CA1067090A - Process for the esterification of chlorosilanes - Google Patents
Process for the esterification of chlorosilanesInfo
- Publication number
- CA1067090A CA1067090A CA257,515A CA257515A CA1067090A CA 1067090 A CA1067090 A CA 1067090A CA 257515 A CA257515 A CA 257515A CA 1067090 A CA1067090 A CA 1067090A
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- CA
- Canada
- Prior art keywords
- reaction
- mol
- ilane
- alcohols
- esterification
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
Abstract
ABSTRACT OF THE DISCLOSURE :
The present invention relates to a process for the esterification of halosilanes by reaction with alcohols, characterized in that the reaction takes place in the presence of chlorohydrocarbons and in the absence of acid-binding means.
The alcohols are selected from the group consisting of primary or secondary alcohols and phenols. Several organosilaneesters are used as building preservative agents. A number of other organosilaneesters and hydrogensilane esters have increasing technical importance for the synthesis of very valuable organo-functional silanes,
The present invention relates to a process for the esterification of halosilanes by reaction with alcohols, characterized in that the reaction takes place in the presence of chlorohydrocarbons and in the absence of acid-binding means.
The alcohols are selected from the group consisting of primary or secondary alcohols and phenols. Several organosilaneesters are used as building preservative agents. A number of other organosilaneesters and hydrogensilane esters have increasing technical importance for the synthesis of very valuable organo-functional silanes,
Description
~067090 The ob~ect o~ the pre~ent i~vention is ~ proces~ for the manufa~ture of alkoxy~ila~es by esterlfi¢ation of ohloro-~ilanes with alcohols.
~he esteriflcation of chlorosilanes generally takes place according to the following reactionS,equation:
Rm SiC14 ~ n R'OH ~ ~ Si(ORl)nC14_m ~ n HCl.
In this equation R' ~tands for an alkyl radical with 1 to 11 C-atoms, m can take on values between O and 3 and n value~ between 1 and 4. R ~tands for H or an alkyl radi¢al with 1-11 C-atom~.
~he practical carrying out of this reaction causes difficultie~, because the hydrochloric acid thereby re~ulting in ~reat quantity dissociat~s not only the al~oxy group to alGohol and chloro~ilane~ but also (especially in the presence of alkanol) the hydrogensilane bo.nd with the by-productio~ of hydrogen and formation of an alkoxysilane- and chlorosilane bond. Furthermore the hydrochloric a¢id form~ with the added ~lkanols, chloro~lkanes and ~ntermedlary water, which in it~ turn affects the chlorosilane and alkoxy~llane by hydrolysi~. Because of th~ side reaction, if certain process conditions are not observed, the desired silane e~ter i~ mostly lost ¢ompletely.
Therefore several attempts have already bee~ made to produce compounds of this klnd as economically as possible. The problems, originally associated with the batch proces~es, of the condensate formation a3 a re~ult of the mentioned s1de reactions of the escaping h~drochloric acid with the aloohol~
introduced for the esterification, can indeed be avoided to a ~ large extent by u~ing modern batch method~. However there are -~ limits to its tran~er to the field of large scale i~dustry, e~pecially because o~ the dif~icult oontrol of the large amounts 3 of hydrochlori¢ acid in combi~ation with base materials which if ~ece~sary have low boil~ points, and of the quick and high heat tranæfers necessary for the reliable carrying out of the ~ 067090 reaction not only in the reaction space but al90 in the e~haust ga3 .
Continuous proce~se3 have already been suggested, in which chloro~ilanesl iD fluid phase, are e~terified either i~ a reactor with overflow, borrowed from the simplest batch proce~s, or in several reactors conneeted in ~eries according to the method of the ¢ounter- n ow principle. However, thi~ method haY the dlsad~antage that the hydrochlorio acid is too 810wly and in-completely removed. That leads to reverse dissociatioD~ of alread~
10 present ester groups and side reactions between the alcohols and the hydrochlori¢ acid, with uDdesired hydrolysate ~o~matio~.
Another process describes the esterlfication of chloro~ilane~
with al¢ohol~ in the gas phase and utiliee~ temperatures, which are above the boiling poiDts of all the sub~tanoe~ ¢oncerned (base aDd end products).
~ he latterly mentioned pro¢ess however has a quite particular disadvantage, because the hydrochloric acia present in the system ls induced, as a result of the raised temperature, to a particularly fast ~tart Or the known sid~ reaction~, in particular therefore, re~ers~ dissociation, alcohol-dehydration and hydrolysate formation.
~ he particular weaknesses of all the continuous e~ter-ification processes described abo~e i8 that the ~eparation of the hydrochloric acid from the reaction mixture is too slow and lncomplete. It has also beeD sugge~ted that the hydrochloric acid be blown out by the pas~ing over or through o~ inert gases for example nitrogen, If neces~ary with the aid of a falling ff lm evaporator, whereby an upper temperature limit may not be exceeded. ~hi8 technique however also ha~ the considerable disadvantage that the volume of exhaust ga~ from the hydrochloric a¢id i~ lDcrea~ed; in thi~ way the los~es by e~aporation determin-ed by the partial pressure of the products i9 unJu~tifiably high, and re-~ing the hydroohlori¢ a¢id i~ praotically ruled out.
