CN109942220B - Preparation method of salt-resistant amphoteric polycarboxylic acid high-performance water reducing agent - Google Patents
Preparation method of salt-resistant amphoteric polycarboxylic acid high-performance water reducing agent Download PDFInfo
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- CN109942220B CN109942220B CN201910162764.3A CN201910162764A CN109942220B CN 109942220 B CN109942220 B CN 109942220B CN 201910162764 A CN201910162764 A CN 201910162764A CN 109942220 B CN109942220 B CN 109942220B
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- chloride
- unsaturated
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- bromide
- reducing agent
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 57
- 239000002253 acid Substances 0.000 title claims abstract description 43
- 150000003839 salts Chemical class 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 125000002091 cationic group Chemical group 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 24
- 239000003999 initiator Substances 0.000 claims abstract description 22
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 10
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 10
- 150000003624 transition metals Chemical class 0.000 claims abstract description 10
- -1 unsaturated cationic quaternary ammonium salt Chemical class 0.000 claims abstract description 10
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 16
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 14
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 14
- 229910021575 Iron(II) bromide Inorganic materials 0.000 claims description 12
- 229940046149 ferrous bromide Drugs 0.000 claims description 12
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 claims description 12
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 11
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 11
- 229940045803 cuprous chloride Drugs 0.000 claims description 11
- 229960002089 ferrous chloride Drugs 0.000 claims description 11
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 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
- VMGSQCIDWAUGLQ-UHFFFAOYSA-N n',n'-bis[2-(dimethylamino)ethyl]-n,n-dimethylethane-1,2-diamine Chemical compound CN(C)CCN(CCN(C)C)CCN(C)C VMGSQCIDWAUGLQ-UHFFFAOYSA-N 0.000 claims description 8
- DWFKOMDBEKIATP-UHFFFAOYSA-N n'-[2-[2-(dimethylamino)ethyl-methylamino]ethyl]-n,n,n'-trimethylethane-1,2-diamine Chemical compound CN(C)CCN(C)CCN(C)CCN(C)C DWFKOMDBEKIATP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000005457 ice water Substances 0.000 claims description 7
- JAOSYYPULNBONK-UHFFFAOYSA-N n'-(pyridin-2-ylmethyl)ethane-1,2-diamine Chemical compound NCCNCC1=CC=CC=N1 JAOSYYPULNBONK-UHFFFAOYSA-N 0.000 claims description 7
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 7
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000011033 desalting Methods 0.000 claims description 5
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims description 5
- LOYZVRIHVZEDMW-UHFFFAOYSA-N 1-bromo-3-methylbut-2-ene Chemical compound CC(C)=CCBr LOYZVRIHVZEDMW-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- ZGCZDEVLEULNLJ-UHFFFAOYSA-M benzyl-dimethyl-(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C=CC(=O)OCC[N+](C)(C)CC1=CC=CC=C1 ZGCZDEVLEULNLJ-UHFFFAOYSA-M 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 claims description 4
- TZYULTYGSBAILI-UHFFFAOYSA-M trimethyl(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC=C TZYULTYGSBAILI-UHFFFAOYSA-M 0.000 claims description 4
- MMJRFDNQONQATR-UHFFFAOYSA-N 1-chloro-4-methylpent-3-en-2-one Chemical compound CC(C)=CC(=O)CCl MMJRFDNQONQATR-UHFFFAOYSA-N 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- OHXAOPZTJOUYKM-UHFFFAOYSA-N 3-Chloro-2-methylpropene Chemical compound CC(=C)CCl OHXAOPZTJOUYKM-UHFFFAOYSA-N 0.000 claims description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 claims description 3
- UCDOJQCUOURTPS-UHFFFAOYSA-N ethyl 2-bromoprop-2-enoate Chemical compound CCOC(=O)C(Br)=C UCDOJQCUOURTPS-UHFFFAOYSA-N 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-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
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 claims description 3
- OIFLLGNCLZLPAF-UHFFFAOYSA-M trimethyl-(5-methyl-4-oxohex-5-enyl)azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)CCC[N+](C)(C)C OIFLLGNCLZLPAF-UHFFFAOYSA-M 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- ZDGHPWNIHFBZIE-UHFFFAOYSA-N 1-bromo-4-methylpent-3-en-2-one Chemical compound CC(C)=CC(=O)CBr ZDGHPWNIHFBZIE-UHFFFAOYSA-N 0.000 claims description 2
- JKXQKGNGJVZKFA-UHFFFAOYSA-N 1-chloro-3-methylbut-2-ene Chemical compound CC(C)=CCCl JKXQKGNGJVZKFA-UHFFFAOYSA-N 0.000 claims description 2
- 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
- USEGQJLHQSTGHW-UHFFFAOYSA-N 3-bromo-2-methylprop-1-ene Chemical compound CC(=C)CBr USEGQJLHQSTGHW-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims description 2
- 229910021590 Copper(II) bromide Inorganic materials 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 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
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- 229940032296 ferric chloride Drugs 0.000 claims description 2
- LXBZUPCFTQRHSP-UHFFFAOYSA-M hexyl-bis(methylamino)-(2-methylprop-2-enoyloxy)azanium bromide Chemical compound [Br-].C(CCCCC)[N+](NC)(NC)OC(C(=C)C)=O LXBZUPCFTQRHSP-UHFFFAOYSA-M 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 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
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 10
- 229920000570 polyether Polymers 0.000 abstract description 10
