CN105367721B - The preparation method and application of viscosity reduction type polycarboxylic acid super-plasticizer - Google Patents
The preparation method and application of viscosity reduction type polycarboxylic acid super-plasticizer Download PDFInfo
- Publication number
- CN105367721B CN105367721B CN201510852628.9A CN201510852628A CN105367721B CN 105367721 B CN105367721 B CN 105367721B CN 201510852628 A CN201510852628 A CN 201510852628A CN 105367721 B CN105367721 B CN 105367721B
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- CN
- China
- Prior art keywords
- monomer
- plasticizer
- polycarboxylic acid
- reduction type
- viscosity reduction
- Prior art date
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- 239000002253 acid Substances 0.000 title claims abstract description 58
- 239000008030 superplasticizer Substances 0.000 title claims abstract description 49
- 230000009467 reduction Effects 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 96
- 239000004568 cement Substances 0.000 claims abstract description 20
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 7
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 239000002202 Polyethylene glycol Substances 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 229920001223 polyethylene glycol Polymers 0.000 claims description 27
- 239000004593 Epoxy Substances 0.000 claims description 23
- -1 3- vinyl benzyl Chemical group 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 20
- 239000003999 initiator Substances 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 239000011734 sodium Substances 0.000 claims description 13
- 229910052708 sodium Inorganic materials 0.000 claims description 13
- 150000003254 radicals Chemical class 0.000 claims description 11
- 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 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 claims description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- 239000012986 chain transfer agent Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000007858 starting material Substances 0.000 claims description 5
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 4
- IRQWEODKXLDORP-UHFFFAOYSA-N 4-ethenylbenzoic acid Chemical class OC(=O)C1=CC=C(C=C)C=C1 IRQWEODKXLDORP-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical class C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 3
- IFSSSYDVRQSDSG-UHFFFAOYSA-N 3-ethenylaniline Chemical compound NC1=CC=CC(C=C)=C1 IFSSSYDVRQSDSG-UHFFFAOYSA-N 0.000 claims description 3
- VWXZFDWVWMQRQR-UHFFFAOYSA-N 3-ethenylbenzoic acid Chemical class OC(=O)C1=CC=CC(C=C)=C1 VWXZFDWVWMQRQR-UHFFFAOYSA-N 0.000 claims description 3
- LBSXSAXOLABXMF-UHFFFAOYSA-N 4-Vinylaniline Chemical compound NC1=CC=C(C=C)C=C1 LBSXSAXOLABXMF-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000003444 phase transfer catalyst Substances 0.000 claims description 3
- 239000012312 sodium hydride Substances 0.000 claims description 3
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 3
- SYBQEKBVWDPVJM-UHFFFAOYSA-N (3-ethenylphenyl)boronic acid Chemical class OB(O)C1=CC=CC(C=C)=C1 SYBQEKBVWDPVJM-UHFFFAOYSA-N 0.000 claims description 2
- QWMJEUJXWVZSAG-UHFFFAOYSA-N (4-ethenylphenyl)boronic acid Chemical class OB(O)C1=CC=C(C=C)C=C1 QWMJEUJXWVZSAG-UHFFFAOYSA-N 0.000 claims description 2
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical class C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 2
- 150000001346 alkyl aryl ethers Chemical class 0.000 claims description 2
- 210000003608 fece Anatomy 0.000 claims description 2
- 235000021050 feed intake Nutrition 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- IJJSYKQZFFGIEE-UHFFFAOYSA-N naphthalene;potassium Chemical compound [K].C1=CC=CC2=CC=CC=C21 IJJSYKQZFFGIEE-UHFFFAOYSA-N 0.000 claims description 2
- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 claims description 2
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 2
- QHFAXRHEKNHTDH-UHFFFAOYSA-N (2-ethenylphenyl)boronic acid Chemical class OB(O)C1=CC=CC=C1C=C QHFAXRHEKNHTDH-UHFFFAOYSA-N 0.000 claims 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- 230000014509 gene expression Effects 0.000 claims 1
- 238000006206 glycosylation reaction Methods 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 150000003222 pyridines Chemical class 0.000 claims 1
- 239000004567 concrete Substances 0.000 abstract description 26
- 239000011372 high-strength concrete Substances 0.000 abstract description 17
- 238000000034 method Methods 0.000 abstract description 11
- 238000010276 construction Methods 0.000 abstract description 4
- 238000005086 pumping Methods 0.000 abstract description 4
- 125000004122 cyclic group Chemical group 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 42
- 238000003756 stirring Methods 0.000 description 25
- 229910052757 nitrogen Inorganic materials 0.000 description 21
- 239000000047 product Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000010792 warming Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 150000007513 acids Chemical class 0.000 description 8
- 239000003638 chemical reducing agent Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000012423 maintenance Methods 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- 229960000583 acetic acid Drugs 0.000 description 4
- 239000012362 glacial acetic acid Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920005646 polycarboxylate Polymers 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 230000001603 reducing effect Effects 0.000 description 4
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical class OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical class [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005461 lubrication Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 2
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 description 2
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical class OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 description 2
- DPZYLEIWHTWHCU-UHFFFAOYSA-N 3-ethenylpyridine Chemical class C=CC1=CC=CN=C1 DPZYLEIWHTWHCU-UHFFFAOYSA-N 0.000 description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical class OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 2
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical class [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical class [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 2
- 208000014903 transposition of the great arteries Diseases 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- GHKCSRZBNZQHKW-UHFFFAOYSA-N 1-sulfanylethanol Chemical class CC(O)S GHKCSRZBNZQHKW-UHFFFAOYSA-N 0.000 description 1
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- WULAHPYSGCVQHM-UHFFFAOYSA-N 2-(2-ethenoxyethoxy)ethanol Chemical class OCCOCCOC=C WULAHPYSGCVQHM-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- YTANEKIWKFMOHV-UHFFFAOYSA-N 4,5-bis(2-methylpropyl)-4,5-dihydro-1H-imidazole hydrochloride Chemical compound Cl.C(C(C)C)C1C(N=CN1)CC(C)C YTANEKIWKFMOHV-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- LXXNWCFBZHKFPT-UHFFFAOYSA-N Ethyl 2-mercaptopropionate Chemical compound CCOC(=O)C(C)S LXXNWCFBZHKFPT-UHFFFAOYSA-N 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
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- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
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- 125000005907 alkyl ester group Chemical group 0.000 description 1
- PMNLUUOXGOOLSP-UHFFFAOYSA-N alpha-mercaptopropionic acid Natural products CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
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- 239000000908 ammonium hydroxide Substances 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- AJSHDAOMUKXVDC-UHFFFAOYSA-N butan-1-amine;sulfuric acid Chemical compound CCCC[NH3+].OS([O-])(=O)=O AJSHDAOMUKXVDC-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
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- 239000013530 defoamer Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical group OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
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- 239000003292 glue Substances 0.000 description 1
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- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000001261 hydroxy acids Chemical group 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
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- 230000003472 neutralizing effect Effects 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 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
- 230000036314 physical performance Effects 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 239000011150 reinforced concrete Substances 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical class [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000012032 thrombin generation assay Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a kind of preparation method and applications of viscosity reduction type polycarboxylic acid super-plasticizer, this method operating process is simple, prepared polycarboxylic acid super-plasticizer is used for high and super high strength concrete, concrete viscosity can effectively be reduced, the workability and flowing velocity of concrete are improved, is advantageous to pumping construction.Methods described is：By carboxylic monomer a, the side chain containing branching type monomer b and the monomer c containing rigid cyclic group in molar ratio (4~15):1:(0.5~2) carry out free radicals copolymerization reaction and obtain viscosity reduction type polycarboxylic acid super-plasticizer.Polycarboxylic acid super-plasticizer obtained by the method for the invention may be used as cement dispersants, and the water-cement ratio of concrete is greatly lowered, and can effectively reduce the high viscosity with super high strength concrete, improve its workability and flowing velocity, pumpability is excellent.
