CN109942754A - The method that atom transfer radical polymerization prepares retardation setting type super plasticizer - Google Patents
The method that atom transfer radical polymerization prepares retardation setting type super plasticizer Download PDFInfo
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- CN109942754A CN109942754A CN201910162754.XA CN201910162754A CN109942754A CN 109942754 A CN109942754 A CN 109942754A CN 201910162754 A CN201910162754 A CN 201910162754A CN 109942754 A CN109942754 A CN 109942754A
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- setting type
- retardation setting
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- 239000008030 superplasticizer Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 title claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 66
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- 239000003999 initiator Substances 0.000 claims abstract description 16
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 11
- 239000003446 ligand Substances 0.000 claims abstract description 6
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 6
- 150000003624 transition metals Chemical class 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 29
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 238000010792 warming Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 230000001476 alcoholic effect Effects 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 7
- 239000006227 byproduct Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 7
- 238000010612 desalination reaction Methods 0.000 claims description 7
- 239000005457 ice water Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 6
- 238000006392 deoxygenation reaction Methods 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 5
- 239000001119 stannous chloride Substances 0.000 claims description 5
- 235000011150 stannous chloride Nutrition 0.000 claims description 5
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 4
- 229910021575 Iron(II) bromide Inorganic materials 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- -1 bromoallylene Chemical compound 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 claims description 4
- 229940046149 ferrous bromide Drugs 0.000 claims description 4
- 150000007529 inorganic bases Chemical class 0.000 claims description 4
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 claims description 4
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- JPAOMENBKRZQDR-UHFFFAOYSA-N CC=CC.[Na] Chemical compound CC=CC.[Na] JPAOMENBKRZQDR-UHFFFAOYSA-N 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 3
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 3
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- 238000010526 radical polymerization reaction Methods 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- 229960001124 trientine Drugs 0.000 claims description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- PHMRPWPDDRGGGF-UHFFFAOYSA-N 2-bromoprop-1-ene Chemical compound CC(Br)=C PHMRPWPDDRGGGF-UHFFFAOYSA-N 0.000 claims description 2
- OHXAOPZTJOUYKM-UHFFFAOYSA-N 3-Chloro-2-methylpropene Chemical compound CC(=C)CCl OHXAOPZTJOUYKM-UHFFFAOYSA-N 0.000 claims description 2
- USEGQJLHQSTGHW-UHFFFAOYSA-N 3-bromo-2-methylprop-1-ene Chemical compound CC(=C)CBr USEGQJLHQSTGHW-UHFFFAOYSA-N 0.000 claims description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- HETCEOQFVDFGSY-UHFFFAOYSA-N Isopropenyl acetate Chemical compound CC(=C)OC(C)=O HETCEOQFVDFGSY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003125 aqueous solvent Substances 0.000 claims description 2
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 claims description 2
- 125000006355 carbonyl methylene group Chemical group [H]C([H])([*:2])C([*:1])=O 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- GRFXWQHNWFFNKW-UHFFFAOYSA-N methyl 2-bromo-3-methylbut-2-enoate Chemical class COC(=O)C(Br)=C(C)C GRFXWQHNWFFNKW-UHFFFAOYSA-N 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims description 2
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 235000019260 propionic acid Nutrition 0.000 claims 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims 1
- 239000004567 concrete Substances 0.000 abstract description 23
- 239000004568 cement Substances 0.000 abstract description 22
- 239000002994 raw material Substances 0.000 abstract description 11
- 229920000570 polyether Polymers 0.000 abstract description 9
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 8
- 238000013461 design Methods 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 230000000977 initiatory effect Effects 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000003467 diminishing effect Effects 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 230000000979 retarding effect Effects 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000151 polyglycol Polymers 0.000 description 3
- 239000010695 polyglycol Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 125000005499 phosphonyl group Chemical group 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LMHAGAHDHRQIMB-UHFFFAOYSA-N 1,2-dichloro-1,2,3,3,4,4-hexafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(Cl)C1(F)Cl LMHAGAHDHRQIMB-UHFFFAOYSA-N 0.000 description 1
- LOYZVRIHVZEDMW-UHFFFAOYSA-N 1-bromo-3-methylbut-2-ene Chemical compound CC(C)=CCBr LOYZVRIHVZEDMW-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical group NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- IQEKRNXJPCBUAT-UHFFFAOYSA-N 2-[hydroperoxy(hydroxy)phosphoryl]acetic acid Chemical group OOP(O)(=O)CC(O)=O IQEKRNXJPCBUAT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to the methods that atom transfer radical polymerization prepares retardation setting type super plasticizer.The present invention uses retardation setting type monomer, carboxylic acids minor comonomer for main reaction raw materials, retardation setting type super plasticizer is prepared by the method for first atom transfer radical polymerization (ATRP) alcoholysis combined polymerization again afterwards, i.e. using retardation setting type monomer as reactant, atom transfer radical polymerization (ATRP), which is carried out, under the initiation system that unsaturated initiator, transition metal halide, ligand form obtains unsaturated polymeric monomer, then alcoholysis obtains retardation setting type polymeric monomer, then combined polymerization is made in aqueous solution with carboxylic acids minor comonomer.The present invention utilizes the technological means of controllable polymerization, innovatively design has synthesized the functional side being made of latent structural unit, instead of traditional polyether lateral chain structure, super plasticizer shows the ability of excellent dispersion cement paste, and it can significantly postpone the setting time of cement paste, the later strength for improving concrete realizes high water reduction, protects and collapse and the multi-efficiencies such as slow setting.
