CN102504238A - 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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- CN102504238A CN102504238A CN2011103074427A CN201110307442A CN102504238A CN 102504238 A CN102504238 A CN 102504238A CN 2011103074427 A CN2011103074427 A CN 2011103074427A CN 201110307442 A CN201110307442 A CN 201110307442A CN 102504238 A CN102504238 A CN 102504238A
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- Prior art keywords
- monomer
- acid
- formula
- methyl
- comb
- Prior art date
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- Granted
Links
- 239000000178 monomer Substances 0.000 title claims abstract description 78
- 239000004568 cement Substances 0.000 title claims abstract description 53
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229920005605 branched copolymer Polymers 0.000 title claims abstract description 16
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 15
- 229920000570 polyether Polymers 0.000 title claims abstract description 15
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000005647 linker group Chemical group 0.000 claims abstract description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 56
- 238000003756 stirring Methods 0.000 claims description 28
- 229920006305 unsaturated polyester Polymers 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000004567 concrete Substances 0.000 claims description 17
- 239000003999 initiator Substances 0.000 claims description 15
- -1 (methyl) Hydroxyethyl Chemical group 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 11
- 238000009413 insulation Methods 0.000 claims description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 239000012986 chain transfer agent Substances 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 8
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 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
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- 125000006353 oxyethylene group Chemical group 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
- 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
- 229960000583 acetic acid Drugs 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
- 239000012362 glacial acetic acid Substances 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
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 3
- WSNSMPZJJIYZCV-UHFFFAOYSA-N [Na]C Chemical compound [Na]C WSNSMPZJJIYZCV-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
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 3
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 238000002791 soaking Methods 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
- 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 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 239000012736 aqueous medium Substances 0.000 claims description 2
- 239000003054 catalyst 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
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 239000007858 starting material Substances 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
- 239000004593 Epoxy Substances 0.000 claims 1
- LXXNWCFBZHKFPT-UHFFFAOYSA-N Ethyl 2-mercaptopropionate Chemical compound CCOC(=O)C(C)S LXXNWCFBZHKFPT-UHFFFAOYSA-N 0.000 claims 1
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 1
- 239000011707 mineral Substances 0.000 claims 1
- 150000002924 oxiranes Chemical class 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 abstract description 19
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract description 2
- 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 44
- 229910052757 nitrogen Inorganic materials 0.000 description 22
- 238000010792 warming Methods 0.000 description 14
- 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
- 239000003638 chemical reducing agent Substances 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
- 230000000052 comparative effect Effects 0.000 description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-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
- 238000012423 maintenance 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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000002118 epoxides Chemical class 0.000 description 3
- 239000008187 granular material Substances 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
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-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
- 230000033228 biological regulation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 229940047670 sodium acrylate Drugs 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000001179 sorption measurement 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
- 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
- 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
- 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
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007812 deficiency Effects 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
- 238000011156 evaluation Methods 0.000 description 1
- 239000011372 high-strength concrete Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 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
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012925 reference material Substances 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
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 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
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, used monomer and gained comb-branched copolymer cement dispersants, belong to technical field of concrete additives.
Background technology
In recent years; Continuous development along with comb-shaped copolymer cement dispersant; For the construction of 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 one type of high molecular weight water soluble polymer with comb shaped structure, is through free-radical polymerized and preparation gained by unsaturated acid and the big monomer of unsaturated active polyether.Its employed unsaturated acid mainly comprises unsaturated carboxylic acid (salt) and unsaturated sulfonic acid (salt); Like (methyl) vinylformic acid (salt), toxilic acid (acid anhydride), methylene-succinic acid, (methyl) sodium allyl sulfonate, SSS etc.; For the dispersion agent main chain provides the ionic adsorption site; After it was adsorbed onto cement particle surface, ionic group made and has produced electrostatic repulsion between the cement granules each other; The big monomer of unsaturated polyether mainly comprises (methyl) vinylformic acid polyoxyethylene ester, toxilic acid T 46155 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, it is close to each other that cement granules is difficult to, thereby improved the dispersed and stable of cement granules; Concrete wc be can effectively reduce, concrete flowability and mobile hold facility improved.
