CN102504238B - Unsaturated polyether monomer, comb-like branched copolymer cement dispersant prepared by the same, and preparation method thereof - Google Patents
Unsaturated polyether monomer, comb-like branched copolymer cement dispersant prepared by the same, and preparation method thereof Download PDFInfo
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- CN102504238B CN102504238B CN201110307442.7A CN201110307442A CN102504238B CN 102504238 B CN102504238 B CN 102504238B CN 201110307442 A CN201110307442 A CN 201110307442A CN 102504238 B CN102504238 B CN 102504238B
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- monomer
- methyl
- comb
- acid
- formula
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- 239000000178 monomer Substances 0.000 title claims abstract description 80
- 239000004568 cement Substances 0.000 title claims abstract description 55
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 40
- 229920005605 branched copolymer Polymers 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000004721 Polyphenylene oxide Substances 0.000 title abstract description 12
- 229920000570 polyether Polymers 0.000 title abstract description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- -1 oxypropylene group Chemical group 0.000 claims description 18
- 239000003999 initiator Substances 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000012986 chain transfer agent Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 125000006353 oxyethylene group Chemical group 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- WSNSMPZJJIYZCV-UHFFFAOYSA-N [Na]C Chemical compound [Na]C WSNSMPZJJIYZCV-UHFFFAOYSA-N 0.000 claims description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 4
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- QXIQCNFSNJEMOD-UHFFFAOYSA-N 3-hydroxybutan-2-yl prop-2-enoate Chemical compound CC(O)C(C)OC(=O)C=C QXIQCNFSNJEMOD-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
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- PMNLUUOXGOOLSP-UHFFFAOYSA-N alpha-mercaptopropionic acid Natural products CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 claims description 3
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 3
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 3
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical group [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 239000012736 aqueous medium Substances 0.000 claims description 2
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical compound OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- LXXNWCFBZHKFPT-UHFFFAOYSA-N Ethyl 2-mercaptopropionate Chemical compound CCOC(=O)C(C)S LXXNWCFBZHKFPT-UHFFFAOYSA-N 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 abstract description 19
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 abstract description 10
- 125000005647 linker group Chemical group 0.000 abstract description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract description 3
- 230000032050 esterification Effects 0.000 abstract description 2
- 238000005886 esterification reaction Methods 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 54
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 44
- 229920006305 unsaturated polyester Polymers 0.000 description 23
- 229910052757 nitrogen Inorganic materials 0.000 description 22
- 238000003756 stirring Methods 0.000 description 22
- 239000004567 concrete Substances 0.000 description 16
- 238000010792 warming Methods 0.000 description 14
- 238000005227 gel permeation chromatography Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- 239000003638 chemical reducing agent Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 238000009835 boiling Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 125000005395 methacrylic acid group Chemical group 0.000 description 4
- 229920005646 polycarboxylate Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 2
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical compound C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 description 2
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- WCASXYBKJHWFMY-UHFFFAOYSA-N crotyl alcohol Chemical compound CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 229940117927 ethylene oxide Drugs 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229940047670 sodium acrylate Drugs 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 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 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229940048053 acrylate Drugs 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical class [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- IZZSMHVWMGGQGU-UHFFFAOYSA-L disodium;2-methylidenebutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(=C)C([O-])=O IZZSMHVWMGGQGU-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011372 high-strength concrete Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000001261 hydroxy acids Chemical group 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- IJJSYKQZFFGIEE-UHFFFAOYSA-N naphthalene;potassium Chemical compound [K].C1=CC=CC2=CC=CC=C21 IJJSYKQZFFGIEE-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- BYTCDABWEGFPLT-UHFFFAOYSA-L potassium;sodium;dihydroxide Chemical compound [OH-].[OH-].[Na+].[K+] BYTCDABWEGFPLT-UHFFFAOYSA-L 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2641—Polyacrylates; Polymethacrylates
- C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/40—Surface-active agents, dispersants
- C04B2103/408—Dispersants
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention relates to an unsaturated polyether monomer, a comb-like branched copolymer cement dispersant prepared by the monomer, and preparation methods of the monomer and the dispersant. The unsaturated polyether monomer has the general formula (I), wherein R1 is H or -CH3; X is a linking group selected from -CH2-, -CH2CH2-, -OCH2CH2-, -OCH2CH2CH2CH2-; AO is ethylene oxide group and/or propene oxide group; l, m and n are all repeating units of AO; and the sum of l, m and n is an natural number of 10 to 50. The dispersant has the following chemical structure (VI), wherein x, y and z represent mole percentages of three structural units in the copolymer, and the sum of x, y and z is 100%. Preferably, x is 10% to 50%, y is 40% to 80% and z is 0% to 30%. The preparation method of the dispersant is simple and does not need organic solvents or complex esterification. The dispersant is advantageous in low dosage, good dispersibility and small slump loss.