Description
Technical field
The present invention relates to a kind of preparation method and application of viscosity reduction type polycarboxylic acid super-plasticizer, belongs to concrete admixture technology
Field.
Background technology
With the high stratification of modern building, big collapsing and lightweight development, construction and quality requirement to concrete are got over
Come it is higher, high intensity, high pumping and high-durability turn into modern concrete developing direction.It is high compared with normal concrete
Reinforced concrete (C60~C90) and super high strength concrete (C100 and more than) have significant superiority：Structure can effectively be mitigated certainly
Weight；Increase building usable floor area；Material and the energy are saved, reduces building cost；Concrete durability etc. is lifted, is had preferable
Economic and social benefit.At present, improving the method for concrete strength mainly has the cement using high grade, increase folk prescription water
Mud dosage, reduce ratio of mud etc..However, these technical measures directly result in concrete viscosity increase, mobility declines therewith, from
And pumpability of concrete is reduced, efficiency of construction is influenceed, popularization and application are restricted.How high and superelevation strong coagulation is reduced
The viscosity of soil causes the concern of many scholars.
Patent document CN103613348A is reported in the super high strength concrete that mean intensity is 120MPa is prepared, and is used
The superfine powders such as large dosage silicon ash, miberal powder and microballon, super high strength concrete viscosity is reduced, realize more than 300m Super High
Pumping.Patent document CN102775110A is reported in super high strength concrete is prepared, and is made using zeolite powder and sodium gluconate
For viscosity reduction plasticity-maintaining agent, then ultrafine slag powder, fine agstone and microballon are aided in, greatly reduce the viscous of super high strength concrete
Degree.Patent document CN103145360A reports a kind of high and viscosity modifier of super high strength concrete, and it uses silicon ash, fine coal
Ash, super-fine limestone powder or quartz powder and Inorganic form by a certain percentage, for having in super high strength concrete
The effect of viscosity reduction.But the measure of these viscosity reductions is all that the scheme of physics filling lubrication is carried out using admixture ultrafine inorganic powder,
Volume is up to more than 10%, increases considerably Cost of Concrete, and ultrafine inorganic powder bulk density is small, mass per volume
It is small, it has not been convenient to transport and use.
Polycarboxylic acid super-plasticizer is as third generation high performance concrete water reducer, and its raw material sources is extensive, and molecular structure is more
Sample, can be using sulfonic group, carboxylic acid group, phosphate etc. as adsorption group, and possesses abundant adjustable hydrophilic side chain and play sky
Between steric hindrance, drastically increase the scattered lubrication to cement, have volume is low, water-reducing rate is high, concrete batching system
Mobility and flowing the advantages that retentivity is good, lower shrinkage, molecular structure designability are strong, simple production process, in building work
It is widely used in journey, promotes concrete quality to develop to high performance direction.
Because polycarboxylic acid super-plasticizer molecular structure has stronger designability, by adjusting its main chain and side chain knot
Structure, the high performance and functionalization of polycarboxylic acid super-plasticizer are realized, in height with also being shown in terms of super high strength concrete viscosity reduction
Great potential.Patent document CN104262550A discloses a kind of preparation method of viscosity reduction type polycarboxylate water-reducer, first with containing
Acid anhydrides minor comonomer and the binary primary amine of unsaturated double-bond are reacted, and are prepared unsaturated primary amine class minor comonomer, are then carried out season again
Ammonium obtains quaternary ammonium salt unsaturation minor comonomer, then gathers with unsaturated esters minor comonomer, unsaturated acids minor comonomer and unsaturation
Ester polymeric monomer is polymerize, and viscosity reduction type polycarboxylate water-reducer is prepared.This method preparation process is more, and process is cumbersome, quaternary ammonium
Salt unsaturation minor comonomer preparation time grows (5~72h), and prepared polycarboxylate water-reducer viscosity reducing effect is limited.Patent document
CN103865007A discloses a kind of preparation method of viscosity reduction type polycarboxylate water-reducer, and it uses random polyoxyethylene unsaturated acids
Ester, unsaturated modified APEO, unsaturated alkyl ester and (methyl) acrylic acid are copolymerized and obtained.But the polycarboxylic acids subtracts
Aqua is in the concrete that water-cement ratio is 0.24, and its bucket of falling slump emptying time is up to more than 39s, and viscosity reducing effect has very much
Limit, it is difficult to meet workability requirement of the high and super high strength concrete to low viscosity.
