NO133502B - - Google Patents
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- NO133502B NO133502B NO216070A NO216070A NO133502B NO 133502 B NO133502 B NO 133502B NO 216070 A NO216070 A NO 216070A NO 216070 A NO216070 A NO 216070A NO 133502 B NO133502 B NO 133502B
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- water
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- zirconium
- organoalkoxysilanes
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 230000007062 hydrolysis Effects 0.000 claims description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229940046892 lead acetate Drugs 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000004821 distillation Methods 0.000 description 9
- MFFVROSEPLMJAP-UHFFFAOYSA-J zirconium(4+);tetraacetate Chemical compound [Zr+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O MFFVROSEPLMJAP-UHFFFAOYSA-J 0.000 description 8
- DOEHJNBEOVLHGL-UHFFFAOYSA-N trichloro(propyl)silane Chemical compound CCC[Si](Cl)(Cl)Cl DOEHJNBEOVLHGL-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000005871 repellent Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000005055 methyl trichlorosilane Substances 0.000 description 4
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- -1 trifluorotolylethyldichlorosilanes Chemical class 0.000 description 3
- 150000003738 xylenes Chemical class 0.000 description 3
- 150000003755 zirconium compounds Chemical class 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-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
- 239000007795 chemical reaction product Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- BYLOHCRAPOSXLY-UHFFFAOYSA-N dichloro(diethyl)silane Chemical compound CC[Si](Cl)(Cl)CC BYLOHCRAPOSXLY-UHFFFAOYSA-N 0.000 description 2
- GNEPOXWQWFSSOU-UHFFFAOYSA-N dichloro-methyl-phenylsilane Chemical compound C[Si](Cl)(Cl)C1=CC=CC=C1 GNEPOXWQWFSSOU-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000011505 plaster Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical class Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- FQEKAFQSVPLXON-UHFFFAOYSA-N butyl(trichloro)silane Chemical compound CCCC[Si](Cl)(Cl)Cl FQEKAFQSVPLXON-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- BGPCFXZWLWDDDU-UHFFFAOYSA-N chloro(propyl)silane Chemical class CCC[SiH2]Cl BGPCFXZWLWDDDU-UHFFFAOYSA-N 0.000 description 1
- OZWCXTBBBIAOAT-UHFFFAOYSA-N chloromethane silane Chemical class [SiH4].ClC OZWCXTBBBIAOAT-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- CVAGYCLEIYGJQT-UHFFFAOYSA-N dichloro(dioctyl)silane Chemical class CCCCCCCC[Si](Cl)(Cl)CCCCCCCC CVAGYCLEIYGJQT-UHFFFAOYSA-N 0.000 description 1
- UOZZKLIPYZQXEP-UHFFFAOYSA-N dichloro(dipropyl)silane Chemical compound CCC[Si](Cl)(Cl)CCC UOZZKLIPYZQXEP-UHFFFAOYSA-N 0.000 description 1
- PNECSTWRDNQOLT-UHFFFAOYSA-N dichloro-ethyl-methylsilane Chemical compound CC[Si](C)(Cl)Cl PNECSTWRDNQOLT-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052806 inorganic carbonate Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000011499 joint compound Substances 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UIDUKLCLJMXFEO-UHFFFAOYSA-N propylsilane Chemical class CCC[SiH3] UIDUKLCLJMXFEO-UHFFFAOYSA-N 0.000 description 1
- 239000005053 propyltrichlorosilane Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- ZOYFEXPFPVDYIS-UHFFFAOYSA-N trichloro(ethyl)silane Chemical compound CC[Si](Cl)(Cl)Cl ZOYFEXPFPVDYIS-UHFFFAOYSA-N 0.000 description 1
- LFXJGGDONSCPOF-UHFFFAOYSA-N trichloro(hexyl)silane Chemical class CCCCCC[Si](Cl)(Cl)Cl LFXJGGDONSCPOF-UHFFFAOYSA-N 0.000 description 1
- PYJJCSYBSYXGQQ-UHFFFAOYSA-N trichloro(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](Cl)(Cl)Cl PYJJCSYBSYXGQQ-UHFFFAOYSA-N 0.000 description 1