Description
Technical field
The present invention relates to a kind of cement concrete technical fields of retardation setting type super plasticizer, are related specifically to a kind of use
Retardation setting type monomer first carries out atom transferred free radical auto polymerization, and alcoholysis obtains retardation setting type polymeric monomer again, then with carboxylic acids minor comonomer
The specific preparation method of copolymerization retardation setting type super plasticizer.
Background technique
In recent years, with the rapid development of building industry, the dosage of cement and concrete is continuously increased, due to concrete outside
Add agent that can be obviously improved the properties of concrete, it has also become essential important component in building industry.It is many at present mixed
There is adaptability in solidifying soil additive and cement, the dispersibility and slump retaining of concrete are unstable etc., to specific
Engineering construction brings great inconvenience.In practical construction application, frequently with chemical slow release method, change polyether lateral chain length or
Person's compounded technology is to reach slump retaining requirement.However, the method for above-mentioned solution concrete slump retaining does not get rid of conventional polyether still
Molecular structure, the molecular structure limitation of concrete admixture can not be fundamentally solved, so must find can obvious postpone
It is super to enrich concrete for cement setting and the new raw material for substituting propylene oxide and ethylene oxide, synthesizing new retardation setting type super plasticizer
The type of plasticiser.
Polymer molecular structure design method using more and more extensive, for us designs synthesis in concrete admixture field
Ideal polymeric monomer molecular structure provides theoretical direction.This patent designs the big of this new concrete super plasticizer of synthesis
Monomer has polyhydroxy structure, while having both the characteristic similar to polyoxyethylene ether, and it is significant to ensure that the product of synthesis has
While steric hindrance dispersibility, shows good slow setting, protects effect of collapsing.The retardation setting type super plasticizer of the method synthesis is not
Only with the various performances of conventional set retarder, while also the diminishing with high-performance water reducing agent protects characteristic of collapsing, diversification of feedstock, side
Method is simply controllable, there is wide application value.
Patent CN104945634A (publication date: on 09 30th, 2015) reports a kind of urethane type slow setting polycarboxylic-acid and subtracts
The preparation method of aqua.The patent carries out normal temperature oxidation-first with unsaturated acids minor comonomer and hydroxyl unsaturation minor comonomer
Reduction Raolical polymerizable obtains hydroxyl copolymerization product；Then excessive diisocyanate will be added in poly glycol monomethyl ether
In ester, reaction obtains poly glycol monomethyl ether monoisocyanates under the effect of the catalyst；Finally obtained hydroxyl is copolymerized
Product is reacted with poly glycol monomethyl ether monoisocyanates, with alkali neutralization adjustment pH value up to urethane type slow setting polycarboxylic acids after reaction
Based water reducer.The advantages of patent is reaction process without using organic solvent, and nontoxic and pollution-free, easy to operate, properties of product are steady
It is fixed, but polymeric monomer used in the invention is still common polyether structure, chemical structure still belongs to esters super plasticizer scope, is not implemented
Essence on molecular structure is broken through.
Patent CN108276533A (publication date: on 07 13rd, 2018) reports a kind of high adaptive polycarboxylate water-reducer
And preparation method thereof.The invention is by polyether macromonomer, unsaturated carboxylic acid monomer and unsaturated esters monomer containing phosphonyl group
The free-radical polymerized synthesis under aqueous solution.The advantages of invention is: synthetic method is simple, to the adaptability of concrete raw material
By force, there is excellent diminishing and retarding effect.But the unsaturated esters monomer containing phosphonyl group described in the invention is by secondary nitrogen
The reaction product of base triacetic acid and phosphorous acid and isomery unsaturated alcohol are esterified generation, higher cost and big list used at high temperature
The raw material of body is still ethylene oxide, strong by raw material restriction.
