CN104944827B - A kind of preparation method of slump-retaining polycarboxylic acid type water reducing agent - Google Patents
A kind of preparation method of slump-retaining polycarboxylic acid type water reducing agent Download PDFInfo
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- CN104944827B CN104944827B CN201510296715.0A CN201510296715A CN104944827B CN 104944827 B CN104944827 B CN 104944827B CN 201510296715 A CN201510296715 A CN 201510296715A CN 104944827 B CN104944827 B CN 104944827B
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- preparation
- reducing agent
- glycol monomethyl
- monomethyl ether
- poly glycol
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- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000002253 acid Substances 0.000 title claims abstract description 19
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 43
- 229920000151 polyglycol Polymers 0.000 claims abstract description 42
- 239000010695 polyglycol Substances 0.000 claims abstract description 42
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 40
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 150000001412 amines Chemical class 0.000 claims abstract description 19
- 230000000694 effects Effects 0.000 claims abstract description 17
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000010612 desalination reaction Methods 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 5
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 3
- 239000012312 sodium hydride Substances 0.000 claims abstract description 3
- 229910000104 sodium hydride Inorganic materials 0.000 claims abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- -1 peroxide Compound Chemical class 0.000 claims description 16
- 239000002202 Polyethylene glycol Substances 0.000 claims description 12
- 230000033116 oxidation-reduction process Effects 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- PMNLUUOXGOOLSP-UHFFFAOYSA-N alpha-mercaptopropionic acid Natural products CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 4
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical group O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- YOMSJEATGXXYPX-UHFFFAOYSA-N 2-methoxy-4-vinylphenol Chemical class COC1=CC(C=C)=CC=C1O YOMSJEATGXXYPX-UHFFFAOYSA-N 0.000 claims description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 3
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical class CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 claims description 3
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 3
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 150000001541 aziridines Chemical class 0.000 claims description 2
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 claims description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical class CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000014509 gene expression Effects 0.000 claims description 2
- ATEAWHILRRXHPW-UHFFFAOYSA-J iron(2+);phosphonato phosphate Chemical compound [Fe+2].[Fe+2].[O-]P([O-])(=O)OP([O-])([O-])=O ATEAWHILRRXHPW-UHFFFAOYSA-J 0.000 claims description 2
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 235000010378 sodium ascorbate Nutrition 0.000 claims description 2
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 2
- 229960005055 sodium ascorbate Drugs 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims description 2
- YICILWNDMQTUIY-UHFFFAOYSA-N 2-methylidenepentanamide Chemical compound CCCC(=C)C(N)=O YICILWNDMQTUIY-UHFFFAOYSA-N 0.000 claims 1
- XUIKGJQOQAHGQE-UHFFFAOYSA-N CC(=CC)[Na] Chemical compound CC(=CC)[Na] XUIKGJQOQAHGQE-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- LXXNWCFBZHKFPT-UHFFFAOYSA-N Ethyl 2-mercaptopropionate Chemical compound CCOC(=O)C(C)S LXXNWCFBZHKFPT-UHFFFAOYSA-N 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- WBZKQQHYRPRKNJ-UHFFFAOYSA-N disulfurous acid Chemical compound OS(=O)S(O)(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-N 0.000 claims 1
- 235000003642 hunger Nutrition 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 claims 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 16
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 41
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 25
- 238000000034 method Methods 0.000 description 15
- 230000001681 protective effect Effects 0.000 description 12
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 10
- 239000004593 Epoxy Substances 0.000 description 5
- 238000010276 construction Methods 0.000 description 5
- 229920005646 polycarboxylate Polymers 0.000 description 5
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical class OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- CCIDRBFZPRURMU-UHFFFAOYSA-N 2-methyl-n-propylprop-2-enamide Chemical class CCCNC(=O)C(C)=C CCIDRBFZPRURMU-UHFFFAOYSA-N 0.000 description 2
- 229920000858 Cyclodextrin Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000001116 FEMA 4028 Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 2
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 2
- 229960004853 betadex Drugs 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000003335 steric effect Effects 0.000 description 2
- AKUNSTOMHUXJOZ-UHFFFAOYSA-N 1-hydroperoxybutane Chemical compound CCCCOO AKUNSTOMHUXJOZ-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical class OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 235000019187 sodium-L-ascorbate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a kind of preparation methods of slump-retaining polycarboxylic acid type water reducing agent, are prepared using following steps：1) hydroxyl unsaturation minor comonomer, amine unsaturation minor comonomer, initiator, reducing agent, chain-transferring agent carry out redox Raolical polymerizable and obtain amino-contained copolymerization product；2) excessive sodium hydride is added in poly glycol monomethyl ether, epoxychloropropane is added in after reaction, desalination after reacting is stirred for and obtains epoxy group poly glycol monomethyl ether；3) after obtained amino-contained copolymerization product being added in the reaction of epoxy group poly glycol monomethyl ether, slump-retaining polycarboxylic acid type water reducing agent is obtained with alkali neutralization adjustment pH value；The present invention adjusts properties of product by controlling molecular structure/molecular weight of amino-contained copolymerization product and the molecular weight of poly glycol monomethyl ether, is swift in response efficient and does not use organic solvent, nontoxic and pollution-free, easy to operate.Prepared poly carboxylic acid series water reducer is a kind of polycarboxylic acid series high efficiency water reducing agent of collapse protection type, and properties of product are stablized, and especially protects effect of collapsing with preferable to containing silt particle building stones.