- KWDQAHIRKOXFAV-UHFFFAOYSA-N trichloro(pentyl)silane Chemical compound CCCCC[Si](Cl)(Cl)Cl KWDQAHIRKOXFAV-UHFFFAOYSA-N 0.000 description 1
Description
Det er k-jent å anvende organopolysiloxaner, omfattende også "d éi hydrolys a ter av organoalkoxysil-oxaner, som middel for å gjøre overflater av murverk og glass vannavstøtende. Et mål for vann-avstøtende midlers virkning er størrelsen av den kontaktvinkel som en vanndråpe danner med en med midlet behandlet overf-late (jf-f ..eks. W. Noll "Chemie und Technologie der S-ilicone" Weinheim 1968, s.387).. "En rekke av t3e "i handelen forekommende midler for å gjøre overflater vannavstøtende danner imidlertid overraskende -små kontakt-vinkler. It is known to use organopolysiloxanes, including "the hydrolysates of organoalkoxysiloxanes", as a means of making surfaces of masonry and glass water-repellent. A measure of the effect of water-repellent agents is the size of the contact angle that a drop of water forms with a surface treated with the agent (cf-f ..eg. W. Noll "Chemie und Technologie der S-ilicone" Weinheim 1968, p.387).. "A number of t3e "commercially available agents to making surfaces water-repellent, however, forms surprisingly small contact angles.
De ved foreliggende fremgangsmåte fremstilte midler danner derimot spesielt store kontaktvlnkler uten at de overflater som er blitt behandlet med disse midler, mister sin gass- og vanndamp-gjennomslippbarhet. Den vannavstøtning som oppnås ved anvendelse av de ifølge foreliggende fremgangsmåte fremstilte midler,, holder seg selv efter lengre innvirkning av vær og vind. The agents produced by the present method, on the other hand, form particularly large contact angles without the surfaces that have been treated with these agents losing their gas and water vapor permeability. The water repellency achieved by using the agents produced according to the present method is maintained even after prolonged exposure to weather and wind.
Oppfinnelsen angår en fremgangsmåte ved fremstil]ing av midler til hydrofoberrng av overflater, spesielt av murverk og glass, ved delvis hydrolyse av organoal-koxysilaner som "er fremstilt ved omsetning .av The invention relates to a method for the production of agents for hydrophobicizing surfaces, especially of masonry and glass, by partial hydrolysis of organo- oxysilanes which "are produced by the reaction of
JV) organohalegensilaner med den generelle formel R SiX. JV) organohalogen silanes with the general formula R SiX.
, J Tri 4—m hvori R betegner like eller forskjellige, eventuelt substituerte^hyd-rocarbongrupper, X betegner halogen, og m er 1 eller 2, med , J Tri 4—m in which R denotes the same or different, optionally substituted hydrocarbon groups, X denotes halogen, and m is 1 or 2, with
B) énverdige alkoholer, B) monohydric alcohols,
og f remgangsmåten er--særpreget ved at den delvise hydrolyse -ut-føres ved tilsetning av den beregnede vannmengde efter at organoalkoxysilanene er blitt underkastet en 1-10 timers oppvarming under, tilbakeløp med zirkonium- og/eller ±>lyacetat i en mengde tilsvarende 0,25-4,5% metall,-basert på -vekten av organoalkoxysilanene, .idet disse er beregnet som organohalogensilaner. and the method is characterized by the fact that the partial hydrolysis is carried out by adding the calculated amount of water after the organo-alkoxysilanes have been subjected to heating for 1-10 hours under reflux with zirconium and/or lyoacetate in an amount corresponding to 0.25-4.5% metal,-based on the weight of the organo-alkoxysilanes, since these are calculated as organohalosilanes.