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 6
- 238000013461 design Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 150000003254 radicals Chemical class 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 238000006467 substitution reaction Methods 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 239000004568 cement Substances 0.000 description 18
- 230000000694 effects Effects 0.000 description 9
- 229920005646 polycarboxylate Polymers 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000008030 superplasticizer Substances 0.000 description 6
- 125000000129 anionic group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000858 Cyclodextrin Polymers 0.000 description 2
- 238000007059 Strecker synthesis reaction Methods 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention relates to a preparation method of a salt-tolerant amphoteric polycarboxylic acid high-performance water reducing agent. The salt-resistant amphoteric polycarboxylic acid high-performance water reducing agent is synthesized by taking an unsaturated cationic quaternary ammonium salt monomer, an unsaturated small monomer, an unsaturated initiator, a transition metal complex and the like as main raw materials through a method of self-polymerization and graft copolymerization, namely, the salt-resistant amphoteric polycarboxylic acid high-performance water reducing agent is prepared by taking the unsaturated cationic quaternary ammonium salt monomer as a reactant, carrying out Atom Transfer Radical Polymerization (ATRP) under a system consisting of the unsaturated initiator and the transition metal complex to obtain a cationic large monomer, and then carrying out free radical graft copolymerization with the unsaturated small monomer under the action of the initiator and a chain transfer agent. The invention carries out innovative design and synthesis of molecular structure based on the principles of traditional free radical polymerization and atom transfer free radical polymerization, the prepared water reducing agent has the advantage of keeping good dispersibility under the condition of high-concentration salt, the process is simple, the process is controllable, energy is saved, environment is protected, and the cationization substitution of the traditional polyether side chain is realized.
Description
Technical Field
The invention relates to the technical field of water reducing agents for cement concrete, in particular to a specific preparation method for synthesizing a salt-resistant amphoteric polycarboxylic acid high-performance water reducing agent by self-polymerization of unsaturated cationic quaternary ammonium salt monomers to obtain cationic macromonomers and graft copolymerization.
Background
The polycarboxylic acid high-performance water reducing agent has the advantages of low mixing amount, high water reducing rate, good slump retaining property, strong designability of molecular structure and the like, and becomes an important component of concrete admixture. The common polycarboxylic acid water reducing agent has main chains of-COOH and-SO3H and the like, and the side chain is a comb-shaped structure polymer of polyether, but the spatial configuration of the traditional comb-shaped structure polycarboxylate superplasticizer is easily influenced by cement or high-concentration salt ions in the external environment, so that the adsorption rate is slow, the side chain is seriously curled, and the sufficient side chain steric hindrance effect cannot be realized, so that the performances such as workability are reduced, and the application of the polycarboxylate superplasticizer in practical engineering is hindered.
With the continuous maturity of a molecular structure design method, the amphoteric comb-shaped concrete water reducer is creatively designed and synthesized based on the structural designable characteristics of the polycarboxylate water reducer. The amphoteric comb-shaped concrete water reducing agent has a molecular structure with cationic and anionic groups, is beneficial to solving the defects of poor cement adaptability and unstable dispersibility of the traditional anionic polycarboxylic acid high-performance water reducing agent in a cement system with high-concentration salt, and has better popularization and application potentials in hydraulic engineering or marine engineering.
A patent CN 106188418A (published: 2016, 12, month and 07) reports a preparation method of an amphoteric polycarboxylic acid water reducing agent. The method comprises the steps of taking unsaturated aldehyde small monomers or unsaturated ketone small monomers and unsaturated macromonomers as raw materials, carrying out oxidation-reduction free radical polymerization under the action of an initiator, a reducing agent and a chain transfer agent to obtain a polycarboxylate superplasticizer prepolymer containing aldehyde groups or carbonyl groups, and carrying out Strecker reaction on the polycarboxylate superplasticizer prepolymer containing aldehyde groups or carbonyl groups, sodium cyanide and ammonium chloride to obtain an amphoteric copolymerization product with a main chain containing amino and carboxyl. The amphoteric polycarboxylate superplasticizer prepared by the invention has good adaptability to cement, improves the dispersibility of cement, and improves the slump retentivity on the premise of high water reduction. However, the conversion rate of the Strecker reaction is unknown, and the synthesized side chain is still in a polyether structure, so that the innovation of a molecular structure is not fundamentally realized.