As the important component part of comb-shaped copolymer cement dispersant, the big monomer of unsaturated polyether receives numerous investigators' favor.Many researchs have been reported and have been adopted the big monomer of unsaturated polyether of the synthetic different structure of the whole bag of tricks, and have been used for the preparation of comb-shaped copolymer cement dispersant.This type of cement dispersants has improved the flowability and the slump retentivity of fresh concrete to a certain extent; But the deficiency that exists is; The big monomeric substruction of unsaturated polyether is double bond containing single polyoxyalkylene long-chain; Through after the copolymerization in dispersant molecule the sterically hindered effect of performance limited in one's ability, thereby the comb-shaped copolymer cement dispersant of the type generally need could improve concrete effectively than higher volume and newly mix performance.
Patent US2004/0204517 has reported that employing vinyl carbinol and methallyl alcohol are initiator; With the oxyethane addition; The strand allyl polyethenoxy ether and the methacrylic Soxylat A 25-7 that have synthesized different molecular weight; Carry out free-radical polymerizedly with the toxilic acid of different ratios and Hydroxyethyl acrylate then, prepared polycarboxylate water-reducer.When this polycarboxylate water-reducer volume is 0.3% left and right sides of cement quality, just have dispersive ability and slump hold facility preferably.
Patent CN100545118 is a raw material with the different molecular weight allyl polyglycol of strand and maleic anhydride, methyl acrylate, has synthesized polycarboxylate water-reducer, can make cement paste have degree of mobilization and degree of mobilization hold facility preferably.
Patent EP1179517 has prepared the methallyl alcohol Soxylat A 25-7 of different molecular weight at first with methallyl alcohol and reacting ethylene oxide, and the vinylformic acid with methallyl alcohol Soxylat A 25-7 and different ratios carries out copolymerization then, has synthesized polycarboxylate water-reducer.This water reducer is 0.18% of cement quality～0.25% o'clock at volume, have initial dispersion ability preferably, 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 is 0.5% o'clock of cement gross weight, shows slump hold facility preferably.
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 of this monomer preparation and preparation method thereof; Gained comb-shaped copolymer cement dispersant volume is low, can effectively improve cement dispersiveness and dispersion stabilization thereof.
The monomeric chemical structure of unsaturated polyether according to the invention is represented with following general formula (I):
R in the formula
1For H or-CH
3X is a 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.
Above-mentioned unsaturated polyether is monomeric preparation method comprise the steps:
(1) carries out opening by compound d and the monoethanolamine shown in the formula (III), obtain the midbody e shown in the formula (IV);
(2) be initiator with midbody e, under the effect of catalyzer, carry out alkoxylation, obtain unsaturated polyester ether monomer a with the epoxide f shown in the formula V;
The mol ratio that compound d and monoethanolamine carry out opening in the said step 1) is preferably 1: 1; Preferred concrete operation method is: the compound d shown in the formula (III) is added dropwise to lentamente in the monoethanolamine that continues to stir; Dropping temperature is 60～80 ℃; The dropping time is 4～8h, and dripping end continued soaking time is 1～4h.
Said step 2) epoxide f is the mixture of one or both arbitrary proportions in oxyethane (EO), the propylene oxide (PO) in; It can be separately or with the arbitrary proportion mixed polymerization to the midbody molecule; So that produce homopolymer, segmented copolymer or the random copolymers of alkoxy polyether; Through the consumption and the feed way of adjustment epoxide, can prepare the big monomer of unsaturated branch polyether of different molecular weight and structure.