The content of the invention
Goal of the invention
It is an object of the present invention to provide a kind of preparation method of viscosity reduction type polycarboxylic acid super-plasticizer, this method operated
Journey is simple, and prepared polycarboxylic acid super-plasticizer is used for high and super high strength concrete, can effectively reduce concrete viscosity, improves mixed
The workability and flowing velocity of soil are coagulated, is advantageous to pumping construction.
It is a further object to provide application of the viscosity reduction type polycarboxylic acid super-plasticizer as cement dispersants.
Summary of the invention
Researcher of the present invention has found through experiment, after polycarboxylic acid super-plasticizer is adsorbed in cement particle surface, due to its side chain
Strongly hydrophilic so that cement particle surface forms water membrane layer, and the lubrication of water film is reduced between cement granules
Friction, so as to reduce the viscosity of concrete, water film is thicker, and viscosity reducing effect is more notable.By improving polycarboxylic acid super-plasticizer
The steric hindrance effect of side chain, be advantageous to increase the thickness of water film, so as to reduce the viscosity of concrete.And use branching type side
Chain, while rigid cyclic group is introduced in the molecule, polycarboxylic acids molecular conformation can be made more to stretch, further improve the space of its side chain
Steric hindrance, so as to which the high viscosity with super high strength concrete be greatly lowered.
In the first aspect of the present invention, there is provided a kind of preparation method of viscosity reduction type polycarboxylic acid super-plasticizer, by monomer a,
Monomer b and monomer c is in molar ratio (4~15):1:(0.5~2) carry out free radicals copolymerization reaction and obtain, wherein：
Monomer a is represented with formula (I)：
R in formula1For-H or-COOM；R2For-H ,-CH3Or-CH2COOM；And work as R1For-COOM when, R2For H；M represents that hydrogen is former
Son, alkali metal ion or ammonium ion；
Monomer b is represented with formula (II)：
R in formula3For-H or-CH3；R4For C1~C4 alkyl；X is-CH2-、-CH2OCH2CH2-、-CH2CH2-、-
CH2CH2OCH2CH2-、-OCH2CH2-、-OCH2CH2OCH2CH2-、-OCH2CH2CH2CH2- ,-C6H4- ,-C6H4CH2-；M=20
~45, n=5~10, p=1~5；
Monomer c is the monomer containing rigid cyclic group, specially NVP, N- caprolactams, 1-
Vinyl imidazole, 2- vinylpyridines, 3- vinylpyridines, 4-vinylpridine, 3- vinyl aniline, 4- vinyl aniline,
3- vinyl benzoic acids, 4- vinyl benzoic acids, 3- vinyl benzyl amines, 4- vinyl benzyl amines, 3- vinylphenylboronic acids, 2- ethene
Base phenyl boric acid or 4- vinylphenylboronic acids, preferably NVP, N- caprolactams, 1- vinyl miaows
Azoles, 2- vinylpyridines, 3- vinylpyridines, 4-vinylpridine, 3- vinyl aniline, 4- vinyl aniline, 3- vinyl
Benzoic acid, 4- vinyl benzoic acids, 3- vinyl benzyl amines or 4- vinyl benzyl amines.
The monomer a contains at least one of material material represented by formula (I), it is preferred that monomer a is selected from propylene
At least one of acid, methacrylic acid, maleic acid, fumaric acid or their univalent metal salt, ammonium salt.These monomers individually make
Used with or with the arbitrary proportion form of mixtures of two or more compositions, its hydroxy-acid group provides adsorption site in cement dispersants
And electrostatic repulsion.
The monomer b can obtain through alkoxylation well known to those skilled in the art, specifically, monomer b is not by
Saturated alcohols obtain with oxirane, epoxy terminated alkyl polyethylene glycol through blocked alkoxylation,
The unsaturated alcohol is represented with formula (III)：
The epoxy terminated alkyl polyethylene glycol is represented with formula (IV)：
Common unsaturated alcohol includes 2- propylene -1- alcohol, methallyl alcohol, 2- (2- methyl allyloxies) second
Alcohol, 3- butene-1-ols, 3- methyl-3-butene-1-alcohols, 2- (3- methyl alkene butoxy) ethanol, ethylene glycol vinyl ether, diethyl
Glycol vinyl ethers, 4- hydroxy butyl vinyl ethers, preferably 4-Vinyl phenol, 4- vinyl benzyl alcohols, unsaturated alcohol include 2- third
Alkene -1- alcohol, methallyl alcohol, 2- (2- methyl allyloxies) ethanol, 3- butene-1-ols, 3- methyl -3- butylene -
1- alcohol, 2- (3- methyl alkene butoxy) ethanol, ethylene glycol vinyl ether, diethylene glycol vinyl ethers, 4- hydroxy butyl vinyl ethers.
Common epoxy terminated alkyl polyethylene glycol includes epoxy terminated methyl polyethylene glycol, epoxy terminated ethyl polyethylene glycol, end ring
Epoxide propyl group polyethylene glycol, epoxy terminated butyl polyethylene glycol.In order to ensure the preferable polymerization activity of epoxy terminated polyethylene glycol,
Its polyoxyethylene adduct number should not be too big, and adduct number is preferably 1~5.If adduct number is too big, when being reacted, molecular weight
Too high polyoxyethylene chain can cause bigger steric hindrance to act on terminal epoxy groups, influence reaction conversion ratio, cause to produce
Physical performance declines.
