=
2400) 60 DEG C, are warming up to, is in a liquid state to methoxy poly (ethylene glycol) (molecular weight=2400), is vacuumized moisture in removing system, add
Enter 6.05g p-methyl benzenesulfonic acid, stir 15 minutes, temperature is increased to that 14.38g hexamethylene is added at 90 DEG C, is continuously heating to 120 DEG C
Reaction gained water is separated while reaction, sloughs hexamethylene by vacuumizing after reaction 6 hours by lower carry out esterification
Alkane obtains esterification reaction product, is cooled to 35 DEG C, is eventually adding the graft esterification that 106.77g water is 40% up to mass fraction
The cement dispersants solution of cationic side chain.
Embodiment 2
After the cement dispersants solution that the concentration that embodiment 1 is obtained is 40% is stored 20 days at 6 DEG C, its implementation is measured
Effect.
Embodiment 3
First by 7.83g methacrylic acid, 1.18g itaconic acid, 13.51g water, 1.38g mercaptopropionic acid and 12.29g mass
The ammonium persulfate that score is 22% is added in reactor, and each feeding interval 20 minutes is warming up at 55 DEG C and carries out polymerization reaction,
Reaction 8 hours to get polycarboxylic acids main chain aqueous solution；Then 29.80g methacryl propyl is successively added into another reactor
Trimethyl ammonium chloride, 0.88g n-amyl alcohol and 736.35g water, 3 deoxygenations seal reactor inflated with nitrogen after twenty minutes repeatedly, are added
5.37g Cericammoniumsulfate is uniformly mixed to it, is continuously heating to carry out polymerization reaction at 50 DEG C, react 8 hours for stirring 18 minutes,
Up to terminal hydroxy group cationic side chain aqueous solution, then gained polycarboxylic acids main chain aqueous solution and the poly- second of 30g are separately added into reactor
Glycol (molecular weight=1200), is warming up to 68 DEG C, is in a liquid state, is vacuumized in removing system to polyethylene glycol (molecular weight=1200)
2.4g phosphoric acid is added in moisture, stirs 10 minutes, and 17.32g benzene is added when temperature is increased to 80 DEG C, be continuously heating at 140 DEG C into
Reaction gained water is separated while reaction, sloughs benzene by vacuumizing after reaction 5 hours, obtain ester by row esterification
Change reaction product, be cooled to 30 DEG C, is eventually adding the graft esterification cationic side chain that 102.99g water is 40% up to mass fraction
Cement dispersants solution.
Embodiment 4
After the cement dispersants solution that the concentration that embodiment 3 obtains is 40% is stored 20 days at 5 DEG C, its implementation is measured
Effect.
Embodiment 5
First by 1.2g acrylic acid, 8.17g maleic anhydride, 18.74g water, 0.7908g methylpropene sodium sulfonate and 23.81g
The sodium peroxydisulfate that mass fraction is 1% is added in reactor, each feeding interval 12 minutes, is warming up at 65 DEG C and polymerize instead
It answers, reacts 3 hours to get polycarboxylic acids main chain aqueous solution；Then 46.73g methacryl is successively added into another reactor
Oxy-ethyl-trimethyl salmiac, 0.9g isopropanol and 632.84g water, 5 deoxygenations seal reactor inflated with nitrogen after ten minutes repeatedly,
0.36g Cericammoniumsulfate is added, is uniformly mixed to it within stirring 25 minutes, is continuously heating to carry out polymerization reaction at 55 DEG C, reaction 6 is small
When to get terminal hydroxy group cationic side chain aqueous solution, then be separately added into reactor gained polycarboxylic acids main chain aqueous solution and 57g first
Oxygroup polyethylene glycol (molecular weight=3000), is warming up to 55 DEG C, is in a liquid state to methoxy poly (ethylene glycol) (molecular weight=3000), takes out
Moisture in system is removed in vacuum, 1.43g sulfamic acid is added, stirs 8 minutes, temperature is increased to that 9.12g toluene is added at 95 DEG C,
It is continuously heating to carry out esterification at 145 DEG C, separate reaction gained water while reaction, reaction passes through after 2 hours
It vacuumizes and sloughs toluene, obtain esterification reaction product, be cooled to 28 DEG C, being eventually adding 264.58g water up to mass fraction is
The cement dispersants solution of 30% graft esterification cationic side chain.