Step 2) catalyzer commonly used in comprises potassium metal (sodium), naphthalene potassium (sodium), potassium hydride KH (sodium), alkyl potassium alcoholate (sodium), Pottasium Hydroxide (sodium) etc.Oxyalkylated catalyst levels is preferably 0.05%～0.2% of products therefrom weight after the alkoxylate; Oxyalkylated temperature of reaction is preferably 110～130 ℃; Reaction pressure is preferably 0.2～0.6MPa.
Step 2) said alkoxylation intact after, the alkalescence of product is stronger, is unfavorable for prolonged storage, like the need prolonged storage, in just need carrying out and aftertreatment.Post-processing temperature remains between 60～90 ℃, and temperature is low excessively, and product viscosity is bigger, even solidifies, and is difficult to neutralization; Temperature is too high, can cause too much by product to produce.Middle back aftertreatment adopts organic acid to carry out, and organic acid is preferably Glacial acetic acid min. 99.5, oxalic acid, Hydrocerol A.
Adopt the comb-branched copolymer cement dispersants of above-mentioned unsaturated polyester ether monomer preparation to have following chemical structure:
Wherein, x, y, z represent the molecular fraction of three kinds of structural units in the multipolymer, x+y+z=100%.As preferred version, x=10%～50%, y=40%～80%, z=0～30%.
A representes with general formula (VII):
R in the formula
1For H or-CH
3X is a 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.
B representes with general formula (VIII):
R in the formula
2For Wasserstoffatoms or-COOM; R
3Be Wasserstoffatoms or methyl; M representes Wasserstoffatoms, 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 big or too little, all can weaken dispersion effect to cement.
Free radicals copolymerization reaction takes place monomer a, b, c and is prepared from above-mentioned comb-branched copolymer cement dispersants in aqueous medium, wherein:
Monomer a representes with general formula (I):
R in the formula
1For H or-CH
3X is a 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 b representes with general formula (II):
R in the formula
2For Wasserstoffatoms or-COOM; R
3Be Wasserstoffatoms or methyl; M representes Wasserstoffatoms, alkalimetal ion, alkaline-earth metal ion, ammonium ion or organic amine group.
Above-mentioned monomer b contains at least a material in the represented material of general formula (II), is preferably at least a in vinylformic acid, methylacrylic acid, toxilic acid, fumaric acid, methylene-succinic acid or their univalent metal salt, divalent metal salt, ammonium salt, the organic amine salt.These monomers use 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 (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) sodium allyl sulfonate, (methyl) acrylic amide, the vinyl acetate any one.
Test repeatedly through the applicant, the preferred molecular fraction consumption of above-mentioned monomer a, b, c is respectively: 10%～50%, 40%～80%, 0～30%.
The initiator of monomer a, b and c copolyreaction is conventional radical water soluble starter; Comprise independent persulphate; The compsn of persulphate and hydrosulphite, sulphite, thiosulphate, pyrosulfite or ferrous salt; The compsn of superoxide and L-xitix or metals ion, initiator account for 0.5%～5% of monomer a+b+c total mole number, and wherein both mole ratios are 4～6: 1 in the compsn.
In the copolyreaction process,, can select not add chain-transfer agent, also can select to add water miscible chain-transfer agent to regulate the molecular weight of multipolymer according to monomeric polymerization activity.Aforementioned water-soluble chain transfer agent is preferably mercaptan type chain transfer agent; Like the mixture of at least a or its arbitrary proportion in 2 mercaptopropionic acid, 3-thiohydracrylic acid, 2-mercaprol, 3-mercaprol, Thiovanic acid, the 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 the copolyreaction is preferably between 30%～60%, and temperature of reaction is 40～90 ℃, and it is main relevant with employed initiator type.The mode that monomer and initiator solution are taked separately to drip is simultaneously controlled the homogeneity of multipolymer chain link distribution and the stability of polyreaction.Monomer and initiator solution dropping time were controlled at 1～5 hour.In order to improve monomeric transformation efficiency, need drip the continued insulation at monomer and initiator, soaking time is preferably 2～6 hours.
