CN114075316B - Super plasticizer for ultra-high performance concrete and preparation method thereof - Google Patents
Super plasticizer for ultra-high performance concrete and preparation method thereof Download PDFInfo
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- CN114075316B CN114075316B CN202010850544.2A CN202010850544A CN114075316B CN 114075316 B CN114075316 B CN 114075316B CN 202010850544 A CN202010850544 A CN 202010850544A CN 114075316 B CN114075316 B CN 114075316B
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- superplasticizer
- polyether
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- 239000008030 superplasticizer Substances 0.000 title claims abstract description 76
- 239000011374 ultra-high-performance concrete Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 93
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 60
- 125000000524 functional group Chemical group 0.000 claims abstract description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 82
- 239000000203 mixture Substances 0.000 claims description 61
- 239000000178 monomer Substances 0.000 claims description 54
- 229920000570 polyether Polymers 0.000 claims description 50
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 48
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 31
- -1 alkenyl amine Chemical group 0.000 claims description 28
- 239000003999 initiator Substances 0.000 claims description 25
- 239000007864 aqueous solution Substances 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 23
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 22
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 20
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 15
- 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 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 239000011574 phosphorus Substances 0.000 claims description 12
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- 235000010323 ascorbic acid Nutrition 0.000 claims description 11
- 229960005070 ascorbic acid Drugs 0.000 claims description 11
- 239000011668 ascorbic acid Substances 0.000 claims description 11
- 150000003384 small molecules Chemical class 0.000 claims description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 10
- 238000010526 radical polymerization reaction Methods 0.000 claims description 10
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 125000003172 aldehyde group Chemical group 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 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 7
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 7
- 239000012986 chain transfer agent Substances 0.000 claims description 7
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 7
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 6
- 230000000977 initiatory effect Effects 0.000 claims description 6
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 6
- 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 5
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 5
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 5
- 239000011790 ferrous sulphate Substances 0.000 claims description 5
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 5
- 229910001380 potassium hypophosphite Inorganic materials 0.000 claims description 5
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 claims description 5
- 239000012966 redox initiator Substances 0.000 claims description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 5
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 3
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 3
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 3
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 3
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 3
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 claims description 2
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 2
- 235000018417 cysteine Nutrition 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 229960003151 mercaptamine Drugs 0.000 claims description 2
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000004296 sodium metabisulphite Substances 0.000 claims 1
- 239000004567 concrete Substances 0.000 abstract description 55
- 229920000642 polymer Polymers 0.000 abstract description 26
- 230000001603 reducing effect Effects 0.000 abstract description 12
- 239000002002 slurry Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 abstract description 6
- 125000003282 alkyl amino group Chemical group 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 239000004568 cement Substances 0.000 description 29
- 238000007792 addition Methods 0.000 description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- 239000002253 acid Substances 0.000 description 23
- 239000006185 dispersion Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 238000001179 sorption measurement Methods 0.000 description 14
- 238000002156 mixing Methods 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000004570 mortar (masonry) Substances 0.000 description 9
- 229910021487 silica fume Inorganic materials 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000002202 Polyethylene glycol Substances 0.000 description 7
- 239000011372 high-strength concrete Substances 0.000 description 7
- 229920001223 polyethylene glycol Polymers 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 239000004576 sand Substances 0.000 description 5
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 229920005646 polycarboxylate Polymers 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 235000011837 pasties Nutrition 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229940001584 sodium metabisulfite Drugs 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical group OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical group C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229940048053 acrylate Drugs 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001356 alkyl thiols Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
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- 230000001186 cumulative effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- PCIBVZXUNDZWRL-UHFFFAOYSA-N ethylene glycol monophosphate Chemical compound OCCOP(O)(O)=O PCIBVZXUNDZWRL-UHFFFAOYSA-N 0.000 description 1
- 210000003722 extracellular fluid Anatomy 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-L phosphoramidate Chemical compound NP([O-])([O-])=O PTMHPRAIXMAOOB-UHFFFAOYSA-L 0.000 description 1
- 150000008298 phosphoramidates Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical group [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- CCEKAJIANROZEO-UHFFFAOYSA-N sulfluramid Chemical compound CCNS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F CCEKAJIANROZEO-UHFFFAOYSA-N 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/243—Phosphorus-containing polymers
- C04B24/246—Phosphorus-containing polymers containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/32—Superplasticisers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention provides a superplasticizer for ultra-high performance concrete and a preparation method thereof. The superplasticizer for the ultra-high performance concrete consists of a branch functional group R 21 and a water reducer polymer chain segment; each branched functional group R 21 is linked with 3-4 water reducer polymer chain segments; the structure of the branched functional group R 21 comprises an alkylamino phosphoric acid functional group which is connected with ethyl or isopropyl through saturated alkyl or phenyl containing 1-9 carbon atoms, wherein two carbon atoms in the ethyl and the isopropyl and P are branching sites, and the branching functional group R 21 is connected with a water reducing agent polymer chain segment through a single bond. The superplasticizer comprehensively enhances the adhesive capacity, thereby effectively reducing the viscosity of slurry, and in addition, the superplasticizer has lower solution viscosity and weaker bridging effect than the common commercial superplasticizer under the condition of the same solution concentration, and can remarkably improve the fluidity of ultra-high-performance concrete and reduce the viscosity of the concrete compared with the prior art.
Description
Technical Field
The invention relates to the field of concrete superplasticizers, in particular to a superplasticizer for ultra-high-performance concrete and a preparation method thereof.
Background
The term "concrete" as used herein generally refers to concrete, mortar or grouting, among other things, as well as other places herein.
High-performance water reducers (especially polycarboxylate water reducers or polycarboxylate superplasticizers) have been widely used and greatly developed since their spontaneous emission, and have become an indispensable component in concrete. The polycarboxylic acid water reducer is generally prepared by free radical polymerization of vinyl monomers, wherein a main chain (generally-CH 2-CH2 -structure or-CH 1-CH2 -structure substituted by functional groups) is connected with charged functional groups (such as carboxyl groups, sulfonic groups and the like), and corresponding side chains are mainly water-soluble polyethylene glycol chains, and in concrete, the charged functional groups are adsorbed on the main chain through electrostatic interaction with the surfaces of cement particles, and the corresponding long side chains are prevented from mutually approaching to agglomerate through steric hindrance (repulsive interaction), so that the wrapped moisture is released, the workability of the concrete is improved, and the water-cement ratio is reduced.
Ultra-high performance concrete (compressive strength of 100MPa and above) is widely paid attention to due to excellent service performance, however, the water-cement ratio is extremely low (generally not higher than 0.2), the superfine powder content in the cementing material component is extremely high, and in addition, the total cement content is remarkably reduced compared with common commercial concrete, so that the concrete has poor fluidity and high viscosity, and becomes one of the key problems restricting construction. However, the traditional polycarboxylic acid superplasticizer is poor in universality and performance in an ultra-high-performance concrete complex cementing material system aiming at cement design, and is difficult to meet the basic requirements of fluidity and low viscosity.
Aiming at the problems, new water reducing agent technology for greatly reducing the water-cement ratio of concrete, reducing the shearing resistance and improving the workability is developed.
The design scheme of the water reducer of EP1775271A2 is that the viscosity of concrete can be reduced, and the water reducer has good slump retaining performance, but is difficult to be applied to high/ultra-high strength concrete aiming at common concrete design.
CN106467604a reports a viscosity-reducing polycarboxylate water reducer prepared by copolymerizing an unsaturated carboxylic ester monomer with double functionalities, an unsaturated phosphate ester monomer, an unsaturated anhydride and a polyether monomer.
CN103553413a discloses a viscosity-adjusting water reducing agent which introduces viscosity-adjusting monomers (unsaturated alkyl esters, fluorine-containing esters, alkyl acrylamides or concrete thereof) and can effectively reduce the viscosity of concrete, but has an air entraining function to different degrees.
CN106431060a reports that a viscosity-reducing polycarboxylic acid water reducer for high-strength concrete adopts a scheme of compounding a water reducer, a viscosity reducer and a slump retaining agent, and can reduce the viscosity of the high-strength concrete to different degrees.
The early-strength polycarboxylate compound water reducer disclosed by CN10147533 adopts compound viscosity-reducing component polyethylene glycol, so that the viscosity of concrete is obviously reduced, and the fluidity requirement of the concrete construction process is met.
CN103865007a discloses a preparation method of a viscosity-reducing polycarboxylic acid water reducer, which introduces and controls a certain amount of hydrophobic units and hydrophobic groups into the molecular structure of a carboxylic acid copolymer, plays a role in reducing the viscosity of cement-based materials under the action of the water reducer, and has excellent performance.
CN105367721a discloses a preparation method and application of viscosity-reducing polycarboxylic acid superplasticizer, mainly introducing monomer b containing branched side chain and monomer c containing rigid ring group into the structure to make free radical polymerization, can greatly reduce water-gel ratio of concrete and can effectively reduce viscosity of concrete.
