CA2364343A1 - Oligomeric silasesquioxanes and a process for preparing oligomeric silasesquioxanes - Google Patents
Oligomeric silasesquioxanes and a process for preparing oligomeric silasesquioxanes Download PDFInfo
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- CA2364343A1 CA2364343A1 CA002364343A CA2364343A CA2364343A1 CA 2364343 A1 CA2364343 A1 CA 2364343A1 CA 002364343 A CA002364343 A CA 002364343A CA 2364343 A CA2364343 A CA 2364343A CA 2364343 A1 CA2364343 A1 CA 2364343A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
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- 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
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
Abstract
The invention relates to novel oligomeric silasesquioxanes having the formula R6Si6O9 (R = alkyl, cycloalkyl (c-C3H5, c-C4H7, c-C5H9, c-C7H13, c-C6H15, c-C9H17, c-C10H19), alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl) and the structure I and also to a process for preparing oligomeric silasesquioxanes having the formula R6Si6O9 (R = alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl) and the structure 1 and also to their use for the synthesis of incompletely condensed silasesquioxanes, of catalysts and their starting compounds and also of polymers.
Description
. . Q.Z. 5688 ~Oli ora~eric silases uioxanes and a rocess for Grin oli omeric silasespuioxanes The invention relates to oligomeric silasesquioxanes having the formula RsSis08 (R = alkyl, cycloalkyl (c-C3H5, c-C4H~, c-CsHs, c-C~H~3, c-CeH~~, c-C9W", c-C~oH~a), alkenyl, cyclo2~lkenyl, alkynyl, cycloalkynyl, aryl, hetervaryl) and the structure I and also to a process for preparing ofs~arrcerrc s~lasesqcriax~rtes C~~ving fete fQrmuta ~S~s~s ~ = ate, cycloalkyl, alkenyt, cycloalkenyi, alkynyl, cycloalkynyl, aryl, heteroaryl) and 1 o the structure I and also to their use for the synthesis of incompletely condensed silasesquivxanes, of catalysts and their starting compounds and also of polymers.
.H. .
' O.Z. 5688 - 2 -R
Si O
-5~~~ ~~i--~R
R ~ R is; ~ I
a a o 0 o s~
R R
This compound of the structure 1 has hitherto been prepared in an isolatable yield only for R = cyclohexyl. In this case, the synthesis of the compound having the structure I, which is frequently also described by it.s .empirical formula (c-CsH"Si4,.5)B gives an unsatisfactory yield of 7°i6 after an extraordinarily long reaction time of over one year (J. Am_ Chem. Soc.
1989, 1 f 9, 1 x'41-1748). Compounds of the structure I containing other hydrocarbon radicals R are not known in isolated farm.
~o The compound of the stnrcture 1. in which R = c-CsH" can be obtained by a reaction in which the monomer concentration employed is 0.2 molll, which is generally customary for the synthesis of oligomeric silasesquioxanes and has hitherto not been exceeded in order to avoid direct polycondensation to form polysilasesquioxanes (Top. Curr Chem. 1982, 1p2, 199-236)_ Compounds of the structure 1 in which R = ~-CsH" are of great importance because, inter alia, they can be reacted in the presence of basic catalysts 2o with R'Si(OMe)3 (R' -. vinyl) to give functiona(ized, incompletely condensed silasesquioxanes of the structure Il, e_g. RsR'Si~O~(OH)3 where R = c-C8H" and R' = vinyl CChem. Commun. 1999, 2153-2154, Polym_ Mater. Sci. Eng. 2000, 82, 301-302).
O.z. 5688 OH
SI'~
OH
~~SI- i0-.~g~'"'R OH
_1_~ ~
- p 0 ~Si~R
i l,~
R F!
However, only few silasesquioxanes which differ in terms of their hydrocarbon radicals R and R' have up to now been able to be prepared by this route.
It is therefore an object of the present invention to provide hitherto unobtainable oligomeric sitasesquioxanes having. the formula ReSig09 and the structure I whose radicals R are different from cyclohexyl, and also an 2 o efficient process for preparing oligomeric silasesquioxanes having the formula RBSisOs (R = alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl) and the structure 1.
ft has surprisingly been found that hitherto unobtainable silasesquioxanes having the formula ReSis09 and the structure I can not only be prepared with a variety of radicals R = alkyl, cycloalkyl (c-C3Ws, c-C4H~, o-C5H9, c-C~H~3, c-CBM~$. C-CaH,~. c-C,oH~s). alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, but that the silasesquioxanes having the formula ReSisOs (R ~ alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, 2o cycloalkynyl, aryl, heteroaryl) and the structure I can also be synthesized in significantly improved yields compared to processes known hitherto for preparing (cyclohexyl)6SisOs (J. Am. Chem. Soc. 1989, 9 9 9, 1741-1746;
Orgranomet'allics 1991, 90, 2526-2528) in a greatly shortened reaction time when the concentration of the monomer is greater than 0.2 molll.
The present invention accordingly provides oligomeric silasesquioxanes having the formula R6Sie09 where R = alkyl, cycloalkyl ether than cyetohexyl, alkenyl, cycloatkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl) and the structure l as claimed in claim 1 _ o.Z. 5688 - 4 "
The present invention likewise provides a process as claimed in claim 8 for preparing oligomeric silasesquioxanes having the formula RaSisOs where R = alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl andlor heteroaryl and the structure 1 by condensation of monomers of the formula RSiX3, where X can be a hydrolyzable group or a group capable of a condensation reaction, wherein the condensation is carried out in s n _ i r n r ~ ~ ~ m m ~i rrr~l~r lhnn ft'1 mnlll siiasesquioxanes prepares as ciaimea m ac ~eas~ u~m m c:mnm v m m «~
the synthesis of catalysts, their starting compounds and also polymers.
The present invention likewise provides for the use of oligomeric silasesquioxanes as claimed in any of claims 1 to 5 or of oligomeric silasesquioxanes prepared as claimed in at least one of claims 6 to 16 for hydrolysis to form incompletely condensed silasesquioxanes.
The present invention provides previously unknown vligomeric silasesquioxanes which can serve as important starting materials for further conversion into functionalized, incompletely condensed silasesquioxanes and a variety of downstream products thereof.
Compounds of the structure 1 were hitherto known only for R = eyclohexyl.
The process of the present invention has the advantage that silasesquivxanes having the empirical formula F~SiB09 where R ~ alkyl, cycloalkyl, alkenyl, cycloalkenyi, alkynyl, cycloalkynyl, aryl and/or heteroaryl and the structure I can be synthesized in good yields after short reaction times. These compounds can be used for the preparation of 3o incompletely condensed silasesquioxanes, of catalysts and their starting compounds and also of polymers.