Description
Technical field
The present invention relates to a kind of preparation method of comb-branched copolymer cement dispersants, monomer used and gained comb-branched copolymer cement dispersants, belong to technical field of concrete additives.
Background technology
In recent years, development along with comb-shaped copolymer cement dispersant, for the construction of the Infrastructure such as high-speed railway, bridge, water power, urban track traffic and airport provides powerful guarantee, promoted further developing of high-strength concrete and Highrise buildings concrete construction simultaneously.
Comb-shaped copolymer cement dispersant is the high molecular weight water soluble polymer that a class has comb shaped structure, is through free-radical polymerized and prepare gained by unsaturated acid and the large monomer of unsaturated active polyether.Its unsaturated acid using mainly comprises unsaturated carboxylic acid (salt) and unsaturated sulfonic acid (salt), as (methyl) vinylformic acid (salt), toxilic acid (acid anhydride), methylene-succinic acid, (methyl) sodium allyl sulfonate, Sodium styrene sulfonate etc., for dispersion agent main chain provides ionic adsorption site, be adsorbed onto after cement particle surface, ionic group makes mutually to have produced between cement granules electrostatic repulsion; The large monomer of unsaturated polyether mainly comprises (methyl) acrylic ester, toxilic acid polyoxyethylene monoesters and dibasic acid esters, allyl polyethenoxy ether, methacrylic Soxylat A 25-7 of different molecular weight etc., it is as the side chain of cement dispersants, bringing into play sterically hindered repulsion, cement granules is difficult to close to each other, thereby dispersiveness and the stability thereof of cement granules have been improved, concrete water cement ratio be can effectively reduce, concrete mobility and mobility hold facility improved.
As the important component part of comb-shaped copolymer cement dispersant, the large monomer of unsaturated polyether is subject to numerous investigators' favor.The large monomers of unsaturated polyether that adopt the synthetic different structure of the whole bag of tricks have been reported in many research, and for the preparation of comb-shaped copolymer cement dispersant.This type of cement dispersants has improved mobility and the slump retentivity of fresh concrete to a certain extent, but the deficiency existing is, the basic structure of the large monomer of unsaturated polyether is double bond containing single polyoxyalkylene long-chain, after copolymerization, in dispersant molecule, bring into play the limited in one's ability of sterically hindered effect, thereby the higher volume of the general needs of comb-shaped copolymer cement dispersant of the type could effectively improve concrete and newly mix performance.
Patent US2004/0204517 has reported that employing vinyl carbinol and methallyl alcohol are initiator, with ethyleneoxide addition, the strand allyl polyethenoxy ether and the methacrylic Soxylat A 25-7 that have synthesized different molecular weight, then carry out free-radical polymerizedly with the toxilic acid of different ratios and Hydroxyethyl acrylate, prepared polycarboxylate water-reducer.During 0.3% left and right that this polycarboxylate water-reducer volume is cement quality, just there is good dispersive ability and slump hold facility.
It is raw material that patent CN100545118 be take the different molecular weight allyl polyglycol of strand and maleic anhydride, methyl acrylate, has synthesized polycarboxylate water-reducer, can make cement paste have good degree of mobilization and degree of mobilization hold facility.
Patent EP1179517, first with methallyl alcohol and reacting ethylene oxide, has prepared the methyl allyl alcohol polyoxyethylene ether of different molecular weight, and then the vinylformic acid with methyl allyl alcohol polyoxyethylene ether and different ratios carries out copolymerization, has synthesized polycarboxylate water-reducer.This water reducer is cement quality at volume 0.18%～0.25% time, have good initial dispersion ability, but the slump hold facility of 30min is limited.
Patent CN101492518 report has synthesized a kind of ethers polycarboxylic acid water reducing agent, and it adopts molecular weight is that 2000～3000 strand allyl polyethenoxy ether and vinylformic acid, Hydroxyethyl acrylate carry out copolyreaction, has prepared ethers polycarboxylic acid water reducing agent.This water reducer volume be cement gross weight 0.5% time, show good slump hold facility.