Patent CN 106750046A (published: 2017, 05 and 31) reports a star-shaped amphoteric polycarboxylic acid water reducer and a preparation method thereof. The star-shaped initiator is obtained by esterification of cyclodextrin, and atom transfer radical polymerization of polyethylene glycol (meth) acrylate, sodium (meth) acrylate, methacryloyloxyethyl trimethyl ammonium chloride and hydroxyethyl (meth) acrylate is initiated to obtain the star-shaped copolymer of the four monomers. The invention has the advantages that the safe and environment-friendly natural cyclodextrin is used as the star nucleus, the cost is lower, and the mud resistance is good. However, the ratio of the cationic monomer in the product of the invention is low, and ester substances are used in a large amount, so that the product performance is easy to be unstable in the alkaline environment of cement.
Patent CN107265907A (published: 2017, 10 and 20) reports an amphoteric antibacterial polycarboxylic acid high-efficiency water reducing agent and a preparation method thereof. The invention takes carbonyl-containing unsaturated small monomer, amino-terminated copolymerization product and unsaturated polyester macromonomer as raw materials to prepare the quaternary ammonium salt structure polycarboxylate superplasticizer with three polyether macromolecular branched chains on a single side chain. The method has the advantages of high reaction efficiency, no toxicity or pollution, simple operation and antibacterial capability. However, the degree of cationization of the side chains of the amphoteric product is too low, each side chain has only one cationic unit, and macromolecules with balanced amphoteric properties of the anionic main chain and the cationic side chains are not really realized.
The amphoteric concrete water reducer synthesized by the invention has good antibacterial property, dispersibility, slump keeping property, mud resistance and other properties, and provides a new design idea for preparation and application of a polycarboxylic acid high-performance water reducer. However, the amphoteric polymer prepared by the invention has low proportion of cationic components, does not show good dispersion and dispersion stability in a high-concentration salt cement system, and the synthesis method has a certain degree of defects, most of the inventors adopt traditional polyether as a reaction raw material to prepare a target product, molecular structure innovation is not really realized, meanwhile, modification modes are mostly concentrated on replacing partial groups of a main chain or side chain modification, and a complete cationic side chain (each chain link of the side chain is a cationic structure) is rarely adopted to replace the traditional polyether structure, so that the theoretical technical development of the amphoteric water reducing agent and the popularization and application of the amphoteric water reducing agent in the field of cement concrete are severely limited. Therefore, a concrete water reducing agent with a novel molecular structure is urgently needed, has the amphoteric characteristic and excellent functions in a balanced manner, and can ensure a simple and controllable preparation process and preparation raw materials with wide sources, and relevant reports are not found in the work related to the aspect.
Disclosure of Invention
The salt-resistant amphoteric polycarboxylic acid high-performance water reducing agent is synthesized by taking an unsaturated cationic quaternary ammonium salt monomer, an unsaturated small monomer, an unsaturated initiator, a transition metal complex and the like as main raw materials through a method of self-polymerization and graft copolymerization, namely, the salt-resistant amphoteric polycarboxylic acid high-performance water reducing agent is prepared by taking the unsaturated cationic quaternary ammonium salt monomer as a reactant, carrying out Atom Transfer Radical Polymerization (ATRP) under a system consisting of the unsaturated initiator and the transition metal complex to obtain a cationic large monomer, and then carrying out free radical graft copolymerization with the unsaturated small monomer under the action of the initiator and a chain transfer agent. The innovative design and synthesis of the molecular structure are carried out based on the principles of traditional free radical polymerization and atom transfer free radical polymerization, the prepared salt-tolerant amphoteric polycarboxylic acid high-performance water reducing agent has the advantage of maintaining good dispersion on cement under the condition of high-concentration salt, the process is simple, controllable, energy-saving and environment-friendly, the cationization substitution of the traditional polyether side chain is realized, and the application potential and the development prospect are good.
