TWI865449B - Defoaming agent for hydraulic composition and hydraulic composition - Google Patents
Defoaming agent for hydraulic composition and hydraulic composition Download PDFInfo
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- TWI865449B TWI865449B TW108114938A TW108114938A TWI865449B TW I865449 B TWI865449 B TW I865449B TW 108114938 A TW108114938 A TW 108114938A TW 108114938 A TW108114938 A TW 108114938A TW I865449 B TWI865449 B TW I865449B
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- Taiwan
- Prior art keywords
- hydraulic composition
- poly
- carbon atoms
- adduct
- defoaming agent
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 114
- 239000002518 antifoaming agent Substances 0.000 title claims description 43
- 239000013530 defoamer Substances 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 43
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 19
- 125000003342 alkenyl group Chemical group 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 239000006260 foam Substances 0.000 abstract description 14
- 229920001451 polypropylene glycol Polymers 0.000 description 52
- -1 fatty acid esters Chemical class 0.000 description 42
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 34
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 24
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 21
- 239000003054 catalyst Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 125000006353 oxyethylene group Chemical group 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000004567 concrete Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- 239000003638 chemical reducing agent Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000004568 cement Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 6
- 239000011398 Portland cement Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000003760 tallow Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical class FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000009172 bursting Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000005063 tetradecenyl group Chemical group C(=CCCCCCCCCCCCC)* 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 101000766096 Halorubrum sodomense Archaerhodopsin-3 Proteins 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000003493 decenyl group Chemical group [H]C([*])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000011968 lewis acid catalyst Substances 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 2
- CUQOHAYJWVTKDE-UHFFFAOYSA-N potassium;butan-1-olate Chemical compound [K+].CCCC[O-] CUQOHAYJWVTKDE-UHFFFAOYSA-N 0.000 description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910021487 silica fume Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910000567 Amalgam (chemistry) Inorganic materials 0.000 description 1
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000012359 Methanesulfonyl chloride Substances 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- LVZGQWKTUCVPBQ-UHFFFAOYSA-N acetic acid;trifluoroborane Chemical compound CC(O)=O.FB(F)F LVZGQWKTUCVPBQ-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011400 blast furnace cement Substances 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 235000014121 butter Nutrition 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229960004275 glycolic acid Drugs 0.000 description 1
- 125000000755 henicosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KAJZYANLDWUIES-UHFFFAOYSA-N heptadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCN KAJZYANLDWUIES-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002463 lignoceryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- CHNLPLHJUPMEOI-UHFFFAOYSA-N oxolane;trifluoroborane Chemical compound FB(F)F.C1CCOC1 CHNLPLHJUPMEOI-UHFFFAOYSA-N 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- VENBJVSTINLYEU-UHFFFAOYSA-N phenol;trifluoroborane Chemical compound FB(F)F.OC1=CC=CC=C1 VENBJVSTINLYEU-UHFFFAOYSA-N 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 125000002469 tricosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005040 tridecenyl group Chemical group C(=CCCCCCCCCCCC)* 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000005065 undecenyl group Chemical group C(=CCCCCCCCCC)* 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/12—Nitrogen containing compounds organic derivatives of hydrazine
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Dispersion Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Polyethers (AREA)
- Degasification And Air Bubble Elimination (AREA)
Abstract
本發明係提供一種水硬性組合物用消泡劑及含有該消泡劑之水硬性組合物，其與摻合物的相容性高，且具有優異之消泡性與泡沫穩定性。本發明所提供之水硬性組合物用消泡劑含有特定之含氮聚氧化烯化合物。 The present invention provides a defoamer for a hydraulic composition and a hydraulic composition containing the defoamer, which has high compatibility with an admixture and has excellent defoaming properties and foam stability. The defoamer for a hydraulic composition provided by the present invention contains a specific nitrogen-containing polyoxyalkylene compound.
Description
本發明是關於一種水硬性組合物用消泡劑以及包含該消泡劑之水硬性組合物。詳言之，本發明是關於一種與摻合物相容性高，且具優異的消泡性及泡沫穩定性的水硬性組合物用消泡劑以及包含該消泡劑之水硬性組合物。 The present invention relates to a defoaming agent for a hydraulic composition and a hydraulic composition containing the defoaming agent. Specifically, the present invention relates to a defoaming agent for a hydraulic composition having high compatibility with an admixture and excellent defoaming property and foam stability and a hydraulic composition containing the defoaming agent.
以混凝土為代表的水硬性組合物，係將水泥、水、細骨材、粗骨材及摻合物等混合攪拌來加以製造。所使用的摻合物，除了木質素磺酸(鹽)、羥基羧酸(鹽)、萘磺酸-甲醛縮合物(鹽)、三聚氰胺磺酸甲醛縮合物(鹽)、多元羧酸化合物等等的減水成分外，為了減少由於混合攪拌之卷吸所造成水硬性組合物中之粗大空氣，或是將空氣量調整至適當範圍，也常搭配消泡劑。做為上述消泡劑，已知有氧化烯類、矽類、醇類、礦物油類、脂肪酸類或脂肪酸酯類等。 Hydraulic compositions represented by concrete are manufactured by mixing cement, water, fine aggregate, coarse aggregate and admixtures. In addition to water-reducing components such as lignin sulfonic acid (salt), hydroxycarboxylic acid (salt), naphthalenesulfonic acid-formaldehyde condensate (salt), melamine sulfonic acid formaldehyde condensate (salt), polycarboxylic acid compounds, etc., admixtures used are often used with defoamers to reduce the coarse air in the hydraulic composition caused by the entrainment of mixing and stirring, or to adjust the air volume to an appropriate range. As the above-mentioned defoamers, known alkylene oxides, silicones, alcohols, mineral oils, fatty acids or fatty acid esters, etc.
為了達到即使搭配消泡劑仍能保持均勻水溶液狀態的目的，目前已經提出有由多元羧酸化合物與特定的含氮聚氧化烯化合物的混合物所形成的添加劑(專利文獻1)，或者是特定的聚氧化烯化合物(專利文獻2~6)，用以形成強度及耐久度優異的硬化物等。 In order to achieve the goal of maintaining a uniform aqueous solution even when used with a defoaming agent, additives formed by a mixture of a polycarboxylic acid compound and a specific nitrogen-containing polyoxyalkylene compound (Patent Document 1), or specific polyoxyalkylene compounds (Patent Documents 2 to 6), have been proposed to form a hardened material with excellent strength and durability.
[先前技術文獻] [Prior Art Literature]
專利文獻 Patent Literature
專利文獻1：日本發明公開平7-232945號公報 Patent document 1: Japanese Patent Publication No. 7-232945
專利文獻2：日本發明公開平10-226550號公報 Patent document 2: Japanese Patent Publication No. 10-226550
專利文獻3：日本發明公開2003-226565號公報 Patent document 3: Japanese Patent Publication No. 2003-226565
專利文獻4：日本發明公開2003-226566號公報 Patent document 4: Japanese Patent Publication No. 2003-226566
專利文獻5：日本發明公開2003-226567號公報 Patent document 5: Japanese Patent Publication No. 2003-226567
專利文獻6：日本發明公開2003-300766號公報 Patent document 6: Japanese Patent Publication No. 2003-300766
但是，通常具有高消泡性的消泡劑疏水性較高，搭配了摻合物時，由於密度的不同，該消泡劑會隨著時間經過會分離至摻合物上部，而衍生難以控制水硬性組合物之空氣量的穩定性的問題。專利文獻1~6所示的消泡劑雖似可改善與摻合物的相容性，卻存在無法同時兼具優異消泡性或泡沫穩定性的問題。 However, defoamers with high defoaming properties are usually highly hydrophobic. When mixed with an admixture, the defoamer will separate to the top of the admixture over time due to the difference in density, which leads to the problem of difficulty in controlling the stability of the air volume of the hydraulic composition. Although the defoamers shown in patent documents 1 to 6 can improve the compatibility with the admixture, they have the problem of not being able to have excellent defoaming properties or foam stability at the same time.
有鑑於上述情事，本發明所欲解決之課題即提供一種與摻合物之相容性高、具有優異之消泡性以及具有優異之泡沫穩定性的水硬性組合物用消泡劑，以及含有該消泡劑之水硬性組合物。 In view of the above situation, the problem to be solved by the present invention is to provide a defoaming agent for a hydraulic composition that has high compatibility with an admixture, excellent defoaming properties, and excellent foam stability, as well as a hydraulic composition containing the defoaming agent.
本發明人為了解決上述課題而深入研究的結果，發現在特定的烷基胺以特定比例添加聚氧化烯之水硬性組合物用消泡劑特別適合。依據本發明，提供了如以下的水硬性組合物用消泡劑及含有該消泡劑的水硬性組合物。 As a result of in-depth research to solve the above problems, the inventors found that a defoamer for a hydraulic composition in which a specific alkylamine is added with polyoxyalkylene in a specific ratio is particularly suitable. According to the present invention, a defoamer for a hydraulic composition and a hydraulic composition containing the defoamer are provided as follows.