It has hitherto been assumed that monomer concentrations above ~.2 molll favor the polycondensation to form polysilasesquioxanes arid that for this reason relatively large amounts of polysilasesquioxanes are formed as by-products in addition to oligomeric silasesquiuxanes. The relatively high concentrations used in the process of the invention do not lead to preferential formation of the incompletely condensed silasesquioxanes known from the literature (Organometallics 1991, 90, 2526-2528), but, in O.Z. 5688 - 5 -contrast, the completely condensed hexameric silasesquioxanes having the formula RsSiB09 and the structure l are obtained in goad yield after a short reaction time. These have the advantage that they open up an easier route to incompletely condensed silasesquioxanes, to catalysts and their starting compounds and also to polymers.
One aspect of the present invention is therefore the provision of oligomeric silasesquioxanes having the formula RsSisOg vrrhere R = alkyl, cycloalkyl other than cyclohexyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl and/or heteroaryl and the structure I
R
..r ~~~4 ~'~~-~ R
~ ~_s\ ~ r .
o ~ o a n ~~
R R
The radicals R in these oligomeric silasesquioxanes preferably include at least one methyl, ethyl, propyf, butyl, i-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cycloheptyl, cyclooctanyi, cyclononanyl, cyclodecanyl, vinyl, propenyl, monounsaturated or polyunsaturated butenyl, cyclopropenyl, monounsaturated or polyunsaturated cyclobutenyl, monounsaturated or polyunsaturated cyclopentenyl, monounsaturated or polyunsaturated cyclohexenyl, monounsaturated or polyunsaturated cycloheptenyl, monounsaturated or polyunsaturated cyclooctenyl, ethynyl, propynyl, ,:
monounsaturated or polyunsaturated butynyl, benzyl andlor pyridyl group.
These radicals R may each be either substituted or unsubstituted_ Substituted radicals R have, for example, a halogen atom such as chlorine 2 5 or bromine in place of a hydrogen atom.
- O.Z. 5688 - 6 -- The otigomeric silasesquioxane very particularly preferably has at least one cyclopentyl group andlor cyclohexyl group as radical R. The radicals R in the oligomeric silasesquioxanes may be identical or different. In the case of different radicals Ra, Rb,... to R~, the empirical formula is, strictly speaking, R',"Rb"R~oRdPReqRfgSIsOs where m, n, o, p, q and s are each an integer less than or equalto6or0andm+n+o+p~-q+s=6. In the , case of identical radicals R, i.e. Ra = Rb = R' = Rd = R° = R', the empirical formula once again reduces to RsSIsOs- The oligomeric silasesquiaxanEs of the invention particularly preferably have identical groups as radicals R.
TO
The oligomeric silasesquioxanes of the invention and also other known silasesquioxanes can be prepared by means of the process of the invention. This process of the invention is suitable for preparing oligomaric silasesquioxanes having the formula RsSi6O9 where R = alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl andlor heteroaryl and the structure ! by condensation of monomers of the formula RSiX3, where X
reaction, in solution at a concentration of monomers of greater than 0_2 moill. The concentration of monomers in the sofutivn is preferably 2 o greater than 0_4 molll and very particularly preferably from 0.5 molll to 2.5 molll.
The condensation reaction can be carried out in a manner known to those skilled in the art.
As monomers of the type RSiX~, preference is given to using compounds in which the groups X include at least vne group selected from among --OH, -ONa, -OK, -OR', -OCOR', -OSiR'$, -CI, -Br, -I and -NR'z, where R' is an organic radical or hydrogen. It is also possible to use compounds in which the groups X are identical, e.g. (methyl)SiCla or (cyclohexyl)Si(OH}3, and also compounds containing different groups as groups X, e.g.
(methyl)SiCl2(OH) or (cyclohexyl)Si(OR')zCl, as monomers_ Preference is given to using compounds of the type RSiX3 in which all three groups X
are identical as monomers.
As monomer, use is made of at least one compound of the type RSiX3 in which the radical R is a methyl, ethyl, propyl, butyl, i-butyl, cyclapropyl, cyclobutyl, cyclopentyl, cycloheptyl, cyclooctanyl, cyclononanyl, cyclodecanyl, vinyl, propenyl, monounsaturated or polyunsaturated p.2. 5688 - ~ -butenyl, cyclopropenyl, monounsaturated or polyunsaturated cyclobutenyl, monounsaturated or polyunsaturated cyclopentenyl, monounsaturated ar polyunsaturated cyclohexenyl, monounsaturated or polyunsaturated cycloheptenyl, monounsaturated or polyunsaturated cyclooctenyl, ethynyl, propynyl, monounsaturated or polyunsaturated butynyl, benzyl or pyridyl group.
It may also be advantageous to use two or more different monomers, e.g.
RSiCl3 and RSi(OH)3, in the solution. The condensation is preferably 1 o carried out in a solution comprising only one type of monomer.
The hydrolytic condensation is preferably carried vut in the absence of catalysts. However, the use of catalysts can be advantageous far ' controlling or accelerating the reaction. The condensation process of the invention can therefore be carried out in the absence of a catalyst or in the presence of at least one acidic catalyst or basic catalyst. As basic catalyst, preference is given to using an organic or inorganic base. A very particularly preferred basic catalyst is a compound selected from among KOH, NaOH, (CzHs)aNOH, CBHSCH2(CHa)3NOH, (CH3)oNOH and (CZHS)~N
or a mixture of these compounds. As acidic catalyst, preference is given to using an organic or inorganic acid. A very particularly preferred acidic catalyst is a compound selected from among hydrochloric acid (HCi), ZnClz, AIC19, HC104, acetic acid (CH3COOH), nitric acid (HN03) and sulfuric acid (H2S04) or a mixture of these compounds.
The. condensation is carried out in solution. As solvent, it is possible to use either a polar solvent or a nonpolar solvent. The condensation is particularly preferably carried out in a solution comprising as solvent at least one compound selected from. among alcohols, ketones, aldehydes, ethers, acids, esters, anhydrides, alkanes, aromatics and nitrites and mixtures of two or more of these compounds. Particular preference is given to using alcohols, ethers, acetone, acetonitrile, benzene or toluene as solvent. It is of course also possible to use mixtures of solvents.
Depending on the type of monomers used, it may be necessary for water to be present during the condensation. This depends on whether or not the monomers contain hydroxyl groups. If the monomers are, for example, compounds of the formula RSi(OH)3, the condensation can also be carried out without addition of water. If the monomers are, for example, O.Z. 5688 - 8 -' compounds of the formula RSiCl3, wafer needs to be present as a reactant to allow the condensation to occur (via the silanols formed as intermediates. The condensation is therefore preferably commenced in the presence of water_ Preference is given to adding water, preferably in . 5 an amount of from 0.1 to 50°~6 by weight, parkicularly preferably from 5 to 50°~b by weight, based on the mvnomer~ontaining solution, to the reaction mixture prior to commencement of the condensation. However, depending on the water content of the solvent, the traces of water present in the solvent can also be utilized_ The process of the invention or the condensation can be carried out at a temperature of from -20°C to 300°C, preferably from 0°C
to 200°C. It may be advantageous to alter the temperature during the reaction. Thus, in particular, it can be advantageous to reduce the temperature toward the end of the reaction in order to isolate the product as completely as possible. The way in which the condensation reaction is carried out will be known per se to those skilled in the art_ The reaction ran be carried out at atmospheric pressure, subatmospheric 2 o pressure or superatmospheric pressure. The reaction or condensation is preferably carried out at atmospheric pressure.
