CN115746312B - Preparation method of polyethylene glycol derivative grafted polycarboxylate water reducer - Google Patents
Preparation method of polyethylene glycol derivative grafted polycarboxylate water reducer Download PDFInfo
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- CN115746312B CN115746312B CN202210114191.9A CN202210114191A CN115746312B CN 115746312 B CN115746312 B CN 115746312B CN 202210114191 A CN202210114191 A CN 202210114191A CN 115746312 B CN115746312 B CN 115746312B
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- copolymer
- polyethylene glycol
- reaction
- glycol derivative
- gas
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 64
- 239000002202 Polyethylene glycol Substances 0.000 title claims abstract description 45
- 229920001223 polyethylene glycol Polymers 0.000 title claims abstract description 45
- 150000002334 glycols Chemical class 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920005646 polycarboxylate Polymers 0.000 title claims description 13
- 229920001577 copolymer Polymers 0.000 claims abstract description 111
- 238000006243 chemical reaction Methods 0.000 claims abstract description 72
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 53
- 239000004005 microsphere Substances 0.000 claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- 239000002798 polar solvent Substances 0.000 claims abstract description 17
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 238000012673 precipitation polymerization Methods 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 229920000578 graft copolymer Polymers 0.000 claims description 44
- 239000007789 gas Substances 0.000 claims description 41
- 239000000178 monomer Substances 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 26
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 19
- 238000009835 boiling Methods 0.000 claims description 19
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 16
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 14
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical group C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims description 14
- 230000002950 deficient Effects 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 11
- 238000006386 neutralization reaction Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000012986 chain transfer agent Substances 0.000 claims description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- -1 allyl naphthalene Chemical compound 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 125000004018 acid anhydride group Chemical group 0.000 claims description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 4
- ANSIWEGOCFWRSC-UHFFFAOYSA-N 1,2-dimethyl-1h-indene Chemical compound C1=CC=C2C(C)C(C)=CC2=C1 ANSIWEGOCFWRSC-UHFFFAOYSA-N 0.000 claims description 3
- GRFNSWBVXHLTCI-UHFFFAOYSA-N 1-ethenyl-4-[(2-methylpropan-2-yl)oxy]benzene Chemical compound CC(C)(C)OC1=CC=C(C=C)C=C1 GRFNSWBVXHLTCI-UHFFFAOYSA-N 0.000 claims description 3
- OBRYRJYZWVLVLF-UHFFFAOYSA-N 1-ethenyl-4-ethoxybenzene Chemical compound CCOC1=CC=C(C=C)C=C1 OBRYRJYZWVLVLF-UHFFFAOYSA-N 0.000 claims description 3
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 claims description 3
- LCJNYCWJKAWZKZ-UHFFFAOYSA-N 1-prop-1-en-2-ylnaphthalene Chemical compound C1=CC=C2C(C(=C)C)=CC=CC2=C1 LCJNYCWJKAWZKZ-UHFFFAOYSA-N 0.000 claims description 3
- RJFCFNWLPJRCLR-UHFFFAOYSA-N 1-prop-2-enylnaphthalene Chemical compound C1=CC=C2C(CC=C)=CC=CC2=C1 RJFCFNWLPJRCLR-UHFFFAOYSA-N 0.000 claims description 3
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 claims description 3
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 claims description 3
- KXYAVSFOJVUIHT-UHFFFAOYSA-N 2-vinylnaphthalene Chemical compound C1=CC=CC2=CC(C=C)=CC=C21 KXYAVSFOJVUIHT-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- HDBWAWNLGGMZRQ-UHFFFAOYSA-N p-Vinylbiphenyl Chemical group C1=CC(C=C)=CC=C1C1=CC=CC=C1 HDBWAWNLGGMZRQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 150000001346 alkyl aryl ethers Chemical class 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 16
- 239000007790 solid phase Substances 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000003472 neutralizing effect Effects 0.000 abstract description 2
- 239000004568 cement Substances 0.000 description 34
- 239000002245 particle Substances 0.000 description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 20
- 238000001035 drying Methods 0.000 description 20
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 19
- 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 description 18
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 15
- 238000012360 testing method Methods 0.000 description 14
- 239000000843 powder Substances 0.000 description 13
- 238000010992 reflux Methods 0.000 description 13
- 238000002390 rotary evaporation Methods 0.000 description 13
- 238000010998 test method Methods 0.000 description 13
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 239000007795 chemical reaction product Substances 0.000 description 10
- 239000003517 fume Substances 0.000 description 10
- 239000012046 mixed solvent Substances 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 239000003208 petroleum Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 229940117955 isoamyl acetate Drugs 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 description 6
- 229940051841 polyoxyethylene ether Drugs 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 6
- 239000012159 carrier gas Substances 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 4
- 238000005273 aeration Methods 0.000 description 4
- 150000008064 anhydrides Chemical group 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- PVBRSNZAOAJRKO-UHFFFAOYSA-N ethyl 2-sulfanylacetate Chemical compound CCOC(=O)CS PVBRSNZAOAJRKO-UHFFFAOYSA-N 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000000703 high-speed centrifugation Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 125000000542 sulfonic acid group Chemical group 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 2
- ZHUWXKIPGGZNJW-UHFFFAOYSA-N 6-methylheptyl 3-sulfanylpropanoate Chemical compound CC(C)CCCCCOC(=O)CCS ZHUWXKIPGGZNJW-UHFFFAOYSA-N 0.000 description 2
- BGHHEZXOMKZYON-UHFFFAOYSA-N CCCCCCC.CC(C)CCOC(C)=O Chemical compound CCCCCCC.CC(C)CCOC(C)=O BGHHEZXOMKZYON-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 2
- BYEVBITUADOIGY-UHFFFAOYSA-N ethyl nonanoate Chemical compound CCCCCCCCC(=O)OCC BYEVBITUADOIGY-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000007602 hot air drying Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
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- 229910001220 stainless steel Inorganic materials 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- MTLWTRLYHAQCAM-UHFFFAOYSA-N 2-[(1-cyano-2-methylpropyl)diazenyl]-3-methylbutanenitrile Chemical compound CC(C)C(C#N)N=NC(C#N)C(C)C MTLWTRLYHAQCAM-UHFFFAOYSA-N 0.000 description 1
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- YSAXEHWHSLANOM-UHFFFAOYSA-N 2-methyl-1h-indene Chemical compound C1=CC=C2CC(C)=CC2=C1 YSAXEHWHSLANOM-UHFFFAOYSA-N 0.000 description 1
- ZJCZFAAXZODMQT-UHFFFAOYSA-N 2-methylpentadecane-2-thiol Chemical compound CCCCCCCCCCCCCC(C)(C)S ZJCZFAAXZODMQT-UHFFFAOYSA-N 0.000 description 1
- ZAYGISOXMIXWHX-UHFFFAOYSA-N 2-methylpropoxycarbonyloxy 2-methylpropyl carbonate Chemical compound CC(C)COC(=O)OOC(=O)OCC(C)C ZAYGISOXMIXWHX-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- KBEBGUQPQBELIU-CMDGGOBGSA-N Ethyl cinnamate Chemical compound CCOC(=O)\C=C\C1=CC=CC=C1 KBEBGUQPQBELIU-CMDGGOBGSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a preparation method of a polyethylene glycol derivative grafted polycarboxylic acid type water reducer, which comprises the steps of firstly preparing copolymer microspheres through self-stabilizing precipitation polymerization, then obtaining sulfonated copolymer microspheres through gas-solid phase sulfonation, then carrying out grafting reaction with the polyethylene glycol derivative in a low-boiling-point polar solvent, and finally neutralizing by alkali to obtain the polyethylene glycol derivative grafted polycarboxylic acid type water reducer. The preparation method disclosed by the invention is environment-friendly, high in production efficiency and easy for industrial production, and the obtained water reducer has good uniformity, dispersion capacity and high water reducing performance.
Description
Technical Field
The invention belongs to the field of concrete water reducers, and particularly relates to a preparation method of a polyethylene glycol derivative grafted polycarboxylate type water reducer.