[1]下述通式(1)所表示的含有氮聚氧化烯化合物的水硬性組合物用消泡劑。 [1] A defoaming agent for a hydraulic composition containing a nitrogen-polyoxyalkylene compound represented by the following general formula (1).
惟，式中之R1係表示碳數10~24之烷基或烯基，R2及R3為相同或不同，係表示氫原子及/或碳數1~10的烴基，A1O及A2O為相同或不同，係表示碳數2~4的氧化烯基，m及n為相同或不同，係0~100之整數，且滿足20≦m+n≦100的條件，A1O及A2O內，碳數3及/或4的 氧化烯基占65莫耳%以上。 However, R1 in the formula represents an alkyl or alkenyl group having 10 to 24 carbon atoms, R2 and R3 are the same or different and represent a hydrogen atom and/or a alkyl group having 1 to 10 carbon atoms, A1O and A2O are the same or different and represent an oxyalkylene group having 2 to 4 carbon atoms, m and n are the same or different and are integers of 0 to 100 and satisfy the condition of 20≦m+n≦100, and in A1O and A2O , the oxyalkylene group having 3 and/or 4 carbon atoms accounts for more than 65 mol%.
[2]如上述[1]所記載的水硬性組合物用消泡劑，其中，所述A1O及所述A2O之中，碳數3及/或4的氧化烯基占86莫耳%以上。 [2] The defoaming agent for a hydraulic composition according to the above [1], wherein among the A 1 O and the A 2 O, oxyalkylene groups having 3 and/or 4 carbon atoms account for 86 mol% or more.
[3]如上述[1]所記載的水硬性組合物用消泡劑，其中，所述A1O及所述A2O之中，碳數3及/或4的氧化烯基占90莫耳%以上。 [3] The defoaming agent for a hydraulic composition according to the above [1], wherein among the A 1 O and the A 2 O, oxyalkylene groups having 3 and/or 4 carbon atoms account for 90 mol% or more.
[4]如上述[1]~[3]中任一者所記載的水硬性組合物用消泡劑，其中，所述m及所述n為相同或不同，係0~80之整數，且滿足30≦m+n≦80的條件。 [4] A defoaming agent for a hydraulic composition as described in any one of [1] to [3] above, wherein m and n are the same or different, are integers between 0 and 80, and satisfy the condition of 30≦m+n≦80.
[5]如所述[1]~[3]中任一者所記載的水硬性組合物用消泡劑，其中，所述m、所述n為相同或不同，係0~80之整數，且滿足35≦m+n≦80的條件。 [5] A defoamer for a hydraulic composition as described in any one of [1] to [3], wherein m and n are the same or different, are integers between 0 and 80, and satisfy the condition of 35≦m+n≦80.
[6]如所述[1]~[5]中任一者所記載的水硬性組合物用消泡劑，其中所述R2及R3是表示氫原子。 [6] The defoaming agent for a hydraulic composition according to any one of [1] to [5], wherein R2 and R3 represent a hydrogen atom.
[7]所述[1]~[6]中任一者所記載的水硬性組合物用消泡劑，其中所述R1表示碳數14~18的烷基或烯基。 [7] The defoaming agent for a hydraulic composition according to any one of [1] to [6], wherein R1 represents an alkyl or alkenyl group having 14 to 18 carbon atoms.
[8]所述[1]~[7]中任一者所記載的水硬性組合物用消泡劑，其中所述A1O及所述A2O為相同或不同，係碳數2及/或3的氧化烯基(惟，A1O及A2O之中的至少一個係包含碳數3的氧化烯基)。 [8] The defoaming agent for a hydraulic composition according to any one of [1] to [7], wherein A1O and A2O are the same or different and are oxyalkylene groups having 2 and/or 3 carbon atoms (provided that at least one of A1O and A2O contains an oxyalkylene group having 3 carbon atoms).
[9]一種水硬性組合物，包含有所述[1]~[8]中任一者所記載的水硬性組合物用消泡劑。 [9] A hydraulic composition comprising the defoaming agent for a hydraulic composition as described in any one of [1] to [8].
[10]如[9]所記載的水硬性組合物，其pH值為8以下。 [10] The hydraulic composition as described in [9] has a pH value of less than 8.
本發明的水硬性組合物用消泡劑，可達成與摻合物之相容性高、具有優越消泡性以及具有優越泡沫穩定性的效果。 The defoamer for the hydraulic composition of the present invention can achieve the effects of high compatibility with the admixture, superior defoaming properties and superior foam stability.
以下，就本發明之實施態樣加以說明。惟，本發明不 限於以下之實施態樣。因此，應理解在不脫離本發明之精神之範圍內，本技術領域之通常知識者基於一般知識可對以下實施態樣加以適當變更或改良等。而以下之實施例中，除非特別說明，否則%代表質量%，份代表質量份。 The following is an explanation of the implementation of the present invention. However, the present invention is not limited to the following implementation. Therefore, it should be understood that within the scope of the spirit of the present invention, a person skilled in the art can make appropriate changes or improvements to the following implementation based on general knowledge. In the following embodiments, unless otherwise specified, % represents mass % and parts represents mass parts.
本發明的水硬性組合物用消泡劑是以下述通式(1)所表示的含氮聚氧化烯化合物。 The defoaming agent for the hydraulic composition of the present invention is a nitrogen-containing polyoxyalkylene compound represented by the following general formula (1).
通式(1)中的R1係碳數10~24的烷基或是碳數10~20的烯基，可具有直鏈或支鏈之構造。雖然沒有特別限定，然其可源自例如石油原料、棕梠油或葵花仔油等植物性油，或牛油等動物性油。 R1 in the general formula (1) is an alkyl group having 10 to 24 carbon atoms or an alkenyl group having 10 to 20 carbon atoms, and may have a straight chain or a branched chain structure. Although not particularly limited, it may be derived from, for example, petroleum raw materials, plant oils such as palm oil and sunflower oil, or animal oils such as butter.
做為碳數10~24的烷基，可列舉有癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基、十九烷基、二十烷基、二十一烷基、二十二烷基、二十三烷基或二十四烷基等。其中，做為上述烷基，優選為十四烷基、十五烷基、十六烷基、異十六烷基、十七烷基或十八烷基等碳數14~18的烷基。然而，R1為碳數未滿10的烷基的化合物消泡性或泡沫穩定性低，而R1為碳數超過24的烷基的化合物，則疏水性高而與摻合物的相容性低。 As the alkyl group having 10 to 24 carbon atoms, there can be listed decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl or tetracosyl. Among them, the alkyl group is preferably an alkyl group having 14 to 18 carbon atoms, such as tetradecyl, pentadecyl, hexadecyl, isohexadecyl, heptadecyl or octadecyl. However, compounds in which R1 is an alkyl group having less than 10 carbon atoms have low defoaming properties or foam stability, and compounds in which R1 is an alkyl group having more than 24 carbon atoms have high hydrophobicity and low compatibility with the admixture.
作為碳數10~24烯基，可列舉有癸烯基、十一烯基、十二烯基、十三烯基、十四烯基、十五烯基、十六烯基、十七烯基、十八烯基、十九烯基、二十烯基、二十一烯基、二十二烯基、二十三烯基或二十四烯基等。其中，做為上述的烯基，優選十四烯基、十五烯基、十六烯基、十七烯基或十八烯基等碳數14~18的烯基。然而，R1為碳數不滿10的烯基的化合物，其消泡性或泡沫穩定性低，而R1為碳數超過24的烯基的化合物，其疏水性高而與摻合物的相容性低。 As the alkenyl group having 10 to 24 carbon atoms, there can be listed decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl, docosenyl, tricosenyl or tetracosenyl. Among them, as the alkenyl group, alkenyl groups having 14 to 18 carbon atoms such as tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl or octadecenyl are preferred. However, compounds in which R1 is an alkenyl group having less than 10 carbon atoms have low defoaming properties or foam stability, and compounds in which R1 is an alkenyl group having more than 24 carbon atoms have high hydrophobicity and low compatibility with the blend.
通式(1)中的R2及R3為相同或不同，係氫原子及/或碳數1~10的烴基。 In the general formula (1), R2 and R3 are the same or different and are hydrogen atoms and/or a carbon number of 1 to 10 carbon atoms.
