Patent Application
20130204027
1. Field of the Invention
The present invention relates to a process for preparing silaoxacycles having structural units in which silicon and oxygen atoms are bonded to one another via a CH2 group.
2. Description of the Related Art
Silaoxacycles in which silicon and oxygen atoms are bonded to one another via a CH2 group are excellent reagents for the preparation of (hydroxymethyl)-polysiloxanes by termination of silicone oils according to the following reaction equation:
Since the silaoxacycle used as the terminating reagent, being a cyclic compound, has no end groups or the like which have to be eliminated in the reaction, the reaction I is a smooth addition reaction without any condensation products which would have to be removed thereafter. The thus produced carbinol oil terminated with Si—CH2—OH groups is of excellent suitability for the preparation of “AA-BB” polymers, for example by reaction with diisocyanates, provided that the termination is quantitative, since every Si—OH group which is not terminated with an Si—CH2—OH group is converted in the course of subsequent preparation of AA-BB polymers by means of diisocyanates to an Si—O—C(O)—NH— group, the Si—O bond of which constitutes a hydrolysis-sensitive cleavage site. The greater the purity of the silaoxacycle used, the smoother the termination.
The specialist literature describes various methods for preparation of silaoxacycles in which silicon and oxygen atoms are bonded to one another via a CH2 group.
For instance, the preparation of 2,2,5,5-tetramethyl-1,4-dioxa-2,5-disilacyclohexane by heating of 1,3-bis-(hydroxymethyl)-1,1,3,3-tetramethyldisiloxane over calcium oxide as a desiccant has been described in U.S. Pat. No. 2,898,346 and Journal of Organic Chemistry 1960, vol. 25, p. 1637-1640. However, this process gives the product only in a 40-60% yield and requires the use of calcium oxide in a molar amount, in order that the water formed can be fully bound. The process gives an impure product, recognizable by the broad boiling range of the product fraction and by the elemental analysis reported, which has distinct deviations from the theoretical values. The poor purity of the product thus prepared is confirmed by Chemische Berichte 1966, vol. 99, p. 1368-1383 (see footnote 10 therein on p. 1373).
Chemische Berichte 1966, vol. 99, p. 1368-1383 describes a process for preparing 2,2,5,5-tetramethyl-1,4-dioxa-2,5-disilacyclohexane (1) by heating (acetoxymethyl)ethoxydimethylsilane with a large excess of 13 molar equivalents of methanol in the presence of p-toluenesulfonic acid (p-TsOH) to give ethoxy(hydroxymethyl)dimethylsilane, neutralizing the resulting primary product and then, after again adding p-toluenesulfonic acid, distilling gradually with elimination of ethanol (reaction III):
This process, however, is uneconomical since it enables only poor space-time yields, because more than ⅔ of the reaction volume consists of methanol. After distillative removal of methyl acetate, a neutralization step is conducted with potassium hydroxide and CO2, and then the actual product, 2,2,5,5-tetramethyl-1,4-dioxa-2,5-disilacyclohexane (1), after again adding p-toluenesulfonic acid, is obtained by distillation. These individual steps additionally make the process laborious. In the case of distillation in the presence of free p-toluenesulfonic acid, there is the risk of formation of linear or cyclic ether moieties Si—CH2—O—CH2—Si which, as likewise described in Chem. Ber. 1966, vol. 99, page 1371, form readily with elimination of water under the influence of the p-toluenesulfonic acid. This mode of operation means that the distillation step has only poor reproducibility. The presence of such ether moieties limits the use of the silaoxacycles as end-capping reagents for polysiloxanes, since they recur unchanged in the product.
The reference Organosilicon Chemistry, Scientific Communications, Prague, 1965, p. 120-124 shows basically the same reaction route in the form of reaction equations, but does not contain any working or procedural instructions which would enable skilled persons to comprehend the reaction sequence shown therein or to isolate a product.
2,2,5,5-Tetramethyl-1,4-dioxa-2,5-disilacyclohexane (1), 2,5-dimethyl-2,5-diphenyl-1,4-dioxa-2,5-disilacyclohexane and 2,2,5,5-tetraphenyl-1,4-dioxa-2,5-disilacyclohexane were prepared by condensation of (hydroxymethyl)dimethylsilane, (hydroxymethyl)methyl-phenylsilane and (hydroxymethyl)diphenylsilane respectively, with elimination of hydrogen (Zeitschrift fur Naturforschung B, 1983, vol. 38, p. 190-193). The reacting groups are in the same molecule, as a result of which safe storage of the reactant in industry is impossible.
Moreover, the specialist literature describes various methods for transesterification of silanes bearing an acyloxyalkyl group.
DE 1 251 961 B describes the preparation of cyclic silane compounds whose structure can be represented by the formula *-O—R′—SiR″2-* where * is the point of ring closure and R′ is a divalent hydrocarbyl radical which connects the silicon and oxygen atoms via at least three carbon atoms. This involves subjecting an ester of the structure acyl-O—R′—SiR″2—OR′″ to a transesterification reaction with an alcohol. If the thus prepared compounds of the structure *-O—R′—SiR″2-* are reacted analogously to reaction I with silicone oils, the products formed, however, have a comparatively high organic component since R′ has at least three carbon atoms, which is disadvantageous with regard to properties such as flame retardancy of the successor products.
Union Carbide has described, in several applications (see EP 129 121 A1, EP 120 115 A1, EP 107 211 A2, EP 106 062 A2, EP 93 806 A1, EP 73 027 A2 and EP 49 155 A2), the preparation of acyclic products having repeat units of the structure *[O—R′—SiR″2—]p* (*=end groups or undefined groups). This involves subjecting an ester of the structure acyl-O—R′—SiR″2—OR′″ to a trans-esterification reaction with elimination of an ester acyl-OR′″, which is distilled out of the reaction mixture, the chain length distribution p of the product being controlled by the extent to which the trans-esterification is driven, and it is possible to add, as regulators to limit the extent of transesterification, high-boiling esters such as ethyl benzoate, methyl benzoate or ethyl laurate, which bring about blocking of the * end groups of the product by incorporating the acyl radical and the alkoxy radical of the high-boiling ester added into the product as * end groups. However, the preparation of cyclic compounds which could be isolated or purified, for example, by distillation has not been described.
The preparation of homocondensates of (hydroxymethyl)-silanes is also described in DE 44 07 437 A1. However, the document describes only how transesterification of (acyloxymethyl)silanes with alcohols gives an inhomo-geneous mixture of linear or branched condensates.
The invention provides a process for preparing silaoxacycles of the general formula I
in which compounds of the general formula II
R1—C(═O)—[O—CH2—Si(R2)2]nOR3 (II)
are converted in the presence of acidic catalyst and alcohol A, using 0.01 to 7 molar equivalents of alcoholic OH groups of the alcohol A per 1 molar equivalent of [O—CH2—Si(R2)2] units of the compounds of the general formula II and isolating the silaoxacycles of the general formula I after removing the acidic catalyst, where
The process is efficient and economic. By virtue of the process, the silaoxacycles of the general formula I can be made available in a purity which allows direct further use, for example according to the above reaction I.