Patent CN107987227A (publication date: on May 04th, 2018) reports a kind of poly- carboxylic of low hydration heat extra retarded set type
The preparation method of sour water-reducing agent.The invention passes through acylated esterification, and monomer blend, copolyreaction and four step of neutralization reaction are anti-
It answers, the diminishing agent molecule containing 1-hydroxy ethylidene-1,1-diphosphonic acid and/or 2- hydroxyphosphonoacetic acid structure is prepared, in concrete alkalinity item
The 1-hydroxy ethylidene-1,1-diphosphonic acid and/or 2- hydroxyphosphonoacetic acid with extra retarded set effect gradually released under part, so that product
With excellent extra retarded set effect.The advantages of invention is that gained water-reducing agent can have simultaneously preferable diminishing, retarding effect simultaneously
Reduce the release of hydrated cementitious heat, but the inventive method complex steps and acylated esterification reaction product is mixture, it is unknown
Proportion of products larger uncertainty is brought to subsequent applications, while main component is still traditional polyether macromonomer in raw material.
Have at present the super plasticizer that more patent report is invented have good mobility, slow setting and guarantor collapse etc. it is comprehensive
Close effect.However, there is a degree of shortcoming in above-mentioned preparation method, polymeric monomer sheet used in super plasticizer is synthesized
Polyethers polymeric monomer is still fallen in matter, is required to rely on ethylene oxide or propylene oxide is made, raw material variety is too single, synthesis
Method is also more harsh, and the molecular structure of Concrete superplastizer can not fundamentally be driven to innovate.So this just there is an urgent need to
It synthesizes the completely new polymeric monomer structure of one kind and substitutes traditional polyether structure obtained by propylene oxide and ethylene oxide, and pass through
The synthetic method of atom transfer radical polymerization is precisely controlled molecular structure, makes the main chain and functional side chain of the super plasticizer of synthesis
Group can play the composite efficacy of diminishing and slow setting, while also ensure simple and direct technological operation and cheap preparation cost,
Easy to industrialized production, related this respect work has not been reported both at home and abroad.
Summary of the invention
The present invention uses retardation setting type monomer, carboxylic acids minor comonomer for main reaction raw materials, passes through first atom transferred free radical
The method of polymerization (ATRP) alcoholysis combined polymerization again afterwards prepares retardation setting type super plasticizer, i.e., using retardation setting type monomer as reactant, not
Progress atom transfer radical polymerization (ATRP) under the initiation system of initiator, transition metal halide, ligand composition is saturated to obtain
To unsaturated polymeric monomer, then alcoholysis obtains retardation setting type polymeric monomer, then combined polymerization is made in aqueous solution with carboxylic acids minor comonomer.
The present invention utilizes the technological means of controllable polymerization, and innovatively design has synthesized the functional side being made of latent structural unit
Chain, instead of traditional polyether lateral chain structure, the retardation setting type super plasticizer finally prepared shows excellent dispersion cement paste
Ability, and can significantly postpone the setting time of cement paste, improve the later strength of concrete, realize high water reduction,
Guarantor is collapsed and the multi-efficiencies such as slow setting, has huge potentiality to be exploited and wide application prospect.
1. the retardation setting type super plasticizer of atom transfer radical polymerization preparation, which is characterized in that its molecular structural formula is as follows:
Wherein, a is the integer of 10-150, and b is the integer of 3-50, and n is the integer of 10-150；R1For H, CH3Or CH2COOM,
Wherein M is H or alkali metal；R2For H or COOM, wherein M is H or alkali metal, but R1And R2COOM cannot be contained simultaneously；R3For NH2
Or OM, wherein M is H or alkali metal；R4、R6、R8For H or CH3；R5For H, CH3Or COOM, wherein M is H or alkali metal；R7For nothing
(both ends carbon is connected directly), CH2Or COCH2, and work as R5When for COOM, R7It is only without (both ends carbon is connected directly)；R9For Br or
Cl。
2. the method that atom transfer radical polymerization prepares retardation setting type super plasticizer, which is characterized in that turned by first atom
Move the free radical polymerization method that alcoholysis obtains the then combined polymerization of retardation setting type polymeric monomer again prepare retardation setting type super plasticizer condition and
Steps are as follows:
(1) atom transition free radical polymerization reaction: first retardation setting type monomer is uniformly mixed to be added with organic solvent and is reacted
In device, then unsaturated initiator, transition metal halide, ligand be added thereto, inflated with nitrogen is repeatedly in ice-water bath for reactor