做為碳數1~10的烴基，可具有直鏈或支鏈的構造，亦可為飽和烴基或不飽和烴基。作為碳數1~10的烴基，可列舉有例如碳數1~10的烷基或是碳數2~10的烯基。做為碳數1~10的烷基可列舉有例如甲基、乙基、丙基、異丙基、丁基、戊基、己基、庚基、辛基、異辛基、壬基或癸基等。其中，做為項這樣的烷基，優選甲基、乙基或丙基等碳數1~3的烷基。然而，R2及R3為碳數超過10的烷基的化合物，其疏水性高而與摻合物的相容性低。又，做為碳數2~10的烯基，可列舉有例如乙烯基、丙烯基、丁烯基、戊烯基、己烯基、庚烯基、辛烯基、壬烯基或癸烯基等。其中，做為如上述的烯基，優選乙烯基、丙烯基等碳數2及3的烯基。然而，R2及R3為碳數超過10的烯基的化合物，其疏水性高而與摻合物的相容性低。 As a alkyl group with 1 to 10 carbon atoms, it may have a straight chain or a branched chain structure, and may be a saturated alkyl group or an unsaturated alkyl group. As a alkyl group with 1 to 10 carbon atoms, for example, an alkyl group with 1 to 10 carbon atoms or an alkenyl group with 2 to 10 carbon atoms may be listed. As an alkyl group with 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a nonyl group or a decyl group may be listed. Among them, as such an alkyl group, an alkyl group with 1 to 3 carbon atoms such as a methyl group, an ethyl group or a propyl group is preferred. However, compounds in which R2 and R3 are alkyl groups with more than 10 carbon atoms have high hydrophobicity and low compatibility with the admixture. As the alkenyl group having 2 to 10 carbon atoms, for example, vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl or decenyl can be cited. Among them, as the alkenyl group as mentioned above, vinyl, propenyl and other alkenyl groups having 2 and 3 carbon atoms are preferred. However, compounds in which R2 and R3 are alkenyl groups having more than 10 carbon atoms have high hydrophobicity and low compatibility with the blend.
而通式(1)中的R2及R3優選為氫原子。 In the general formula (1), R 2 and R 3 are preferably hydrogen atoms.
通式(1)中，A1O及A2O為相同或不同，係碳數2~4的氧化烯基，可列舉有氧乙烯基、氧丙烯基或氧丁烯基等。做為氧丙烯基，可列舉包括1,2-氧丙烯基以及1,3-氧丙烯基等。做為氧丁烯基，可列舉包括1,2-氧丁烯基、1,3-氧丁烯基、1,4-氧丁烯基、2,3-氧丁烯基及氧異丁烯基等。A1O及A2O為相同或不同，係碳數2及/或3的氧化烯基。惟，此時A1O及A2O中之至少一個包含碳數3的氧化烯基。做為如上述的氧化烯基，優選氧乙烯基及氧丙烯基。A1O及A2O分別為2種以上的情況，亦可為隨機加合物、嵌段加合物或替代加合物之型態。 In the general formula (1), A1O and A2O are the same or different and are oxyalkylene groups having 2 to 4 carbon atoms, and examples thereof include oxyethylene, oxypropylene or oxybutylene groups. Examples of oxypropylene groups include 1,2-oxypropylene and 1,3-oxypropylene groups. Examples of oxybutylene groups include 1,2-oxybutylene, 1,3-oxybutylene, 1,4-oxybutylene, 2,3-oxybutylene and oxyisobutylene groups. A1O and A2O are the same or different and are oxyalkylene groups having 2 and/or 3 carbon atoms. However, in this case, at least one of A1O and A2O includes an oxyalkylene group having 3 carbon atoms. As the above-mentioned oxyalkylene groups, oxyethylene and oxypropylene groups are preferred. When there are two or more A 1 O and A 2 O, the adduct may be in the form of a random adduct, a block adduct, or a substitution adduct.
通式(1)中，m是表示A1O的加成莫耳數，n是表示A2O的加成莫耳數。m及n為相同或不同，係0~100之整數，而優選為0~80之整數。又同時，m及n係滿足20≦m+n≦100的條件的整數，且優選為滿足30≦m+n≦80的條件的整數，且更優選為滿足35≦m+n≦80的條件的整數。m及n合計不滿20時，消泡性不足，泡沫穩定性 亦較低，當合計超過100會因高黏度而難以製造，另外，與摻合物的相容性亦不足。 In the general formula (1), m represents the addition molar number of A 1 O, and n represents the addition molar number of A 2 O. m and n are the same or different and are integers of 0 to 100, preferably integers of 0 to 80. At the same time, m and n are integers satisfying the condition of 20≦m+n≦100, preferably integers satisfying the condition of 30≦m+n≦80, and more preferably integers satisfying the condition of 35≦m+n≦80. When the sum of m and n is less than 20, the defoaming property is insufficient and the foam stability is also low. When the sum exceeds 100, it is difficult to manufacture due to high viscosity, and the compatibility with the admixture is also insufficient.
又，為了得到優異的消泡性，通式(1)中，A1O及A2O之中，碳數3及/或4的氧化烯基占65莫耳%以上，優選為占86莫耳%以上，更優選為占90莫耳%以上。A1O及A2O之中，碳數3及/或4的氧化烯基小於65莫耳%時，由於水溶性過於被提升，無法得到充足的消泡性，泡沫穩定性亦低落。 Furthermore, in order to obtain excellent defoaming properties, in general formula (1), the oxyalkylene groups having 3 and/or 4 carbon atoms account for 65 mol% or more, preferably 86 mol% or more, and more preferably 90 mol% or more of A1O and A2O . If the oxyalkylene groups having 3 and/or 4 carbon atoms in A1O and A2O are less than 65 mol%, sufficient defoaming properties cannot be obtained due to excessive increase in water solubility, and foam stability is also reduced.
以上所說明之通式(1)所表示的含氮聚氧化烯化合物的實際具體例子，可列舉有癸胺-(聚)氧乙烯/聚氧丙烯加合物、十一胺-(聚)氧乙烯/聚氧丙烯加合物、十二烷基胺-(聚)氧乙烯/聚氧丙烯加合物、十三烷基胺-(聚)氧乙烯/聚氧丙烯加合物、十四烷基胺-(聚)氧乙烯/聚氧丙烯加合物、十五烷基胺-(聚)氧乙烯/聚氧丙烯加合物、十六烷基胺-(聚)氧乙烯聚氧丙烯加合物、2-己基癸胺-(聚)氧乙烯/聚氧丙烯加合物、十七烷基胺-(聚)氧乙烯聚氧丙烯加合物、十八烷基胺-(聚)氧乙烯聚氧丙烯加合物、十九烷基胺-(聚)氧乙烯/聚氧丙烯加合物、二十烷胺-(聚)氧乙烯-聚氧丙烯加合物、二十一烷基胺-(聚)氧乙烯-聚氧丙烯加合物、二十二烷基胺-(聚)氧乙烯/聚氧丙烯加合物、三氯胺-(聚)氧乙烯/聚氧丙烯加合物、四環胺-(聚)氧乙烯/聚氧丙烯加合物、癸烯胺-(聚)氧乙烯/聚氧丙烯加合物、十一烯基胺-(聚)氧乙烯/聚氧丙烯加合物、十二烯基胺-(聚)氧乙烯/聚氧丙烯加合物、十三烯基胺-(聚)氧乙烯/聚氧丙烯加合物、十四烯基胺-(聚)氧乙烯/聚氧丙烯加合物、十五烯基胺-(聚)氧乙烯/聚氧丙烯加合物、十六烷烯基胺-(聚)氧乙烯聚氧丙烯加合物、十七烯基胺-(聚)氧乙烯聚氧丙烯加合物、十八烯基胺-(聚)氧乙烯聚氧丙烯加合物、十九烯基胺-(聚)氧乙烯/聚氧丙烯加合物、二十烯基胺-(聚)氧乙烯/聚氧丙烯加合物、二十一烯基胺-(聚)氧乙烯/聚氧丙烯加合物、二十二烯基胺-(聚)氧乙烯/聚氧丙烯加合物、三環胺-(聚)氧乙烯/聚氧丙烯加合物、四甲基胺-(聚)氧乙烯/聚氧丙烯加合物、 牛脂胺-(聚)氧乙烯聚氧丙烯加合物、醃製牛脂胺-(聚)氧乙烯聚氧丙烯加合物、十四烷基胺-聚氧丙烯加合物、十五烷基胺-聚氧丙烯加合物、十六烷基胺-聚氧丙烯加合物、2-己基癸胺-聚氧丙烯加合物、十七烷基胺-聚氧丙烯加合物、十八烷基胺-聚氧丙烯加合物、十四烯基胺-聚氧丙烯加合物、十五烯基胺-聚氧丙烯加合物、十六烯基胺-聚氧丙烯加合物、十七烯基胺-聚氧丙烯加合物、十八烯基胺-聚氧丙烯加合物、牛脂胺-聚氧丙烯加合物、固化的牛油胺-聚氧丙烯加合物、十四烷基胺-(聚)氧乙烯(聚)氧丙烯(聚)氧丁烯加合物、十五烷基胺-(聚)氧乙烯(聚)氧丙烯(聚)氧丁烯加合物、十六烷基胺-(聚)氧乙烯(聚)氧丙烯(聚)氧丁烯加合物、2-己基癸胺-(聚)氧乙烯(聚)氧丙烯(聚)氧丁烯加合物、十七烷基胺-(聚)氧乙烯(聚)氧丙烯(聚)氧丁烯加合物、十八烷基胺-(聚)氧乙烯(聚)氧丙烯(聚)氧丁烯加合物、十四烯基胺-(聚)氧乙烯(聚)氧丙烯(聚)氧丁烯加合物、十五烯基胺-(聚)氧乙烯(聚)氧丙烯(聚)氧丁烯加合物、十六烯基胺-(聚)氧乙烯(聚)氧丙烯(聚)氧丁烯加合物、十七烯基胺-(聚)氧乙烯(聚)氧丙烯(聚)氧丁烯加合物、十八烯基胺-(聚)氧乙烯(聚)氧丙烯(聚)氧丁烯加合物、牛脂胺(聚)氧乙烯(聚)氧丙烯(聚)氧丁烯加合物、固化牛脂胺-(聚)氧乙烯(聚)氧丙烯(聚)氧丁烯加合物等。其中，優選十四烷基胺-(聚)氧乙烯/聚氧丙烯加合物、十五烷基胺-(聚)氧乙烯/聚氧丙烯加合物、十六烷基胺-(聚)氧乙烯聚氧丙烯加合物、2-己基癸胺-(聚)氧乙烯/聚氧丙烯加合物、十七烷基胺-(聚)氧乙烯聚氧丙烯加合物、十八烷基胺-(聚)氧乙烯聚氧丙烯加合物、十四烯基胺-(聚)氧乙烯/聚氧丙烯加合物、十五烯基胺-(聚)氧乙烯/聚氧丙烯加合物、十六烯基胺-(聚)氧乙烯聚氧丙烯加合物、十七烯基胺-(聚)氧乙烯聚氧丙烯加合物、十八烯基胺-(聚)氧乙烯聚氧丙烯加合物、牛脂胺-(聚)氧乙烯聚氧丙烯加合物、固化牛脂胺-(聚)氧乙烯聚氧丙烯加合物等。 