CN101353267A - Aqueous emulsion containing organic silicon compound, preparation and use thereof in surface treatment - Google Patents
Aqueous emulsion containing organic silicon compound, preparation and use thereof in surface treatment Download PDFInfo
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- CN101353267A CN101353267A CNA2007101676242A CN200710167624A CN101353267A CN 101353267 A CN101353267 A CN 101353267A CN A2007101676242 A CNA2007101676242 A CN A2007101676242A CN 200710167624 A CN200710167624 A CN 200710167624A CN 101353267 A CN101353267 A CN 101353267A
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- alkyl
- emulsion
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- water
- chain
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- 239000000839 emulsion Substances 0.000 title claims abstract description 177
- 238000002360 preparation method Methods 0.000 title abstract description 37
- 238000004381 surface treatment Methods 0.000 title abstract description 7
- 150000003377 silicon compounds Chemical class 0.000 title abstract 6
- -1 alkoxy silane Chemical compound 0.000 claims abstract description 99
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 46
- 238000009826 distribution Methods 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 31
- 229910000077 silane Inorganic materials 0.000 claims abstract description 29
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 7
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 6
- 239000011147 inorganic material Substances 0.000 claims abstract description 6
- 239000007764 o/w emulsion Substances 0.000 claims abstract 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 83
- 239000000203 mixture Substances 0.000 claims description 57
- 125000000217 alkyl group Chemical group 0.000 claims description 56
- 239000003995 emulsifying agent Substances 0.000 claims description 42
- 229910052799 carbon Inorganic materials 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 35
- 239000013543 active substance Substances 0.000 claims description 34
- 238000004945 emulsification Methods 0.000 claims description 33
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 31
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 29
- 125000004432 carbon atom Chemical group C* 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 29
- 229910052710 silicon Inorganic materials 0.000 claims description 26
- 239000010703 silicon Substances 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- 239000003921 oil Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 15
- 230000002209 hydrophobic effect Effects 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- 238000010276 construction Methods 0.000 claims description 14
- 230000000694 effects Effects 0.000 claims description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 238000007598 dipping method Methods 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 10
- 238000004132 cross linking Methods 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229920000151 polyglycol Polymers 0.000 claims description 9
- 239000010695 polyglycol Substances 0.000 claims description 9
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 9
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- 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 7
- 239000002253 acid Substances 0.000 claims description 7
- 125000000278 alkyl amino alkyl group Chemical group 0.000 claims description 7
- 230000000903 blocking effect Effects 0.000 claims description 7
- 239000012928 buffer substance Substances 0.000 claims description 7
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- 125000005358 mercaptoalkyl group Chemical group 0.000 claims description 7
- 229920001451 polypropylene glycol Polymers 0.000 claims description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 235000010755 mineral Nutrition 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- 229930182470 glycoside Natural products 0.000 claims description 4
- 150000002338 glycosides Chemical class 0.000 claims description 4
- 125000000962 organic group Chemical group 0.000 claims description 4
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 3
- 239000003619 algicide Substances 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000003973 alkyl amines Chemical class 0.000 claims description 3
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims description 3
- 239000003205 fragrance Substances 0.000 claims description 3
- 150000002402 hexoses Chemical class 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 230000003641 microbiacidal effect Effects 0.000 claims description 3
- 229940124561 microbicide Drugs 0.000 claims description 3
- 239000002855 microbicide agent Substances 0.000 claims description 3
- 150000007522 mineralic acids Chemical group 0.000 claims description 3
- 229940031815 mycocide Drugs 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 150000002972 pentoses Chemical class 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000003623 enhancer Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 125000001165 hydrophobic group Chemical group 0.000 claims description 2
- 239000012442 inert solvent Substances 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 2
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 239000004566 building material Substances 0.000 abstract description 3
- 239000011368 organic material Substances 0.000 abstract description 3
- 150000007529 inorganic bases Chemical class 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 23
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 21
- 239000004094 surface-active agent Substances 0.000 description 19
- 229920001296 polysiloxane Polymers 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 12
- 150000001282 organosilanes Chemical class 0.000 description 12
- 230000035515 penetration Effects 0.000 description 12
- 238000003860 storage Methods 0.000 description 12
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 10
- 239000004141 Sodium laurylsulphate Substances 0.000 description 10
- 102220042174 rs141655687 Human genes 0.000 description 10
- 102220076495 rs200649587 Human genes 0.000 description 10
- 102220043159 rs587780996 Human genes 0.000 description 10
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000013019 agitation Methods 0.000 description 9
- 239000008346 aqueous phase Substances 0.000 description 9
- 239000004567 concrete Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 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 7
- 239000002245 particle Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002250 absorbent Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- NESLVXDUKMNMOG-UHFFFAOYSA-N triethoxy-(propyltetrasulfanyl)silane Chemical compound CCCSSSS[Si](OCC)(OCC)OCC NESLVXDUKMNMOG-UHFFFAOYSA-N 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000002902 bimodal effect Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 3
- 229960003493 octyltriethoxysilane Drugs 0.000 description 3
- 125000005375 organosiloxane group Chemical group 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
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- 125000000129 anionic group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
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- 125000004122 cyclic group Chemical group 0.000 description 2
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- MMHCDZUIHWASJS-UHFFFAOYSA-N diethoxy-methyl-(2-methylpropyl)silane Chemical compound CCO[Si](C)(CC(C)C)OCC MMHCDZUIHWASJS-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
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- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
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- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 description 2
- HXOGQBSDPSMHJK-UHFFFAOYSA-N triethoxy(6-methylheptyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCCCC(C)C HXOGQBSDPSMHJK-UHFFFAOYSA-N 0.000 description 2
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 2
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- 239000013638 trimer Substances 0.000 description 2
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- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- MKPJTXOAVWTILI-UHFFFAOYSA-N 1,3,3-trimethoxy-3-silylpropane-1-thiol Chemical class COC(CC([SiH3])(OC)OC)S MKPJTXOAVWTILI-UHFFFAOYSA-N 0.000 description 1
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- SZNHHZLRLYDOJR-UHFFFAOYSA-N COC(CC([SiH3])(OC)OC)SS Chemical class COC(CC([SiH3])(OC)OC)SS SZNHHZLRLYDOJR-UHFFFAOYSA-N 0.000 description 1
- NXKGJIRLCQBHFD-UHFFFAOYSA-N CO[SiH](OC)CC(C)C Chemical compound CO[SiH](OC)CC(C)C NXKGJIRLCQBHFD-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
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- 206010020852 Hypertonia Diseases 0.000 description 1
- BWRPYSJNBVBIRP-FLFBIERCSA-N Ineketone Chemical compound O[C@H]1C[C@@](C)(C=C)C=C2C(=O)C[C@]3(O)C(C)(C)CCC[C@H]3[C@@]21C BWRPYSJNBVBIRP-FLFBIERCSA-N 0.000 description 1
- BWRPYSJNBVBIRP-UHFFFAOYSA-N Ineketone Natural products OC1CC(C)(C=C)C=C2C(=O)CC3(O)C(C)(C)CCCC3C21C BWRPYSJNBVBIRP-UHFFFAOYSA-N 0.000 description 1
- 239000004439 Isononyl alcohol Substances 0.000 description 1
- 235000017858 Laurus nobilis Nutrition 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
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- 229920000297 Rayon Polymers 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 235000005212 Terminalia tomentosa Nutrition 0.000 description 1
- 244000125380 Terminalia tomentosa Species 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000011509 cement plaster Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- SSLNXNMYNJKQTO-UHFFFAOYSA-N diethoxy-octyl-(2,2,2-trifluoroethoxy)silane Chemical compound FC(CO[Si](OCC)(OCC)CCCCCCCC)(F)F SSLNXNMYNJKQTO-UHFFFAOYSA-N 0.000 description 1
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 229940043264 dodecyl sulfate Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 150000002433 hydrophilic molecules Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 1
- NCWQJOGVLLNWEO-UHFFFAOYSA-N methylsilicon Chemical compound [Si]C NCWQJOGVLLNWEO-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 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
- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 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 1
- 235000011837 pasties Nutrition 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002990 reinforced plastic Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 235000020354 squash Nutrition 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- XYNHSIKVRCOMSV-UHFFFAOYSA-N triethoxy(3-methylbutyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(C)C XYNHSIKVRCOMSV-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- OYGYKEULCAINCL-UHFFFAOYSA-N triethoxy(hexadecyl)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC OYGYKEULCAINCL-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- FZMJEGJVKFTGMU-UHFFFAOYSA-N triethoxy(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC FZMJEGJVKFTGMU-UHFFFAOYSA-N 0.000 description 1
- VYHWVLSMXFMGPI-UHFFFAOYSA-N trimethoxy(3-methylbutyl)silane Chemical compound CO[Si](OC)(OC)CCC(C)C VYHWVLSMXFMGPI-UHFFFAOYSA-N 0.000 description 1
- WYDMCUJHXCLUPN-UHFFFAOYSA-N trimethoxy(4-methylpentyl)silane Chemical compound CO[Si](OC)(OC)CCCC(C)C WYDMCUJHXCLUPN-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Classifications
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
- C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
- C04B41/4922—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
Abstract
The invention provides a waterborne emulsion containing an organic silicon compound, and a preparation thereof and the application to surface treatment thereof. The invention discloses the waterborne emulsion containing the organic silicon compound which is used for surface treatment of inorganic base material, and also discloses a preparation thereof, a preparation of a specific organic silicon compound, and the application of the waterborne emulsion. On one hand, the invention relates to the waterborne emulsion containing the organic silicon compound, which is suitable for impregnating inorganic materials, especially for impregnating building materials, and also relates to the preparation of the special organic silicon compound such as the compound with the general formula II, and the application of the emulsion; on the other hand, the invention relates to a waterborne oil-in-water emulsion of functional alkoxy silane and siloxane oligomer, the preparation of the emulsion in a high-pressure emulsifying device, and the application of the emulsion to surface treatment of organic materials and inorganic materials. The size distribution of drops which is from 0.6 to 1.2 of the oil-in-water emulsion is preferably selected, and the size distribution is expressed by the value of Span.
Description
Technical field:
The invention discloses the water-based emulsion that contains silicoorganic compound, it is used to handle the inorganic substrate surface, also discloses the preparation of emulsion and the preparation of special silicoorganic compound, also discloses the application of emulsion.
One aspect of the present invention relates to the water-based emulsion that contains silicoorganic compound, and it is particularly suitable for flooding material of construction, the invention still further relates to the preparation of special silicoorganic compound, and for example the compound of formula II also relates to the application of this emulsion.
In addition, the oil-in-water water-based emulsion of functional alkoxysilanes and siloxane oligomer is disclosed also, the preparation of this emulsion in high-pressure emulsification equipment and its application in the surface treatment of organic and inorganic materials, the especially application on mineral construction material hydrophobization.
Background technology:
The water-based emulsion of organoalkoxysilane and organopolysiloxane, its preparation method has description with being applied in a lot of publications.
In the past, the preparation of dipping building piece, concrete etc. usually contains organic solvent (DE-PS2029446), and people have avoided this point in further developing.DE-PS2751714 relates to a kind of dipping preparation that is used for porous material, and it is made of the emulsion that organoalkoxysilane forms in water or water-alcohol mixture, and it contains the tensio-active agent as emulsifying agent.But the shortcoming of this preparation is a lot, the hydrophobic effect that adds affiliation reduction organoalkoxysilane of this tensio-active agent, its depth of penetration deficiency.According to US-PS4661551, can cause any dilutable micro emulsion though in polysiloxane (so-called " silicone surfactant "), introduce water soluble group, behind 12-24h, must use.
European patent application EP-A-234024 and EP-A-340816 disclose the water-based emulsion that contains silane, and it can prepare when using the tensio-active agent of determining.The described emulsion of EP-A-340816 also contains pH value buffer substance in addition, thereby has improved stability in storage.