Furthermore, with thi~ operation, powerful ¢ooling ~
device~ are required to reduce the e~cape of produot~ through inert gas flow; in additio~ e~tremely dry gase~ are a requi~ite for a method of this kiDd, a~ otherwise increa~ed siloxane formation occur~.
It i~ al~o known to increa~e the exit velocity of the hydrogen halide out of the reaction medium during the e~teri~ica-tion proces~ by the introductio~ of benzol or benzlne ~olvents : to the halogen ~lane, in order thus to reduce the above-mentlo~ed formation of siloxanes. De~pite these mea~ures, not inconsider-abls re~idue aciditie~ are left behind in the reaction product, with the~e method~, which mu~t be eliminated as salts by the addition of acid-binding means. ~his introduces the disadvantage Or additional operatio~ proce~es such a~ filtration~ o~ the raw ester and wa~hing out the salt~ for reducing the y~eld los~es.
Also the e~terification Or ¢hlorosilanes with aloohols ln the prese~Gs of ¢hlorohydrocarbo~s is de~cribed, whereby the introduction of textiary-aleoholic component~ i8 effected in the presence of ami~es. However with thi~ method large amount~ of : salt al~o oc¢ur, which must be remo~ed by additional process ~tep~ for thair reprocessing.
Now a process for the s~terification of ¢hlorosilane~
has been found, which 1~ characteri~ed in that the conYersion takes place i~ the presence o~ chlorohydrocarbons and in the absence of acid-binding mean3. These ~easure~ lead to a greater simplificatioD of the proce~ and to an unexpected yield iDcrease.
~hi~ is true not only ~or primary but al80 for ~econdary aloohol3 and phenols.
Tha reaction take~ place in ac¢ordance w$th the aboYe-~entioned equation. Suitable base material~ of the geDeral 1067~90 formula ~SiC14 m are for example triohloro~ilane, tetra¢hloro-~ilan~, methyldichloros~lane, trimethylchlorosllane, methyl-trichloro~ ne, ethyltrlchloro~llane, ethyldichlora~ilane, n-propyldichloro~ilane, propyltrichloro~ilane, i~obutyldichloro-silaDe, vinyldichloro~ilane, vinyltri¢hlorosilane, vinylmethyl-dichlorosilane, dimethyldlchloro3ilane, propenyltrichloro~ilane, allyltrichloro~ilane, 3-chloropropytrichlorosllane and ma~y others. It appears from thi~ that R may ~tand not only for ~atu-rated and unsaturated alkyl radicals with up to 11, preferably up to 6 C-atom3, but al80 for hydrogen. The alkyl radical~ may al80 be different, a~ for example ln the methylethyldlchloro~ilane or methylphenyldichloro3ilane. Al~o phenyltrichloro~ilane may be sub~tituted. ~he radical R may al80 be ~ub~tituted by halogen, as for example in the chloropropyltrichloro~ilane, chloroethyl-trichloro~ilane, to the methylchlorethyltrichloro~ilane or CF3-CH2-SiC13 or al~o CF3-CH~-O-(CH2)3-SiC13.
Simple aliphati¢ alcohol3 such as for example methanol, ethanol, n-propanol, ~-butanol, octanol come into consideration as alcohol~ of the general formula R~OH for the production of the silane esters, but al~o for example 2-methoxyethanol, 2-ethoxy-etbaDol, tetrah~drofurfuryl al¢ohol, 2-methoxyathyldiethyleneglycol ether or polyethyleneglycolmonoether.
The radi¢al R~ may therefore be a linear-chain or cyclic alkyl radi¢al which is interrupted by heteroatoms such as -O- or -~-. The corresponding ~e~ondary alcohols or phe~ols or mixed aromaticaliphatic alcohol~, such as for example benzyl alcohol, may al80 be introduced.
Compound~ ~uch as carbon tetrachloride, chloroform, methylene chloride, dichloro ethane, dichloro ethylene, 1,1,1-trichloroethane, trichloroeth~l~ne, perchloroethyle.ne, tetra-chloroetbylene, tetrachloroethane can be considered as chloro-hydrocarbons wh~ch may be u~ed.
1067~:190 The chlorohydrooarbon~ w ed should be fluid under normal conditions, and have boiling pointa below 150. The number of C-atom~ i~ preferably 1-3; the hydrocarbon radical maJ not only be ~aturated but ~180 unsaturated.
The ratio of chlorosilanes to chlorohydrocarbon during the esterificatioD may vary wi~hin wlde limit~, mostly a ratio chlorosilane/chlorohydrocarbon of 1/0.5-1 i8 sufncient for a¢hie~ing neutral end products and maximum ~ields.
~ he amount of chlorohydrooarbons may be 0.5-3 times as much as the halosilane added during the e3terification.
For example, ac¢ording to the invertion the following product~ are obtalned: trimethoxysilane, triethoxysilane, tetraethoxysllane, tris-2-methoxyethoxysilane, tetra-2-methoxy-etho~ysilanes, methyldimethoYysilane, methyldiethoxysilane, vlnylmethyldiethoxy~ilane, methyltriethoxysilane, ~inyltrieohoxy-~ilane, ~inyltri-2-methoxyethoxysilane, 3-chloropropyltriethoxy-~ilane and many others.