Specific examples of the nitrogen-containing polyoxyalkylene compound represented by the general formula (1) described above include decylamine-(poly)ethylene oxide/polyoxypropylene adducts, undecylamine-(poly)ethylene oxide/polyoxypropylene adducts, dodecylamine-(poly)ethylene oxide/polyoxypropylene adducts, tridecylamine-(poly)ethylene oxide/polyoxypropylene adducts, tetradecylamine-(poly)ethylene oxide/polyoxypropylene adducts, pentadecylamine-(poly)ethylene oxide/polyoxypropylene adducts, Hexadecylamine-(poly)ethylene oxide-polyoxypropylene adduct, 2-hexyldecylamine-(poly)ethylene oxide/polyoxypropylene adduct, heptadecylamine-(poly)ethylene oxide-polyoxypropylene adduct, octadecylamine-(poly)ethylene oxide-polyoxypropylene adduct, nonadecylamine-(poly)ethylene oxide/polyoxypropylene adduct, eicosylamine-(poly)ethylene oxide-polyoxypropylene adduct, heneicosylamine-(poly)ethylene oxide-polyoxypropylene adduct, docosylamine-(poly)ethylene oxide-polyoxypropylene adduct ethylene/polyoxypropylene adducts, trichloramine-(poly)ethylene oxide/polyoxypropylene adducts, tetracycline-(poly)ethylene oxide/polyoxypropylene adducts, decenylamine-(poly)ethylene oxide/polyoxypropylene adducts, undecenylamine-(poly)ethylene oxide/polyoxypropylene adducts, dodecenylamine-(poly)ethylene oxide/polyoxypropylene adducts, tridecenylamine-(poly)ethylene oxide/polyoxypropylene adducts, tetradecenylamine-(poly)ethylene oxide/polyoxypropylene adducts, pentadecenylamine- (Poly)ethylene oxide/polypropylene oxide adduct, hexadeceneamine-(poly)ethylene oxide/polypropylene oxide adduct, heptadeceneamine-(poly)ethylene oxide/polypropylene oxide adduct, octadeceneamine-(poly)ethylene oxide/polypropylene oxide adduct, nonadecenylamine-(poly)ethylene oxide/polypropylene oxide adduct, eicoseneamine-(poly)ethylene oxide/polypropylene oxide adduct, heneicoseneamine-(poly)ethylene oxide/polypropylene oxide adduct, docoseneamine-(poly)ethylene oxide/polypropylene oxide adduct Olefin adduct, tricyclic amine-(poly)ethylene oxide/polypropylene oxide adduct, tetramethylamine-(poly)ethylene oxide/polypropylene oxide adduct, tallow amine-(poly)ethylene oxide polypropylene oxide adduct, pickled tallow amine-(poly)ethylene oxide polypropylene oxide adduct, tetradecylamine-polypropylene oxide adduct, pentadecylamine-polypropylene oxide adduct, hexadecylamine-polypropylene oxide adduct, 2-hexyldecylamine-polypropylene oxide adduct, heptadecanylamine-polypropylene oxide adduct, octadecane 1,4-diamino- ... Oxybutylene adduct, hexadecylamine-(poly)oxyethylene(poly)oxypropylene(poly)oxybutylene adduct, 2-hexyldecylamine-(poly)oxyethylene(poly)oxypropylene(poly)oxybutylene adduct, heptadecylamine-(poly)oxyethylene(poly)oxypropylene(poly)oxybutylene adduct, octadecylamine-(poly)oxyethylene(poly)oxypropylene(poly)oxybutylene adduct, tetradecylamine-(poly)oxyethylene(poly)oxypropylene(poly)oxybutylene adduct, pentadecylamine-(poly)oxyethylene(poly)oxypropylene(poly)oxybutylene adduct Oxyethylene (poly)oxypropylene (poly)oxybutylene adduct, hexadecenylamine-(poly)oxyethylene (poly)oxypropylene (poly)oxybutylene adduct, heptadecenylamine-(poly)oxyethylene (poly)oxypropylene (poly)oxybutylene adduct, octadecenylamine-(poly)oxyethylene (poly)oxypropylene (poly)oxybutylene adduct, tallow amine-(poly)oxyethylene (poly)oxypropylene (poly)oxybutylene adduct, cured tallow amine-(poly)oxyethylene (poly)oxypropylene (poly)oxybutylene adduct, and the like. Among them, tetradecylamine-(poly)oxyethylene/polyoxypropylene adduct, pentadecylamine-(poly)oxyethylene/polyoxypropylene adduct, hexadecylamine-(poly)oxyethylene/polyoxypropylene adduct, 2-hexyldecylamine-(poly)oxyethylene/polyoxypropylene adduct, heptadecylamine-(poly)oxyethylene-polyoxypropylene adduct, octadecylamine-(poly)oxyethylene-polyoxypropylene adduct, tetradecylamine-(poly)oxyethylene/polyoxypropylene adduct, pentadecylamine-(poly)oxyethylene/polyoxypropylene adduct, hexadecylamine-(poly)oxyethylene-polyoxypropylene adduct, heptadecylamine-(poly)oxyethylene-polyoxypropylene adduct, octadecylamine-(poly)oxyethylene-polyoxypropylene adduct, tallowamine-(poly)oxyethylene-polyoxypropylene adduct, cured tallowamine-(poly)oxyethylene-polyoxypropylene adduct, etc. are preferred.
通式(1)所表示的含氮聚氧化烯化合物的製造方法沒 有特別限制。例如，可舉例對特定的烷基胺或烯基胺加成特定的氧化烯，藉此製造通式(1)所表示的含氮聚氧化烯化合物。 The method for producing the nitrogen-containing polyoxyalkylene compound represented by the general formula (1) is not particularly limited. For example, a nitrogen-containing polyoxyalkylene compound represented by the general formula (1) can be produced by adding a specific oxyalkylene to a specific alkylamine or alkenylamine.
在此，加合氧化烯時，可使用觸媒，可使用來做為觸媒的，可列舉有鹼金屬和鹼土金屬及其氫氧化物，如鹼金屬氫化物、醇化物等鹼性催化劑或路易斯酸催化劑，或者複合金屬催化劑等，其中優選使用鹼性催化劑。 Here, a catalyst may be used when adding alkylene oxide. Examples of catalysts include alkali metals and alkali earth metals and their hydroxides, such as alkali metal hydrides, alcoholates and other alkaline catalysts or Lewis acid catalysts, or composite metal catalysts, among which alkaline catalysts are preferably used.
可使用的鹼性催化劑，可列舉如鈉、鉀、鈉鉀汞齊、氫氧化鈉、氫氧化鉀、氫化鈉、甲醇鈉、甲醇鉀、乙醇鈉、乙醇鉀及丁醇鉀等，其中優選為氫氧化鈉、氫氧化鉀、甲醇鈉、甲醇鉀及丁醇鉀。 The alkaline catalysts that can be used include sodium, potassium, sodium-potassium amalgam, sodium hydroxide, potassium hydroxide, sodium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide and potassium butoxide, among which sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide and potassium butoxide are preferred.