It has been found that, surprisingly, the desired silaoxacycles can be prepared easily in a robust process and in high purity when silanes having acyloxymethyl and alkoxy groups are subjected to a transesterification in a particular manner.
The compounds of the general formula II, the alcohol A and the acidic catalyst can each be used in a mixture or as a pure substance. The silaoxacycles of the general formula I can likewise be obtained as a mixture or as a pure substance. Identical or different compounds of the general formula II, identical or different catalysts and identical or different alcohols A can be added successively in a plurality of steps.
Preferably, at least one compound of the general formula I is isolated from the reaction mixture. The isolation of the compound of the general formula I from the reaction mixture is preferably accomplished by distillation, in which case the compound of the general formula I is distilled over as distillate.
In the process, a by-product of the general formula III
R1—C(═O)—OR3 (III)
is generally likewise removed, for example by distillation, in which case the by-product of the general formula III, according to the choice of R1 and R3 radicals, can be obtained as distillate or as distillation residue.
x preferably assumes values from 1 to 30, more preferably values from 1 to 3, and most preferably the value of 1. x may assume, for example, the values of 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.
n preferably assumes values from 1 to 30, more preferably values from 1 to 3, and most preferably the value of 1. n may assume, for example, the values of 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.
R1 is, for example, a hydrogen atom or a linear or branched, saturated or mono- or polyunsaturated hydro-carbyl radical which is cyclic or acyclic or contains a plurality of cycles or - when R1 is an OR3 group - a hydrocarbyloxy radical. R1 is preferably a hydrogen atom or a C1-C40 alkyl radical, a C6-C40 aryl radical, a C7-C40 alkylaryl radical or a C7-C40 arylalkyl radical. R1 is more preferably a hydrogen atom, a C1-C20 alkyl radical, a C6-C20 aryl radical, a C7-C20 alkylaryl radical or a C7-C20 arylalkyl radical. R1 is most preferably a hydrogen atom, a C1-C12 alkyl radical, a C6-C12 aryl radical, a C7-C12 alkylaryl radical or a C7-C12 arylalkyl radical. R1 preferably contains zero to four heteroatoms, especially zero heteroatoms. R1 is preferably unsubstituted. R1 most preferably consists exclusively of carbon and hydrogen atoms or is a hydrogen atom. Examples of R1 are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-heptyl, 1-ethylpentyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-tridecyl, n-pentadecyl, n-heptadecyl, n-nonadecyl, phenyl, benzyl, 2-methylphenyl, 3-methylphenyl, and 4-methylphenyl.
R2 is, for example, a linear or branched, saturated or mono- or polyunsaturated hydrocarbyl radical which is cyclic or acyclic or contains a plurality of cycles, or when R2 is an OR4 group, contains a hydrocarbyloxy radical. R2 is preferably a C1-C40 alkyl radical, a C6-C40 aryl radical, a C7-C40 alkylaryl radical, a C7-C40 arylalkyl radical, a C1-C40 alkoxy radical, a C2-C40 (alkoxy)alkoxy radical, a C6-C40 aryloxy radical, a C7-C40 arylalkoxy radical or a C7-C40 alkylaryloxy radical. R2 is more preferably a C1-C20 alkyl radical, a C6-C20 aryl radical, a C7-C20 alkylaryl radical or a C7-C20 arylalkyl radical, a C1-C20 alkoxy radical, a C2-C20 (alkoxy)alkoxy radical, a C6-C20 aryloxy radical, a C7-C20 arylalkoxy radical or a C7-C20 alkylaryloxy radical. R2 is most preferably a C1-C12 alkyl radical, a C6-C12 aryl radical, a C7-C12 alkylaryl radical or a C7-C12 arylalkyl radical, a C1-C12 alkoxy radical, a C2-C12 (alkoxy)alkoxy radical, a C6-C12 aryloxy radical, a C7-C12 arylalkoxy radical or a C7-C12 alkylaryloxy radical. R2 preferably contains zero to four heteroatoms, more preferably zero or one heteroatom, and most preferably no heteroatom when R2 is not OR4, and more preferably one to two oxygen atoms, especially one oxygen atom, when R2 is OR4. R2 is preferably unsubstituted or substituted by one alkoxy group, especially unsubstituted. Most preferably, R2 consists exclusively of carbon and hydrogen atoms or of carbon and hydrogen atoms and one oxygen atom; in the latter case, this oxygen atom is preferably bonded to the silicon atom. Examples of R2 are methyl, ethyl, vinyl, allyl, ethynyl, propargyl, 1-propenyl, 1-methylvinyl, methallyl, phenyl, benzyl, ortho-, meta- or para-tolyl, methoxy, ethoxy, 2-methoxyethoxy, 2-methoxy-1-methylethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, tert-pentoxy, n-hexoxy, 2-ethylhexoxy, n-octoxy, n-decoxy, n-dodecoxy, n-tetradecoxy, n-octadecoxy, n-eicosoxy, phenoxy or benzyloxy.
R3 is, for example, a linear or branched, saturated or mono- or polyunsaturated hydrocarbyl radical which is cyclic or acyclic or contains a plurality of cycles. R3 is preferably a C1-C40 alkyl radical, a C6-C40 aryl radical, a C7-C40 alkylaryl radical, a C7-C40 arylalkyl radical or a C2-C40 (alkoxy)alkyl radical. R3 is more preferably a C1-C20 alkyl radical, a C6-C20 aryl radical, a C7-C20 alkylaryl radical, a C7-C20 arylalkyl radical or a C2-C20 (alkoxy)alkyl radical. R3 is most preferably a C1-C12 alkyl radical, a C6-C12 aryl radical, a C7-C12 alkylaryl radical, a C7-C12 arylalkyl radical or a C2-C12 (alkoxy)alkyl radical. R3 preferably contains zero to four heteroatoms, more preferably zero or one heteroatom, and most preferably no heteroatom. R3 is preferably unsubstituted or substituted by one alkoxy group, especially unsubstituted. R3 most preferably consists exclusively of carbon and hydrogen atoms or of carbon and hydrogen atoms and one oxygen atom, this oxygen atom being part of an ether group, i.e. bonded to two carbon atoms. Examples of R3 are methyl, ethyl, 2-methoxyethyl, 1-methyl-2-methoxyethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, 2-ethylhexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl, phenyl or benzyl.