Fra US patentskrift nr. 3474069 er det riktignok kjent å hydrolysere organoalkoxysilaner efter forutgående oppvarming med en zirkoniumforbindelse (eksempel 3). De fremstilte, delvis hydrolyserte produkter ble bl.a. anvendt til fremstilling av fleksible belegg. Det kan imidlertid ikke utledes fra patent-skriftet at disse belegg virker vannavstøtende. Dessuten anvendes bare zirkoniumforbindelser som alkoxyder og slike organiske salter som danner chelater. From US patent no. 3474069, it is admittedly known to hydrolyze organo-alkoxysilanes after prior heating with a zirconium compound (example 3). The produced, partially hydrolysed products were, among other things, used for the production of flexible coatings. However, it cannot be inferred from the patent that these coatings are water-repellent. Moreover, only zirconium compounds such as alkoxides and such organic salts which form chelates are used.
Eksempler på organohalogensilaner som anvendes som ut-gangsmaterialer ved fremgangsmåten ifølge oppfinnelsen, er methyltriklorsilan, ethyltriklorsilan, propyltriklorsilan, dimethyldiklorsilan, ethylmethyldiklorsilan, butyltriklorsilan, amyltriklor-silan, hexyltriklorsilaner, octyltriklorsilaner, diethyldiklorsilan, dibutyldiklorsilaner, dihexyldiklorsilaner, dioctyldiklorsilaner, dipropyldiklorsilaner, fenyltriklorsilan, fenylmethyldiklorsilån, octylmethyldiklorsilaner, stearyltriklorsilan, klorfenylmethyldi-klorsilaner, trifluortolylethyldiklorsilaner og blandinger av to eller flere av disse silaner. Examples of organohalosilanes that are used as starting materials in the method according to the invention are methyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane, dimethyldichlorosilane, ethylmethyldichlorosilane, butyltrichlorosilane, amyltrichlorosilane, hexyltrichlorosilanes, octyltrichlorosilanes, diethyldichlorosilane, dibutyldichlorosilanes, dihexyldichlorosilanes, dioctyldichlorosilanes, dipropyldichlorosilane, phenylmethyldichlorosilane, phenylmethyldichlorosilane, , stearyltrichlorosilane, chlorophenylmethyldichlorosilanes, trifluorotolylethyldichlorosilanes and mixtures of two or more of these silanes.
Den gjenværende destillasjonsrest efter at methylklbrsilanene er blitt destillert av fra produktene dannet ved omsetning av silicium med methylklorid, kan også anvendes for omsetning med■ aikanoler. På samme måte kan den destillasjonsrest med et kokepunkt over 142°C som blir igjen efter at n-propyltriklorsilan er blitt destillert av fra de ved fremstillingen av propylklorsilaner dannede produkter, anvendes. The remaining distillation residue after the methyl chloride silanes have been distilled off from the products formed by reaction of silicon with methyl chloride can also be used for reaction with aicanols. In the same way, the distillation residue with a boiling point above 142°C that remains after n-propyltrichlorosilane has been distilled off from the products formed during the production of propylchlorosilanes can be used.
Ifølge en foretrukken utførelsesform a-v oppfinnelsen anvendes blandinger av organohalogensilaner, og spesielt av methyltriklorsilan, dimethyldiklorsilan og n-propyltriklorsilan, for fremstillingen av organoalkoxysilanene. Forholdet mellom organohalogensilanene i disse blandinger er ikke av avgjørende betydning, men molforholdet mellom organotrihalogensilan og organodihalogensilan bør fortrinnsvis være minst 2:1, og helst 3:1-4:1. Det foretrekkes spesielt å.anvende en blanding av methyltriklorsilan, dimethyl-triklorsilan og n-propyltriklorsilan i et molforhold av 3:1:1. Dersom n-propyltriklorsilanet i disse blandinger erstattes med den destillasjonsrest med et kokepunkt over 142°C som blir igjen efter at n-propyltriklorsilan er blitt destillertav fra de ved fremstillingen av propylsilaner dannede produkter, bør forholdet mellom propylgruppene og de andre organiske grupper være-1:1-1:10, fortrinnsvis 1:5. According to a preferred embodiment of the invention, mixtures of organohalosilanes, and in particular of methyltrichlorosilane, dimethyldichlorosilane and n-propyltrichlorosilane, are used for the preparation of the organoalkoxysilanes. The ratio between the organohalosilanes in these mixtures is not of decisive importance, but the molar ratio between organotrihalosilane and organodihalosilane should preferably be at least 2:1, and preferably 3:1-4:1. It is particularly preferred to use a mixture of methyltrichlorosilane, dimethyltrichlorosilane and n-propyltrichlorosilane in a molar ratio of 3:1:1. If the n-propyltrichlorosilane in these mixtures is replaced by the distillation residue with a boiling point above 142°C that remains after n-propyltrichlorosilane has been distilled from the products formed during the production of propylsilanes, the ratio between the propyl groups and the other organic groups should be -1 :1-1:10, preferably 1:5.