EP-A 0442098 discloses a kind of preparation method of clear aqueous organic polysiloxane emulsion, and wherein, the mean particle size of non-aqueous phase is less than 0.3 μ m (preferably less than 0.1 μ m).At first, is 0.01-1MPa (HBS) under to be prepared into a kind of concentrated solution by suitable turbulent flow mixing device at pressure by liquid organopolysiloxane, water and the emulsifying agent that is dissolved in the organopolysiloxane, second step, water is diluted to the concentration of hope with it under conditions of similarity, and the pH value by adding acid with emulsion is adjusted to 3-7.Emulsion can also be used as the coating agent or the soaker of material of construction.
Disclosing a kind of activity substance content among the US-A5746810 is the water-based emulsion of the stable alkylalkoxy silane of 5-70 weight %, and the droplet dia that its disperse phase has is 0.5-10 μ m, and is suitable for the hydrophobic treatment material of construction.By selecting to be used for the emulsive machine and operational conditions reaches desirable granularity.In addition, can also use commercial high pressure to stir evenly device.
It is the organoalkoxysilane of 1-65 weight %, the stable aqueous emulsion that the alkylalkoxy silane conduct is used for the hydrophobizing agent of timber and material of construction that US-A6103001 or WO00/3406 disclose activity substance content.The viscosity that emulsion has is for＞5 to 1000mm
2/ second, the granularity of disperse phase is lower than 10 μ m, preferably is lower than 1 μ m, especially the most preferably is lower than 0.5 μ m or 0.276 μ m to 0.924 μ m.Except water and organoalkoxysilane, emulsion also contains at least the emulsification system of being made up of two kinds of emulsifying agents with different HLB values.By the pre-emulsification of composition and subsequently two stage pressures under 52MPa/16MPa pressure stir evenly the adjustment of finishing granularity.
EP-A0761724 discloses by single-stage or multi stage process and has prepared the water-based organic polysiloxane emulsion continuously, and it is by being that 0.98-1.37 crust down cut intensity was at least 100 seconds at pressure
-1, preferred 10000 to 300000 seconds
-1Two-stage stir evenly and carry out.Mean particle size is 0.3 μ m or 0.4 μ m.Prepare a kind of paste emulsion by the dimethyl polysiloxane of terminal trimethylsiloxy and polyoxyethylene laurel ether and hexadecyl tri-chlorination ammonium as emulsifying agent.
US-A5591818 and EP-A0590270 disclose organosilane and polycondensation product thereof, and it is by the functional aminosilane hydrogen salt of hydrolysis or by the hydrolytic-polymeric reaction of aminosilane and subsequently by functionalized preparation the with the reaction of sense alkyl halide.Compound can be formulated as the stabilized aqueous emulsion, and can be used as the tackiness agent between inorganic materials and the organic materials.
US-A5073195 discloses the hydrophobic composition of handling porous surface, and it is to have C on silane linking agent and the Siliciumatom
1-C
6The aqueous solution of the alkyltrialkoxysilaneand of alkyl.This solution is used to handle solid support material, as timber, concrete, lime sandstone or other nonactive building material surfaces.
E.P.Plueddemann 16-19 day in January, 1984, has reported that silanol and siloxanes are as linking agent and be used to prime (Grundierung) in reinforced plastics/the 39th research of the connection material annual meeting of Plastics Industry Company.
US-A3734763 discloses the unsaturated amino-functional silane of Plueddemann positively charged ion linking agent.(CH
3O)
3Si (CH
2)
3NHCH
2CH
2NH
2(CH
3O)
3Si (CH
2)
3NHCH
2CH
2NHCH
2C
6H
4-CH=CH
2Obtain by the controlled hydrolysis reaction.Hydrolysate can exist with the form of partial concentration.This patent disclosure numerous organic functional amine and aminosilane and organic functional alkyl halide in organic solvent, react.Product is as the tackiness agent between organic and the inorganic surfaces and be used to prime (Grundierung).
EP-A 0616989 discloses the hydrophobization water-based dipping emulsion that is used for the mineral construction material, and it contains organosilane and/or the organosiloxane resins with active group.The mean particle size that disperse phase has is 0.55-1.1 μ m, and the width of size-grade distribution is lower than 1.3.In the radiation decollator or high pressure stir evenly the adjustment of finishing size-grade distribution in the device, wherein, under high pressure extrude pre-emulsion by nozzle, emulsion need have the device of a plurality of nozzles successively by multistage extrusion of nozzle or use.
EP-A0819665 discloses the silicoorganic compound water-based cream that is used for the material of construction hydrophobization, and it contains C
8-C
20Alkyl silane, C
2-C
6Organoalkoxysilane and/or the organoalkoxysilane or organopolysiloxane, emulsifying agent and the water that contain the organopolysiloxane of alkoxyl group and have aminoalkyl in case of necessity.Stator-rotor-the whipping appts of pressure emulsification machine, colloidal mill or fast turn-around is used for preparation.
Disclosed silicoorganic compound paste water-based emulsion and EP-A0819665 different only are to exist the immiscible organic solvent of water among the WO00/46167.
Summary of the invention:
Task of the present invention provides the emulsion of improving, especially porous and/or the inorganic substrate surface that is used for substrate surface treatment and/or modification, and especially, emulsion should have good depth of penetration and discharge more a spot of organic solvent after use.
Another task of the present invention is that invention is used for the functional alkoxysilanes that material surface handles and/or the water-based emulsion of siloxane oligomer (hereinafter referred is an oligopolymer), all is enough stable storings behind its conc forms and the simple dilute with water.
Described task is finished with the corresponding description of claim.
Theme of the present invention is the water-based emulsion that contains silicoorganic compound, and it contains organoalkoxysilane and/or at least a siloxane oligomer and emulsifying agent and water, and wherein siloxane oligomer has chain, ring-type and/or crosslinked structure.
Siloxane oligomer with chain and/or ring texture represents with two general formulas in ideal form,
Wherein, crosslinking structure-it does not represent with ideal form-in, its substituent R, and the substituent R of following formula ideal structure is made up of organic group and/or hydroxyl, wherein oligomeric degree is 2-20.The oligomeric degree of siloxane oligomer meets the unitary quantity of per molecule Si.
Particularly preferably be, the oligomeric degree of chain and/or annular siloxane oligopolymer is between 2 and 20, and the oligomeric degree of the unitary siloxane oligomer of chain-like structure is preferably 2-20 especially, especially is 2-10.
Consider practical situation, the composition of each siloxane oligomer produces like this, and promptly each Sauerstoffatom on the monomer siloxane unit can be used as two bridge connectors between the Siliciumatom.Therefore, the quantity of the Sauerstoffatom that may have by organoalkoxysilane is determined the functionality of single siloxane unit; Therefore the organo-siloxane unit be single-, two-, three-and part four-functionalized.For synthetic siloxane oligomer with chain, ring-type and/or crosslinking structure, in view of the above, the tectonic element of existence comprises the simple function of representing with mark M (R)
3-Si-O-, the difunctionality-O-Si (R) that represents with mark D
2-O-, the trifunctional of representing with mark T (O-)
3SiR and the four sense Si that represent with mark Q are (O-)
4The mark of tectonic element is represented with mark M, D, T and Q according to its functionality.
For example, dipolymer M2 only is made of the simple function tectonic element.For synthetic chain, need the combination of simple function and difunctionality tectonic element, thereby, can form trimer (M2D), tetramer (M2D2) until line style M2Dn oligopolymer.In order to form cyclic oligomer, need difunctionality tectonic element (D).In this way, for example can form D3, D4, D5 or higher ring.M official can be also referred to as terminal thing or instrumentality by tectonic element, and the D unit is called the chaining thing or becomes the ring thing, and T unit and Q unit in case of necessity are called cross-linking agent.
So-called co-oligomer can obtain by the hydrolysis and the condensation of the different alkoxysilane mixture that replace.The co-oligomer that the organoalkoxysilane that is replaced by difference constitutes generally has the unitary statistics of Si and forms.
The mixture of siloxane oligomer can contain the mixture of the siloxane oligomer of even formation, even siloxane oligomer and the mixture of co-oligomer or the mixture of co-oligomer.
Water-based emulsion of the present invention, especially O/w emulsion, it for example can contain the organoalkoxysilane of following formula or the mixture of organoalkoxysilane,
R
1-Si (OR
2)
3, (R
1)
2-Si (OR
2)
2And/or (R
1)
3-Si (OR
2)
Wherein, R
1Be identical or different and be chain, ring-type and/or ramose C
3-C
18Alkyl, especially propyl group or octyl group, has the C of halogen
3-C
18Alkyl or the amino C that replaces
3-C
18Alkyl, vinyl, mercaptoalkyl, methacryloyl oxyalkyl, acryloyloxyalkyl, alkyl aminoalkyl, dialkyl amino alkyl, diethylidene aminoalkyl, triethylene aminoalkyl, Racemic glycidol oxyalkyl, bis-alkoxy silyl alkyl, list or polythioalkane, 2-20 EO-or unitary methyl blocking of PO-or hydroxy-end capped polyoxyethylene glycol or polypropylene glycol are arranged, wherein can there be R in alkyl with chain, ring-type and/or branch's form
2Identical or different and be to have 1-6 carbon atom, the line style of preferred 1 or 2 carbon atom or branch's alkyl.
In addition, what meet goal of the invention is that at least a emulsifying agent is selected from nonionogenic tenside, anion surfactant, cats product or amphoterics.The preferred mixture that uses half ester, carboxylate salt, alkyl oxide phosphonate, alkyl aryl ether phosphonate, alkyl polyglycol ether, alkaryl polyglycol ether, alkyl polyglycoside or oligomeric many glycosides or these emulsifying agents of Silicon surfactant, alkyl-sulphate, alkylsulfonate, sulfo-succinic acid.
The preferred especially emulsifying agent (synonym is a tensio-active agent) that uses is selected from has C
8-C
18The alkyl-sulphate of alkyl, on hydrophobic group, has C
8-C
18Alkyl and have 1-40 ethylene oxide (EO) unit and/or unitary alkyl-sulphate of propylene oxide (PO) and alkyl aryl ether sulfate, have C
8-C
18The alkylsulfonate of alkyl, has C
8-C
18The alkylaryl sulfonate of alkyl, the monohydroxy-alcohol of a sulfo-succinic acid and 5-15 carbon atom or the half ester of alkylphenol, alkyl, aryl, the an alkali metal salt and the ammonium salt that have the carboxylic acid of 8-20 carbon atom in alkaryl or the aralkyl, the alkyl and the alkaryl phosphonate that have 8-20 carbon atom in the organic group, have 8-20 carbon atom in alkyl and/or the alkaryl and have 1-40 unitary alkyl oxide phosphonate of EO and/or alkyl aryl ether phosphonate, have in 8-40 EO unit and the alkyl or aryl and have C
8-C
20The alkyl polyglycol ether of individual carbon atom and alkaryl polyglycol ether, have 8-40 EO and/or the unitary ethylene oxide/propylene oxide of PO (EO/PO) segmented copolymer, have C
8-C
22The adduct of the alkylamine of alkyl and ethylene oxide or propylene oxide, have line style or the saturated or unsaturated C of ramose
8-C
24Alkyl and have 1-10 hexose or the mixture of alkyl polyglycoside, Yelkin TTS, functionalized silicon tensio-active agent or these emulsifying agents of the unitary oligomeric glycosides base of pentose.
Usually, water-based emulsion of the present invention, especially O/w emulsion, contain other conventional auxiliary agents, these auxiliary agents are selected from inorganic or organic acid, buffer substance, mycocide, sterilant, algicide, microbicide, odorant agent, corrosion inhibitor, sanitas, Abperl effect enhancer, viscosity modifier, catalyzer.