Summary of the invention
The object of the present invention is to provide a kind of unsaturated polyester ether monomer, adopt comb-branched copolymer cement dispersants prepared by this monomer and preparation method thereof, gained comb-shaped copolymer cement dispersant volume is low, can effectively improve cement dispersiveness and dispersion stabilization thereof.
Following general formula for the chemical structure of unsaturated polyester ether monomer of the present invention (I) represents:
R in formula
1for H or-CH
3; X is linking group, for-CH
2-,-CH
2cH
2-,-OCH
2cH
2-,-OCH
2cH
2cH
2cH
2-or
aO is oxyethylene group and/or oxypropylene group; L, m, n are the number of repeat unit of AO, the natural number of l+m+n=10～50.
The preparation method of above-mentioned unsaturated polyester ether monomer comprises the steps:
(1) by compound d and the monoethanolamine shown in formula (III), carry out opening, obtain the intermediate e shown in formula (IV);
(2) take intermediate e as initiator, under the effect of catalyzer, carry out alkoxylation with the epoxide f shown in formula (V), obtain unsaturated polyester ether monomer a;
Described step 1) mol ratio that in, compound d and monoethanolamine carry out opening is preferably 1: 1, preferred concrete operation method is: the compound d shown in formula (III) is added dropwise to lentamente in the monoethanolamine that continues to stir, dropping temperature is 60～80 ℃, time for adding is 4～8h, and dripping the follow-up continuous soaking time of end is 1～4h.
Described step 2) in, epoxide f is the mixture of one or both arbitrary proportions in oxyethane (EO), propylene oxide (PO), its can be separately or with arbitrary proportion mixed polymerization to intermediate molecule, to produce homopolymer, segmented copolymer or the random copolymers of alkoxy polyether, by consumption and the feed way of adjustment ring oxide compound, can prepare the unsaturated branching polyether macromonomer of different molecular weight and structure.
Step 2) in, conventional catalyzer comprises potassium metal (sodium), naphthalene potassium (sodium), potassium hydride KH (sodium), alkyl potassium alcoholate (sodium), potassium hydroxide (sodium) etc.Oxyalkylated catalyst levels is preferably 0.05%～0.2% of products therefrom weight after alkoxylate; Oxyalkylated temperature of reaction is preferably 110～130 ℃; Reaction pressure is preferably 0.2～0.6MPa.
Step 2) described alkoxylation complete after, the alkalescence of product is stronger, is unfavorable for prolonged storage, as needs prolonged storage, in just need to carrying out and aftertreatment.Post-processing temperature remains between 60～90 ℃, and temperature is too low, and product viscosity is larger, even solidifies, and is difficult to neutralization; Excess Temperature, can cause too much by product to produce.In after aftertreatment adopt organic acid to carry out, organic acid is preferably Glacial acetic acid, oxalic acid, citric acid.
The comb-branched copolymer cement dispersants that adopts above-mentioned unsaturated polyester ether monomer to prepare has following chemical structure:
Wherein, x, y, z represents the molecular fraction of three kinds of structural units in multipolymer, x+y+z=100%.As preferred version, x=10%～50%, y=40%～80%, z=0～30%.
General formula for A (VII) represents:
R in formula
1for H or-CH
3; X is linking group, for-CH
2-,-CH
2cH
2-,-OCH
2cH
2-,-OCH
2cH
2cH
2cH
2-or
aO is oxyethylene group and/or oxypropylene group; L, m, n are the number of repeat unit of AO, the natural number of l+m+n=10～50.
General formula for B (VIII) represents:
R in formula
2for hydrogen atom or-COOM; R
3for hydrogen atom or methyl; M represents hydrogen atom, alkalimetal ion, alkaline-earth metal ion, ammonium ion or organic amine group.
The weight-average molecular weight of above-mentioned comb-branched copolymer cement dispersants is controlled at 30,000～70, and 000, if molecular weight is too large or too little, all can weaken the dispersion effect to cement.
By monomer a, b, c, in aqueous medium, there is free radicals copolymerization reaction and be prepared from above-mentioned comb-branched copolymer cement dispersants, wherein:
Monomer is general formula (I) expression for a:
R in formula
1for H or-CH
3; X is linking group, for-CH
2-,-CH
2cH
2-,-OCH
2cH
2-,-OCH
2cH
2cH
2cH
2-or
aO is oxyethylene group and/or oxypropylene group; L, m, n are the number of repeat unit of AO, the natural number of l+m+n=10～50.
Monomer is general formula (II) expression for b:
R in formula
2for hydrogen atom or-COOM; R
3for hydrogen atom or methyl; M represents hydrogen atom, alkalimetal ion, alkaline-earth metal ion, ammonium ion or organic amine group.