Background
With the continuous advancement of industrialization, the demands of large concrete engineering projects such as hydraulic and hydroelectric dams, cross-sea bridges, cross-river bridges, subways and other infrastructures on concrete mobility are increasing, because the large facilities are all poured by pumping ready-mixed concrete, and water reducing agents are important additives for improving the pumpability of cement paste.
The polycarboxylate water reducer is a concrete water reducer with better comprehensive performance in the current market, has the advantages of low mixing amount, high water reducing rate, small slump loss, high processability and the like, and can obviously improve the performance of the concrete mixture. The main mechanisms of action of polycarboxylate water reducers include electrostatic repulsion and steric hindrance. Through the two functions, the cement particles are not mutually coagulated in the initial mixing stage, and the flowability is enhanced.
At present, two main methods for synthesizing the polycarboxylate superplasticizer are available. One is a functional monomer copolymerization method, namely, a final product is obtained by carrying out radical copolymerization on monomers with strong polar groups such as acrylic acid, methacrylic acid, maleic anhydride, sodium vinylsulfonate and the like and macromers such as Allyl Polyoxyethylene Ether (APEG), methallyl polyoxyethylene ether (TPEG), isoprenyloxy Polyoxyethylene Ether (IPEG) and the like. The other is a polymerization-before-grafting method, namely, a main chain with a certain molecular weight and containing an anhydride group or a carboxyl group is synthesized, and then an esterification reaction is utilized to graft polyethylene glycol derivative to obtain a final product. For the first method which is studied more at present, the defects are obvious, the uniform copolymerization composition is difficult to control due to the larger reactivity ratio difference of the comonomers, and meanwhile, the requirement on the process of the polymerization reaction is high, and complex operations such as stepwise dripping or separate dripping are needed. For the second method, little research is currently done. Therefore, the green and efficient synthesis of the water reducer is still an important point and a difficult point of the current research in the civil engineering community.
In order to be able to synthesize polycarboxylic acid water reducers green and efficiently, some efforts have been made in the prior art. For example, patent document 1 discloses a "method for producing a polyether-grafted polycarboxylic acid type concrete water reducing agent", which synthesizes a polyether-grafted polycarboxylic acid type water reducing agent having a polyoxyethylene ether side chain by a method of polymerization followed by functionalization. Specifically, firstly, a styrene maleic anhydride copolymer is sulfonated in 1, 2-dichloroethane by utilizing sulfur trioxide to obtain a sulfonated styrene maleic anhydride copolymer, then the sulfonated styrene maleic anhydride copolymer is mixed with polyethylene glycol monomethyl ether to obtain a polycarboxylic acid copolymer containing polyoxyethylene ether side chains, and then the polycarboxylic acid copolymer is prepared into an aqueous solution and pH is regulated by calcium hydroxide to obtain the polyether grafted polycarboxylic acid type concrete water reducer containing polyoxyethylene ether side chains.
Patent document 2 discloses a method for producing a sulfonated styrene-maleic anhydride grafted polyether type shrinkage-reducing water reducer. Similar to patent document 1, a styrene-maleic anhydride copolymer is first produced, the styrene-maleic anhydride copolymer is sulfonated with sulfur trioxide in 1, 2-dichloroethane, then the resulting sulfonated styrene-maleic anhydride copolymer is mixed with polyethylene oxide propylene oxide, the resulting graft copolymer is formulated into an aqueous solution, and the pH is adjusted with a base to obtain a sulfonated styrene-maleic anhydride grafted polyether type water reducer.
Citation literature:
patent document 1: CN 1712381A;
patent document 2: CN 111363159A;
disclosure of Invention
Problems to be solved by the invention
The methods disclosed in patent documents 1 and 2 each carry out sulfonation of a styrene maleic anhydride copolymer by a solution sulfonation reaction in dichloroethane, which is inefficient and requires the use of a large amount of solvent, and which is relatively serious in environmental pollution.
Therefore, development of a green and efficient synthetic method of a polycarboxylate water reducing agent is demanded.
Solution for solving the problem
In view of the problems in the prior art, the present inventors have found that copolymer microspheres prepared by self-stabilizing precipitation polymerization are prepared using sulfur trioxide (SO 3 ) The sulfonated copolymer with high main chain charge density can be obtained by directly sulfonating gas, and then the polyethylene glycol derivative is grafted by using a low boiling point solvent, so that the obtained grafted copolymer has good uniformity, dispersibility and high water reducing performance as a water reducer, and the method is environment-friendly, high in production efficiency and easy for industrial production, thereby completing the invention.
Specifically, the present invention solves the problems of the present invention by the following means.
[1] The preparation method of the polyethylene glycol derivative grafted polycarboxylate type water reducer is characterized by comprising the following steps of:
(a) Dissolving an electron-rich monomer, an electron-deficient monomer, an initiator and an optional chain transfer agent in an organic solvent, and performing self-stabilizing precipitation polymerization to obtain copolymer microspheres; wherein the electron-deficient monomer is itaconic anhydride or/and maleic anhydride;
(b) Contacting the copolymer microsphere in the step (a) with a gas containing sulfur trioxide to carry out sulfonation reaction to obtain a sulfonated copolymer microsphere, wherein the sulfonation degree of the sulfonated copolymer microsphere is more than 10%;
(c) Dissolving the sulfonated polymer microspheres and polyethylene glycol derivatives in the step (b) in a low-boiling-point polar solvent for grafting reaction to obtain a graft copolymer, wherein the boiling point of the low-boiling-point polar solvent is below 150 ℃, and the polyethylene glycol derivatives are one or more selected from polyethylene glycol monoalkyl ether and alkoxyl polyethylene glycol amino groups;
(d) The resulting graft copolymer is contacted with a base to effect a neutralization reaction.
[2] The production method according to [1], characterized in that: the electron-rich monomer is one or more selected from styrene and derivatives thereof, vinyl naphthalene and derivatives thereof, allyl naphthalene and derivatives thereof, indene and derivatives thereof; preferably one or more selected from styrene, p-methylstyrene, p-tert-butylstyrene, alpha-methylstyrene, 4-methoxystyrene, 4-ethoxystyrene, 4-tert-butoxystyrene, indene, dimethylindene, 4-vinylbiphenyl, 2-vinylnaphthalene, 1- (1-methylvinyl) naphthalene, 2- (2-methylallyloxy) naphthalene, 1-allylnaphthalene, C8 mixtures, C9 mixtures.
[3] The production method according to [1] or [2], characterized in that the proportion of structural units derived from maleic anhydride or itaconic anhydride in the copolymer obtained in the step (a) is 10mol% or more relative to the total structural units of the copolymer; the number average molecular weight of the copolymer is 1000-10000.
[4] The process according to [1] or [2], wherein the organic solvent used in the step (a) is one or more selected from esters, ethers, aromatic hydrocarbons and alkane solvents.
[5] The production method according to [1] or [2], characterized in that in the step (b), the volume fraction of sulfur trioxide in the sulfur trioxide-containing gas is 10% or less; the sulfonation time in the step (b) is 0.5-10 h, and the sulfonation reaction temperature is 50-150 ℃.
[6] The production method according to [1] or [2], characterized in that in the step (c), the polyethylene glycol derivative is one, two or three or more selected from the polyethylene glycol derivatives represented by the following general formulae:
wherein R is 1 Is C 1 -C 12 Branched, straight-chain or cyclic alkyl of (2), n is an integer from 4 to 100, R 2 Is amino or hydroxy.
[7] The production method according to [1] or [2], characterized in that the ratio of the number of moles of the polyethylene glycol derivative in the step (c) to the number of moles of the acid anhydride group in the sulfonated copolymer is 1: (1-10).
[8] The production process according to [1] or [2], wherein the alkali used in the step (d) is one or more selected from the group consisting of alkali liquid and alkaline gas; the alkali liquor is preferably one or more selected from sodium hydroxide solution, potassium hydroxide solution and ammonia water; the alkaline gas is one or more selected from pure ammonia gas, mixed gas of ammonia and nitrogen gas and mixed gas of ammonia and air.