CN106397683a reports a polycarboxylic acid water reducing agent for reducing the viscosity of high-grade concrete and a preparation method thereof, wherein the polycarboxylic acid water reducing agent is prepared by free radical polymerization of alkenyl polyoxyethylene ether, unsaturated acid (benzenesulfonic acid, benzoic acid, acrylic acid and the like) and unsaturated ester (unsaturated hydroxy ester) through molecular rearrangement of a viscosity reducing regulator, and has the advantages of high water reducing rate, good viscosity reducing effect and the like.
CN104262550a discloses a preparation method of a viscosity-reducing polycarboxylic acid water reducer, which adopts unsaturated primary amine small monomers, organic small molecules with epoxy groups and halogen-containing groups to prepare unsaturated quaternary ammonium salts, and then reacts with unsaturated acid tools, the prepared viscosity-reducing polycarboxylic acid water reducer is simple and easy to control, and the viscosity of concrete can be effectively reduced.
The preparation method of the quick dispersion viscosity reduction type polycarboxylic acid cement dispersant disclosed in CN104371081A uses unsaturated single molecular monomer containing tertiary amino as a polymerizable reducer to obtain the hyperbranched polycarboxylic acid cement dispersant, and the viscosity of concrete is greatly improved.
The concrete viscosity reducer reported in CN106008784A is polymerized by 4-hydroxybutyl vinyl polyether, unsaturated amide and unsaturated phosphate, can reduce the viscosity of concrete without affecting the fluidity of the concrete, and improves the pumping construction performance.
The concrete viscosity modifier reported in CN105837740B is a terpolymer obtained by free radical polymerization of monomers prepared from glycidyl methacrylate and iminodiacetic acid, acrylic acid/methacrylic acid and cationic monomers, and effectively reduces the viscosity of C50 concrete.
The viscosity-reducing polycarboxylic acid reported by CN105732911B is prepared by polymerizing unsaturated acid, unsaturated polyether macromonomer and N- (4-vinyl benzyl) -N, N-dialkylamine, has simple reaction, easy preparation and high water-reducing rate, and can be used for viscosity reduction of high-strength (about 0.3) concrete.
The polycarboxylic acid concrete admixture disclosed in CN100402457C is prepared from (methyl) acrylic acid alkyl ester monomer, specific polyalkylene glycol unsaturated macromer and unsaturated acid monomer through free radical polymerization reaction, wherein the introduced third monomer acrylic acid alkyl ester monomer with hydrophobic effect can effectively help the water reducing agent to reduce the yield stress and viscosity of concrete.
CN105367721B reports a preparation method and application of a viscosity-reducing polycarboxylic acid superplasticizer, wherein branched side chain polyether is adopted in the superplasticizer to increase the thickness of a water film layer, and other monomers of rigid rings such as vinyl pyrrolidone and the like are introduced at the same time to improve the stretching degree of molecular conformation, so that the viscosity of high-strength and ultra-high-strength concrete is greatly reduced.
The concrete viscosity regulator reported by CN104973817B and suitable for being used together with the water reducer is mainly compounded by a clay stabilizer, an air entraining agent, a foam stabilizer and a thickener, can reduce ineffective adsorption of the water reducer, stabilize air bubbles, is suitable for C30-C50 concrete, and improves workability.
CN104031217B reports a loose anti-sticking type high-performance polycarboxylic acid additive, which is prepared by polymerizing ester type or ether type macromonomer, unsaturated carboxyl monomer, organic phosphate type compound and acrylic acid-lignin polymer through aqueous solution, can enhance adsorbed water molecules, and can effectively reduce the viscosity of high-strength concrete.
CN109535341a reports a polycarboxylic acid superplasticizer prepared from polyethylene glycol containing terminal hydrophobic modification, which has excellent viscosity reduction performance.
CN108623756a reports a polycarboxylic acid prepared by polymerization of N-ethyl perfluorooctyl sulfonamide acrylate, which can be used for ultra-high performance concrete.
However, according to the studies of the inventors, the terminal hydrophobically modified functional group very affects the polymer adsorption conformation and thus its steric hindrance, especially in very low water to gel ratio cement-based materials, and thus its dispersing ability is limited.
In general, the surface properties of different particles in the slurry are greatly different, and the adsorption capacities of different surface water reducers for attaching different particles are completely different. The adhesion of the common water reducer on the surfaces of particles such as silica fume is weak, and the common water reducer cannot effectively cover the surfaces of all powder particles. In general concrete, the volume fraction of particles such as silica fume is not high, and the effect is not obvious; however, in ultra-high performance concrete, the volume fraction of particles such as silica fume is high, the adsorption capacity of the common water reducer to the particles is limited, so that the slurry viscosity is high, and the construction is difficult. In addition, the common water reducer has higher mixing amount in the concrete with extremely low water-gel ratio, the effective adsorption efficiency is lower, and according to the research of the inventor, the solution residue can reach 70-90% of the mixing amount, and the viscosity of interstitial fluid is extremely high, which is very unfavorable for the viscosity of the ultra-high performance concrete.
The water reducer products mentioned in the prior art cannot solve the problem of the particle adsorption capacity of the ultra-high performance concrete, and the water reducer is not specially designed and cannot effectively cover the surfaces of all particles, so that the concrete has poor fluidity and high viscosity, the water reducer effect is very limited, the reported water-cement ratio of the concrete is 0.2-0.35, the water reducer belongs to conventional high-strength concrete, and the water reducer is freshly involved in the ultra-high-strength concrete.
Disclosure of Invention
The invention provides a superplasticizer with a novel structure and a preparation method thereof, aiming at solving the problems of poor dispersing capability, low water reducing rate and insufficient viscosity reducing effect of the traditional water reducer in ultra-high performance concrete. The superplasticizer comprehensively enhances the adhesive capacity, thereby effectively reducing the viscosity of slurry, and in addition, the superplasticizer has lower solution viscosity and weaker bridging effect than the common commercial superplasticizer under the condition of the same solution concentration, and can remarkably improve the fluidity of ultra-high-performance concrete and reduce the viscosity of the concrete compared with the prior art.
The superplasticizer for the ultra-high performance concrete consists of a branch functional group R 21 and a water reducer polymer chain segment; each branched functional group R 21 is linked with 3-4 water reducer polymer chain segments;
The structure of the branched functional group R 21 comprises an alkylamino phosphoric acid functional group which is connected with ethyl or isopropyl through saturated alkyl or phenyl containing 1-9 carbon atoms, wherein two carbon atoms in the ethyl and the isopropyl and P are branching sites, and the branching sites are connected with a water reducing agent polymer chain segment through single bonds;
the structural formula of the alkylamino phosphate functional group is as follows:
X 0 represents a saturated alkyl group having 1 to 9 carbon atoms or a phenyl group,
R 11 represents H or a saturated alkyl group having 1 to 4 carbon atoms,
R 12 represents a saturated alkyl group of 1 to 6 carbon atoms or a phenyl or carboxyl group,
M 1 + represents H + or Na + or K +,
R 13 represents H or a methyl group,
Represents the site of attachment to the water reducing agent polymer segment;
The water reducer polymer chain segment refers to residues of existing water reducer molecules, and is obtained by copolymerization of unsaturated carboxylic acid, unsaturated polyether, unsaturated phosphoramidate or phosphoramidate and/or unsaturated alkoxyphosphonic acid or alkoxyphosphinic acid.
The branched functional group R 21 may also consist of an alkylamino phosphate functional group and an auxiliary branched functional group;
The structural formula of the auxiliary branch functional group is shown as the following formula (1-2) or (1-3):
wherein R 14 and R 16 each independently represent H or methyl,
Y 0 and Y 0' each independently represent carbonyl, -CH 2-、-CH2CH2 -or-C 6H4-CH2 -, represents-C 6H4-CH2 -phenyl-C 6H4 -attached to a double bond;
R 15 and R 17 each independently represent-OH or H or
In the above general formula (1-2) or (1-3)Represents the site of attachment to the water reducing agent polymer segment;
The functional groups of hydroxyethyl phosphoric acid or phosphorous acid (when R 15 and R 17 are hydroxyl groups) or phosphate or phosphite (when R 15 and R 17 are not hydroxyl groups) are connected to ethyl or isopropyl through saturated alkoxy, ester or phenoxy groups of 1-9 carbon atoms and carbon atoms of hydroxyethyl, wherein two carbon atoms of ethyl and isopropyl and P are branch sites, and are connected with the water reducing agent polymer chain segment through single bonds.
The auxiliary branching functional group is obtained by glycidol ring opening, and a hydroxyl group is necessarily generated.
The weight average molecular weight of the superplasticizer polymer for the ultra-high performance concrete is in the range of 2000-100000.
The water reducing agent polymer chain segment is any one of structures shown in the following general formula (2):
The general formula (2) does not limit the chirality of the carbon atom, and may be any configuration;
The general formula (2) is not limited to the distribution and connection manner of the repeating units (chain links) in the polymer chain segment, and may be head-to-head connection, head-to-tail connection, block connection or random connection.
Wherein R 22 is a chain unit of a polymer, and is any one of the following structural formulas 3-1 to 3-3, and the structure of the R 22 chain unit in a single molecule of the polymer superplasticizer can be the same or different:
Wherein R 33 represents H or methyl.