1. The salt-resistant amphoteric polycarboxylic acid high-performance water reducing agent is characterized by comprising the following molecular structural formula:
wherein a is an integer of 10-150, b is an integer of 3-50, and n is an integer of 10-150; r1Is H, CH3Or CH2COOM, wherein M is H or an alkali metal; r2Is H or COOM, wherein M isH or alkali metals, but R1And R2Do not contain COOM at the same time; r3Is NH2Or OM, wherein M is H or an alkali metal; r4、R6、R8Is H or CH3；R5Is H, CH3Or COOM, wherein M is H or an alkali metal; r7Is nothing (carbon at both ends is directly connected), CH2Or COCH2And when R is5When it is COOM, R7Can only be absent (the two ends are directly connected with carbon); r9Is CH2、COOCH2CH2Or CONHCH2CH2CH2；R10Br or Cl; p is quaternary ammonium group.
2. The preparation method of the salt-resistant amphoteric polycarboxylic acid high-performance water reducing agent is characterized in that the conditions and the steps for synthesizing the polycarboxylic acid high-performance water reducing agent by a method of firstly obtaining cationic macromonomer through self-polymerization and then graft copolymerization are as follows:
(1) self-polymerization reaction: firstly, uniformly mixing an unsaturated cationic quaternary ammonium salt monomer and solvent water, then adding an unsaturated initiator and a transition metal complex into a reactor, filling nitrogen into the reactor under ice-water bath, repeatedly deoxidizing for 10-30 minutes for 3-5 times, stirring for 10-30 minutes until the unsaturated initiator and the transition metal complex are uniformly mixed, sealing under the protection of nitrogen, continuously heating to 10-100 ℃ for polymerization reaction for 5-50 hours, desalting, and distilling under reduced pressure to remove the solvent to obtain a cationic macromonomer;
(2) graft copolymerization: uniformly mixing the cationic macromonomer obtained in the step (1) with solvent water, sequentially adding unsaturated small monomers and a chain transfer agent, stirring and heating to 45-90 ℃, dropwise adding 1-30% of initiator aqueous solution for 1-5 hours, continuing constant temperature reaction for 1-5 hours after dropwise adding is finished, cooling to 25-40 ℃, and adding water for dilution to obtain a salt-tolerant amphoteric polycarboxylic acid high-performance water reducing agent solution with the required concentration;
wherein, the unsaturated cation quaternary ammonium salt in the step (1) is one or more of trimethyl allyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, methacryloylpropyl trimethyl ammonium chloride, N-hexyl-N-methacryloyloxy-N, N-dimethylamino ammonium bromide, methacryloyloxyethyl dimethyl benzyl ammonium chloride or acryloyloxyethyl dimethyl benzyl ammonium chloride, and the molar ratio of the dosage to the unsaturated initiator in the step (1) is 10-200: 1; the solvent water in the step (1) is used in an amount that the concentration of the unsaturated monomer is 20% -50%; the unsaturated initiator in the step (1) is one or more of methallyl bromide, allyl bromide, methallyl chloride, allyl chloride, 1-bromo-3-methyl-2-butene, 1-chloro-3-methyl-2-butene, 2-ethyl bromoacrylate, 2-bromo-3-methyl butenoate, 1-bromo-4-methyl-3-penten-2-one or 1-chloro-4-methyl-3-penten-2-one; the transition metal complex in the step (1) is ferrous bromide/N, N, N, N, N-pentamethyl divinyl triamine, cuprous bromide/N, N, N, N-pentamethyl divinyl triamine, cuprous chloride/N, N, N, N-pentamethyl divinyl triamine, ferrous chloride/N, N, N, N-pentamethyl divinyl triamine, cuprous bromide/2, 2-bipyridine, ferrous chloride/2, 2-bipyridine, ferrous bromide/1, 1,4,7,10, 10-hexamethyl triethylene tetramine, cuprous bromide/1, 1,4,7,10, 10-hexamethyl triethylene tetramine, Cuprous chloride/1, 1,4,7,10, 10-hexamethyltriethylenetetramine, ferrous chloride/1, 1,4,7,10, 10-hexamethyltriethylenetetramine, cuprous bromide/tetrakis [ (2-pyridyl) methyl ] ethylenediamine, ferrous bromide/N, N-tetrakis [ (2-pyridyl) methyl ] ethylenediamine, cuprous chloride/N, N-tetrakis [ (2-pyridyl) methyl ] ethylenediamine, ferrous bromide/tris [2- (dimethylamino) ethyl ] amine, cuprous bromide/tris [2- (dimethylamino) ethyl ] amine, ferrous chloride/tris [2- (dimethylamino) ethyl ] amine, or cuprous chloride/tris [2- (dimethylamino) ethyl ] amine One or more of the above-mentioned raw materials are used, and the mole ratio of the used raw materials to the unsaturated initiator described in the step (1) is 1-4: 1; the salt removed in the step (1) is one or more of cuprous bromide, cupric chloride, cupric bromide, ferric bromide, cuprous chloride, ferric chloride, ferrous bromide or ferrous chloride;
the mass ratio of the solvent water used in the step (2) to the cationic macromonomer obtained in the step (1) is 0.8-1.2: 1; the chain transfer agent in the step (2) is thioglycolic acid, mercaptopropionic acid or sodium methallyl sulfonate, and the molar ratio of the dosage of the chain transfer agent to the cationic macromonomer obtained in the step (1) is 0.05-0.3: 1; the solute of the initiator aqueous solution in the step (2) is ammonium persulfate, potassium persulfate, sodium persulfate or hydrogen peroxide, and the molar ratio of the solute amount to the cationic macromonomer obtained in the step (1) is 0.05-0.3: 1; the unsaturated small monomer in the step (2) is one or more of methacrylic acid, acrylic acid, acrylamide, itaconic acid, maleic anhydride, fumaric acid, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate or hydroxypropyl acrylate, and the molar ratio of the used amount to the cationic macromonomer obtained in the step (1) is 3-10: 1.
