CN103803846A - Mud-resistant and salt-resistant polycarboxylate superplasticizer and preparation method thereof - Google Patents
Mud-resistant and salt-resistant polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
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- CN103803846A CN103803846A CN201410030504.8A CN201410030504A CN103803846A CN 103803846 A CN103803846 A CN 103803846A CN 201410030504 A CN201410030504 A CN 201410030504A CN 103803846 A CN103803846 A CN 103803846A
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- reducer
- mud
- acid
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- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims description 14
- 239000008030 superplasticizer Substances 0.000 title abstract description 6
- 150000003839 salts Chemical class 0.000 title abstract 5
- 239000000178 monomer Substances 0.000 claims abstract description 67
- 239000000203 mixture Substances 0.000 claims abstract description 39
- -1 methyl vinyl Chemical group 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 12
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 9
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 8
- 229920000570 polyether Polymers 0.000 claims abstract description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 36
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 30
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 17
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- 239000012986 chain transfer agent Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 6
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 230000000977 initiatory effect Effects 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 4
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 3
- JPAOMENBKRZQDR-UHFFFAOYSA-N CC=CC.[Na] Chemical compound CC=CC.[Na] JPAOMENBKRZQDR-UHFFFAOYSA-N 0.000 claims description 3
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 3
- 239000012966 redox initiator Substances 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 3
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 2
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims description 2
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005047 Allyltrichlorosilane Substances 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 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
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 claims description 2
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 claims description 2
- HKFSBKQQYCMCKO-UHFFFAOYSA-N trichloro(prop-2-enyl)silane Chemical compound Cl[Si](Cl)(Cl)CC=C HKFSBKQQYCMCKO-UHFFFAOYSA-N 0.000 claims description 2
- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-UHFFFAOYSA-N 0.000 claims description 2
- 239000005050 vinyl trichlorosilane Substances 0.000 claims description 2
- 239000004568 cement Substances 0.000 abstract description 27
- 239000004567 concrete Substances 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 2
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 abstract 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 abstract 1
- 150000008064 anhydrides Chemical class 0.000 abstract 1
- 229960003328 benzoyl peroxide Drugs 0.000 abstract 1
- 125000001309 chloro group Chemical group Cl* 0.000 abstract 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 abstract 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 239000008187 granular material Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000032050 esterification Effects 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- 235000019395 ammonium persulphate Nutrition 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 235000019394 potassium persulphate Nutrition 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 239000004160 Ammonium persulphate Substances 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 235000019154 vitamin C Nutrition 0.000 description 3
- 239000011718 vitamin C Substances 0.000 description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004159 Potassium persulphate Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002986 polymer concrete Substances 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 2
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- CAQWNKXTMBFBGI-UHFFFAOYSA-N C.[Na] Chemical compound C.[Na] CAQWNKXTMBFBGI-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000004574 high-performance concrete Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000001261 hydroxy acids Chemical group 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229920001427 mPEG Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910001380 potassium hypophosphite Inorganic materials 0.000 description 1
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical class CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical class OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention provides a mud-resistant and salt-resistant polycarboxylate superplasticizer, which is prepared from a monomer mixture comprising a monomer a, a monomer b and a monomer c in a copolymerization manner, wherein the monomer a is one or a mixture of more than two of unsaturated polyethers according with a general formula (A) as shown in the specification; n is an integer of 0-3; m is an integer of 10-90; R1 represents hydrogen or methyl; R2O represents ethyoxyl or propoxy or a mixture thereof; R3 represents hydrogen or methyl or ethyl; the monomer b is an unsaturated acid, an unsaturated anhydride or a mixture thereof; the monomer c is represented by a general formula (B); Y is vinyl, methyl vinyl, acrylyl oxygroup, or methylacryloyl oxygroup; X is chlorine group, methoxyl, ethyoxyl, methoxyethoxy or acetoxyl; k is an integer of 0-3. By adopting the mud-resistant and salt-resistant polycarboxylate superplasticizer provided by the invention, the adaptability of the cement in concrete can be greatly improved, the mud-resistant and salt-resistant effects are improved, and meanwhile, the mud-resistant and salt-resistant polycarboxylate superplasticizer has the advantages of low mixing amount, high water-reducing rate, low slump loss and the like.