Eksempler på énverdige "alkoholer som alkoxygruppene-i de ifølge oppfinnelsen anvendte organoalkoxy.silaner er avledet fra,, er spesielt de primære og sekundære alkoholer med 1-4 carbonatomer, som methanol, ethanol og isopropanol. Examples of monohydric "alcohols" from which the alkoxy groups in the organoalkyl silanes used according to the invention are derived are, in particular, the primary and secondary alcohols with 1-4 carbon atoms, such as methanol, ethanol and isopropanol.
Omsetningen -av organohalogensilanene-med alkoholene kan -på kjent måte utføres ved en temperatur av 0-50°C. Den utføres fortrinnsvis i et organisk oppløsningsmiddel, og spesielt i ._et aromatisk oppløsningsmiddel som benzen, toluen eller xylener. Ved denne omsetning omdannes organohalogensilanene til organoalkoxysilaner under avspaltning av nydrogenhalogenid. Efter omsetningen økes temperaturen -for å fjerne uomsatt alkohol og en -del av Jaydro-gennalogenidet-Resten av hydrogenhalogen-idet kan fjernes eller minskes raéngdemessig ved å biatfde organoalkoxysilanene med et egnet basisk materiale. For-denne nøytralisering-kan f.eks. alkaTlmetailalkoholater som natriummethylat, alkalimetallhydroxyder som -na triumhydroxyd., uorganiske carbonater som natrr-umcarbonat-og kalsi-umca-rbonat, og bioarboriater -som natriumbicarbonat., -anvendes^ The reaction - of the organohalosilanes - with the alcohols can - in a known manner - be carried out at a temperature of 0-50°C. It is preferably carried out in an organic solvent, and in particular in an aromatic solvent such as benzene, toluene or xylenes. In this reaction, the organohalogenosilanes are converted into organoalkoxysilanes during the elimination of nitrogen halide. After the reaction, the temperature is increased - to remove unreacted alcohol and a - part of the Jaydro gen halide - The rest of the hydrogen halide can be removed or reduced to a certain extent by reacting the organo-alkoxysilanes with a suitable basic material. For-this neutralization-can e.g. alkali metal alcoholates such as sodium methylate, alkali metal hydroxides such as sodium hydroxide, inorganic carbonates such as sodium carbonate and calcium carbonate, and bioarboriates such as sodium bicarbonate are used
"Tiet -ifølge oppfinnelsen anvendte zirkonium og/eller bly-, aoetat anvendes i .en mengde av 0-, 25-4., 5 vekt%, fortrinnsvis "The zirconium and/or lead acetate used according to the invention is used in an amount of 0-, 25-4., 5% by weight, preferably
<L,"3-3 vekti;, hvert-beregnet som .metall og basert på vekten av organoa-l-koxysilanene., beregnet som de for fremstilling -av organoalkoxysilanene anvendte organohalogensilaner . Oppløsn-inger med et innhold av inntil .3 vekt% zirkoniumtetraacetat, beregnet og basert som angitt ovenfor., kan lagres i minst 6 måneder ved værelse-temperatur -uten at-de gelerær.^Høyere zirkoniumkonsentras joner <L,3-3 by weight, each calculated as metal and based on the weight of the organo-l-oxysilanes, calculated as the organohalosilanes used for the production of the organo-alkoxysilanes. Solutions with a content of up to .3 weight % zirconium tetraacetate, calculated and based as indicated above., can be stored for at least 6 months at room temperature -without them gelling.^Higher zirconium concentrations ions
gir ennu større kontaktvinkler- provides even greater contact angles-
-For å påskynde omsetningen av organoalkoxysilanene med zirkonium-og/eller blyacetat-oppvarmes blandingene av -reaksjons-deltagerne i 1-10^ti-mer, -fortrinnsvis 1-6 -timer, og helst 1-2 timer,'under tilbakeløpsdestiller ing. -Som regel anvendes .derved islandingen av reaksjohsdeltagerne i det forekommende oppløsnings-middel for fremstillingen av alkoxysilånene. - In order to speed up the reaction of the organoalkoxysilanes with zirconium and/or lead acetate, the mixtures of the reaction participants are heated for 1-10 hours, preferably 1-6 hours, and most preferably 1-2 hours, under reflux distillation . - As a rule, the isolation of the reaction participants in the occurring solvent is used for the production of the alkoxysilanes.