Above-mentioned monomer b contains at least one material in the represented material of general formula (II), is preferably at least one in vinylformic acid, methacrylic acid, toxilic acid, fumaric acid, methylene-succinic acid or their univalent metal salt, divalent metal salt, ammonium salt, organic amine salt.These monomers are used separately or use with the arbitrary proportion form of mixtures of two or more composition, and its hydroxy-acid group provides adsorption site and electrostatic repulsion in cement dispersants.
Monomer c is the 3rd functional monomer, the proportion of composing of adjustable carboxylic group and polyether lateral chain, is selected from any one in (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) sodium allyl sulfonate, (methyl) acrylamide, vinyl acetate.
Through applicant, repeatedly test, the preferred molecular fraction consumption of above-mentioned monomer a, b, c respectively: 10%～50%, 40%～80%, 0～30%.
The initiator of monomer a, b and c copolyreaction is conventional free radical water soluble starter, comprise independent persulphate, the composition of persulphate and hydrosulphite, sulphite, thiosulphate, pyrosulfite or ferrous salt, the composition of superoxide and L-AA or metal ion, initiator accounts for 0.5%～5% of monomer a+b+c total mole number, and wherein in composition, both mole ratios are 4～6: 1.
In copolyreaction process, according to the polymerization activity of monomer, can select not add chain-transfer agent, also can select to add water miscible chain-transfer agent to regulate the molecular weight of multipolymer.Aforementioned water-soluble chain transfer agent is preferably mercaptan type chain transfer agent, as at least one or the mixture of its arbitrary proportion in 2 mercaptopropionic acid, 3-thiohydracrylic acid, 2-mercaprol, 3-mercaprol, Thiovanic acid, mercaptoethanol, the consumption of chain-transfer agent in polymerization process is 0.2%～3% of monomer a+b+c total mole number.
Monomer weight concentration total in copolyreaction is preferably between 30%～60%, and temperature of reaction is 40～90 ℃, and it is main relevant with used initiator type.Monomer and initiator solution take the mode separately simultaneously dripping to control the homogeneity of multipolymer chain link distribution and the stability of polyreaction.Monomer and initiator solution time for adding are controlled at 1～5 hour.In order to improve the transformation efficiency of monomer, need to drip follow-up continuation of insurance temperature at monomer and initiator, soaking time is preferably 2～6 hours.
After copolyreaction finishes, the principal constituent that can directly serve as cement dispersants is used, and more preferably further uses in alkaline matter and rear use, to strengthen the stability in storage of product.The alkaline matter using comprises oxyhydroxide, oxide compound or the carbonate of monovalence metal and/or divalent metal, ammonium hydroxide, organic amine.The consumption of alkaline matter be take and regulated the pH value of reaction product to be advisable as 7 left and right.
Comb-branched copolymer cement dispersants of the present invention conventional volume is in use 0.08%～0.6% of total gelling material weight, and optimum adding quantity of pulverized is 0.1%～0.25%.Volume is too low, can not be satisfactory to the dispersion effect of cement; Volume is too high, causes waste economically, and dispersion effect does not further increase.Engineering staff can be preferred within the scope of this according to practical situation.
The present invention introduces new unsaturated polyester ether monomer in comb-branched copolymers cement dispersants, in this monomer molecule structure, there are unsaturated activity double key and three branching polyoxyalkylene long-chains, itself and other monomer are carried out to free radical aqueous solution copolymerization to react, there is higher Copolymerization activity, can obtain having the multipolymer of comb-branched structure.Due to the Hydrophilicrto polyether side chain of distributing in this copolymer molecule structure a certain proportion of carboxylic group and branching, the greatly sterically hindered effect between refinforced cement particle during as cement dispersants, the dispersion stabilization of raising cement.The preparation method of dispersion agent of the present invention is simple, production operation is convenient, not with an organic solvent, does not need through loaded down with trivial details esterification, meanwhile, this dispersion agent also has advantages of that volume is low, good dispersity, water-reducing rate are high, little loss of slump, body air content are low.
Embodiment
The preparation of unsaturated polyester ether monomer a
The preparation of unsaturated polyester ether monomer a-1:
73.2g monoethanolamine is placed in to the four-hole boiling flask with reflux condensing tube, thermometer, nitrogen conduit and agitator; continue to lead to nitrogen protection in reaction flask; flask is placed in to water-bath; then be warming up to 60 ℃, under continuously stirring, slowly in flask, continue to drip 136.8g glycidyl allyl ether; time for adding 6h; dropwise rear continuation and stir insulation 4h, cooling, obtain intermediate.