Description
Technical field
The application relates to a kind of concrete polycarboxylate water-reducer, is specifically related to a kind of anti-mud anti-salt type polycarboxylate water-reducer and preparation method thereof.
Background technology
Concrete is consumption maximum, most widely used material of construction in the world, and recent decades, concrete technology has entered the high speed development stage, and Application Areas is in further expansion.Application admixture is the main path of concrete technology progress, wherein, water reducer is a kind of slag-based gelling material and requisite a kind of chemical admixture of concrete product of improving, it can be compared with low water-cement ratio in the situation that, significantly improving the over-all properties such as workability, degree of compactness, intensity and weather resistance of goods, is the widest, the maximum one of consumption of application surface in admixture.Polycarboxylic acids dehydragent, as water reducer product, has the features such as volume is low, water-reducing rate is high, mobility keeps, and cement adaptability is good, and oxious component content is low, properties of hardened concrete good, suitable preparation high performance concrete, and application prospect is very extensive.Meanwhile, polycarboxylate high performance water-reducing agent, due to its good performance and environmental protection characteristic, has represented concrete admixture developing direction from now on.
From day nineteen eighty-two the disclosure since first patent about new polycarboxylic acid water reducer (JP57118058), poly carboxylic acid series water reducer has obtained paying close attention to widely and studying.Typical poly carboxylic acid molecule is comb shaped structure, conventionally has two elements of main chain and side chain.On its main chain, generally contain a large amount of ionizable hydroxy-acid groups, after ionization, make between cement granules, to there is electrostatic repulsion by interionic reactive force; Side chain is generally the Hydrophilicrto polyether long-chain such as Soxylat A 25-7 that relative molecular weight is 500-3000, for cement granules provides sterically hindered repulsion, improves the dispersiveness of cement granules.Different from the connecting mode of main chain according to polyether lateral chain, poly carboxylic acid can be divided into polyester type and polyether-type, by changing main chain polymerization single polymerization monomer and side chain polyethers kind, can design and develop the tandem product of different performance feature, meet the diversified requirement of construction work to concrete material.
Between poly carboxylic acid series water reducer molecule and cement granules, mutually adsorb by electrostatic force or Van der Waals force, make cement granules with identical negative surface charge, the electrostatic repulsion that surface produces disperses solid particulate.Meanwhile, poly carboxylic acid series water reducer is adsorbed on particle surface and also forms one deck lubricant film, and the polyethers side chain in water reducer molecule has also produced sterically hindered effect disperses cement granules.In a word, current research thinks that the dispersion of cement granules is to cause owing to bearing the composition of dissemination in high efficiency water reducing agent and be adsorbed on three-dimensional repulsion that the interaction of electrostatic repulsion that cement particle surface produces, Adsorbed polymer layers produces and the wetting action of water molecules.Electrostatic force or Van der Waals force all belong to weak interaction, and the change along with microcosmic condition in hydration process can lose adsorptive power gradually, reduce water reducer water-reducing effect.Simultaneously, in the powder using in concrete production process and sand material, can contain a certain amount of earth and various inorganic salt, as vitriol, sulphite etc., these earth and inorganic salt can be adsorbed onto cement surface, compete with the absorption of poly carboxylic acid, have a strong impact on result of use and the concrete strength of water reducer.At present, conventional solution is to introduce cationic functional groups in poly carboxylic acid molecular structure, forms both sexes poly carboxylic acid polymer.Chinese patent CN102617811B discloses the preparation method of the anti-mud agent of a kind of amphoteric ethylene polymer concrete, use methacrylic acid and poly glycol monomethyl ether to carry out esterification and prepare polyethylene glycol monomethyl ethermethacrylic acid esters, and then by polyethylene glycol monomethyl ethermethacrylic acid esters, acrylic monomer, cationic vinyl monomer and vinyl sulfonic acid salt monomer by free radical polymerization, prepare the anti-mud agent of a kind of amphoteric ethylene polymer concrete.It can improve concrete anti-mud performance, can effectively be suppressed at the impact of the silt content in sandstone on concrete work performance while using poly carboxylic acid series water reducer.But the method still belongs to physical adsorption pattern, and persistence is poor.Therefore, researchist is finding the mode that between water reducer molecule and cement granules, chemical bond is connected always, makes connection between the two more firm, resists the competitive influence of other adsorbents.