做為可使用的路易斯酸催化劑，可列舉如四氯化錫、三氟化硼、三氟化硼二乙醚絡合物、三氟化硼二正丁醚絡合物、三氟化硼四氫呋喃複合物、三氟化硼苯酚絡合物及三氟化硼乙酸鹽絡合物等三氟化硼化合物等。 As the Lewis acid catalyst that can be used, boron trifluoride compounds such as tin tetrachloride, boron trifluoride, boron trifluoride diethyl ether complex, boron trifluoride di-n-butyl ether complex, boron trifluoride tetrahydrofuran complex, boron trifluoride phenol complex and boron trifluoride acetate complex can be listed.
這些催化劑可以在加成反應後中和並除去，但一方面保持含有的狀態也沒有關係。要將催化劑中和，可以通過已知方法進行。 These catalysts can be neutralized and removed after the addition reaction, but it is also OK to keep them contained. To neutralize the catalyst, it can be done by known methods.
本發明的水硬性組合物用消泡劑亦可不只含有通式(1)所表示的含氮聚氧化烯化合物，而在不損及本發明效果的情況下含有其他任意成分。如上述任意之成分可列舉有抗氧化劑，其他消泡劑如聚氧化烯烷基醚，以及稀釋劑如水和醇類等。 The defoamer for the hydraulic composition of the present invention may not only contain the nitrogen-containing polyoxyalkylene compound represented by the general formula (1), but may also contain other arbitrary components without impairing the effect of the present invention. Examples of the above-mentioned arbitrary components include antioxidants, other defoamers such as polyoxyalkylene alkyl ethers, and diluents such as water and alcohols.
本發明的水硬性組合物用消泡劑係使用於如土木工程、建築或二次產品等含有水硬性黏合劑的水硬性組合物。 The defoamer for hydraulic compositions of the present invention is used in hydraulic compositions containing hydraulic binders such as civil engineering, construction or secondary products.
本發明的水硬性組合物用消泡劑可以和已知的摻合物合併使用。相關的摻合物可列舉有AE減水劑、高效AE減水劑、 AE劑、消泡劑、減縮劑、增稠劑、硬化促進劑等。 The defoamer for hydraulic composition of the present invention can be used in combination with known admixtures. The relevant admixtures include AE water reducer, high-efficiency AE water reducer, AE agent, defoamer, reducer, thickener, hardening accelerator, etc.
自獲得與水硬性組合物用消泡劑具優異相容性的觀點來看，要與本發明的水硬性組合物用消泡劑併用的摻合物，其pH值優選為8以下，更優選為7以下，再更優選為6以下。 From the perspective of obtaining excellent compatibility with the defoaming agent for hydraulic compositions, the pH value of the admixture to be used in combination with the defoaming agent for hydraulic compositions of the present invention is preferably 8 or less, more preferably 7 or less, and even more preferably 6 or less.
成為本發明的水硬性組合物用消泡劑的使用對象，亦即水硬性組合物，其製備所需使用的水硬性黏合劑，除了普通波特蘭水泥、早強波特蘭水泥、中熱波特蘭水泥和低溫波特蘭水泥等各種波特蘭水泥外，還可列舉有各種混合水泥，如高爐水泥、粉煤灰水泥或矽粉水泥。又，高爐礦渣細粉、粉煤灰或矽粉等各種摻合物可單獨使用，或亦與剛才列舉的各種水泥合併使用。 The hydraulic binder required for the preparation of the hydraulic composition used as the defoaming agent of the present invention, i.e., the hydraulic composition, includes various Portland cements such as ordinary Portland cement, early strength Portland cement, medium heat Portland cement, and low temperature Portland cement, as well as various mixed cements such as blast furnace cement, fly ash cement, or silica fume cement. In addition, various admixtures such as blast furnace slag powder, fly ash, or silica fume can be used alone or in combination with the various cements just listed.
又，製備水硬性組合物需要使用骨材時，做為骨材可列舉有細骨材或粗骨材，細骨材可列舉有河砂、山砂、海砂、碎砂及礦渣細骨材等，粗骨材可列舉有礫石、碎石、輕質骨材、顆粒狀礦渣、再生骨材等。該等骨材可單獨或合併使用。 Furthermore, when aggregates are needed to prepare hydraulic compositions, the aggregates may include fine aggregates or coarse aggregates. The fine aggregates may include river sand, mountain sand, sea sand, crushed sand, and slag fine aggregates, and the coarse aggregates may include gravel, crushed stone, lightweight aggregates, granular slag, recycled aggregates, etc. These aggregates may be used alone or in combination.
再者，水硬性組合物的水膠比並無特別限制。通常使用的水膠比可表現出較優異的效果。 Furthermore, there is no particular restriction on the water-to-cement ratio of the hydraulic composition. The commonly used water-to-cement ratio can show a better effect.
本發明的水硬性組合物，對於每100質量份之水硬性黏合劑100，本發明的水硬性組合物用消泡劑的比例優選為含0.0001~0.1質量份。當以這樣的比例含有本發明的水硬性組合物用消泡劑，則可達到高消泡性或泡沫穩定性，且對所合併使用的摻合物具高相容性的效果。 The hydraulic composition of the present invention preferably contains 0.0001 to 0.1 parts by mass of the defoamer for every 100 parts by mass of the hydraulic adhesive. When the defoamer for the hydraulic composition of the present invention is contained in such a ratio, high defoaming properties or foam stability can be achieved, and the defoamer has a high compatibility with the admixture used in combination.
以下，列舉數個實施例以更具體說明本發明的構成及效果，然而本發明並不限定於該等實施例。而以下的實施例及比較例中，氧化烯基的加成莫耳數表示平均加成莫耳數，且沒有特別說明的情況下「份」表示質量份，「%」表示質量%。 Several examples are listed below to more specifically illustrate the structure and effects of the present invention, but the present invention is not limited to these examples. In the following examples and comparative examples, the added molar number of oxyalkylene groups represents the average added molar number, and "parts" represents mass parts, and "%" represents mass % unless otherwise specified.
試驗類別1(水硬性組合物用消泡劑的合成) Test Category 1 (Synthesis of defoaming agent for hydraulic compositions)
水硬性組合物用消泡劑(A-1)的合成 Synthesis of defoaming agent (A-1) for hydraulic composition
在高壓反應器中加入1347.6份之十八烷基胺，將高壓反應器內完全置換為氮氣。一邊攪拌一邊維持在150℃，將660.8份的環氧乙烷以0.4MPa一邊反應一邊注入後，在同溫度下老化0.5小時。冷卻至80℃後，投入12份做為觸媒的氫氧化鉀粉末，並將高壓反應器內完全置換為氮氣。一邊攪拌一邊維持在，將17430份的環氧丙烷在0.4MPa下一邊反應一邊壓入後，在同溫度下老化，並結束反應。去除觸媒，得到十八烷基胺-聚氧乙烯(3莫耳)聚氧丙烯(60莫耳)加合物(A-1)。 1347.6 parts of octadecylamine were added to the high-pressure reactor, and the high-pressure reactor was completely replaced with nitrogen. While stirring and maintaining at 150°C, 660.8 parts of ethylene oxide were injected at 0.4 MPa while reacting, and then aged at the same temperature for 0.5 hours. After cooling to 80°C, 12 parts of potassium hydroxide powder as a catalyst were added, and the high-pressure reactor was completely replaced with nitrogen. While stirring and maintaining at 150°C, 17430 parts of propylene oxide were injected at 0.4 MPa while reacting, and then aged at the same temperature to terminate the reaction. The catalyst was removed to obtain octadecylamine-polyoxyethylene (3 mol) polyoxypropylene (60 mol) adduct (A-1).
水硬性組合物用消泡劑(A-2)、(A-4)、(A-5)、(A-11)~(A-15)、(AR-1)、(AR-2)及(AR-4)的合成 Synthesis of defoamers (A-2), (A-4), (A-5), (A-11)~(A-15), (AR-1), (AR-2) and (AR-4) for hydraulic compositions
與水硬性組合物用消泡劑(A-1)相同地合成(A-2)、(A-4)、(A-5)、(A-11)~(A-15)、(AR-1)、(AR-2)及(AR-4)。 (A-2), (A-4), (A-5), (A-11) to (A-15), (AR-1), (AR-2) and (AR-4) are synthesized in the same manner as the defoaming agent for hydraulic compositions (A-1).