The general monomer b directly uses the mixture after alkoxylation, without purifying (because of monomer in mixture
Mixture when considering monomer a, b, c mol ratio, is directly considered as pure monomer b and calculated by b concentration close to 100%).Therefore
The actual conditions (selection of such as catalyst) of the blocked alkoxylation can by those skilled in the art with reference to it is described from
By the characteristics of base copolymerization system and the application requirement of target product viscosity reduction type polycarboxylic acid super-plasticizer is selected.It is preferred that
, the blocked alkoxylation is with potassium, sodium, naphthalene potassium, naphthalene sodium, hydrofining, sodium hydride, alkyl potassium alcoholate, sodium alkyl alcohol, hydrogen
As catalyst, catalyst amount is the 0.1%~0.3% of gained monomer b mass for potassium oxide or sodium hydroxide.More preferably use
Following reaction condition：The reaction temperature of unsaturated alcohol and oxirane be 100~130 DEG C, reaction pressure be 0.2~
0.4MPa, oxirane is by the way of continuous charging；After oxirane feeds, continue under constant temperature to reaction system pressure
Be down to below -0.05MPa, then epoxy terminated alkyl polyethylene glycol added by the way of continuous charging, feed time be 2~
6h, reaction temperature are 110~140 DEG C, and reaction pressure is below -0.05MPa, after charging terminates, 0.5~2h of constant temperature, and reaction knot
Product temperatur is kept to use organic acid to be neutralized to pH value as 6~8 between 60~80 DEG C after beam.As common sense in the field, neutralize
The application environment of organic acid reply free radicals copolymerization reaction used and the viscosity reduction type polycarboxylic acid super-plasticizer is friendly, preferably described
Organic acid is any one in glacial acetic acid, oxalic acid, citric acid, benzoic acid.
The preparation method of epoxy terminated alkyl polyethylene glycol is that fine chemical fields disclose ripe method, art technology
Personnel can according to pertinent literature (the fine chemistry industries such as Guo Limei, 2005,22：108-111) prepared by method, common preparation
Method is：React directly raw in the presence of sodium hydroxide and phase transfer catalyst by epoxychloropropane and polyalkylene glycol monoalkyl ether
Into epoxy terminated alkyl polyethylene glycol.
The weight average molecular weight range of the viscosity reduction type polycarboxylic acid super-plasticizer and the super modeling of polycarboxylic acids well known in the prior art
Agent typically requires identical, it is preferred that the weight average molecular weight of the polycarboxylic acid super-plasticizer is 10000~30000.Molecular weight
It is too big or too small, it can all weaken its combination property.
Preferably, the free radicals copolymerization reaction is water-based free radical copolyreaction.It is furthermore preferred that the water-based free radical
Copolyreaction uses water soluble starter and water-soluble chain transfer agent, the matter of the water soluble starter and water-soluble chain transfer agent
0.1%~1%, the 0.1%~0.4% of amount respectively monomer a, monomer b and monomer c three's gross mass, the water-based free radical
The polymerization concentration of copolyreaction is 30%~50%, and wherein polymerization concentration refers to the mass percent concentration sum of all monomers.
Optional water soluble starter includes single persulfate, water-soluble azo class initiator, and oxidant mistake
The composition of sulfate and reducing agent bisulfites, sulphite, thiosulfate, pyrosulfite or ferrous salt, oxidation
The composition of agent peroxide and reducing agent formaldehyde sodium sulfoxylate, L-AA, phosphorous acid and its salt, hypophosphorous acid and its salt, wherein group
In compound, the mole ratio of both oxidant and reducing agent is (4~8):1.
Water-soluble chain transfer agent is used to control polycarboxylic acids molecular weight.Thio-alcohol chain tra nsfer can be used in water-soluble chain transfer agent
Agent, such as 2 mercaptopropionic acid, 3- mercaptopropionic acids, 2- mercaprols, 3- mercaprols, TGA, mercaptoethanol, dimercapto third
Alcohol, mistabrom；The secondary alcohols such as isopropanol；Phosphorous acid and its sodium, sylvite；At least one in hypophosphorous acid and its sodium, sylvite
Kind.
Polymerization concentration in the free radicals copolymerization reaction is preferably 30%~50%, and concentration is too low, monomer conversion compared with
It is low, low production efficiency；Excessive concentration, then polymerization is whard to control, implode gel easily occurs, has a strong impact on product property.Polymerization
Reaction temperature is preferably 30~80 DEG C, and it is mainly relevant with used initiator, generally, be used alone persulfate and
During water-soluble azo class initiator, when selecting slightly higher polymerization temperature, and using redox initiation system, it may be selected relatively low
Polymerization temperature.
Still more preferably, the feed way of the water-based free radical copolyreaction is：Monomer b is before other material droppings
Disposable all to feed intake, the aqueous solution of the aqueous solution and initiator of monomer a and monomer c mix monomers takes what is separated while be added dropwise
Mode is fed, and chain-transferring agent is added in the aqueous solution of mix monomer or the aqueous solution of initiator and is added dropwise together, the water of mix monomer
The aqueous solution time for adding of solution and initiator is 2~5h, after the aqueous solution of mix monomer and the aqueous solution of initiator drip
Continue 1~4h of insulation.
After copolyreaction terminates, reaction product can use directly as the principal component of cement dispersants, be more preferably into one
Step uses after being neutralized with alkaline matter, to strengthen the storage stability of product.This is techniques known.Used alkali
Property material include hydroxide, oxide or the carbonate of monovalent metal and/or divalent metal, ammonium hydroxide, organic amine.Alkalescence
The dosage of material is advisable using the pH value for adjusting reaction product as 6~8.Due to neutralizing to the viscosity reduction type polycarboxylic acid super-plasticizer
Molecular weight effects very little, the present invention ignore to it.
According to the second aspect of the invention, there is provided the viscosity reduction type polycarboxylic acid super-plasticizer should as cement dispersants
With.
Polycarboxylic acid super-plasticizer of the present invention can be used directly as cement dispersants, can also with defoamer, draw
The functional form such as gas agent, retarder, thickener, economization agent auxiliary agent or other types of polycarboxylic acid super-plasticizer are carried out by a certain percentage
Used after compounding, specific to compound type and ratio, engineers and technicians can pass through preferred after experiment according to Practical Project demand.
In use, the conventional volume of polycarboxylic acid super-plasticizer of the present invention is the 0.05%~0.3% of total binder materials weight.Mix
Measure it is too low, then it is unsatisfactory to the dispersion effect of cement；Volume is too high, causes waste economically, and dispersion effect is simultaneously
Do not increase further, engineering staff can be preferred within this range according to actual conditions.
The water-cement ratio of concrete can be greatly lowered in polycarboxylic acid super-plasticizer of the present invention, and can effectively reduce it is high with
The viscosity of super high strength concrete, its workability and flowing velocity are improved, pumpability is excellent, and more conventional polycarboxylic acid super-plasticizer has
Significant advantage.
Embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely to the following examples.
In the embodiment of the present invention, the test of conversion ratio is entered using LabTech LC600 high performance liquid chromatographs (HPLC)
OK.Test condition is that chromatographic column uses Kromasil C18 posts, mobile phase CH3OH/H2O=80/20 (v/v), flow velocity are
0.6ml/min, detector are differential refraction detector, and 35 DEG C of detector temperature, sample size is the water-soluble of the samples of 20 μ l 0.5%
Liquid.
In the embodiment of the present invention, the weight average molecular weight of polymer uses Agilent-1260 gel permeation chromatographs (GPC)
Measure.Test condition is gel column：The root chromatogram columns of Shodex SB806+803 two are connected；Elutriant：0.1M NaNO3Solution；
Flow phase velocity：0.8ml/min；Injection：The aqueous solution of the samples of 20 μ l 0.5%；Detector：Differential refraction detector；Standard
Thing：Polyethylene glycol GPC standard specimens (Sigma-Aldrich, molecular weight 1010000,478000,263000,118000,44700,
18600,6690,1960,628,232)。
Raw material used in the embodiment of the present invention is commercially available general analysis pure chemistry reagent, and oxirane is three rivers
The high-class product of work production, purity 99.95%.
Monomer b preparation
The preparation of epoxy terminated alkyl polyethylene glycol：
0.5mol epoxychloropropane, 0.2mol sodium hydroxide, 0.005mol are added in the three-necked flask with stirring
Phase transfer catalyst 4-n-butyl ammonium hydrogen sulfate, the 0.05mol quick stirring 5h of 60 DEG C of mono-alkyl polyethylene glycol constant temperature, mistake
Filter, filtrate remove excessive epoxychloropropane through being evaporated under reduced pressure, and the conversion ratio that product tests mono-alkyl polyethylene glycol through HPLC is
85%~90%, product uses silica gel column chromatography (ethyl acetate is eluent) to carry out separating-purifying again, and it is big to obtain purity
In 99% epoxy terminated alkyl polyethylene glycol.
Epoxy terminated alkyl polyethylene glycol prepared by table 1 collects
| Code | Title | End group type | p | Molecular weight |
| E-1 | Epoxy terminated methyl polyethylene glycol | Methyl | 1 | 132 |
| E-2 | Epoxy terminated propyl group polyethylene glycol | Propyl group | 3 | 248 |
| E-3 | Epoxy terminated butyl polyethylene glycol | Butyl | 4 | 306 |
| E-4 | Epoxy terminated methyl polyethylene glycol | Methyl | 5 | 308 |
| E-5 | Epoxy terminated propyl group polyethylene glycol | Propyl group | 2 | 204 |
Monomer b-1 preparation：
In the 2L reactors of the drying with stirring, 62.5g 2- propylene -1- alcohol, 4.99g sodium methoxides are added, unlatching is stirred
Mix to sodium methoxide and be completely dissolved, seal reactor.It is repeated below operation twice：Be evacuated to after nitrogen displacement -0.09MPa with
Under.Then it is continuous into reactor that 948.28g epoxy second is slowly at the uniform velocity added dropwise after persistently stirring and being warming up to 120~130 DEG C
Alkane, 0.3~0.4MPa of maintenance reaction pressure.After constant temperature charging terminate after, continue constant temperature keep system pressure drop to-
Below 0.05MPa, it is then continuous into reactor that 711.21g E-1, feed time 2h is slowly at the uniform velocity added dropwise, while keep anti-
Answer 130~140 DEG C of temperature.After charging terminates, continue constant temperature and keep 2h, pH value is neutralized to glacial acetic acid as 7 after being cooled to 60 DEG C
Left and right, discharge to obtain monomer b-1, and it is 99.5% that HPLC, which tests conversion ratio, molecular weight 1598.
Monomer b-2 preparation：
In the 2L reactors of the drying with stirring, 38.6g methallyl alcohols, 3.71g hydrogenations are added
Sodium, open stirring to sodium hydride and be completely dissolved, seal reactor.It is repeated below operation twice：Be evacuated to after nitrogen displacement-
Below 0.09MPa.Then after persistently stirring and being warming up to 100~110 DEG C, continuously slowly at the uniform velocity it is added dropwise into reactor
754.84g oxirane, 0.25~0.35MPa of maintenance reaction pressure.After constant temperature charging terminates, continue constant temperature and keep system pressure
Power is dropped to below -0.06MPa, then continuous into reactor that 1063.64g E-2, feed time 6h is slowly at the uniform velocity added dropwise,
Keep 110~120 DEG C of reaction temperature simultaneously.After charging terminates, continue constant temperature and keep 2h, neutralized after being cooled to 80 DEG C with benzoic acid
It is 7 or so to pH value, discharge to obtain monomer b-2, and it is 99.1% that HPLC, which tests conversion ratio, molecular weight 3464.
Monomer b-3 preparation：
In the 2L reactors of the drying with stirring, 56.2g 2- (2- methyl allyloxies) ethanol, 2.7g second are added
Potassium alcoholate, open stirring to potassium ethoxide and be completely dissolved, seal reactor.It is repeated below operation twice：Be evacuated to after nitrogen displacement-
Below 0.09MPa.Then after persistently stirring and being warming up to 105~115 DEG C, continuously slowly at the uniform velocity it is added dropwise into reactor
852.69g oxirane, 0.2~0.3MPa of maintenance reaction pressure.After constant temperature charging terminates, continue constant temperature and keep system pressure
Drop to below -0.06MPa, it is then continuous into reactor that 889.51g E-3, feed time 5h is slowly at the uniform velocity added dropwise, together
When keep 120~130 DEG C of reaction temperature.After charging terminates, continue constant temperature and keep 2h, be neutralized to after being cooled to 70 DEG C with benzoic acid
PH value is 7 or so, and discharge to obtain monomer b-3, and it is 99.5% that HPLC, which tests conversion ratio, molecular weight 3712.