For den delvise -hydrolyse anvendes fortrinnsvis så meget vann at 50-80% av de Si-bundne-alkoxygrupper blir hydrolysert. For the partial hydrolysis, so much water is preferably used that 50-80% of the Si-bonded alkoxy groups are hydrolysed.
-Ved beregningen av den for den delvise hydrolyse anvendte vann- -When calculating the water used for the partial hydrolysis-
mengde må den eventuelt dannede vannmengde ved nøytraliseringen av hydrogenhalogenid med f.eks. natriumbicarbonat eller natrium-hydroxyd også tas i betraktning. Dette skyldes at en' hydrolyse av mer enn 8 5% av alkoxygruppene kan føre til geldanrielse. Ifølge en forétrukken utførelsesform av oppfinnelsen oppvarmes blandingen av reaksjonsproduktet av organoalkoxysilaner med zirkonium-og/eller blyacetat, oppløsningsmiddel og vann i 1-6 timer under tilbakeløpsdestillering. amount, the possibly formed amount of water during the neutralization of hydrogen halide with e.g. sodium bicarbonate or sodium hydroxide are also taken into account. This is because a hydrolysis of more than 85% of the alkoxy groups can lead to gelation. According to a preferred embodiment of the invention, the mixture of the reaction product of organoalkoxysilanes with zirconium and/or lead acetate, solvent and water is heated for 1-6 hours during reflux distillation.
Efter den délvise hydrolyse kan den derved frigjorte alkohol fjernes på'kjent måte, f.eks. ved fraksjonert destillasjon. En organbpolysiloxanharpiks som for det meste er" oppløst, blir'tilbake. After partial hydrolysis, the alcohol released thereby can be removed in a known manner, e.g. by fractional distillation. An organopolysiloxane resin that is mostly dissolved is left behind.
De ved foreliggende fremgangsmåte fremstilte midler kan på The means produced by the present method can be applied
en hvilken som helst egnet måte påføres på de overflater som skal gjøres vannavstøtende.. Fortrinnsvis påføres de i form av en fortynnet oppløsning i et organisk oppløsningsmiddel.. Oppløsnings-midlet bør være tilstrekkelig flyktig til at det vil fordampe under vanlige atomsfæriske betingelser, dvs. at det bør~ha et kokepunkt under 200°C/760 mmHg (abs.). Eksempler på foretrukne oppløsningsmidler er toluen, xylener, benzen, iigroin og lavt-kokende hydrocarboner og halogenerte hydrocarboner, spesielt klor-hydrocarbone-r. Oppløsningene bør inneholde 4-20 vekt%, fortrinnsvis 5-8 vekt%, basert på vekten av oppløsningene, av det delvis hydrolyserte reaksjonsprodukt. De kan påføres på de overflater som skal gjøres vannavstøtende ved 'f.eks. neddykkihg, sprøyting eller stryking, og efter fordampning åv oppløsningsmidlet "blir det tilbake en tynn harpiksfilm. any suitable way is applied to the surfaces to be made water repellent.. Preferably they are applied in the form of a dilute solution in an organic solvent.. The solvent should be sufficiently volatile that it will evaporate under normal atomic conditions, i.e. that it should have a boiling point below 200°C/760 mmHg (abs.). Examples of preferred solvents are toluene, xylenes, benzene, hydrogen and low-boiling hydrocarbons and halogenated hydrocarbons, especially chlorinated hydrocarbons. The solutions should contain 4-20% by weight, preferably 5-8% by weight, based on the weight of the solutions, of the partially hydrolyzed reaction product. They can be applied to the surfaces to be made water-repellent by 'e.g. immersion, spraying or ironing, and after evaporation of the solvent, a thin resin film remains.