The material that can add at least a adjusting pH value in emulsion is to regulate the pH value.Can directly when the preparation emulsion and/or before using, add the material of regulating the pH value in the short period of time.Especially can consider inorganic acid salt and/or alkali salt and conventional buffer reagent as pH value adjusting material, these all are that those skilled in the art fully understand.
According to goal of the invention, water-based emulsion has organoalkoxysilane and/or the siloxane oligomer with total restatement 1 to the 90 weight % content of emulsion.According to application target described later, preferably, if emulsion should be for example when pasty state or emulsifiable paste shape, the content of adjusting organoalkoxysilane and/or siloxane oligomer surpasses 80 weight %, is preferably about 85 weight % especially.For example, if overhanging surface, in the time of need handling as the spatial cover plate, such adjustment is preferred, thereby has stoped downward drippage.
Another theme of the present invention relates to the water-based emulsion that contains silicoorganic compound that is used to flood material of construction, randomly it contains anion surfactant and pH value buffer substance, contain in total amount 1-80 weight %, the particularly organoalkoxysilane of at least a general formula I of 1-60 weight %
Wherein,
R1:C
1-C
3Alkyl,
R3:C
1-C
20Alkyl, be straight chain or ramose, particularly C
1-C
10Alkyl, phenyl,
X:H, Cl, Br, I, NH
2, SCN, CN, N
3, NHR, NR
2,
+NR
3,-Sx, aryl, thiazolinyl, especially H, Cl,
A:0 or 1,
B:1 or 2, wherein a+b preferably equals 1 or 2,
The integer of c:1-18 is preferably 1-8,
And contain 1-20 weight %, and the silicoorganic compound of the general formula I I of preferred 1-5 weight %, it generally meets Silicon surfactant,
Wherein,
R2, R3: identical or different, be C
1-C
20Alkyl, be straight chain or ramose, especially C
1-C
10Alkyl, phenyl,
R4:C
1-C
3-alkoxyl group, { OCH
2-CH
2ROR5,
R5:H, C
1-C
20Alkyl, C
2-C
36Thiazolinyl, C
5-C
8Cycloalkyl, C
7-C
36Aralkyl, especially phenmethyl and the phenyl that replaces with alkyl, wherein, alkyl randomly can also have side chain, when p=0 and r=0, OR5 represents:
Wherein, s=3-50, t=3-25,
M:0,1 or 2,
N:0,1 or 2, its precondition is, if p=0, (m+n)=1 or 2 then, in p ≠ 0 o'clock, (m+n)=0,1 or 2,
P:0,1,2 or 3,
Integer between the r:0 and 50,
Also contain 1-95 weight %, the water of preferred 1-75 weight %, weight content meets 100% certainly.
Emulsion is except containing the compound of formula (I), also contains the siloxane oligomer that its condensation product, beginning are mentioned, for example dipolymer, trimer or other oligopolymer, and it is known that this is generally those skilled in the art.
The pH value of emulsion preferably is adjusted into about 7.5.In a special embodiment, in emulsion, add buffer substance in emulsion total amount 0.1-5 weight % content.It for example is meant sodium bicarbonate, yellow soda ash or sodium phosphate.Just before using emulsion, can preferably the pH value be adjusted into acidity with 3-sulfo group propyl group ortho-siliformic acid.
One preferred embodiment in, in emulsion, add one or more known anionic tensio-active agents in emulsion total amount 0.2-8.0 weight %.
Randomly, emulsion of the present invention also contains same known thickeners in emulsion total amount 0.1-1.0 weight %, and thickening material for example is selected from derivatived cellulose or starch derivative, particularly its ether, perhaps vinylformic acid dispersion liquid and polyacrylate solution.
Contain the compound of general formula (II) as the suitable emulsion of soaker, wherein:
When p ≠ 0: (m+n)=2, especially preferably contain the compound of general formula (II), wherein
When p ≠ 0: (m+n)=0 or 1,
When p=0: (m+n)=1 or 2.
Compound prepares in having the organic solvent of alkali.
Theme of the present invention is the novel method of a kind of preparation general formula (II) silicoorganic compound equally, wherein, p=0, wherein, with the compound of the compound of general formula (III) and the general formula (IV) that contains reactive hydrogen under the reflux temperature of reaction mixture and pH value when being 3.5-5.5, especially reacted at about 5 o'clock
(R
2)
n(R
3)
mSi(R
6)
4-(m+n) (III)
Wherein, the alkoxyl group of R6:C1-C3 and R
2, R
3, m and n have aforementioned implication,
R5-O{CH
2-CH
2O}rH (IV)，
Wherein, R5 and r have aforementioned implication.The interpolation of organic solvent is optional.Usually use a spot of acid, for example HCl is adjusted to a pH value with organosilane and tensio-active agent, heats then until reaching reflux temperature.
Reaction can also be carried out at low temperatures, but can be slower.
After reaction finishes, take out the alcohol that is discharged, generally be methyl alcohol or ethanol.
Tensio-active agent preferably uses with excessive 0.1-5 mole % usually with equimolar amount, and wherein, one or both alkoxyl groups can replace with tensio-active agent.
Another theme of the present invention is the preparation method of the silicoorganic compound of general formula (II), p=1,2 or 3 wherein, wherein, the compound of general formula V in inert organic solvents with the alcoholization sodium of general formula VI under 20-100 ℃, preferably under reflux temperature, react, the then NaCl that goes out of filtering-depositing and take out solvent
Wherein, R2, R3, R6, m, n and p (except p=0) have aforementioned implication, and X is Cl,
R
5-O{CH
2-CH
2O}rNa (VI)，
R
5Has aforementioned implication with r.
In the method for a change, can carry out like this, be about to tensio-active agent and place inert organic solvents, for example in aliphatic series, cyclic aliphatic and the aromatic hydrocarbon, then add the sodium of preferred equimolar amount, be no more than 90 ℃ by being heated to, under the condition that produces hydrogen, form alcoholate.After sodium reacts completely, preferably be cooled to room temperature once more, be added dropwise to the silicoorganic compound of formula V with preferred equimolar amount.After being heated to 50-60 ℃, be settled out NaCl.Then, after salt filtration and separation solvent, obtain desirable compound.
After this, according to preceding method, its can with the reaction of other tensio-active agents, its must with replace first different.This compound is novel and is also comprised by claim.
But, tensio-active agent can also with sodium ethylate (Natriumethylat) reaction, thereby compound that can preparation formula (VI).
Functionality Silicon surfactant required for protection is characterized in that its tangible emulsifying agent effect, especially the pH scope between 6 and 9.Also still stable through several weeks in this pH scope with its prepared emulsion.In the Application Areas of determining, necessary is tensio-active agent of the present invention is separated into interfacial activity immediately after the organosilane emulsion has satisfied this purpose part.The stability of emulsion must meet its application purpose.Prepare stable as far as possible emulsion and always do not meet goal of the invention.For a series of Application Areass,, after achieving the goal, to decompose (division) once more and be its composition though emulsion should be stable under the most definite condition.
Emulsion applications required for protection is in following change porous inorganic material, for example the surface properties of natural stuffing (Wollastonit, talcum or the like), powder silicic acid and silicate: make to can be used as the special dimension that the customization filler is used for rubber, pitch and range of polymers.
When using alkylalkoxy silane, especially can give material of construction, masonry material, concrete and outer facade water repellency.
One preferred embodiment in; especially; in the emulsion that contains short chain silane; for example contain in the emulsion of C3-and C4-alkylidene group silane; can also in the short period of time before using, add an acidic catalyst; it can make the Si-O-bond rupture in the organoalkoxysilane required for protection and not make the Si-C-bond rupture, improves on the base material of neutral, faintly acid and alkalescence the silane validity on the especially problematic base material thus.
In a special embodiment, when using the functionalized silicon tensio-active agent of following general formula, can produce the fluid of viscose glue structure, this can make the interpolation of viscosity enahncers become unnecessary, and when using, can not have a negative impact, wherein to required character with dilute form
Perhaps
Wherein, R2, R3 and p have above-mentioned implication, and Ts is (CH
2CH
2O)
n-R5, n=3-15,
N=3-15 or
M=3-50 and n=3-25.
Stability of emulsion not only, and the physicochemical property of emulsion all depend on the flexible selection of used functionality Silicon surfactant, used ionic surface active agent with technology application matter, also depend on the content ratio and the pH value of hydrophobic molecule and hydrophilic molecules to a great extent.
It is known to those skilled in the art that when the quick property of alkali contains the additive of silicic acid and alkali hydroxide reaction, in concrete, alkali-silica reaction can take place.Usually alkali is introduced in the concrete from the outside by condensation agent (Taumittel) (for example NaCl).The alkali silicate hydrated gel that produces by alkali-silica reaction can cause crackle under inappropriate situation, peel off even the disintegrating of concrete structure.
Especially by the water miscible liquid that contains organic silane compound of the present invention, to the 3-sulfo group propyl silane triol (Si285) that wherein adds as the alkali buffer additive, preferably the pH value is to 3-5.5 before being coated to the place's of building material, and this special prevention makes concrete not be subjected to the destruction of alkali-silica reaction.
1. embodiment:
Embodiment 1.1:
The method according to this invention, the silicoorganic compound of preparation formula (II).
Common technology:
Organoalkoxysilane and tensio-active agent or surfactant mixture mix with equimolar amount or the excessive 0.1-5 mole of tensio-active agent %, and with sour, especially hydrochloric acid is adjusted into about 5 with the pH value.
Be heated to reflux temperature, make reaction carry out, wherein, temperature reduces continuously.After reaction finished, the alcohol of formation took out under vacuum.
Common productive rate 〉=97% that obtains.But according to the known method of prior art, also possible is that described compound is prepared by corresponding chlorosilane cpd.
Chlorine atom according to how many ratios should be replaced by surfactant molecule or alkoxyl group, uses one or more tensio-active agents or the alcohol of corresponding equimolar amount or preferred excessive 0.1-5 mole %.
In the quantity of chlorine atom, it is useful waiting mole to add the organic bases (for example triethylamine) that is used to react, but is not Compulsory Feature.Then, sedimentary hydrochloride is filtered to be used to distill inert solvent (for example toluene).
Below table 1.1 and 1.2 show the compound of representing with Silicon surfactant according to method preparation of the present invention.
Table 1.1
Table 1.2
Embodiment 1.2:
Equally, the compound of the following type described silane that replaces by two surfactant molecules of usefulness of corresponding dichlorosilane or dialkoxy silicane preparation of embodiment as described above.
Table 1.3 comprises prepared following type compound,
Table 1.3
Embodiment 1.3
The preparation of the Silicon surfactant of following type has been described in this embodiment.
If in ethanol, operate, so at first dissolve sodium to form dealing with alcohol sodium, then add tensio-active agent in the equimolar amount of basic metal, preferably be heated to reflux temperature then.After about 2 hours, reaction finishes, and drips the 3-chloropropyl triethoxysilane with its cooling and in this settled solution.Postheating is to 50-65 ℃.After 1-2 hour, reaction finishes under this temperature.After the cooling, the NaCl that filtering-depositing goes out is by fractionation by distillation alcohol.This reaction is completely.
In another version, tensio-active agent is placed inert organic solvents, for example in the toluene, introduce the sodium of about equimolar amount subsequently, thereby directly prepare tensio-active agent-O-Na-compound.Finish reaction at 70 ℃-80 ℃ after 1-2 hour.Be cooled to room temperature and in this settled solution, drip chloropropyl triethoxysilane.Then be heated to 50-65 ℃.After about 1 hour, under this temperature, finish reaction.After the cooling, the NaCl that filtering-depositing goes out also distills out toluene under vacuum condition.
Table 1.4
The preparation of emulsion
Diverting device well known by persons skilled in the art (rotor-stator-system, high pressure stirs evenly device) is used for preparation.
Embodiment 1.4:
In factory, prepare emulsion.