After copolyreaction finished, the principal constituent that can directly serve as cement dispersants was used, more preferably further with using with the back in the alkaline matter, to strengthen the stability in storage of product.Employed alkaline matter comprises oxyhydroxide, oxide compound or the carbonate of monovalence metal and/or divalent metal, volatile caustic, organic amine.The consumption of alkaline matter is about 7 to be advisable with the pH value of conditioned reaction product.
Comb-branched copolymer cement dispersants of the present invention conventional volume in use is 0.08%～0.6% of total gelling material weight, and optimum volume is 0.1%～0.25%.Volume is low excessively, then can not be satisfactory to the dispersion effect of cement; Volume is too high, causes waste economically, and dispersion effect does not further increase.The engineering staff can be preferred in this scope according to practical situation.
The present invention introduces new unsaturated polyester ether monomer in the comb-branched copolymers cement dispersants; Have unsaturated activity double key and three branching polyoxyalkylene long-chains in this monomer molecule structure; Itself and other monomer is carried out the reaction of radical aqueous solution copolymerization; It is active to have higher copolymerization, the multipolymer that can obtain having comb-branched structure.Because the Hydrophilicrto polyether side chain of a certain proportion of carboxylic group and the branching of distributing in this copolymer molecule structure, the greatly sterically hindered effect between the refinforced cement particle improves dispersion stability of cement during as cement dispersants.The preparation method of dispersion agent according to the invention is simple; Production operation is convenient, not with an organic solvent, need not pass through loaded down with trivial details esterification; Simultaneously, this dispersion agent have also that volume is low, good dispersivity, water-reducing rate is high, slump-loss is little, the body air content is low advantage.
Embodiment
The preparation of unsaturated polyester ether monomer a
The preparation of unsaturated polyester ether monomer a-1:
The 73.2g monoethanolamine is placed the four-hole boiling flask that has reflux condensing tube, TM, nitrogen conduit and whisking appliance, continue logical nitrogen protection in reaction flask, flask is placed water-bath; Be warming up to 60 ℃ then, under the continuously stirring, slowly in flask, continue to drip the 136.8g glycidyl allyl ether; Dropping time 6h; Dropwise continued and stir insulation 4h, cooling promptly gets midbody.
Above-mentioned synthetic midbody of 70g and 0.44g sodium Metal 99.5 are placed 1L exsiccant stainless steel autoclave, sealed reactor.After reaction kettle found time,, be warming up to 130 ℃ under continuing to stir with air in the nitrogen replacement still three times; Heat up simultaneously, stop after the maintenance reaction kettle continues to vacuumize 30min, slowly feed 775g oxyethane then continuously; Keep 130 ℃ of temperature, under the pressure of 0.25MPa, up to whole reinforced the finishing of oxyethane; Continue constant temperature and stir 30min, be evacuated to then-below the 0.08MPa, cool to 90 ℃; Discharging is neutralized to about pH=7 with oxalic acid, obtains molecular weight and be about 2100 unsaturated polyester ether monomer a-1.
The preparation of unsaturated polyester ether monomer a-2:
The 91.5g monoethanolamine is placed the four-hole boiling flask that has reflux condensing tube, TM, nitrogen conduit and whisking appliance, continue logical nitrogen protection in reaction flask, flask is placed water-bath; Be warming up to 80 ℃ then, under the continuously stirring, slowly in flask, continue to drip 192g methacrylic glycidyl ether; Dropping time 4h; Dropwise continued and stir insulation 2h, cooling promptly gets midbody.