M 2 +、M3 +、M4 +、M5 + and M 6 + each independently represent H + or NH 4 + or Na + or K +;
Any of the structural units described above, if attached to the polymer backbone as a mer, the average number of R 22 mer in the superplasticizer polymer molecule is aa;
wherein R 23、R24、R25、R26 and R 32 each independently represent H or methyl;
Z 0 in the structure shown in the general formula (2) represents carbonyl or phenyl or-OCH 2CH2 -or-OCH 2CH2CH2CH2 -or-CO-NH-CH 2CH2 -or- (CH 2)pp -, wherein pp is an integer between 1 and 6, including 1 and 6;
in the general formula (2), mm and nn respectively represent the average repeating unit number of isopropoxy and ethoxy, which may or may not be integers, the value range of (mm+nn) is 8-114, and mm/(mm+nn) is not more than 1/2, so that the water solubility of polyether and the extensibility of the molecular chain thereof in aqueous solution can be ensured; the structure of the general formula (2) is not limited to the connection sequence of the ethoxy and isopropoxy repeating units, and can be blocked or random;
x 1 in the general formula (2) represents a saturated alkyl group having 1 to 9 carbon atoms or a phenyl group;
Y 1 and Y 2 in the general formula (2) each independently represent a carbonyl group, -CH 2-、-CH2CH2 -, or-C 6H4-CH2 -, represents-C 6H4-CH2 -phenyl-C 6H4 -attached to a double bond;
R 27 in the general formula (2) represents H or saturated alkyl containing 1 to 4 carbon atoms, R 28 represents saturated alkyl containing 1 to 6 carbon atoms or phenyl or carboxyl, and R 29 represents-PO 3H2 or-PO 2H2 or-PO 2 HNa or-PO 2 HK;
r 30 and R 31 in the general formula (2) each independently represent-PO 3H2 or-PO 2H2 or-POH 2 or the corresponding Na salt and potassium salt functional groups.
Aa, bb, cc, dd and ee in the structure shown in the general formula (2) respectively represent the average number of corresponding chain units of a polymer, the average number of branch functional groups R 21 in the molecular structure of the polymer of the superplasticizer for ultra-high-performance concrete is ff, and the average number of R 21 conforming to the general formula (1-1) is counted as ff 1, then the values of aa, bb, cc, dd, ee and ff need to simultaneously satisfy the following conditions ：(1)0≤aa/(aa+bb+cc+dd+ee+ff)≤0.8;(2)0.1≤bb/(aa+bb+cc+dd+ee+ff)≤0.9;(3)0.05≤ff/(aa+bb+cc+dd+ee+ff)≤0.9.(4)0.05≤(ff1+cc)/(aa+bb+cc+dd+ee+ff)≤0.9.
The skeleton structure of the superplasticizer for the ultra-high performance concrete is shown as the following formula (3):
Wherein R 21 represents a branching functional group.
The invention relates to a preparation method of a superplasticizer for ultra-high performance concrete, which comprises the steps of polymerizing a phosphorus-containing composition C, an alkenyl amine B, small molecules D containing aldehyde groups and optional polymerizable monomers E to form a prepolymer containing branched functional groups capable of undergoing chain transfer, and then carrying out free radical copolymerization with unsaturated carboxylic acid F and unsaturated polyether G to obtain the superplasticizer for ultra-high performance concrete.
Wherein the amount of the polymerizable monomer E is 0 to 80% of the total molar amount of the terminal alkenylamine B, the polymerizable monomer E, the unsaturated carboxylic acid F and the polyether G in the whole reaction.
The terminal alkenyl amine B is one or more than one of the following general formula (4) or the corresponding hydrochloride and sulfate thereof:
Wherein R 1 represents-H or methyl, X represents saturated alkyl having 1 to 9 carbon atoms or phenyl, and R 2 represents H or saturated alkyl having 1 to 4 carbon atoms.
The phosphorus-containing composition C is a mixture of a component I and a component J, wherein the component I is any mixture of one or more of phosphorous acid, hypophosphorous acid, sodium hypophosphite and potassium hypophosphite, and the component J is one or more of phosphoric acid, polyphosphoric acid, pyrophosphoric acid, phosphorus pentoxide, water, disodium hydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate and potassium dihydrogen phosphate;
the total molar amount of hypophosphorous acid and hypophosphite in the phosphorus-containing composition corresponds to 5-90% of the total molar amount of terminal alkenylamine B, polymerizable monomer E, unsaturated carboxylic acid F and polyether G.
The molar amount of the terminal alkenylamine B corresponds to 5 to 90% of the total molar amount of the terminal alkenylamine B, the polymerizable monomer E, the unsaturated carboxylic acid F and the polyether G. This ratio is to ensure that sufficient branching and characteristic adsorption groups are introduced into the product superplasticizer.
The small molecule D containing aldehyde group is one or more than one of the following structures shown in the general formula (5):
wherein R 3 represents H or a saturated alkyl group having 1 to 6 carbon atoms or a phenyl or carboxyl group, an excessively long carbon chain will impair the solubility of the small molecule D in the solvent A.
The polymerizable monomer E is any mixture of one or more than one of the structures shown in the following general formula (6):
Wherein R 4 represents H or CH 3, Y represents carbonyl, -CH 2-、-CH2CH2 -or-C 6H4-CH2 -, represents-C 6H4-CH2 -and phenyl-C 6H4 -is linked to a double bond;
The unsaturated carboxylic acid F is one or more than one of acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, fumaric anhydride, itaconic acid or corresponding sodium, potassium and ammonium salts thereof.
The unsaturated polyether G is any mixture of one or more than one of structures shown in the following general formula (7):
Wherein R 6 and R 7 each independently represent-H or methyl,
Z represents carbonyl or phenyl or-OCH 2CH2 -or-OCH 2CH2CH2CH2 -or-CO-NH-CH 2CH2 -or- (CH 2)p -, wherein p is an integer in the range of 1-6, including 1 and 6;
M and n in the general formula (7) respectively represent the number of repeating units of isopropoxy and ethoxy, which may or may not be integers, the value range of (m+n) is 8-114, and m/(m+n) is not more than 1/2, so that the water solubility of polyether and the extensibility of the molecular chain thereof in an aqueous solution can be ensured; the structure of the general formula (7) is not limited to the order of attachment of the ethoxy and isopropoxy repeat units, and may be either block or random.
The value of (m+n) reflects the length of the side chain, and the side chain is shorter when the value is too small, which does not mean that the dispersant with the structure cannot be prepared, but because the short side chain can cause poor dispersion performance, the preparation difficulty of the plasticizer is increased when the value is too high, the reaction efficiency is difficult to improve, the conversion rate is low, and in addition, the adsorption group is shielded by the side chain when the side chain is too long, so that the adhesion capability on the surface of the solid particles is not favorable to be improved to a certain extent.
The molar amount of the small molecule D containing aldehyde group is 1-3 times of the total amount of active functional groups of the terminal alkenyl amine B, wherein the total amount of active functional groups of the terminal alkenyl amine B is calculated by the molar amount of H atoms connected by N atoms (denoted as N (B-H)), so that the conversion efficiency of amino groups is ensured, the reaction of the second stage is prevented from being influenced, and the excessively high proportion is not unreactive but is disadvantageous to economy.
The phosphorus-containing composition C is used in an amount required to satisfy the following conditions simultaneously: (a) The amount of the component I is calculated by the molar weight of the element P (denoted as N (I-P)), and the molar weight of H atoms connected with the terminal alkenyl amine B by N atoms is calculated, wherein the ratio of the component I to the terminal alkenyl amine B is in the range of 1 to N (I-P)/N (B-H) to 3, the ratio is used for ensuring that branching sites can be reserved at the end of the reaction in the step (1), but a large amount of residues influence the polymerization reaction in the step (2) when the ratio is too high, so that the polymerization conversion rate is low; (b) The proportion of the phosphorous acid to the hypophosphorous acid or the hypophosphite in the component I is arbitrary; (c) The molar amount of phosphorus in component J is n (J-P), which satisfies the following relationship with the molar amount n (E) of polymerizable monomer E: when the polymerizable monomer E is not used in the preparation process of the superplasticizer, the component J can be not used, and the ratio is used for ensuring the ring opening efficiency of the epoxy functional group of the monomer E; (d) The molar amounts of hydrogen and alkali metal ions in the component J are n (J-H) and n (J-M), respectively, and the dosages of the component J and the terminal alkenylamine B need to satisfy the following relation:
This ratio is to ensure that the terminal alkenylamine B is in an ionized state so that it does not affect the ring opening of the epoxy functional group by component J, and is too high to be unreactive, but is disadvantageous in terms of economy.
The total molar amount of hypophosphorous acid and hypophosphite in component I corresponds to 5-90% of the total molar amount of terminal alkenylamine B, polymerizable monomer E, unsaturated carboxylic acid F and polyether G. The proportion is used for ensuring that enough sites which can generate branches in the double bond monomer participating in free radical copolymerization generate chain transfer reaction to generate a branched structure, and the upper limit of the dosage is used for ensuring the effective content of long side chains in the product superplasticizer so as to ensure the dispersion performance of the product superplasticizer.