At present, silane coupling agent is considered to a kind of good chemical bonded refractory mould assembly monomer.Silane coupling agent is a kind of siloxane compound with special construction, in water, there is hydrolytie polycondensation in this compounds, generate silicic acid quasi-oligomer can with cement in silicate carry out chemical bonds, play the surface bond ability stronger than adsorption.Chinese patent CN103073687A discloses a kind of preparation method of polymolecularity polycarboxylic acid super-plasticizer, adopt methoxy poly (ethylene glycol) monomethyl ether and the advanced esterification of methacrylic acid of different molecular weight, carry out copolymerization with (methyl) vinylformic acid, unsaturated sulfonic acid salt and Trimethoxy silane class unsaturated monomer again, obtained a kind of to sulfate radical have stronger resistivity product.Chinese patent CN103011680A discloses organically-modified poly carboxylic acid series super plasticizer of sulfate resistance type and preparation method thereof, adopt methoxy polyoxyethylene (methyl) acrylate, silicone based monomer, carboxylic-acid monomer, carboxylic acid esters monomer, sulphonic acids monomer etc. to carry out radical polymerization for raw material, the product of preparation forms strong chemical bond by introducing silane key and silicate, the competitive adsorption effect of opposing sulfate ion.The product of above technical scheme is polyester type polycarboxylate water-reducer, in building-up process, first need to carry out esterification, and then carry out radical polymerization, esterification process temperature is high, difficulty is controlled, transformation efficiency is not high, technique relative complex, do not meet the requirement of green energy conservation, mostly replaced by polyether-type polycarboxylate water-reducer synthesis technique at present.
Summary of the invention
For the defect of prior art, the invention provides a kind of anti-mud anti-salt type polycarboxylate water-reducer and preparation method thereof.The silane coupling agent that contains two keys by introducing, reaches better adsorptive power, suitably controls molecular weight product simultaneously, makes product have the effect of the anti-salt of anti-mud.
In order to achieve the above object, the present invention is by the following technical solutions:
A kind of anti-mud anti-salt type polycarboxylate water-reducer, this water reducer is obtained by the monomer mixture copolymerization that comprises monomer a, monomer b and monomer c;
Described monomer a is for meeting one or more the mixture in the unsaturated polyether of general formula (A);
In formula (A): the integer that n is 0-3; M is the integer of 10-90; R
1represent hydrogen or methyl, R
2o represents oxyethyl group or propoxy-or its mixture, R
3represent hydrogen or methyl or ethyl;
Described monomer b is unsaturated acid, unsaturated acid anhydride or its mixture;
Described monomer c is the silane coupling agent that contains the two keys of a carbon-to-carbon end group, uses general formula (B) to represent:
Y(CH
2)
k SiX
3 (B)
In formula (B): Y is the organic functions group that contains the two keys of a carbon-to-carbon end group, preferred vinyl, allyl group, methacrylic, acryloxy or methacryloxy; X is hydrolyzable group, preferably chloro, methoxyl group, oxyethyl group, methoxy ethoxy or acetoxyl group; K is the integer of 0-3.