R4 is, for example, a linear or branched, saturated or mono- or polyunsaturated hydrocarbyl radical which is cyclic or acyclic or contains a plurality of cycles. R4 is preferably a C1-C40 alkyl radical, a C6-C40 aryl radical, a C7-C40 alkylaryl radical, a C7-C40 arylalkyl radical or a C2-C40 (alkoxy)alkyl radical. R4 is more preferably a C1-C20 alkyl radical, a C6-C20 aryl radical, a C7-C20 alkylaryl radical, a C7-C20 arylalkyl radical or a C2-C20 (alkoxy)alkyl radical. R4 is most preferably a C1-C12 alkyl radical, a C6-C12 aryl radical, a C7-C12 alkylaryl radical, a C7-C12 arylalkyl radical or a C2-C12 (alkoxy)alkyl radical. R4 preferably contains zero to four heteroatoms, more preferably zero or one heteroatom, and most preferably no heteroatom. R4 is preferably unsubstituted or substituted by one alkoxy group, especially unsubstituted. R4 most preferably consists exclusively of carbon and hydrogen atoms or of carbon and hydrogen atoms and one oxygen atom, in which case this oxygen atom is part of an ether group, i.e. is bonded to two carbon atoms. Examples of R4 are methyl, ethyl, 2-methoxyethyl, 1-methyl-2-methoxyethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, 2-ethylhexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl, phenyl or benzyl.
Q1 is preferably a halogen atom, for example a fluorine, chlorine, bromine or iodine atom, a hydrocarbyloxy group, for example a C1-C40 alkoxy group or a C6-C40 aryloxy group, an acyl group, for example an aliphatic C1-C40 acyl group, or an aromatic C7-C40 acyl group, a hydrocarbyl sulfide group, for example a C1-C40 alkyl sulfide group or a C6-C40 aryl sulfide group, a cyano group or a nitro group.
In a particularly preferred combination, the above-defined groups are selected such that the R1 radical is a hydrogen atom, a methyl group or an ethyl group, the R2 radicals are each independently methyl, methoxy or ethoxy groups, especially methyl groups, the R3 radical is a methyl or ethyl group, n assumes integer values from 1 to 3, especially 1, and x assumes integer values from 1 to 3, especially 1.
The structural unit [O—CH2—Si(R2)2]n in the general formula II may be linear or branched. If, for example, the compounds of the general formula II selected were compounds where R1=Me, R2=OMe and OR3=OMe, the general formula II may represent structures including the following:
Me-C(═O)—[O—CH2—Si(OMe)2]—OMe n=1
Me-C(═O)—[O—CH2—Si(OMe)2-O—CH2—Si(OMe)2]—OMe n=2 (linear)
Me-C(═O)—[O—CH2—Si(OMe)2-O—CH2—Si(OMe)2-O—CH2—Si(OMe)2]—OMe n=3 (linear)
Me-C(═O)—[O—CH2—Si(O—CH2—Si(OMe)3)2]—OMe n=3 (branched)
Me-C(═O)—[O—CH2—Si(O—CH2—Si(OMe)3)2—O—CH2—Si(OMe)2]—OMe, n=4 (branched, selected example)
where the structural units in square brackets always have the empirical formula of [O—CH2—Si(OMe)2]n with the particular specified value of n.
Compounds of the general formula II are, for example, when n=1, preparable by a process as described in Monatshefte fur Chemie 2003, vol. 134, p. 1081-1092 (see the section “General Procedure for the Synthesis of 1-4” in the reference at p. 1090); instead of the methacrylic acid described therein, it is also possible to use another carboxylic acid of the general formula R1COOH.
The process is executed in the presence of at least one acidic catalyst.
Acidic catalysts usable in the process are Brønsted acids (proton donors) preferably with pKa values of −12 to +9. Suitable Brønsted acids are, for example, hydrohalic acids, e.g. HF, HCl, HBr and HI.
Suitable acidic catalysts are oxygen acids of the elements of main groups 3 to 7, the acidic salts thereof and acidic esters thereof, where one or more oxygens may be substituted by halogen, especially fluorine, for example boric acid, carbonic acid, nitrous acid, nitric acid, phosphorous acid, lithium dihydrogenphosphite, sodium dihydrogenphosphite, potassium dihydrogenphosphite, rubidium dihydrogenphosphite and cesium dihydrogenphosphite, mono- or diesters of phosphorous acid [(R5O)qP(OH)3-q) where q=1 or 2], phosphoric acid, lithium dihydrogenphosphate, sodium dihydrogenphosphate, potassium dihydrogenphosphate, rubidium dihydrogenphosphate and cesium dihydrogenphosphate, mono- or diesters of phosphoric acid [(R6O)qP(O)(OH)3-q) where q=1 or 2], sulfurous acid, lithium hydrogensulfite, sodium hydrogensulfite, potassium hydrogensulfite, rubidium hydrogensulfite and cesium hydrogensulfite, sulfuric acid, lithium hydrogensulfate, sodium hydrogensulfate, potassium hydrogensulfate, rubidium hydrogensulfate and cesium hydrogensulfate, monoesters of sulfuric acid (R7OSO3H), chloric acid and perchloric acid, bromic acid and perbromic acid, iodic acid and periodic acid, tetrafluoroboric acid, hexafluorophosphoric acid.
Suitable acidic catalysts are also carboxylic acids (R8—COOH). Suitable acidic catalysts are also oxygen acids of the elements P and S which bear a carbonaceous radical covalently bonded to P or S, for example sulfonic acids (R9—SO3H) and phosphonic acids [R10—P(O)(OH)2].
Suitable acidic catalysts are also carboxyl-containing organic polymers which may be linear, branched or crosslinked. The polymers contain preferably 0.1 mol to 10 mol and more preferably 1 mol to 5 mol of carboxyl groups per kg of polymer.
Suitable acidic catalysts are also sulfo-containing organic polymers which may be linear, branched or crosslinked. The polymers preferably contain 0.1 mol to mol and more preferably 1 mol to 5 mol of sulfo groups per kg of polymer.
The carboxyl-containing and sulfo-containing organic polymers are preferably crosslinked, which means that they are in the form of resins. The polymeric base skeleton of the resins consists, for example, of polycondensates of phenol and formaldehyde, of copolymers of styrene and divinylbenzene or of copolymers of methacrylates and divinylbenzene.
Suitable acidic catalysts are also amidosulfonic acids (R11R12NSO3H).
Suitable acidic catalysts are also acidic alumina, clay minerals, montmorillonites, attapulgites, bentonites, acidic zeolites, iso- and heteropolyacids.
Acidic zeolites are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry vol. 39, p. 646 (Wiley-VCH 2003).
Isopolyacids are condensates of inorganic polybasic acids with a central atom type selected from Si, P, V, Mo and W, for example polymeric silica, molybdic acid and tungstic acid. Heteropolyacids are inorganic polyacids with at least two different central atoms from in each case polybasic oxygen acids of a metal, especially Cr, Mo, V, W, and of a nonmetal, especially As, I, P, Se, Si, Te, for example 12-molybdato-phosphoric acid (H3[PMo12O40]) or 12-tungstophosphoric acid (H3[PW12O40]).