The above-mentioned synthetic intermediate of 70g and 0.44g sodium Metal 99.5 are placed in to the stainless steel autoclave that 1L is dry, sealed reactor.After reactor is found time, with air in nitrogen replacement still three times, under continuing to stir, be warming up to 130 ℃, heat up simultaneously, after keeping reactor to continue to vacuumize 30min, stop, then slowly pass into continuously 775g oxyethane, keep 130 ℃ of temperature, under the pressure of 0.25MPa, until oxyethane is all reinforced complete, continue constant temperature and stir 30min, then be evacuated to-below 0.08MPa, cool to 90 ℃, discharging, with oxalic acid, be neutralized to pH=7 left and right, obtaining molecular weight is the unsaturated polyester ether monomer a-1 of 2100 left and right.
The preparation of unsaturated polyester ether monomer a-2:
91.5g monoethanolamine is placed in to the four-hole boiling flask with reflux condensing tube, thermometer, nitrogen conduit and agitator; continue to lead to nitrogen protection in reaction flask; flask is placed in to water-bath; then be warming up to 80 ℃, under continuously stirring, slowly in flask, continue to drip 192g methacrylic glycidyl ether; time for adding 4h; dropwise rear continuation and stir insulation 2h, cooling, obtain intermediate.
The above-mentioned synthetic intermediate of 151.2g and 0.86g potassium methylate are placed in to the stainless steel autoclave that 1L is dry, sealed reactor.After reactor is found time, with air in nitrogen replacement still three times, under continuing to stir, be warming up to 125 ℃, heat up simultaneously, after keeping reactor to continue to vacuumize 30min, stop, then slowly pass into continuously 730g oxyethane, keep 125 ℃ of temperature, under the pressure of 0.4MPa, until oxyethane is all reinforced complete, continue constant temperature and stir 30min, then be evacuated to-below 0.08MPa, cool to 80 ℃, discharging, with Glacial acetic acid, be neutralized to pH=7 left and right, obtaining molecular weight is the unsaturated polyester ether monomer a-2 of 1100 left and right.
The preparation of unsaturated polyester ether monomer a-3:
79.3g monoethanolamine is placed in to the four-hole boiling flask with reflux condensing tube, thermometer, nitrogen conduit and agitator; continue to lead to nitrogen protection in reaction flask; flask is placed in to water-bath; then be warming up to 70 ℃, under continuously stirring, slowly in flask, continue to drip 184.6g methyl alkene butylglycidyl ether; time for adding 8h; dropwise rear continuation and stir insulation 3h, cooling, obtain intermediate.
The above-mentioned synthetic intermediate of 81.2g and 1.32g sodium ethylate are placed in to the stainless steel autoclave that 1L is dry, sealed reactor.After reactor is found time, with air in nitrogen replacement still three times, under continuing to stir, be warming up to 110 ℃, heat up simultaneously, after keeping reactor to continue to vacuumize 30min, stop, then slowly pass into continuously the mixture being formed by 576g oxyethane and 68g propylene oxide, keep 110 ℃ of temperature, under the pressure of 0.6MPa, until the mixture of oxyethane and propylene oxide is all reinforced complete, continue constant temperature and stir 30min, then be evacuated to-below 0.08MPa, cool to 70 ℃, discharging, with citric acid, be neutralized to pH=7 left and right, obtaining molecular weight is the unsaturated polyester ether monomer a-3 of 1800 left and right.
The preparation of unsaturated polyester ether monomer a-4:
109.8g monoethanolamine is placed in to the four-hole boiling flask with reflux condensing tube, thermometer, nitrogen conduit and agitator; continue to lead to nitrogen protection in reaction flask; flask is placed in to water-bath; then be warming up to 65 ℃, under continuously stirring, slowly in flask, continue to drip 205.2g glycidyl allyl ether; time for adding 7h; dropwise rear continuation and stir insulation 1h, cooling, obtain intermediate.
The above-mentioned synthetic intermediate of 175g and 0.85g potassium hydroxide are placed in to the stainless steel autoclave that 1L is dry, sealed reactor.After reactor is found time, with air in nitrogen replacement still three times, under continuing to stir, be warming up to 120 ℃, heat up simultaneously, after keeping reactor to continue to vacuumize 30min, stop, then slowly pass into continuously 586g oxyethane, keep 120 ℃ of temperature, under the pressure of 0.3MPa, until oxyethane is all reinforced complete, slowly pass into continuously again 45g propylene oxide, keep 120 ℃ of temperature, under the pressure of 0.3MPa, until propylene oxide is all reinforced complete, continuing constant temperature stirs after 30min, be evacuated to-below 0.08MPa, cool to 60 ℃, discharging, with Glacial acetic acid, be neutralized to pH=7 left and right, obtaining molecular weight is the unsaturated polyester ether monomer a-4 of 800 left and right.