水硬性組合物用消泡劑(A-3)的合成 Synthesis of defoaming agent (A-3) for hydraulic composition
於高壓反應器中加入1207.3份的十六烷基以及做為觸媒的氫氧化鉀粉末13.4份，將高壓反應器內完全置換為氮氣。一邊攪拌一邊維持在100℃，將440.5份的環氧乙烷在0.4MPa下一邊反應一邊注入後將溫度升高至150℃，將881份的環氧乙烷在0.4MPa下一邊反應一邊壓入。之後，一邊攪拌一邊維持在同溫度，將19754份的環氧丙烷在0.4MPa下一邊反應一邊注入後，在相同溫度下老化1小時，並結束反應。去除觸媒，得到十六烷基胺-聚氧乙烯(6莫耳)聚氧丙烯(68莫耳)加合物(A-3)。 1207.3 parts of hexadecyl and 13.4 parts of potassium hydroxide powder as a catalyst were added to the high-pressure reactor, and the high-pressure reactor was completely replaced with nitrogen. While stirring and maintaining at 100°C, 440.5 parts of ethylene oxide were injected while reacting at 0.4 MPa, and the temperature was raised to 150°C, and 881 parts of ethylene oxide were injected while reacting at 0.4 MPa. After that, while stirring and maintaining at the same temperature, 19754 parts of propylene oxide were injected while reacting at 0.4 MPa, and then aged at the same temperature for 1 hour to terminate the reaction. The catalyst was removed to obtain hexadecylamine-polyoxyethylene (6 mol) polyoxypropylene (68 mol) adduct (A-3).
水硬性組合物用消泡劑(A-6)的合成 Synthesis of defoaming agent (A-6) for hydraulic composition
於高壓反應器加入1296.8份的牛脂胺(胺值216.3mg/g)，並將高壓反應器內完全置換為氮氣。一邊攪拌一邊將溫度維持150℃，將1162份的環氧丙烷以0.4MPa一邊反應一邊注入後，在鄉同溫度下老化1小時。冷卻至80℃後，投入8.2份的氫氧化鉀粉末做為觸媒，並將高壓反應器內完全置換為氮氣。一邊攪拌一邊將溫度維持在150℃，將9296份的環氧丙烷在0.4MPa下一邊反應一邊注入後，在 相同溫度下老化1小時，並結束反應。去除觸媒，得到牛脂胺-聚氧丙烯(36莫耳)加合物(A-6)。 1296.8 parts of tallow amine (amine value 216.3 mg/g) was added to the high-pressure reactor, and the high-pressure reactor was completely replaced with nitrogen. While stirring, the temperature was maintained at 150°C, and 1162 parts of propylene oxide was injected at 0.4 MPa while reacting, and then aged at the same temperature for 1 hour. After cooling to 80°C, 8.2 parts of potassium hydroxide powder was added as a catalyst, and the high-pressure reactor was completely replaced with nitrogen. While stirring, the temperature was maintained at 150°C, and 9296 parts of propylene oxide was injected at 0.4 MPa while reacting, and then aged at the same temperature for 1 hour, and the reaction was terminated. The catalyst was removed to obtain the tallow amine-polyoxypropylene (36 mol) adduct (A-6).
水硬性組合物用消泡劑(A-7)的合成 Synthesis of defoaming agent (A-7) for hydraulic composition
於玻璃製的反應容器中，加入3140份的甲氧基聚乙烯(2莫耳)聚氧丙烯(25莫耳)加合物以及2024份的三乙基胺，並冷卻至0℃，並將反應容器內完全置換為氮氣。一邊攪拌一邊滴入252份的甲磺酰氯後，加溫至20℃並攪拌2個小時。接著將反應系統冷卻至0℃，將630份乙醇溶解有270份的十八烷基胺的溶液慢慢予以滴入，滴入完成後，加溫至40℃並老化、純化2個小時，得到十八烷基胺-甲氧基聚氧乙烯(4莫耳)聚氧丙烯(50莫耳)加合物(A-7)。 In a glass reaction container, add 3140 parts of methoxy polyethylene (2 mol) polyoxypropylene (25 mol) adduct and 2024 parts of triethylamine, cool to 0°C, and completely replace the reaction container with nitrogen. After dropping 252 parts of methanesulfonyl chloride while stirring, heat to 20°C and stir for 2 hours. Then cool the reaction system to 0°C, slowly drop 630 parts of ethanol dissolved with 270 parts of octadecylamine solution, and after the drop is completed, heat to 40°C and age and purify for 2 hours to obtain octadecylamine-methoxy polyoxyethylene (4 mol) polyoxypropylene (50 mol) adduct (A-7).
水硬性組合物用消泡劑(A-8)的合成 Synthesis of defoaming agent (A-8) for hydraulic composition
於高壓反應器中加入1207.3份的十七烷基胺，並將高壓反應器內完全置換為氮氣。一邊攪拌一邊將溫度維持在150℃，將440.5份的環氧乙烷在0.4MPa下一邊反應一邊壓入後，在同溫度下老化0.5小時。冷卻至80℃後，加入做為觸媒的8.3份氫氧化鉀粉末，之後將高壓反應器內完全置換為氮氣。一邊攪拌一邊將為溫度維持在100℃，將881份之環氧乙烷在0.4MPa下一邊反應一邊注入後，將溫度升溫至150℃，將11329.5份之環氧丙烷在0.4MPa下一邊反應一邊注入。在同樣的溫度下老化1小時，並結束反應。去除觸媒，得到十七烷基胺-聚氧乙烯(6莫耳)聚氧丙烯(39莫耳)加合物(A-8)。 1207.3 parts of heptadecylamine were added to the high pressure reactor, and the high pressure reactor was completely replaced with nitrogen. While stirring, the temperature was maintained at 150°C, and 440.5 parts of ethylene oxide were injected under 0.4 MPa while reacting, and then aged at the same temperature for 0.5 hours. After cooling to 80°C, 8.3 parts of potassium hydroxide powder were added as a catalyst, and then the high pressure reactor was completely replaced with nitrogen. While stirring, the temperature was maintained at 100°C, and 881 parts of ethylene oxide were injected under 0.4 MPa while reacting, and then the temperature was raised to 150°C, and 11329.5 parts of propylene oxide were injected under 0.4 MPa while reacting. Aging was carried out at the same temperature for 1 hour, and the reaction was terminated. The catalyst was removed to obtain heptadecylamine-polyoxyethylene (6 mol) polyoxypropylene (39 mol) adduct (A-8).
水硬性組合物用消泡劑(A-9)、(A-10)、(A-16)、(A-17)、(AR-3)及(AR-5)的合成 Synthesis of defoamers (A-9), (A-10), (A-16), (A-17), (AR-3) and (AR-5) for hydraulic compositions
以與水硬性組合物用消泡劑(A-7)同樣地方式合成了(A-9)、(A-10)、(A-16)、(A-17)、(AR-3)及(AR-5)。 (A-9), (A-10), (A-16), (A-17), (AR-3) and (AR-5) were synthesized in the same manner as the defoaming agent for hydraulic compositions (A-7).
水硬性組合物用消泡劑(AR-6)的合成 Synthesis of defoaming agent (AR-6) for hydraulic composition
於高壓反應器加入1352.5份之十八烷醇以及做為觸媒之8.3份氫氧化鉀粉末，並將高壓反應器內完全置換為氮氣。一邊攪拌一邊將溫度維持在100℃，將881份環氧乙烷在0.4MPa下一邊反應一邊注 入後，將溫度升溫至150℃，將11620份之環氧丙烷在0.4MPa下一邊反應一邊壓入後，在同溫度下老化1小時，並結束反應。去除觸媒，得到十八烷醇-聚氧乙烯(4莫耳)聚氧丙烯(40莫耳)加合物(AR-6)。AR-6是使用來做為比較例的水硬性組合物用消泡劑。 1352.5 parts of octadecyl alcohol and 8.3 parts of potassium hydroxide powder as a catalyst were added to the high-pressure reactor, and the high-pressure reactor was completely replaced with nitrogen. The temperature was maintained at 100°C while stirring, and 881 parts of ethylene oxide were injected while reacting at 0.4 MPa. The temperature was raised to 150°C, and 11620 parts of propylene oxide were pressed while reacting at 0.4 MPa. The mixture was aged at the same temperature for 1 hour and the reaction was terminated. The catalyst was removed to obtain octadecyl alcohol-polyoxyethylene (4 mol) polyoxypropylene (40 mol) adduct (AR-6). AR-6 is used as a defoamer for water-hardening compositions as a comparative example.
水硬性組合物用消泡劑(AR-7)的合成 Synthesis of defoaming agent (AR-7) for hydraulic composition
以與合成水硬性組合物用消泡劑(AR-6)同樣地方是，合成水硬性組合物用消泡劑(AR-7)。AR-7是使用來做為比較例的水硬性組合物用消泡劑。 The same as the defoamer for synthetic hydraulic composition (AR-6) is the defoamer for synthetic hydraulic composition (AR-7). AR-7 is a defoamer for hydraulic composition used as a comparative example.