In a particularly preferred embodiment of the process of the invention, a solution of at least one monomer of the formula RSi7(3 in at least one solution is placed in a reaction vessel with superposed condenser. This solution is heated to boiling under reflux and water is carefully added to the boiling solution while stirring vigorously. The solution is slowly brought to room temperature by switching off the source of heat and is stirred further for at least 24 hours, preferably at least 168 hours_ 3a snasesqmoxane or the rorrrluW rcsms~.t9'wruc:n' is m~b~cu un fium uiG ,.
solution and washed at least once with the solvent which was present in the solution_ It may be advantageous to grind the filtered-off residue in a mortar, to disperse it again in a small amount of the solvent and ' subsequently to filter it off again_ This procedure' can be repeated until the filter residue has the desired purity.
- 0.2. 5688 - 9 -To purify the residue further, in particular to separate incompletely condensed silasesquioxanes from the completely condensed silasesquioxanes of the formula RaSie09, it can be advantageous to dry the filter residue and admix it with from three to ten times, preferably from four to seven times, its weight of pyridine. In contrast to the incompletely condensed silasesquioxanes, the completely condensed silasesquioxane is virtually insoluble in pyridine and can be filtered off. This procedure, too, can be repeated until the desired purity is obtained.
1, o After purification by means of pyridine, it can be advantageous to recrystaliize the completely condensed silasesquioxane. The recrystallization is preferably carried vut using chloroform-The oligomeric silasesquioxanes of the invention or the ofigomeric z5 silasesquioxanes prepared by the process of the invention and having the formula RsSi8O9 (R = alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloaikynyl, aryl, heteroaryl) and the structure t can be used in processes for preparing incompletely condensed silasesquioxanes. Examples of incompletely condensed silasesquioxanes are compounds of the type ;
2o RySi~08(OH)3 and RsSig07(OH)4. In these processes, the oligomeric silasesquioxanes having the formula RaSieO9 (R = alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cyeloalkynyl, aryl, heteroaryl) and the structure I can be reacted, for example, with Bu4NOH andlor a compound of the formula R'Si(OR2)3, where R' is an alkyl group containing at least one unsaturated 2 5 C-C double bond and RZ is an alkyl group, preferably a methyl group.
These incompletely condensed silasesquioxanes can serve as starting compounds in processes for preparing polymers, e.g. by hydrolytic polycondensation, yr as starting compounds for the preparation of 30 catalysts, e.g. by reaction of the incompletely condensed silasesquioxanes with metal compounds to form metal-modified silasesquioxanes (metallasilasesquioxanes). Subsequent modification or replacement of the radicals R is of course also possible-35 The incompletely condensed silasesquioxanes aye particularly preferably modified by means of metals. Preference is given to modifying silasesquioxanes with metal compounds of the transition groups including the lanthanides and actinides and of main groups 3 and 4. In these processes, the incompletely condensed silasesquioxanes are reacted, for O.Z. 5688 - 10 -example, with metal alkoxides such as Ti(OBu'),,. Examples of metal-modified silasesquioxanes which can be obtained in this way are the titanasilasesquioxanes (CSH9)6(CHzCH)Si,0,2Ti(OBu') and (C,H,3)g{CH2CH)Si~O,zTi(08u').
The following examples illustrate the invention wifhout restricting its scope:
Example 1: Preparation of an oligomeric silasesquioxane of the formula (CsH")sSisOs 1, 0 100 ml of H20 were carefully added while .stirring to a solution of 100 g (460 mmvl) of CsH"SiCl3 in 400 ml of acetone; with the solution being maintained at the boiling point during the additibn. The reaction mixture was stirred at room temperature for another 168 hours- The crude product was filtered off and washed with acetone- The filter residue was ground in a mortar and dispersed in. 70 ml of acetone by stirring. After 1 hour, the solid was isolated by filtration and dried at 4o°C for 12 hours. The product mixture was admixed with five times its weight of pyridine and the suspension was stirred for 30 minutes. After filtration and washing with pyridine, the product was recrystallized from chloroform. This gave 15.4 g (19.0 mmol) of (CsH")sSisO9. This corresponded to a yield of 24.9°i6.
Example 2: Preparation of an oligomeric silasesquioxane of the formula (CSH9)BS X809 100 ml of Hz0 are carefully added while stirring to a solution of 93 g (457 rnmol) of CSHgSiCla in 400 ml of acetone, with the solution being ~ .
maintained at the boiling point during the additior~_ The reaction mixture is stirred at room temperature for another 168 hours. The crude product is :30 filtered off and washed with acetone. The filter residue is ground in a mortar and dispersed in 70 ml of acetone by stirring. Altar 7 hour, the solid is isolated by filtration and dried at 40°C for 12 hours. The product mixture is admixed with five times its weight of pyridine and the suspension is stirred for 30 minutes. After filtration and washing with pyridine, the 35 product is recrystallized from chloroform- This gives 11.6 g {16.0 mmol) of (C5H9)sSisOa. This corresponds to a yield of 21.0°~.
Example 3: Preparation of an oligomeric silasesquioxane of the formula (C~Ht3)eSisOs O.Z. 5688 - 11 -100 ml of H20 are carefully added while stirring to a solution of 106 g (458 mmol) of C,H~3SiCl3 in 400 ml of acetone, with the solution being , maintained at the boiling point during the addition. The reaction mixture is stirred at roam temperature for another 968 hours. The crude product is filtered off and washed with acetone. The filter residue is ground in a mortar and dispersed in 70 ml of acetone by stirring. After 1 hour, the solid is isolated by filtration and dried at 40°C for 12 hours. The product mixture is admixed with five times its weight of pyridine and the suspension is to stirred for 30 minutes- After filtration and washing with pyridine, the product is recrystallized from chloroform- This gives 13.0 g (14.5 mmol) of (C7H13}65809~ This corresponds to a yield of 19Ø
Example 4: Preparation of incompletely condensed silasesquioxanes , using a compound of the formula ReSi6Oa A solution of 1.99 g (2.74 mmol) of (CSH9)~Sis08 in 10 ml of THF is admixed with 1 _85 ml (2.77 mmol) of aqueous Bu,NOH and stirred at 25°C for 1 hour. The mixture is subsequently neutralized using 2M hydrochloric acid-2o The solvent is removed, the residue is dissolved in diethyl ether and the solution is dried over magnesium sulfate. Evaporation of the solvent gives {CSH9)sSisO~(OH), in quantitative yield.