The preparation of comb-branched copolymer cement dispersants
The molecular weight of multipolymer described in embodiment and comparative example adopts gel permeation chromatography (GPC) carry out measure and calculation and obtain, and test condition is as described below, take polyoxyethylene glycol as reference material drawing standard curve.
The test condition of GPC is:
Gel column: Shodex SB806+803 two root chromatogram column series connection
Column temperature: 40 ℃
Eluant: 0.1M NaNO
3the aqueous solution
Flow velocity: 1.0ml/min
Sample size: the aqueous solution of 20 μ l 0.5% samples
Detector: Shodex RI-71 type differential refraction detector
Standard curve making standard substance: polyoxyethylene glycol GPC standard specimen (Sigma-Aldrich, molecular weight 1010000,478000,263000,118000,44700,18600,6690,1960,628,232)
The test of comb-shaped copolymer cement dispersant to the dispersing property of cement and slump hold facility, carries out with reference to standard GB/T 8076-2008 " concrete admixture " relevant regulations.
Embodiment 1
In the 1L glass reactor of thermometer, agitator, dropping funnel and nitrogen conduit is housed, add 200g distilled water and 460g unsaturated polyester ether monomer a-1.Reactor is leading under nitrogen protection, the large monomer of stirring and dissolving, and be warming up to 90 ℃, and then 58.6g vinylformic acid, 5.62g acrylamide and 60g water mix and blend are made to uniform monomer solution, it is at the uniform velocity dropped in reactor, time for adding is 4h.Meanwhile, at the uniform velocity drip the initiator solution that 90g contains 2.45g Potassium Persulphate, time for adding is 4.5h.Complete soln dropwises follow-up continuation of insurance temperature 4h, is then cooled to 50 ℃, adds 30% aqueous sodium hydroxide solution that product is neutralized to pH=7 left and right, obtains solid content and be 57.3% transparent liquid, and molecular weight of copolymer is determined as 57,600 through GPC.
Embodiment 2
In the 1L glass reactor of thermometer, agitator, dropping funnel and nitrogen conduit is housed, add 210g distilled water and 320g unsaturated polyester ether monomer a-2.Reactor is leading under nitrogen protection, the large monomer of stirring and dissolving, and be warming up to 80 ℃; then by 22.6g sodium acrylate, 15.6g methylene-succinic acid; 0.89g Thiovanic acid and 100g water mix and blend are made uniform monomer solution, and it is at the uniform velocity dropped in reactor, and time for adding is 4.5h.Meanwhile, drip at the uniform velocity respectively the 110g aqueous solution that contains 4.66g Sodium Persulfate and the 110g aqueous solution that contains 0.48g sodium bisulfite, time for adding is 5h.Complete soln dropwises follow-up continuation of insurance temperature 6h, is then cooled to 50 ℃, adds 20% ammonia soln that product is neutralized to pH=7 left and right, obtains solid content and be 38.6% transparent liquid, and molecular weight of copolymer is determined as 68,400 through GPC.
Embodiment 3
In the 1L glass reactor of thermometer, agitator, dropping funnel and nitrogen conduit is housed, add 200g distilled water, the hydrogen peroxide that 380g unsaturated polyester ether monomer a-3 and 3.96g massfraction are 27.5%.Reactor is leading under nitrogen protection, the large monomer of stirring and dissolving, and be warming up to 45 ℃; then by 34.2g toxilic acid, 24.7g Propylene glycol monoacrylate; 2.06g 3-thiohydracrylic acid and 100g water mix and blend are made uniform monomer solution, and it is at the uniform velocity dropped in reactor, and time for adding is 1h.Meanwhile, at the uniform velocity drip the aqueous solution that 120g contains 1.75g iron vitriol, time for adding is 1.5h.Complete soln dropwises follow-up continuation of insurance temperature 2h, then adds monoethanolamine that product is neutralized to about pH=7, obtains solid content and be 50.8% transparent liquid, and molecular weight of copolymer is determined as 34,200 through GPC.