Additive:
40.00% organosilane (or organosilane system) (=formula I)
58.40%VE water
1.25% Silicon surfactant (=formula II)
0.35% anion surfactant (alkylsulfonate, for example: sodium octyl)
(VE=desalts fully)
Use is used to prepare emulsion with lower device:
Initial container with agitator,
The high pressure that is used to have 2 grades of decompressing unit stirs evenly the charging pump of device feeding,
Emulsion is cooled to 10-20 ℃ heat exchanger.
The emulsifying agent (or emulsifying agent ligand (Emulgatorenpaar)) of in initial container, under agitation condition, inserting VE water in advance and all measuring.Add after the organosilane, the pH value is adjusted to pH7.5 by adding sodium bicarbonate.
Embodiment 1.5:
In the laboratory, prepare emulsion.
Weighing:
50g water
0.12g NaHCO
3(the pH value about 7.5 of emulsion)
1.37g Silicon surfactant (formula II-silicoorganic compound)
33.3g organosilane (formula I-organoalkoxysilane)
With the order of listing composition being weighed successively is added in the 50ml reaction flask, uses Ultraturrax (rotor-stator) to stir evenly under 18000Upm then 3 minutes.Subsequently, emulsion was handled 1 minute under (500Upm) condition of stirring in ultra sonic bath again.
Emulsion appearance: emulsus
Character: can arbitrarily dilute
The gained emulsion is still stable through several weeks, i.e. its do not occur being separated (" formation oil reservoir ").Whenever, all can prepare stand-by (gebrauchsfertige) emulsion by simple stirring, it does not lose effect at all.
Thick emulsion is sent into high pressure by charging pump and is stirred evenly device, there, stirs evenly under 80-500 crust condition.The cooling emulsion stirs evenly it under 100-700 crust condition after 10-20 ℃ once more.2 pressure stages, pressure drop is 20%.Again after being cooled to room temperature, form emulsion.
Emulsion appearance: emulsus
Character: can arbitrarily dilute
The gained emulsion is still stable through several weeks, i.e. its do not occur being separated (" formation oil reservoir ").Whenever, all can prepare stand-by emulsion by simple stirring, it does not lose effect at all.
Prepare in the type the known ionic surface active agent of interpolation itself a preferred emulsions.Need to introduce the energy of much less, with the stable dispersion liquid of preparation heat power.In a special embodiment, add the tensio-active agent of ionic, preferred anionic in mutually at organosilane, add the tensio-active agent of functionalized silicon at aqueous phase.
Except using the precaution of emulsion in the porousness of material of construction and the practice, granularity has also determined the hypertonicity of active substance.By with Si functional surface promoting agent and ionic surface active agent combination, can realize particle＜1 μ m.Formula well known by persons skilled in the art is introduced gas (normally air) meeting negative impact life properties in thick emulsion preparation, even causes the damage of diverting device in some cases.
Therefore, also form such possibility, promptly product stream (organosilane, Si functional surface promoting agent/water, ionic surface active agent) directly is formulated into and stirs evenly device.
Water-based emulsion of the present invention can be used for handling and/or modification is organic and/or inorganic substrate, in particular for the hydrophobicity of porous, inorganic base material, is particularly preferred for the hydrophobicity of material of construction.
The technology applicating evaluating
The sandstone sample of 5 * 5 * 5cm at first under conventional weather condition (23 ℃, 50% relative air humidity) place several weeks, weigh subsequently.The organosilane emulsion that 200ml makes places the 400ml beaker, and per three sample rooms of weighing are every 1 minute twice of thorough impregnation half an hour.After finishing silanization, the sandstone sample was at room temperature placed 14 days.In order to determine water-absorbent, according to DIN12 103, with the protrusion water column flushing with 5cm in water-bath of per 2 samples, and after 10,30,60 minutes, 2,4,8 and 24 hours sense weight.In order to measure depth of penetration, with hammer and chisel the sample cubes is divided into aliquot, and sprays with the water of the ink that dyeed.The Abperl effect is visual test, and it can still be tested by applying with the water droplet of dropper on horizontal contact surface usually by flooding in water.After 15 minutes, shake off water droplet, estimate contact surface.Thus, its implication numbering is as follows:
1. substrate surface does not have moistening
The substrate surface water droplet distribute 50% do not dye black
3. surface arrangement, i.e. the light/dark balance part of substrate surface, water droplet is moistening fully
4. the aterrimus part of surface in contact, water section sucks.Water-absorbent has shown hydrophobic effect.It is few more to absorb water, and hydrophobicity is good more.
The meaning of depth of penetration is that soaker can enter in sandstone how dark.For the positive surface properties of emulsion of the present invention is described, use product to carry out simultaneous test according to prior art.
In test 1, the siloxanes that use can be buied (oligomeric oxyalkylsiloxane) micro emulsion, it contains the functionalized silicon surfacant (silicone surfactant) of following structure.
It typically refers to the multipolymer of polysiloxane and one or more polyglycol ether chains.In test 2, use the described emulsion of forming by organosilane and surfactant mixture of buying of EP-A-340816.
Test is carried out with two step enrichment steps, and this shows, emulsion of the present invention even when low actives concentrations (5%) is considered its water-absorbent and depth of penetration, and it demonstrates than the obvious better result of the prior art emulsion of 40% active material concentration.
Test 8 and 9 and show, even on neutral substance, for example
On the sandstone, can realize improved validity, especially when using to the combination of the silane of forming by short chain and chain alkyl.
Embodiment 1.6: cement plaster
Before with the emulsion dipping, the mortar cubes is dried to constant weight.Be 72 hours and 105 ℃ general time of drying.Be no more than 0.1% when weight changed within 24 hours, then think to have reached constant weight.Cool off after 2 hours the sandstone of at room temperature weighing.Afterwards, in the 400ml beaker, apply above 1 minute with the 150ml dipping solution.After placing 30 minutes, re-treatment at room temperature.Water-absorbent is measured as mentioned above, and depth of penetration and Abperl effect are measured too.
Embodiment 1.8
Adding under alkalescence or an acidic catalyst condition, hydrophobic property obviously improves.Add 3-sulfo group propyl group ortho-siliformic acid (Si285)
(HO)
3Si-CH
2CH
2CH
2-SO
3H
Be proved to be particularly advantageous.By gentle agitation in emulsion, before using, directly the pH value is adjusted into about 4.
Table 1.9:
| Test | Active substance | Active material concentration (wt%) | Tensio-active agent | Water-absorbent after 24 hours (%) |
| 1 | C 3H 7Si(OC 2H 5) 3 | 40 20 10 | (SL 51-0-15) | 1.79 5.03 7.20 |
| 2 | C 3H 7Si(OC 2H 5) 3 (+Si285) | 40 20 10 | (SL 51-0-15) | 0.72 0.73 0.75 |
Table 1.9: the result of lime sandstone (blind test sample: the water-absorbent behind the 24h: 11.97%)
Even the use short-chain alkyl, during as the n-propyl-triethoxysilicane, the system that has catalyzer with the present invention can reach better until extraordinary result.
According to the second little aspect (Teilaspekt), the present invention relates to O/w emulsion, it contains with the total restatement 1-70 of emulsion weight %, (it also comprises organic oxyalkylsiloxane for the functional alkoxysilanes of preferred 5-50 weight % and/or siloxane oligomer, wherein siloxane oligomer can be corresponding to the condensation product of functional alkoxysilanes), at least a emulsifying agent and water, wherein, the pH value of emulsion is 5-9, be preferably 7-8.5, the width of droplets size distribution is 0.6-1.2, expresses with following Span value.
In addition, the second little aspect according to the present invention, be used to prepare the method for water-based O/w emulsion, this emulsion comprises functional alkoxysilanes and/or siloxane oligomer, at least a emulsifying agent and water, this method is by these compositions of (i) premix, and be that the high pressure of 2-15MPa stirs evenly emulsification in the device (ii), thereby the width of droplets size distribution is 0.6-1.2, expresses with following Span value having at least one pressure stage and pressure.
Here, the average droplet size of disperse phase is lower than 0.5 μ m suitably, is preferably especially＜0.4 μ m, is preferably 0.1-0.3 μ m especially.
Average droplet size (drop size) is appreciated that the diameter that calculates into by the volume averaging value of drop.Here, the volume averaging value is obtained divided by amount of droplets by the cumulative volume of all drops.Diameter is used for the calculating of almost spherical drop.
The numerical value that is used for the width of droplets size distribution calculates like this, promptly the maximum diameter drop (D90) not considering to remain to the minimum diameter drop (D10) of many 10 weight % droplet content in to the drop amount and be no more than 10 weight % content, the difference of the diameter of remaining maximum drop and the minimum drop that is left is divided by the diameter of drop (D50).Drop (D50) is greater than 50 weight % of all drops, and less than 50 weight % of all drops.The numerical value of this Tile Width [(D90-D10)/D50] can be described as Span in the context of the present invention.
Droplet dia and Tile Width can be used
-LS-grain size analysis instrument is measured, and wherein, when needed, droplets size distribution can be drawn with diagrammatic representation (this is preferably with the logarithm standard) with respect to droplet dia by using droplet size percentage ratio.
During unimodal distribution, curve has maximum value, has two maximum values when bimodal distribution.
If the peaked position of following this distribution curve represents that with μ m in bimodal or multimodal distributed, this expression was relevant with first maximum value with minimum droplet dia so.
Droplets size distribution realizes by using selected emulsification condition and emulsifier unit.Described radiation decollator or high pressure stir evenly device and are proved to be specially suitable, for example described in EP-A0101007 or the EP-A0761724.This device that stirs evenly for example can be available from APV Gaulin GmbH, L ü beck.In this device, pressure adjustment and pressure indication comprise the mechanical alignment of nozzle width or nozzle wavelength width of a slit.
Preferably at least one pressure stage, use the pressure of 4-8MPa, especially the most preferably use the pressure of 5-6MPa.
The emulsification of step in (ii) can be finished with two pressure stages with different pressures.
(emulsion contains functional alkoxysilanes and/or the siloxane oligomer with the total restatement 1-70 of emulsion weight % in an embodiment of preparation water-based O/w emulsion method, at least a emulsifying agent and water), in the oligopolymer share, especially the oligopolymer of functional alkoxysilanes with the silicoorganic compound gross weight count 〉=during 25 weight %, following method: (i) these compositions of premix, and be that the high pressure of 2-15MPa stirs evenly emulsification in the device (ii) having at least one pressure stage and pressure, thereby average droplet size is preferably less than 0.5 μ m, especially less than 0.4 μ m, the width of droplets size distribution is 0.6-1.2, expresses with following Span value.
(emulsion contains functional alkoxysilanes and/or the siloxane oligomer with the total restatement 1-70 of emulsion weight % in another embodiment of preparation water-based O/w emulsion method, functional alkoxysilanes oligopolymer particularly, at least a emulsifying agent and water), count under 5 to＜25 weight % with the silicoorganic compound gross weight in the siloxane oligomer share, following method: (i) these compositions of premix, be that the high pressure of 10-70MPa stirs evenly pre-emulsification in the device (iii) having at least one pressure stage and pressure, and be that the high pressure of 2-15MPa stirs evenly emulsification in the device (ii) having at least one pressure stage and pressure, thereby average droplet size is preferably less than 0.5 μ m, especially less than 0.4 μ m, the width of droplets size distribution is 0.6-1.2, expresses with the Span value.
In certain embodiment of the method for the invention, preferably afterwards in premix step (i), emulsifying step (ii) before, being provided with one in addition is 10-70MPa having at least one pressure stage and pressure, the high pressure that is preferably 20-40MPa stirs evenly device.
When leaving high pressure and stir evenly device, can cool off emulsion, perhaps pre-cooled mixture also can be emulsified.