[9] A polyethylene glycol derivative grafted polycarboxylate water reducer prepared by the method of any one of [1] to [8 ].
[10] A water reducing agent composition comprising the polyethylene glycol derivative-grafted polycarboxylic acid type water reducing agent described in [9 ].
ADVANTAGEOUS EFFECTS OF INVENTION
The preparation method adopts gas-solid phase sulfonation, can avoid producing a large amount of acid waste liquid in the sulfonation step, and can recycle gaseous sulfur trioxide, thereby reducing the production cost and improving the environmental friendliness.
The preparation method of the invention utilizes the morphological characteristics of the copolymer microsphere obtained by self-stabilization precipitation polymerization to improve the sulfonation degree and uniformity during gas-solid phase sulfonation, and the water reducer obtained by the method has good adsorption and dispersion capacity, and has the advantages of small slump loss of cement paste and high fluidity under the condition of lower mixing amount.
The preparation method adopts the low-boiling polar solvent to carry out the grafting reaction, and the solvent can be easily removed after the reaction, thereby reducing the production cost and the energy consumption.
The preparation method disclosed by the invention is environment-friendly, high in production efficiency and easy for industrial production.
Detailed Description
The following describes the present invention in detail. The following description of the technical features is based on the representative embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples.
Terms and definitions
In the present specification, "self-stabilizing precipitation polymerization" means a heterogeneous polymerization method in which a polymerization system in the form of a stable colloid composed of polymer particles having a uniform particle diameter and a dispersion medium is formed by static polymerization and a self-nucleation-surface deposition growth process in the polymerization process.
In the present specification, the degree of sulfonation refers to the mole percentage of sulfonic acid groups in the sulfonated copolymer relative to structural units derived from the electron-rich monomer, and can be determined by acid-base titration or can be determined by elemental analysis testing.
In the present specification, "particle size" means the median particle diameter D of the particles described 50 Which can be measured by a laser particle sizer.
In the present specification, the "electron-rich monomer" means a monomer having an electron-donating group on a carbon-carbon double bond participating in polymerization.
In the present specification, the "electron-deficient monomer" refers to a monomer having an electron withdrawing group on a carbon-carbon double bond participating in polymerization.
In this specification, the term "solubility parameter" refers to the square root of cohesive energy density, which can be used to determine the solvent's ability to dissolve a polymer.
In the present specification, the term "particle size distribution index" as used with respect to the copolymer microspheres means a particle size polydispersity index, which is defined as
U＝D w /D n
Wherein Dn is the average particle size of the microsphere, dw is the defined mathematical average particle size, di is the diameter of the ith particle, k is the sample volume, and U is the particle size distribution index.
In the present specification, the "micropore volume" described for the copolymer microsphere means the micropore of a sample per unit mass measured by BET method<Volume (unit is m) of 2nm 3 /g)。
In the present specification, the numerical range indicated by the term "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In the present specification, a numerical range indicated by "above" or "below" is a numerical range including the present number.
In the present specification, the meaning of "can" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
In this specification, the use of "optionally" or "optional" means that certain substances, components, steps of performing, conditions of applying, etc. may or may not be used.
In the present specification, unit names used are international standard unit names, and "%" used denote volume percent unless otherwise specified.
Reference in the specification to "a preferred embodiment," "an embodiment," and the like, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the elements may be combined in any suitable manner in the various embodiments.
The invention aims at providing a preparation method of a polyethylene glycol derivative grafted polycarboxylic acid type water reducer, which is characterized by comprising the following steps of:
(a) Dissolving an electron-rich monomer, an electron-deficient monomer, an initiator and an optional chain transfer agent in an organic solvent, and performing self-stabilizing precipitation polymerization to obtain copolymer microspheres; wherein the electron-deficient monomer is itaconic anhydride and/or maleic anhydride;
(b) Contacting the copolymer microsphere in the step (a) with a gas containing sulfur trioxide to carry out sulfonation reaction to obtain a sulfonated copolymer microsphere, wherein the sulfonation degree of the sulfonated copolymer microsphere is more than 10%;
(c) Dissolving the sulfonated polymer microspheres and the polyethylene glycol derivative in the step (b) in a low-boiling-point polar solvent for grafting reaction to obtain a graft copolymer, wherein the boiling point of the low-boiling-point polar solvent is below 150 ℃;
(d) The resulting graft copolymer is contacted with a base to effect a neutralization reaction.
The steps of the preparation method of the present invention are described in detail below.
Step (a)
In the step (a), an electron-rich monomer, an electron-deficient monomer, an initiator and optionally a chain transfer agent are dissolved in an organic solvent, and self-stabilization precipitation polymerization is performed to obtain copolymer microspheres. Wherein itaconic anhydride and/or maleic anhydride are used as electron-deficient monomers. The microsphere obtained in the step (a) has a loose and porous structure and proper specific surface area and particle size, is favorable for obtaining a polymer with uniform sulfonation, further improves the quality of a final water reducing agent product, can enable cement paste to have high flowability under low mixing amount, and has small slump loss.
In one embodiment, the monomers and organic solvent are selected such that the solubility parameter of the copolymer comprising the copolymer microsphere is 1 to 7MPa greater than the solubility parameter of the organic solvent 1/2 Preferably greater than 2 to 5MPa 1/2 If too much is too little solution will form and if too much macroscopic precipitation will occur. And by making the difference in the solubility parameter within the above range, the resulting copolymer microsphere can have a suitable specific surface area and micropore volume, thereby enabling subsequent gas-solid phase sulfonationIs sulfonated uniformly in the process.
In the present specification, the solubility parameter may be obtained by searching in technical manuals or publications in the art, for example, polymer physics (Hua Youqing, golden sunlight, chemical industry Press, 2013, page 83), or may be calculated by methods known in the art.
In one embodiment, the amount of dispersant or surfactant used in step (a) is 0.5wt% or less, preferably 0.1wt% or less, particularly preferably no dispersant or surfactant is used, relative to the amount of monomer (total of electron rich and electron poor monomers).
In one embodiment, the polymerization of step (a) is carried out without the application of agitation.
The order of adding the reaction raw materials in the step (a) is not particularly limited, and the electron-rich monomer, the electron-deficient monomer, the initiator and the optional chain transfer agent may be added to the organic solvent simultaneously or stepwise, or may be added to the organic solvent after premixing, or may be dissolved in a concentrated solution and then diluted to a desired concentration.
In one embodiment, the polymerization time in step (a) is from 1 to 10 hours, preferably from 2 to 8 hours, more preferably from 3 to 7 hours. In one embodiment, the polymerization temperature in step (a) is from 50 to 120 ℃, more preferably from 60 to 100 ℃.
The polymerization reaction of step (a) may be carried out in any suitable vessel known in the art, such as a reaction vessel, a reaction tube, etc.; the material of the reactor can be stainless steel, enamel or glass, etc.
Step (a) also optionally includes one or more of separating, washing and drying the resulting copolymer microspheres. Separation may be performed by filtration, centrifugation, etc. in a manner known in the art; washing may be carried out by dipping, rinsing, etc. in a manner known in the art, the solvent used for washing being a nonpolar solvent such as one or more of the paraffinic solvents listed above; drying may be performed by oven drying, hot air drying, or the like, as known in the art.
Step (a)(a) The resulting copolymer is microspheroidal and in one embodiment the particle size of the copolymer microsphere obtained in step (a) is in the range 200nm to 10 μm, preferably 200nm to 2 μm; specific surface area of 5m 2 Preferably 10m or more per gram 2 Above/g, the particle size distribution index is 1-5, and the micropore volume is 0.01cm 3 And/g.
In a preferred embodiment, the water content of the copolymer microspheres obtained in step (a) is in the range of 0 to 100ppm, preferably 0 to 30ppm.