After 3-5 deoxygenation 10-30 minutes, it is uniformly mixed to it within stirring 10-30 minutes, sealing is continuously heating to 10-100 under nitrogen protection
Carry out polymerization reaction at DEG C, react 5-60 hour, desalination and be evaporated under reduced pressure slough organic solvent after up to unsaturation polymeric monomer；
(2) alcoholysis reaction: unsaturation polymeric monomer obtained in step (1) is added in alcoholic solvent, stirs and is warming up to 30-
70 DEG C, the inorganic base aqueous solution that mass fraction is 20-50% is added, after alcoholysis 10-120 minutes, alcoholic solvent is sloughed in vacuum distillation
And by-product, obtain retardation setting type polymeric monomer；
(3) copolymerization: retardation setting type polymeric monomer obtained in step (2) is dissolved in aqueous solvent, and chain-transferring agent is added,
It stirs and is warming up to 50-90 DEG C, carboxylic acids minor comonomer is added, then the initiator solution 1-5 that mass fraction is 5-20% is added dropwise
Hour, continue isothermal reaction 1-5 hours after completion of dropwise addition, be cooled to 25-40 DEG C, adds the alkali that mass fraction is 20-50%
Property solution be neutralized to pH value be 6-8, be eventually adding the retardation setting type super plasticizer solution that water obtains required concentration；
Wherein, organic solvent described in step (1) is toluene, paraxylene, dimethylformamide or ethyl alcohol, dosage and slow
The mass ratio of solidifying type monomer is 2-10:1；Retardation setting type monomer described in step (1) is vinyl acetate, methylvinyl acetate, third
The molar ratio of the one or more of vinyl acetate or vinyl butyrate, dosage and unsaturated initiator is 10-200:1；Step (1)
Described in unsaturated initiator be methallyl bromide, allyl bromide, bromoallylene, methallyl chloride, allyl chloride, the bromo- 3- first of 1-
Base -2- butylene, 1,3,2-CMB, 2- bromopropene acetoacetic ester, the bromo- 3- methylcrotonic acid methyl esters of 2-, the bromo- 4- first of 1-
The one or more of base -3- amylene -2- ketone or the chloro- 4- methyl -3- amylene -2- ketone of 1-；Transition metal halogen described in step (1)
Compound is the one or more of cuprous bromide, stannous chloride, ferrous bromide or frerrous chloride, described in dosage and step (1)
The molar ratio of unsaturated initiator is 1-4:1；Ligand described in step (1) is N, N, N, N, N- pentamethyl divinyl three
Amine, 2,2- bipyridyl, 1,1,4,7,10,10- hexamethyl trien, N, N, N, N- tetra- [(2- pyridyl group) methyl] second two
The one or more of amine or three [2- (dimethylamino) ethyl] amine, dosage are rubbed with unsaturated initiator described in step (1)
You are than being 1-6:1；The salt sloughed described in step (1) is cuprous bromide, copper chloride, copper bromide, ferric bromide, stannous chloride, chlorine
Change the one or more of iron, ferrous bromide or frerrous chloride；
Alcoholic solvent described in step (2) is methanol, ethyl alcohol or propyl alcohol, retardation setting type list described in dosage and step (1)
The molar ratio of body is 2-5:1；Inorganic base described in step (2) is sodium hydroxide or potassium hydroxide, and dosage and alcoholic solvent rub
You are than being 0.001-0.01:1；
Obtained retardation setting type polymeric monomer mass ratio is 0.8- in solvent water consumption described in step (3) and step (2)
1.2:1；Chain-transferring agent described in step (3) is thioacetic acid, mercaptopropionic acid or methylpropene sodium sulfonate, dosage and step
(2) obtained retardation setting type polymeric monomer molar ratio is 0.05-0.3:1 in；Carboxylic acids minor comonomer described in step (3) is methyl
The one or more of acrylic acid, acrylic acid, acrylamide, itaconic acid, maleic anhydride or fumaric acid, dosage are obtained with step (2)
The retardation setting type polymeric monomer molar ratio arrived is 3-10:1；The solute of initiator solution described in step (3) is ammonium persulfate, mistake
Potassium sulfate, sodium peroxydisulfate or hydrogen peroxide, solute dosage are 0.05- with obtained retardation setting type polymeric monomer molar ratio in step (2)
0.3:1；The solute of alkaline solution described in step (3) is potassium hydroxide or sodium hydroxide, institute in solute dosage and step (3)
The molar ratio of the carboxylic acids minor comonomer of addition is 0.8-2:1.
The method of the present invention has the advantages that compared with prior art
1. being based on polymer molecular structure design theory, the present invention synthesizes unsaturation in a manner of atom transfer radical polymerization
Polymeric monomer synthesizes retardation setting type polymeric monomer through alcoholysis, then is polymerized to using polyalkenylalcohols be side chain, polycarboxylic acids for main chain with carboxylic acid minor comonomer
Retardation setting type super plasticizer, structure is different from traditional combed polycarboxylic acid super-plasticizer, be on concrete admixture direction again
Primary innovation and breakthrough have widened thinking and direction for subsequent deep level development new varieties concrete admixture.