Example 5: Preparation of incompletely condensed silasesquioxanes using a compound of the formula RsS~6O9 1 _85 ml (2.77 mmol) of an aqueous solution of Bu4NOH are added to a solution of 1.99 g (2.74 mmol) of {CsH9)sSisO9 and 0.42 ml of (vinyl}Si(OMe)3 in 10 ml of THF. The solution is stirred for 12 hours, the 3o solvent is removed, the residue is dissolved in diethyl ether and the solution is dried aver magnesium sulfate. Evaporation of the solvent gives (CSHs)s(ChIzCH)Si,O9(ON)3 in quantitative yield.
Example 6: Preparation of incompletely condensed silasesquioxanes using a compound of the formula R6Si608 A solution of 2_45 g (2.74 mmol) of (C7H13)6S~g09 in 10 ml of TH!= is admixed with 1.85 ml (2.77 mmol) of aqueous Bu,~NOH and stirred at 25°C
for 1 hour. The mixture is subsequently neutralized using 2M hydrochloric O.Z. 5688 - 12 -acid. The solvent is removed, the residue is dissolved in diethyl ether and the solution is dried over magnesium sulfate. Evaporation of the solvent gives (C7H,3)6S~6O7(OH)4 in quantitative yield.
Example 7: Preparation of incompletely condensed silasesquioxanes using a compound of the formula ReSisO9 1.85 ml (2.77 mmoi) of an aqueous solution of Bu4NOH are added to a solution of 2.45 g (2.74 mmol) of (C~H,3)eSis09 and 0.42 ml of (vinyl)Si(OMe)3 in 10 ml of TWF. The solution is stirred for 12 hours, the solvent is removed, the residue is dissolved in diethyl ether and the solution is dried over magnesium sulfate. Evaporation of the solvent gives (C,H,3)e(CHzCH)Si,Oa(OH)s in quantitative yield.
Example 8: Preparation of titanium-modified silasesquioxanes using incompletely condensed silasesquioxanes 1 g (2.94 mmol) of Ti(OBu'),, is added tv a solution of 2.3 g (2.76 mmol) of (CsH9)e(CHZCH)Si,O9(OH)3 in 100 m( of toluene and the reaction mixture is 2o stirred for 30 minutes. The solid is subsequently filtered off, dissolved in toluene and reprecipitated by means of acetonitrile. This gives 1 _58 g (1.66~mmol) of (CSHA)s(CH2CH)Si,O,zTi(OBu') as a white solid (60% yield).
Example 9: Preparation of titanium-modified silasesquivxanes using incompletely condensed silasesquioxanes 1 g (2.94 mmol) of Ti(OBu')a is added to a solution of 2.7 g (2.74 mmol) of (C,H~3)s(CHZCW)Si,09(OH)3 in 100 ml of toluene and the reaction mixture is stirred for 30 minutes. The solid is subsequently filtered off, dissolved in 3o toluene and reprecipitated by means of acetonitrile. This gives 1_66 g (1.49 mmol) of (C,H,3)e(CHZCH)Si~O,zTi(OBu') as a white solid (55% yield).
.H. .
' O.Z. 5688 - 2 -R
Si O
-5~~~ ~~i--~R
R ~ R is; ~ I
a a o 0 o s~
R R
This compound of the structure 1 has hitherto been prepared in an isolatable yield only for R = cyclohexyl. In this case, the synthesis of the compound having the structure I, which is frequently also described by it.s .empirical formula (c-CsH"Si4,.5)B gives an unsatisfactory yield of 7°i6 after an extraordinarily long reaction time of over one year (J. Am_ Chem. Soc.
1989, 1 f 9, 1 x'41-1748). Compounds of the structure I containing other hydrocarbon radicals R are not known in isolated farm.
~o The compound of the stnrcture 1. in which R = c-CsH" can be obtained by a reaction in which the monomer concentration employed is 0.2 molll, which is generally customary for the synthesis of oligomeric silasesquioxanes and has hitherto not been exceeded in order to avoid direct polycondensation to form polysilasesquioxanes (Top. Curr Chem. 1982, 1p2, 199-236)_ Compounds of the structure 1 in which R = ~-CsH" are of great importance because, inter alia, they can be reacted in the presence of basic catalysts 2o with R'Si(OMe)3 (R' -. vinyl) to give functiona(ized, incompletely condensed silasesquioxanes of the structure Il, e_g. RsR'Si~O~(OH)3 where R = c-C8H" and R' = vinyl CChem. Commun. 1999, 2153-2154, Polym_ Mater. Sci. Eng. 2000, 82, 301-302).
O.z. 5688 OH
SI'~
OH
~~SI- i0-.~g~'"'R OH
_1_~ ~
- p 0 ~Si~R
i l,~
R F!
However, only few silasesquioxanes which differ in terms of their hydrocarbon radicals R and R' have up to now been able to be prepared by this route.
It is therefore an object of the present invention to provide hitherto unobtainable oligomeric sitasesquioxanes having. the formula ReSig09 and the structure I whose radicals R are different from cyclohexyl, and also an 2 o efficient process for preparing oligomeric silasesquioxanes having the formula RBSisOs (R = alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl) and the structure 1.
ft has surprisingly been found that hitherto unobtainable silasesquioxanes having the formula ReSis09 and the structure I can not only be prepared with a variety of radicals R = alkyl, cycloalkyl (c-C3Ws, c-C4H~, o-C5H9, c-C~H~3, c-CBM~$. C-CaH,~. c-C,oH~s). alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, but that the silasesquioxanes having the formula ReSisOs (R ~ alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, 2o cycloalkynyl, aryl, heteroaryl) and the structure I can also be synthesized in significantly improved yields compared to processes known hitherto for preparing (cyclohexyl)6SisOs (J. Am. Chem. Soc. 1989, 9 9 9, 1741-1746;
Orgranomet'allics 1991, 90, 2526-2528) in a greatly shortened reaction time when the concentration of the monomer is greater than 0.2 molll.
The present invention accordingly provides oligomeric silasesquioxanes having the formula R6Sie09 where R = alkyl, cycloalkyl ether than cyetohexyl, alkenyl, cycloatkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl) and the structure l as claimed in claim 1 _ o.Z. 5688 - 4 "
The present invention likewise provides a process as claimed in claim 8 for preparing oligomeric silasesquioxanes having the formula RaSisOs where R = alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl andlor heteroaryl and the structure 1 by condensation of monomers of the formula RSiX3, where X can be a hydrolyzable group or a group capable of a condensation reaction, wherein the condensation is carried out in s n _ i r n r ~ ~ ~ m m ~i rrr~l~r lhnn ft'1 mnlll siiasesquioxanes prepares as ciaimea m ac ~eas~ u~m m c:mnm v m m «~
the synthesis of catalysts, their starting compounds and also polymers.