Embodiment 6
The cement dispersants solution that the mass fraction that embodiment 5 is obtained is 30% is after 5 DEG C are stored 30 days, and measurement is in fact
Apply effect.
Embodiment 7
First by 4.3g methacrylic acid, 5.8g fumaric acid, 10.11g water, 1.1528g Sodium Allyl Sulfonate and 6.09g matter
It measures the ammonium persulfate that score is 30% to be added in reactor, each feeding interval 15 minutes is warming up at 60 DEG C and polymerize instead
It answers, reacts 5 hours to get polycarboxylic acids main chain aqueous solution；Then two allyl of 58.2g dimethyl is successively added into another reactor
Ammonium chloride, 0.89g isobutanol and 652.84g water, 3 deoxygenations seal reactor inflated with nitrogen after 25 minutes repeatedly, and 0.2g is added
Ammonium ceric nitrate, stirring 10 minutes to its be uniformly mixed, be continuously heating to carry out polymerization reaction at 30 DEG C, react 16 hours to get
Terminal hydroxy group cationic side chain aqueous solution, then it is separately added into reactor gained polycarboxylic acids main chain aqueous solution and 46g methoxyl group is poly-
Ethylene glycol (molecular weight=2000), is warming up to 50 DEG C, is in a liquid state to methoxy poly (ethylene glycol) (molecular weight=2000), vacuumizes and remove
Moisture in system to be removed, 9.2g p-methyl benzenesulfonic acid is added, is stirred 20 minutes, temperature is increased to that 19.11g toluene is added at 85 DEG C, after
Continuous be warming up at 115 DEG C carries out esterification, and reaction while separates reaction gained water, and reaction passed through pumping after 8 hours
Vacuum sloughs toluene, obtains esterification reaction product, is cooled to 25 DEG C, and being eventually adding 295.8g water up to mass fraction is 30%
The cement dispersants solution of graft esterification cationic side chain.
Embodiment 8
The cement dispersants solution that the mass fraction that embodiment 7 is obtained is 30% is after 6 DEG C are stored 40 days, and measurement is in fact
Apply effect.
Embodiment 9
First by 1.6g acrylic acid, 2.89g itaconic acid, 2.58 maleic acids, 3.87g fumaric acid, 8.75g water, 0.72g positive ten
The sodium peroxydisulfate that dialkyl group mercaptan and 23.81g mass fraction are 3% is added in reactor, each feeding interval 8 minutes, heating
Polymerization reaction is carried out to 80 DEG C, reacts 1.5 hours to get polycarboxylic acids main chain aqueous solution；Then successively into another reactor
Addition 48.42g acrylyl oxy-ethyl-trimethyl salmiac, 1.5g normal propyl alcohol and 695.14g water, reactor inflated with nitrogen 5 times repeatedly
Deoxygenation seals after 18 minutes, be added 13.71g ammonium ceric nitrate, stirring 30 minutes to its be uniformly mixed, be continuously heating at 60 DEG C into
Row polymerization reaction reacts 6.5 hours to get terminal hydroxy group cationic side chain aqueous solution, then is separately added into gained into reactor and gathers
Carboxylic acid main chain aqueous solution and 8.5g polyethylene glycol (molecular weight=500), are warming up to 70 DEG C, to polyethylene glycol (molecular weight=500)
It is in a liquid state, vacuumizes moisture in removing system, 0.26g p-methyl benzenesulfonic acid is added, stir 13 minutes, when temperature is increased to 100 DEG C
32.78g hexamethylene is added, is continuously heating to carry out esterification at 135 DEG C, separates out reaction gained moisture while reaction
It goes, sloughs hexamethylene by vacuumizing after reaction 10 hours, obtain esterification reaction product, be cooled to 40 DEG C, be eventually adding
The cement dispersants solution for the graft esterification cationic side chain that 108.53g water is 50% up to mass fraction.
Embodiment 10
The cement dispersants solution that the mass fraction that embodiment 9 is obtained is 50% is after 7 DEG C are stored 40 days, and measurement is in fact
Apply effect.