Above-mentioned synthetic midbody of 151.2g and 0.86g potassium methylate are placed 1L exsiccant stainless steel autoclave, sealed reactor.After reaction kettle found time,, be warming up to 125 ℃ under continuing to stir with air in the nitrogen replacement still three times; Heat up simultaneously, stop after the maintenance reaction kettle continues to vacuumize 30min, slowly feed 730g oxyethane then continuously; Keep 125 ℃ of temperature, under the pressure of 0.4MPa, up to whole reinforced the finishing of oxyethane; Continue constant temperature and stir 30min, be evacuated to then-below the 0.08MPa, cool to 80 ℃; Discharging is neutralized to about pH=7 with Glacial acetic acid min. 99.5, obtains molecular weight and be about 1100 unsaturated polyester ether monomer a-2.
The preparation of unsaturated polyester ether monomer a-3:
The 79.3g monoethanolamine is placed the four-hole boiling flask that has reflux condensing tube, TM, nitrogen conduit and whisking appliance, continue logical nitrogen protection in reaction flask, flask is placed water-bath; Be warming up to 70 ℃ then, under the continuously stirring, slowly in flask, continue to drip 184.6g methyl alkene butylglycidyl ether; Dropping time 8h; Dropwise continued and stir insulation 3h, cooling promptly gets midbody.
Above-mentioned synthetic midbody of 81.2g and 1.32g sodium ethylate are placed 1L exsiccant stainless steel autoclave, sealed reactor.After reaction kettle found time,, be warming up to 110 ℃ under continuing to stir with air in the nitrogen replacement still three times; Heat up simultaneously, stop after the maintenance reaction kettle continues to vacuumize 30min, slowly feed the mixture of forming by 576g oxyethane and 68g propylene oxide then continuously; Keep 110 ℃ of temperature, under the pressure of 0.6MPa, up to whole reinforced the finishing of the mixture of oxyethane and propylene oxide; Continue constant temperature and stir 30min, be evacuated to then-below the 0.08MPa, cool to 70 ℃; Discharging is neutralized to about pH=7 with Hydrocerol A, obtains molecular weight and be about 1800 unsaturated polyester ether monomer a-3.
The preparation of unsaturated polyester ether monomer a-4:
The 109.8g monoethanolamine is placed the four-hole boiling flask that has reflux condensing tube, TM, nitrogen conduit and whisking appliance, continue logical nitrogen protection in reaction flask, flask is placed water-bath; Be warming up to 65 ℃ then, under the continuously stirring, slowly in flask, continue to drip the 205.2g glycidyl allyl ether; Dropping time 7h; Dropwise continued and stir insulation 1h, cooling promptly gets midbody.
Above-mentioned synthetic midbody of 175g and 0.85g Pottasium Hydroxide are placed 1L exsiccant stainless steel autoclave, sealed reactor.After reaction kettle found time,, continue to stir down and be warming up to 120 ℃, heat up the while with air in the nitrogen replacement still three times; Stop after keeping reaction kettle to continue to vacuumize 30min, slowly feed 586g oxyethane then continuously, keep 120 ℃ of temperature, under the pressure of 0.3MPa; Up to whole reinforced the finishing of oxyethane, slowly feed the 45g propylene oxide more continuously, 120 ℃ of maintenance temperature are under the pressure of 0.3MPa; Up to whole reinforced the finishing of propylene oxide, after continuation constant temperature stirs 30min, be evacuated to-below the 0.08MPa, cool to 60 ℃; Discharging is neutralized to about pH=7 with Glacial acetic acid min. 99.5, obtains molecular weight and be about 800 unsaturated polyester ether monomer a-4.
The preparation of comb-branched copolymer cement dispersants
The employing GPC of the molecular weight of multipolymer described in embodiment and the comparative example (GPC) is measured and is calculated and get, and test condition is described below, and is reference material drawing standard curve with the polyoxyethylene glycol.