Monomer b-4 preparation：
In the 2L reactors of the drying with stirring, 28.6g 3- methyl-3-butene-1-alcohols, 1.71g metals are added
Sodium, open stirring to metallic sodium and be completely dissolved, seal reactor.It is repeated below operation twice：Be evacuated to after nitrogen displacement-
Below 0.09MPa.Then after persistently stirring and being warming up to 110~120 DEG C, continuously slowly at the uniform velocity it is added dropwise into reactor
658.47g oxirane, 0.25~0.35MPa of maintenance reaction pressure.After constant temperature charging terminates, continue constant temperature and keep system pressure
Power is dropped to below -0.05MPa, then continuous into reactor that 1024.28g E-4, feed time 5h is slowly at the uniform velocity added dropwise,
Keep 125~135 DEG C of reaction temperature simultaneously.After charging terminates, continue constant temperature and keep 2h, neutralized after being cooled to 65 DEG C with glacial acetic acid
It is 7 or so to pH value, discharge to obtain monomer b-4, and it is 99.2% that HPLC, which tests conversion ratio, molecular weight 5146.
Monomer b-5 preparation：
In the 2L reactors of the drying with stirring, 79.5g 4- hydroxy butyl vinyl ethers, 4.26g hydroxides are added
Potassium, open stirring to potassium hydroxide and be completely dissolved, seal reactor.It is repeated below operation twice：Be evacuated to after nitrogen displacement-
Below 0.09MPa.Then after persistently stirring and being warming up to 110~120 DEG C, continuously slowly at the uniform velocity it is added dropwise into reactor
784.03g oxirane, 0.2~0.3MPa of maintenance reaction pressure.After constant temperature charging terminates, continue constant temperature and keep system pressure
Drop to below -0.055MPa, it is then continuous into reactor that 838.86g E-5, feed time 4h is slowly at the uniform velocity added dropwise, together
When keep 115~125 DEG C of reaction temperature.After charging terminates, continue constant temperature and keep 0.5h, neutralized after being cooled to 60 DEG C with glacial acetic acid
It is 7 or so to pH value, discharge to obtain monomer b-5, and it is 99.3% that HPLC, which tests conversion ratio, molecular weight 2484.
Monomer b molecular structure informations prepared by table 2 collect
[embodiment 1]
In the present embodiment, monomer a, monomer b and monomer c molar ratio are 4:1:0.5.
In the 1L glass reactors equipped with thermometer, agitator, dropping funel and nitrogen conduit, 191g distilled water is added
With 286.5g monomers b-1.Reactor is under the protection of logical nitrogen, and stirring is warming up to 80 DEG C to being completely dissolved, then by 51.63g
Acrylic acid, 9.95gN- vinyl pyrrolidones, 0.35g 3- mercaptopropionic acids and 67g water mix and uniform monomer water are made
Solution, it is at the uniform velocity added dropwise in reactor, time for adding 5h.At the same time, be at the uniform velocity added dropwise by 0.35g ammonium persulfates with
The initiator solution that 86g water mixes, time for adding 5h.After complete soln is added dropwise, continues constant temperature and keep 4h, then
40 DEG C are cooled to, product is neutralized to pH=7 or so with sodium hydroxide, the viscosity reduction type polycarboxylic acids that solid content is 49.8% is obtained and surpasses
Plasticiser, molecular weight are determined as 10,600 through GPC.
[embodiment 2]
In the present embodiment, monomer a, monomer b and monomer c molar ratio are 6.7:1:1.85.
In the 1L glass reactors equipped with thermometer, agitator, dropping funel and nitrogen conduit, 164g distilled water is added
With 245.5g monomers b-2.Reactor is under the protection of logical nitrogen, and stirring is warming up to 75 DEG C to being completely dissolved, then by 28.07g
Acrylic acid, 9.14g Sodium methacrylates, 13.77g 4-vinylpridines, 0.59g mercaptoethanols and 87g water are mixed and are made
Uniform monomer solution, it is at the uniform velocity added dropwise in reactor, time for adding 4h.At the same time, at the uniform velocity it is added dropwise by 1.48g
The initiator solution that potassium peroxydisulfate mixes with 105g water, time for adding 4h.After complete soln is added dropwise, continue constant temperature
3h is kept, 40 DEG C is then cooled to, product is neutralized to pH=7 or so with potassium hydroxide, obtains the drop that solid content is 45.8%
Viscous type polycarboxylic acid super-plasticizer, molecular weight are determined as 15,700 through GPC.
[embodiment 3]
In the present embodiment, monomer a, monomer b and monomer c molar ratio are 9.5:1:1.2.
In the 1L glass reactors equipped with thermometer, agitator, dropping funel and nitrogen conduit, 143.5g distillations are added
Water and 215.3g monomers b-3.For reactor under the protection of logical nitrogen, stirring is warming up to 65 DEG C to being completely dissolved, and then will
43.73g maleic acids, 16.36g PAAs, 9.67g N- caprolactams, 0.71g TGAs and the mixing of 120g water
Uniform monomer solution is made in stirring, it is at the uniform velocity added dropwise in reactor, time for adding 4h.At the same time, at the uniform velocity drip
Add the initiator solution mixed by 1.85g azos diisobutyl amidine hydrochloride and 158g water, time for adding 4h.It is all molten
After liquid is added dropwise, continues constant temperature and keep 2h, be then cooled to 40 DEG C, product is neutralized to pH=7 or so with triethylamine, obtained
Solid content is 40.5% viscosity reduction type polycarboxylic acid super-plasticizer, and molecular weight is determined as 24,800 through GPC.
[embodiment 4]
In the present embodiment, monomer a, monomer b and monomer c molar ratio are 15:1:2.
In the 1L glass reactors equipped with thermometer, agitator, dropping funel and nitrogen conduit, 124g distilled water is added
With 186.2g monomers b-4.Reactor is under the protection of logical nitrogen, and stirring is warming up to 45 DEG C to being completely dissolved, then by 29.96g
Acrylic acid, 14.69g fumaric acid, 9.62g 4- vinyl benzyl amines, 2.16g sodium hydrogensulfites, 0.96g sodium hypophosphites and 185g water
Uniform monomer solution is made in mixing, it is at the uniform velocity added dropwise in reactor, time for adding 3h.At the same time, it is even
The initiator solution mixed by 0.21g sodium peroxydisulfates and 236g water, time for adding 3h is added dropwise in speed.Complete soln drips
Bi Hou, continue constant temperature and keep 4h, be then cooled to 40 DEG C, product is neutralized to pH=7 or so with sodium hydroxide, obtains solid content
For 30.9% viscosity reduction type polycarboxylic acid super-plasticizer, molecular weight is determined as 29,600 through GPC.