2. the retardation setting type super plasticizer of synthesis has the structure of pectination, main chain is adsorbed on cement particle surface, polyalkenylalcohols
The great amount of hydroxy group structure that side chain contains can form hydrogen bond and reach good retarding effect while have both good steric hindrance effect
It answers, has good effect improving flowing degree of net paste of cement and its holding, delaying cement setting and protecting landslide face.
3. the synthetic method of this product is compared with traditional polycarboxylic acid super-plasticizer, atom transfer radical polymerization method more may be used
Control, raw materials required for the reaction is more common is easy to get, cheap, special operation and expensive reagent is not necessarily to, to equipment and experimental situation
Without particular/special requirement, it is easy to accomplish industrialized production.
4. this product preparation process is controllable, environmentally protective, mild condition, raw material sources are extensive and cheap, can effectively put
De- Concrete superplastizer industry is to the dependence of propylene oxide and ethylene oxide raw material, before improving product competitiveness and development
Scape.
5. ability that the retardation setting type super plasticizer that the present invention synthesizes disperses with good diminishing and guarantor is collapsed, is incorporated into cement slurry
Excellent workability can be shown in body and significantly delays condensation and other effects.While the synthetic method is simply controllable, close
At product still there is excellent performance indexes, have biggish application market and potentiality.
Specific embodiment
The present invention is described in further detail below with reference to embodiment, but implementation of the invention is without being limited thereto.
Embodiment 1
4.31g vinyl acetate, 5.71g vinyl butyrate are added in the reactor of the toluene containing 86.09g first, again will
1.21g allyl bromide, bromoallylene, 4.31g cuprous bromide, 6.85gN, N, N, N, N- pentamethyldivinyltriamine are added thereto, reactor
Inflated with nitrogen is uniformly mixed to it repeatedly after 3 deoxygenations 30 minutes, seals and continue under nitrogen protection for stirring 18 minutes in ice-water bath
It is warming up at 30 DEG C and carries out polymerization reaction, react 50 hours, desalination and being evaporated under reduced pressure is sloughed after solvent up to unsaturated polymeric monomer；
Gained unsaturation polymeric monomer is added in 12.82g methanol, stirring is warming up to 60 DEG C, and the hydrogen that 1.92g mass fraction is 50% is added
Aqueous solution of sodium oxide alcoholysis 30 minutes, is evaporated under reduced pressure after the completion of alcoholysis and sloughs solvent and by-product, obtain retardation setting type polymeric monomer；
Finally retardation setting type polymeric monomer is dissolved in 6.73g water, 0.28g thioacetic acid is added, stir and is warming up to 90 DEG C, addition 2.16g
Acrylic acid, then it is ammonium persulfate aqueous solution 1 hour of 5% that 10.04g mass fraction, which is added dropwise, continues isothermal reaction 4 after completion of dropwise addition
Hour, be cooled to 25 DEG C, adding the potassium hydroxide aqueous solution that 3.36g mass fraction is 40% and being neutralized to pH value is 8, finally plus
Enter 9.14g water and obtains the retardation setting type super plasticizer solution that concentration is 20%.
Embodiment 2
The retardation setting type super plasticizer solution of 20% mass percent concentration obtained in embodiment 1 is stored 15 at 6 DEG C
After it, its implementation result is measured.
Embodiment 3
50.06g vinyl propionate is added first in the reactor of the paraxylene containing 400g, again by 0.91g methallyl
Base chlorine, 0.99g stannous chloride, 0.72g cuprous bromide, 2.34g2,2- bipyridyl are added thereto, reactor nitrogen charging in ice-water bath
Gas is uniformly mixed repeatedly after 5 deoxygenations 25 minutes for stirring 30 minutes to it, under nitrogen protection sealing be continuously heating at 50 DEG C into
Row polymerization reaction is reacted 30 hours, and desalination and being evaporated under reduced pressure is sloughed after solvent up to unsaturated polymeric monomer；Gained is unsaturated big
Monomer is added in 103.66g ethyl alcohol, and stirring is warming up to 40 DEG C, and the potassium hydroxide aqueous solution that 1.89g mass fraction is 20% is added,
It alcoholysis 80 minutes, is evaporated under reduced pressure after the completion of alcoholysis and sloughs solvent and by-product, obtain retardation setting type polymeric monomer；It is finally that retardation setting type is big
Monomer is dissolved in 22.91g water, and 0.26g mercaptopropionic acid is added, and is stirred and is warming up to 60 DEG C, and 4.31g methacrylic acid is added, then
Persulfate aqueous solution 4 hours that 5.41g mass fraction is 10% are added dropwise, continue isothermal reaction 2 hours after completion of dropwise addition, it is cooling
To 40 DEG C, adding the sodium hydrate aqueous solution that 15g mass fraction is 20% and being neutralized to pH value is 7, is eventually adding 63.76g water
Obtain the retardation setting type super plasticizer solution that concentration is 30%.