Functional alkoxysilanes is selected from the mixture of alkylalkoxy silane or following formula,
R
1-Si (OR
2)
3, (R
1)
2-Si (OR
2)
2And/or (R
1)
3-Si (OR
2)
Wherein, substituent R
1Identical or different and be chain, ring-type and/or ramose C
3-C
18Alkyl, especially propyl group or octyl group, has the C of halogen
3-C
18Alkyl or the amino C that replaces
3-C
18Alkyl, vinyl, mercapto alkyl, methacryloxy alkyl, acryloxyalkyl, alkyl aminoalkyl, dialkyl amino alkyl, diethylidene aminoalkyl, triethylene aminoalkyl, glycidyl oxyalkyl, bis-alkoxy silyl alkyl, list or polythioalkane, have 2-20 EO or the polyoxyethylene glycol unitary methyl blocking of PO or hydroxy-end capped or polypropylene glycol, R
2Identical or different and R
2Be to have 1-6 carbon atom, the line style of preferred 1 or 2 carbon atom or ramose alkyl.
For example, methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, ethyl triethoxysilane, just with the sec.-propyl Trimethoxy silane, just with the sec.-propyl triethoxyl silane, just with the isobutyl-Trimethoxy silane, just with the isobutyl-triethoxyl silane, just with the isopentyl Trimethoxy silane, just with the isopentyl triethoxyl silane, just with the isohexyl Trimethoxy silane, just and isooctyltrimethoxysi,ane, just with the iso-octyl triethoxyl silane, the hexadecyl Trimethoxy silane, the hexadecyl triethoxyl silane, the octadecyl Trimethoxy silane, octadecyltriethoxy silane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, just with the isobutyl-methyldiethoxysilane, just with the isobutyl-methyldiethoxysilane, cyclohexyl methyl dimethoxy silane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, isobutyl--sec.-propyl dimethoxy silane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three-(2-methoxy ethoxy silane), the 3-aminopropyl trimethoxysilane, the 3-aminopropyl triethoxysilane, N-(just-butyl)-the 3-aminopropyl trimethoxysilane, 3-aminopropyl methyldiethoxysilane, 3-uride (Ureido) propyl trimethoxy silicane, 3-uride propyl-triethoxysilicane, N-aminoethyl-3-aminopropyl trimethoxysilane, N-aminoethyl-3-aminopropyl triethoxysilane, the functional propyl trimethoxy silicane of triamino, 3-(4,5-glyoxalidine base) propyl-triethoxysilicane, 3-glycidyl oxygen propyl trimethoxy silicane, 3-glycidyl oxygen propyl-triethoxysilicane, ten trifluoro octyltri-ethoxysilane, ten trifluoro octyl group Trimethoxy silanes, 13 fluoro-1,1,2,2-tetrahydrochysene octyltri-ethoxysilane, 13 fluoro-1,1,2,2-tetrahydrochysene octyl group Trimethoxy silane, the acryloyl-oxy propyl trimethoxy silicane, the acryloyl-oxy propyl-triethoxysilicane, the 3-methyl allyl acyloxypropyl trimethoxysilane, 3-methacryloxypropyl triethoxyl silane, 3-methacryloxypropyl-2-trimethoxysilyl propyl methacrylate TMOS, 3-methacryloxypropyl-2-methyl-propyl triethoxyl silane, mercaptopropyl trimethoxysilane, mercaptopropyltriethoxysilane, two (triethoxysilylpropyltetrasulfide)-four sulfanes, two (trimethoxy-silylpropyl)-four sulfanes, two (triethoxysilylpropyltetrasulfide)-disulphanes, two (trimethoxy-silylpropyl)-disulphanes, two (triethoxysilylpropyltetrasulfide)-sulfanes, two (trimethoxy-silylpropyl)-sulfanes, two (triethoxysilylpropyltetrasulfide)-five sulfanes, two (trimethoxy-silylpropyl)-five sulfanes.
Particularly preferred functional alkoxysilanes be just with the isobutyl-Trimethoxy silane, just with isobutyl-triethoxyl silane, n-propyl Trimethoxy silane, n-propyl triethoxyl silane, just with isooctyltrimethoxysi,ane, just with iso-octyl triethoxyl silane, vinyltrimethoxy silane, vinyltriethoxysilane.
Siloxane oligomer can also use jointly with functional alkoxysilanes, especially based on the above-mentioned siloxane oligomer that is used for the functional alkoxysilanes of oil phase.Advantage is that in the compound or its mixture that form emulsion, the boiling point and the burning-point of oil phase are improved.Can also be by adding the content that appropriate organic solvent is adjusted silane, oligopolymer or siloxanes in the oil phase, described organic solvent for example-but be not limited to-boiling point is higher than the aliphatic series and the aromatic hydrocarbon of room temperature, as C
6-C
12Alkane, gasoline, clean gasoline (Waschbenzin), diesel oil, kerosene, toluene, dimethylbenzene, alcohol or polyvalent alcohol, as the mixture of amylalcohol, hexanol, octanol, nonyl alcohol, isononyl alcohol, glycerine, ether, ester, aldehyde, ketone or at least two kinds of aforementioned organic solvents.
Be surprisingly found out that,, improved the emulsifying property of oil phase, and can reach the droplet dia littler than the emulsification of common organoalkoxysilane owing to there is oligopolymer.
The siloxane oligomer that meets goal of the invention is counted at least 5 weight % with the oil phase gross weight of the mixture of functional alkoxysilanes and oligopolymer.Oligomer can be 5-45 weight % with the total restatement of oil phase, is preferably 5-66.7 weight %, but also can be 100 weight % at the most.
Siloxane oligomer is based on chain, ring-type and/or crosslinked structure, desired form shown in wherein the chain-like structure of siloxane oligomer meets hereinafter.
Siloxane oligomer or its mixture with alkyl functional basically (with reference to the R of following formula
1) organoalkoxysilane be the basis, wherein its alkyl functional group is substituted in case of necessity or can contains two keys, promptly there is alkenyl-functional groups, and can has the alkoxy-functional that partly is hydrolyzed in case of necessity, and be selected from the oligopolymer or the oligomer mixture of following formula:
The substituting group of the siloxane oligomer of chain, ring-type and/or crosslinking structure has as radicals R
1C
3-C
18Alkyl, has the C of halogen
3-C
18Alkyl or the amino C that replaces
3-C
18Alkyl, vinyl, mercapto alkyl, methacryloyl oxyalkyl, acryloyloxyalkyl, alkyl aminoalkyl, dialkyl amino alkyl, diethylidene aminoalkyl, triethylene aminoalkyl, glycidyl oxyalkyl, bis-alkoxy silyl alkyl, list or polythioalkane, have 2-20 EO or the polyoxyethylene glycol unitary methyl blocking of PO or hydroxy-end capped or polypropylene glycol, wherein alkyl exists with line style, ring-type and/or branching type, R
2Be identical or different group and R
2Be to have 1-6 carbon atom, the hydrocarbon of preferred 1 or 2 carbon atom or line style or ramose alkyl, n is defined as 2-40, preferred 2-20, the oligomeric degree of preferred especially 3-6.
Relate to the oligomer mixture that oligomeric degree is 2-20 here, its average oligomeric degree is 3-20, is preferably 4-6.Siloxane oligomer not only may reside in line style, the annular form, can also be present in branch's form, preferably uses line style and/or cyclic oligopolymer, the most preferred linear oligomer with described oligomeric degree that uses.Existing oligopolymer can also be according to its functionality (R
1) constitute even oligopolymer, promptly it can be made of identical replacement functional alkoxysilanes equably.
Preferred oligopolymer embodiment has these groups:
R
1=CH
3-, C
2H
5-, C
3H
7-, C
4H
9-, different C
4H
9-, C
6H
13-, different C
6H
13-, C
8H
16-, different C
8H
16-, CH
2=CH, methacryloxypropyl-, glycidyl oxygen propyl group-, aminopropyl-, the aminoethyl aminopropyl-, the triethylene aminopropyl-, the mercapto propyl group-, and
R
2=methyl or ethyl.
Particularly preferred oligopolymer be the n-propyl oxyalkylsiloxane, just with the isobutyl-organoalkoxysilane, just with iso-octyl oxyalkylsiloxane, vinyl alkoxy siloxanes.
Particularly preferred oligopolymer or its mixture have formed with the functional alkoxysilanes that is used for emulsion of the present invention has enough oil phases of high burning-point.
When using functional alkoxysilanes or mixture separately, preferred same such material that uses, promptly its burning-point is higher than 55 ℃, especially preferably is higher than 100 ℃.
Mixture at functional alkoxysilanes and siloxane oligomer, especially, with the mixture of the oligopolymer of functional alkoxysilanes, and/or with the mixture of the described co-oligomer in back in, the share of oligopolymer and/or co-oligomer is counted 1-100 weight % with the oil phase gross weight.Oligopolymer and/or the co-oligomer content in oil phase is preferably 70-100 weight % and 1-40 weight %, and particularly preferably being in the oil phase oligopolymer and/or co-oligomer content is the system of 90-98 weight % and 5-30 weight %.
Described co-oligomer is organic alkoxy siloxanes or its mixture of oligomeric degree 〉=2, and it can be represented with the ideal form of the chain co-oligomer that is used for following formula:
Shown in chemical formula in, m and n are identical or different and in (n+m) 〉=2 o'clock be number among the 0-20.Correspondingly, this also is suitable for the co-oligomer of ring-type and/or crosslinking structure.In all cases, the composition from the co-oligomer of used organoalkoxysilane is on the statistics fully.The composition of co-oligomer mainly determines that by the quantity of used different functional alkoxysilanes and the active degree of reaction of concentration and single organoalkoxysilane these organoalkoxysilanes can become co-oligomer by hydrolysis and condensation reaction.Siloxane oligomer can be included in the mixture that is formed by the even siloxane oligomer of forming, in the mixture that perhaps is included in the mixture that is formed by co-oligomer or is formed by even siloxane oligomer of forming and co-oligomer.
The substituent R of co-oligomer and R
2Can be identical or different, and it represents hydrogen (H), C
1-C
18Alkyl, has the C of halogen
1-C
18Alkyl or the amino C that replaces
1-C
18Alkyl, phenyl, vinyl, mercapto alkyl, methacryloyl oxyalkyl, acryloyloxyalkyl, alkyl aminoalkyl, dialkyl amino alkyl, diethylidene aminoalkyl, triethylene aminoalkyl, glycidyl oxyalkyl, bis-alkoxy silyl alkyl, list or polythioalkane, have 2-20 EO or the polyoxyethylene glycol unitary methyl blocking of PO or hydroxy-end capped or polypropylene glycol, wherein, alkyl can be line style, ring-type and/or branch-like, R
1Identical or different and R
1Expression hydrogen or have the line style and/or the ramose alkyl of 1-6 carbon atom is preferably 1 or 2 carbon atom.Except described structure, co-oligomer can contain the structure based on tetraalkoxysilane equally.
In chain, ring-type and/or crosslinked co-oligomer, preferably have the chain and/or the annular siloxane of the oligomeric degree of 2-20, preferred especially chain siloxanes.In addition, aforementioned organo-siloxane can be called the mixing oligopolymer.
Exemplary the enumerating of mixture oligopolymer (n+m satisfies the identical standard under the n condition in the aforementioned even oligopolymer):
R
1: methyl or ethyl or H,
R：C
3H
7-，R
2：CH
2＝CH-，
R: mercapto propyl group, R
2: propyl group,
R: methyl, R
2: aminopropyl or aminoethyl aminopropyl or ethylidene three aminopropyls,
R: propyl group, R
2: aminopropyl or aminoethyl aminopropyl or ethylidene three aminopropyls,
R: isobutyl-, R
2: aminopropyl or aminoethyl aminopropyl or ethylidene three aminopropyls,
R: octyl group, R
2: aminopropyl or aminoethyl aminopropyl or ethylidene three aminopropyls,
R: iso-octyl, R
2: aminopropyl or aminoethyl aminopropyl or ethylidene three aminopropyls,
R: ten trifluoro octyl groups, R
2: aminopropyl or aminoethyl aminopropyl or ethylidene three aminopropyls,
R: methacryloxypropyl, R
2: aminopropyl or aminoethyl aminopropyl or ethylidene three aminopropyls,
R: Racemic glycidol oxygen propyl group, R
2: aminopropyl or aminoethyl aminopropyl or ethylidene three aminopropyls.