The test condition of GPC is:
Gel column: Shodex SB806+803 two root chromatogram columns 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% sample
Detector: Shodex RI-71 type differential refraction detector
Standard curve making is used standard substance: polyoxyethylene glycol GPC standard specimen (Sigma-Aldrich, molecular weight 1010000,478000,263000,118000,44700,18600,6690,1960,628,232)
Comb-shaped copolymer cement dispersant is carried out with reference to standard GB 8076-2008 " concrete admixture " relevant regulations the dispersing property of cement and the test of slump hold facility.
Embodiment 1
In the 1L glass reactor of TM, whisking appliance, tap funnel and nitrogen conduit is housed, add 200g zero(ppm) water and 460g unsaturated polyester ether monomer a-1.Reactor drum is leading under the nitrogen protection, the big monomer of stirring and dissolving, and be warming up to 90 ℃, and then 58.6g vinylformic acid, 5.62g acrylic amide and 60g water are mixed to stir and process uniform monomer solution, it is at the uniform velocity dropped in the reactor drum, the dropping time is 4h.Meanwhile, at the uniform velocity drip the initiator solution that 90g contains the 2.45g Potassium Persulphate, the dropping time is 4.5h.Complete soln dropwises continued insulation 4h, is cooled to 50 ℃ then, adds 30% aqueous sodium hydroxide solution product is neutralized to about pH=7, 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 TM, whisking appliance, tap funnel and nitrogen conduit is housed, add 210g zero(ppm) water and 320g unsaturated polyester ether monomer a-2.Reactor drum is leading under the nitrogen protection, the big monomer of stirring and dissolving, and be warming up to 80 ℃; Then with 22.6g sodium acrylate, 15.6g methylene-succinic acid; Process uniform monomer solution 0.89g Thiovanic acid and 100g water mix to stir, it is at the uniform velocity dropped in the reactor drum, the dropping time is 4.5h.Meanwhile, drip the 110g aqueous solution that contains the 4.66g Sodium Persulfate and the 110g aqueous solution that contains the 0.48g sodium sulfite anhy 96 at the uniform velocity respectively, the dropping time is 5h.Complete soln dropwises continued insulation 6h, is cooled to 50 ℃ then, adds 20% ammonia soln product is neutralized to about pH=7, 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 TM, whisking appliance, tap funnel and nitrogen conduit is housed, add 200g zero(ppm) water, 380g unsaturated polyester ether monomer a-3 and 3.96g massfraction are 27.5% ydrogen peroxide 50.Reactor drum is leading under the nitrogen protection, the big monomer of stirring and dissolving, and be warming up to 45 ℃; Then with 34.2g toxilic acid, 24.7g Propylene glycol monoacrylate; Process uniform monomer solution 2.06g 3-thiohydracrylic acid and 100g water mix to stir, it is at the uniform velocity dropped in the reactor drum, the dropping time is 1h.Meanwhile, at the uniform velocity drip the aqueous solution that 120g contains the 1.75g iron vitriol, the dropping time is 1.5h.Complete soln dropwises continued insulation 2h, adds monoethanolamine then 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 TM, whisking appliance, tap funnel and nitrogen conduit is housed, add 200g zero(ppm) water and 420g unsaturated polyester ether monomer a-4.Reactor drum is under logical nitrogen protection; The big monomer of stirring and dissolving; And be warming up to 70 ℃, then with 77.3g toxilic acid disodium, 7.54g Hydroxyethyl acrylate, 15.1g sodium allyl sulfonate, 0.27g mercaptoethanol and 70g water mix to stir processes uniform monomer solution; It is at the uniform velocity dropped in the reactor drum, and the dropping time is 2h.Meanwhile, at the uniform velocity drip 76g and contain the 4.28g ammonium persulfate solution, the dropping time is 2.5h.After complete soln dropwises, be warming up to 90 ℃ and continue insulation 5h, be cooled to 50 ℃ then, add saturated calcium hydroxide aqueous solution product is neutralized to about pH=7, 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 TM, whisking appliance, tap funnel and nitrogen conduit was housed, adding 300g zero(ppm) water and 240g unsaturated polyester ether monomer a-1 and 1.74g massfraction were 27.5% ydrogen peroxide 50.Reactor drum is under logical nitrogen protection; The big monomer of stirring and dissolving, and be warming up to 65 ℃, then with 29.2g sodium acrylate, 18.2g toxilic acid; 6.58g sodium itaconate; Process uniform monomer solution 2.85g methyl acrylate and 210g water mix to stir, it is at the uniform velocity dropped in the reactor drum, the dropping time is 3h.Meanwhile, at the uniform velocity drip the aqueous solution that 180g contains 0.42g L-xitix, the dropping time is 3.5h.Complete soln dropwises continued insulation 4h, is cooled to 50 ℃ then, and the potassium hydroxide aqueous solution of middle adding 30% is neutralized to product about pH=7, obtains solid content and be 30.5% transparent liquid, and molecular weight of copolymer is determined as 46,100 through GPC.