The amount of unsaturated carboxylic acid F is 0 to 80% of the total molar amount of terminal alkenylamine B, polymerizable monomer E, unsaturated carboxylic acid F and polyether G. The dosage of the unsaturated carboxylic acid F cannot be excessively high, otherwise, the characteristic adsorption group in the product superplasticizer is connected to the superplasticizer molecule after being polymerized through the terminal alkenyl amine B and the polymerizable monomer E; the amount is too low, the surface adsorption capacity is limited, and the dispersion capacity and the economy cannot show advantages in the ultra-high performance concrete.
The amount of polyether G is equivalent to 10% -90% of the total molar amount of terminal alkenylamine B, polymerizable monomer E, unsaturated carboxylic acid F and polyether G. The super plasticizer of the product has weaker adsorption capacity when the value is too high, and the steric hindrance provided after the super plasticizer is adsorbed is smaller when the value is too low, and in addition, the early flowability of the concrete is quickly lost possibly due to the excessively strong adsorption capacity.
The invention relates to a preparation method of a superplasticizer for ultra-high performance concrete, which comprises the following steps:
(1) Adding a certain amount of solvent A and phosphorus-containing composition C into a reactor, regulating the reactor to 70-120 ℃, uniformly stirring, continuously and uniformly adding terminal alkenyl amine B and micromolecule D containing aldehyde groups into the reactor, regulating the temperature of the reactor to 0-120 ℃ after the reaction time is 6-24 hours, continuously and uniformly adding polymerizable monomer E into the reactor, stopping the reaction after stirring for 1-24 hours, and removing the solvent and the volatilizable micromolecule in vacuum to obtain an intermediate mixture;
(2) And (3) carrying out free radical polymerization on all intermediate mixtures prepared in the step (1), unsaturated carboxylic acid F and unsaturated polyether G in an aqueous solution at the temperature of 0-90 ℃ to prepare the superplasticizer for the ultra-high-performance concrete. The polymerization is initiated by an initiator H, and the chain transfer agent is K.
The reaction temperature of the first stage in the step (1) is 70-120 ℃ and the reaction time is 6-24h. The reaction temperature of the second stage in the step (1) is 0-120 ℃ and the reaction time is 1-24h. The reaction time required for each step depends on the reaction rate and conversion, and the reaction time is generally longer with low temperature.
In the step (2), the reaction temperature is 0-90 ℃, and the reaction time is accumulated for 1-12h when the initiator is added. Similarly, the reaction temperature in this step depends on the initiating system used, and in general, the reaction temperature is relatively low with redox initiating systems, and the reaction rate is fast and the reaction time is short due to the higher rate of free radical generation; the temperature used is relatively high when thermal initiation is adopted, and the reaction time is long. And can be adjusted by one skilled in the art according to experience.
The intermediate mixture, unsaturated carboxylic acid and unsaturated polyether are added and reacted in such a manner that they are added at once, in portions or continuously and uniformly during a period of time before or during the start of the reaction. The initiator is added to the reaction in such a manner that it is added in one portion before or during the start of the reaction, in portions or continuously and uniformly during a period of the reaction. The reaction is started from the addition of the initiator, the reaction is carried out for a period of time, and the solution of the required polymer superplasticizer is obtained after stopping the reaction.
The solvent A in the step (1) is any one of water, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and acetonitrile or a mixture of any proportion thereof.
The initiator H in the step (2) is a conventional free radical polymerization initiation system adopted by a person skilled in the art, and the initiator can be a thermal initiation or redox initiator, and can be added at one time or continuously and uniformly in a certain time, and the initiator must meet the following conditions: the initiator can be dissolved in the solvent at the corresponding temperature and successfully initiates polymerization, and the initiator is fully decomposed in the reaction process so as to prevent the stability of the polymer from being influenced by the change after the reaction is finished. Including but not limited to the initiator systems listed below:
the thermal initiator is any one of azodiisobutyronitrile, azodiisoheptonitrile, azodiisobutylamidine hydrochloride, azodiiso Ding Mi hydrochloride, ammonium persulfate, potassium persulfate and sodium persulfate;
The redox initiator is formed by combining an oxidant and a reducing agent, wherein the oxidant is any one of hydrogen peroxide, ammonium persulfate, potassium persulfate and sodium persulfate;
When the oxidizing agent is hydrogen peroxide, the reducing agent may be one or any combination of more than one of saturated alkyl mercaptan, thioglycollic acid, ascorbic acid or mercaptopropionic acid containing 2-6 carbon atoms, and further, may or may not contain one or any combination of more than one of ferrous acetate, ferrous sulfate or ferrous ammonium sulfate as a catalyst, the catalyst being measured in terms of the molar amount of Fe element, and the amount thereof being not more than 10% of the molar amount of the above reducing agent. Too high a catalyst level may result in uncontrolled polymer molecular weight.
When the oxidant is any one of ammonium persulfate, potassium persulfate and sodium persulfate, the reducing agent is any one of the following compositions: (1) Any combination of one or more of thioglycollic acid, ascorbic acid, rongalite or mercaptopropionic acid, and in addition, any combination of one or more of ferrous acetate, ferrous sulfate or ferrous ammonium sulfate may be contained or not contained as a catalyst, and the catalyst is metered by the molar amount of Fe element, and the dosage of the catalyst is not more than 10% of the molar amount of the reducing agent. Too high a catalyst level may cause a loss of control of the polymer molecular weight; (2) Any combination of one or more of sodium bisulfite, sodium sulfite, and sodium metabisulfite.
The initiator dosage is calculated based on the following method, and if the initiator is a thermal initiator, the initiator mass is 0.2-4% of the total mass of the terminal alkenyl amine B, the polymerizable monomer E, the unsaturated carboxylic acid F and the unsaturated polyether G; in the case of redox initiator, the molar ratio of the oxidant to the reducing agent is 0.25-4, calculated as the larger one of the oxidant and the reducing agent, based on the total molar amount of the terminal alkenylamine B, the polymerizable monomer E, the unsaturated carboxylic acid F and the unsaturated polyether G.
The chain transfer agent K in the step (2) is a conventional free radical polymerization chain transfer agent adopted by a person skilled in the art, and is only used for adjusting the molecular weight of the product superplasticizer, so that the weight average molecular weight of the product superplasticizer is between 2000 and 100000. Chain transfer agents K used include, but are not limited to: (1) Thiol-containing small organic molecules including, but not limited to, saturated alkyl thiols containing 2-6 carbon atoms, mercaptoethanol, mercaptoethylamine, cysteine, mercaptoacetic acid, or mercaptopropionic acid; (2) sodium bisulphite, sodium sulfite and sodium metabisulfite. The amount of the catalyst can be adjusted according to the target molecular weight of the product, and is generally between 0 and 15 percent of the total molar weight of the polymerizable double bonds in the reaction system. The total molar amount of polymerizable double bonds is numerically equivalent to the total molar amount of terminal alkenylamine B, polyether G and unsaturated carboxylic acid F.
The concentration of the effective reactant in the step (1) needs to be determined according to the reaction conditions, and the typical percentage range of the total mass of the effective reactant to the total mass of the system is 10-90%, so that the reactant needs to be ensured to be in a dissolved state in the system. The effective reactants are phosphorus-containing composition C, terminal alkenyl amine B, small molecule D containing aldehyde group and polymerizable monomer E.
The concentration of the effective reactant in the step (2) is the concentration of a conventional free radical polymerization system adopted by a person skilled in the art, and can be adjusted according to economy, monomer feeding sequence and the like, and the typical effective reactant concentration range is 30-80wt%, and the effective reactant is the sum of an intermediate mixture, polyether G and unsaturated carboxylic acid F.
The weight average molecular weight of the superplasticizer polymer in the finally prepared sample is between 2000 and 100000. Too low will impair the adsorption capacity and too high molecular weights will cause side effects such as an enhanced interaction between the solid particles by "bridging", reducing the fluidity of the concrete, while at the same time a faster fluidity loss will result due to an excessively fast adsorption rate, requiring an additional increase in plasticizer usage to achieve the same fluidity, which is disadvantageous for economy and reduced viscosity of the concrete.
Compared with the common commercial superplasticizer, the superplasticizer disclosed by the invention is applied to ultra-high-performance concrete (the water-cement ratio is not higher than 0.2) according to the reference example, the mixing amount of the superplasticizer can be reduced by 16-42% compared with that of the common commercial polycarboxylic superplasticizer, the viscosity is effectively reduced, and the shearing viscosity can be reduced by 20-49%. In addition, the maximum dispersion capacity of the superplasticizer is obviously better than that of the commercial superplasticizer, and the superplasticizer can effectively improve the flowability of concrete under the condition of extremely low water-to-gel ratio (often not higher than 0.16), and the commercial superplasticizer cannot realize the effective flowability of concrete no matter how much the superplasticizer is mixed. It should be noted that the amount of superplasticizer of the present invention added to achieve the same fluidity in ordinary commercial concrete may be increased as compared to commercial superplasticizers.