In specific embodiments, the electron-rich monomer is one or more selected from the group consisting of styrene and its derivatives, vinyl naphthalene and its derivatives, allyl naphthalene and its derivatives, indene and its derivatives; preferably one or more selected from styrene, p-methylstyrene, p-tert-butylstyrene, alpha-methylstyrene, 4-methoxystyrene, 4-ethoxystyrene, 4-tert-butoxystyrene, indene, dimethylindene, 4-vinylbiphenyl, 2-vinylnaphthalene, 1- (1-methylvinyl) naphthalene, 2- (2-methylallyloxy) naphthalene, 1-allylnaphthalene, C8 mixtures, C9 mixtures. Wherein the C8 mixture and the C9 mixture are complex mixtures produced in petrochemical industry, the components of the complex mixtures are mainly hydrocarbons with corresponding carbon numbers, for example, the main components of the C8 mixture are hydrocarbons with 8 carbon atoms, including styrene, octene, octane, xylene, indene, ethylbenzene and the like.
The electron-deficient monomer is itaconic anhydride and/or maleic anhydride. By using electron-deficient monomers with anhydride groups, the introduction of anhydride groups into the copolymer provides reactive sites for subsequent grafting reactions.
In one embodiment, the proportion of structural units derived from maleic anhydride or itaconic anhydride in the copolymer obtained in step (a) is 10mol% or more, preferably 20mol% or more, more preferably 30 mol% or more, even more preferably 40mol% or more, relative to the total structural units of the copolymer. By making the proportion of the structural unit derived from maleic anhydride or itaconic anhydride in the copolymer within the above range, a sufficient reaction site can be provided for the subsequent grafting reaction, so that the graft copolymer has a suitable number of branched chains, and the adsorption capacity and the dispersing capacity of the water reducer on the surface of cement particles are improved.
The proportion of the structural unit derived from maleic anhydride or itaconic anhydride in the copolymer obtained in step (a) is 90mol% or less, preferably 80mol% or less, more preferably 70mol% or less, even more preferably 60 mol% or less, relative to the total structural units of the copolymer, from the viewpoint of facilitating the subsequent sulfonation reaction to proceed smoothly and ensuring that the sulfonated copolymer has an appropriate sulfonic acid group content.
In one embodiment, the number average molecular weight of the copolymer obtained in step (a) is from 1000 to 10000, preferably from 1500 to 7000. Wherein the number average molecular weight is determined by Gel Permeation Chromatography (GPC). If the number average molecular weight of the copolymer obtained in the step (a) is too small, the hydrated layer formed on the surface of the cement particles by the final water reducing agent is too thin to achieve a good stable dispersion effect. If the molecular weight is too large, the fluidity of the cement slurry is poor after the water reducer is added due to the influence of bridging flocculation.
In one embodiment, the initiator used in step (a) is a free radical polymerization initiator, preferably a thermal free radical initiator, more preferably one or more selected from azo-type initiators and peroxide initiators. Specific examples of initiators include, but are not limited to, azobisisobutyronitrile (AIBN), azobisisovaleronitrile, azobisisoheptonitrile (ABVN), dimethyl azobisisobutyrate, dibenzoyl peroxide (BPO), dicumyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, diisobutyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, lauroyl peroxide, and terbutyl peroxypivalate. The amount of the initiator to be used is 0.1 to 5% by mass, preferably 0.5 to 4% by mass, more preferably 1 to 3% by mass, based on the total mass of the electron-rich monomer and the electron-deficient monomer.
In one embodiment, a chain transfer agent is used in step (a) to adjust and control the molecular weight of the resulting copolymer. The present invention is not particularly limited in the specific kind of the chain transfer agent, and for example, sulfur-containing compounds such as one or more selected from dodecyl mercaptan, hexadecyl mercaptan, octadecyl mercaptan, mercaptoethanol, mercaptoacetic acid, ethyl mercaptoacetate, 2-mercaptopropionic acid, 3-mercaptopropionic acid, isooctyl 3-mercaptopropionate (IOMP) may be used. The molecular weight of the copolymer can be controlled by adjusting the amount of chain transfer agent. In one embodiment, the chain transfer agent may be used in an amount of 0.1 to 20%, preferably 0.2 to 15%, more preferably 0.5 to 10% by weight based on the total mass of the monomers.
In one embodiment, in step (a), the organic solvent may be selected from esters including ethyl acetate, methyl acetate, n-butyl acetate, amyl acetate, isoamyl acetate, ethyl propionate, ethyl butyrate, ethyl lactate, ethyl formate, ethyl pelargonate, ethyl cinnamate, butyl cinnamate, ethyl caproate, ethyl phosphate, and diethyl phthalate; ethers include dimethyl ether, diethyl ether, methyl ethyl ether, anisole, diphenyl ether, phenetole, and phenylpropyl ether; aromatic hydrocarbons include benzene, toluene, ortho-xylene, meta-xylene, para-xylene, ethylbenzene, cumene, and diethylbenzene; alkanes, including petroleum ether, n-hexane, cyclohexane, n-heptane, octane, isooctane, and isopentane. The solvent in the above step (a) includes not only a single solvent but also a mixture of two or more solvents.
In one embodiment, in step (a), the amount of monomer (total of electron rich monomer and electron deficient monomer) is from 5 to 50wt%, preferably from 20 to 30wt%, based on the total mass of the polymerization system.
Step (b)
Step (b) is a step of performing a gas-solid phase sulfonation reaction by reacting the copolymer microspheres obtained in step (a) with a catalyst containing sulfur trioxide (SO 3 ) Is contacted with the gas to carry out sulfonation reaction.
The present invention is not particularly limited with respect to the specific contact method, and any known method of bringing a gas and a solid into contact may be employed. In one embodiment, the SO-containing microspheres may be introduced into a vessel containing the copolymer microspheres from step (a) 3 Wherein the gas contains SO 3 The gas of (2) can be introduced once or multiple times, or can be continuously introduced. In another embodiment, the copolymer microspheres obtained in step (a) may be incorporatedIs internally filled with SO 3 The copolymer microspheres may also be loaded in one or more portions.
As the sulfonation reactor used in the step (b), the present invention is not particularly limited, and any known vessel suitable for gas-solid phase reaction may be employed, preferably a reaction vessel equipped with a seal, including but not limited to a tank type, a tube type, a fluidized bed type reactor, etc. The material of the reaction vessel is preferably a corrosion resistant material such as stainless steel, polytetrafluoroethylene, glass, enamel, etc.
The copolymer microspheres obtained in step (a) are kept in a microsphere state throughout the course of performing step (b), for example, after the drying treatment in step (a).
In the preparation method of the present invention, the reaction time, the reaction temperature and the SO in the gas in the step (b) can be adjusted 3 The degree of sulfonation of the product is controlled by the content of the product, etc., so that the product is suitable for different purposes.
In one embodiment, the reaction time in step (b), i.e., the copolymer microsphere and SO-containing 3 The time of the gas contact of (2) may vary depending on the degree of sulfonation, and may be, for example, 0.1 hour or more, 0.5 hour or more, 1 hour or more, 2 hours or more, 3 hours or more, 4 hours or more, 20 hours or less, 15 hours or less, 12 hours or less, 10 hours or less. The reaction time in step (b) is generally 0.5 hours or more, preferably 1 hour or more, more preferably 2 hours or more, in view of obtaining copolymer microspheres with uniform sulfonation of the surface and the interior, and is generally 12 hours or less, preferably 10 hours or less, in view of saving energy and avoiding excessive sulfonation.
In one embodiment, the reaction temperature of step (b), i.e. the temperature within the sulfonation reactor of step (b), is 50 to 150 ℃, preferably 55 to 130 ℃, more preferably 60 to 120 ℃.
Introducing SO-containing microspheres into a vessel containing the copolymer microspheres obtained in step (a) 3 In step (b), the gas comprises SO relative to 100g of copolymer microspheres 3 Is introduced into the furnaceThe rate is 0.1 to 5g/min, preferably 0.2 to 1.5g/min. The introduced SO-containing material 3 The temperature of the gas is 50-100 ℃, preferably 60-90 ℃, avoiding SO 3 Too high a gas feed rate or too high a reaction temperature results in more byproduct formation.