R5, R6, R7, R8, R9 and R10 are each independently hydrocarbyl radicals which are unsubstituted or substituted by one or more Q2 groups and may be interrupted by one or more heteroatoms, where Q2 is a monovalent, divalent or trivalent heteroatom-containing radical.
R11 and R12 are each independently hydrogen or hydrocarbyl radicals which are unsubstituted or substituted by one or more Q3 groups and which may be interrupted by one or more heteroatoms, where Q3 is a monovalent, divalent or trivalent heteroatom-containing radical.
R5 is, for example, a linear or branched, saturated or mono- or polyunsaturated, cyclic or acyclic or polycyclic hydrocarbyl radical. R5 is preferably a C1-C40 alkyl radical, a C6-C40 aryl radical, a C7-C40 alkylaryl radical, a C7-C40 arylalkyl radical or C2-C40 (alkoxy)alkyl radical. R5 is most preferably a C1-C20 alkyl radical, a C6-C20 aryl radical, a C7-C20 alkylaryl radical, a C7-C20 arylalkyl radical or C2-C20 (alkoxy)alkyl radical. R5 is especially preferably a C1-C12 alkyl radical, a C6-C12 aryl radical, a C7-C12 alkylaryl radical, a C7-C12 arylalkyl radical or C2-C12 (alkoxy)alkyl radical. R5 contains preferably zero to four heteroatoms, more preferably zero or one heteroatom, and most preferably no heteroatom. R5 is preferably unsubstituted or substituted by one alkoxy group, especially unsubstituted. More preferably, R5 consists exclusively of carbon and hydrogen atoms or of carbon and hydrogen atoms and one oxygen atom, in which case this oxygen atom is part of an ether group, i.e. is bonded to two carbon atoms. Examples of R5 are methyl, ethyl, 2-methoxyethyl, 1-methyl-2-methoxyethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, 2-ethyl-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl, phenyl or benzyl.
R6 and R7 may each independently assume the definition of R5.
R8 is, for example, hydrogen or a linear or branched, saturated or mono- or polyunsaturated, cyclic or acyclic or polycyclic hydrocarbyl radical. R8 is preferably hydrogen or a C1-C40 alkyl radical, a C6-C40 aryl radical, a C7-C40 alkylaryl radical or a C7-C40 arylalkyl radical. R8 is more preferably hydrogen or a C1-C20 alkyl radical, a C6-C20 aryl radical, a C7-C20 alkylaryl radical or a C7-C20 arylalkyl radical. R8 is most preferably hydrogen or a C1-C12 alkyl radical, a C6-C12 aryl radical, a C7-C12 alkylaryl radical or a C7-C12 arylalkyl radical.
Individual hydrogens in R8 may preferably be replaced by halogen, preferably fluorine, chlorine or bromine, nitro, hydroxyl, sulfo groups and/or further carboxylic acid groups. Preference is given to 0 to 13 fluorine, chlorine or bromine atoms, 0 to 5 nitro groups, 0 to 5 hydroxyl groups, 0 to 5 sulfo groups and 0 to 10 carboxylic acid groups, particular preference being given to 0 to 9 fluorine, chlorine or bromine atoms, 0 to 3 nitro groups, 0 to 3 hydroxyl groups and 0 to 5 carboxylic acid groups.
Examples of R8—COOH are acetic acid, chloroacetic acid, trifluoroacetic acid, trichloroacetic acid, oxalic acid, citric acid, malonic acid, benzoic acid, 3-nitro-benzoic acid, phthalic acid, naphthalenecarboxylic acid, 4-hydroxybenzoic acid.
R9 is, for example, a linear or branched, saturated or mono- or polyunsaturated, cyclic or acyclic or polycyclic hydrocarbyl radical. R9 is preferably a C1-C40 alkyl radical, a C6-C40 aryl radical, a C7-C40 alkylaryl radical or a C7-C40 arylalkyl radical. R9 is more preferably a C1-C20 alkyl radical, a C6-C20 aryl radical, a C7-C20 alkylaryl radical or a C7-C20 arylalkyl radical. R9 is most preferably a C1-C12 alkyl radical, a C6-C12 aryl radical, a C7-C12 alkylaryl radical or a C7-C12 arylalkyl radical.
Individual hydrogens in R9 may preferably be replaced by halogen, preferably fluorine, chlorine or bromine, nitro, hydroxyl, carboxyl groups and/or further sulfo groups. Preference is given to 0 to 13 fluorine or chlorine atoms, 0 to 5 nitro groups, 0 to 5 hydroxyl groups, 0 to 5 carboxyl groups and 0 to 10 sulfo groups, and with particular preference to 0 to 9 fluorine or chlorine atoms, 0 to 3 nitro groups, 0 to 3 hydroxyl groups and 0 to 5 sulfo groups. Examples of R9—SO2H are methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, 2-naphthalenesulfonic acid, trifluoromethanesulfonic acid, naphthalene-1,5-disulfonic acid.
R10 is, for example, a linear or branched, saturated or mono- or polyunsaturated, cyclic or acyclic or polycyclic hydrocarbyl radical. R10 is preferably a C1-C40 alkyl radical, a C6-C40 aryl radical, a C7-C40 alkylaryl radical or a C2-C40 arylalkyl radical. R10 is more preferably a C1-C20 alkyl radical, a C6-C20 aryl radical, a C7-C20 alkylaryl radical or a C7-C20 arylalkyl radical. R10 is most preferably a C1-C12 alkyl radical, a C6-C12 aryl radical, a C7-C12 alkylaryl radical or a C7-C12 arylalkyl radical. R10 preferably contains zero to four heteroatoms, most preferably no heteroatom. R10 is preferably unsubstituted. R10 most preferably consists exclusively of carbon and hydrogen atoms or is a hydrogen atom. Examples of R10 are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-heptyl, 1-ethylpentyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-tridecyl, n-pentadecyl, n-heptadecyl, n-nonadecyl, phenyl, benzyl, 2-methylphenyl, 3-methylphenyl, and 4-methylphenyl.
R11 and R12 are each independently, for example, hydrogen or linear or branched, saturated or mono- or polyunsaturated, cyclic or acyclic or polycyclic hydrocarbyl radicals. R11 and R12 are preferably hydrogens, C1-C40 alkyl radicals, C6-C40 aryl radicals, C7-C40 alkylaryl radicals, C7-C40 arylalkyl radicals or C2-C40 (alkoxy)alkyl radicals. R11 and R12 are more preferably hydrogens or C1-C20 alkyl radicals, C6-C20 aryl radicals, C7-C20 alkylaryl radicals, C7-C20 arylalkyl radicals or C2-C20 (alkoxy)alkyl radicals. R11 and R12 are most preferably hydrogen, C1-C12 alkyl radicals, C6-C12 aryl radicals, C7-C12 alkylaryl radicals, C7-C12 arylalkyl radicals or C2-C12 (alkoxy)alkyl radicals. R11 and R12 each preferably contain zero to four heteroatoms, more preferably zero or one heteroatom, and most preferably no heteroatom. R11 and R12 are preferably unsubstituted or substituted by one alkoxy group, especially unsubstituted. R11 and R12 most preferably each consist exclusively of carbon and hydrogen atoms. Examples of R11 and R12 are methyl, ethyl or phenyl.