Description
Technical field
The present invention relates to a kind of technical fields of cement concrete poly carboxylic acid series water reducer, are related specifically to a kind of use
The preparation method of amido-epoxy reaction and the slump-retaining polycarboxylic acid type water reducing agent of oxidationreduction free radical polymerization.
Background technology
The world today, social economy flourish, and urban construction is advanced by leaps and bounds, and the thing followed is and traffic, water power, city
The rapid rising of the related constructions such as political affairs, the emergence of high-rise and the raising of construction material construction requirement, to mixed
The aid pumpability requirement for coagulating soil is also higher and higher, and high efficiency water reducing agent is then the required part for preparing pumping, and polycarboxylic acid
Water-reducing agent becomes wherein part and parcel.However, for a long time, how the use of concrete is but effectively controlled slump always
Degree loses this problem and is perplexed.From concrete mixing plant produce pump concrete generally require long range transport and
Construction environment (higher temperature etc.) is different, inevitably leads to the slump-loss of concrete, so as to influence concrete
Construction.At present be mainly used to reduce mix water-reducing agent the method for concrete slump mainly includes, water-reducing agent repeatedly repeatedly addition,
Water-reducing agent latter admixing method, compound retarder and sustained release method etc..But the effect acquired by these methods is not apparent, environment friend
Good property difference or cost are higher.
Polycarboxylate water-reducer prepared by traditional polymerization, the performance influence that sour ether compares product is very big, if it is desired to
Sour ether is reduced than will necessarily reduce the performance of polycarboxylate water-reducer to improve space steric effect.There is presently no a kind of methods
Ensure electrostatic repulsion in fixed acid mole and improve steric hindrance to increase side chain density.CN103613308B reports a kind of poly-
The preparation method of carboxylic acid high-thin arch dam agent：The itaconic acid introduced in molecular structure delays hydrated cementitious, phenyl ring is introduced in molecular structure
Space steric effect is generated, enhances water-reducing agent dispersion stabilization, but the conversion ratio of the invention is not high, and the inadequate ring of preparation process
It protects, is unfavorable for producing and applying on a large scale.CN102153711A reports a kind of by allyl sulphonic acid salt monomer, acrylic acid
Class monomer, Methylacrylic acid polyethylene glycol single armor ether ester polymeric monomer and maleic anhydride graft beta-cyclodextrin polymeric monomer pass through free radical
Copolyreaction obtains a kind of slow-setting polycarboxylic acid water reducing agent, make gained polycarboxylate dehydragent have preferable retarding performance,
Micro- bleed performance and better mobile performance, but the maleic anhydride graft beta-cyclodextrin polymeric monomer grafting rate of the invention is not high,
And its be influenced by temperature it is larger, it is impossible to fundamentally solve the problems, such as the concrete slump loss under different condition, be unfavorable for
Large-scale production and application.
Invention content
A kind of slump-retaining polycarboxylic acid type water reducing agent is provided the purpose of the invention is to improve the deficiencies in the prior art
Preparation method can assign water-reducing agent new function in this way.