Preferably methoxy or ethoxy is 2-4 as the mixing propyl group/vinylsiloxane and the especially oligomeric degree (n+m) of alkoxyl group and its mixture.
Described oligopolymer or co-oligomer can also contain respectively the low of the organoalkoxysilane that uses but measurable share according to the preparation method.But this share is no more than 10 weight % in mixture total weight.
The maximum value of the droplets size distribution of emulsion of the present invention is preferred≤0.36 μ m.
The D10 value of emulsion of the present invention is preferably≤0.3 μ m, is preferably 0.05 μ m-0.28 μ m especially.
The D90 value is preferred≤0.88 μ m, be in particular 0.2-0.5 μ m.
In addition, preferred D50 value is≤0.5 μ m, is preferably especially≤0.4 μ m, is in particular 0.1-0.3 μ m.
Emulsion of the present invention contains at least a emulsifying agent, the preferred emulsification system of being made up of two or more emulsifying agents.The emulsifying agent amount is counted 0.02-2 weight % with the emulsion gross weight.
Suitable emulsifying agent for example is selected from has C
8-C
18The alkyl-sulphate of alkyl, in hydrophobic grouping, has C
8-C
18Alkyl and have 1-40 ethylene oxide (EO)-or propylene oxide (PO)-unitary alkyl-sulphate and alkyl aryl ether sulfate, have C
8-C
18The alkylsulfonate of alkyl, has C
8-C
18The alkylaryl sulfonate of alkyl, sulfo-succinic acid with have the monohydroxy-alcohol of 5-15 carbon atom or a half ester of alkylphenol, at alkyl, aryl, the an alkali metal salt and the ammonium salt that have the carboxylic acid of 8-20 carbon atom in alkaryl or the aralkyl, the alkylphosphonic and the alkaryl phosphoric acid salt that in organic group, have 8-20 carbon atom, in alkyl or alkaryl, have 8-20 carbon atom and 1-40 unitary alkyl oxide phosphonate of EO or alkaryl phosphonate, have 8-40 EO unit and in alkyl or aryl, have C
8-C
20The alkyl polyglycol ether of carbon atom and alkaryl polyglycol ether, have 8-40 EO or the unitary ethylene oxide/propylene oxide of PO (EO/PO) segmented copolymer, have C
8-C
22The adduct of the alkylamine of alkyl and ethylene oxide or propylene oxide, have line style or the saturated or unsaturated C of ramose
8-C
24Alkyl and the mixture that alkyl polyglycoside, Yelkin TTS, functionalized silicon tensio-active agent or these emulsifying agents of 1-10 hexose or the unitary oligomerization glycosides of pentose base are arranged.In addition, particularly preferably be the functionalized silicon tensio-active agent of following general formula
Wherein, R
1And R
2Identical or different, and be the C of straight or branched
1-C
20Alkyl, C preferably
1-C
10Alkyl, phenyl, R
3Be C
1-C
10Alkyl, p is the integer of 0-3, Ts is a surface active groups, it is selected from
-(CH
2CH
2-O)
n-R
4，
Wherein, n is the integer of 3-15, and m is the integer of 3-50, and l is the integer of 3-25, R
4Be H, C
1-C
20Alkyl, C
2-C
36Thiazolinyl, C
5-C
8Cycloalkyl, C
7-C
36Aralkyl.
Particularly preferably be and have C
8-C
18The alkyl-sulphate of alkyl, lauryl sulfate for example, with the binding substances of following formula functionalized silicon tensio-active agent,
Wherein, R is methyl, ethyl, methoxy or ethoxy, and surface active groups is
-(CH
2CH
2-O)
10C
13H
27Or
Wherein, n is the integer of 5-15, R
5Be the C of straight or branched
6-C
10Alkyl.
Specially suitable is the tensio-active agent of preceding formula, wherein R=CH
3, n=1-30 and R
5=different nonyl.This tensio-active agent is called as surfactant A hereinafter.
Except hydrophobic active substances water and at least a emulsifying agent, water-based emulsion of the present invention can also contain conventional auxiliary agent, this auxiliary agent is selected from inorganic or organic acid, buffer substance, mycocide, sterilant, algicide, microbicide, odorant agent, corrosion inhibitor, sanitas, the auxiliary rheological agents of pyrolysis silicic acid or bentonite for example, the Abperl auxiliary agent of fluoropolymer for example, hydrophobic pyrolysis silicic acid, those materials based on active organosilicon oxygen alkane, silicone resin, organotin for example, the catalyzer of titanium or zirconium compounds, for example dibutyl tin dilaurate, the alkoxide of titanium or the alkoxide of zirconium (for example tetrabutyl titanate salt).
The amount of auxiliary agent is counted 0.005-10 weight % with the emulsion gross weight.
By adding acid or basic cpd or by common buffer system, as NaHCO
3, acetate/acetic or alkali metal phosphate, finish the adjustment of desirable pH value.
The property because non newtonian flows, the viscosity of accurately measuring emulsion of the present invention is difficult.But, can be used in the rotary viscosity design determining parameter value (Richtwert) that has definite main shaft and corresponding slow speed under the room temperature (20 ℃).
The viscosity of determining with this method is≤100mPas to be preferably 4-100mPas, the most special 10-20mPas that is preferably.
Water-based emulsion of the present invention according to the preceding method preparation can be used as hydrophobic treatment and the surface modification treatment that separating agent (Trennmittel) is used for textiles, leather, cellulosics and starchbased product, be used for the coating of glass fibre and mineral fibre, be used for the surface modification treatment of filler.Particularly preferably be the hydrophobic treatment that is used for porous mass, porous mineral matter material of construction especially is as concrete, Wingdale, lime sandstone and brick material.
Further set forth the present invention according to following examples, but be not restriction theme of the present invention.
2. embodiment:
The comparative example 2.1
Emulsion is formed:
48.3 weight % water
49.2 weight % n-propyl triethoxyl silane
0.96 weight % functionalized silicon emulsifier type A
0.64 weight % Sodium Lauryl Sulphate BP/USP (C
12-C
16)
0.8 weight %Abperl agent (active organopolysiloxane)
0.1 weight % sanitas CIT/MIT
*),
1.5g/kg silane NaHCO
3
*) CIT=chlormethylisothiazo,ine ketone, the MIT=methylisothiazolinone
At the aqueous phase that provides in advance, oil phase is sneaked in the solvable composition dissolving at first will forming under agitation condition then, should avoid introducing air here.Mixing time is 5-10 minute.Then, high pressure stir evenly in first pressure stage of device with 16MPa and in second pressure stage with the pre-emulsification of 3MPa 20 minutes.
At first manifest uniform creamy emulsion instability, after 24 hours, the clarification on surface begins to separate mutually.
Droplets size distribution is as follows after the pre-emulsification:
Peaked position is at 1.1 μ m.
D90=4-7 μ m, D50=0.83 μ m, D10=0.17 μ m, the Span value is 4.6-8.2.
In second step, stir evenly in first pressure stage of device at high pressure and to continue emulsification with 10MPa with 50MPa with in second pressure stage.
Reach the average droplet size of 0.1 μ m.The maximum value position of particle size distribution is at 0.07 μ m.
D90=0.18 μ m, D50=0.082 μ m, D10=0.054 μ m, the Span value is 1.6.
The stability in storage of conc forms is proved to be enough, but also unsatisfactory when simple dilute with water.
Comparative example 2.1 shows that in order to reach the emulsion of the very careful distribution with narrow droplets size distribution, with organoalkoxysilane emulsification in having the water of emulsifying agent, still, emulsifying property is unsatisfactory.
Embodiment 2.2
Emulsion is formed:
48.3 weight % water
49.2 the propyl-triethoxysilicane oxygen alkane of the oligomeric degree of weight % 2-4
0.96 weight % functionalized silicon emulsifier type A
0.64 weight % Sodium Lauryl Sulphate BP/USP (C
12-C
16)
0.8 weight %Abperl agent (active organopolysiloxane)
0.1 weight % sanitas CIT/MIT,
1.5g/kg silane NaHCO
3
At the aqueous phase that provides in advance, oil phase is sneaked in the solvable composition dissolving at first will forming under agitation condition 5-10 minute then, should avoid introducing air here.Then, high pressure stir evenly in first pressure stage of device with 15MPa and in second pressure stage with 3MPa emulsification 25 minutes.
The gained emulsion-stabilizing stored above 6 months.Stability in storage behind the simple dilute with water also is proved to be good.
Emulsion has following droplets size distribution:
Average droplet size 0.25 μ m, the maximum value position of droplets size distribution curve is at 0.25 μ m.
D90=0.35 μ m, D50=0.25 μ m, D10=0.16 μ m, the Span value is 0.76.
Embodiment 2.2 shows that the oligopolymer of used organoalkoxysilane has than the obvious better emulsifying property of monomeric silanes among the embodiment 2.1.Do not use pre-emulsification can reach desirable harmonic(-)mean drop size and narrow droplets size distribution yet.
Embodiment 2.3
Emulsion is formed:
48.3 weight % water
35.9 weight % n-propyl triethoxy silica alkane
13.6 the propyl-triethoxysilicane oxygen alkane of the oligomeric degree of weight % 2-4
0.96 weight % functionalized silicon emulsifier type A
0.64 weight % Sodium Lauryl Sulphate BP/USP (C
12-C
16)
0.8 weight %Abperl agent (active organopolysiloxane)
0.1 weight % sanitas CIT/MIT,
1.5g/kg silane NaHCO
3
At the aqueous phase that provides in advance, oil phase is sneaked in the solvable composition dissolving at first will forming under agitation condition 5-10 minute then, should avoid introducing air.Then, high pressure stir evenly in first pressure stage of device with 15MPa and in second pressure stage with 3MPa emulsification 10 minutes.
The gained emulsion-stabilizing stored above 6 months.Stability in storage behind the simple dilute with water also is proved to be good.
Emulsion has following droplets size distribution:
Average droplet size 0.13 μ m, the maximum value position of droplets size distribution curve is at 0.13 μ m.
D90=0.20 μ m, D50=0.12 μ m, D10=0.07 μ m, the Span value is 1.16.
Embodiment shows that the common use of oligopolymer has improved the emulsifying property of alkylalkoxy silane in water, promptly can reach the emulsion of the very careful distribution with narrow droplets size distribution.
The comparative example 2.4
Emulsion is formed:
48.25 weight % water
49.2 weight % triethoxy octyl group silane
0.96 weight % functionalized silicon emulsifier type A
0.64 weight % Sodium Lauryl Sulphate BP/USP (C
12-C
16)
0.15 weight % sanitas CIT/MIT
0.8 weight %Abperl agent (active silicone resin)
1.5g/kg silane NaHCO
3
At the aqueous phase that provides in advance, oil phase is sneaked in the solvable composition dissolving at first will forming under agitation condition then, should avoid introducing air.Then, stir evenly at high pressure and to finish emulsification in the device, wherein, at first adjusting pressure in pressure stage II is 3.0MPa, and adjusting pressure then in pressure stage I is 15MPa.Emulsification times: 10 minutes.
Emulsion has following droplets size distribution:
Average droplet size 0.71 μ m, the maximum value position of droplets size distribution curve is at 0.32 μ m.
D90=1.61 μ m, D50=0.38 μ m, D10=0.12 μ m, the Span value is 3.9.Can also only reduce average particle size particle size a little by other back emulsifications that stir evenly at high pressure in the device.Attainable droplets size distribution width does not meet desirable little width.