Embodiment 4
In the 1L glass reactor of thermometer, agitator, dropping funnel and nitrogen conduit is housed, add 200g distilled water and 420g unsaturated polyester ether monomer a-4.Reactor is under logical nitrogen protection; the large monomer of stirring and dissolving; and be warming up to 70 ℃; then by 77.3g toxilic acid disodium, 7.54g Hydroxyethyl acrylate, 15.1g sodium allyl sulfonate; 0.27g mercaptoethanol and 70g water mix and blend are made uniform monomer solution; it is at the uniform velocity dropped in reactor, and time for adding is 2h.Meanwhile, at the uniform velocity drip 76g and contain 4.28g ammonium persulfate solution, time for adding is 2.5h.After complete soln dropwises, be warming up to 90 ℃ and continue insulation 5h, be then cooled to 50 ℃, add saturated calcium hydroxide aqueous solution that product is neutralized to pH=7 left and right, obtain solid content and be 59.4% transparent liquid, molecular weight of copolymer is determined as 52,600 through GPC.
Embodiment 5
In the 1L glass reactor of thermometer, agitator, dropping funnel and nitrogen conduit is housed, add the hydrogen peroxide that 300g distilled water and 240g unsaturated polyester ether monomer a-1 and 1.74g massfraction are 27.5%.Reactor is under logical nitrogen protection; the large monomer of stirring and dissolving; and be warming up to 65 ℃; then by 29.2g sodium acrylate, 18.2g toxilic acid; 6.58g sodium itaconate; 2.85g methyl acrylate and 210g water mix and blend are made uniform monomer solution, and it is at the uniform velocity dropped in reactor, and time for adding is 3h.Meanwhile, at the uniform velocity drip the aqueous solution that 180g contains 0.42g L-AA, time for adding is 3.5h.Complete soln dropwises follow-up continuation of insurance temperature 4h, is then cooled to 50 ℃, in add 30% potassium hydroxide aqueous solution that product is neutralized to pH=7 left and right, obtain solid content and be 30.5% transparent liquid, molecular weight of copolymer is determined as 46,100 through GPC.
Comparative example 1
By the 460g unsaturated polyester ether monomer a-1 adding in embodiment 1, replace to that to add 482g molecular weight be the common strand allyl polyethenoxy ether of 2200 left and right, other synthesis condition is constant, obtains solid content and be 59.5% transparent liquid, molecular weight of copolymer is 51,200 through GPC test.
Comparative example 2
By the 320g unsaturated polyester ether monomer a-2 adding in embodiment 2, change that to add 320g molecular weight be the common methacrylic Soxylat A 25-7 of 1800 left and right into, other synthesis condition is constant, obtains solid content and be 38.5% transparent liquid, molecular weight of copolymer is 78,300 through GPC test.
Comb-shaped copolymer cement dispersant synthetic in Evaluation operation example 1～5 and comparative example 1～2, to the dispersing property of cement and slump hold facility, is carried out with reference to standard GB/T 8076-2008 " concrete admixture " relevant regulations.Test is carried out under 25 ℃ of environment, and test cement adopts little Ye field, the south of the River 52.5 P.II cement, fixing water consumption, and adjusting dispersant dosage, to make the initial slump of fresh concrete be 21.0 ± 1cm, adopting identical defoamer adjustment concrete 's air-containing is 3% left and right.The volume of copolymer cement dispersant is with solid component meter, and to take the weight of cement be benchmark to volume simultaneously.Test-results sees the following form:
Table 1. comb-branched copolymer cement dispersants of the present invention for the Performance Ratio of fresh concrete
From result shown in table 1, can find out, compare with the concrete sample of comparative example 2 cement dispersants with use comparative example 1, use the concrete sample of the cement dispersants of the present invention of embodiment 1～5 all can make concrete obtain the specific slump and divergence with less incorporation, demonstrate the good performance that cement is disperseed.In addition, use the concrete sample of the cement dispersants of the present invention of embodiment 1～5 after 60 minutes, all to show the less slump and divergence loss, illustrate that this sample has good cement dispersiveness and dispersed hold facility.