In preferred embodiments of the present invention, one or more mixtures in allyl polyethenoxy ether that described monomer a preferred molecular weight is 600-4000, methacrylic Soxylat A 25-7, methyl alkene butyl Soxylat A 25-7, allyl group polyethenoxy ether, methacrylic polyethenoxy ether, methyl alkene butyl polyethenoxy ether; The mixture of one or more in further preferred allyl polyethenoxy ether, methacrylic Soxylat A 25-7 or methacrylic polyethenoxy ether;
In preferred embodiments of the present invention, one or more mixtures in the described preferred vinylformic acid of monomer b, methacrylic acid, butenoic acid, toxilic acid, maleic anhydride, methylene-succinic acid, itaconic anhydride; The mixture of one or more in further preferred vinylformic acid, methacrylic acid or maleic anhydride;
In preferred embodiments of the present invention, the mixture of one or more of described monomer c preferred vinyl Trimethoxy silane, vinyltriethoxysilane, allyltrimethoxysilanis, allyltriethoxysilane, vinyl three ('beta '-methoxy oxyethyl group) silane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxyl silane, vinyl trichloro silane, allyltrichlorosilane, allyl group triacetoxysilane, methacrylic triacetoxysilane; The further mixture of one or more in preferred vinyl Trimethoxy silane, vinyltriethoxysilane, vinyl three ('beta '-methoxy oxyethyl group) silane or γ-methacryloxypropyl trimethoxy silane.
In preferred embodiments of the present invention, described monomer mixture further comprises monomer d, and described monomer d is selected from one or more the mixture in methyl methacrylate, methyl acrylate, methylpropene sodium sulfonate, acrylamide, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, sodium p styrene sulfonate, 2-acrylamide-2-methyl propane sulfonic; The further mixture of one or more in preferable methyl sodium allylsulfonate, 2-acrylamide-2-methyl propane sulfonic or Hydroxyethyl acrylate.
The preferred anti-mud anti-salt type polycarboxylate water-reducer of one of the present invention, by weight percentage, it is by the monomer a of 60%-94%, the monomer b of 5%-25%, the monomer d copolymerization of the monomer c of 1%-20% and 0%-20% obtains.
Further preferred anti-mud anti-salt type polycarboxylate water-reducer of the present invention, by weight percentage, it is by the monomer a of 75%-90%, the monomer b of 8%-18%, the monomer d copolymerization of the monomer c of 2%-12% and 0%-10% obtains.
Described polymerization preferably, in the aqueous solution, completes in next step polymerization of condition of initiator and chain-transfer agent existence; Preferably 30-90 ℃ of described temperature of reaction, the reaction times is preferably 2-12 hour.
Described chain-transfer agent is a kind of or its mixture in Thiovanic acid, thiohydracrylic acid, mercaptoethanol, mercaprol, the 0.1%-5% that the consumption of chain-transfer agent is total monomer weight; Described initiator is thermal decomposition initiating or redox initiator.
Described thermal decomposition initiating is one or more miscellanys in ammonium persulphate, Potassium Persulphate, Sodium Persulfate, hydrogen peroxide.
Described redox initiator is made up of thermal decomposition initiating and reductive agent, wherein, thermal decomposition initiating is one or more miscellanys in ammonium persulphate, Potassium Persulphate, Sodium Persulfate, hydrogen peroxide, and reductive agent is one or more the mixture in sodium bisulfite, Potassium hydrogen sulfite, Sodium Pyrosulfite, Hypophosporous Acid, 50, sodium hypophosphite, potassium hypophosphite, ferrite, glucose or vitamins C; The consumption of thermal decomposition initiating is the 0.1%-10% of monomer total mass, and the consumption of reductive agent is the 0%-5% of monomer total mass.
The present invention also provides the method for the described anti-mud anti-salt type polycarboxylate water-reducer of preparation, comprises the following steps:
The monomer of described ratio and chain-transfer agent, initiator are added to reaction unit, at 30-90 ℃, in the aqueous solution, react 2-12 hour, obtain described anti-mud anti-salt type polycarboxylate water-reducer through one-step polymerization.
After copolyreaction finishes, can regulate pH value with alkaline aqueous solution as required.
Anti-mud anti-salt type polycarboxylate water-reducer of the present invention has been introduced the silane coupling agent monomer that contains two keys in poly carboxylic acid structure, the silicic acid quasi-oligomer that silane coupling agent hydrolysis produces can with concrete in silicate form strong chemical bond, thereby more effectively coated cement granules, increase water-reducing effect, and can intercept the absorption to cement of other inorganic ions and earth, greatly improve the adaptability of cement in concrete, promoted the effect of the anti-salt of anti-mud.Meanwhile, adopt the large monomer of unsaturated polyether type, saved the step of polyester type high temperature esterification, greatly saved the energy, reduced production cost.