Most preferred are sulfonic acids, organic resins with sulfo groups, acidic alumina, clay minerals, montmorillonites, acidic zeolites, and iso- and heteropolyacids.
Especially preferred are also organic resins with sulfo groups and acidic montmorillonites.
Examples of organic resins with sulfo groups are gel-type or macroreticular resins which differ especially in terms of pore size, surface area, density and particle size, for example the commercially available acidic ion exchange resins with the trade names Amberlyst® or Amberlite® (from Rohm and Haas/Dow), Lewatit® (from Lanxess) and Dowex® (from Dow Chemical).
Hydrous resins are preferably dried, for example under reduced pressure, or by washing with an alcohol, preferably of the general formula R13—OH, or with a volatile inert water-miscible solvent, for example THF, with subsequent removal of the inert solvent under reduced pressure.
Examples of montmorillonites are the commercially available products K10, K20 and KP 10.
Catalysts in heterogeneous form can be used, for example, in the form of powders, granules or shaped bodies, for example rings or rods. They may likewise comprise an inert support. Supports are, for example, crosslinked polymers or silica gel or alumina.
The acidic catalyst is preferably used in proportions by weight of at least 0.01%, more preferably at least 0.1%, and especially at least 0.5%, and at most 100%, more preferably at most 50%, and especially at most 10%, based on the mass of the compound of the general formula II used.
The catalyst can be used in combination with cocatalysts, promoters, moderators or catalyst poisons. Promoters can enhance the action of catalysts. Catalyst poisons can attenuate the action of catalysts or suppress unwanted catalytic effects.
The catalysts can be used directly in the reaction vessel. Heterogeneous catalysts can additionally be used in a parallel catalyst section through which the reaction solution is constantly circulated, for example by pumping, convection or circulation. The catalyst is removed here, for example, by stopping the pumping, convection or circulation operation.
The reaction is performed in the presence of one or more alcohols A. The alcohols A preferably have the formula R13—OH, where R13 may assume the same definitions and preferred definitions as R3 and may additionally bear OH substituents. In the aforementioned formulae, the OR3 and OR4 groups may be partly or fully replaced by OR13 groups, in which case alcohols of the structure R3—OH or R4—OH can be formed, and the R1—C(═O)— groups in the aforementioned formulae may be replaced by hydrogen. When R13 has a plurality of alcoholic OH functions, several exchange reactions of this kind can take place, such that corresponding structures bridged via R13 are formed.
In contrast to the process described in Chemische Berichte 1966, volume 99, p. 1368-1383, in which 13 molar equivalents of alcohol are present in the reaction mixture, the presence of a significantly smaller amount of alcohol of not more than 7 molar equivalents in the process according to the invention achieves significantly higher space-time yields.
Preferably at least 0.05, more preferably at least 0.1 and at most 4 and more preferably at most 2 molar equivalents of alcoholic OH groups of the alcohol A are present per 1 molar equivalent of [O—CH2—Si(R2)2] units of the compounds of the general formula II in the reaction mixture.
The amounts may be lower than the upper limits specified by virtue of supply of alcohol A, especially of the formula R13—OH, and removal of a corresponding amount of the reaction product of the general formula III, alcohol of the formula R13—OH and/or R3—OH and/or R4—OH, which may be present as mixtures, from the mixture (for example distillation, possibly together with other compounds present in the mixture), such that the molar equivalent limits specified for the alcohols in the mixture are not exceeded, or by virtue of supply, over the course of the process, of a total of preferably more than 0.1 but less than 4 molar equivalents of alcohol A in total, based on 1 molar equivalent of [O—CH2—Si(R2)2] units of the compounds of the general formula II.
The reaction through which the compounds of the general formula II react to give compounds of the general formula I can be executed, for example, in the gas phase, in the liquid phase, in the solid phase, in the supercritical state, in supercritical media, in solution or in substance, i.e. neat. Preference is given to executing the process in the liquid phase, in solution or in substance, preferably in the liquid phase, preferably in substance, more preferably in the liquid phase and in substance.
The process can be performed over a wide temperature range, for example at least 0° C., preferably at least 30° C., more preferably at least 40° C., and most preferably at least 50° C., and, for example, at most 400° C., preferably at most 300° C., more preferably at most 250° C., and most preferably at most 200° C.
The process can be executed over a wide pressure range, for example at least 0.1 Pa, preferably at least 1 Pa, more preferably at least 10 Pa, and most preferably at least 100 Pa and, for example, at most 500 MPa, preferably at most 10 MPa, more preferably at most 1 MPa, and most preferably at most 500 kPa absolute. In a particularly preferred embodiment, the process is executed at atmospheric pressure, which, according to the ambient conditions, is generally within a range between 90 and 105 kPa absolute.
The process can be executed continuously or batchwise. In the batchwise embodiment, the process can be executed, for example, in a cascade reactor or in a stirred tank. In the continuous embodiment, the process can be executed, for example, in a tubular, delay, circulation or cascade reactor, or a dynamic or static mixer.
If compounds of the general formula II in which n has a particular value or particular values are used as the reactant in the process, in the course of execution of the process, compounds of the general formula IIa may occur
R1—C(═O)—[O—CH2—Si(R2)2]m—OR3 (IIa)
where R1, R2 and R3 may assume the definitions given above and m may assume integer values greater than or equal to 1, and in which m has values which differ from the values for n as possessed by the compounds of the formula II used.
If, in the process, for example, the particularly preferred compounds of the general formula II in which n has the value of 1 are used as the reactant, in the course of execution of the process, compounds of the general formula IIa in which m has values greater than or equal to 2 may occur.
m may assume, for example, values of 2 to 100, for example 2, 3, 4, 5, 6, 7, 8, 9 or 10.