Claims (11)
1. a comb-branched copolymer cement dispersants, is characterized in that having following chemical structure:
Wherein, x, y, z represents the molecular fraction of three kinds of structural units in multipolymer, x+y+z=100%, x=10%～50%, y=40%～80%, z=0～30%;
General formula for A (VII) represents:
R in formula
1for H or-CH
3; X is-CH
2-,-CH
2cH
2-,-OCH
2cH
2-,-OCH
2cH
2cH
2cH
2-or
aO is oxyethylene group and/or oxypropylene group; L, m, n are the number of repeat unit of AO, the natural number of l+m+n=10～50;
General formula for B (VIII) represents:
R in formula
2for hydrogen atom or-COOM; R
3for hydrogen atom or methyl; M represents hydrogen atom, alkalimetal ion, alkaline-earth metal ion, ammonium ion or organic amine group;
C is the structural unit after any one polymerization in (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) sodium allyl sulfonate, (methyl) acrylamide, vinyl acetate.
2. comb-branched copolymer cement dispersants as claimed in claim 1, is characterized in that the weight-average molecular weight of described comb-branched copolymer cement dispersants is controlled at 30,000～70,000.
3. the preparation method of comb-branched copolymer cement dispersants described in claim 1 or 2, is characterized in that, by monomer a, b, c, free radicals copolymerization reaction occurs in aqueous medium, wherein
Monomer a represents with logical formula I:
R in formula
1for H or-CH
3; X is-CH
2-,-CH
2cH
2-,-OCH
2cH
2-,-OCH
2cH
2cH
2cH
2-or
aO is oxyethylene group and/or oxypropylene group; L, m, n are the number of repeat unit of AO, the natural number of l+m+n=10～50;
Monomer b represents with logical formula II:
R in formula
2for hydrogen atom or-COOM; R
3for hydrogen atom or methyl; M represents hydrogen atom, alkalimetal ion, alkaline-earth metal ion, ammonium ion or organic amine group;
Monomer c is the 3rd functional monomer, is selected from any one in (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) sodium allyl sulfonate, (methyl) acrylamide, vinyl acetate.
4. method as claimed in claim 3, is characterized in that monomer a, b, the shared molecular fraction of c are respectively 10%～50%, 40%～80%, 0～30%.
5. method as claimed in claim 3, is characterized in that monomer b is at least one material containing in the logical represented material of formula II.
6. method as claimed in claim 5, is characterized in that monomer b is selected from least one in vinylformic acid, methacrylic acid, toxilic acid, fumaric acid or their univalent metal salt, divalent metal salt, ammonium salt, organic amine salt.
7. method as claimed in claim 3, the initiator that it is characterized in that monomer a, b and c copolyreaction is selected from independent persulphate, the composition of persulphate and hydrosulphite, sulphite, thiosulphate, pyrosulfite or ferrous salt, the composition of superoxide and L-AA or metal ion, initiator accounts for 0.5%～5% of monomer a+b+c total mole number, and wherein in composition, both mole ratios are 4～6:1.
8. method as claimed in claim 3, it is characterized in that adding water miscible chain-transfer agent to regulate the molecular weight of multipolymer in copolyreaction process, aforementioned water-soluble chain transfer agent is mercaptan type chain transfer agent, and the consumption of chain-transfer agent in polymerization process is 0.2%～3% of monomer a+b+c total mole number.
9. method as claimed in claim 8, is characterized in that described mercaptan type chain transfer agent is selected from least one or the mixture of its arbitrary proportion in 2 mercaptopropionic acid, 3-thiohydracrylic acid, 2-mercaprol, 3-mercaprol, Thiovanic acid, mercaptoethanol.
10. method as claimed in claim 3, is characterized in that monomer weight concentration total in copolyreaction is between 30%～60%, and temperature of reaction is 40～90 ℃.
11. methods as claimed in claim 3, it is characterized in that mode that monomer and initiator solution are taked separately to drip simultaneously controls homogeneity that multipolymer chain link distributes and the stability of polyreaction, monomer and initiator solution time for adding are controlled at 1～5 hour, and monomer and initiator solution drip follow-up continuation of insurance temperature 2～6 hours.
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| CN108585594A (en) * | 2018-05-25 | 2018-09-28 | 湖北工业大学 | A kind of high and easy retentivity polycarboxylate water-reducer of 1800 molecular weight polyethers and preparation method |
| EP3828154A1 (en) * | 2019-11-29 | 2021-06-02 | Sika Technology Ag | Branched copolymers as additives for reducing the viscosity of mineral binder compositions |
| CN114478906B (en) * | 2020-10-26 | 2023-05-02 | 中国石油化工股份有限公司 | Polyacrylamide-based symmetrical branched polymer surfactant, and preparation method and application thereof |
| CN115975124B (en) * | 2022-12-16 | 2024-07-26 | 科之杰新材料集团有限公司 | Hyperbranched polyether monomer, hyperbranched EPEG type polycarboxylate superplasticizer and preparation method thereof |
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