Detailed Description
For a better understanding of the present invention, the following examples are further illustrated, but are not limited to the following examples. The units used below are parts by mass, all compounds used are commercial products or synthetic products reported in the literature.
The sources of solvent A, terminal alkenylamine B, aldehyde group small molecule D, polymerizable monomer E, polyether G (except G3 and G6), unsaturated carboxylic acid F, initiator H and chain transfer agent K are all commercially available (carbofuran reagent, TCI reagent, sigma-Aldrich, huntsman, ron reagent, etc.). Some polyethers are commercial products and are prepared by ring-opening polymerization of ethylene oxide anions under the catalysis of alkenyl alcohol bases and are manufactured by Su Bote company.
Table 1 names of compounds used in examples
Some of the compounds listed in Table 1 have the structures shown below:
polyethers G3 and G6 are prepared by dehydrating condensation of corresponding polyethylene glycol or substituted polyethylene glycol ether with unsaturated carboxylic acid:
(1) And G3: prepared by reacting acrylic acid with aminopoly (ethylene oxide-propylene oxide) monomethyl ether (number average molecular weight 2000, m/(m+n) =0.3, from Huntsman).
Acrylic acid (7.56G, 0.105 mol) and aminopoly (ethylene oxide-propylene oxide) monomethyl ether (number average molecular weight 2000, 200G,0.1 mol) were dissolved with 1000mL of methylene chloride, DMAP (0.122G, 1 mmol) was added thereto, a solution of DCC (22.67G, 0.11 mol) dissolved in methylene chloride (200 mL) was added dropwise thereto at room temperature, dropwise addition was continued for 4 hours, stirring was continued for 6 hours after the dropwise addition, white solid precipitate was removed by filtration, distillation under reduced pressure was performed, the obtained pasty solid was dissolved with methylene chloride, and then subjected to precipitation with diethyl ether, centrifugation, and then the obtained pasty solid was subjected to repeated methylene chloride/diethyl ether precipitation for 2 times, and finally the obtained product was dried in vacuo to obtain monomer G3, yield 83%.
(2) G6: prepared by reacting methacrylic acid with aminopolyethylene glycol (O- (2-aminoethyl) polyethylene glycol, number average molecular weight 5000, number of ethylene glycol repeat units about 113, derived from Sigma).
Methacrylic acid (0.0903G, 0.00105 mol) and the above aminopolyethylene glycol (5G, 0.01 mol) were dissolved with 50mL of methylene chloride, DMAP (0.00122G, 0.01 mmol) was added thereto, a solution of DCC (0.2267G, 0.001 mol) dissolved in methylene chloride (5 mL) was added dropwise thereto at room temperature, and dropwise addition was carried out for 12 hours, white precipitate appeared in the system, stirring was continued for 12 hours after completion of dropwise addition, filtration, distillation under reduced pressure, the obtained solid was dissolved with methylene chloride, and then ether was precipitated, filtration was carried out, and the obtained solid was repeated methylene chloride/ether precipitation 2 times, and finally the obtained product was dried in vacuo to obtain polyether G6, yield 77%.
The following is a specific procedure of the example, the measurement of all reactions is based on the alkenylamine B, the amount of the substance for the alkenylamine B is calculated to be 0.1 molar part, the following table shows the feeding ratio of the example, the molecular weight of the product is measured by using Shimadzu GPC (LC-20A), the gel column is TSK-GELSW series of TOSOH company, a differential refractive detector is used, the mobile phase is 0.1MNaNO 3 aqueous solution, and polyethylene glycol is used as the molecular weight measurement reference.
Example 1
(1) Acetonitrile (206.58 parts) was added to the reactor, then 14.35 parts of phosphorous acid, 0.99 parts of hypophosphorous acid (50% aqueous solution, 0.99 parts of water), 0.88 parts of sodium hypophosphite, 4.9 parts of anhydrous phosphoric acid and 6 parts of sodium dihydrogen phosphate were added thereto, the reactor was adjusted to 70 ℃ and stirred uniformly, 7.112 parts of B1 and D1 (17.14 parts of aqueous solution, 35 wt%) were continuously and uniformly added to the reactor, the feeding time was 6 hours, the reaction was continued for 6 hours after the feeding, the reactor temperature was adjusted to 0 ℃, 11.414 parts of E1 was continuously and uniformly added to the reactor within 2 hours, the reaction was stopped after the addition, and the solvent and the volatilizable organic small molecules were removed in vacuo to obtain an intermediate mixture.
(2) To the flask was added water (22.06 parts), polyether G1 (125 parts) and the intermediate mixture prepared in the step (1), the temperature of the reactor was adjusted to 80℃and stirred and mixed uniformly, 0.422 parts of azobisisobutyronitrile powder was added thereto at one time, then an aqueous solution (20 parts of water) of sodium methacrylate (2.7 parts) and sodium acrylate (1.8 parts) was added thereto dropwise uniformly for 4 hours, 0.422 parts of azobisisobutyronitrile powder was added thereto at every half hour from the start of the monomer dropwise addition, 6 batches were total, the reaction was continued for 3 hours after the completion of the addition, the temperature was adjusted to room temperature, and the reaction was stopped to obtain a superplasticizer sample PCE-DP01 having a weight average molecular weight of 67.2kDa.
Example 2
(1) Water (11.08 parts) was added to the reactor, followed by 26.4 parts of hypophosphorous acid and 1.96 parts of anhydrous phosphoric acid, the reactor was adjusted to 100℃and stirred uniformly, 16.93 parts of B2 and 28.84 parts of D2 were continuously and uniformly added to the reactor, the feeding time was 1h, the reaction was continued for 5h after the feeding, the reactor temperature was adjusted to 60℃and 25.626 parts of E2 was added to the reactor, the reaction was stopped after the addition was continued for 8h, and the solvent and the volatilizable small organic molecules were removed in vacuo to obtain an intermediate mixture.
(2) Into a flask, water (105.05 parts), polyether G2 (240 parts) and the intermediate mixture prepared in the step (1) are added, the temperature of a reactor is adjusted to 50 ℃, the mixture is stirred and mixed uniformly, a mixed aqueous solution (105.05 parts of water) of acrylic acid (7.2 parts) and an initiator azobisisobutyronium hydrochloride (11.59 parts) is added dropwise into the mixture uniformly, the feeding lasts for 4 hours, the reaction is continued for 8 hours after the dropwise addition, the temperature is adjusted to room temperature, the reaction is stopped, and a superplasticizer sample PCE-DP02 with a weight average molecular weight of 95.1kDa is obtained.
Example 3
(1) To the reactor was added water (2382.684 parts), followed by 52.8 parts of sodium hypophosphite, phosphorus pentoxide (21.6 parts) (7.8 parts of water in the present reaction composition C was contained in a solvent, not separately listed) and 14.2 parts of disodium hydrogen phosphate, the reactor was adjusted to 120 ℃ and stirred uniformly, 9.356 parts of B3 and 44.4 parts of D3 were continuously and uniformly added to the reactor, respectively, the feeding time was 0.5h, the reaction was continued for 5.5h after the feeding was completed, the reactor temperature was adjusted to 80 ℃, 113.72 parts of E3 was continuously and uniformly added to the reactor over 4h, and the reaction was stopped after the addition was continued with stirring for 4h, and the solvent and the volatilizable small organic molecules were removed in vacuo to obtain an intermediate mixture.
(2) To the flask were added water (207.675 parts), polyether G3 (400 parts) and the intermediate mixture prepared in step (1), the temperature of the reactor was adjusted to 60 ℃, stirred and mixed uniformly, and simultaneously, mercaptopropionic acid (1.06 parts) aqueous solution (water 69.225 parts), ammonium persulfate aqueous solution (2.28 parts dissolved in 69.225 parts) and sodium bisulphite (4.16 parts) dissolved in 69.225 parts) were respectively and uniformly dropped thereto, and the dropping was completed for 2 hours, the temperature was adjusted to room temperature, and the reaction was stopped to obtain a superplasticizer sample PCE-DP03 having a weight average molecular weight of 49.8kDa.
Example 4
(1) N, N-dimethylacetamide (75.85 parts) was added to the reactor, then 24.6 parts of phosphorous acid, 13.2 parts (50 wt%) of hypophosphorous acid solution and 3.92 parts of anhydrous phosphoric acid were added thereto, the reactor was adjusted to 70℃and stirred uniformly, 11.916 parts of B6 and 21.2 parts of D3 were continuously and uniformly added to the reactor, respectively, the feeding time was 6 hours, the reaction was continued for 6 hours after the feeding, the reactor temperature was adjusted to 100℃and 7.61 parts of E4 was continuously and uniformly added to the reactor within 3 hours, the reaction was stopped after the addition was continued with stirring for 1 hour, and the solvent and the volatilizable small organic molecules were removed in vacuo to obtain an intermediate mixture.