In one embodiment, the SO-containing agent used in step (b) 3 Is comprised of SO 3 A gas and a carrier gas, wherein the carrier gas may be selected from air, N 2 And Ar gas, the water content in the carrier gas is 50ppm or less, preferably 30ppm or less. In the presence of SO 3 SO in the gas of (2) 3 The volume fraction of the gas is below 10%, preferably below 5%. In the presence of SO 3 SO in the gas of (2) 3 The volume fraction of the gas is usually 1% or more.
SO-containing used in step (b) 3 Can be obtained by mixing SO with 3 Mixing the gas with carrier gas. The invention relates to SO 3 The source of the gas and carrier gas is not particularly limited, e.g. SO 3 The gas can be prepared by dehydration of concentrated sulfuric acid, and can be prepared by SO in sulfuric acid plant 3 Is prepared from SO 2 The oxidation can be prepared by heating and decomposing fuming sulfuric acid.
The preparation process of the present invention optionally further comprises a step of post-treating the product after the sulfonation reaction of step (b) is completed. Wherein the post-treatment step comprises one or more of aging, washing and drying.
The degree of sulfonation of the copolymer obtained in step (b) is 10% or more, preferably 30% or more, more preferably 50% or more, even more preferably 70% or more. By setting the sulfonation degree in the above range, the charge density on the water reducing agent can be increased, the adsorption effect can be improved, and further, better dispersibility can be obtained. The upper limit of the sulfonation degree of the copolymer obtained in the step (b) is usually 150% or less, preferably 120% or less, more preferably 110% or less.
In one embodiment, the degree of sulfonation of the copolymer obtained in step (b) is from 10% to 150%, preferably from 50 to 120%, more preferably from 70 to 110%.
The degree of sulfonation described above can be measured and calculated by the methods described in the examples section below.
Step (c)
In the step (c), the obtained sulfonated copolymer and polyethylene glycol derivative are dissolved or dispersed in a low boiling point polar solvent, so that an acid anhydride group in the sulfonated copolymer and a terminal group in the polyethylene glycol derivative react, and a polyethylene glycol segment is grafted onto the sulfonated copolymer as a side chain, thereby obtaining a graft copolymer.
The low-boiling polar solvent used in the present invention has a boiling point of 150℃or less, preferably 120℃or less. By carrying out the esterification grafting reaction in the polar solvent with low boiling point, the viscosity of the reaction system can be reduced, thereby facilitating the reaction between functional groups and obtaining higher grafting rate. And since the boiling point of the solvent is low, it is easy to remove after the reaction, so that the production cost and the energy consumption can be reduced. The low boiling point polar solvent used has a boiling point of 50℃or higher, preferably 60℃or higher, more preferably 70℃or higher, and most preferably 80℃or higher, from the viewpoint of avoiding environmental pollution by solvent volatilization and allowing a sufficiently high esterification reaction temperature.
In one embodiment, the low boiling polar solvent has a boiling point of 50 to 150 ℃, preferably 60 to 135 ℃, more preferably 70 to 120 ℃, and most preferably 80 to 110 ℃.
The present invention is not particularly limited as to the specific kind of the low boiling point polar solvent. For example, ethers, ketones, nitrile solvents and the like having boiling points in the above range can be used. In one embodiment, the low boiling point polar solvent is one or more selected from dioxane, acetone, butanone, methyl isobutyl ketone, acetonitrile and butyronitrile, preferably one or more selected from dioxane, acetone, butanone and acetonitrile, more preferably dioxane and/or acetonitrile.
In one embodiment, the polyethylene glycol derivative is one, two or more selected from the polyethylene glycol derivatives represented by the following general formula:
wherein R is 1 Is C 1 -C 12 Straight-chain, branched or cyclic alkyl of (C) is preferred 1 -C 8 Straight, branched or cyclic alkyl of (2), more preferably C 1 -C 5 Straight or branched alkyl of (a). In particular embodiments, R 1 Is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, cyclopentyl, n-hexyl or cyclohexyl.
n represents the number of repetitions of the oxyethylene structural unit, n is an integer of 4 to 100, preferably an integer of 50 to 100.
R 2 Amino or hydroxy, preferably hydroxy.
In one embodiment, the ratio of the moles of polyethylene glycol derivative used in step (c) to the moles of anhydride groups in the sulfonated copolymer is 1: (1-10), preferably (4-7).
In one embodiment, in step (c), the content of the sulfonated copolymer and the polyethylene glycol derivative is 10 to 50wt%, preferably 20 to 40wt%, based on the total weight of the sulfonated copolymer, the polyethylene glycol derivative and the low boiling point polar solvent. By making the content of the sulfonated copolymer and the polyethylene glycol derivative within the above-described range, the progress of the grafting reaction is facilitated while avoiding the use of a large amount of solvent.
In one embodiment, the grafting reaction is carried out at a temperature of from 80 to 130℃and preferably from 100 to 120 ℃. The grafting reaction is preferably carried out with stirring. After the reaction, the resulting graft copolymer is optionally isolated and purified, for example, by separating the graft copolymer from the low-boiling polar solvent by conventional separation means such as distillation solvent (e.g., spin drying), petroleum ether precipitation, etc., and optionally drying it. Drying may be performed by drying or hot air drying or the like in a manner known in the art. Depending on the particular molecular weight, the resulting graft copolymer may be either liquid or solid.
Step (d)
Step (d) is a step of neutralizing the graft copolymer obtained in step (c) by contacting it with a base. As the alkali, one or more of alkali liquid or alkaline gas may be used. In the step (d), the sulfonic acid group and the carboxylic acid group in the polymer are required to be fully neutralized, so that the water reducer has higher adsorption and dispersion capacity.
In one embodiment, the amount of base is selected such that in a particular embodiment, the degree of neutralization is 90 mole% or greater, preferably 95 mole% or greater, more preferably 99 mole% or greater, and most preferably 100 mole%. Wherein "degree of neutralization" refers to the molar ratio of neutralized carboxyl groups relative to the total of neutralized carboxyl groups and non-neutralized carboxyl groups.
In one embodiment, the graft copolymer obtained in step (c) is neutralized by immersing in an alkaline solution, preferably one or more selected from the group consisting of sodium hydroxide solution, potassium hydroxide solution and aqueous ammonia. Wherein the concentration of the sodium hydroxide solution or potassium hydroxide solution may be 0.1 to 10mol/L, preferably 1 to 10mol/L, and the concentration of the aqueous ammonia may be 0.5 to 5mol/L, preferably 3 to 5mol/L. Preferably, the ratio of the amount of the graft copolymer to the amount of the alkali solution is adjusted, or the concentration of the alkali solution is adjusted so that the pH of the solution after the neutralization reaction is 8 to 9. By bringing the pH within this range, the sulfonic acid groups in the graft copolymer are completely neutralized, and the two carboxyl groups resulting from the acid anhydride groups are completely neutralized one by one and partially or completely neutralized the other. In the case where the carboxyl group is partially neutralized, after the water reducing agent is added to the concrete, the water reducing agent is converted into a completely neutralized state due to the higher pH of the concrete. The inventors found that the water reducer obtained by adjusting the pH of the solution after the neutralization reaction to 8 to 9 can increase the fluidity of the cement paste and improve the fluidity.
In the embodiment using lye, water is optionally added after neutralization so that the resulting water-reducing agent solution has a solids content of 20 to 50 wt.%, more preferably 30 to 40 wt.%.
In embodiments where the neutralization reaction is carried out using lye, one or more post-treatment operations of separating, washing or drying the resulting water reducer are optionally also included. Wherein the separation may be performed by filtration, centrifugation, or the like. The temperature of the drying may be 50-100 ℃.
In one embodiment, the graft copolymer obtained in step (c) is contacted with an alkaline gas, preferably one or more selected from pure ammonia, an ammonia-nitrogen mixture and an ammonia-air mixture, for neutralization.
In one embodiment, the temperature of step (d) is below 50 ℃, preferably below 40 ℃, more preferably at room temperature.