The technical scheme is that：A kind of preparation method of slump-retaining polycarboxylic acid type water reducing agent, is as follows：
1) preparation of amino-contained copolymerization product：Hydroxyl unsaturation minor comonomer and the unsaturated minor comonomer containing amine are existed
Under initiator, reducing agent and chain-transferring agent effect, 25~45 DEG C of conditions carry out oxidationreduction Raolical polymerizables 30~
90min obtains amino-contained copolymerization product；Wherein described hydroxyl unsaturation minor comonomer, draws the unsaturated minor comonomer containing amine
The molar ratio for sending out agent, reducing agent and chain-transferring agent is 1：(0.1~1)：(0.01~0.1)：(0.03~0.2)：(0.001~
0.01)；
2) preparation of epoxy group poly glycol monomethyl ether：At 0~25 DEG C, excessive hydrogen is added in poly glycol monomethyl ether
Change sodium, add in epoxychloropropane after reacting 10~40min, after being stirred for 30~90min of reaction, desalination obtains the poly- second two of epoxy group
Alcohol monomethyl ether；Wherein the molar ratio of poly glycol monomethyl ether, sodium hydride and epoxychloropropane is 1：(1.01~1.05)：(1.01
~1.1)；
3) preparation of slump-retaining polycarboxylic acid type water reducing agent：Step 2) system will be added in amino-contained copolymerization product made from step 1)
The epoxy group poly glycol monomethyl ether obtained, after reacting 10~50min, it is 6~7 to add alkali neutralization adjustment pH value, obtains collapse protection type
Poly carboxylic acid series water reducer；Wherein the molar ratio of amino-contained copolymerization product and epoxy group poly glycol monomethyl ether is 1：(0.5~1).
It is preferred that above-mentioned steps 1) in the molecular weight of obtained amino-contained copolymerization product be 3000~5000.
Preferred steps 1) described in initiator be persulfuric acid object or peroxide；More preferable tert-butyl hydroperoxide, mistake
Hydrogen oxide, ammonium persulfate, benzoyl peroxide, isopropyl benzene hydroperoxide, potassium peroxydisulfate or sodium peroxydisulfate it is one or two kinds of with
Upper combination.
Preferred steps 1) described in reducing agent for rongalite, sodium pyrosulfite, n,N-Dimethylaniline, bisulfite
One kind of sodium, rongalite, ferrous sulfate, N, N- diethylanilines, ferrous pyrophosphate, four aziridines etc. or sodium ascorbate or
Two or more combinations.
Preferred steps 1) described in chain-transferring agent for thioacetic acid, 2 mercaptopropionic acid, 3- mercaptopropionic acids, methylpropenyl
One or more kinds of combinations of sodium sulfonate or lauryl mercaptan.
Preferred steps 1) described in hydroxyl unsaturation minor comonomer general formula：R1OH expressions, wherein R1For 4~14 carbon
Atom ethylenic unsaturation alkyl or phenyl and its derivative；More preferably the hydroxyl unsaturation minor comonomer is 2- methallyls
Alcohol, propenyl, acrylate, hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxy propyl methacrylate, 4- ethylene
Base phenol, 2- methoxyl-4-vinyl phenols, hydroxyethyl methacrylate N-butyl, hydroxypropyl acrylate or acrylic acid hydroxyl N-butyl
One or more kinds of combinations.
Preferred steps 1) described in amine unsaturation minor comonomer general formula：R2NHR3It represents, wherein R2For 3~8 carbon atoms
Ethylenic unsaturation alkyl, R3For H or the alkyl of 2-5 carbon atom；More preferably the amine unsaturation minor comonomer is acryloyl
Amine, allylamine, Methacrylamide, N- ethyl acrylamides, n-isopropyl acrylamide or N- propyl Methacrylamides one
Kind or two or more combinations.
Preferred steps 2) described in poly glycol monomethyl ether molecular weight be 400~5000.
Preferred steps 3) described in alkali be sodium hydroxide, potassium hydroxide or calcium hydroxide.
Amido-epoxy addition grafting method that this patent uses effectively reduces the difficulty on long side chain branch knot to main chain,
It is swift in response efficient and does not use organic solvent, it is nontoxic and pollution-free, it is easy to operate.The polycarboxylic-acid prepared with the method for the present invention
Water-reducing agent is a kind of functional polycarboxylic acid series high efficiency water reducing agent, since a primary amine groups can be therefore same with two epoxy reactions
Polycarboxylate water-reducer its side chain quantity that sample side chain positions are prepared using amido-epoxy addition grafting method is that traditional polycarboxylic acids subtracts
2 times of aqua, considerably increase steric hindrance, make the more excellent stabilization of properties of product, especially have preferably to containing silt particle building stones
Guarantor collapse effect.