(2) To the flask was added water (98.55 parts), polyether G4 (123 parts) and the intermediate mixture prepared in step (1), the reactor temperature was adjusted to 40 ℃, an aqueous hydrogen peroxide solution (30 wt%,0.45 parts) was added thereto, and stirred and mixed uniformly, while a mixed aqueous solution of mercaptoethanol (0.936 parts) and ascorbic acid (0.352 parts dissolved in 98.55 parts of water) was added dropwise thereto uniformly, the dropwise addition was continued for 1 hour, the reaction was continued for 1 hour after the completion of the dropwise addition, the temperature was adjusted to room temperature, and the reaction was stopped to obtain a superplasticizer sample PCE-DP04 having a weight average molecular weight of 6.2kDa.
Example 5
(1) Dimethyl sulfoxide (6.57 parts) was added to the reactor, then 4.1 parts of phosphorous acid, 33 parts (50 wt%) of hypophosphorous acid solution and 8.9 parts of pyrophosphoric acid (0.9 part of water in the present reaction composition C was contained in the hypophosphorous acid solution, not separately listed) were added thereto, the reactor was adjusted to 100℃and stirred uniformly, 9.917 parts of B5 and D1 (17.14 parts of aqueous solution, 35 wt%) were continuously and uniformly added to the reactor, the charging time was 12 hours, the reaction was continued for 4 hours after the charging was completed, the reactor temperature was adjusted to 80℃and 12.813 parts of E2 was continuously and uniformly added to the reactor over 5 hours, and the reaction was stopped after the addition was continued with stirring for 1 hour, and the vacuum solvent and the volatilizable small organic molecules were removed to obtain an intermediate mixture.
(2) Into a flask, water (559.39 parts), polyether G5 (600 parts) and the intermediate mixture prepared in the step (1) were added, the temperature of the reactor was adjusted to 5 ℃, an aqueous solution of hydrogen peroxide (30 wt%,2.27 parts) and ferrous sulfate (0.139 parts) were added thereto, and stirred and mixed uniformly, while a mixture of acrylic acid (7.2 parts) and ethanethiol (0.795 parts), an aqueous solution of ascorbic acid (0.88 parts) and water were added dropwise thereto uniformly, the dropwise addition was continued for 1.5 hours, the reaction was continued for 0.5 hour after the dropwise addition, the temperature was adjusted to room temperature, and the reaction was stopped to obtain a superplasticizer sample PCE-DP05 having a weight average molecular weight of 31.9kDa.
Example 6
(1) N-methylpyrrolidone (85.89 parts) was added to the reactor, then 4.1 parts of phosphorous acid, 6.6 parts (50 wt%) of hypophosphorous acid solution and 9.8 parts of anhydrous phosphoric acid were added thereto, the reactor was adjusted to 100℃and stirred uniformly, 11.32 parts of B4 and 21.633 parts of D2 were continuously and uniformly added to the reactor, the feeding time was 4 hours, the reaction was continued for 2 hours after the feeding, the reactor temperature was adjusted to 80℃and 7.11 parts of E3 was continuously and uniformly added to the reactor within 2 hours, the reaction was stopped after the addition was continued for 4 hours with stirring, and the solvent and the volatilizable small organic molecules were removed in vacuo to obtain an intermediate mixture.
(2) To the flask was added water (21.53 parts), itaconic acid (26 parts) and the intermediate mixture prepared in step (1), the temperature of the reactor was adjusted to 35 ℃ and stirred and mixed uniformly, 0.611 parts of azobisiso Ding Mi-in hydrochloride was added thereto at one time, simultaneously, a mixed aqueous solution of methacrylic acid (8.6 parts) and polyether G6 (252.5 parts) was continuously and uniformly added thereto dropwise over 8 hours (150 parts of water), simultaneously, an aqueous solution of sodium bisulphite as a chain transfer agent (7.8 parts dissolved in 150 parts of water) was added thereto dropwise, the reaction was continued for 4 hours after the completion of the addition, the temperature was adjusted to room temperature and the reaction was stopped to obtain a superplasticizer sample PCE-DP06 having a weight average molecular weight of 14.6kDa.
Example 7
(1) Water (8.029 parts) was added to the reactor, then 30.75 parts of phosphorous acid, 13.2 parts (50 wt%) of hypophosphorous acid solution and 13 parts of potassium hypophosphite were added thereto, the reactor was adjusted to 80 ℃ and stirred uniformly, 7.112 parts of B1 and 14.8 parts of D3 were continuously and uniformly added to the reactor, respectively, the feeding time was 8 hours, the reaction was continued for 4 hours after the feeding was completed, the reaction was stopped, and the solvent and the volatilizable small organic molecules were removed in vacuo to obtain an intermediate mixture. (the amount of the polymerizable monomer E used in this example was 0)
(2) To a flask, water (202.02 parts), polyether G2 (120 parts), itaconic acid 6.5 parts and the intermediate mixture prepared in step (1) were added, the temperature of the reactor was adjusted to 45 ℃, hydrogen peroxide (30% aqueous solution, 0.28 parts) was added thereto at one time, stirred and mixed uniformly, a mixed solution of acrylic acid (3.6 parts), mercaptopropionic acid (0.795 parts) and ascorbic acid (0.44 parts) was continuously and uniformly added thereto (dissolved in 100 parts of water), the cumulative addition time was 45 minutes, the reaction was continued for 15 minutes after the addition, the temperature was adjusted to room temperature, and the reaction was stopped to obtain a superplasticizer sample PCE-DP07 having a weight average molecular weight of 22.6kDa.
Example 8
(1) Water (41.80 parts) was added to the reactor, 13.2 parts of hypophosphorous acid, 14.41 parts (85 wt.%) of phosphoric acid, 4.35 parts of dipotassium hydrogen phosphate and 6.8 parts of potassium dihydrogen phosphate were then added thereto, the reactor was adjusted to 80 ℃ and stirred uniformly, 7.112 parts of B1 and 42.4 parts of D4 were continuously and uniformly added to the reactor, the feeding time was 4 hours, the reaction was continued for 8 hours after the feeding, the reactor temperature was adjusted to 60 ℃, 11.414 parts of E1 was continuously and uniformly added to the reactor within 1 hour, the reaction was stopped after the addition was continued with stirring for 1 hour, and the solvent and the volatilizable small organic molecules were removed in vacuo to obtain an intermediate mixture.
(2) To the flask was added water (344.68 parts) and the intermediate mixture prepared in step (1), the reactor temperature was adjusted to 60 ℃, ammonium persulfate (1.08 parts) was added thereto at one time, stirred and mixed uniformly, and thereto was continuously and uniformly added a mixed solution of polyether G1 (900 parts), mercaptopropionic acid (4.24 parts) and ascorbic acid (0.88 parts) dissolved in 300 parts of water, the addition time was 4 hours, the reaction was continued for 2 hours, the temperature was adjusted to room temperature, and the reaction was stopped to obtain a superplasticizer sample PCE-DP08 having a weight average molecular weight of 25.8kDa.
Example 9
(1) N, N-dimethylformamide (59.18 parts) was added to the reactor, then 22.96 parts of phosphorous acid and 7.92 parts of hypophosphorous acid were added thereto, the reactor was adjusted to 100℃and stirred uniformly, 9.356 parts of B3 and D1 (51.42 parts of aqueous solution, 35 wt%) were continuously and uniformly added to the reactor, the charging time was 5 hours, the reaction was continued for 1 hour after the charging, the reactor temperature was adjusted to 90℃and 0.948 parts of E3 was continuously and uniformly added to the reactor over 1 hour, the reaction was stopped after the addition was continued for 2 hours, and the solvent and the volatilizable small organic molecules were removed in vacuo to obtain an intermediate mixture.
(2) To the flask, water (30 parts of water) was added, the reactor temperature was adjusted to 75 ℃, ammonium persulfate (0.130 parts) was added thereto at one time, stirred and mixed uniformly, and to this was continuously and uniformly added a mixture solution of the intermediate mixture prepared in step (1), polyether G4 (54.67 parts) and thioglycolic acid (0.147 parts) dissolved in 121.98 parts of water, the feeding time was continued for 4 hours, the remaining ammonium persulfate was divided into 4 batches, 0.13 parts was added to the reaction system every 1 hour, the reaction was continued for 4 hours, the temperature was adjusted to room temperature, and the reaction was stopped to obtain a superplasticizer sample PCE-DP09 having a weight average molecular weight of 37.6kDa.
Example 10
(1) N, N-dimethylformamide (89.90 parts) was added to the reactor, then 8.2 parts of phosphorous acid and 26.4 parts of hypophosphorous acid (50% aqueous solution) were added thereto, the reactor was adjusted to 120℃and stirred uniformly, 9.917 parts of B5 and 7.211 parts of D2 were continuously and uniformly added to the reactor, respectively, the charging time was 9 hours, the reaction was continued for 3 hours after the charging was completed, the reaction was stopped, and the solvent and the volatilizable small organic molecules were removed in vacuo to obtain an intermediate mixture. (the amount of the polymerizable monomer E used in this example was 0)
(2) To a flask, water (101.4 parts) was added, the temperature of the reactor was adjusted to 30 ℃, hydrogen peroxide (30% aqueous solution, 1.13 parts) was added thereto at one time, and stirred and mixed uniformly, and to this was continuously and uniformly added a mixed solution (dissolved in 101.4 parts of water) of the intermediate mixture prepared in step (1), methacrylic acid (68.8 parts), polyether G4 (205 parts), rongalite (0.385 parts) and mercaptoethanol (3.9 parts), the feeding time was continued for 4 hours, the reaction was continued for 1 hour, the temperature was adjusted to room temperature, and the reaction was stopped, to obtain a superplasticizer sample PCE-DP10 having a weight average molecular weight of 16.9kDa.