The structural unit [O—CH2—Si(R2)2]m in the general formula IIa may be linear or, if at least one of the R2 radicals has been selected from radicals of the structure OR4, branched, in which case R4 may assume the definitions given above and in which case reaction with the alcohols R13—OH may result in exchange of OR4 for OR13. If, for example, the compound of the general formula II chosen was (acetoxymethyl)trimethoxysilane (i.e. the choices were: R1=Me, R2=OMe, OR3=OMe, n=1), in the course of the reaction, for example, compounds including the following compounds of the formula IIa may occur:
Me-C(═O)—[O—CH2—Si(OMe)2-O—CH2—Si(OMe)2]—OMe m=2 (linear)
Me-C(═O)—[O—CH2—Si(OMe)2-O—CH2—Si(OMe)2-O—CH2—Si(OMe)2]—OMe m=3 (linear)
Me-C(═O)—[O—CH2—Si(O—CH2—Si(OMe)3)2]—OMe m=3 (branched)
Me-C(═O)—[O—CH2—Si(O—CH2—Si(OMe)3)2—O—CH2—Si(OMe)2]—OMe, m=4 (branched, selected example)
where the structural units in square brackets always have the empirical formula of [O—CH2—Si(OMe)2]m with the particular value specified for m.
In the compounds of the general formula IIa, in the presence of alcohol R13—OH, the R1CO radicals may be replaced by hydrogen; these compounds are represented by the formula IIb:
H—[O—CH2—Si(R2)2]m—OR3 (IIb)
In the aforementioned formulae, in the presence of one or more alcohols R13—OH, the OR3 groups and possibly the OR4 groups may be partly or fully replaced by OR13 groups, in which case alcohols of the structure R3—OH and possibly R4—OH may be formed.
The compounds of the general formulae IIa and IIb may, in the process according to the invention, be converted further to compounds of the general formula I. This can possibly form compounds of the general formula III and/or alcohols R13—OH, R3—OH and possibly R4—OH as by-products.
In the presence of alcohol of the general formula R13—OH, the compounds of the general formula IIb are in an equilibrium dependent on the amount of alcohol with the compounds of the general formula I. Removal of the alcohol, which can be effected, for example, by distillation, results in a shift in the equilibrium in favor of the compounds of the general formula I.
The process can be executed, for example, under reflux or under distillative conditions, optionally under partial reflux, for example in a distillation apparatus, a thin-film or falling-film evaporator, optionally in a column with separating performance. For example, one or more compounds of the general formulae I, II or III and optionally the alcohols R13—OH and R3—OH and any R4—OH can be distilled out of the mixture.
In a first preferred embodiment, the compound of the general formula III (in which the OR3 groups may be partly or fully replaced by OR13 groups) is distilled out and the compounds of the general formulae I, IIa, IIb and II and the alcohols R13—OH and R3—OH and any R4—OH are at first kept partly or completely in the reaction mixture, for example via return or reflux, and, once the compound of the general formula III has been partly or fully distilled off, the alcohols R13—OH and R3—OH and any R4—OH are optionally distilled off.
The removal of the acidic catalyst preferably follows substantially complete formation of the compound of the general formula III or, equally preferably, follows removal of the compound of the general formula III from the reaction mixture, or, equally preferably, follows removal of the compound of the general formula III and optionally of the alcohols R13—OH and R3—OH and any R4—OH from the reaction mixture.
The acidic catalyst can be removed, for example, by chemical elimination of the acid function, such as neutralization with a base, or else physically, for example by filtration, decantation, centrifugation, or by physical interruption of the contact of the reaction mixture with the acidic catalyst.
In the case of use of heterogeneous acidic catalysts, the removal is preferably effected physically, by removal by filtration, removal by decantation, removal by centrifugation, or by physical interruption of the contact of the reaction mixture with the acidic catalyst, and in the case of use of an external catalyst section, most preferably by interruption of the contact between acidic catalyst and the predominant portion of the reaction solution, for instance by interrupting the circulation of the reaction mixture through the catalyst section. The physical removal enables, in a simple manner, the repeated use of the acidic catalyst.
If the removal is effected by neutralization, preferably at least 0.5, more preferably at least 0.9 and especially at least 1 molar equivalent, and preferably at most 3, more preferably at most 1.5 and especially at most 1.2 molar equivalents of a base are used, based on 1 mol of the catalytically active acid groups used in the acidic catalyst.
The base used is preferably metal hydrogencarbonate, metal carbonate, metal hydroxide or metal oxide, preferably metal hydrogencarbonate or metal carbonate, and most preferably metal hydrogencarbonate, with a metal selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Fe, Co, Ni or Zn, preferably Li, Na, K, Mg, Ba, Fe or Zn, most preferably Na, K, Mg, Ca or Fe, ammonia, alkylammonium hydroxide, amine base, or guanidine base, amidine base or basic ion exchange resins. Examples of neutralizing bases are sodium hydrogencarbonate, sodium carbonate, barium carbonate, potassium hydrogencarbonate, potassium carbonate, calcium carbonate, calcium hydroxide, lithium hydroxide, magnesium oxide, ammonia, triethylamine, ethylenediamine, cyclohexylamine, pyridine, piperidine, DBN, DBU, DABCO, guanidine or tetramethylguanidine, and basic ion exchangers.
The product of the general formula I can subsequently be distilled over, in which case the compounds of the general formulae II, IIa and IIb are kept partly or fully in the reaction mixture, for example via return or reflux.
In a further preferred embodiment, the product of the general formula I, after distillative removal of the compounds of the general formula III and optionally of the alcohols R13—OH and R3—OH and/or R4—OH and after removal of the acidic catalyst, is left in a mixture with the compounds of the general formulae IIa, IIb and II.
Preferably, unconverted compounds of the general formula II and any compounds of the general formulae IIa and IIb obtained are used in a new batch which is preferably executed after the process according to the invention. The compounds of the general formulae IIa or IIb which may originate from other sources can likewise be used in the process according to the invention.
In the process, it is optionally possible to add esters of the structure R14—C(═O)—OR13 where R13 may assume the same definitions as defined above and R14 may assume the same definitions as defined above for R1. In this case, in the aforementioned formulae, the OR3 and any OR4 groups may be partly or fully replaced by OR13 groups and the R1—C(═O)— groups may be partly or fully replaced by R14—C(═O)— groups.
In the process, it is optionally possible to use or add solvents or mixtures of solvents. Examples of usable solvents are optionally halogenated, for example chlorinated, or halogen-free hydrocarbons, ketones, ethers and esters. If esters are used as solvents, further transesterification reactions may occur, which, if these effects are unwanted, can lead to a restriction in the selection of esters. The solvents may be saturated or unsaturated; unsaturated solvents preferably have aromatic unsaturation. Examples of usable solvents are isomers of C5-C40 hydrocarbons, for example cyclohexane, heptane, octane, isooctane, nonane, decane, dodecane, benzene, toluene, ortho-, meta- or para-xylene or -cymene, cumene, ethylbenzene, diethylbenzene, or hydrocarbon mixtures, for example those from the Shellsol series from Shell or from the Hydroseal series from Total, C3-C40 ketones such as acetone, butanone, 2-pentanone, 3-pentanone, 3-methylbutanone, 4-methylpentan-2-one, cyclohexanone, ethers such as tetrahydrofuran, diethyl ether, tert-butyl methyl ether, tert-amyl methyl ether, diisopropyl ether, halogenated hydrocarbons such as chlorobenzene, ortho-, meta- or para-dichlorobenzene, or the isomers of trichlorobenzene.