Compared with the prior art, the method of the invention has the following beneficial effects:
1. the method is characterized in that a polymer structure design theory is used as guidance, a cationic macromonomer is synthesized by adopting a controllable synthesis method of atom transfer radical polymerization, and then radical polymerization is carried out to obtain the comb-shaped concrete water reducing agent with an anionic main chain and a cationic side chain.
2. The method of the invention adopts an atom transfer radical polymerization method, avoids the defects of special catalyst, high temperature and high pressure, single raw material and the like in the ring-opening polymerization of ethylene oxide/propylene oxide of the traditional polyether macromonomer, and utilizes the polymerization characteristics of fast initiation and slow growth of the atom transfer radical polymerization, so that the synthesized polymer has controllable molecular weight and less side reaction. This not only enriches the variety of macromonomers, but also provides a new method for the controlled synthesis of macromonomers.
3. Different from other methods which only copolymerize a small amount of cationic structures in the molecular main chain or modify polyether side chains, the side chains of the salt-tolerant amphoteric polycarboxylic acid high-performance water reducing agent synthesized by the method completely replace polyether structures with cationic structures, so that the side chain extension capacity of the water reducing agent in a cement high-salt concentration solution can be effectively improved, and the dispersing capacity of the salt-tolerant amphoteric polycarboxylic acid high-performance water reducing agent is improved.
4. The method has the advantages of simple and controllable synthesis, mild conditions, safety, environmental protection, no solvent poison, cleanness and no pollution, and the used atom transfer radical polymerization method can provide cationic macromonomers with narrow molecular weight distribution and wide optional range, is favorable for large-scale popularization and application of diversified products, and has great application potential.
5. The salt-tolerant amphoteric polycarboxylic acid high-performance water reducing agent synthesized by the method has more excellent dispersibility and water-reducing slump-retaining capacity than the traditional polycarboxylic acid high-performance water reducing agent, and can still show better fluidity and retaining capacity at high salt concentration. In addition, the concrete water reducing agent product is stable in state, does not delaminate after standing at high concentration, does not crystallize after being stored at low temperature, and is not affected in performance.
Detailed Description
The present invention will be described in further detail with reference to examples, but the practice of the present invention is not limited thereto.
Example 1
Firstly, 162.76g of trimethyl allyl ammonium chloride and 244.14g of water are uniformly mixed, then 0.91g of methyl allyl chloride, 8.63g of ferrous bromide and 6.93g of N, N, N, N, N-pentamethyl divinyl triamine are added into a reactor, the reactor is deaerated for 20 minutes 4 times in an ice-water bath, stirred for 20 minutes until the mixture is uniformly mixed, sealed under the protection of nitrogen and continuously heated to 40 ℃ for polymerization reaction, the reaction is carried out for 20 hours, and the cationic macromonomer is obtained after desalting and reduced pressure distillation to remove the solvent; and uniformly mixing the cationic macromonomer with 180.03g of water, adding 5.76g of acrylic acid and 0.14g of thioglycollic acid, heating to 55 ℃, simultaneously dropwise adding 3.42g of 20% ammonium persulfate aqueous solution, reacting for 2 hours, then preserving the temperature for 4 hours, cooling to 25 ℃, and adding 23.49g of water for dilution to obtain the salt-tolerant amphoteric polycarboxylic acid high-performance water reducing agent solution with the concentration of 45%.
Example 2
The salt-tolerant amphoteric polycarboxylic acid high-performance water reducing agent solution having a concentration of 45% obtained in example 1 was stored at 5 ℃ for 30 days, and then the effect thereof was measured.