Example 11
(1) Dimethyl sulfoxide (115.84 parts) is added into a reactor, 3.28 parts of phosphorous acid, 10.56 parts of hypophosphorous acid and 1.96 parts of anhydrous phosphoric acid are then added into the reactor, the reactor is regulated to 80 ℃, stirring is uniform, 9.917 parts of B5 and 14.8 parts of D3 are respectively and continuously and uniformly added into the reactor, the feeding time is 4 hours, the reaction is continued for 20 hours after the feeding, the temperature of the reactor is regulated to 90 ℃, 9.131 parts of E1 are continuously and uniformly added into the reactor within 0.5 hour, stirring is continued for 2.5 hours after the feeding, the reaction is stopped, and the solvent and the volatilizable small organic molecules are removed in vacuum, so that an intermediate mixture is obtained.
(2) To the flask was added water (30.118 parts) and the intermediate mixture prepared in step (1), then hydrogen peroxide (0.45 parts, 30 wt%) and ferrous ammonium sulfate (0.003336 parts) were added thereto, stirred and mixed uniformly, the reactor temperature was adjusted to 40 ℃, a mixed solution of acrylic acid (0.72 parts), itaconic acid (6.5 parts), polyether G1 (80 parts) and mercaptoethanol (0.25 parts) was continuously and uniformly added thereto over 2.5 hours (dissolved in 240.94 parts of water), while an aqueous solution of ascorbic acid (0.2112 parts of ascorbic acid was dissolved in 30.118 parts of water) was continuously and uniformly added thereto over 3 hours, the reaction was continued for 1 hour, the temperature was adjusted to room temperature, and the reaction was stopped to obtain a superplasticizer sample PCE-DP11 having a weight average molecular weight of 63.6kDa.
Example 12
(1) N, N-dimethylformamide (107.45 parts) was added to the reactor, then 3.28 parts of phosphorous acid, 10.56 parts of hypophosphorous acid and 7.84 parts of anhydrous phosphoric acid were added thereto, the reactor was adjusted to 80℃and stirred uniformly, 11.916 parts of B6 and 63.6 parts of D4 were continuously and uniformly added to the reactor, the charging time was 1h, the reaction was continued for 9h after the charging was completed, the reactor temperature was adjusted to 120℃and 10.25 parts of E2 was continuously and uniformly added to the reactor within 2.5h, the reaction was stopped after the addition was continued for 0.5h, and the solvent and the volatilizable small organic molecules were removed in vacuo to obtain an intermediate mixture.
(2) To the flask, water (62.788 parts) and polyether G2 (240 parts) were added, stirred and mixed uniformly, the reactor temperature was adjusted to 90 ℃, and a mixed solution of the intermediate mixture prepared in step (1), maleic anhydride (11.76 parts), ascorbic acid (0.704 parts) and mercaptopropionic acid (0.254 parts) was continuously and uniformly added thereto (dissolved in 251.152 parts of water), while a sodium persulfate aqueous solution (1.9 parts dissolved in 251.152 parts of water) was continuously and uniformly added thereto for 1 hour, and the reaction was continued for 1 hour, and the temperature was adjusted to room temperature, and the reaction was stopped to obtain a superplasticizer sample PCE-DP12 having a weight average molecular weight of 59.4kDa.
Application examples
The use effect of the superplasticizer is illustrated by adopting an extremely low water-cement ratio cement paste experiment and an ultra-high performance concrete experiment.
The clear slurry was prepared by using crane Lin Shuini (P.O.42.5), the concrete was prepared by using Jiang Naxiao field cement (P.II.52.5), and all materials were kept at the desired temperature before the experiment. The comparative sample was a conventional commercial polycarboxylic superplasticizer (commercial 1 being an ester and commercial 2 being an ether, side chain length 2400). It should be noted that all the percentages expressed below are in comparison with the corresponding index in the commercial sample.
(1) Cement paste
The fluidity of the cement paste is measured according to GB/T8077-2000 method for testing the homogeneity of concrete admixture, and the mixing amount of all the dispersing agents is the percentage (wt%) of pure solids relative to the mass of cement. To characterize the dispersion/dispersion retention properties of the samples at very low water to gel ratios, a cement paste was prepared using 270g cement and 30g silica fume, with a water usage fixed at 53.1g. Cement and silica fume are mixed in advance by a mixer to ensure uniformity.
The paste flow of different superplasticizers was tested based on a standard paste mixing procedure, while the cement paste was tested for 30min of flow. The samples prepared in the examples were compared with commercially available polycarboxylic superplasticizer samples and the results were as follows:
TABLE 2 Cement paste test results (20 ℃ C.)
As can be seen from the results in Table 2, although the dispersion ability of the superplasticizer prepared in the examples of the present invention was high or low in relation to the structural parameters, the dispersion performance was much stronger than that of the commercial sample at a water-gel ratio of 0.177, and the fluidity retention ability of most of the samples, except for PCE-DP04 and PCE-DP06, was substantially equivalent to that of the commercial sample 2, being more excellent than that of the commercial sample 1.
(2) Ultra-high performance concrete (UHPC) test (dispersion comparison, mortar)
In order to examine the maximum dispersion capability of different samples under different mixing amounts, the fluidity of cement mortar under the condition of extremely low water-cement ratio is examined under the condition of given mixing ratio.
Table 3UHPC mortar mix ratio (weight ratio)
| Cement and its preparation method | Silica fume | Superfine mineral powder | Sand and sand | Water and its preparation method |
| 0.68 | 0.12 | 0.2 | 0.7 | 0.15 |
The initial fluidity was examined at (240.+ -.5) mm for shear viscosity of the mortar, the initial slurry rheology profile was measured using a Rheometer (Brookfield R/S300 Rheometer) (cf. Literature Constrat. Build. Mater.2017,149,359-366, maximum shear rate 25S -1), and the shear viscosity of 15S -1 was selected for comparison (the shear rate was at the same level as the rate of slurry handling such as stirring). The V funnel time of this fluidity mortar was also measured, and the results are shown in table 4:
table 4UHPC mortar test results (20 ℃ C., blank is untested)
As can be seen from the results in table 4, all samples showed a tendency that the mortar fluidity increased first and then not increased again with increasing amount of the mixture under the test mixing conditions, and the increase of the fluidity of some samples was slightly decreased due to the increase of viscosity, the slow flow rate and the slightly smaller fluidity during the measurement time. The maximum fluidity appearing in the table is taken as the limit water reduction of the sample, i.e. the maximum degree of dispersion that can be achieved, irrespective of the sample loading.
All samples in the table have far greater maximum dispersion capacity than the commercial samples, which demonstrates the superior dispersion capacity of the samples prepared according to the examples of the present invention. In addition, even when the mortar fluidity was compared to an amount of 240mm, the sample of the present invention required an amount of 0.1 to 0.3wt% lower than that of the commercially available sample (corresponding to a 16 to 42% decrease in percentage).
The samples PCE-DP01-12 prepared by the embodiment of the invention can reduce the shearing viscosity by 20-49% and the V funnel time by comparing the shearing viscosity (15 s -1) of the mortar with the fluidity (240+/-5) mm, and the V funnel time can be shortened by 18-50% and the viscosity reduction property of the samples is fully illustrated.
(3) Ultra High Performance Concrete (UHPC) test (concrete, fiber containing)
The application performance of the superplasticizer prepared by the invention in UHPC is examined by changing the mixing proportion, and the concrete mixing proportion is as follows:
Table 5UHPC mix ratio (weight ratio, fiber volume fraction)
| Cement and its preparation method | Silica fume | Fly ash | Sand and sand | Fiber/V% | Water and its preparation method |
| 0.75 | 0.13 | 0.12 | 0.9 | 2 | 0.148 |
In the test, the slump ((20+/-1) cm) of UHPC is controlled to be equivalent to the expansion ((45+/-2) cm) by adjusting the dosage of the superplasticizer, and the used defoamer is a common and conventional PXP-I concrete defoamer sold by Jiangsu Su Bote New material Co., ltd. If the fluidity of the concrete is difficult to reach the index, the fluidity of the concrete at the mixing amount of the superplasticizer of 1.0 weight percent is uniformly inspected, and the fluidity of the concrete when the concrete is discharged from the machine is inspected. At this yield, the sample dispersing ability has reached a limit, and concrete fluidity is difficult to enhance by adding a superplasticizer.
Adding cement, silica fume, fly ash and sand into a stirrer, stirring for 2min, adding fiber, continuously stirring for 3min, and discharging, respectively testing the slump and the expansion degree of UHPC, and recording as the initial/discharge amount and the mixing amount of the super plasticizer. The results were as follows:
Table 6 characterization of UHPC (20 ℃ C.)
