Method for producing functionalized oligomeric silsesquioxanes and the use of the same
The invention relates to a process for preparing functionalized oligomeric silsesquioxanes by reacting incompletely condensed oligomeric silsesquioxanes with alkoxysilanes and also to their use for further derivatizations, for the synthesis of catalysts and their starting compounds, and for the synthesis and modification of polymers.
1 . A process for preparing functionalized oligomeric silsesquioxanes, which comprises reacting incompletely condensed oligomeric silsesquioxanes with alkoxysilanes under base catalysis and the molar ratio of the incompletely condensed oligomeric silsesquioxane to the basic catalyst is from 1000:1 to 1:1.
2 . The process as claimed in claim 1 , wherein the compounds of the formula X m Si(OR′) n are used as alkoxysilanes, where X is a hydrogen, oxy, hydroxyl, alkoxy, carboxyl, silyl, silyloxy, halogen, epoxy, ester, fluoroalkyl, isocyanate, acrylate, methacrylate, nitrile, amino, phosphine group, where—where possible—these radicals X can in turn be further functionalized, and/or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl radical which is functionalized with oxy, hydroxyl, alkoxy, carboxyl, silyl, silyloxy, halogen, epoxy, ester, fluoroalkyl, isocyanate, acrylate, methacrylate, nitrile, amino, phosphine groups, R′ is a hydrogen atom, a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl radical, and m and n can adopt values from 1 to 3, with the proviso that the sum of m and n is 4.
3 . The process as claimed in claim 1 , wherein functionalized oligomeric silsesquioxanes of structure 1
are prepared by reacting incompletely condensed oligomeric silsesquioxanes of structure 2
with alkoxysilanes XSi(OR′) 3 under base catalysis,
where X is a hydrogen, oxy, hydroxyl, alkoxy, carboxyl, silyl, silyloxy, halogen, epoxy, ester, fluoroalkyl, isocyanate, acrylate, methacrylate, nitrile, amino, phosphine group, and—where possible—these radicals X may in turn be further functionalized, and/or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl radical which is functionalized with oxy, hydroxyl, alkoxy, carboxyl, silyl, silyloxy, halogen, epoxy, ester, fluoroalkyl, isocyanate, acrylate, methacrylate, nitrile, amino, phosphine groups, R is a hydrogen atom, a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl radical or in all or some cases a group X, and R′ is a hydrogen atom, a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl radical.
4 . The process as claimed in claim 1 , wherein as basic catalyst at least one from the group consisting of OH − , RO − , RCOO − , RNH − , RCONR − , R − , CO 3 2− , PO 4 3− , SO 4 2− , NO 3 − , F − , NR 3 , and R 3 NO is used, it being possible for R to be a hydrogen atom, a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl radical.
5 . The process as claimed in claim 4 , wherein KOH, NaOH, (C 2 H 5 ) 4 NOH, C 6 H 5 CH 2 (CH 3 ) 3 NOH, (CH 3 ) 4 NOH and/or (C 2 H 5 ) 3 N is used as basic catalyst.
6 . The process as claimed in claim 5 , wherein (C 2 H 5 ) 4 NOH is used as basic catalyst.
7 . The process as claimed in claim 1 , wherein the reaction of incompletely condensed oligomeric silsesquioxanes with alkoxysilanes takes place in solution.
8 . The process as claimed in claim 7 , wherein halogen-free systems selected from alcohols, ketones, aldehydes, ethers, acids, esters, anhydrides, alkanes, aromatics, and nitriles or mixtures thereof are used as solvents.
9 . The process as claimed in claim 8 , wherein THF, acetone, methanol, and ethanol or mixtures of these solvents are used as solvents.
10 . The process as claimed in claim 9 , wherein THF is used as solvent.
11 . The process as claimed in claim 7 , wherein the concentration of the incompletely condensed oligomeric silsesquioxane in the reaction solution at the beginning of the reaction is from 0.01 mol/l to 10 mol/l.
12 . The process as claimed in claim 11 , wherein the concentration of the incompletely condensed oligomeric silsesquioxane in the reaction solution at the beginning of the reaction is from 0.2 mol/l to 1 mol/l.
13 . The process as claimed in claim 1 , wherein the molar ratio of the incompletely condensed oligomeric silsesquioxane to the basic catalyst is from 20:1 to 5:1.
14 . The process as claimed in claim 1 , wherein the reaction is carried out in the presence of water.
15 . The process as claimed in claim 14 , wherein the molar ratio of water to the incompletely condensed oligomeric silsesquioxane at the beginning of the reaction is from 1000:1 to 0.1:1.
16 . The process as claimed in claim 15 , wherein the molar ratio of water that is used to the incompletely condensed oligomeric silsesquioxane is from 10:1 to 1:1.
17 . The process as claimed in claim 1 , wherein the preparation of the functionalized oligomeric silsesquioxanes is carried out at a temperature of from −50° C. to 300° C.
18 . The process as claimed in claim 17 , wherein the preparation of the functionalized oligomeric silsesquioxanes is carried out at a temperature of from 0° C. to 100° C.