Comparative example 1
With the 460g unsaturated polyester ether monomer a-1 that adds among the embodiment 1; Replace to that to add the 482g molecular weight be about 2200 common strand allyl polyethenoxy ether, other synthesis condition is constant, obtains solid content and be 59.5% transparent liquid; Molecular weight of copolymer is 51,200 through the GPC test.
Comparative example 2
With the 320g unsaturated polyester ether monomer a-2 that adds among the embodiment 2; Change that to add the 320g molecular weight be about 1800 common methacrylic Soxylat A 25-7 into, other synthesis condition is constant, obtains solid content and be 38.5% transparent liquid; Molecular weight of copolymer is 78,300 through the GPC test.
The synthetic comb-shaped copolymer cement dispersant is carried out with reference to standard GB 8076-2008 " concrete admixture " relevant regulations the dispersing property and the slump hold facility of cement in evaluation embodiment 1～5 and the comparative example 1～2.Test is carried out under 25 ℃ of environment, and test cement adopts little wild field, the south of the River 52.5 P.II cement, fixing water consumption, and it is 21.0 ± 1cm that the adjustment dispersant dosage makes the initial slump of fresh concrete, adopting identical skimmer to adjust concrete 's air-containing is about 3%.The volume of copolymer cement dispersant is with solid component meter, and volume is a benchmark in the weight of cement simultaneously.Test-results sees the following form:
The performance that table 1. comb-branched copolymer cement dispersants according to the invention is used for fresh concrete compares
Can find out from result shown in the table 1; 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, demonstrate good cement dispersive performance with less incorporation.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, explain that this sample has the dispersed and dispersed hold facility of cement preferably.
Claims (16)
1. unsaturated polyester ether monomer is characterized in that its chemical structure representes with general formula (I):
R in the formula
1For H or-CH
3X is a 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.
2. the monomeric preparation method of the described unsaturated polyether of claim 1 is characterized in that comprising the steps:
(1) carries out opening by compound d and the monoethanolamine shown in the formula (III), obtain the midbody e shown in the formula (IV);
(2) be initiator with midbody e, under the effect of catalyzer, carry out alkoxylation, obtain unsaturated polyester ether monomer a with the epoxide f shown in the formula V;
3. method as claimed in claim 2 is characterized in that it is 1: 1 that compound d and monoethanolamine in the step (1) are carried out the mol ratio of opening.
4. like claim 2 or 3 described methods; Its thing is levied the concrete operation method that is step 1): the compound d shown in the formula (III) is added dropwise to lentamente in the monoethanolamine that continues to stir; Dropping temperature is 60～80 ℃; The dropping time is 4～8h, and dripping end continued soaking time is 1～4h.
5. method as claimed in claim 2 is characterized in that step 2) in epoxy compounds f be the mixture of one or both arbitrary proportions in oxyethane (EO), the propylene oxide (PO).