Embodiment
Embodiment mono-:
By mass, the allyl polyethenoxy ether of 60 parts of molecular weight 1000,2 parts of hydrogen peroxide, 40 parts of water are added in reaction unit; 20 parts of vinylformic acid, 10 parts of vinyltrimethoxy silanes, 10 parts of methallylsulfonic acid sodium, 2 parts of Thiovanic acids, 1 part of vitamins C, 50 parts of water are added dropwise to reaction unit after mixing, in 4 hours, dropwise; 50 ℃ of temperature of reaction, reaction total time is 12 hours.After reaction finishes, be cooled to 30-40 ℃, add aqueous sodium hydroxide solution to regulate pH value and solid content, obtain certain density silane-modified polycarboxylate water-reducer.
Embodiment bis-:
By mass, the methacrylic Soxylat A 25-7 of 90 parts of molecular weight 2400,70 parts of water are added in reaction unit; 9 parts of methacrylic acids, 1 part of vinyl three ('beta '-methoxy oxyethyl group) silane, 0.5 part of thiohydracrylic acid, 30 parts of water are added dropwise to reaction unit after mixing, in 3 hours, dropwise; Meanwhile, 5 parts of ammonium persulphates, 3 parts of Potassium hydrogen sulfites, 20 parts of water are added dropwise to reaction unit after mixing, in 4 hours, dropwise; 60 ℃ of temperature of reaction, reaction total time is 6 hours.After reaction finishes, be cooled to 30-40 ℃, add aqueous sodium hydroxide solution to regulate pH value and solid content, obtain certain density silane-modified polycarboxylate water-reducer.
Embodiment tri-:
By mass, the methacrylic polyethenoxy ether of 80 parts of molecular weight 5000,50 parts of water are added in reaction unit; 6 parts of maleic anhydrides, 10 parts of γ-methacryloxypropyl trimethoxy silane, 4 parts of 2-acrylamide-2-methyl propane sulfonics, 5 parts of Thiovanic acids, 50 parts of water are added dropwise to reaction unit after mixing, in 2 hours, dropwise; Meanwhile, 10 parts of Potassium Persulphates, 30 parts of water are added dropwise to reaction unit after mixing, in 3 hours, dropwise; 85 ℃ of temperature of reaction, reaction total time is 4 hours.After reaction finishes, be cooled to 30-40 ℃, add potassium hydroxide aqueous solution to regulate pH value and solid content, obtain certain density silane-modified polycarboxylate water-reducer.
Embodiment tetra-:
By mass, the allyl polyethenoxy ether of 70 parts of molecular weight 2400,5 parts of hydrogen peroxide, 70 parts of water are added in reaction unit; 5 parts of vinylformic acid, 5 parts of vinyltriethoxysilanes, 20 parts of Hydroxyethyl acrylates, 0.1 part of mercaptoethanol, 0.1 part of vitamins C, 40 parts of water are added dropwise to reaction unit after mixing, in 4 hours, dropwise; 60 ℃ of temperature of reaction, reaction total time is 12 hours.After reaction finishes, be cooled to 30-40 ℃, add aqueous sodium hydroxide solution to regulate pH value and solid content, obtain certain density silane-modified polycarboxylate water-reducer.
Embodiment five:
By mass, the methacrylic polyoxyethylene ether mixture of the allyl polyethenoxy ether of 65 parts of molecular weight 1000 and molecular weight 2400,5 parts of hydrogen peroxide, 5 parts of Potassium Persulphates, 40 parts of water are added in reaction unit; 25 parts of vinylformic acid, 10 parts of vinyltrimethoxy silanes, 0.5 part of Thiovanic acid, 5 parts of vitamins Cs, 50 parts of water are added dropwise to reaction unit after mixing, in 4 hours, dropwise; 30 ℃ of temperature of reaction, reaction total time is 12 hours.After reaction finishes, add aqueous sodium hydroxide solution to regulate pH value and solid content, obtain certain density silane-modified polycarboxylate water-reducer.