水硬性組合物用消泡劑(AR-8)的合成 Synthesis of defoaming agent (AR-8) for hydraulic composition
於高壓反應器加入750.9份之三甘醇以及做為觸媒之4.7份氫氧化鉀粉末，並將高壓反應器內完全置換為氮氣。一邊攪拌一邊將溫度維持在150℃，將8715份的環氧丙烷在0.4MPa下一邊反應一邊注入後，在同樣溫度下老化1小時，並結束反應。去除觸媒，聚氧乙烯(3莫耳)聚氧丙烯(30莫耳)縮合物(AR-8)。AR-8是使用來做為比較例的水硬性組合物用消泡劑。 Add 750.9 parts of triethylene glycol and 4.7 parts of potassium hydroxide powder as a catalyst into the high-pressure reactor, and completely replace the high-pressure reactor with nitrogen. While stirring, maintain the temperature at 150°C, inject 8715 parts of propylene oxide while reacting at 0.4MPa, age at the same temperature for 1 hour, and terminate the reaction. Remove the catalyst, polyoxyethylene (3 mol) polyoxypropylene (30 mol) condensate (AR-8). AR-8 is used as a defoamer for water-hardening compositions as a comparative example.
以上所合成的水硬性組合物用消泡劑(A-1)~(A-17)以及使用來做為比較例的水硬性組合物用消泡劑(AR-1)~(AR-8)的內容總結表示於表1中。 The contents of the defoaming agents for hydraulic compositions (A-1) to (A-17) synthesized above and the defoaming agents for hydraulic compositions (AR-1) to (AR-8) used as comparative examples are summarized in Table 1.
表1中：AR-6：十八烷醇-聚氧乙烯(4莫耳)聚氧丙烯(40莫耳)加合物；AR-7：十二烷基醇-聚氧乙烯(3莫耳)/聚氧丙烯(60莫耳)加合物；AR-8：聚氧乙烯(3莫耳)聚氧丙烯(30莫耳)縮合物。 In Table 1: AR-6: Octadecanol-polyoxyethylene (4 mol) polyoxypropylene (40 mol) adduct; AR-7: Dodecyl alcohol-polyoxyethylene (3 mol)/polyoxypropylene (60 mol) adduct; AR-8: polyoxyethylene (3 mol) polyoxypropylene (30 mol) condensate.
關於R1係如下所示：C8：辛基 The R1 is as follows: C8: Octyl
C12：十二烷基 C12: Dodecyl
C14 *：十四烯基 C14*:Tetradecenyl
C15：十五烷基 C15: Pentadecyl
C16：十六烷基 C16: Hexadecyl
C16分支：2-己基癸基 C16 branch: 2-hexyldecyl
C17：十七烷基 C17: Heptadecyl
C18：十八烷基 C18: Octadecyl
C18 *：十八烯基 C18*: Octadecenyl
C20：二十烷基 C20: Eicosyl
C25 *：五十二烯基 C25*: Pentodecene
試驗類別2(做為摻合物之聚羧酸減水劑的合成) Test Category 2 (Synthesis of polycarboxylic acid water reducer as admixture)
聚羧酸減水劑(B-1)的合成 Synthesis of polycarboxylic acid water reducer (B-1)
於反應容器中加入離子交換水以及α-(3-甲基-3-丁烯基)-ω-羥基-聚(45莫耳)氧乙烯，將環境氣體置換為氮氣，一邊攪拌一邊緩緩加溫。將反應系統的溫度於溫水浴中保持在70℃，使溫度穩定。之後，將丙烯酸花費3小時滴入。同時，將水中溶解有巰基乙酸，L-抗壞血酸的水溶液以及5%的過氧化氫溶液花費3小時滴入，開始自由基聚合反應。滴入結束經過1小時後，在所得到的共聚物中加入水及30%的氫氧化鈉水溶液，得到固體成分濃度25%的聚羧酸減水劑(B-1)。分析該聚羧酸減水劑的結果，質量平均分子量為42000，pH為3.6。而共聚物的質量平均分子量是以凝膠滲透色譜法來進行量測。 Add ion exchange water and α-(3-methyl-3-butenyl)-ω-hydroxy-poly(45 mol)ethylene oxide to the reaction vessel, replace the ambient gas with nitrogen, and slowly heat it while stirring. Keep the temperature of the reaction system at 70°C in a warm water bath to stabilize the temperature. Then, drip acrylic acid over 3 hours. At the same time, drip an aqueous solution of hydroxyacetic acid, L-ascorbic acid, and 5% hydrogen peroxide solution dissolved in water over 3 hours to start free radical polymerization. After 1 hour after the dripping is completed, add water and a 30% sodium hydroxide aqueous solution to the obtained copolymer to obtain a polycarboxylic acid water reducer (B-1) with a solid content concentration of 25%. The results of analyzing the polycarboxylic acid water reducer showed that the mass average molecular weight was 42,000 and the pH was 3.6. The mass average molecular weight of the copolymer was measured by gel permeation chromatography.
聚羧酸減水劑(B-2)及(B-3)的調整 Adjustment of polycarboxylic acid water reducer (B-2) and (B-3)
於聚羧酸減水劑(B-1)中加入30%的氫氧化鈉水溶液及水，得到為25%水溶液的(B-2)及(B-3)。測量pH值的結果，(B-2)為6.8，而(B-3)為8.9。 Add 30% sodium hydroxide aqueous solution and water to polycarboxylic acid water reducer (B-1) to obtain 25% aqueous solution of (B-2) and (B-3). The pH value of (B-2) was 6.8, and that of (B-3) was 8.9.
質量平均分子量的量測條件GPC法 Measurement conditions of mass average molecular weight GPC method
裝置：Shodex GPC-101(昭和電工公司製造) Device: Shodex GPC-101 (manufactured by Showa Denko Co., Ltd.)
管柱：OHpak SB-G+SB-806M HQ+SB-806M HQ(昭和電工公司製 造) Column: OHpak SB-G+SB-806M HQ+SB-806M HQ (manufactured by Showa Denko Co., Ltd.)
檢測器：差示折光儀(RI) Detector: Differential Refractometer (RI)
溶析液：50mM硝酸鈉水溶液 Dissolution solution: 50mM sodium nitrate aqueous solution
流量：0.7mL/分鐘 Flow rate: 0.7mL/min
管柱溫度：40℃ Column temperature: 40℃
樣品濃度：樣品濃度0.5質量%的溶析液溶液 Sample concentration: Sample concentration 0.5 mass% of the eluent solution
標準物質：PEG/PEO(安捷倫公司製造) Standard material: PEG/PEO (manufactured by Agilent)
pH值的測量條件 pH measurement conditions
在1g的聚羧酸減水劑中加入100g的離子交換水，並在20℃下以pH值量測器(HORIBA公司製造)進行量測。 100 g of ion exchange water was added to 1 g of polycarboxylic acid water reducer and measured at 20°C using a pH meter (manufactured by HORIBA).
所使用的摻合物之內容顯示於表2。 The contents of the blends used are shown in Table 2.
表2中：B-4：多元羧酸化合物(竹本油脂公司製造的混凝土用高性能AE減水劑，商品名稱Tupole HP-11)；B-5：改性木質素磺酸化合物與多元羧酸化合物的複合物(竹本油脂公司製造的混凝土用AE減水劑，商品名稱Tupole EX60)。 In Table 2: B-4: polycarboxylic acid compound (high performance AE water reducer for concrete manufactured by Takemoto Oil & Fats Co., Ltd., trade name Tupole HP-11); B-5: complex of modified lignin sulfonic acid compound and polycarboxylic acid compound (AE water reducer for concrete manufactured by Takemoto Oil & Fats Co., Ltd., trade name Tupole EX60).
試驗類別3(評價用摻合物組合物之製備) Test Category 3 (Preparation of blend compositions for evaluation)
將表1所示的水硬性組合物用消泡劑(A-1)~(A-17)及(AR-1)~(AR-8)與表2所示的摻合物(B-1)~(B-5)混合攪拌，製備完成評價用的摻合物組合物(共125個樣本)。然而，混合比例係摻合物(B-1)~(B-4)中，摻合物為99.5質量%，水硬性組合物用消泡劑為0.5質量%，摻合物(B-5)中，摻合物為99.7質量%，水硬性組合物用消泡劑為0.3質量%。 The defoamers for hydraulic compositions (A-1) to (A-17) and (AR-1) to (AR-8) shown in Table 1 were mixed and stirred with the blends (B-1) to (B-5) shown in Table 2 to prepare the blend compositions for evaluation (a total of 125 samples). However, the mixing ratio was such that in blends (B-1) to (B-4), the blend was 99.5% by mass and the defoamer for hydraulic compositions was 0.5% by mass, and in blend (B-5), the blend was 99.7% by mass and the defoamer for hydraulic compositions was 0.3% by mass.