In one embodiment, step (d) is performed under conditions where agitation is applied.
According to different neutralization modes, the polyethylene glycol derivative grafted polycarboxylic acid type water reducer obtained in the step (d) can be in a powder state or a liquid state. In the embodiment in powder form, the particle size of the dried powder is 10 μm or less.
The invention also correspondingly relates to the polyethylene glycol derivative grafted polycarboxylic acid type water reducer prepared by the preparation method and application thereof in concrete water reduction or improvement of concrete construction performance.
Another object of the present invention is to provide a water reducing agent composition comprising the polyethylene glycol derivative grafted polycarboxylate water reducing agent according to the present invention.
In addition to the polyethylene glycol derivative grafted polycarboxylic acid type water reducing agent of the present invention, the water reducing agent composition of the present invention may optionally further comprise one or more selected from sodium lignin sulfate, urea, sodium gluconate, and carboxymethyl cellulose without affecting the effect of the present invention.
In one embodiment, the mass fraction of the polyethylene glycol derivative grafted polycarboxylic acid type water reducer is 1-100%.
Examples
The invention is further illustrated by the following examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications of the invention will become apparent to those skilled in the art upon reading the description herein, and such equivalents are intended to fall within the scope of the invention as defined by the appended claims.
The number average molecular weight described in the examples below was determined by Gel Permeation Chromatography (GPC), measured by gel liquid chromatography (Waters 1515), calibrated for monodisperse PS, with a crosslinked PS column (HT 6E+HT5+HT 3. Mu. -styragel) and THF as the eluent.
The degree of sulfonation described in the examples below was calculated by the following formula:
wherein W is S1 And W is C1 Respectively represent the S, C element content, M of the experimental sample obtained by elemental analysis and test S And M C Representing the relative atomic masses, W, of the two elements S, C, respectively S0 And W is C0 Each represents the S, C element content of the blank obtained by elemental analysis testing, and N represents the number of C atoms in one polymer repeat unit.
Elemental analysis testing was performed by elemental analyzer (Vairo EL CUBE, elementar, germany) and gave the C, S element content (mass content) of the microsphere as a whole; XPS analysis tests were performed by Thermo ESCALAB 250XI spectrometer (Scientific, america) and gave the C, S element content (atomic content) of the microsphere surface.
SO-containing used in the following examples 3 SO in the gas of (a) 3 Is 5% by volume, the balance being nitrogen.
The concentration of the aqueous sodium hydroxide solution used in the following examples was 1mol/L.
Example 1
(a) 10g of styrene, 10g of maleic anhydride, 0.2g of Azobisisobutyronitrile (AIBN) and 2g of ethyl thioglycolate were dissolved in a mixed solvent of 70g of isoamyl acetate-N-heptane (volume ratio 4:7), and nitrogen (N) was introduced 2 ) For 20min to remove oxygen in the system, and reacting at 80 ℃ for 6h. Then, the resulting copolymer microspheres were separated by high-speed centrifugation and washed with petroleum ether 2 3 times, and drying in a vacuum oven at 45 ℃ to obtain white powder. The number average molecular weight of the copolymer was about 2000, designated copolymer A.
(b) 10g of copolymer A was charged into a sulfonation reactor (250 mL two-necked flask), stirring was started and the sulfonation reactor was heated to 75℃and purged with nitrogen for 30 minutes to remove moisture in the reaction system. Controlling the feed SO-containing 3 The temperature of the gas was 75℃and the flow rate was 0.4L/min. The reaction was heated for 7.5h while maintaining the aerated state. After the reaction was completed, the reaction product was placed in a fume hood and aged at room temperature for 2 hours. The obtained sulfonated copolymer is washed 3-4 times by using a mixed solvent of isoamyl acetate and n-heptane (the volume ratio is 3:7), and then is placed in an oven at 80 ℃ for drying for 24 hours. The sulfonation degree of the obtained sulfonated copolymer was 96%, which was designated as sulfonated copolymer A.
(c) 1g of sulfonated copolymer A and 7.3g of MPEG2000 are dissolved in 15mL of dioxane at 90 ℃, heated to 120 ℃ for reflux reaction for 12 hours, and dried by rotary evaporation after the reaction is completed, thus obtaining the graft copolymer.
(d) And adding sodium hydroxide aqueous solution into the obtained graft copolymer until the pH value is 8-9 measured by using a precise pH test paper, and continuously adding water to prepare an aqueous solution with the concentration of 30wt% of the graft copolymer. According to the test method in national standard GBT8077-2012, the measured fluidity of the 2h cement paste is 312mm, the water cement ratio is 0.29, and the addition amount of the water reducer is 0.3wt%.
Example 2
The sulfonated copolymer a was prepared in the same manner as in (a) and (b) in example 1.
(c) 1g of sulfonated polymer A and 3.7g of MPEG2000 are dissolved in 15mL of dioxane at 90 ℃, heated to 120 ℃ for reflux reaction for 12 hours, and dried by rotary evaporation after the reaction is completed, thus obtaining the graft copolymer.
(d) Adding sodium hydroxide aqueous solution into the obtained graft copolymer until the pH value is 8-9 measured by a precise pH test paper, and continuously adding water to prepare 30% aqueous solution. According to the test method in national standard GBT8077-2012, the measured fluidity of the 2h cement paste is 286mm, the water cement ratio is 0.29, and the addition amount of the water reducer is 0.3wt%.
Example 3
The sulfonated copolymer a was prepared in the same manner as in (a) and (b) in example 1.
(c) 0.5g of sulfonated copolymer A and 7.3g of MPEG4000 are dissolved in 20mL of dioxane at 90 ℃, heated to 120 ℃ for reflux reaction for 18h, and dried by rotary evaporation after the reaction is completed, thus obtaining the graft copolymer.
(d) Adding sodium hydroxide aqueous solution into the obtained graft copolymer until the pH is regulated to 8-9 by using a precise pH test paper, and continuously adding water to prepare 40% aqueous solution. According to the test method in national standard GBT8077-2012, the measured fluidity of the 2h cement paste is 322mm, the water cement ratio is 0.29, and the addition amount of the water reducer is 0.3wt%.
Example 4
The sulfonated copolymer a was prepared in the same manner as in (a) and (b) in example 1.
(c) 0.5g of sulfonated copolymer A and 3.65g of MPEG4000 are dissolved in 20mL of dioxane at 90 ℃, heated to 120 ℃ for reflux reaction for 18h, and dried by rotary evaporation after the reaction is completed, thus obtaining the graft copolymer.
(d) Adding sodium hydroxide aqueous solution into the obtained graft copolymer until the pH value is 8-9 measured by a precise pH test paper, and continuously adding water to prepare 40% aqueous solution. According to the test method in national standard GBT8077-2012, the measured fluidity of the 2h cement paste is 301mm, the water cement ratio is 0.29, and the addition amount of the water reducer is 0.3wt%.
Example 5
The sulfonated copolymer a was prepared in the same manner as in (a) and (b) in example 1.
(c) 1g of sulfonated copolymer A and 3.65g of MPEG1000 are taken and dissolved in 20mL of dioxane at 90 ℃, heated to 120 ℃ for reflux reaction for 18h, and the reaction is completed and then rotary evaporation and drying are carried out to obtain the graft copolymer.
(d) Adding sodium hydroxide aqueous solution into the obtained graft copolymer until the pH value is 8-9 measured by a precise pH test paper, and continuously adding water to prepare 20% aqueous solution. According to the test method in national standard GBT8077-2012, the measured fluidity of the 2h cement paste is 256mm, the water cement ratio is 0.29, and the addition amount of the water reducer is 0.3wt%.
Example 6
The sulfonated copolymer a was prepared in the same manner as in (a) and (b) in example 1.
(c) 1g of sulfonated copolymer A and 1.9g of MPEG1000 are dissolved in 10mL of dioxane at 90 ℃, heated to 120 ℃ for reflux reaction for 18h, and dried by rotary evaporation after the reaction is completed, thus obtaining the graft copolymer.