Example 3
Firstly, 77.47g of acryloyloxyethyl trimethyl ammonium chloride, 83.08g of methacryloyloxyethyl trimethyl ammonium chloride and 189.37g of water are uniformly mixed, then 0.61g of allyl bromide, 0.75g of 1-bromo-3-methyl-2-butene, 0.72g of cuprous bromide, 0.49g of cuprous chloride, 1.73g of N, N, N, N, N-pentamethyl divinyl triamine are added into a reactor, the reactor is filled with nitrogen in an ice water bath, oxygen is removed for 30 minutes repeatedly, stirring is carried out for 25 minutes until the mixture is uniform, the reactor is sealed under the protection of nitrogen, and is continuously heated to 50 ℃ for carrying out polymerization reaction, the reaction is carried out for 15 hours, and desalinization and reduced pressure distillation are carried out to remove the solvent, so as to obtain the cationic macromonomer; and uniformly mixing the cationic macromonomer with 140.53g of water, adding 2.14g of acrylamide, 2.16g of acrylic acid and 0.21g of mercaptopropionic acid, heating to 70 ℃, simultaneously dropwise adding 1.62g of 25 mass percent potassium persulfate aqueous solution, reacting for 4 hours, then preserving the temperature for 2 hours, cooling to 30 ℃, and adding 106.9g of water for dilution to obtain the salt-resistant amphoteric polycarboxylic acid high-performance water reducing agent solution with the concentration of 40%.
Example 4
The salt-tolerant amphoteric polycarboxylic acid high-performance water reducing agent solution having a concentration of 40% obtained in example 3 was stored at 6 ℃ for 40 days, and then the effect thereof was measured.
Example 5
Firstly, uniformly mixing 20.77g of methacryloyloxyethyl trimethyl ammonium chloride and 83.08g of water, then adding 1.49g of 1-bromo-3-methyl-2-butene, 2.15g of cuprous bromide and 2.34g of 2, 2-bipyridine into a reactor, filling nitrogen into the reactor under ice-water bath, repeatedly deoxidizing for 10 minutes, stirring for 15 minutes until the materials are uniformly mixed, sealing under the protection of nitrogen, continuously heating to 10 ℃ for polymerization reaction, reacting for 50 hours, desalting, and distilling under reduced pressure to remove a solvent to obtain a cationic macromonomer; and uniformly mixing the cationic macromonomer with 26.71g of water, adding 3.48g of fumaric acid and 0.08g of sodium methallyl sulfonate, heating to 90 ℃, simultaneously dropwise adding 1.98g of sodium persulfate aqueous solution with the mass fraction of 30%, reacting for 3 hours, then preserving the temperature for 3 hours, cooling to 40 ℃, and adding 74.19g of water for dilution to obtain the salt-tolerant amphoteric polycarboxylic acid high-performance water reducing agent solution with the concentration of 20%.
Example 6
The salt-tolerant amphoteric polycarboxylic acid high-performance water reducing agent solution with the mass fraction of 20% obtained in example 5 was stored at 5 ℃ for 20 days, and then the implementation effect thereof was measured.
Example 7
Firstly, 110.37g of methacrylpropyl trimethyl ammonium chloride and 257.53g of water are uniformly mixed, 1.34g of 1-chloro-4-methyl-3-penten-2-one, 2.54g of ferrous chloride and 3.12g of 2, 2-bipyridine are added into a reactor, the reactor is filled with nitrogen in ice water bath for repeatedly removing oxygen for 4 times for 15 minutes, the mixture is stirred for 10 minutes until the mixture is uniformly mixed, the mixture is sealed under the protection of nitrogen, the temperature is continuously raised to 80 ℃ for polymerization reaction, the reaction is carried out for 10 hours, and the cationic macromonomer is obtained after desalting, reduced pressure distillation and solvent removal; and uniformly mixing the cationic macromonomer with 111.71g of water, adding 4.64g of hydroxyethyl acrylate and 0.23g of thioglycolic acid, heating to 60 ℃, simultaneously dropwise adding 4.42g of 1% hydrogen peroxide aqueous solution by mass fraction, reacting for 5 hours, then preserving the temperature for 1 hour, cooling to 35 ℃, and adding 155.13g of water to dilute to obtain the salt-tolerant amphoteric polycarboxylic acid high-performance water reducing agent solution with the concentration of 30%.
Example 8
The salt-tolerant amphoteric polycarboxylic acid high-performance water reducing agent solution with the mass fraction of 30% obtained in example 7 was stored at 6 ℃ for 40 days, and then the effect thereof was measured.