The present invention likewise provides for the use of oligomeric silasesquioxanes as claimed in any of claims 1 to 5 or of oligomeric silasesquioxanes prepared as claimed in at least one of claims 6 to 16 for hydrolysis to form incompletely condensed silasesquioxanes.
The present invention provides previously unknown vligomeric silasesquioxanes which can serve as important starting materials for further conversion into functionalized, incompletely condensed silasesquioxanes and a variety of downstream products thereof.
Compounds of the structure 1 were hitherto known only for R = eyclohexyl.
The process of the present invention has the advantage that silasesquivxanes having the empirical formula F~SiB09 where R ~ alkyl, cycloalkyl, alkenyl, cycloalkenyi, alkynyl, cycloalkynyl, aryl and/or heteroaryl and the structure I can be synthesized in good yields after short reaction times. These compounds can be used for the preparation of 3o incompletely condensed silasesquioxanes, of catalysts and their starting compounds and also of polymers.
It has hitherto been assumed that monomer concentrations above ~.2 molll favor the polycondensation to form polysilasesquioxanes arid that for this reason relatively large amounts of polysilasesquioxanes are formed as by-products in addition to oligomeric silasesquiuxanes. The relatively high concentrations used in the process of the invention do not lead to preferential formation of the incompletely condensed silasesquioxanes known from the literature (Organometallics 1991, 90, 2526-2528), but, in O.Z. 5688 - 5 -contrast, the completely condensed hexameric silasesquioxanes having the formula RsSiB09 and the structure l are obtained in goad yield after a short reaction time. These have the advantage that they open up an easier route to incompletely condensed silasesquioxanes, to catalysts and their starting compounds and also to polymers.
One aspect of the present invention is therefore the provision of oligomeric silasesquioxanes having the formula RsSisOg vrrhere R = alkyl, cycloalkyl other than cyclohexyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl and/or heteroaryl and the structure I
R
..r ~~~4 ~'~~-~ R
~ ~_s\ ~ r .
o ~ o a n ~~
R R
The radicals R in these oligomeric silasesquioxanes preferably include at least one methyl, ethyl, propyf, butyl, i-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cycloheptyl, cyclooctanyi, cyclononanyl, cyclodecanyl, vinyl, propenyl, monounsaturated or polyunsaturated butenyl, cyclopropenyl, monounsaturated or polyunsaturated cyclobutenyl, monounsaturated or polyunsaturated cyclopentenyl, monounsaturated or polyunsaturated cyclohexenyl, monounsaturated or polyunsaturated cycloheptenyl, monounsaturated or polyunsaturated cyclooctenyl, ethynyl, propynyl, ,:
monounsaturated or polyunsaturated butynyl, benzyl andlor pyridyl group.
These radicals R may each be either substituted or unsubstituted_ Substituted radicals R have, for example, a halogen atom such as chlorine 2 5 or bromine in place of a hydrogen atom.
- O.Z. 5688 - 6 -- The otigomeric silasesquioxane very particularly preferably has at least one cyclopentyl group andlor cyclohexyl group as radical R. The radicals R in the oligomeric silasesquioxanes may be identical or different. In the case of different radicals Ra, Rb,... to R~, the empirical formula is, strictly speaking, R',"Rb"R~oRdPReqRfgSIsOs where m, n, o, p, q and s are each an integer less than or equalto6or0andm+n+o+p~-q+s=6. In the , case of identical radicals R, i.e. Ra = Rb = R' = Rd = R° = R', the empirical formula once again reduces to RsSIsOs- The oligomeric silasesquiaxanEs of the invention particularly preferably have identical groups as radicals R.
TO
The oligomeric silasesquioxanes of the invention and also other known silasesquioxanes can be prepared by means of the process of the invention. This process of the invention is suitable for preparing oligomaric silasesquioxanes having the formula RsSi6O9 where R = alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl andlor heteroaryl and the structure ! by condensation of monomers of the formula RSiX3, where X
reaction, in solution at a concentration of monomers of greater than 0_2 moill. The concentration of monomers in the sofutivn is preferably 2 o greater than 0_4 molll and very particularly preferably from 0.5 molll to 2.5 molll.
The condensation reaction can be carried out in a manner known to those skilled in the art.
As monomers of the type RSiX~, preference is given to using compounds in which the groups X include at least vne group selected from among --OH, -ONa, -OK, -OR', -OCOR', -OSiR'$, -CI, -Br, -I and -NR'z, where R' is an organic radical or hydrogen. It is also possible to use compounds in which the groups X are identical, e.g. (methyl)SiCla or (cyclohexyl)Si(OH}3, and also compounds containing different groups as groups X, e.g.
(methyl)SiCl2(OH) or (cyclohexyl)Si(OR')zCl, as monomers_ Preference is given to using compounds of the type RSiX3 in which all three groups X
are identical as monomers.
As monomer, use is made of at least one compound of the type RSiX3 in which the radical R is a methyl, ethyl, propyl, butyl, i-butyl, cyclapropyl, cyclobutyl, cyclopentyl, cycloheptyl, cyclooctanyl, cyclononanyl, cyclodecanyl, vinyl, propenyl, monounsaturated or polyunsaturated p.2. 5688 - ~ -butenyl, cyclopropenyl, monounsaturated or polyunsaturated cyclobutenyl, monounsaturated or polyunsaturated cyclopentenyl, monounsaturated ar polyunsaturated cyclohexenyl, monounsaturated or polyunsaturated cycloheptenyl, monounsaturated or polyunsaturated cyclooctenyl, ethynyl, propynyl, monounsaturated or polyunsaturated butynyl, benzyl or pyridyl group.
It may also be advantageous to use two or more different monomers, e.g.
RSiCl3 and RSi(OH)3, in the solution. The condensation is preferably 1 o carried out in a solution comprising only one type of monomer.
The hydrolytic condensation is preferably carried vut in the absence of catalysts. However, the use of catalysts can be advantageous far ' controlling or accelerating the reaction. The condensation process of the invention can therefore be carried out in the absence of a catalyst or in the presence of at least one acidic catalyst or basic catalyst. As basic catalyst, preference is given to using an organic or inorganic base. A very particularly preferred basic catalyst is a compound selected from among KOH, NaOH, (CzHs)aNOH, CBHSCH2(CHa)3NOH, (CH3)oNOH and (CZHS)~N
or a mixture of these compounds. As acidic catalyst, preference is given to using an organic or inorganic acid. A very particularly preferred acidic catalyst is a compound selected from among hydrochloric acid (HCi), ZnClz, AIC19, HC104, acetic acid (CH3COOH), nitric acid (HN03) and sulfuric acid (H2S04) or a mixture of these compounds.