~ he oarrying out of the eoterification take~ pla¢e a¢cordlng to generally known method~ of e~terification. Prefer-; 20 ably, the chlorosilane i~ prepared with the chlorohydrocarbonand the alcohol 18 add~d i~ Bmall amount~ to the warmed mixture.
The amount of the alcohol to be added is dete i ned according to the d~sired de OE ee o~ esterification. Tha reactlon is prefer-ably e~fected at the boiling temperature of the silane/¢hlorohydro-carbon mi~ture. A~ter separation o~ the solvent, preferably by - distlllatloD, the de~ired e~ter i8 obtained with yields of up to 99% with ~ery high purity.
A number of the mentioned e~ter compound8 of silicon have acquired increaslng technlcal importance. For example some 9ilicic a¢id orthoe~ters are u~ed a~ binders for zinc du~t paint~
and in foundry proce~se~. Several organosilanee~ters are used as bullding preservative agent~. A number of other organo~ilane-~1~67090 esters and hydrogensilane ester~ have increasing technioalimportance for the ~ynthe3is of ~ery valuable organofunctional silanes. ~urthermore, hydroge~silane esters are al~o of intere~t ~or semi-cQnductor chemistry.
EX~MPLE 1:
A 6-litre thre~-necked flask is placed in a mu~hroom-~haped heating ~acket and i9 provided with a stirrer? a reflux conden~or and a separati~g funnel.
1060 g (5 Mol) ~ - chloropropyltrichlorosllane i9 put into the flask; after heating the fluid to 80, 930g (15.5 Mol) n-propanol is added in amounts of 20 ml each, with ~trong agitation. After 4.5 hours the addition i~ ~topped. It is heated agal~ at 90 for a further 4 hours and then the raw produ¢t i8 distllled of~
in ~acuum (1-2 Torr - 101G). 1015 g (72%) of a colourless produot 18 obtained. When one ml is pour~d into 100 ml wat~r, wlth added indicator (methylorange), th~re is a strong acidic reactlon.
EXAMPLE 2:
Apparatus identlcal to example 1, zO 1060 g (5 Mol) ~-chloropropyltrichlorosilane i~ put in the flask together with 900 ~1 tri¢hloroeth~lene. ~he cour~e of ester-ification (15.5 Mol n-propanol) takes place as described in example 1. ~fter removing the trichloroethylene by dist~llatioD, a proportion of 98~ ~ -chloropropyl-tri-(propoxy)-silane i~
determined ga~chromatographically in the fluid in the flask.
When the ester i~ poured into water with added indicator (methylorange) as in example 1, a ncutr~l reaction i~ reglstered.
EXAMP~E 3:
Apparatu~ identical to example 1, 1060 g (5 Mol)~ -ohloropropyltrichloro~ila~e i~ put;in the flask with 900 ml carbo~ tetrachloride. The cour~e of the ester-ifioation (15.5 Mol n-propanol) takes place as described in 1a)67090 example 1 (reflux boiling o~ the ¢arbon tetrachloride). ~fter the carbon tetrachlorlde has been removed by di~tillation! a proportlon of 97.5% chloropropyltrlpropoxysilane i8 determined gaschromatographic~lly in the product. A neutral reactlon 18 indicated when it i9 poured into water (with added methylorange).
EXAMP~E 4:
1060 g (5 m) ~-chloropropyltrichlorosilane is put in the flask together with 2.7 1 trichloroethylene. The cour~e of ester-ificatlon (15.5 Mol n-propanol) take~ pla¢e as described in example 1. After the trichloroethylene i8 remo~ed by distillation, a proportion o~ 98.6% ¢hloropropyltripropoxysilane i8 gaschromato-graphi¢ally determined in the n a~X product. A neutral rea¢tion is indicated ~hen the ester is poured into water (with added ethylorange).
EXAMPLE 5:
; Apparatus identical to ~xample 1, ~ 785 g (5 Mol diethyldichloro~ilane) i~ put in the flask. The ; esterification process(l5.g Mol n-propanol) takes place as desGribed in example 1. ~he raw ester i8 distllled of~ in ~acuum (20 Torr (60). 725 g (71~) of a colourless product is obtained, `~ which, as in example 1, ~hows a strongl~ acidic reaction when added to water (containing methylorange).
EXAMPIE 6:
Apparatu~ identlcal to example 1, 785 g (5 Mol) diethyldichlorosilane i8 put in the flas~ together with 2 1 tetrachloroethylene. ~he esterification (15.5 Mol n-propanol) takes place as described in example 1. After the tetrachloroethylene ha~ been removed by distillation, the flask contents are analyzed gaschromatographically. A proportion of 97.2% diethyldlpropoxysilane is determined. When this i~ poured into water (with added methylorange) a neutral reaction is indicated.