Advantageous effect：
Compared with prior art, the present invention it has the following advantages：
1. the raw material sources that the method for the present invention is utilized enrich, each step has all industrialized, and method is ripe.
2. the method for the present invention amido-epoxy reaction, substantially reduces the reaction time, steric hindrance is increased, is improved anti-
Efficiency is answered, especially protects effect of collapsing with preferable to containing silt particle building stones.
3. polycarboxylate water-reducer prepared by the method for the present invention simplifies it to assign new function, makes properties of product more
Excellent stabilization.
4. collapse protective poly-carboxylic acid water reducing agent product adaptation prepared by the method for the present invention is wide, performance is stablized after aqueous solution, storage
It is not stratified when depositing, do not precipitate.
5. the method for the present invention is safe and reliable in the collapse protective poly-carboxylic acid water reducing agent product whole preparation process of preparation, operation
Step is simple and convenient, nontoxic and pollution-free without using organic solvent, it is environmentally safe the advantages that.
Specific embodiment
Technical solution of the present invention is described in further detail below by embodiment.
Embodiment 1
1) preparation of amine-containing copolymerization product：10mol 2- methallyl alcohols are with 25 DEG C of 10mol acrylamides in uncle 0.1mol
Butylhydroperoxide, 0.3mol rongalites, the effect of 0.01mol methallylsulfonic acids sodium is lower to carry out oxidationreduction radical polymerization
It closes reaction 30min and obtains the copolymerization product that molecular weight is 3000；
2) preparation of epoxy group poly glycol monomethyl ether：The poly glycol monomethyl ether that 10mol molecular weight is 5000 at 0 DEG C adds
Enter 10.1mol sodium hydrides, reaction 40min adds in 10.1mol epoxychloropropane, after being stirred to react 90min desalination obtain epoxy group
Poly glycol monomethyl ether；
3) preparation of collapse protection type water-reducing agent：10mol amino-containeds copolymerization product is added in into 10mol epoxy group polyethyleneglycol first
Ether reaction 10min adds in potassium hydroxide and adjustment pH value obtains a kind of collapse protective poly-carboxylic acid water reducing agent for 6.
Embodiment 2
1) preparation of amine-containing copolymerization product：10mol propenyls are with 30 DEG C of 9mol allylamines in 0.2mol tert-butyl hydroperoxides
Hydrogen, 0.4mol sodium pyrosulfites, the lower progress oxidationreduction Raolical polymerizable 35min of 0.02mol thioacetic acid effect are obtained
Molecular weight is 3500 copolymerization product；
2) preparation of epoxy group poly glycol monomethyl ether：10mol molecular weight is added in for 400 poly glycol monomethyl ethers at 25 DEG C
10.2mol sodium hydrides, reaction 10min add in 11mol epoxychloropropane, after being stirred to react 90min desalination obtain the poly- second of epoxy group
Glycol monomethyl ether；
3) preparation of collapse protection type water-reducing agent：10mol amino-containeds copolymerization product is added in into 5mol epoxy group polyethyleneglycol first
Ether reaction 50min adds in calcium hydroxide and adjustment pH value obtains a kind of collapse protective poly-carboxylic acid water reducing agent for 7.
Embodiment 3：
1) preparation of amine-containing copolymerization product：10mol acrylates are with 35 DEG C of 8mol Methacrylamides in 0.3mol
Benzoyl peroxide, 0.6mol n,N-Dimethylaniline, the effect of 0.03mol 2 mercaptopropionic acids is lower to carry out oxidationreduction freedom
Base polymerisation 40min obtains the copolymerization product that molecular weight is 5000；
2) preparation of epoxy group poly glycol monomethyl ether：10mol molecular weight adds for 2000 poly glycol monomethyl ethers at 20 DEG C
Enter 10.5mol sodium hydrides, reaction 10min adds in 10.2mol epoxychloropropane, after being stirred to react 40min desalination obtain epoxy group
Poly glycol monomethyl ether；
3) preparation of collapse protection type water-reducing agent：10mol amino-containeds copolymerization product is added in into 9mol epoxy group polyethyleneglycol first
Ether reaction 10min adds in sodium hydroxide and adjustment pH value obtains a kind of collapse protective poly-carboxylic acid water reducing agent for 6.5.