[embodiment 5]
In the present embodiment, monomer a, monomer b and monomer c molar ratio are 10:1:0.75.
In the 1L glass reactors equipped with thermometer, agitator, dropping funel and nitrogen conduit, 116.5g distillations are added
Water and 174.8g monomers b-5.For reactor under the protection of logical nitrogen, stirring is warming up to 30 DEG C to being completely dissolved, and then will
22.8g acrylic acid, 53.41g maleic acid lists sodium, 7.81g 4- vinyl benzoic acids, 0.91g 3- mercaprols, 2.59g hang white
Powder and 114g water, which mix, is made uniform monomer solution, it is at the uniform velocity added dropwise in reactor, time for adding 2h.With
The initiator solution mixed by 0.94g hydrogen peroxide and 70g water, time for adding 2h is at the uniform velocity added dropwise simultaneously in this.Complete soln
After being added dropwise, continue constant temperature and keep 2h, product is then neutralized to pH=7 or so with triethylamine, obtaining solid content is
36.2% viscosity reduction type polycarboxylic acid super-plasticizer, molecular weight are determined as 18,500 through GPC.
[embodiment 6]
In the present embodiment, monomer a, monomer b and monomer c molar ratio are 6.2:1:1.45.
In the 1L glass reactors equipped with thermometer, agitator, dropping funel and nitrogen conduit, 160.8g distillations are added
Water and 241.3g monomers b-2.For reactor under the protection of logical nitrogen, stirring is warming up to 55 DEG C to being completely dissolved, and then will
31.1g acrylic acid, 11.21g NVPs, 0.85g 2- mercaprols and 105g water, which mix, to be made uniformly
Monomer solution, it is at the uniform velocity added dropwise in reactor, time for adding 4h.At the same time, at the uniform velocity it is added dropwise by 2.41g azos
The initiator solution that diisobutyl imidazoline hydrochloride mixes with 144g water, time for adding 4.5h.Complete soln is added dropwise
After, continue constant temperature and keep 2.5h, be then cooled to 40 DEG C, product is neutralized to pH=7 or so with sodium hydroxide, consolidate
Content is 40.3% viscosity reduction type polycarboxylic acid super-plasticizer, and molecular weight is determined as 22,600 through GPC.
[comparative example 1]
In the 1L glass reactors equipped with thermometer, agitator, dropping funel and nitrogen conduit, 191g distilled water is added
With the allyl polyglycol polymeric monomer that the commercially available convenient molecular weights of 286.5g are 2400.Reactor is under the protection of logical nitrogen, stirring
To being completely dissolved, and 80 DEG C are warming up to, then by 51.63g acrylic acid, 9.95gN- vinyl pyrrolidones, 0.35g 3- sulfydryls
Propionic acid and 67g water, which mix, is made uniform monomer solution, it is at the uniform velocity added dropwise in reactor, time for adding 5h.
At the same time, the initiator solution mixed by 0.35g ammonium persulfates and 86g water, time for adding 5h is at the uniform velocity added dropwise.All
After solution is added dropwise, continues constant temperature and keep 4h, be then cooled to 40 DEG C, product is neutralized to pH=7 or so with sodium hydroxide,
The polycarboxylic acid super-plasticizer that solid content is 49.4% is obtained, molecular weight is determined as 21,500 through GPC.
[comparative example 2]
In the 1L glass reactors equipped with thermometer, agitator, dropping funel and nitrogen conduit, 124g distilled water is added
With the methyl butene base polyethylene glycol polymeric monomer that the commercially available convenient molecular weights of 186.2g are 2400.Reactor logical nitrogen protection under,
Stirring is warming up to 45 DEG C to being completely dissolved, then by 29.96g acrylic acid, 14.69g fumaric acid, 9.62g 4- vinyl benzyls
Amine, 2.16g sodium hydrogensulfites, 0.96g sodium hypophosphites and 185g water mix and uniform monomer solution are made, by it at the uniform velocity
It is added dropwise in reactor, time for adding 3h.At the same time, at the uniform velocity it is added dropwise and is mixed by 0.21g sodium peroxydisulfates and 236g water
Initiator solution, time for adding 3h.After complete soln is added dropwise, continues constant temperature and keep 4h, be then cooled to 40 DEG C, use
Product is neutralized to pH=7 or so by sodium hydroxide, obtains the polycarboxylic acid super-plasticizer that solid content is 31.8%, molecular weight is through GPC
It is determined as 34,200.
Evaluate the super modeling of polycarboxylic acids of viscosity reduction type polycarboxylic acid super-plasticizer and the preparation of comparative example 1~2 prepared by embodiment 1~6
Influence of the agent to fresh mixing concrete property, with reference to standard GB/T 8076-2008《Concrete admixture》Relevant regulations are held
OK.Experiment is carried out under 20 DEG C of environment, and testing cement uses the cement of south of the River little Ye fields P. II 52.5, the same to water consumption (water of stationary phase
Glue ratio is 0.27), match ratio is shown in Table 3.Adjustment admixture dosage makes fresh concrete initial slump be 23 ± 1cm, using first
Flowing time (hereinafter referred to as T50) and the initial bucket of falling the slump emptying time when beginning concrete divergence is 50cm weigh coagulation
The viscosity of soil, both used times are fewer, show that concrete viscosity is lower, and the viscosity reducing effect of additive is more notable.The volume of additive
For pure solid volume, calculated on the basis of the gross mass of binder materials.As a result it is as shown in table 4.