~` 1067090 EXAMPLE 7:
Apparatus identical to example lf 745 g (~ Mol) methyltrichlorosilane ls put in the flask and i8 e~terified with 1680 g (15.5 Mol) benzyl alcohol as described in example 1 (8tarting temperature: 60C; raised to 80-85C towards the end of the addition of alcohol). ~he esterification product i~ distilled off in vacuum (1-2 Torr, 120C). 1410 g of a colourle~s fluid (72%) i8 obtained, whi¢h, when added to:~ater (containing methylorange), produce~ a ~trongly acidi¢ reaction.
EXAMP~E 8:
Apparatus identical to example 1, 745 g (5 Mol) methyltrichlorosilane is put in the flask together with 1900 ml tetrachloroethane and i~ esterified with 1680 g (15.5 Mol) ben~yl alcohol as described in example 1. After the removal of the chlorohydrocarbon by di~tillation, the flask -contents are analyzed easchromatographically and a proportion of 98% methyltrlbenzyloxysilane is found. The vacuum-distilled processing of the fla~k contents re~ults in 1750 g of a colourles~
~luid (96.5%), which when it i9 poured lnto water (with added methylorange) give~ a neutral reaction.
EXAMPLE 9:
Apparatw identicPl to e2ample 1, ; 1060 g (5 Mol)~'-chloropropyltriohlorosilane is put in a flask together with 1900 ml trichloroethylene and is e~terifled, as de~cribed iD example 1, with 906 g (15,5 Mol) isopropanol.
After the removal of the trichloroethylene by distillatlon, a proportion Or 97.8% chloropropyltrii30propo~y~ilane is found gaschromatographioally i~ the flask fluid, A neutral reaction is~hown when it i~ poured into water (with added methylorange), EXAMPIE 10:
Apparatu~ identical to example 1, 815 g (5 ~ol) ethyltrichloro6ilane i~ put in the flask. ~he ~067090 esterl~ication i~ carried out as de~cribed in example 1, with 1180 g (15.5 Mol) methoxyethanol. The e~terification produ¢t is then analyzed ga~chromatog~aphically. A proportioD of 78~
ethyltri -(methoxy-etho~y)-silane is found; al80 several mixed ester~ are registered, which are formed by the separation of the methoxyethanol to methanol and chloroethanol.
EXANP~æ 11:
Apparatus identical to example 1, 815 g (5 Mol) ethyltrichlorosilane i8 put in the flask tog~ther with 900 ml tetrachloroethylene and i8 e~terified, as described in test 1, with 1180 g (15.5 Mol) metho~yethanol. After the tetra¢hloroethylene has been removed by distillation, the ~lask contents are analyzed by gas chromatography. A proportion of 97.9% ethyltris-(methoxyethoxy)-silane is determined. Mixed esters are not registered. After this the fla~k ¢ontents are processed by vacuum di~tillatioD (1-2 Torr; 110C). 1355 g ethyltris-tmethoxyethoxy)-~llane (96~ obtained, whi¢h shows a Deutral rea¢tion when added to water (¢ontaining methylorange).
~XAMPIæ 12:
~o Apparatus identical to examplc 1, 850 g (5 Mol) ~ilicon tetrachloride i9 put iD the ~la~k together with 1900 ml tetrachloroethylene. The e~terification takes place as described in example 1, with 1974 g (21 Mol) phenol.
After the tetrachloroethyl~ne and ~uperfluous phenol~ have been removed by distlllation, the ~lask product i8 analyzed by gas chromatography. A proportlon of 98.7~ tetraphenoxysilane i8 recorded.
When the product i8 added to water (containing methy-lorange) a neutral reaction is shown.
_ g _
~he esteriflcation of chlorosilanes generally takes place according to the following reactionS,equation:
Rm SiC14 ~ n R'OH ~ ~ Si(ORl)nC14_m ~ n HCl.
In this equation R' ~tands for an alkyl radical with 1 to 11 C-atoms, m can take on values between O and 3 and n value~ between 1 and 4. R ~tands for H or an alkyl radi¢al with 1-11 C-atom~.
~he practical carrying out of this reaction causes difficultie~, because the hydrochloric acid thereby re~ulting in ~reat quantity dissociat~s not only the al~oxy group to alGohol and chloro~ilane~ but also (especially in the presence of alkanol) the hydrogensilane bo.nd with the by-productio~ of hydrogen and formation of an alkoxysilane- and chlorosilane bond. Furthermore the hydrochloric a¢id form~ with the added ~lkanols, chloro~lkanes and ~ntermedlary water, which in it~ turn affects the chlorosilane and alkoxy~llane by hydrolysi~. Because of th~ side reaction, if certain process conditions are not observed, the desired silane e~ter i~ mostly lost ¢ompletely.
Therefore several attempts have already bee~ made to produce compounds of this klnd as economically as possible. The problems, originally associated with the batch proces~es, of the condensate formation a3 a re~ult of the mentioned s1de reactions of the escaping h~drochloric acid with the aloohol~
introduced for the esterification, can indeed be avoided to a ~ large extent by u~ing modern batch method~. However there are -~ limits to its tran~er to the field of large scale i~dustry, e~pecially because o~ the dif~icult oontrol of the large amounts 3 of hydrochlori¢ acid in combi~ation with base materials which if ~ece~sary have low boil~ points, and of the quick and high heat tranæfers necessary for the reliable carrying out of the ~ 067090 reaction not only in the reaction space but al90 in the e~haust ga3 .