Embodiment 4：
1) preparation of amine-containing copolymerization product：40 DEG C of 10mol hydroxy-ethyl acrylates and 7mol N- ethyl acrylamides exist
0.4mol ammonium persulfates, 0.8mol sodium hydrogensulfites, the effect of 0.04mol 3- mercaptopropionic acids is lower to carry out oxidationreduction radical polymerization
It closes reaction 45min and obtains the copolymerization product that molecular weight is 5000；
2) preparation of epoxy group poly glycol monomethyl ether：10mol molecular weight adds for 1000 poly glycol monomethyl ethers at 25 DEG C
Enter 10.1mol sodium hydrides, reaction 40min adds in 10.2mol epoxychloropropane, after being stirred to react 30min desalination obtain epoxy group
Poly glycol monomethyl ether；
3) preparation of collapse protection type water-reducing agent：10mol amino-containeds copolymerization product is added in into 8mol epoxy group polyethyleneglycol first
Ether reaction 10min adds in potassium hydroxide and adjustment pH value obtains a kind of collapse protective poly-carboxylic acid water reducing agent for 6.
Embodiment 5：
1) preparation of amine-containing copolymerization product：45 DEG C of 10mol hydroxyethyl methacrylates and 6mol n-isopropyl acrylamide
In 0.5mol hydrogen peroxide, 1mol sodium ascorbates, the effect of 0.05mol methylpropenyls sodium sulfonate is lower to carry out oxidationreduction certainly
The copolymerization product that molecular weight is 4000 is obtained by base polymerisation 50min；
2) preparation of epoxy group poly glycol monomethyl ether：10mol molecular weight adds for 2000 poly glycol monomethyl ethers at 25 DEG C
Enter 10.5mol sodium hydrides, reaction 40min adds in 10.5mol epoxychloropropane, after being stirred to react 50min desalination obtain epoxy group
Poly glycol monomethyl ether；
3) preparation of collapse protection type water-reducing agent：10mol amino-containeds copolymerization product is added in into 8mol epoxy group polyethyleneglycol first
Ether reaction 50min adds in sodium hydroxide and adjustment pH value obtains a kind of collapse protective poly-carboxylic acid water reducing agent for 7.
Embodiment 6：
1) preparation of amine-containing copolymerization product：25 DEG C of 10mol hydroxy propyl methacrylates and 5mol N- propyl Methacrylamides
In 0.6mol hydrogen peroxide, 1.2mol rongalites, the effect of 0.1mol lauryl mercaptans is lower to carry out oxidationreduction Raolical polymerizable
55min obtains the copolymerization product that molecular weight is 4500；
2) preparation of epoxy group poly glycol monomethyl ether：10mol molecular weight is added in for 800 poly glycol monomethyl ethers at 25 DEG C
10.4mol sodium hydrides, reaction 40min add in 10.3mol epoxychloropropane, are stirred to react desalination after 60min and obtain epoxy group and gather
Glycol monoethyl ether；
3) preparation of collapse protection type water-reducing agent：10mol amino-containeds copolymerization product is added in into 9mol epoxy group polyethyleneglycol first
Ether reaction 50min adds in sodium hydroxide and adjustment pH value obtains a kind of collapse protective poly-carboxylic acid water reducing agent for 6.
Embodiment 7：
1) preparation of amine-containing copolymerization product：10mol 4-Vinyl phenols are with 45 DEG C of 4mol acrylamides in 0.7mol over cures
Sour ammonium, 1.4mol ferrous sulfate, the lower progress oxidationreduction Raolical polymerizable 60min of 0.05mol thioacetic acid effect are obtained
Molecular weight is 3000 copolymerization product；
2) preparation of epoxy group poly glycol monomethyl ether：10mol molecular weight adds for 5000 poly glycol monomethyl ethers at 15 DEG C
Enter 10.3mol sodium hydrides, reaction 10min adds in 10.1mol epoxychloropropane, after being stirred to react 30min desalination obtain epoxy group
Poly glycol monomethyl ether；
3) preparation of collapse protection type water-reducing agent：10mol amino-containeds copolymerization product is added in into 5mol epoxy group polyethyleneglycol first
Ether reaction 10min adds in potassium hydroxide and adjustment pH value obtains a kind of collapse protective poly-carboxylic acid water reducing agent for 6.5.