The. condensation is carried out in solution. As solvent, it is possible to use either a polar solvent or a nonpolar solvent. The condensation is particularly preferably carried out in a solution comprising as solvent at least one compound selected from. among alcohols, ketones, aldehydes, ethers, acids, esters, anhydrides, alkanes, aromatics and nitrites and mixtures of two or more of these compounds. Particular preference is given to using alcohols, ethers, acetone, acetonitrile, benzene or toluene as solvent. It is of course also possible to use mixtures of solvents.
Depending on the type of monomers used, it may be necessary for water to be present during the condensation. This depends on whether or not the monomers contain hydroxyl groups. If the monomers are, for example, compounds of the formula RSi(OH)3, the condensation can also be carried out without addition of water. If the monomers are, for example, O.Z. 5688 - 8 -' compounds of the formula RSiCl3, wafer needs to be present as a reactant to allow the condensation to occur (via the silanols formed as intermediates. The condensation is therefore preferably commenced in the presence of water_ Preference is given to adding water, preferably in . 5 an amount of from 0.1 to 50°~6 by weight, parkicularly preferably from 5 to 50°~b by weight, based on the mvnomer~ontaining solution, to the reaction mixture prior to commencement of the condensation. However, depending on the water content of the solvent, the traces of water present in the solvent can also be utilized_ The process of the invention or the condensation can be carried out at a temperature of from -20°C to 300°C, preferably from 0°C
to 200°C. It may be advantageous to alter the temperature during the reaction. Thus, in particular, it can be advantageous to reduce the temperature toward the end of the reaction in order to isolate the product as completely as possible. The way in which the condensation reaction is carried out will be known per se to those skilled in the art_ The reaction ran be carried out at atmospheric pressure, subatmospheric 2 o pressure or superatmospheric pressure. The reaction or condensation is preferably carried out at atmospheric pressure.
In a particularly preferred embodiment of the process of the invention, a solution of at least one monomer of the formula RSi7(3 in at least one solution is placed in a reaction vessel with superposed condenser. This solution is heated to boiling under reflux and water is carefully added to the boiling solution while stirring vigorously. The solution is slowly brought to room temperature by switching off the source of heat and is stirred further for at least 24 hours, preferably at least 168 hours_ 3a snasesqmoxane or the rorrrluW rcsms~.t9'wruc:n' is m~b~cu un fium uiG ,.
solution and washed at least once with the solvent which was present in the solution_ It may be advantageous to grind the filtered-off residue in a mortar, to disperse it again in a small amount of the solvent and ' subsequently to filter it off again_ This procedure' can be repeated until the filter residue has the desired purity.
- 0.2. 5688 - 9 -To purify the residue further, in particular to separate incompletely condensed silasesquioxanes from the completely condensed silasesquioxanes of the formula RaSie09, it can be advantageous to dry the filter residue and admix it with from three to ten times, preferably from four to seven times, its weight of pyridine. In contrast to the incompletely condensed silasesquioxanes, the completely condensed silasesquioxane is virtually insoluble in pyridine and can be filtered off. This procedure, too, can be repeated until the desired purity is obtained.
1, o After purification by means of pyridine, it can be advantageous to recrystaliize the completely condensed silasesquioxane. The recrystallization is preferably carried vut using chloroform-The oligomeric silasesquioxanes of the invention or the ofigomeric z5 silasesquioxanes prepared by the process of the invention and having the formula RsSi8O9 (R = alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloaikynyl, aryl, heteroaryl) and the structure t can be used in processes for preparing incompletely condensed silasesquioxanes. Examples of incompletely condensed silasesquioxanes are compounds of the type ;
2o RySi~08(OH)3 and RsSig07(OH)4. In these processes, the oligomeric silasesquioxanes having the formula RaSieO9 (R = alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cyeloalkynyl, aryl, heteroaryl) and the structure I can be reacted, for example, with Bu4NOH andlor a compound of the formula R'Si(OR2)3, where R' is an alkyl group containing at least one unsaturated 2 5 C-C double bond and RZ is an alkyl group, preferably a methyl group.
These incompletely condensed silasesquioxanes can serve as starting compounds in processes for preparing polymers, e.g. by hydrolytic polycondensation, yr as starting compounds for the preparation of 30 catalysts, e.g. by reaction of the incompletely condensed silasesquioxanes with metal compounds to form metal-modified silasesquioxanes (metallasilasesquioxanes). Subsequent modification or replacement of the radicals R is of course also possible-35 The incompletely condensed silasesquioxanes aye particularly preferably modified by means of metals. Preference is given to modifying silasesquioxanes with metal compounds of the transition groups including the lanthanides and actinides and of main groups 3 and 4. In these processes, the incompletely condensed silasesquioxanes are reacted, for O.Z. 5688 - 10 -example, with metal alkoxides such as Ti(OBu'),,. Examples of metal-modified silasesquioxanes which can be obtained in this way are the titanasilasesquioxanes (CSH9)6(CHzCH)Si,0,2Ti(OBu') and (C,H,3)g{CH2CH)Si~O,zTi(08u').
The following examples illustrate the invention wifhout restricting its scope:
Example 1: Preparation of an oligomeric silasesquioxane of the formula (CsH")sSisOs 1, 0 100 ml of H20 were carefully added while .stirring to a solution of 100 g (460 mmvl) of CsH"SiCl3 in 400 ml of acetone; with the solution being maintained at the boiling point during the additibn. The reaction mixture was stirred at room temperature for another 168 hours- The crude product was filtered off and washed with acetone- The filter residue was ground in a mortar and dispersed in. 70 ml of acetone by stirring. After 1 hour, the solid was isolated by filtration and dried at 4o°C for 12 hours. The product mixture was admixed with five times its weight of pyridine and the suspension was stirred for 30 minutes. After filtration and washing with pyridine, the product was recrystallized from chloroform. This gave 15.4 g (19.0 mmol) of (CsH")sSisO9. This corresponded to a yield of 24.9°i6.
Example 2: Preparation of an oligomeric silasesquioxane of the formula (CSH9)BS X809 100 ml of Hz0 are carefully added while stirring to a solution of 93 g (457 rnmol) of CSHgSiCla in 400 ml of acetone, with the solution being ~ .
maintained at the boiling point during the additior~_ The reaction mixture is stirred at room temperature for another 168 hours. The crude product is :30 filtered off and washed with acetone. The filter residue is ground in a mortar and dispersed in 70 ml of acetone by stirring. Altar 7 hour, the solid is isolated by filtration and dried at 40°C for 12 hours. The product mixture is admixed with five times its weight of pyridine and the suspension is stirred for 30 minutes. After filtration and washing with pyridine, the 35 product is recrystallized from chloroform- This gives 11.6 g {16.0 mmol) of (C5H9)sSisOa. This corresponds to a yield of 21.0°~.