Example 9
Firstly, 271.27 trimethyl allyl ammonium chloride and 271.27g water are mixed uniformly, 1.79g 2-ethyl bromoacrylate, 6.47g ferrous bromide and 12.74g tetra [ (2-pyridyl) methyl ] ethylenediamine are added into a reactor, the reactor is filled with nitrogen in ice water bath for 3 times to remove oxygen for 35 minutes, stirred for 30 minutes until the mixture is mixed uniformly, sealed under the protection of nitrogen and continuously heated to 100 ℃ for polymerization reaction, the reaction is carried out for 5 hours, and desalinization and reduced pressure distillation are carried out to remove solvent, so as to obtain the cationic macromonomer; and uniformly mixing the cationic macromonomer with 218.45g of water, adding 13.02g of hydroxypropyl acrylate and 0.32g of mercaptopropionic acid, heating to 80 ℃, simultaneously dropwise adding 1.14g of 10 mass percent ammonium persulfate aqueous solution, reacting for 1 hour, then preserving the temperature for 5 hours, cooling to 28 ℃, and adding 66.17g of water for dilution to obtain the salt-tolerant amphoteric polycarboxylic acid high-performance water reducing agent solution with the concentration of 50%.
Example 10
The salt-tolerant amphoteric polycarboxylic acid high-performance water reducing agent solution with the mass fraction of 50% obtained in example 9 was stored at 7 ℃ for 40 days, and then the effect thereof was measured.
The implementation effect is as follows:
1. fluidity of cement paste
In order to examine the effect of the salt-tolerant type amphoteric polycarboxylic acid high-performance water reducing agent solution synthesized by the invention on the fluidity of cement, the net slurry fluidity of each example on the reference cement under the same mixing amount is measured by an experiment. The test is carried out according to GB/T8077-2012 'test method for homogeneity of concrete admixture', wherein W/C is 0.29, and the mixing amount is the bending and fixing mixing amount. The conventional comb-shaped polycarboxylic acid water reducing agent (comparative example) which is commercially available at present is selected as a comparative sample, and the test results are shown in Table 1.
TABLE 1 Cement paste flow Performance results
As can be seen from Table 1, the salt-tolerant amphoteric polycarboxylic acid high-performance water reducing agent solution synthesized by the method of the invention can show excellent dispersing ability under the conditions of a water-cement ratio of 0.29 and a folding-fixing content of 0.15%.
2. Salt resistance test
In order to investigate the resistance of the salt-tolerant amphoteric polycarboxylic acid high-performance water reducing agent solution synthesized by the method to high-concentration salt solution, tests determine Na with different concentrations2SO4NaCl effect of each example on the net slurry fluidity of the reference cement. The test is carried out according to GB/T8077-2012 'concrete admixture homogeneity test method', the W/C is 0.29, the water reducing agent mixing amount is 0.15%, and the mixing amount is the bending solid mixing amount. The conventional comb-shaped polycarboxylic acid water reducing agent (comparative example) which is commercially available at present is selected as a comparative sample, and the test results are shown in Table 2.
Table 2 salt resistance test
As can be seen from Table 2, the salt-tolerant type amphoteric polycarboxylic acid high-performance water reducing agent solution synthesized by the method of the invention can show excellent dispersibility and dispersion retention capability in a cement system with high salt concentration.
3. Concrete Properties
The slump, the expansion and the holding properties and the compressive strength of the concrete system exhibited by the examples were determined and the results are shown in Table 3.
TABLE 3 concrete flow Performance results
As can be seen from Table 3, the salt-tolerant amphoteric polycarboxylic acid high-performance water reducing agent solution synthesized by the method of the invention shows better slump, expansion, holding capacity and later strength in a concrete system.