Embodiment 8：
1) preparation of amine-containing copolymerization product：25 DEG C of 10mol 2- methoxyl-4-vinyl phenols and 4mol allylamines exist
0.8mol hydrogen peroxide, 1.6mol ferrous sulfate, the effect of 0.03mol 2 mercaptopropionic acids is lower to carry out oxidationreduction free radical polymerization
Reaction 65min obtains the copolymerization product that molecular weight is 3500；
2) preparation of epoxy group poly glycol monomethyl ether：10mol molecular weight is added in for 500 poly glycol monomethyl ethers at 0 DEG C
10.1mol sodium hydrides, reaction 40min add in 11mol epoxychloropropane, after being stirred to react 90min desalination obtain the poly- second of epoxy group
Glycol monomethyl ether；
3) preparation of collapse protection type water-reducing agent：10mol amino-containeds copolymerization product is added in into 6mol epoxy group polyethyleneglycol first
Ether reaction 50min adds in calcium hydroxide and adjustment pH value obtains a kind of collapse protective poly-carboxylic acid water reducing agent for 6.
Embodiment 9：
1) preparation of amine-containing copolymerization product：45 DEG C of 10mol hydroxyethyl methacrylates N-butyl and 3mol Methacrylamides exist
0.9mol benzoyl peroxides, 1.8molN, N- diethylanilines, the effect of 0.04mol 3- mercaptopropionic acids is lower to carry out oxidationreduction
Raolical polymerizable 70min obtains the copolymerization product that molecular weight is 4000；
2) preparation of epoxy group poly glycol monomethyl ether：10mol molecular weight adds for 1200 poly glycol monomethyl ethers at 25 DEG C
Enter 10.4mol sodium hydrides, reaction 30min adds in 10.6mol epoxychloropropane, after being stirred to react 80min desalination obtain epoxy group
Poly glycol monomethyl ether；
3) preparation of collapse protection type water-reducing agent：10mol amino-containeds copolymerization product is added in into 5mol epoxy group polyethyleneglycol first
Ether reaction 20min adds in potassium hydroxide and adjustment pH value obtains a kind of collapse protective poly-carboxylic acid water reducing agent for 6.
Embodiment 10：
1) preparation of amine-containing copolymerization product：9mol acrylic acid hydroxyls, 1mol propyl ester acrylic acid hydroxyl N-butyl and 1mol N- ethyls
In 1mol benzoyl peroxides, 2mol ferrous pyrophosphates under the effect of 0.1mol lauryl mercaptans aoxidize-go back 25 DEG C of acrylamide
Former Raolical polymerizable 90min obtains the copolymerization product that molecular weight is 4500；
2) preparation of epoxy group poly glycol monomethyl ether：10mol molecular weight is added in for 800 poly glycol monomethyl ethers at 5 DEG C
10.4mol sodium hydrides, reaction 40min add in 10.6mol epoxychloropropane, are stirred to react desalination after 90min and obtain epoxy group and gather
Glycol monoethyl ether；
3) preparation of collapse protection type water-reducing agent：10mol amino-containeds copolymerization product is added in into 10mol epoxy group polyethyleneglycol first
Ether reaction 50min adds in sodium hydroxide and adjustment pH value obtains a kind of collapse protective poly-carboxylic acid water reducing agent for 7.
Paste flowing degree is tested：With reference to GB8077-2000《Methods for testing uniformity of concrete admixture》, to embodiment 1
Paste flowing degree test is carried out to 10 gained sample of embodiment.W/C is 0.29, and the solid volume of additive folding is cement consumption
0.15%, 5h loss are hardly lost；
The paste flowing degree and gradual loss of the different samples of table 1
Testing concrete performance：With reference to GB8076-2008《Concrete admixture》10 gained sample of embodiment is arrived to embodiment 1
Product carry out slump-loss, concrete strength inspection.(relative to cement consumption) when the solid volume of additive folding is 1.8wt%, 3 days
Compression strength raising is all higher than 85%, and compression strength raising in 7 days is all higher than 70%, and compression strength raising in 28 days is all higher than 75%.