Embodiment 2.5
Emulsion is formed:
48.17 weight % water
49.20 weight % octyl group oxyethyl group siloxanes
0.96 weight % functionalized silicon emulsifier type A
0.64 weight % Sodium Lauryl Sulphate BP/USP
0.15 weight % sanitas CIT/MIT
0.80 weight %Abperl agent
0.08 weight %NaHCO
3
Preparation method and stability in storage are with embodiment 2.2.
Emulsion has following droplets size distribution:
Average droplet size 0.30 μ m.
D90=0.41 μ m, D50=0.30 μ m, D10=0.19 μ m, the Span value is 0.73.
Embodiment 2.6
Emulsion is formed:
48.3 weight % water
35.9 weight % triethoxy octyl group silane
13.3 the triethoxy octyl group siloxanes of the oligomeric degree of weight % 2-4
0.96 weight % functionalized silicon emulsifier type A
0.64 weight % Sodium Lauryl Sulphate BP/USP (C
12-C
16)
0.8 weight %Abperl agent (active organopolysiloxane)
0.1 weight % sanitas CIT/MIT,
1.5g/kg silane NaHCO
3
At the aqueous phase that provides in advance, oil phase is sneaked in the solvable composition dissolving at first will forming under agitation condition then, should avoid introducing air here.The dissolving of oil phase and sneak into and need 5-10 minute.Then, high pressure stir evenly in first pressure stage of device with 15MPa and in second pressure stage with 3MPa emulsification 10 minutes.
The gained emulsion-stabilizing stored above 6 months.Stability in storage behind the simple dilute with water also is good.
Emulsion has following droplets size distribution:
Average droplet size 0.27 μ m, the maximum value position of droplets size distribution curve is at 0.28 μ m.
D90=0.37 μ m, D50=0.27 μ m, D10=0.18 μ m, the Span value is 0.71.
Embodiment 2.7
Emulsion is formed:
48.17 weight % water
46.74 weight % octyltri-ethoxysilane
2.46 weight % octyl group oxyethyl group siloxanes
0.96 weight % functionalized silicon emulsifier type A
0.64 weight % Sodium Lauryl Sulphate BP/USP
0.15 weight % sanitas CIT/MIT
0.80 weight %Abperl agent
0.08 weight %NaHCO
3
Preparation method and stability in storage are with embodiment 2.2.
Emulsion has following droplets size distribution:
Average droplet size 0.36 μ m, the maximum value position of droplets size distribution curve is at 0.36 μ m.
D90=0.49 μ m, D50=0.34 μ m, D10=0.19 μ m, the Span value is 0.86.
Embodiment 2.8
Emulsion is formed:
48.17 weight % water
39.36 weight % octyltri-ethoxysilane
9.84 weight % octyl group oxyethyl group siloxanes
0.96 weight % functionalized silicon emulsifier type A
0.64 weight % Sodium Lauryl Sulphate BP/USP
0.15 weight % sanitas CIT/MIT
0.80 weight %Abperl agent
0.08 weight %NaHCO
3
Preparation method and stability in storage are with embodiment 2.2.
Emulsion has following droplets size distribution:
Average droplet size 0.27 μ m, the maximum value position of droplets size distribution curve is at 0.33 μ m.
D90=0.41 μ m, D50=0.29 μ m, D10=0.28 μ m, the Span value is 1.13.
Embodiment 2.9
Emulsion is formed:
48.3 weight % water
41.82 weight % triethoxy octyl group silane
7.38 the propyl-triethoxysilicane oxygen alkane of the oligomeric degree of weight % 2-4
0.96 weight % functionalized silicon emulsifier type A
0.64 weight % Sodium Lauryl Sulphate BP/USP (C
12-C
16)
0.8 weight %Abperl agent (active organopolysiloxane)
0.1 weight % sanitas CIT/MIT,
1.5g/kg silane NaHCO
3
At the aqueous phase that provides in advance, oil phase is sneaked in the solvable composition dissolving at first will forming under agitation condition then, should avoid introducing air here.Then, high pressure stir evenly in first pressure stage of device with 15MPa and in second pressure stage with 3MPa emulsification 10 minutes.
The gained aqueous emulsion is proved stably stored and surpasses 6 months, and the stability in storage behind the simple dilute with water is also satisfactory.
Emulsion has following droplets size distribution:
Average droplet size 0.44 μ m.
Embodiment 2.10
Emulsion is formed:
48.3 weight % water
39.36 weight % triethoxy octyl group silane
9.84 the propyl-triethoxysilicane oxygen alkane of the oligomeric degree of weight % 2-4
0.96 weight % functionalized silicon emulsifier type A
0.64 weight % Sodium Lauryl Sulphate BP/USP (C
12-C
16)
0.8 weight %Abperl agent (active organopolysiloxane)
0.1 weight % sanitas CIT/MIT,
1.5g/kg silane NaHCO
3
At the aqueous phase that provides in advance, oil phase is sneaked in the solvable composition dissolving at first will forming under agitation condition then, should avoid introducing air here.Then, high pressure stir evenly in first pressure stage of device with 15MPa and in second pressure stage with 3MPa emulsification 10 minutes.
The gained emulsion is proved stably stored and surpasses 6 months, only loses very little stability in storage behind the simple dilute with water.
Emulsion has following droplets size distribution:
Average droplet size 0.31 μ m, bimodal droplets size distribution, first maximum value of droplets size distribution curve are less than 0.1 μ m, and second maximum value is 0.36 μ m.
D90=0.46 μ m, D50=0.33 μ m, D10=0.09 μ m, the Span value is 1.2.
Corresponding to the emulsion of embodiment 2 (100% oligopolymer is in oil phase) and the technology application testing that emulsion compares that is purchased based on methyl silicon resin.
Testing respectively on the sample that concrete constitutes with the active substance depth of penetration after the emulsion processing.For the good and persistent validity of hydrophobic treatment, depth of penetration is conclusive.1mm and littler depth of penetration can not be accepted.High as far as possible depth of penetration is desirable.The application of emulsion is carried out in the following manner: each sample each 5 seconds thorough impregnations 2 times in steeping liq, 1 minute timed interval between the dipping.Consumption is determined by weight difference.This dipping method simulated very approx no air assembly common in the practice (
) (a kind of technology) paint application.Higher coated weight only just can be realized (having the two-stage or the multistage spraying process of corresponding extra working cost) by multistage coating.Thus, consumption described in the form repeated the practice in technology attainable coated weight.In the practice relevant with perviousness, natural emulsion advantageously demonstrates, and it can have high as far as possible coated weight in the method.
After 14 day reaction times, sample is split, determine the depth of penetration of hydrophobic substance by the moistening crack surface recently of water.The hydrophobic scope of dipping can be not moistening by water.
Before dipping, it is 40 weight % that water is adjusted to identical activity substance content with emulsion.The original activity substances content of the emulsion of embodiment 2.2 is 50 weight %, and the original activity substances content of contrast emulsion BaysiloneWB is 58 weight %.
The result repeats to be listed in the table below.
Table 2.1
| Soaker | Coated weight g/m 2 | Depth of penetration Mm |
| Baysilone WB(40％) | 80 | 0.5 |
| Embodiment 2 (40%) | 207 | 2.7 |
Emulsion of the present invention is improved burning-point character with respect to another advantage of prior art.Because the hydrolysis of active substance, along with the storage time increases, alcohol appears in the alkyltrialkoxysilaneand emulsion.Formed alcohol generally is meant methyl alcohol or ethanol.Two kinds of materials can greatly reduce the burning-point of observed emulsion.Thereby, be purchased the contrast emulsion, for example Enviroseal 20, its burning-point that shows after storage time at some months is 59 ℃, Baysilone WB (58% active substance) even only be 26 ℃, and under the same stored condition, therefore the burning-point that the emulsion of embodiment 2.2 demonstrates＞75 ℃ can incorporate not flammable liquid classification into.
Claims (26)
1. the water-based emulsion that contains silicoorganic compound, it contains organoalkoxysilane and/or at least a siloxane oligomer and water with chain, ring-type and/or crosslinking structure, it is characterized in that it contains emulsifying agent.
2. the described emulsion of claim 1 is characterized in that, organoalkoxysilane is selected from the alkylalkoxy silane or the mixture of following formula,
R
1-Si (OR
2)
3, (R
1)
2-Si (OR
2)
2And/or (R
1)
3-Si (OR
2)
Wherein, R
1Be identical or different and be chain, ring-type and/or ramose C
3-C
18Alkyl, has the C of halogen
3-C
18Alkyl or the amino C that replaces
3-C
18Alkyl, vinyl, mercaptoalkyl, methacryloyl oxyalkyl, acryloyloxyalkyl, alkyl aminoalkyl, dialkyl amino alkyl, diethylidene aminoalkyl, triethylene aminoalkyl, Racemic glycidol oxyalkyl, bis-alkoxy silyl alkyl, list or polythioalkane, 2-20 EO-or unitary methyl blocking of PO-or hydroxy-end capped polyoxyethylene glycol or polypropylene glycol are arranged, wherein alkyl is respectively chain, ring-type and/or branch's form, R
2Identical or different and be to have 1-6 carbon atom, the line style of preferred 1 or 2 carbon atom or branch's alkyl.
3. the described emulsion of claim 1 is characterized in that, at least a emulsifying agent is selected from has C
8-C
18The alkyl-sulphate of alkyl, on hydrophobic group, has C
8-C
18Alkyl and have 1-40 ethylene oxide (EO) unit and/or unitary alkyl-sulphate of propylene oxide (PO) and alkyl aryl ether sulfate, have C
8-C
18The alkylsulfonate of alkyl, has C
8-C
18The alkylaryl sulfonate of alkyl, sulfo-succinic acid and half ester 5-15 carbon atom monohydroxy-alcohol or alkylphenol, alkyl, aryl, the an alkali metal salt and the ammonium salt that have the carboxylic acid of 8-20 carbon atom in alkaryl or the aralkyl, the alkyl and the alkaryl phosphonate that have 8-20 carbon atom in the organic group, have 8-20 carbon atom in alkyl and/or the alkaryl and have 1-40 unitary alkyl oxide phosphonate of EO and/or alkyl aryl ether phosphonate, have in 8-40 EO unit and the alkyl or aryl and have C
8-C
20The alkyl polyglycol ether of individual carbon atom and alkaryl polyglycol ether, have 8-40 EO and/or the unitary ethylene oxide/propylene oxide of PO (EO/PO) segmented copolymer, have C
8-C
22The adduct of the alkylamine of alkyl and ethylene oxide or propylene oxide, have line style or the saturated or unsaturated C of ramose
8-C
24Alkyl and have 1-10 hexose or the mixture of alkyl polyglycoside, Yelkin TTS, functionalized silicon tensio-active agent or these emulsifying agents of the unitary oligomeric glycosides base of pentose.
4. the described emulsion of claim 1 is characterized in that, uses the siloxane oligomer of oligomeric degree as chain, ring-type and/or the crosslinking structure of 2-20.
5. the described emulsion of claim 1, it is characterized in that, it contains other conventional auxiliary agents, and this auxiliary agent is selected from inorganic or organic acid, buffer substance, mycocide, sterilant, algicide, microbicide, odorant agent, corrosion inhibitor, sanitas, Abperl effect enhancer, viscosity modifier, catalyzer.
6. the described emulsion of claim 1 is characterized in that, it contains at least a pH value regulates material.
7. the described emulsion of claim 1 is characterized in that, it contains organoalkoxysilane and/or siloxane oligomer with total restatement 1 to the 90 weight % of emulsion.