Example 3: Preparation of an oligomeric silasesquioxane of the formula (C~Ht3)eSisOs O.Z. 5688 - 11 -100 ml of H20 are carefully added while stirring to a solution of 106 g (458 mmol) of C,H~3SiCl3 in 400 ml of acetone, with the solution being , maintained at the boiling point during the addition. The reaction mixture is stirred at roam temperature for another 968 hours. The crude product is filtered off and washed with acetone. The filter residue is ground in a mortar and dispersed in 70 ml of acetone by stirring. After 1 hour, the solid is isolated by filtration and dried at 40°C for 12 hours. The product mixture is admixed with five times its weight of pyridine and the suspension is to stirred for 30 minutes- After filtration and washing with pyridine, the product is recrystallized from chloroform- This gives 13.0 g (14.5 mmol) of (C7H13}65809~ This corresponds to a yield of 19Ø
Example 4: Preparation of incompletely condensed silasesquioxanes , using a compound of the formula ReSi6Oa A solution of 1.99 g (2.74 mmol) of (CSH9)~Sis08 in 10 ml of THF is admixed with 1 _85 ml (2.77 mmol) of aqueous Bu,NOH and stirred at 25°C for 1 hour. The mixture is subsequently neutralized using 2M hydrochloric acid-2o The solvent is removed, the residue is dissolved in diethyl ether and the solution is dried over magnesium sulfate. Evaporation of the solvent gives {CSH9)sSisO~(OH), in quantitative yield.
Example 5: Preparation of incompletely condensed silasesquioxanes using a compound of the formula RsS~6O9 1 _85 ml (2.77 mmol) of an aqueous solution of Bu4NOH are added to a solution of 1.99 g (2.74 mmol) of {CsH9)sSisO9 and 0.42 ml of (vinyl}Si(OMe)3 in 10 ml of THF. The solution is stirred for 12 hours, the 3o solvent is removed, the residue is dissolved in diethyl ether and the solution is dried aver magnesium sulfate. Evaporation of the solvent gives (CSHs)s(ChIzCH)Si,O9(ON)3 in quantitative yield.
Example 6: Preparation of incompletely condensed silasesquioxanes using a compound of the formula R6Si608 A solution of 2_45 g (2.74 mmol) of (C7H13)6S~g09 in 10 ml of TH!= is admixed with 1.85 ml (2.77 mmol) of aqueous Bu,~NOH and stirred at 25°C
for 1 hour. The mixture is subsequently neutralized using 2M hydrochloric O.Z. 5688 - 12 -acid. The solvent is removed, the residue is dissolved in diethyl ether and the solution is dried over magnesium sulfate. Evaporation of the solvent gives (C7H,3)6S~6O7(OH)4 in quantitative yield.
Example 7: Preparation of incompletely condensed silasesquioxanes using a compound of the formula ReSisO9 1.85 ml (2.77 mmoi) of an aqueous solution of Bu4NOH are added to a solution of 2.45 g (2.74 mmol) of (C~H,3)eSis09 and 0.42 ml of (vinyl)Si(OMe)3 in 10 ml of TWF. The solution is stirred for 12 hours, the solvent is removed, the residue is dissolved in diethyl ether and the solution is dried over magnesium sulfate. Evaporation of the solvent gives (C,H,3)e(CHzCH)Si,Oa(OH)s in quantitative yield.
Example 8: Preparation of titanium-modified silasesquioxanes using incompletely condensed silasesquioxanes 1 g (2.94 mmol) of Ti(OBu'),, is added tv a solution of 2.3 g (2.76 mmol) of (CsH9)e(CHZCH)Si,O9(OH)3 in 100 m( of toluene and the reaction mixture is 2o stirred for 30 minutes. The solid is subsequently filtered off, dissolved in toluene and reprecipitated by means of acetonitrile. This gives 1 _58 g (1.66~mmol) of (CSHA)s(CH2CH)Si,O,zTi(OBu') as a white solid (60% yield).
Example 9: Preparation of titanium-modified silasesquivxanes using incompletely condensed silasesquioxanes 1 g (2.94 mmol) of Ti(OBu')a is added to a solution of 2.7 g (2.74 mmol) of (C,H~3)s(CHZCW)Si,09(OH)3 in 100 ml of toluene and the reaction mixture is stirred for 30 minutes. The solid is subsequently filtered off, dissolved in 3o toluene and reprecipitated by means of acetonitrile. This gives 1_66 g (1.49 mmol) of (C,H,3)e(CHZCH)Si~O,zTi(OBu') as a white solid (55% yield).
Claims (18)
1. An oligomeric silasesquioxane having the formula R6Si6O9 where R
= alkyl, cycloalkyl other than cyclohexyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl and/or heteroaryl and the structure 1
= alkyl, cycloalkyl other than cyclohexyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl and/or heteroaryl and the structure 1
2. An oligomeric silasesquioxane as claimed in claim 1, wherein the radicals R include at least one methyl, ethyl, propyl, butyl, i-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cycloheptyl, cyclooctanyl, cyclononanyl, cyclodecanyl, vinyl, propenyl, monounsaturated or polyunsaturated butenyl, cyclopropenyl, monounsaturated or poly unsaturated cyclobutenyl, monounsaturated or polyunsaturated cyclopentenyl, monounsaturated or polyunsaturated cyclohexenyl, monounsaturated or polyunsaturated cycloheptenyl, monounsaturated or polyunsaturated cyclooctenyl, ethynyl, propynyl, monounsaturated or polyunsaturated butynyl, benzyl and/or pyridyl group.
3. An oligomeric silasesquioxane as claimed in claim 1 or 2, wherein the radicals R are substituted or unsubstituted.
4. An oligomeric silasesquioxane as claimed in any of claims 1 to 3, wherein the radicals R include at least one cyclopentyl and/or cycloheptyl group.
5. An oligomeric silasesquioxane as claimed in any of claims 1 to 4, wherein the radicals R are all identical.
6. A process for preparing oligomeric silasesquioxanes having the formula R6Si6O9 where R = alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl and/or heteroaryl and the structure I by condensation of monomers of the formula RSiX3, where X can be a hydrolyzable group or a group capable of a condensation reaction, wherein the condensation is carried out in solution at a concentration of monomers of greater than 0.2 mot/l.
7. The process as claimed in claim 6, wherein the concentration of monomers in the solution is greater than 0.4 mol/l.
8. The process as claimed in claim 6 or 7, wherein the concentration of monomers is from 0.5 mol/l to 2.5 mol/l.
9. The process as claimed in at least one of claims 6 to 8, wherein the monomers used are compounds of the type RSiX3 in which the groups X include at least one group selected from among -OH, -ONa, -OK, -OR', -OCOR', -OSiR'3, -Cl, -Br, -I and/or -NR'2, where R' is an organic radical or hydrogen.