Uttrykket "murverk" omfatter formede gjenstander av sten, mørtel, puss, brent leire eller slam, betong og gips og overtrekk av de ovenfor angitte med vann hydraulisk og ikke-hydraulisk herdede materialer før eller efter oppføring av byggverk. The term "masonry" includes shaped objects of stone, mortar, plaster, burnt clay or mud, concrete and plaster and coatings of the above-mentioned water-hydraulic and non-hydraulic hardened materials before or after construction.
De i eksemplene angitte deler og. prosenter er basert på vekt dersom intet annet er angitt. The parts specified in the examples and. percentages are based on weight unless otherwise stated.
Eksempel 1 Example 1
(a) 84,9 deler vannfri methanol ble satt til en blanding av 89,7 deler methyltriklorsilan, 25,8 deler dimethyldiklorsilan og 35,5 deler n-propyltriklorsilan i 175 deler av den i handelen (a) 84.9 parts of anhydrous methanol were added to a mixture of 89.7 parts of methyltrichlorosilane, 25.8 parts of dimethyldichlorosilane and 35.5 parts of n-propyltrichlorosilane in 175 parts of the commercial
vanlige blanding av de tre xylenisomerer, og blandingen ble oppvarmet i 4 timer under tilbakeløpsdestillering og derefter avkjølt til ca. 25 C. Blandingen ble nøytralisert ved dråpevis tilsetning av ca. 66 deler av en 25% natriummethylatoppløsning i methanol slik at et indikatorpapir viste at en prøve hadde en pH av 4,0-4,5. Reaksjonsblandingen ble filtrert, hvorved det ble oppnådd et farve-løst, klart filtrat. usual mixture of the three xylene isomers, and the mixture was heated for 4 hours under reflux distillation and then cooled to approx. 25 C. The mixture was neutralized by the dropwise addition of approx. 66 parts of a 25% sodium methylate solution in methanol so that an indicator paper showed that a sample had a pH of 4.0-4.5. The reaction mixture was filtered, whereby a colorless, clear filtrate was obtained.
2,5 deler zirkoniumtetraacetat ble satt til filtratet under omrøring, og blandingen ble oppvarmet i 2 timer under tilbakeløps-destillering og avkjølt til 55°C, hvorefter 15,1 deler vann ble tilsatt og blandingen på ny oppvarmet i 2 timer til ca. 7 0°C under tilbakeløpsdestillering, hvorefter den ved hydrolyse dannede methylalkohol ble destillert av. Resten ble filtrert, hvorved det som filtrat ble oppnådd en klar og farveløs organopolysiloxan-harpiksoppløsning. 2.5 parts of zirconium tetraacetate were added to the filtrate with stirring, and the mixture was heated for 2 hours under reflux distillation and cooled to 55°C, after which 15.1 parts of water were added and the mixture was reheated for 2 hours to approx. 7 0°C under reflux distillation, after which the methyl alcohol formed by hydrolysis was distilled off. The residue was filtered, whereby a clear and colorless organopolysiloxane resin solution was obtained as filtrate.