Embodiment 4
The retardation setting type super plasticizer solution of 30% mass percent concentration obtained in embodiment 3 is stored 20 at 10 DEG C
After it, its implementation result is measured.
Embodiment 5
114.14g vinyl butyrate is added first in the reactor of the dimethylformamide containing 570.7g, again by 1.49g1-
It is added in bromo- 3- methyl-2-butene, 8.63g ferrous bromide, 13.82g1,1,4,7,10,10- hexamethyl trien
In, reactor inflated with nitrogen in ice-water bath is uniformly mixed, nitrogen protection repeatedly after 4 deoxygenations 15 minutes for stirring 25 minutes to it
Lower sealing is continuously heating to carry out polymerization reaction at 60 DEG C, reacts 20 hours, and desalination and being evaporated under reduced pressure is sloughed after solvent up to not
It is saturated polymeric monomer；Gained unsaturation polymeric monomer is added in 180.21g propyl alcohol, stirring is warming up to 30 DEG C, and 4g mass fraction is added
For 30% sodium hydrate aqueous solution, alcoholysis 120 minutes, it is evaporated under reduced pressure after the completion of alcoholysis and sloughs solvent and by-product, delayed
Solidifying type polymeric monomer；Finally retardation setting type polymeric monomer is dissolved in 40.94g water, 0.32g methylpropene sodium sulfonate is added, stirs and rises
5.69g acrylamide is added to 80 DEG C in temperature, then it is sodium persulfate aqueous solution 2 hours of 20% that 3.57g mass fraction, which is added dropwise, is dripped
Continue isothermal reaction 5 hours after adding, be cooled to 30 DEG C, it is water-soluble to add the potassium hydroxide that 15.36g mass fraction is 35%
It is 8 that liquid, which is neutralized to pH value, and finally plus 31.85g water is the retardation setting type super plasticizer solution for obtaining concentration and being 45%.
Embodiment 6
The retardation setting type super plasticizer solution of 45% mass percent concentration obtained in embodiment 5 is stored 30 at 6 DEG C
After it, its implementation result is measured.
Embodiment 7
129.14g vinyl acetate is added first in the reactor of the ethyl alcohol containing 387.41g, again by 1.79g2- bromopropene
Acetoacetic ester, 3.17g frerrous chloride, 16.98g tetra- [(2- pyridyl group) methyl] ethylenediamine are added thereto, and reactor is in ice-water bath
3 deoxygenations after ten minutes, are uniformly mixed, sealing is continuously heating to 100 under nitrogen protection inflated with nitrogen for stirring 28 minutes to it repeatedly
Carry out polymerization reaction at DEG C, react 5 hours, desalination and be evaporated under reduced pressure slough solvent after up to unsaturated polymeric monomer；Not by gained
It is saturated monomer to be added in 240.3g methanol, stirring is warming up to 70 DEG C, and it is water-soluble that the potassium hydroxide that 1.05g mass fraction is 40% is added
Liquid alcoholysis 10 minutes, is evaporated under reduced pressure after the completion of alcoholysis and sloughs solvent and by-product, obtain retardation setting type polymeric monomer；Finally by slow setting
Type polymeric monomer is dissolved in 74.57g water, and 0.14g thioacetic acid is added, and is stirred and is warming up to 50 DEG C, and 4.64g fumaric acid is added, then
Aqueous hydrogen peroxide solution 5 hours that 0.1g mass fraction is 18% are added dropwise, continues isothermal reaction 1 hour after completion of dropwise addition, is cooled to
35 DEG C, adding the sodium hydrate aqueous solution that 7.11g mass fraction is 45% and being neutralized to pH value is 6, is eventually adding 5.77g water i.e.
Obtain the retardation setting type super plasticizer solution that concentration is 40%.
Embodiment 8
The retardation setting type super plasticizer solution of 40% mass percent concentration obtained in embodiment 7 is stored 30 at 10 DEG C
After it, its implementation result is measured.