C70 mix proportion of high-strength concrete (the kg/m of table 33)
| Cement | Flyash | Miberal powder | Sand | Gravelstone | Great Shi | Water | Water-cement ratio |
| 4.95 | 2.06 | 1.25 | 10.99 | 4.56 | 10.62 | 2.23 | 0.27 |
Table 4 newly mixes Properties of High Strength Concrete contrast
It is can be seen that from result shown in table 4 in the application of C70 concrete, with using comparative example 1 and comparative example 2 made
Standby polycarboxylic acid super-plasticizer is compared, using the viscosity reduction type polycarboxylic acid super-plasticizer prepared by embodiment 1~6 substantially suitable
In the case of initial slump and divergence, volume has and significantly reduced, and initial water-reducing effect is notable, while the 60min slumps
Loss is also significantly better than comparative example 1 and 2.From the point of view of viscosity test data, the viscosity reduction type polycarboxylic acids prepared by embodiment 1~6 surpasses
Plasticiser is used for concrete initial extension degree flowing time T50 substantially all in 15s or so, the bucket of falling slump emptying time 11~
Between 14s, and the T50 flowing times of comparative example 1 and 2 reach more than 21s, and the bucket of falling slump emptying time, can up to 30s or so
See that the viscosity reduction type polycarboxylic acid super-plasticizer prepared by the embodiment of the present invention 1~6 can significantly reduce the viscosity of high-strength concrete, apply
Significant effect.
Claims (10)
1. a kind of preparation method of viscosity reduction type polycarboxylic acid super-plasticizer, it is characterised in that massaged by monomer a, monomer b and monomer c
You are than (4~15):1:(0.5~2) carry out free radicals copolymerization reaction and obtain, wherein：
Monomer a is represented with formula (I)：
R in formula1For-H or-COOM；R2For-H ,-CH3Or-CH2COOM；And work as R1For-COOM when, R2For H；M expressions hydrogen atom,
Alkali metal ion or ammonium ion；
Monomer b is represented with formula (II)：
R in formula3For-H or-CH3；R4For C1~C4 alkyl；X is-CH2-、-CH2OCH2CH2-、-CH2CH2-、-
CH2CH2OCH2CH2-、-OCH2CH2-、-OCH2CH2OCH2CH2-、-OCH2CH2CH2CH2- ,-C6H4- ,-C6H4CH2-；M=20
~45, n=5~10, p=1~5；
Monomer c is NVP, N- caprolactams, 1- vinyl imidazoles, 2- vinylpyridines, 3- ethene
Yl pyridines, 4-vinylpridine, 3- vinyl aniline, 4- vinyl aniline, 3- vinyl benzoic acids, 4- vinyl benzoic acids,
3- vinyl benzyl amines, 4- vinyl benzyl amines, 3- vinylphenylboronic acids, 2- vinylphenylboronic acids or 4- vinylphenylboronic acids.
2. the preparation method of viscosity reduction type polycarboxylic acid super-plasticizer as claimed in claim 1, it is characterised in that the viscosity reduction type gathers
The weight average molecular weight of carboxylic acid super plasticizer is 10000~30000.
3. the preparation method of viscosity reduction type polycarboxylic acid super-plasticizer as claimed in claim 1, it is characterised in that the free radical is total to
Poly- reaction is water-based free radical copolyreaction.
4. the preparation method of viscosity reduction type polycarboxylic acid super-plasticizer as claimed in claim 3, it is characterised in that the water-based freedom
Base copolyreaction uses water soluble starter and water-soluble chain transfer agent, the water soluble starter and water-soluble chain transfer agent
Quality is respectively 0.1%~1%, the 0.1%~0.4% of monomer a, monomer b and monomer c three's gross mass, the water-based freedom
The polymerization concentration of base copolyreaction is 30%~50%.
5. the preparation method of viscosity reduction type polycarboxylic acid super-plasticizer as claimed in claim 4, it is characterised in that the water-based freedom
The feed way of base copolyreaction is：Monomer b is disposable before other material droppings all to feed intake, and monomer a and monomer c mixing are single
The aqueous solution of body and the aqueous solution of initiator take the mode for separating while being added dropwise to feed, and chain-transferring agent adds the water of mix monomer
It is added dropwise together in the aqueous solution of solution or initiator, the aqueous solution of mix monomer and the aqueous solution time for adding of initiator be 2~
5h, the aqueous solution of mix monomer and the aqueous solution of initiator drip 1~4h of follow-up continuation of insurance temperature.
6. such as the preparation method of viscosity reduction type polycarboxylic acid super-plasticizer according to any one of claims 1 to 5, it is characterised in that
Monomer b is obtained by unsaturated alcohol and oxirane, epoxy terminated alkyl polyethylene glycol through blocked alkoxylation,
The unsaturated alcohol is represented with formula (III)：
The epoxy terminated alkyl polyethylene glycol is represented with formula (IV)：
7. the preparation method of viscosity reduction type polycarboxylic acid super-plasticizer as claimed in claim 6, it is characterised in that the blocked alkane
Oxygen glycosylation reaction is with potassium, sodium, naphthalene potassium, naphthalene sodium, hydrofining, sodium hydride, alkyl potassium alcoholate, sodium alkyl alcohol, potassium hydroxide or hydroxide
For sodium as catalyst, catalyst amount is the 0.1%~0.3% of gained monomer b mass.
8. the preparation method of viscosity reduction type polycarboxylic acid super-plasticizer as claimed in claim 7, it is characterised in that unsaturated alcohol and ring
The reaction temperature of oxidative ethane is 100~130 DEG C, and reaction pressure is 0.2~0.4MPa, and oxirane uses the side of continuous charging
Formula；After oxirane feeds, continue constant temperature to reaction system pressure and drop to below -0.05MPa, then using continuous charging
Mode add epoxy terminated alkyl polyethylene glycol, feed time is 2~6h, and reaction temperature is 110~140 DEG C, reaction pressure
For below -0.05MPa, after charging terminates, 0.5~2h of constant temperature, reaction keeps product temperatur to be adopted between 60~80 DEG C after terminating
PH value is neutralized to as 6~8 with organic acid.
9. the preparation method of viscosity reduction type polycarboxylic acid super-plasticizer as claimed in claim 6, it is characterised in that described epoxy terminated
Alkyl polyethylene glycol reacts by epoxychloropropane and polyalkylene glycol monoalkyl ether in the presence of sodium hydroxide and phase transfer catalyst,
Purification obtains.
10. viscosity reduction type polycarboxylic acid super-plasticizer obtained by any one of claim 1~9 preparation method should as cement dispersants
With.
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