6. method as claimed in claim 2 is characterized in that catalyst levels in the step (2) is preferably 0.05%～0.2% of products therefrom weight after the alkoxylate; Oxyalkylated temperature of reaction is preferably 110～130 ℃; Reaction pressure is preferably 0.2～0.6MPa.
7. method as claimed in claim 2 is characterized in that the intact back of alkoxylation neutralizes to the product employing organic acid that obtains, so that the product temperature is between keeping 60～90 ℃; The used mineral acid that neutralizes is preferably Glacial acetic acid min. 99.5, oxalic acid, Hydrocerol A.
8. adopt the comb-branched copolymer cement dispersants of the said unsaturated polyester ether monomer preparation of claim 1, it is characterized in that having following chemical structure:
Wherein, x, y, z represent the molecular fraction of three kinds of structural units in the multipolymer, x+y+z=100%.As preferred version, x=10%～50%, y=40%～80%, z=0～30%.
A representes with general formula (VII):
R in the formula
1For H or-CH
3X is a 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.
B representes with general formula (VIII):
R in the formula
2For Wasserstoffatoms or-COOM; R
3Be Wasserstoffatoms or methyl; M representes Wasserstoffatoms, alkalimetal ion, alkaline-earth metal ion, ammonium ion or organic amine group.
9. the weight-average molecular weight of comb-branched copolymer cement dispersants as claimed in claim 8 is controlled at 30,000～70, and 000.
10. the making method of claim 8 or 9 said comb-branched copolymer cement dispersants is characterized in that by monomer a, b, c free radicals copolymerization reaction taking place in aqueous medium, wherein:
Monomer a representes with general formula (I):
R in the formula
1For H or-CH
3X is a 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 b representes with general formula (II):
R in the formula
2For Wasserstoffatoms or-COOM; R
3Be Wasserstoffatoms or methyl; M representes Wasserstoffatoms, alkalimetal ion, alkaline-earth metal ion, ammonium ion or organic amine group.
Monomer c is the 3rd functional monomer, is selected from (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) sodium allyl sulfonate, (methyl) acrylic amide, the vinyl acetate any one.
11. method as claimed in claim 10 is characterized in that monomer a, b, the shared molecular fraction of c are respectively 10%～50%, 40%～80%, 0～30%.
12. method as claimed in claim 10; It is characterized in that monomer b is at least a material that contains in the represented material of general formula (II), be preferably at least a in vinylformic acid, methylacrylic acid, toxilic acid, fumaric acid, methylene-succinic acid or their univalent metal salt, divalent metal salt, ammonium salt, the organic amine salt.
13. method as claimed in claim 10; The initiator that it is characterized in that monomer a, b and c copolyreaction is conventional radical water soluble starter; Comprise independent persulphate, the compsn of persulphate and hydrosulphite, sulphite, thiosulphate, pyrosulfite or ferrous salt, the compsn of superoxide and L-xitix or metals ion; Initiator accounts for 0.5%～5% of monomer a+b+c total mole number, and wherein both mole ratios are 4～6: 1 in the compsn.
14. method as claimed in claim 10; It is characterized in that adding in the copolyreaction process 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; Like the mixture of at least a or its arbitrary proportion in 2 mercaptopropionic acid, 3-thiohydracrylic acid, 2-mercaprol, 3-mercaprol, Thiovanic acid, the mercaptoethanol, the consumption of chain-transfer agent in polymerization process is 0.2%～3% of monomer a+b+c total mole number.
15. method as claimed in claim 10 is characterized in that monomer weight concentration total in the copolyreaction is between 30%～60%, temperature of reaction is 40～90 ℃.
16. method as claimed in claim 10; It is characterized in that mode that monomer and initiator solution are taked separately to drip simultaneously controls the homogeneity that the multipolymer chain link distributes and the stability of polyreaction; Monomer and initiator solution dropping time were controlled at 1～5 hour, and monomer and initiator solution drip continued insulation 2～6 hours.
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