Embodiment 9
200.24g vinyl propionate is added first in the reactor of the dimethylformamide containing 400.48g, again will
The chloro- 4- methyl -3- amylene -2- ketone of 1.34g1-, 2.87g cuprous bromide, 4.26g tri- [2- (dimethylamino) ethyl] amine,
2.31g1, Isosorbide-5-Nitrae, 7,10,10- hexamethyl triens are added thereto, and reactor inflated with nitrogen in ice-water bath removes for 5 times repeatedly
After oxygen 22 minutes, it is uniformly mixed to it within stirring 10 minutes, sealing is continuously heating to carry out polymerization reaction at 10 DEG C under nitrogen protection,
Reaction 60 hours, desalination and being evaporated under reduced pressure are sloughed after solvent up to unsaturated polymeric monomer；Gained unsaturation polymeric monomer is added
In 240.28g propyl alcohol, stirring is warming up to 50 DEG C, and the sodium hydrate aqueous solution that 1.78g mass fraction is 45% is added, and alcoholysis 50 divides
Clock is evaporated under reduced pressure after the completion of alcoholysis and sloughs solvent and by-product, obtains retardation setting type polymeric monomer；Finally retardation setting type polymeric monomer is dissolved in
In 71.45g water, 0.05g mercaptopropionic acid is added, stirs and is warming up to 70 DEG C, 7.21g acrylic acid is added, then 1.52g mass is added dropwise
Score is ammonium persulfate aqueous solution 3 hours of 15%, continues isothermal reaction 3 hours after completion of dropwise addition, is cooled to 28 DEG C, adds
It is 7 that the potassium hydroxide aqueous solution that 11.2g mass fraction is 50%, which is neutralized to pH value, is eventually adding 11.32g water and obtains concentration and is
50% retardation setting type super plasticizer solution.
Embodiment 10
The retardation setting type super plasticizer solution of 50% mass percent concentration obtained in embodiment 9 is stored 30 at 6 DEG C
After it, its implementation result is measured.
Implementation result:
1. flowing degree of net paste of cement
To investigate the retardation setting type super plasticizer solution of the invention synthesized to the mobility function and effect of cement, test is determined
Paste flowing degree of each embodiment to reference cement under identical volume.By GB/T8077-2012, " concrete admixture is even for test
Matter test method " it carries out, W/C=0.29, volume is to roll over solid volume.Select existing commercially available traditional super modeling of comb shape polycarboxylic-acid
Agent (comparative example) is as a comparison sample, and test result is shown in Table 1.
1 pulp flowage results of property of table
From table 1 it follows that the method for the present invention synthesis retardation setting type super plasticizer solution, 0.29 the ratio of mud and
0.15% folding is consolidated under volume, and excellent dispersibility and cement adaptability can be shown.
2. cement setting time
To investigate the retardation setting type super plasticizer solution of the invention synthesized to the retarding effect of cement, test is determined identical
Setting time of each embodiment to reference cement under volume.By GB/T1346-2011, " cement normal consistency water consumption coagulates for test
Tie time, stability detection method " it carries out, W/C=0.29, volume is to roll over solid volume.Select existing commercially available traditional comb shape poly-
Carboxylic acid series super plasticizer (comparative example) is as a comparison sample, and test result is shown in Table 2.
2 cement setting time of table
From Table 2, it can be seen that the retardation setting type super plasticizer solution of the method for the present invention synthesis can extend cement setting time,
With apparent retarding effect.
3. concrete performance
Test determines the slump, divergence and its retention property that each embodiment is shown in concrete system and resists
Compressive Strength, test result are shown in Table 3.
3 concrete flowability energy result of table
From table 3 it is observed that the retardation setting type super plasticizer solution of the method for the present invention synthesis shows in concrete system
The preferable slump, divergence and its holding capacity and later strength out.
Claims (2)
1. retardation setting type super plasticizer, which is characterized in that its molecular structural formula is as follows:
Wherein, a is the integer of 10-150, and b is the integer of 3-50, and n is the integer of 10-150；R1For H, CH3Or CH2COOM, wherein
M is H or alkali metal；R2For H or COOM, wherein M is H or alkali metal, but R1And R2COOM cannot be contained simultaneously；R3For NH2Or OM,
Wherein M is H or alkali metal；R4、R6、R8For H or CH3；R5For H, CH3Or COOM, wherein M is H or alkali metal；R7For nothing, CH2Or
COCH2, and work as R5When for COOM, R7It is only nothing；R9For Br or Cl.