Continuous proce~se3 have already been suggested, in which chloro~ilanesl iD fluid phase, are e~terified either i~ a reactor with overflow, borrowed from the simplest batch proce~s, or in several reactors conneeted in ~eries according to the method of the ¢ounter- n ow principle. However, thi~ method haY the dlsad~antage that the hydrochlorio acid is too 810wly and in-completely removed. That leads to reverse dissociatioD~ of alread~
10 present ester groups and side reactions between the alcohols and the hydrochlori¢ acid, with uDdesired hydrolysate ~o~matio~.
Another process describes the esterlfication of chloro~ilane~
with al¢ohol~ in the gas phase and utiliee~ temperatures, which are above the boiling poiDts of all the sub~tanoe~ ¢oncerned (base aDd end products).
~ he latterly mentioned pro¢ess however has a quite particular disadvantage, because the hydrochloric acia present in the system ls induced, as a result of the raised temperature, to a particularly fast ~tart Or the known sid~ reaction~, in particular therefore, re~ers~ dissociation, alcohol-dehydration and hydrolysate formation.
~ he particular weaknesses of all the continuous e~ter-ification processes described abo~e i8 that the ~eparation of the hydrochloric acid from the reaction mixture is too slow and lncomplete. It has also beeD sugge~ted that the hydrochloric acid be blown out by the pas~ing over or through o~ inert gases for example nitrogen, If neces~ary with the aid of a falling ff lm evaporator, whereby an upper temperature limit may not be exceeded. ~hi8 technique however also ha~ the considerable disadvantage that the volume of exhaust ga~ from the hydrochloric a¢id i~ lDcrea~ed; in thi~ way the los~es by e~aporation determin-ed by the partial pressure of the products i9 unJu~tifiably high, and re-~ing the hydroohlori¢ a¢id i~ praotically ruled out.
Furthermore, with thi~ operation, powerful ¢ooling ~
device~ are required to reduce the e~cape of produot~ through inert gas flow; in additio~ e~tremely dry gase~ are a requi~ite for a method of this kiDd, a~ otherwise increa~ed siloxane formation occur~.
It i~ al~o known to increa~e the exit velocity of the hydrogen halide out of the reaction medium during the e~teri~ica-tion proces~ by the introductio~ of benzol or benzlne ~olvents : to the halogen ~lane, in order thus to reduce the above-mentlo~ed formation of siloxanes. De~pite these mea~ures, not inconsider-abls re~idue aciditie~ are left behind in the reaction product, with the~e method~, which mu~t be eliminated as salts by the addition of acid-binding means. ~his introduces the disadvantage Or additional operatio~ proce~es such a~ filtration~ o~ the raw ester and wa~hing out the salt~ for reducing the y~eld los~es.
Also the e~terification Or ¢hlorosilanes with aloohols ln the prese~Gs of ¢hlorohydrocarbo~s is de~cribed, whereby the introduction of textiary-aleoholic component~ i8 effected in the presence of ami~es. However with thi~ method large amount~ of : salt al~o oc¢ur, which must be remo~ed by additional process ~tep~ for thair reprocessing.
Now a process for the s~terification of ¢hlorosilane~
has been found, which 1~ characteri~ed in that the conYersion takes place i~ the presence o~ chlorohydrocarbons and in the absence of acid-binding mean3. These ~easure~ lead to a greater simplificatioD of the proce~ and to an unexpected yield iDcrease.
~hi~ is true not only ~or primary but al80 for ~econdary aloohol3 and phenols.
Tha reaction take~ place in ac¢ordance w$th the aboYe-~entioned equation. Suitable base material~ of the geDeral 1067~90 formula ~SiC14 m are for example triohloro~ilane, tetra¢hloro-~ilan~, methyldichloros~lane, trimethylchlorosllane, methyl-trichloro~ ne, ethyltrlchloro~llane, ethyldichlora~ilane, n-propyldichloro~ilane, propyltrichloro~ilane, i~obutyldichloro-silaDe, vinyldichloro~ilane, vinyltri¢hlorosilane, vinylmethyl-dichlorosilane, dimethyldlchloro3ilane, propenyltrichloro~ilane, allyltrichloro~ilane, 3-chloropropytrichlorosllane and ma~y others. It appears from thi~ that R may ~tand not only for ~atu-rated and unsaturated alkyl radicals with up to 11, preferably up to 6 C-atom3, but al80 for hydrogen. The alkyl radical~ may al80 be different, a~ for example ln the methylethyldlchloro~ilane or methylphenyldichloro3ilane. Al~o phenyltrichloro~ilane may be sub~tituted. ~he radical R may al80 be ~ub~tituted by halogen, as for example in the chloropropyltrichloro~ilane, chloroethyl-trichloro~ilane, to the methylchlorethyltrichloro~ilane or CF3-CH2-SiC13 or al~o CF3-CH~-O-(CH2)3-SiC13.
Simple aliphati¢ alcohol3 such as for example methanol, ethanol, n-propanol, ~-butanol, octanol come into consideration as alcohol~ of the general formula R~OH for the production of the silane esters, but al~o for example 2-methoxyethanol, 2-ethoxy-etbaDol, tetrah~drofurfuryl al¢ohol, 2-methoxyathyldiethyleneglycol ether or polyethyleneglycolmonoether.