8. the described emulsion of emulsion, particularly claim 1, it contains the silicoorganic compound that are useful on the dipping inorganic materials, and randomly it contains anion surfactant and pH value buffer substance, it is characterized in that, contain the organoalkoxysilane of at least a general formula I of 1-80 weight %
Wherein,
R1:C
1-C
3Alkyl,
R3:C
1-C
20Alkyl, be straight chain or ramose, particularly C
1-C
10Alkyl or phenyl,
X:H, Cl, Br, I, NH
2, SCN, CN, N
3, NHR, NR
2,
+NR
3,-Sx-, aryl or thiazolinyl,
A:0 or 1,
B:1 or 2,
The integer of c:1-18,
And the silicoorganic compound that contain the general formula I I of 1-20 weight %,
Wherein,
R2, R3: identical or different, be C
1-C
20Alkyl, be straight chain or ramose, especially C
1-C
10Alkyl or phenyl,
R4:C
1-C
3Alkoxyl group, { OCH
2-CH
2ROR5, perhaps
When p=0 and r=0, R5:H, C
1-C
20Alkyl, C
2-C
36Thiazolinyl, C
5-C
8Cycloalkyl or C
7-C
36Aralkyl,
Wherein,
M:0,1 or 2,
N:0,1 or 2, its precondition is, when p=0, (m+n)=1 or 2 then, in p ≠ 0 o'clock, (m+n)=0,1 or 2,
P:0,1,2 or 3,
Integer between the r:0 and 50,
s＝3-50，t＝3-25，
Also contain the water that complements to 100% weight content.
9. prepare the method for general formula (II) silicoorganic compound, wherein p=0 is characterized in that, under the reflux temperature of reaction mixture and the pH value between the 3.5-5.5 with the compound and the general formula I V compound reaction that contains active hydrogen of general formula III,
Wherein,
R2, R3: identical or different, be C
1-C
20Alkyl, be straight chain or ramose, especially C
1-C
10Alkyl or phenyl,
M:0,1 or 2,
N:0,1 or 2, its precondition is, (m+n)=1 or 2,
R6:C
1-C
3Alkoxyl group,
R5-O{CH
2-CH
2O}rH (IV)，
Wherein, when p=0 and r=0, R5:H, C
1-C
20Alkyl, C
2-C
36Thiazolinyl, C
5-C
8Cycloalkyl or C
7-C
36Aralkyl,
Integer between the r:0 and 50,
s＝3-50，t＝3-25。
10. the method for preparing general formula (II) silicoorganic compound, wherein p=1,2 or 3 is characterized in that, reacts in the inert solvent of 20-100 ℃ of alcoholization sodium that the compound of general formula V and the general formula I V compound that contains active hydrogen is had a general formula VI, the NaCl that subsequent filtration is settled out also takes out solvent
Wherein,
R2, R3, R6, m, n and p (except p=0),
R2, R3: identical or different, be C
1-C
20Alkyl, be straight chain or ramose, especially C
1-C
10Alkyl or phenyl,
M:0,1 or 2,
N:0,1 or 2, its precondition is, (m+n)=0,1 or 2,
R6:C
1-C
3Alkoxyl group,
R5-O{CH
2-CH
2O}rH (IV)，
Wherein R5:H, C
1-C
20Alkyl, C
2-C
36Thiazolinyl, C
5-C
8Cycloalkyl or C
7-C
36Aralkyl,
Integer between the r:0 and 50,
X is a chlorine,
R5-O{CH
2-CH
2O}rNa (VI)，
Wherein, R5 and r have aforementioned implication.
11. the compound of general formula I I,
R2, R3: identical or different, be C
1-C
20Alkyl, be straight chain or ramose, especially C
1-C
10Alkyl or phenyl,
When p=0 and r=0, R5:H, C
1-C
20Alkyl, C
2-C
36Thiazolinyl, C
5-C
8Cycloalkyl or C
7-C
36Aralkyl,
P:0,1,2 or 3,
Integer between the r:0 and 50,
M:0,1 or 2,
N:0,1 or 2,
-its precondition is, if p=0, (m+n)=1 then,
R4:C
1-C
3Alkoxyl group or { OCH
2-CH
2ROR5,
-its precondition is, if p ≠ 0 o'clock, (m+n)=0,1 or 2 then,
R4:C
1-C
3Alkoxyl group and/or { OCH
2-CH
2ROR5.
12. the method for dipping material of construction is characterized in that claim 1 or 8 described emulsions were adjusted to 3-5.5 with the pH value immediately before being coated to material of construction, preferably adds 3-sulfo group propyl group ortho-siliformic acid, and with this mixture process material of construction to be impregnated.
13. claim 1 or 2 described water-based O/w emulsions, it contains functional alkoxysilanes and/or siloxane oligomer with the total restatement 1-70 of emulsion weight %, at least a emulsifying agent and water, wherein, the pH value of emulsion is 5-9, and the width of droplets size distribution is 0.6-1.2, express with the Span value
14. the described emulsion of claim 13 is characterized in that, the share of siloxane oligomer is counted 1-100 weight % with the oil phase gross weight.
15. the described emulsion of claim 13 is characterized in that, has siloxane oligomer or its mixture of chain, ring-type and/or crosslinking structure, wherein, the chain-like structure of formula Ib siloxane oligomer is
Wherein, the substituent R of chain, ring-type and/or crosslinking structure
1Be C
3-C
18Alkyl, has the C of halogen
3-C
18Alkyl, the amino C that replaces
3-C
18Alkyl, vinyl, mercapto alkyl, methacryloyl oxyalkyl, acryloyloxyalkyl, alkyl aminoalkyl, dialkyl amino alkyl, diethylidene aminoalkyl, triethylene aminoalkyl, glycidyl oxyalkyl, bis-alkoxy silyl alkyl, list or polythioalkane, have 2-20 EO or the polyoxyethylene glycol unitary methyl blocking of PO or hydroxy-end capped or polypropylene glycol, wherein, alkyl is respectively chain, ring-type and/or ramose, radicals R
2Identical or different and R
2Be hydrogen or have 1-6 carbon atom, the line style of preferred 1 or 2 carbon atom or ramose alkyl, wherein, oligomeric degree and n are in the 2-20 scope.
16. the described emulsion of claim 13 is characterized in that, the siloxane oligomer with chain, ring-type and/or crosslinking structure is selected from co-oligomer or its mixture, oligomeric degree 〉=2, and wherein, the co-oligomer with formula IIb chain-like structure is
Wherein, m and n are identical or different or o'clock be the integer of 0-20 in (n+m) 〉=2, wherein, and the substituent R of chain, ring-type and/or crosslinking structure and/or R
2Identical or different, and be hydrogen, C
1-C
18Alkyl, has the C of halogen
1-C
18Alkyl or the amino C that replaces
1-C
18Alkyl, phenyl, vinyl, mercapto alkyl, methacryloyl oxyalkyl, acryloyloxyalkyl, alkyl aminoalkyl, dialkyl amino alkyl, diethylidene aminoalkyl, triethylene aminoalkyl, glycidyl oxyalkyl, bis-alkoxy silyl alkyl, list or polythioalkane, have 2-20 EO or the polyoxyethylene glycol unitary methyl blocking of PO or hydroxy-end capped or polypropylene glycol, wherein, alkyl is respectively chain, ring-type and/or branch-like, R
1Identical or different and R
1Represent hydrogen or have line style 1-6 carbon atom, preferred 1 or 2 carbon atom and/or ramose alkyl.
17. the described emulsion of claim 13 is characterized in that, has at least a emulsifying agent with the total restatement 0.02-2 of emulsion weight % content.
18. the described emulsion of claim 13 is characterized in that, average droplet size≤0.5 μ m.
19. prepare the method for water-based O/w emulsion, it contains organoalkoxysilane and/or siloxane oligomer with the total restatement 1-70 of emulsion weight %, at least a emulsifying agent and water, this method is passed through these compositions of (i) premix, and with the total restatement of silicoorganic compound, the share of siloxane oligomer 〉=25 weight %, and be that the high pressure of 2-15MPa stirs evenly emulsification in the device (ii) having at least one pressure stage and pressure, make that the width of droplets size distribution is 0.6-1.2, express with the Span value
20. prepare the method for water-based O/w emulsion, it contains organoalkoxysilane and/or siloxane oligomer with the total restatement 1-70 of emulsion weight %, at least a emulsifying agent and water, this method is by these compositions of (i) premix, and with the total restatement of silicoorganic compound, share 5 to＜25 weight % of siloxane oligomer, be that the high pressure of 10-70MPa stirs evenly pre-emulsification in the device (iii) having at least one pressure stage and pressure, and be that the high pressure of 2-15MPa stirs evenly emulsification in the device (iv) having at least one pressure stage and pressure, make that the width of droplets size distribution is 0.6-1.2, express with the Span value
21. the described method in one of claim 19 or 20 is characterized in that the pressure at least one pressure stage is 4-8MPa, is preferably 5-6MPa.
22. the described method in one of claim 19 or 20, it is characterized in that, premix step (i) afterwards, emulsifying step (ii) before, be 10-70MPa having at least one pressure stage and pressure (iii) extraly, the high pressure that is preferably 20-40MPa stirs evenly finishes pre-emulsification in the device, makes average droplet size≤0.5 μ m, the width of droplets size distribution is 0.6-1.2
23. the described method in one of claim 19 or 20 is characterized in that, the emulsification of step in (ii) realized with 2 pressure stages with different pressures.
24. the described method in one of claim 19 or 20 is characterized in that, cooling emulsion when leaving high pressure and stir evenly device.
25. the water-based O/w emulsion, it obtains according to the described method in one of claim 19 or 20.
26. the application on porous mineral matter material of construction hydrophobic treatment of the described water-based emulsion of claim 13.
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| CNA2007101676242A CN101353267A (en) | 2007-07-27 | 2007-07-27 | Aqueous emulsion containing organic silicon compound, preparation and use thereof in surface treatment |
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|---|---|---|---|
| CNA2007101676242A CN101353267A (en) | 2007-07-27 | 2007-07-27 | Aqueous emulsion containing organic silicon compound, preparation and use thereof in surface treatment |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103462243A (en) * | 2013-08-21 | 2013-12-25 | 昆山铁牛衬衫厂 | Waterproof down jacket |
| CN104529528A (en) * | 2015-01-22 | 2015-04-22 | 重庆锦弘建设工程有限公司 | Silane impregnant |
| CN108753159A (en) * | 2018-06-29 | 2018-11-06 | 无锡鸿孚硅业科技有限公司 | A kind of organic silicon emulsion concrete waterproofer and preparation method thereof |
| CN112513151A (en) * | 2018-05-18 | 2021-03-16 | 埃肯有机硅法国有限公司 | Preparation method of porous silicone material |
| CN114249897A (en) * | 2020-09-24 | 2022-03-29 | 深圳市鸿信顺电子材料有限公司 | Impregnation liquid and application thereof in surface treatment process of sheet type element |
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2007
- 2007-07-27 CN CNA2007101676242A patent/CN101353267A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103462243A (en) * | 2013-08-21 | 2013-12-25 | 昆山铁牛衬衫厂 | Waterproof down jacket |
| CN104529528A (en) * | 2015-01-22 | 2015-04-22 | 重庆锦弘建设工程有限公司 | Silane impregnant |
| CN112513151A (en) * | 2018-05-18 | 2021-03-16 | 埃肯有机硅法国有限公司 | Preparation method of porous silicone material |
| CN112513151B (en) * | 2018-05-18 | 2022-12-23 | 埃肯有机硅法国有限公司 | Preparation method of porous silicone material |
| CN108753159A (en) * | 2018-06-29 | 2018-11-06 | 无锡鸿孚硅业科技有限公司 | A kind of organic silicon emulsion concrete waterproofer and preparation method thereof |
| CN114249897A (en) * | 2020-09-24 | 2022-03-29 | 深圳市鸿信顺电子材料有限公司 | Impregnation liquid and application thereof in surface treatment process of sheet type element |
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