Preference is given to using a minimum amount of solvent in the process: the mass of solvent, the total of all solvents, is preferably less than five times the mass of compounds of the general formula II used in total, more preferably less than twice the amount, most preferably less than half the amount. In a particularly preferred embodiment, the process is executed without added solvents.
The process is preferably executed under inert conditions. Solvents and reactants used contain preferably less than 10,000 ppm of water, more preferably less than 1000 ppm, and most preferably less than 200 ppm. Gases used, for example protective gas, contain preferably less than 10,000 ppm of water, more preferably less than 1000 ppm, and most preferably less than 200 ppm, and preferably less than 10,000 ppm of oxygen, more preferably less than 1000 ppm, and most preferably less than 200 ppm. Catalysts used contain preferably less than 50% water, more preferably less than 20%, and most preferably less than 5%.
Compounds of the general formula I prepared by the process according to the invention can, for example, be used directly as obtained, i.e. possibly in a mixture with compounds of the general formulae II, IIa, IIb, III and further additives present in the reaction mixture, for subsequent chemical reactions or other applications.
Preference is given to enriching the compounds of the general formula I in the reaction mixture. This is preferably accomplished by removing the compounds of the general formula III and the alcohols R13—OH and R3—OH from the reaction mixture, preferably by distillation.
If the conversion to form compounds of the general formula III is complete, the residue comprises, after removal of compounds of the general formula III and the alcohols R13—OH and R3—OH, as well as the product of the general formula I, especially also compounds of the general formula IIb (see also examples 3, 6, 8 and 9 below) which, like the compounds of the general formula I, are suitable for terminating reagents for polysiloxanes analogously to equation 1; cf. examples 11 and 12 of the application DE 10-2009-046254.
Optionally, however, a distillation of the compounds of the general formula I may follow; in the bottoms, the compounds of the general formulae IIa and IIb are converted further here to I.
Optionally, redistillation can be effected.
Prepared compound of the general formula I may be obtained, for example, in liquid form or may solidify or crystallize.
All above symbols in the above formulae are each defined independently of one another.
In the examples which follow, unless stated otherwise in each case, all amounts and percentages are based on the weight, all pressures are 0.10 MPa (abs.) and all temperatures are 20° C.
20.0 g (135 mmol) of formoxymethyldimethylmethoxysilane (formula II where R1═H, R2═R3═CH3, n=1) were admixed with 8 ml (corresponding to 6.3 g, 197 mmol) of methanol and 200 mg of p-toluenesulfonic acid, and the mixture was heated to 63° C. The methyl formate formed was distilled off using a distillation apparatus in a mixture with methanol and the volume distilled off was replaced in the bottoms by methanol. A total of 8.5 ml (corresponding to 6.72 g, 210 mmol) of methanol were added. Toward the end of the reaction, the bottom temperature rose to 71° C. and the top temperature to 64° C. (boiling point of methanol).
500 mg of sodium hydrogencarbonate were added for removal of acid and the mixture was fractionally distilled under reduced pressure. This gave approx. 8 g (68%) of 2,2,5,5-tetramethyl-2,5-disila-1,4-dioxacyclohexane (formula I, x=1) with boiling point 57° C./20 mbar.
20.0 g (135 mmol) of acetoxymethyldimethylethoxysilane (formula II where R1═CH3, R2═CH3, R3═CH2CH3, n=1) were admixed with 8 ml (corresponding to 6.3 g, 197 mmol) of methanol and 200 mg of p-toluenesulfonic acid, and the mixture was heated to 75° C. The methyl acetate formed was distilled off using a distillation apparatus in a mixture with methanol and the volume distilled off was replaced in the bottoms by methanol. A total of 33 ml (corresponding to 26 g, 816 mmol) of methanol were added. The top temperature rose to 64° C. The reaction mixture contained, during the conversion, a maximum of 2 equivalents of methanol (NMR analysis).
510 mg of sodium hydrogencarbonate were added for removal of acid and the mixture was fractionally distilled under reduced pressure. This gave approx. 8 g (80%) of 2,2,5,5-tetramethyl-2,5-disila-1,4-dioxacyclohexane (formula I, x=1) with boiling point 57° C./20 mbar.
200 g (1.35 mol) of formoxymethyldimethylmethoxysilane (formula II where R1═H, R2═R3═CH3, n=1) were admixed with 31 g (0.97 mol) of methanol and heated to 80° C. The mixture was pumped continuously through a column which was filled with the acidic ion exchange resin Amberlyst® 46 w containing sulfo groups and was purged with methanol for removal of water (total volume 70 ml, Amberlyst® 46 bed volume: 35 ml) at a pumping rate of 124 ml/min back into the reaction vessel. At the same time, methyl formate formed (formula III, R1═H, R2═CH3) was distilled off in a mixture with methanol through a short column with random packing and the distillate in the reaction vessel was replaced by the same volume of methanol. During the distillation, the proportion of methanol in the distillate rose to above 90%. A total of 158 g, corresponding to 4.39 mol, of methanol were used. After a reaction time of about 3.5 h, the pumping was ended and residual methanol was removed from the bottoms by distillation at standard pressure. This gave 93 g of residue of the composition 55% 2,2,5,5-tetramethyl-2,5-disila-1,4-dioxacyclohexane (formula I, x=1) and about 45% of the compounds according to formula IIb where R2═R3═CH3.
During the reaction, the percentage content of formate groups was determined as a measure for the degree of conversion (NMR analysis in d6-benzene, measurement points after 60, 90, 120, 150, 180 and 210 min). After 210 min, the proportion of formate groups was 0.2%, i.e. 99.8% conversion had been attained; see table 1.
The experiment according to example 2 was repeated with the catalyst from example 2 and the kinetic analyses were conducted analogously Within the range of measurement accuracy, the reaction proceeded with approximately the same reaction rate as in example 3 (table 1). No deactivation of the catalyst takes place.
After distillative removal of methanol, this gave 96.5 g of residue. 87.7 g thereof were fractionally distilled at 21 mbar. At the top temperature of 54-57° C., 76 g (87% based on crude product used) of 2,2,5,5-tetramethyl-2,5-disila-1,4-dioxacyclohexane (formula I where x=1) of purity 99.5% were obtained in a mixture with about 0.4% 2,2,5,5,8,8-hexamethyl-2,5,8-trisila-1,4,7-trioxacyclononane (formula I where x=2).