Claims (1)
1. The preparation method of the salt-resistant amphoteric polycarboxylic acid high-performance water reducing agent comprises the following steps:
wherein a is an integer of 10-150, b is an integer of 3-50, and n is an integer of 10-150; r1Is H, CH3Or CH2COOM, wherein M is H or an alkali metal; r2Is H or COOM, where M is H or an alkali metal, but R1And R2Do not contain COOM at the same time; r3Is NH2Or OM, wherein M is H or an alkali metal; r4、R6、R8Is H or CH3；R5Is H, CH3Or COOM, wherein M is H or an alkali metal; r7Is nothing, CH2Or COCH2And when R is5When it is COOM, R7Can only be absent; r9Is CH2、COOCH2CH2Or CONHCH2CH2CH2；R10Br or Cl; p is quaternary ammonium group;
the method is characterized by comprising the following steps:
(1) self-polymerization reaction: firstly, uniformly mixing an unsaturated cationic quaternary ammonium salt monomer and solvent water, then adding an unsaturated initiator and a transition metal complex into a reactor, filling nitrogen into the reactor under ice-water bath, repeatedly deoxidizing for 10-30 minutes for 3-5 times, stirring for 10-30 minutes until the unsaturated initiator and the transition metal complex are uniformly mixed, sealing under the protection of nitrogen, continuously heating to 10-100 ℃ for polymerization reaction for 5-50 hours, desalting, and distilling under reduced pressure to remove the solvent to obtain a cationic macromonomer;
(2) graft copolymerization: uniformly mixing the cationic macromonomer obtained in the step (1) with solvent water, sequentially adding unsaturated small monomers and a chain transfer agent, stirring and heating to 45-90 ℃, dropwise adding 1-30% of initiator aqueous solution for 1-5 hours, continuing constant temperature reaction for 1-5 hours after dropwise adding is finished, cooling to 25-40 ℃, and adding water for dilution to obtain a salt-tolerant amphoteric polycarboxylic acid high-performance water reducing agent solution with the required concentration;
wherein, the unsaturated cation quaternary ammonium salt in the step (1) is one or more of trimethyl allyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, methacryloylpropyl trimethyl ammonium chloride, N-hexyl-N-methacryloyloxy-N, N-dimethylamino ammonium bromide, methacryloyloxyethyl dimethyl benzyl ammonium chloride or acryloyloxyethyl dimethyl benzyl ammonium chloride, and the molar ratio of the dosage to the unsaturated initiator in the step (1) is 10-200: 1; the solvent water in the step (1) is used in an amount that the concentration of the unsaturated monomer is 20% -50%; the unsaturated initiator in the step (1) is one or more of methallyl bromide, allyl bromide, methallyl chloride, allyl chloride, 1-bromo-3-methyl-2-butene, 1-chloro-3-methyl-2-butene, 2-ethyl bromoacrylate, 2-bromo-3-methyl butenoate, 1-bromo-4-methyl-3-penten-2-one or 1-chloro-4-methyl-3-penten-2-one; the transition metal complex in the step (1) is ferrous bromide/N, N, N, N, N-pentamethyl divinyl triamine, cuprous bromide/N, N, N, N-pentamethyl divinyl triamine, cuprous chloride/N, N, N, N-pentamethyl divinyl triamine, ferrous chloride/N, N, N, N-pentamethyl divinyl triamine, cuprous bromide/2, 2-bipyridine, ferrous chloride/2, 2-bipyridine, ferrous bromide/1, 1,4,7,10, 10-hexamethyl triethylene tetramine, cuprous bromide/1, 1,4,7,10, 10-hexamethyl triethylene tetramine, Cuprous chloride/1, 1,4,7,10, 10-hexamethyltriethylenetetramine, ferrous chloride/1, 1,4,7,10, 10-hexamethyltriethylenetetramine, cuprous bromide/tetrakis [ (2-pyridyl) methyl ] ethylenediamine, ferrous bromide/N, N-tetrakis [ (2-pyridyl) methyl ] ethylenediamine, cuprous chloride/N, N-tetrakis [ (2-pyridyl) methyl ] ethylenediamine, ferrous bromide/tris [2- (dimethylamino) ethyl ] amine, cuprous bromide/tris [2- (dimethylamino) ethyl ] amine, ferrous chloride/tris [2- (dimethylamino) ethyl ] amine, or cuprous chloride/tris [2- (dimethylamino) ethyl ] amine One or more of the above-mentioned raw materials are used, and the mole ratio of the used raw materials to the unsaturated initiator described in the step (1) is 1-4: 1; the salt removed in the step (1) is one or more of cuprous bromide, cupric chloride, cupric bromide, ferric bromide, cuprous chloride, ferric chloride, ferrous bromide or ferrous chloride;
the mass ratio of the solvent water used in the step (2) to the cationic macromonomer obtained in the step (1) is 0.8-1.2: 1; the chain transfer agent in the step (2) is thioglycolic acid, mercaptopropionic acid or sodium methallyl sulfonate, and the molar ratio of the dosage of the chain transfer agent to the cationic macromonomer obtained in the step (1) is 0.05-0.3: 1; the solute of the initiator aqueous solution in the step (2) is ammonium persulfate, potassium persulfate, sodium persulfate or hydrogen peroxide, and the molar ratio of the solute amount to the cationic macromonomer obtained in the step (1) is 0.05-0.3: 1; the unsaturated small monomer in the step (2) is one or more of methacrylic acid, acrylic acid, acrylamide, itaconic acid, maleic anhydride, fumaric acid, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate or hydroxypropyl acrylate, and the molar ratio of the used amount to the cationic macromonomer obtained in the step (1) is 3-10: 1.
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