Embodiment six:
By mass, the methacrylic polyoxyethylene ether mixture of the allyl polyethenoxy ether of 65 parts of molecular weight 1000 and molecular weight 2400,0.1 part of ammonium persulphate, 40 parts of water are added in reaction unit; 15 parts of vinylformic acid, 15 parts of γ-methacryloxypropyl trimethoxy silane, 5 parts of vinyltriethoxysilanes, 1 part of Thiovanic acid, 50 parts of water are added dropwise to reaction unit after mixing, in 1 hour, dropwise; 90 ℃ of temperature of reaction, reaction total time is 2 hours.After reaction finishes, be cooled to 30-40 ℃, add aqueous sodium hydroxide solution to regulate pH value and solid content, obtain certain density silane-modified polycarboxylate water-reducer.
Experimental example
By the sample of embodiment mono-to three preparation, adopt standard cement, volume is pressed 1.0% of cement quality, according to " GB8076-2008 concrete admixture ", survey its concrete water-reducing ratio, the slump and through time the slump.Concrete mix is: cement 345kg/m
3, sand 800kg/m
3, stone 980kg/m
3, the slump is controlled at 220 ± 10mm, acquired results as shown in Table 1:
Table one
| Sample | Water-reducing rate/% | The initial slump/mm | 1 hour slump retention value/mm |
| Benchmark | / | 215 | 140 |
| Embodiment mono- | 31.5 | 220 | 205 |
| Embodiment bis- | 30.5 | 215 | 200 |
| Embodiment tri- | 30.5 | 210 | 195 |
| Comparative example one | 24.5 | 210 | 165 |
| Comparative example two | 28.5 | 220 | 150 |
Wherein, the water reducer that comparative example one and comparative example two adopt is the commercially available silane-modified polyether-type polycarboxylate water-reducer that do not carry out.
As shown in Table 1, the polycarboxylate water-reducer that adopts the present invention to prepare, has the advantages such as low-dosage, high water reducing rate, low slump degree of loss.
Embodiment, by the sample of embodiment mono-and two preparation, is adopted to standard cement, and volume is pressed 1.0% of cement quality, according to " GB8076-2008 concrete admixture ", survey its under different silt contents the concrete slump and through time the slump.Concrete mix is: cement 345kg/m
3, sand 800kg/m
3, stone 980kg/m
3, water cement ratio 0.3, acquired results as shown in Table 2:
Table two
As shown in Table 2, water reducer of the present invention, in the time of low silt content, still keeps the higher slump and the good slump to keep effect; In the time of higher silt content, also have than the better initial slump of ordinary water-reducing agent, comparing ordinary water-reducing agent has anti-mud function.
Embodiment, by the sample of embodiment mono-and two preparations, is adopted to standard cement, and volume is pressed 1.0% of cement quality, according to " GB8076-2008 concrete admixture ", surveys its concrete water-reducing rate under different sodium sulphate contents.Concrete mix is: cement 345kg/m
3, sand 800kg/m
3, stone 980kg/m
3, the slump is controlled at 220 ± 10mm, acquired results as shown in Table 3:
Table three
As shown in Table 3, water reducer of the present invention is in the situation that having vitriol to exist, and water-reducing effect has good hold facility, compares ordinary water-reducing agent and has anti-salt functional.
Claims (9)
1. an anti-mud anti-salt type polycarboxylate water-reducer, is characterized in that: it is obtained by the monomer mixture copolymerization that comprises monomer a, monomer b and monomer c;
Described monomer a is for meeting one or more the mixture in the unsaturated polyether of general formula (A);
In formula (A): the integer that n is 0-3; M is the integer of 10-90; R
1represent hydrogen or methyl, R
2o represents oxyethyl group or propoxy-or its mixture, R
3represent hydrogen or methyl or ethyl;
Described monomer b is unsaturated acid, unsaturated acid anhydride or its mixture;
Described monomer c is the silane coupling agent that contains the two keys of a carbon-to-carbon end group, uses general formula (B) to represent:
Y(CH
2)
k SiX
3 (B)
In formula (B): Y is vinyl, allyl group, methacrylic, acryloxy or methacryloxy; X is chloro, methoxyl group, oxyethyl group, methoxy ethoxy or acetoxyl group; K is the integer of 0-3.