(b) Adding sodium hydroxide aqueous solution into the obtained graft copolymer until the pH value is 8-9 measured by a precise pH test paper, and continuously adding water to prepare 40% aqueous solution. According to the test method in national standard GBT8077-2012, the measured fluidity of the 2h cement paste is 198mm, the water cement ratio is 0.29, and the addition amount of the water reducer is 0.3wt%.
Example 7
The sulfonated copolymer a was prepared in the same manner as in (a) and (b) in example 1.
(c) 1g of sulfonated copolymer A and 2.1g of MPEG550 are dissolved in 10mL dioxane at 90 ℃, heated to 115 ℃ for reflux reaction for 12 hours, and dried by rotary evaporation after the reaction is completed, thus obtaining the graft copolymer.
(d) Adding sodium hydroxide aqueous solution into the obtained graft copolymer until the pH value is 8-9 measured by a precise pH test paper, and continuously adding water to prepare 30% aqueous solution. According to the test method in national standard GBT8077-2012, the measured fluidity of the 2h cement paste is 212mm, the water cement ratio is 0.29, and the addition amount of the water reducer is 0.3wt%.
Example 8
The sulfonated copolymer a was prepared in the same manner as in (a) and (b) in example 1.
(c) 1g of sulfonated copolymer A and 1.05g of MPEG550 are dissolved in 10mL of dioxane at 90 ℃, heated to 110 ℃ for reflux reaction for 12h, and dried by rotary evaporation after the reaction is completed, thus obtaining the graft copolymer.
(d) Adding sodium hydroxide aqueous solution into the obtained graft copolymer until the pH value is 8-9 measured by a precise pH test paper, and continuously adding water to prepare 50% aqueous solution. According to the test method in national standard GBT8077-2012, the measured fluidity of the 2h cement paste is 179mm, the water cement ratio is 0.29, and the addition amount of the water reducer is 0.3wt%.
Example 9
(a) 10g of p-ethylstyrene, 10g of itaconic anhydride, 0.2g of AIBN and 0.5g of ethyl thioglycolate are taken and dissolved in 75g of mixed solvent of isoamyl acetate and n-heptane (volume ratio is 2:3), nitrogen is introduced for 40min to remove oxygen in the system, and the reaction is carried out in an oil bath at 80 ℃ for 6h. Then, the microspheres were separated by high-speed centrifugation, washed 2-3 times with n-hexane, and dried in a vacuum oven at 45℃to obtain a white powder, the copolymer having a molecular weight of about 2500, designated copolymer B.
(b) 10g of copolymer B was charged into a sulfonation reactor (250 mL two-necked flask), stirring was started and the sulfonation reactor was heated to 100℃and N was introduced 2 For 30min to remove the water in the reaction system. Controlling the feed SO-containing 3 The temperature of the gas was 75℃and the flow rate was 0.5L/min. The reaction was heated for 8 hours while maintaining the aeration state. After the reaction was completed, the reaction product was placed in a fume hood and aged at room temperature for 2 hours. Washing 3-4 times by using a mixed solvent with the volume ratio of butyl acetate to n-heptane of 4:6. And (3) drying the mixture in an oven at 80 ℃ for 36 hours to obtain a product with the sulfonation degree of 112 percent, which is marked as sulfonated copolymer B.
(c) 1g of sulfonated copolymer B and 6.5g of MPEG2000 are dissolved in 10mL of dioxane at 90 ℃, heated to 110 ℃ for reflux reaction for 10 hours, and dried by rotary evaporation after the reaction is completed, thus obtaining the graft copolymer.
(d) Adding potassium hydroxide aqueous solution into the obtained graft copolymer until the pH value is 8-9 measured by a precise pH test paper, and continuously adding water to prepare 30% aqueous solution. According to the test method in national standard GBT8077-2012, the measured fluidity of the 2h cement paste is 298mm, the water cement ratio is 0.29, and the addition amount of the water reducer is 0.3wt%.
Example 10
(a) 10g of alpha-methylstyrene, 10g of itaconic anhydride, 0.2g of AIBN and 0.25g of ethyl thioglycolate are taken and dissolved in 75g of isoamyl acetate-N-heptane (volume ratio 2.5:3) mixed solvent, and N is introduced 2 And (3) removing oxygen in the system after 40min, and reacting for 6h at 80 ℃ in an oil bath. Then, the microspheres were separated by high-speed centrifugation, washed 2-3 times with n-hexane, and dried in a vacuum oven at 45℃to obtain a white powder, the copolymer having a molecular weight of about 5000, designated copolymer C.
(b) 8g of copolymer C was charged into a sulfonation reactor (250 mL two-necked flask), stirring was turned on, and the sulfonation reactor was heated to 85℃and N was introduced 2 For 30min to remove the water in the reaction system. Control deviceMaking into SO-containing products 3 The temperature of the gas was 75℃and the flow rate was 0.5L/min. The reaction was heated for 9 hours while maintaining the aeration state. After the reaction was completed, the reaction product was placed in a fume hood and aged at room temperature for 2 hours. Washing 3-4 times by using a mixed solvent of isoamyl acetate and n-heptane with the volume ratio of 1:1. And (3) drying the mixture in an oven at 80 ℃ for 24 hours to obtain a product with the sulfonation degree of 101 percent, which is marked as sulfonated copolymer C.
(c) 1g of sulfonated copolymer C and 6.5g of MPEG2000 are dissolved in 10mL of dioxane at 90 ℃, heated to 110 ℃ for reflux reaction for 10 hours, and dried by rotary evaporation after the reaction is completed, thus obtaining the graft copolymer.
(d) Ammonia gas was introduced into the vessel containing the graft copolymer until the system was no longer exothermic, and the reaction product was aged at room temperature in a fume hood for 2 hours to give a dark brown solid powder.
According to the test method in national standard GBT8077-2012, the measured fluidity of the 2h cement paste is 279mm, the water cement ratio is 0.29, and the addition amount of the water reducer is 0.3wt%.
Example 11
(a) 10g of 2-methylindene, 10g of itaconic anhydride, 0.2g of AIBN and 0.15g of ethyl thioglycolate are taken and dissolved in 70g of mixed solvent of isoamyl acetate and N-heptane (volume ratio 2.5:3), and N is introduced 2 And (3) removing oxygen in the system after 40min, and reacting for 6h at 70 ℃ in an oil bath. Then, the microspheres were separated by high-speed centrifugation, washed with n-hexane 2-3 times, and dried in a vacuum oven at 45℃to obtain a white powder, the copolymer having a molecular weight of about 3500, designated copolymer D.
(b) 8g of copolymer D was charged into a sulfonation reactor (250 mL two-necked flask), stirring was turned on, and the sulfonation reactor was heated to 85℃and N was introduced 2 For 30min to remove the water in the reaction system. Controlling the feed SO-containing 3 The temperature of the gas was 85℃and the flow rate was 0.5L/min. The reaction was heated for 4.5h while maintaining the aerated state. After the reaction was completed, the reaction product was placed in a fume hood and aged at room temperature for 2 hours. Washing 3-4 times by using a mixed solvent of isoamyl acetate and n-heptane with the volume ratio of 1:1. And (3) drying the mixture in an oven at 80 ℃ for 24 hours to obtain a product with the sulfonation degree of 75 percent, and marking the product as sulfonated copolymer D.
(c) 1g of sulfonated copolymer D and 5.5g of MPEG2000 are dissolved in 20mL of dioxane at 90 ℃, heated to 110 ℃ for reflux reaction for 24 hours, and dried by rotary evaporation after the reaction is completed, thus obtaining the graft copolymer.
(d) Ammonia gas was introduced into the vessel containing the graft copolymer until the system was no longer exothermic, and the reaction product was aged at room temperature in a fume hood for 2 hours to give a dark brown solid powder.
According to the test method in national standard GBT8077-2012, the measured fluidity of the 2h cement paste is 255mm, the water cement ratio is 0.29, and the addition amount of the water reducer is 0.3wt%.