Denne oppløsning ble fortynnet med ligroin inntil 5 vekt% harpiksbestanddeler og anbragt på på forhånd rensede glassplater som derefter ble lagret i 48 timer ved 21-32°C og en relativ luft-fuktighet av 50-90% . En vanndråpe ble derefter anbragt på den behandlede overflate på en vannrett flate av glassplatene,og den dannede kontaktvinkel ble målt ved anvendelse av et katetometer og et lite vinkelmåleapparat. (b) De under (a) angitte trekk ble gjentatt, men med den forandring at 5,15 deler zirkoniumtetraacetat ble anvendt istedenfor 2,5 deler. (c) De under (a) angitte trekk ble gjentatt, men med den forandring at 10,3 deler zirkoniumtetraacetat ble anvendt istedenfor 2,5 deler...... (V-^) For sammenlignings skyld ble de under (a) angitte trekk gjentatt, men med den forandring at intet zirkoniumtetraacetat ble anvendt. (V?) For ytterligere sammenligning ble de under (a) angitte trekk gjentatt, men med den forandring at ingen zirkoniumforbindelse ble tilsatt før hydrolysen av alkoxysilanene, men efter hydrolysen og før fortynningen med ligroin ble imidlertid 10,3 deler zirkoniumtetraacetat satt til hydrolysatet som derefter ble oppvarmet i 2 timer under tilbakeløpsdestillering. Resultatene er gjengitt i den følgende tabell: This solution was diluted with ligroin up to 5% by weight of resin components and placed on previously cleaned glass plates which were then stored for 48 hours at 21-32°C and a relative air humidity of 50-90%. A drop of water was then placed on the treated surface on a horizontal plane of the glass plates, and the contact angle formed was measured using a catheter and a small angle measuring device. (b) The steps indicated under (a) were repeated, but with the change that 5.15 parts of zirconium tetraacetate were used instead of 2.5 parts. (c) The steps indicated under (a) were repeated, but with the change that 10.3 parts of zirconium tetraacetate were used instead of 2.5 parts... (V-^) For the sake of comparison, those under (a) were stated feature repeated, but with the change that no zirconium tetraacetate was used. (V?) For further comparison, the steps indicated under (a) were repeated, but with the change that no zirconium compound was added before the hydrolysis of the alkoxysilanes, but after the hydrolysis and before the dilution with ligroin, however, 10.3 parts of zirconium tetraacetate were added to the hydrolyzate which then was heated for 2 hours under reflux distillation. The results are reproduced in the following table:
Eksempel 2 Example 2
-Cen .i eksempel 1 under =<a) angitte fremgangsmåte ble gjentatt, men med den -forandring at 20 deler zirkoniumtetraacetat ble anvendt.istedenfor 2,5-deler. -Kønta-kivinkelen mellom en vann-, dråpe og -glassplatene var større enn 1_00°-. - The procedure stated in example 1 under =<a) was repeated, but with the change that 20 parts of zirconium tetraacetate were used instead of 2.5 parts. -The Kønta-ki angle between a water, drop and -glass plates was greater than 1_00°-.
Eksempel 3 Example 3
^Betongterninger "ble -neddykket i 30 sekunder i en 5% ligroin-oppløsning fremstilt-som angitt vi eksempel 1 (c) , og-lagret i 48 timer ved 21-3"2°C~og en relativ-fuktighet av 5T)-90%. Kontaktvinkelen var ^Concrete cubes "were -immersed for 30 seconds in a 5% ligroin solution prepared -as indicated in Example 1 (c) , and -stored for 48 hours at 21-3"2°C~and a relative humidity of 5T) -90%. The contact angle was
For sammenlignings skyld -ble -betongterninger neddykket i den ~5% ligroinoppløsning-ifølge eksempel 1 (V^) . Kontaktvinkelen var .113 . For the sake of comparison, concrete cubes were immersed in the ~5% ligroin solution according to example 1 (V^). The contact angle was .113 .
Eksempel -. 4 Example -. 4
De i-eksempel .1 -{ a) angitte trekk ble gjentatt, men med den forandring, at 5 deler -blyacetat ble anvendt istedenfor 2.-,-5 deler zirkoniumtetraacetat. Betongterninger ble behandlet i den derved dannede oppløsning som .beskrevet i eksempel 2. Kontaktvinkelen var 125°. The features indicated in Example 1 -{a) were repeated, but with the change that 5 parts of lead acetate were used instead of 2.-,-5 parts of zirconium tetraacetate. Concrete cubes were treated in the resulting solution as described in example 2. The contact angle was 125°.
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Publication number | Priority date | Publication date | Assignee | Title |
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DK151380B (en) * | 1972-12-01 | 1987-11-30 | Dynamit Nobel Ag | PROCEDURES FOR IMPROVING WALLS |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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DK151380B (en) * | 1972-12-01 | 1987-11-30 | Dynamit Nobel Ag | PROCEDURES FOR IMPROVING WALLS |
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