2. the method that atom transfer radical polymerization prepares retardation setting type super plasticizer as described in claim 1, which is characterized in that step
It is rapid as follows:
(1) retardation setting type monomer: being uniformly mixed with organic solvent be added in reactor first by atom transition free radical polymerization reaction,
Unsaturated initiator, transition metal halide, ligand are added thereto again, reactor inflated with nitrogen 3-5 times repeatedly in ice-water bath
After deoxygenation 10-30 minutes, it is uniformly mixed to it within stirring 10-30 minutes, sealing is continuously heating at 10-100 DEG C under nitrogen protection
Polymerization reaction is carried out, is reacted 5-60 hour, desalination and being evaporated under reduced pressure is sloughed after organic solvent up to unsaturation polymeric monomer；
(2) alcoholysis reaction: unsaturation polymeric monomer obtained in step (1) is added in alcoholic solvent, stirs and is warming up to 30-70
DEG C, be added mass fraction be 20-50% inorganic base aqueous solution, after alcoholysis 10-120 minute, be evaporated under reduced pressure slough alcoholic solvent and
By-product obtains retardation setting type polymeric monomer；
(3) copolymerization: retardation setting type polymeric monomer obtained in step (2) is dissolved in aqueous solvent, and chain-transferring agent, stirring is added
And it is warming up to 50-90 DEG C, carboxylic acids minor comonomer is added, then it is initiator solution 1-5 hours of 5-20% that mass fraction, which is added dropwise,
Continue isothermal reaction 1-5 hours after completion of dropwise addition, be cooled to 25-40 DEG C, adds the alkaline solution that mass fraction is 20-50%
Being neutralized to pH value is 6-8, is eventually adding the retardation setting type super plasticizer solution that water obtains required concentration；
Wherein, organic solvent described in step (1) is toluene, paraxylene, dimethylformamide or ethyl alcohol, dosage and retardation setting type
The mass ratio of monomer is 2-10:1；Retardation setting type monomer described in step (1) is vinyl acetate, methylvinyl acetate, propionic acid second
The molar ratio of the one or more of enester or vinyl butyrate, dosage and unsaturated initiator is 10-200:1；Institute in step (1)
The unsaturated initiator stated is methallyl bromide, allyl bromide, bromoallylene, methallyl chloride, allyl chloride, the bromo- 3- methyl -2- of 1-
Butylene, 1,3,2-CMB, 2- bromopropene acetoacetic ester, the bromo- 3- methylcrotonic acid methyl esters of 2-, the bromo- 4- methyl -3- penta of 1-
The one or more of alkene -2- ketone or the chloro- 4- methyl -3- amylene -2- ketone of 1-；Transition metal halide described in step (1) is
The one or more of cuprous bromide, stannous chloride, ferrous bromide or frerrous chloride, unsaturation described in dosage and step (1)
The molar ratio of initiator is 1-4:1；Ligand described in step (1) is N, N, N, N, N- pentamethyldivinyltriamine, 2,2-
Bipyridyl, 1,1,4,7,10,10- hexamethyl trien, N, N, N, N- tetra- [(2- pyridyl group) methyl] ethylenediamine or three
The one or more of [2- (dimethylamino) ethyl] amine, dosage and the molar ratio of unsaturated initiator described in step (1) are
1-6:1；The salt sloughed described in step (1) is cuprous bromide, copper chloride, copper bromide, ferric bromide, stannous chloride, iron chloride, bromine
Change ferrous or frerrous chloride one or more；
Alcoholic solvent described in step (2) is methanol, ethyl alcohol or propyl alcohol, retardation setting type monomer described in dosage and step (1)
Molar ratio is 2-5:1；Inorganic base described in step (2) is sodium hydroxide or potassium hydroxide, the molar ratio of dosage and alcoholic solvent
For 0.001-0.01:1；
Obtained retardation setting type polymeric monomer mass ratio is 0.8-1.2 in solvent water consumption described in step (3) and step (2):
1；Chain-transferring agent described in step (3) is thioacetic acid, mercaptopropionic acid or methylpropene sodium sulfonate, in dosage and step (2)
Obtained retardation setting type polymeric monomer molar ratio is 0.05-0.3:1；Carboxylic acids minor comonomer described in step (3) is metering system
The one or more of acid, acrylic acid, acrylamide, itaconic acid, maleic anhydride or fumaric acid, obtained in dosage and step (2)
Retardation setting type polymeric monomer molar ratio is 3-10:1；The solute of initiator solution described in step (3) is ammonium persulfate, persulfuric acid
Potassium, sodium peroxydisulfate or hydrogen peroxide, solute dosage are 0.05-0.3 with obtained retardation setting type polymeric monomer molar ratio in step (2):
1；The solute of alkaline solution described in step (3) is potassium hydroxide or sodium hydroxide, is added in solute dosage and step (3)
Carboxylic acids minor comonomer molar ratio be 0.8-2:1.
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| CN110845654A (en) * | 2019-11-18 | 2020-02-28 | 江苏博思通新材料有限公司 | Preparation method of polyhydroxy air-entraining type retarder for concrete |
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| CN109942754B (en) | 2021-06-25 |
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