2. anti-mud anti-salt type polycarboxylate water-reducer claimed in claim 1, is characterized in that: described monomer a is that molecular weight is one or more mixtures in the allyl polyethenoxy ether, methacrylic Soxylat A 25-7, methyl alkene butyl Soxylat A 25-7, allyl group polyethenoxy ether, methacrylic polyethenoxy ether, methyl alkene butyl polyethenoxy ether of 600-4000; The mixture of one or more in further preferred allyl polyethenoxy ether, methacrylic Soxylat A 25-7 or methacrylic polyethenoxy ether.
3. anti-mud anti-salt type polycarboxylate water-reducer claimed in claim 1, is characterized in that: described monomer b is one or more mixtures in vinylformic acid, methacrylic acid, butenoic acid, toxilic acid, maleic anhydride, methylene-succinic acid, itaconic anhydride; The mixture of one or more in further preferred vinylformic acid, methacrylic acid or maleic anhydride.
4. anti-mud anti-salt type polycarboxylate water-reducer claimed in claim 1, it is characterized in that: described monomer c is vinyltrimethoxy silane, vinyltriethoxysilane, allyltrimethoxysilanis, allyltriethoxysilane, vinyl three ('beta '-methoxy oxyethyl group) silane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxyl silane, vinyl trichloro silane, allyltrichlorosilane, allyl group triacetoxysilane, the mixture of one or more of methacrylic triacetoxysilane, the further mixture of one or more in preferred vinyl Trimethoxy silane, vinyltriethoxysilane, vinyl three ('beta '-methoxy oxyethyl group) silane or γ-methacryloxypropyl trimethoxy silane.
5. anti-mud anti-salt type polycarboxylate water-reducer claimed in claim 1, it is characterized in that: described monomer mixture further comprises monomer d, described monomer d is selected from one or more the mixture in methyl methacrylate, methyl acrylate, methylpropene sodium sulfonate, acrylamide, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, sodium p styrene sulfonate, 2-acrylamide-2-methyl propane sulfonic; The further mixture of one or more in methylpropene sodium sulfonate, 2-acrylamide-2-methyl propane sulfonic or Hydroxyethyl acrylate.
6. anti-mud anti-salt type polycarboxylate water-reducer claimed in claim 5, is characterized in that: by weight percentage, it is by the monomer a of 60%-94%, the monomer b of 5%-25%, and the monomer d copolymerization of the monomer c of 1%-20% and 0%-20% obtains.
7. anti-mud anti-salt type polycarboxylate water-reducer claimed in claim 5, is characterized in that: by weight percentage, it is by the monomer a of 75%-90%, the monomer b of 8%-18%, and the monomer d copolymerization of the monomer c of 2%-12% and 0%-10% obtains.
8. the anti-mud anti-salt type polycarboxylate water-reducer of any one described in claim 1,6 or 7, is characterized in that: described polymerization is in the aqueous solution, completes in next step polymerization of condition of initiator and chain-transfer agent existence; Described polymeric reaction temperature is 30-90 ℃, and the reaction times is 2-12 hour; Described chain-transfer agent is a kind of or its mixture in Thiovanic acid, thiohydracrylic acid, mercaptoethanol, mercaprol, the 0.1%-5% that the consumption of chain-transfer agent is total monomer weight; Described initiator is thermal decomposition initiating or redox initiator.
9. the method for preparation anti-mud anti-salt type polycarboxylate water-reducer claimed in claim 1, comprise the following steps: the monomer of described ratio and chain-transfer agent, initiator are added to reaction unit, at 30-90 ℃, in the aqueous solution, react 2-12 hour, obtain described anti-mud anti-salt type polycarboxylate water-reducer through one-step polymerization.
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| WO2023020189A1 (en) * | 2021-08-18 | 2023-02-23 | 中国石油化工股份有限公司 | Oil-gas well, well cementation method, and cement composition |
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