* "-" Means slump only, no expansion
It can be seen that commercial superplasticizers have failed to meet the flowability requirements of such low cement ratio concrete, whereas superplasticizer samples prepared using the examples can impart good flowability to cement ratio 0.148 concrete. Compared with the compressive strength of 28 days concrete, the commercial superplasticizer has poor dispersion performance and has strength slightly lower than that of the samples prepared in the examples, which is probably caused by slightly poor uniformity of slurry and aggregate.
Claims (3)
1. The preparation method of the superplasticizer for the ultra-high performance concrete is characterized in that a phosphorus-containing composition C, terminal alkenyl amine B, small molecules D containing aldehyde groups and optional polymerizable monomers E are polymerized into a prepolymer containing branched functional groups capable of undergoing chain transfer, and then the prepolymer is subjected to free radical copolymerization with unsaturated carboxylic acid F and unsaturated polyether G to obtain the superplasticizer for the ultra-high performance concrete;
The terminal alkenyl amine B is one or more than one of the following general formula (4) or the corresponding hydrochloride and sulfate thereof:
Wherein R 1 represents-H or methyl, X represents saturated alkyl having 1 to 9 carbon atoms or phenyl, R 2 represents H or saturated alkyl having 1 to 4 carbon atoms;
The phosphorus-containing composition C is a mixture of a component I and a component J, wherein the component I is any mixture of one or more of phosphorous acid, hypophosphorous acid, sodium hypophosphite and potassium hypophosphite, and the component J is one or more of phosphoric acid, polyphosphoric acid, pyrophosphoric acid, phosphorus pentoxide, water, disodium hydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate and potassium dihydrogen phosphate;
The total molar amount of hypophosphorous acid, sodium hypophosphite and potassium hypophosphite in the component I is 5-90% of the total molar amount of terminal alkenylamine B, polymerizable monomer E, unsaturated carboxylic acid F and polyether G;
The molar amount of the terminal alkenylamine B is 5-90% of the total molar amount of the terminal alkenylamine B, the polymerizable monomer E, the unsaturated carboxylic acid F and the polyether G;
The small molecule D containing aldehyde group is one or more than one of the following structures shown in the general formula (5):
Wherein R 3 represents H or a saturated alkyl group having 1 to 6 carbon atoms or a phenyl or carboxyl group, an excessively long carbon chain will impair the solubility of the small molecule D in the solvent A;
The molar quantity of the small molecule D containing aldehyde group is 1-3 times of the total quantity of active functional groups of the terminal alkenyl amine B,
The polymerizable monomer E is any mixture of one or more than one of the structures shown in the following general formula (6):
Wherein R 4 represents H or CH 3;
y represents carbonyl, -CH 2-、-CH2CH2 -, or-C 6H4-CH2 -;
Y represents-C 6H4-CH2 -where-C 6H4 -is linked to a double bond;
Wherein the dosage of the polymerizable monomer E is 0-80% of the total molar quantity of the terminal alkenyl amine B, the polymerizable monomer E, the unsaturated carboxylic acid F and the polyether G in the whole reaction;
The unsaturated carboxylic acid F is one or more than one of acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, fumaric anhydride, itaconic acid or corresponding sodium, potassium and ammonium salts thereof;
the unsaturated polyether G is any mixture of one or more than one of structures shown in the following general formula (7):
Wherein R 6 and R 7 each independently represent-H or methyl,
Z represents carbonyl or phenyl or-OCH 2CH2 -or-OCH 2CH2CH2CH2 -or-CO-NH-CH 2CH2 -or- (CH 2)p -, wherein p is an integer in the range of 1-6, including 1 and 6;
In the general formula (7), m and n respectively represent the number of repeated units of isopropoxy and ethoxy, which are integers or not, (m+n) has a value range of 8-114, and m/(m+n) is not more than 1/2; the structure of formula (7) does not define the sequence of attachment of the ethoxy and isopropoxy repeat units, either block or random;
The amount of the unsaturated carboxylic acid F is 0 to 80 percent of the total molar amount of the terminal alkenylamine B, the polymerizable monomer E, the unsaturated carboxylic acid F and the polyether G;
The amount of polyether G is equivalent to 10% -90% of the total molar amount of terminal alkenylamine B, polymerizable monomer E, unsaturated carboxylic acid F and polyether G.
2. The method according to claim 1, wherein the amount of phosphorus-containing composition C is such that the following conditions are simultaneously met: (a) The amount of the component I calculated by the mole amount of the element P is denoted as n (I-P); the total amount of active functional groups of terminal alkenylamine B calculated on the molar weight of H atoms to which N atoms are attached is denoted N (B-H); the consumption of the component I is calculated by the mole weight of H atoms connected with terminal alkenyl amine B and N atoms, and the ratio range of the component I is not less than 1 and not more than N (I-P)/N (B-H) is not more than 3; (b) The proportion of the phosphorous acid to the hypophosphorous acid, sodium hypophosphite or potassium hypophosphite in the component I is arbitrary; (c) The molar amount of phosphorus in component J is n (J-P), which satisfies the following relationship with the molar amount n (E) of polymerizable monomer E: 1.ltoreq.n (J-P) +n (I-P) -n (B-H) ]/n (E), when the polymerizable monomer E is not used in the preparation process of the superplasticizer, the component J is used or not used; (d) The molar amounts of hydrogen and alkali metal ions in the component J are n (J-H) and n (J-M), respectively, and the dosages of the component J and the terminal alkenylamine B need to satisfy the following relation:
3. The method according to claim 1, characterized in that it comprises in particular the following steps:
(1) Adding a certain amount of solvent A and phosphorus-containing composition C into a reactor, regulating the reactor to 70-120 ℃, uniformly stirring, continuously and uniformly adding terminal alkenyl amine B and micromolecule D containing aldehyde groups into the reactor, regulating the temperature of the reactor to 0-120 ℃ after the reaction time is 6-24 hours, continuously and uniformly adding polymerizable monomer E into the reactor, stopping the reaction after stirring for 1-24 hours, and removing the solvent and the volatilizable micromolecule in vacuum to obtain an intermediate mixture;
(2) The super plasticizer for the ultra-high performance concrete is prepared by free radical polymerization of all intermediate mixtures prepared in the step (1), unsaturated carboxylic acid F and unsaturated polyether G in aqueous solution at 0-90 ℃; initiating polymerization by adopting an initiator H, wherein a chain transfer agent is K;
The solvent A in the step (1) is any one of water, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and acetonitrile or a mixture of any proportion thereof;
The initiator H in step (2) comprises the following initiator system:
the thermal initiator is any one of azodiisobutyronitrile, azodiisoheptonitrile, azodiisobutylamidine hydrochloride, azodiiso Ding Mi hydrochloride, ammonium persulfate, potassium persulfate and sodium persulfate;
The redox initiator is formed by combining an oxidant and a reducing agent, wherein the oxidant is any one of hydrogen peroxide, ammonium persulfate, potassium persulfate and sodium persulfate;
When the oxidizing agent is hydrogen peroxide, the reducing agent is one or more than one of saturated alkyl mercaptan, thioglycollic acid, ascorbic acid or mercaptopropionic acid containing 2-6 carbon atoms, and in addition, or any combination of one or more than one of ferrous acetate, ferrous sulfate or ferrous ammonium sulfate is used as a catalyst, wherein the catalyst is measured by the molar amount of Fe element and the dosage of the catalyst is not more than 10% of the molar amount of the reducing agent;
When the oxidant is any one of ammonium persulfate, potassium persulfate and sodium persulfate, the reducing agent is any one of the following compositions: (1) Any combination of one or more of thioglycollic acid, ascorbic acid, rongalite or mercaptopropionic acid, and in addition, or any combination of one or more of ferrous acetate, ferrous sulfate or ferrous ammonium sulfate is/are contained or not contained as a catalyst, and the catalyst is metered by the molar quantity of Fe element, and the dosage of the catalyst is not more than 10% of the molar quantity of the reducing agent;
The initiator dosage is calculated based on the following method, and if the initiator is a thermal initiator, the initiator mass is 0.2-4% of the total mass of the terminal alkenyl amine B, the polymerizable monomer E, the unsaturated carboxylic acid F and the unsaturated polyether G; in the case of a redox initiator, the molar ratio of the oxidant to the reducing agent is 0.25-4, calculated by the larger molar amount of the oxidant to the reducing agent, of 0.2-4% of the total molar amount of the terminal alkenylamine B, the polymerizable monomer E, the unsaturated carboxylic acid F and the unsaturated polyether G;
The chain transfer agent K in the step (2) comprises (1) saturated alkyl mercaptan containing 2-6 carbon atoms, mercaptoethanol, mercaptoethylamine, cysteine, mercaptoacetic acid or mercaptopropionic acid; (2) sodium bisulphite, sodium sulphite and sodium metabisulphite; the dosage of the catalyst is 0-15% of the total molar weight of the polymerizable double bonds in the reaction system; the total molar amount of polymerizable double bonds is numerically equivalent to the total molar amount of terminal alkenylamine B, polyether G and unsaturated carboxylic acid F.
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