Comparative example 1
(a) 10g of styrene, 10g of maleic anhydride, 0.2g of AIBN and 2g of thioglycolic acid are dissolved in 80g of butyl acetate and N is introduced 2 For 30min to remove oxygen in the system, and reacting for 5h at 75 ℃. Adding petroleum ether into the reaction system, wherein the volume ratio of petroleum ether to butyl acetate is 6:1, centrifuging to separate out precipitate, adding petroleum ether for washing 2-3 times, drying in a vacuum oven at 75 ℃ to obtain white powder, and grinding the product into 50-mesh particles.
(b) 10g of the polymer particles were charged into a sulfonation reactor (250 mL two-necked flask), stirring was started and the sulfonation reactor was heated to 100℃and N was introduced 2 45min to remove water in the reaction system, and controlling the introduced SO-containing water 3 The temperature of the gas was 85℃and the flow rate was 0.5L/min. The aeration state was maintained during the heating reaction for 12 hours. After the reaction was completed, the reaction product was placed in a fume hood and aged at room temperature for 2 hours. Washing 3-4 times by using an isoamyl acetate-n-heptane mixed solvent with the volume ratio of 3:7. And (5) placing the mixture in an oven at 80 ℃ for drying for 24 hours. The degree of sulfonation of the resulting polymer was 51%.
(c) 1g of the sulfonated polymer and 6.5g of MPEG2000 are dissolved in 10mL of dioxane at 90 ℃, heated to 110 ℃ for reflux reaction for 10 hours, and dried by rotary evaporation after the reaction is completed, thus obtaining the graft copolymer.
(d) Ammonia gas was introduced into the vessel containing the graft copolymer until the system was no longer exothermic, and the reaction product was aged at room temperature in a fume hood for 2 hours to give a dark brown solid powder.
According to the test method in national standard GBT8077-2012, the measured fluidity of the 2h cement paste is 188mm, the water cement ratio is 0.29, the addition amount of the water reducer is 0.3wt%, and the water solubility of the water reducer is poor.
Comparative example 2
(a) 10g of p-methylstyrene, 10g of itaconic anhydride, 0.2g of AIBN and 2g of thioglycolic acid 80g are dissolved in butyl acetate and N is introduced 2 For 30min to remove oxygen in the system, and reacting for 5h at 75 ℃. Adding petroleum ether into the reaction system, wherein the volume ratio of petroleum ether to butyl acetate is 6:1, centrifuging to separate out precipitate, adding petroleum ether for washing 2-3 times, drying in a vacuum oven at 75 ℃ to obtain white powder, and grinding the product into 60-mesh particles.
(b) 10g of the polymer particles were charged into a sulfonation reactor (250 mL two-necked flask), stirring was started and the sulfonation reactor was heated to 100℃and N was introduced 2 45min to remove water in the reaction system, and controlling the introduced SO-containing water 3 The temperature of the gas was 85℃and the flow rate was 0.5L/min. The aeration state was maintained during the heating reaction for 4 hours. After the reaction was completed, the reaction product was placed in a fume hood and aged at room temperature for 2 hours. Washing 3-4 times by using an isoamyl acetate-n-heptane mixed solvent with the volume ratio of 3:7. And (5) placing the mixture in an oven at 80 ℃ for drying for 24 hours. The degree of sulfonation of the resulting polymer was 38%.
(c) 1g of the sulfonated polymer and 8g of MPEG4000 are dissolved in 10mL dioxane at 90 ℃, heated to 110 ℃ for reflux reaction for 10 hours, and dried by rotary evaporation after the reaction is completed, thus obtaining the graft copolymer.
(d) Ammonia gas was introduced into the vessel containing the graft copolymer until the system was no longer exothermic, and the reaction product was aged at room temperature in a fume hood for 2 hours to give a dark brown solid powder.
According to the test method in national standard GBT8077-2012, the measured fluidity of the 2h cement paste is 156mm, the water cement ratio is 0.29, the addition amount of the water reducer is 0.3wt%, and the water solubility of the water reducer is poor.
Industrial applicability
The method of the invention can be widely used for preparing the polycarboxylic acid type water reducer.
Claims (10)
1. The preparation method of the polyethylene glycol derivative grafted polycarboxylate type water reducer is characterized by comprising the following steps of:
(a) Dissolving an electron-rich monomer, an electron-deficient monomer, an initiator and an optional chain transfer agent in an organic solvent, and performing self-stabilizing precipitation polymerization to obtain copolymer microspheres; wherein the electron-deficient monomer is itaconic anhydride or/and maleic anhydride, the electron-rich monomer is one or more selected from styrene and derivatives thereof, vinyl naphthalene and derivatives thereof, allyl naphthalene and derivatives thereof, indene and derivatives thereof, the organic solvent is one or more selected from esters, ethers, aromatic hydrocarbons and alkane solvents, and the solubility parameter of the copolymer forming the copolymer microsphere is 1-7 MPa greater than that of the organic solvent 1/2 The number average molecular weight of the copolymer is 1000-10000;
(b) Contacting the copolymer microsphere in the step (a) with a gas containing sulfur trioxide to carry out sulfonation reaction to obtain a sulfonated copolymer microsphere, wherein the sulfonation degree of the sulfonated copolymer microsphere is more than 10%;
(c) Dissolving the sulfonated copolymer microsphere and the polyethylene glycol derivative in the step (b) in a low-boiling-point polar solvent for grafting reaction to obtain a graft copolymer, wherein the boiling point of the low-boiling-point polar solvent is below 150 ℃, and the polyethylene glycol derivative is one or more selected from polyethylene glycol monoalkyl ether and alkoxyl polyethylene glycol amino;
(d) The resulting graft copolymer is contacted with a base to effect a neutralization reaction.
2. The method of manufacturing according to claim 1, characterized in that: the electron-rich monomer is one or more selected from styrene, p-methylstyrene, p-tert-butylstyrene, alpha-methylstyrene, 4-methoxystyrene, 4-ethoxystyrene, 4-tert-butoxystyrene, indene, dimethylindene, 4-vinylbiphenyl, 2-vinylnaphthalene, 1- (1-methylvinyl) naphthalene, 2- (2-methylallyloxy) naphthalene and 1-allylnaphthalene.
3. The process according to claim 1 or 2, wherein the proportion of structural units derived from maleic anhydride or itaconic anhydride in the copolymer obtained in step (a) is 10mol% or more relative to the total structural units of the copolymer.
4. The production method according to claim 1 or 2, wherein in step (b), the volume fraction of sulfur trioxide in the sulfur trioxide-containing gas is 10% or less; the sulfonation time in the step (b) is 0.5-10 h, and the sulfonation reaction temperature is 50-150 ℃.
5. The production method according to claim 1 or 2, wherein in the step (c), the polyethylene glycol derivative is one, two or three or more selected from the polyethylene glycol derivatives represented by the following general formulae:
，
Wherein R is 1 Is C 1 -C 12 Branched, straight-chain or cyclic alkyl of (2), n is an integer from 4 to 100, R 2 Is amino or hydroxy.
6. The production method according to claim 1 or 2, wherein the ratio of the number of moles of the polyethylene glycol derivative in step (c) to the number of moles of the acid anhydride group in the sulfonated copolymer is 1: (1-10).
7. The process according to claim 1 or 2, wherein the alkali used in step (d) is one or more selected from the group consisting of lye and alkaline gas.
8. The method according to claim 7, wherein the alkaline solution is one or more selected from the group consisting of sodium hydroxide solution, potassium hydroxide solution, and aqueous ammonia; the alkaline gas is one or more selected from pure ammonia gas, mixed gas of ammonia and nitrogen gas and mixed gas of ammonia and air.
9. A polyethylene glycol derivative grafted polycarboxylate water reducer prepared by the method of any one of claims 1-8.
10. A water reducing agent composition comprising the polyethylene glycol derivative grafted polycarboxylate water reducing agent of claim 9.
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| CN1417268A (en) * | 2001-09-19 | 2003-05-14 | 大日精化工业株式会社 | Preparation process of sulfonated solid particle |
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