10. The process as claimed in at least one of claims 6 to 9, wherein the monomers used are compounds of the type RSiX3 in which all three groups X are identical.
11. The process as claimed in at least one of claims 6 to 10, wherein the monomers used include at least one compound of the type RSiXa containing, as radical R, at least one methyl, ethyl, propyl, butyl, i-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cycloheptyl, cyclooctanyl, cyclononanyl, cyclodecanyl, vinyl, propenyl, monounsaturated or polyunsaturated butenyl, cyclopropenyl, mono-unsaturated or polyunsaturated cyclobutenyl, monounsaturated or polyunsaturated cyclopentenyl, monounsaturated or polyunsaturated cyclohexenyl, monounsaturated or polyunsaturated cycloheptenyl, monounsaturated or polyunsaturated cyclooctenyl, ethynyl, propynyl, monounsaturated or polyunsaturated butynyl, benzyl or pyridyl group.
12. The process as claimed in any of claims 6 to 11, wherein the condensation is carried out in the absence of a catalyst or in the presence of at least one acidic catalyst or at least one basic catalyst.
13. The process as claimed in claim 12, wherein KOH, NaOH, (C2H5)4 NOH, C6H5CH2(CH3)3NOH, (CH3)4NOH and/or (C2H5)3N
is/are used as basic catalyst.
is/are used as basic catalyst.
14. The process as claimed in claim 12, wherein hydrochloric acid, sulfuric acid, nitric acid, ZnCl2, AlCl3. HClOA and/or acetic acid is/are used as acidic catalyst.
15. The process as claimed in any of claims 6 to 14, wherein the condensation is carried out in a solution comprising, as solvent, at least one compound selected from among alcohols, ketones, aldehydes, ethers, acids, esters, anhydrides, alkanes, aromatics and nitriles and mixtures of two or more of these compounds.
16. The process as claimed in any of claims 6 to 15, wherein the condensation is carried out at a temperature of from -20°C to 300°C.
17. The use of an oligomeric silasesquioxane as claimed in at least one of claims 1 to 5 or an oligomeric silasesquioxane prepared as claimed in at least one of claims 6 to 16 and having the formula R6Si6O9 (R = alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl) and the structure I for the synthesis of incompletely condensed silasesquioxanes, of catalysts and their starting compounds and also of polymers.
18. The use of an oligomeric silasesquioxane as claimed in at least one of claims 1 to 5 or an oligomeric silasesquioxane prepared as claimed in at least one of claims 6 to 16 and having the formula R6Si6O9 (R = alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl) and the structure I for the hydrolysis to form incompletely condensed silasesquioxanes and further conversion of these incompletely condensed silasesquioxanes into functionalized silasesquioxanes, to form catalysts, to form catalyst precursors and to form polymers.
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| DE10060776A DE10060776A1 (en) | 2000-12-07 | 2000-12-07 | Catalyst system based on polymer compounds containing silase sequioxane-metal complexes |
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| EP (1) | EP1213292B1 (en) |
| JP (1) | JP2002220394A (en) |
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| DE10060775A1 (en) * | 2000-12-07 | 2002-06-13 | Creavis Tech & Innovation Gmbh | Oligomeric silasesquioxanes and process for the preparation of oligomeric silasesquioxanes |
| DE10220853A1 (en) * | 2002-05-08 | 2003-11-20 | Creavis Tech & Innovation Gmbh | Functionalized polyhedral oligomeric silicon-oxygen clusters as crosslinkers |
| DE10321555A1 (en) * | 2003-05-14 | 2004-12-02 | Degussa Ag | Transparent masterbatches for thermoplastic materials |
| DE10330022A1 (en) * | 2003-07-03 | 2005-01-20 | Degussa Ag | Process for the preparation of Iow-k dielectric films |
| DE10331787A1 (en) * | 2003-07-11 | 2005-02-17 | Degussa Ag | NCO-containing compounds with covalently bonded polyhedral oligomeric silicon-oxygen cluster units |
| US9096041B2 (en) | 2004-02-10 | 2015-08-04 | Evonik Degussa Gmbh | Method for coating substrates and carrier substrates |
| DE102004006612A1 (en) | 2004-02-10 | 2005-08-25 | Degussa Ag | Compound ceramic wall coating comprises a carrier layer and at least one ceramic layer containing ceramic particles which are chosen from a group of oxides, nitrides, borides or carbides of metal or semi-metals |
| US7320828B2 (en) * | 2004-02-18 | 2008-01-22 | Fujifilm Corporation | Composition for forming insulating film and process for producing insulating film |
| JP2008534714A (en) * | 2005-03-22 | 2008-08-28 | バイオセーフ インク． | Method for making solvent-free, silicone-containing quaternary ammonium-containing polymer antibacterial agents with excellent and durable antibacterial properties |
| US20080275778A1 (en) * | 2005-07-26 | 2008-11-06 | Johnson James H | Method of Community Service and Disaster Relief |
| EP2052008B1 (en) * | 2006-07-18 | 2017-05-10 | M&G USA Corporation | Poss metal compounds for the manufacture of polycondensation polymers |
| PT3511335T (en) * | 2018-01-10 | 2020-12-21 | Nitrochemie Gmbh | Manufacture of metallasilisesquioxanes |
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| SU668280A1 (en) * | 1976-05-10 | 1981-12-15 | Институт Неорганической Химии Со Ан Ссср | Method of preparing alkylsequioxans |
| US5484867A (en) * | 1993-08-12 | 1996-01-16 | The University Of Dayton | Process for preparation of polyhedral oligomeric silsesquioxanes and systhesis of polymers containing polyhedral oligomeric silsesqioxane group segments |
| US5412053A (en) * | 1993-08-12 | 1995-05-02 | The University Of Dayton | Polymers containing alternating silsesquioxane and bridging group segments and process for their preparation |
| WO1997024344A1 (en) * | 1995-12-27 | 1997-07-10 | Shell Internationale Research Maatschappij B.V. | Preparation of oxirane compounds with titanasilsesquioxane catalysts |
| WO1998046352A1 (en) * | 1997-04-16 | 1998-10-22 | Solvay Deutschland Gmbh | Method for producing silasesquioxane metal complexes, novel silasesquioxane metal complexes and the use thereof |
| US6660823B1 (en) * | 1998-03-03 | 2003-12-09 | The United States Of America As Represented By The Secretary Of The Air Force | Modifying POSS compounds |
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| Publication number | Publication date |
|---|---|
| EP1213292B1 (en) | 2004-02-25 |
| DE50101544D1 (en) | 2004-04-01 |
| JP2002220394A (en) | 2002-08-09 |
| DE10060776A1 (en) | 2002-06-13 |
| US20030096934A1 (en) | 2003-05-22 |
| ATE260286T1 (en) | 2004-03-15 |
| EP1213292A1 (en) | 2002-06-12 |
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