試驗類別4(混凝土組合物的製備) Test Category 4 (Preparation of Concrete Composition)
實施例1~17及比較例1~9 Implementation Examples 1 to 17 and Comparative Examples 1 to 9
使用容量為60公升的強制雙螺桿混合器，以表3所記載的內容進行90秒的混煉混合，製備完成各例子中的混凝土組合物。製備完成的混凝土組合物的溫度為20±3℃。然而，針對未含有水硬性組合物用消泡劑的比較例1所示的混凝土組合物，則使用AE-300(竹本油脂公司製造的商品名稱)作為空氣量調整劑，將空氣量調整為7.0±1.0%，並將遵循JIS A 1150測量的坍落度調整為15±2.5cm，各個例子中的混凝土組合物，摻合物及試驗類別3中所製備的摻合物組合物的使用量是固定的。 The concrete compositions in each example were prepared by mixing the contents listed in Table 3 for 90 seconds using a forced twin-screw mixer with a capacity of 60 liters. The temperature of the prepared concrete composition was 20±3°C. However, for the concrete composition shown in Comparative Example 1 which does not contain a defoaming agent for a hydraulic composition, AE-300 (a trade name manufactured by Takemoto Oil & Fats Co., Ltd.) was used as an air volume adjuster, and the air volume was adjusted to 7.0±1.0%, and the slump measured in accordance with JIS A 1150 was adjusted to 15±2.5 cm. The concrete compositions in each example, the admixtures, and the admixture compositions prepared in Test Category 3 were fixed in the amount used.
表3中：黏合劑：普通波特蘭水泥(密度=3.16g/cm3)；細骨材：大井川河水系統產之陸沙(表面飽和乾燥密度 =2.57g/cm3)；粗骨材：岡崎生產之碎石(表面飽和乾燥密度=2.66g/cm3)。 In Table 3: Binder: ordinary Portland cement (density = 3.16g/cm3); fine aggregate: land sand produced by the Oigawa River system (surface saturated dry density = 2.57g/cm3); coarse aggregate: crushed stone produced in Okazaki (surface saturated dry density = 2.66g/cm3).
試驗類別5(混凝土組合物的試驗及水硬性組合物用消泡劑的評價) Test Category 5 (Testing of concrete compositions and evaluation of defoamers for hydraulic compositions)
就所製備的各個例子中的混凝土組合物，量測空氣量，將水硬性組合物用消泡劑對於摻合物之相容性、消泡性及泡沫穩定性如下述方法加以評價，並將結果總結顯示於表4。 For the concrete compositions prepared in each example, the air volume was measured, and the compatibility, defoaming properties, and foam stability of the hydraulic composition with the defoamer were evaluated as follows, and the results are summarized in Table 4.
空氣量(容積%)：針對剛混煉混合完成的混凝土組合物，遵循JIS A 1128之規範進行量測。 Air volume (volume %): Measured in accordance with JIS A 1128 for freshly mixed concrete compositions.
對於摻合物的相容性：針對剛製備完成的混凝土組合物，比較使用了剛混合完水硬性組合物用消泡劑時的摻合物組合物來量測的空氣量I(容積%)，以及使用在40℃下靜置一週的摻合物組合物中除去上部50質量%的下部50質量%來設量的空氣量II(容積%)，並根據下述基準來評價其對於摻合物的相容性。 Compatibility of admixtures: For the newly prepared concrete composition, the air volume I (volume %) measured using the admixture composition immediately after mixing the defoamer for the hydraulic composition and the air volume II (volume %) measured using the lower 50 mass % of the upper 50 mass % of the admixture composition left at 40°C for one week were compared, and the compatibility with the admixture was evaluated based on the following criteria.
S：非常好(空氣量II減去空氣量I的值小於±0.5) S: Very good (the value of air volume II minus air volume I is less than ±0.5)
A：良好(空氣量II減去空氣量I的值在0.5以上，但小於1.0) A: Good (the value of air volume II minus air volume I is greater than 0.5 but less than 1.0)
B：可(空氣量II減去空氣量I的值在1.0以上，但小於2.0) B: Yes (the value of air volume II minus air volume I is greater than 1.0 but less than 2.0)
C：差(空氣量II減去空氣量I的值在2.0以上) C: Poor (the value of air volume II minus air volume I is greater than 2.0)
消泡性：針對剛製備完成的混凝土組合物，比較使用未包含水硬性組合物用消泡劑的摻合物來量測的空氣量III(容積%、比較例1)與使用剛混合完成的摻合物組合物所量測的空氣量I(容積%)，並依據下述基準加以評價。 Defoaming property: For the concrete composition just prepared, the air volume III (volume %, Comparative Example 1) measured using the admixture that does not contain the defoaming agent for hydraulic composition is compared with the air volume I (volume %) measured using the admixture composition just mixed, and evaluated according to the following criteria.
S：非常好(空氣量III減去空氣量I的值為4.0以上) S: Very good (the value of air volume III minus air volume I is 4.0 or above)
A：良好(空氣量III減去空氣量I的值在3.0以上，但小於4.0) A: Good (the value of air volume III minus air volume I is above 3.0 but less than 4.0)
B：可(空氣量III減去空氣量I的值在2.0以上，但小於3.0) B: Yes (the value of air volume III minus air volume I is greater than 2.0 but less than 3.0)
C：差(空氣量III減去空氣量I的值小於2.0) C: Poor (the value of air volume III minus air volume I is less than 2.0)
泡沫穩定性：針對使用了剛混合了水硬性組合物用消泡劑的摻合物組合物所製備的混凝土組合物，以目視觀察氣泡的狀態，並依 據下述基準評價泡沫穩定性。 Foam stability: The state of bubbles in the concrete composition prepared using the admixture composition freshly mixed with the defoaming agent for hydraulic composition was visually observed and the foam stability was evaluated according to the following criteria.
S：非常好(幾乎無法確認到表面氣泡的破泡) S: Very good (the bursting of surface bubbles is barely detectable)
A：良好(非常輕微地確認到表面氣泡的破泡) A: Good (very slight bursting of bubbles on the surface was observed)
B：可(小幅確認到表面氣泡的破泡) B: Yes (the bursting of surface bubbles can be confirmed slightly)
C：差(大量確認到表面氣泡的破泡) C: Poor (a large number of surface bubbles were confirmed to have broken)
表4中：AR-6：十八烷醇-聚氧乙烯(4莫耳)聚氧丙烯(40莫耳)加合物；AR-7：十二烷基醇-聚氧乙烯(3莫耳)聚氧丙烯(60莫耳)加合物；AR-8：聚氧乙烯(3莫耳)聚氧丙烯(30莫耳)縮合物。 In Table 4: AR-6: Octadecanol-polyoxyethylene (4 mol) polyoxypropylene (40 mol) adduct; AR-7: Dodecyl alcohol-polyoxyethylene (3 mol) polyoxypropylene (60 mol) adduct; AR-8: polyoxyethylene (3 mol) polyoxypropylene (30 mol) condensate.
結果 result
由顯示在表4的結果可以很清楚確認，依據本發明，可提供一種與摻合物的相容性高，且具優異消泡性及泡沫穩定性的水硬性組合物用消泡劑。 The results shown in Table 4 clearly show that according to the present invention, a defoamer for a hydraulic composition having high compatibility with an admixture and excellent defoaming properties and foam stability can be provided.
本發明的水硬性組合物用摻合物可作為在製備水硬性組合物時的消泡劑加以利用。 The admixture for hydraulic composition of the present invention can be used as a defoaming agent when preparing hydraulic composition.
Claims (9)
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| WOPCT/JP2019/014477 | 2019-04-01 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH07232945A (en) * | 1994-02-22 | 1995-09-05 | Nippon Oil & Fats Co Ltd | Additive composition for cement |
| CN1533369A (en) * | 2002-02-06 | 2004-09-29 | 株式会社日本触媒 | Concrete composition, method for producing concrete composition, and cement admixture |
| CN101962585A (en) * | 2010-10-25 | 2011-02-02 | 冯明星 | Gasoline detergent prepared by using fatty amine polyoxypropylene ether |
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| JPS6311557A (en) * | 1986-07-01 | 1988-01-19 | 株式会社日本触媒 | Control for entraining air volume of cement mortar or concrete |
| JP2000247704A (en) * | 1999-03-03 | 2000-09-12 | Lion Corp | Antifoaming agent for cement composition |
| JP4209685B2 (en) * | 2001-05-01 | 2009-01-14 | ダブリュー・アール・グレイス・アンド・カンパニー−コネチカット | Antifoaming agent for water reducing agent admixture |
| JP4470365B2 (en) | 2002-10-21 | 2010-06-02 | 日油株式会社 | Additive composition for cement |
| JP4341273B2 (en) | 2003-03-28 | 2009-10-07 | 日油株式会社 | Additive for cement |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH07232945A (en) * | 1994-02-22 | 1995-09-05 | Nippon Oil & Fats Co Ltd | Additive composition for cement |
| CN1533369A (en) * | 2002-02-06 | 2004-09-29 | 株式会社日本触媒 | Concrete composition, method for producing concrete composition, and cement admixture |
| CN101962585A (en) * | 2010-10-25 | 2011-02-02 | 冯明星 | Gasoline detergent prepared by using fatty amine polyoxypropylene ether |
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