The radi¢al R~ may therefore be a linear-chain or cyclic alkyl radi¢al which is interrupted by heteroatoms such as -O- or -~-. The corresponding ~e~ondary alcohols or phe~ols or mixed aromaticaliphatic alcohol~, such as for example benzyl alcohol, may al80 be introduced.
Compound~ ~uch as carbon tetrachloride, chloroform, methylene chloride, dichloro ethane, dichloro ethylene, 1,1,1-trichloroethane, trichloroeth~l~ne, perchloroethyle.ne, tetra-chloroetbylene, tetrachloroethane can be considered as chloro-hydrocarbons wh~ch may be u~ed.
1067~:190 The chlorohydrooarbon~ w ed should be fluid under normal conditions, and have boiling pointa below 150. The number of C-atom~ i~ preferably 1-3; the hydrocarbon radical maJ not only be ~aturated but ~180 unsaturated.
The ratio of chlorosilanes to chlorohydrocarbon during the esterificatioD may vary wi~hin wlde limit~, mostly a ratio chlorosilane/chlorohydrocarbon of 1/0.5-1 i8 sufncient for a¢hie~ing neutral end products and maximum ~ields.
~ he amount of chlorohydrooarbons may be 0.5-3 times as much as the halosilane added during the e3terification.
For example, ac¢ording to the invertion the following product~ are obtalned: trimethoxysilane, triethoxysilane, tetraethoxysllane, tris-2-methoxyethoxysilane, tetra-2-methoxy-etho~ysilanes, methyldimethoYysilane, methyldiethoxysilane, vlnylmethyldiethoxy~ilane, methyltriethoxysilane, ~inyltrieohoxy-~ilane, ~inyltri-2-methoxyethoxysilane, 3-chloropropyltriethoxy-~ilane and many others.
~ he oarrying out of the eoterification take~ pla¢e a¢cordlng to generally known method~ of e~terification. Prefer-; 20 ably, the chlorosilane i~ prepared with the chlorohydrocarbonand the alcohol 18 add~d i~ Bmall amount~ to the warmed mixture.
The amount of the alcohol to be added is dete i ned according to the d~sired de OE ee o~ esterification. Tha reactlon is prefer-ably e~fected at the boiling temperature of the silane/¢hlorohydro-carbon mi~ture. A~ter separation o~ the solvent, preferably by - distlllatloD, the de~ired e~ter i8 obtained with yields of up to 99% with ~ery high purity.
A number of the mentioned e~ter compound8 of silicon have acquired increaslng technlcal importance. For example some 9ilicic a¢id orthoe~ters are u~ed a~ binders for zinc du~t paint~
and in foundry proce~se~. Several organosilanee~ters are used as bullding preservative agent~. A number of other organo~ilane-~1~67090 esters and hydrogensilane ester~ have increasing technioalimportance for the ~ynthe3is of ~ery valuable organofunctional silanes. ~urthermore, hydroge~silane esters are al~o of intere~t ~or semi-cQnductor chemistry.
EX~MPLE 1:
A 6-litre thre~-necked flask is placed in a mu~hroom-~haped heating ~acket and i9 provided with a stirrer? a reflux conden~or and a separati~g funnel.
1060 g (5 Mol) ~ - chloropropyltrichlorosllane i9 put into the flask; after heating the fluid to 80, 930g (15.5 Mol) n-propanol is added in amounts of 20 ml each, with ~trong agitation. After 4.5 hours the addition i~ ~topped. It is heated agal~ at 90 for a further 4 hours and then the raw produ¢t i8 distllled of~
in ~acuum (1-2 Torr - 101G). 1015 g (72%) of a colourless produot 18 obtained. When one ml is pour~d into 100 ml wat~r, wlth added indicator (methylorange), th~re is a strong acidic reactlon.
EXAMPLE 2:
Apparatus identlcal to example 1, zO 1060 g (5 Mol) ~-chloropropyltrichlorosilane i~ put in the flask together with 900 ~1 tri¢hloroeth~lene. ~he cour~e of ester-ification (15.5 Mol n-propanol) takes place as described in example 1. ~fter removing the trichloroethylene by dist~llatioD, a proportion of 98~ ~ -chloropropyl-tri-(propoxy)-silane i~
determined ga~chromatographically in the fluid in the flask.
When the ester i~ poured into water with added indicator (methylorange) as in example 1, a ncutr~l reaction i~ reglstered.
EXAMP~E 3:
Apparatu~ identical to example 1, 1060 g (5 Mol)~ -ohloropropyltrichloro~ila~e i~ put;in the flask with 900 ml carbo~ tetrachloride. The cour~e of the ester-ifioation (15.5 Mol n-propanol) takes place as described in 1a)67090 example 1 (reflux boiling o~ the ¢arbon tetrachloride). ~fter the carbon tetrachlorlde has been removed by di~tillation! a proportlon of 97.5% chloropropyltrlpropoxysilane i8 determined gaschromatographic~lly in the product. A neutral reactlon 18 indicated when it i9 poured into water (with added methylorange).