The concrete slump retaining performance and mechanical property of the different samples of table 2
Claims (8)
1. a kind of preparation method of slump-retaining polycarboxylic acid type water reducing agent, is as follows：
1) preparation of amino-contained copolymerization product：Hydroxyl unsaturation minor comonomer and the unsaturated minor comonomer containing amine are being caused
Under agent, reducing agent and chain-transferring agent effect, oxidationreduction 30~90min of Raolical polymerizable is carried out in 25~45 DEG C of conditions,
Obtain amino-contained copolymerization product；Wherein described hydroxyl unsaturation minor comonomer, the unsaturated minor comonomer containing amine, initiator,
The molar ratio of reducing agent and chain-transferring agent is 1：(0.1~1)：(0.01~0.1)：(0.03~0.2)：(0.001~0.01)；Its
Described in hydroxyl unsaturation minor comonomer general formula R1OH expressions, wherein R1For 4~14 carbon atom ethylenic unsaturation alkyl or not
Saturation phenyl derivatives；The general formula of the unsaturated minor comonomer containing amine is with R2NHR3It represents, wherein R2For 3~8 carbon
The ethylenic unsaturation alkyl of atom, R3For H or the alkyl of 2-5 carbon atom；
2) preparation of epoxy group poly glycol monomethyl ether：At 0~25 DEG C, excessive hydrogenation is added in poly glycol monomethyl ether
Sodium adds in epoxychloropropane after reacting 10~40min, and after being stirred for 30~90min of reaction, desalination obtains epoxy group polyethylene glycol
Monomethyl ether；Wherein the molar ratio of poly glycol monomethyl ether, sodium hydride and epoxychloropropane is 1：(1.01~1.05)：(1.01~
1.1)；
3) preparation of slump-retaining polycarboxylic acid type water reducing agent：It will be in amino-contained copolymerization product made from step 1) plus made from step 2)
Epoxy group poly glycol monomethyl ether, after reacting 10~50min, it is 6~7 to add alkali neutralization adjustment pH value, obtains the poly- carboxylic of collapse protection type
Sour based water reducer；Wherein the molar ratio of amino-contained copolymerization product and epoxy group poly glycol monomethyl ether is 1：(0.5~1).
2. preparation method according to claim 1, it is characterised in that obtained amino-contained copolymerization product in step 1)
Molecular weight is 3000~5000.
3. preparation method according to claim 1, it is characterised in that the initiator in step 1) is persulfuric acid object or peroxide
Compound.
4. preparation method according to claim 1, it is characterised in that initiator in step 1) is tert-butyl hydroperoxide,
Hydrogen peroxide, ammonium persulfate, benzoyl peroxide, isopropyl benzene hydroperoxide, potassium peroxydisulfate or sodium peroxydisulfate one or two
Combination of the above.
5. preparation method according to claim 1, it is characterised in that the reducing agent in step 1) is rongalite, pyrosulfurous acid
Sodium, n,N-Dimethylaniline, sodium hydrogensulfite, ferrous sulfate, N, N- diethylanilines, ferrous pyrophosphate, four aziridines or
One or more kinds of combinations of sodium ascorbate；The chain-transferring agent is thioacetic acid, 2 mercaptopropionic acid, 3- sulfydryls third
One or more kinds of combinations of acid, methylpropenyl sodium sulfonate or lauryl mercaptan.
6. preparation method according to claim 1, it is characterised in that the hydroxyl unsaturation described in the step 1) is small
Monomer is 2- methallyl alcohols, propenyl, acrylate, hydroxy-ethyl acrylate, hydroxyethyl methacrylate, metering system
Sour hydroxypropyl acrylate, 4-Vinyl phenol, 2- methoxyl-4-vinyl phenols, hydroxyethyl methacrylate N-butyl, hydroxypropyl acrylate or
One or more kinds of combinations of acrylic acid hydroxyl N-butyl.
7. preparation method according to claim 1, it is characterised in that the insatiable hunger containing amine described in the step 1)
With minor comonomer for acrylamide, allylamine, Methacrylamide, N- ethyl acrylamides, n-isopropyl acrylamide or N- just
One or more kinds of combinations of propylacrylamide.
8. preparation method according to claim 1, it is characterised in that point of the poly glycol monomethyl ether described in step 2)
Son amount is 400~5000；The alkali is sodium hydroxide, potassium hydroxide or calcium hydroxide.
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