304 g (2.05 mol) of formoxymethyldimethylmethoxysilane (formula II where R1═H, R2═R3═CH3, n=1) were, as in example 3, converted with addition of 217 g (6.80 mol) of methanol using 27.8 g of Amberlyst® 46 w catalyst dried under reduced pressure. The reaction time was 4 h. After complete removal of methanol, the residue (173 g) was fractionally distilled under reduced pressure. This gave 158 g (87%) of 2,2,5,5-tetramethyl-2,5-disila-1,4-dioxacyclohexane (formula I where x=1) with boiling point 56° C./22 mbar.
The reaction according to example 3 was conducted three times in succession with the same Amberlyst® 39 w catalyst. After removal of methanol, a mixture comprising 63% 2,2,5,5-tetramethyl-2,5-disila-1,4-dioxacyclohexane (formula I where x=1) and 37% compounds of the formula IIb where R2═R3═CH3 was obtained.
During the 2nd and 3rd reaction, the percentage content of formate groups was determined as a measure for the degree of conversion (NMR analysis in d6-benzene, measurement points after 60, 90, 120 and 150 min). No significant differences are found in the curve series, i.e. no catalyst deactivation. After 150 min, the proportion of formate groups was approx. 0.7%, i.e. 99.3% conversion was attained; see table 2.
The reaction according to example 3 was conducted twice using the same Amberlyst® 15 w catalyst.
The kinetic profile of the reaction was in each case determined as in example 3. In both reactions, the conversion after 90 min was 92% and was complete after 4 h, i.e. no catalyst deactivation.
For removal of water, 25 g of Amberlyst® 39 w were washed twice with methanol and the methanol was decanted off. 506 g (3.41 mol) of formoxymethyl-dimethylmethoxysilane (formula II where R1═H, R2═R3═CH3, n=1) were heated to 58 to 78° C. together with the washed Amberlyst® and 198 g (6.18 mol) of methanol, in the course of which the methyl formate formed was distilled off in a mixture with methanol. After complete removal of the methyl formate, the catalyst was filtered off and the methanol was removed on a rotary evaporator. This gave 307 g of residue of the composition 38% 2,2,5,5-tetramethyl-2,5-disila-1,4-dioxacyclohexane (formula I where x=1) and 62% formula IIb where R2═R3═CH3 (NMR analysis).
35.6 g (0.236 mol) of formoxymethyldimethylmethoxy-silane (formula II where R1═H, R2═R3═CH3, n=1) with addition of 5.5 g (0.17 mol) of methanol and 1.78 g (5% by weight) of Amberlyst® 39 w, which had been washed 2× with methanol and dried at 10 mbar beforehand for removal of water, were heated to 70 to 74° C. and the methyl formate formed was distilled off in a mixture with approx. 10% methanol using a column with random packing (length approx. 15 cm, glass spirals). Methanol was removed by distillation at bottom temperature up to 100° C. The ion exchanger was filtered off and traces of methanol were removed distillatively at 1 mbar. The resulting residue consisted of about 42% 2,2,5,5-tetramethyl-2,5-disila-1,4-dioxacyclohexane (formula I, x=1) and 58% of the compounds according to formula IIb where R2═R3═CH3.
Catalyst preparation: the hydrous catalysts Amberlyst® 15 wet, 16 wet, 35 wet, 36 wet and 39 wet, for removal of water, were washed repeatedly with methanol and dried under reduced pressure (10 mbar). All other catalysts were used without pretreatment.
General experimental method: 10.0 g of formoxymethyl-dimethylmethoxysilane (formula II where R1═H, R2═R3═CH3, n=1) of purity 99.1% (66.9 mmol) were admixed with 0.50 g of catalyst and 2.0 g (62.5 mmol) of methanol, and heated to 70° C. over a total period of 1 h. Methyl formate formed was distilled off by means of a microdistillation apparatus.
Tab. 3 shows the percentage conversions obtained after 15 min and 60 min (=100−percentage of formate groups in the reaction mixture) and the amount of distillate obtained in each case, which comprised methyl formate and methanol.
Analogously to example 9, 100.1 g (675 mmol) of formoxymethyldimethylmethoxysilane (formula II where R1═H, R2═R3═CH3, n=1), with addition of 20 ml of methanol and 5.0 g (5% by weight) of K20 montmorillonite, were heated to 72 to 78° C. and the methyl formate formed was distilled off using a column with random packing (length approx. 15 cm, glass spirals) in a mixture with about 10% methanol, in the course of which a further 40 ml of methanol were metered in. Therefore, a total of 60 ml of methanol (47.5 g, 1.48 mol) were used. Methanol was removed by distillation at bottom temperature up to 103° C. The heterogeneous catalyst was filtered off and the reaction mixture was fractionally distilled. This gave g (60%) of 2,2,5,5-tetramethyl-2,5-disila-1,4-dioxacyclohexane (formula I, x=1).
440 g of acetoxymethyldimethylmethoxysilane (purity 99.2%, 2.69 mol) (formula II where R1═R2═R3═CH3, n=1) were admixed with 63 g (1.98 mol) of methanol and heated to 80° C. The mixture was pumped continuously through a column filled with Amberlyst 46® and purged with methanol (total volume 90 ml, Amberlyst® 46 bed volume: 43 ml) at a pumping rate of 130 ml/min back into the reaction vessel. At the same time, methyl acetate formed (formula III, R1═R2═CH3) was distilled off in a mixture with methanol using a short column with random packing and the distillate was replaced in the reaction vessel by the same volume of methanol. In the distillates, the proportions of methanol rose from approx. 55 mol % up to 92 mol % based on methyl acetate. The molar proportion of methanol in the reaction mixture during the conversion was about 1 equivalent based on the amount of Si units. A total of 530 g (16.6 mol) of methanol were used. After a reaction time of about 8 h, the pumping was ended and residual methanol was removed from the bottoms by distillation at standard pressure. The bottoms (amount 183 g—losses caused by dead volume of the apparatus) were fractionally distilled under a reduced pressure of 14 mbar. This gave 140.5 g of 2,2,5,5-tetramethyl-2,5-disila-1,4-dioxacyclohexane (formula I where x=1, yield 77% based on the bottoms used) with boiling point 52° C. in a mixture with about 0.5% 2,2,5,5,8,8-hexamethyl-2,5,8-trisila-1,4,7-trioxacyclononane (formula I where x=2).
A further reaction was conducted under conditions as in example 1 and distilled without neutralization. As well as unidentified products, the distillate (8.6 g) contained not more than 15% 2,2,5,5-tetramethyl-2,5-disila-1,4-dioxacyclohexane (formula I, x=1).
| Number | Date | Country | Kind |
|---|---|---|---|
| 10 2010 003 110.0 | Mar 2010 | DE | national |
This application is the U.S. national phase of PCT Application No. PCT/EP2011/053490 filed Mar. 8, 2011 which claims priority to German application 10 2010 003 110.0 filed Mar. 22, 2010, the disclosures of which are incorporated in their entirety by reference herein.
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP11/53490 | 3/8/2011 | WO | 00 | 11/8/2012 |