EXAMP~E 4:
1060 g (5 m) ~-chloropropyltrichlorosilane is put in the flask together with 2.7 1 trichloroethylene. The cour~e of ester-ificatlon (15.5 Mol n-propanol) take~ pla¢e as described in example 1. After the trichloroethylene i8 remo~ed by distillation, a proportion o~ 98.6% ¢hloropropyltripropoxysilane i8 gaschromato-graphi¢ally determined in the n a~X product. A neutral rea¢tion is indicated ~hen the ester is poured into water (with added ethylorange).
EXAMPLE 5:
; Apparatus identical to ~xample 1, ~ 785 g (5 Mol diethyldichloro~ilane) i~ put in the flask. The ; esterification process(l5.g Mol n-propanol) takes place as desGribed in example 1. ~he raw ester i8 distllled of~ in ~acuum (20 Torr (60). 725 g (71~) of a colourless product is obtained, `~ which, as in example 1, ~hows a strongl~ acidic reaction when added to water (containing methylorange).
EXAMPIE 6:
Apparatu~ identlcal to example 1, 785 g (5 Mol) diethyldichlorosilane i8 put in the flas~ together with 2 1 tetrachloroethylene. ~he esterification (15.5 Mol n-propanol) takes place as described in example 1. After the tetrachloroethylene ha~ been removed by distillation, the flask contents are analyzed gaschromatographically. A proportion of 97.2% diethyldlpropoxysilane is determined. When this i~ poured into water (with added methylorange) a neutral reaction is indicated.
~` 1067090 EXAMPLE 7:
Apparatus identical to example lf 745 g (~ Mol) methyltrichlorosilane ls put in the flask and i8 e~terified with 1680 g (15.5 Mol) benzyl alcohol as described in example 1 (8tarting temperature: 60C; raised to 80-85C towards the end of the addition of alcohol). ~he esterification product i~ distilled off in vacuum (1-2 Torr, 120C). 1410 g of a colourle~s fluid (72%) i8 obtained, whi¢h, when added to:~ater (containing methylorange), produce~ a ~trongly acidi¢ reaction.
EXAMP~E 8:
Apparatus identical to example 1, 745 g (5 Mol) methyltrichlorosilane is put in the flask together with 1900 ml tetrachloroethane and i~ esterified with 1680 g (15.5 Mol) ben~yl alcohol as described in example 1. After the removal of the chlorohydrocarbon by di~tillation, the flask -contents are analyzed easchromatographically and a proportion of 98% methyltrlbenzyloxysilane is found. The vacuum-distilled processing of the fla~k contents re~ults in 1750 g of a colourles~
~luid (96.5%), which when it i9 poured lnto water (with added methylorange) give~ a neutral reaction.
EXAMPLE 9:
Apparatw identicPl to e2ample 1, ; 1060 g (5 Mol)~'-chloropropyltriohlorosilane is put in a flask together with 1900 ml trichloroethylene and is e~terifled, as de~cribed iD example 1, with 906 g (15,5 Mol) isopropanol.
After the removal of the trichloroethylene by distillatlon, a proportion Or 97.8% chloropropyltrii30propo~y~ilane is found gaschromatographioally i~ the flask fluid, A neutral reaction is~hown when it i~ poured into water (with added methylorange), EXAMPIE 10:
Apparatu~ identical to example 1, 815 g (5 ~ol) ethyltrichloro6ilane i~ put in the flask. ~he ~067090 esterl~ication i~ carried out as de~cribed in example 1, with 1180 g (15.5 Mol) methoxyethanol. The e~terification produ¢t is then analyzed ga~chromatog~aphically. A proportioD of 78~
ethyltri -(methoxy-etho~y)-silane is found; al80 several mixed ester~ are registered, which are formed by the separation of the methoxyethanol to methanol and chloroethanol.
EXANP~æ 11:
Apparatus identical to example 1, 815 g (5 Mol) ethyltrichlorosilane i8 put in the flask tog~ther with 900 ml tetrachloroethylene and i8 e~terified, as described in test 1, with 1180 g (15.5 Mol) metho~yethanol. After the tetra¢hloroethylene has been removed by distillation, the ~lask contents are analyzed by gas chromatography. A proportion of 97.9% ethyltris-(methoxyethoxy)-silane is determined. Mixed esters are not registered. After this the fla~k ¢ontents are processed by vacuum di~tillatioD (1-2 Torr; 110C). 1355 g ethyltris-tmethoxyethoxy)-~llane (96~ obtained, whi¢h shows a Deutral rea¢tion when added to water (¢ontaining methylorange).
~XAMPIæ 12:
~o Apparatus identical to examplc 1, 850 g (5 Mol) ~ilicon tetrachloride i9 put iD the ~la~k together with 1900 ml tetrachloroethylene. The e~terification takes place as described in example 1, with 1974 g (21 Mol) phenol.
After the tetrachloroethyl~ne and ~uperfluous phenol~ have been removed by distlllation, the ~lask product i8 analyzed by gas chromatography. A proportlon of 98.7~ tetraphenoxysilane i8 recorded.
When the product i8 added to water (containing methy-lorange) a neutral reaction is shown.