Embodiment 11
First by 2.46g methacrylic acid, 3.72g itaconic acid, 2.8 maleic anhydrides, 1.66g fumaric acid, 19.15g water,
The sodium peroxydisulfate that 1.37g thioacetic acid and 13.52g mass fraction are 10% is added in reactor, each feeding interval 5 minutes,
It is warming up at 90 DEG C and carries out polymerization reaction, react 3.5 hours to get polycarboxylic acids main chain aqueous solution；Then successively to another reaction
76.49g methylacryoyloxyethyl dimethylbutyl ammonium bromide, 1.3g cyclohexanol and 700.15g water, reactor are added in device to fill
4 deoxygenations seal nitrogen after 30 minutes repeatedly, and 3.1g Cericammoniumsulfate is added, and are uniformly mixed within stirring 13 minutes to it, continue to heat up
Polymerization reaction is carried out to 10 DEG C, is reacted 15 hours and is added respectively to get terminal hydroxy group cationic side chain aqueous solution, then into reactor
Enter gained polycarboxylic acids main chain aqueous solution and 12g polyethylene glycol (molecular weight=800), 65 DEG C is warming up to, to polyethylene glycol (molecular weight
=800) it is in a liquid state, vacuumizes moisture in removing system, 1.8g phosphoric acid is added, stir 5 minutes, temperature is increased to addition at 98 DEG C
10.43g benzene is continuously heating to carry out esterification at 150 DEG C, separates reaction gained water while reaction, reaction 4 is small
When after slough benzene by vacuumizing, obtain esterification reaction product, be cooled to 38 DEG C, be eventually adding 99.93g water up to mass fraction
For the cement dispersants solution of 50% graft esterification cationic side chain.
Embodiment 12
After the cement dispersants solution that the concentration that embodiment 11 is obtained is 50% is stored 30 days at 6 DEG C, measurement is in fact
Apply effect.
Implementation result:
1. flowing degree of net paste of cement
The mobility of cement is made to investigate the cement dispersants solution for the graft esterification cationic side chain that the present invention synthesizes
With effect, test determines under identical volume each embodiment to the paste flowing degree of reference cement.GB/T8077- is pressed in test
2012 " Methods for testing uniformity of concrete admixture " carry out, W/C=0.29, and volume is to roll over solid volume.It selects existing commercially available
Traditional comb shape poly carboxylic acid series water reducer (comparative example) is as a comparison sample, and test result is shown in Table 1.
1 pulp flowage results of property of table
From table 1 it follows that the cement dispersants solution of the graft esterification cationic side chain of the method for the present invention synthesis,
0.29 ratio of mud and 0.25% folding are consolidated under volume, and excellent dispersibility and cement adaptability can be shown.
2. concrete slump and divergence
Test determines the divergence and the slump and retention property that each embodiment is shown in concrete system, tests
It the results are shown in Table 2.
2 concrete flowability energy result of table
From Table 2, it can be seen that the cement dispersants solution of the graft esterification cationic side chain of the method for the present invention synthesis exists
Excellent divergence and the slump and holding capacity can be shown in concrete system.
3. agent on crack resistance of concrete mud performance
Test determines the divergence and the slump and retention property that each embodiment is shown in concrete system, tests
It the results are shown in Table 3.
3 concrete flowability energy result of table
From table 3 it is observed that the cement dispersants solution of the graft esterification cationic side chain of the method for the present invention synthesis exists
Preferable divergence and the slump and holding capacity can have been shown under 1.8% clay additive.
Claims (3)
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| CN112028536B (en) * | 2020-08-07 | 2022-02-08 | 北京工业大学 | Method for preparing environment-responsive polymer through composite assembly |
| BR102020022314A2 (en) * | 2020-10-30 | 2022-05-10 | Oxiteno S.A. Indústria E Comércio | Process for the preparation of functional alkoxylated polyacrylates, functional alkoxylated polyacrylates, and use thereof |
| CN113831445A (en) * | 2021-10-12 | 2021-12-24 | 眉山海螺新材料科技有限公司 | Branched anti-mud sacrificial agent and preparation method thereof |
| CN115429849B (en) * | 2022-08-23 | 2023-07-21 | 江西大自然制药有限公司 | Preparation method of pill for strengthening body resistance and prolonging life |
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