_ g _
Claims (4)
1. Process for the esterification of halosilanes by reaction with alcohols, characterized in that the reaction takes place in the presence of chlorohydrocarbons and in the absence of acid-binding means, said alcohols being selected from the group consisting of primary or secondary alcohols and phenols.
2. Process according to claim 1, characterized in that the amount of chlorohydrocarbons is 0.5-3 times as much as the added halosilane.
3. Process according to claim 1, characterized in that the halosilanes are selected from the group consisting of:
chloropropyltrichlorosilane, diethyldichlorosilane, methyl-trichlorosilane and ethyltrichlorosilane.
chloropropyltrichlorosilane, diethyldichlorosilane, methyl-trichlorosilane and ethyltrichlorosilane.
4. Process according to claims 1 and 2, characterized in that the chlorohydrocarbons are selected among tetrachloride and trichloroethylene.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2532887A DE2532887C2 (en) | 1975-07-23 | 1975-07-23 | Process for the esterification of halosilanes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1067090A true CA1067090A (en) | 1979-11-27 |
Family
ID=5952229
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA257,515A Expired CA1067090A (en) | 1975-07-23 | 1976-07-22 | Process for the esterification of chlorosilanes |
Country Status (12)
| Country | Link |
|---|---|
| JP (1) | JPS5949228B2 (en) |
| BE (1) | BE844278A (en) |
| CA (1) | CA1067090A (en) |
| CH (1) | CH606038A5 (en) |
| DD (1) | DD125707A5 (en) |
| DE (1) | DE2532887C2 (en) |
| FR (1) | FR2318873A1 (en) |
| GB (1) | GB1549009A (en) |
| IT (1) | IT1066001B (en) |
| NL (1) | NL7608134A (en) |
| PL (1) | PL103000B1 (en) |
| SU (1) | SU1233802A3 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2800017C2 (en) * | 1978-01-02 | 1983-05-26 | Dynamit Nobel Ag, 5210 Troisdorf | Process for the preparation of organoalkoxysilanes |
| US4172805A (en) * | 1978-02-27 | 1979-10-30 | Dow Corning Corporation | Benzyloxy endblocked organosilicon dielectric fluids and electrical devices containing same |
| JPS59104899A (en) * | 1982-12-08 | 1984-06-16 | Kita Nippon Onkyo Kk | Assembling method of magnetic circuit of speaker |
| DE19755597A1 (en) * | 1997-12-15 | 1999-06-17 | Huels Chemische Werke Ag | Process for the preparation of alkoxysilanes |
| RU2565675C1 (en) * | 2014-05-30 | 2015-10-20 | Федеральное государственное бюджетное учреждение науки Институт синтетических полимерных материалов им. Ениколопова Российской Академии Наук (ИСПМ РАН) | Method of producing methylbenzyl alkoxysilanes |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2701803A (en) * | 1948-10-20 | 1955-02-08 | Socony Vacuum Oil Co Inc | Synthetic lubricants |
| BE814011A (en) * | 1971-11-03 | 1974-08-16 | Organosilanes prepn. from halo- or aminosilanes - by reaction with hydroxy or carboxy cpds. in pentane | |
| DE2409731C2 (en) * | 1974-03-01 | 1983-05-26 | Dynamit Nobel Ag, 5210 Troisdorf | Process for the esterification of trichlorosilane |
-
1975
- 1975-07-23 DE DE2532887A patent/DE2532887C2/en not_active Expired
-
1976
- 1976-07-19 BE BE169028A patent/BE844278A/en not_active IP Right Cessation
- 1976-07-21 PL PL19133676A patent/PL103000B1/en unknown
- 1976-07-21 IT IT5054076A patent/IT1066001B/en active
- 1976-07-21 GB GB3047276A patent/GB1549009A/en not_active Expired
- 1976-07-22 CH CH942676A patent/CH606038A5/xx not_active IP Right Cessation
- 1976-07-22 NL NL7608134A patent/NL7608134A/en not_active Application Discontinuation
- 1976-07-22 CA CA257,515A patent/CA1067090A/en not_active Expired
- 1976-07-22 DD DD19401576A patent/DD125707A5/xx unknown
- 1976-07-22 FR FR7622413A patent/FR2318873A1/en active Granted
- 1976-07-22 JP JP8770776A patent/JPS5949228B2/en not_active Expired
-
1980
- 1980-09-10 SU SU802979302A patent/SU1233802A3/en active
Also Published As
| Publication number | Publication date |
|---|---|
| IT1066001B (en) | 1985-03-04 |
| DD125707A5 (en) | 1977-05-11 |
| FR2318873A1 (en) | 1977-02-18 |
| DE2532887B1 (en) | 1976-07-01 |
| JPS5949228B2 (en) | 1984-12-01 |
| DE2532887C2 (en) | 1982-10-14 |
| PL103000B1 (en) | 1979-05-31 |
| SU1233802A3 (en) | 1986-05-23 |
| JPS5214728A (en) | 1977-02-03 |
| NL7608134A (en) | 1977-01-25 |
| FR2318873B1 (en) | 1982-11-19 |
| GB1549009A (en) | 1979-08-01 |
| CH606038A5 (en) | 1978-10-13 |
| BE844278A (en) | 1976-11-16 |
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