CA2133166C - Base-catalyzed process for preparing hydrogen-containing organopolysiloxanes - Google Patents
Base-catalyzed process for preparing hydrogen-containing organopolysiloxanesInfo
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- CA2133166C CA2133166C CA002133166A CA2133166A CA2133166C CA 2133166 C CA2133166 C CA 2133166C CA 002133166 A CA002133166 A CA 002133166A CA 2133166 A CA2133166 A CA 2133166A CA 2133166 C CA2133166 C CA 2133166C
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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
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- 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
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a process wherein a mixture containing (A) organosilicon compounds selected from (Al) organosilanes (A2) organosiloxanes with the proviso that component A has at least 0.01 - 4 mole of alkoxy groups per mole of silicon atoms and that at least a part of the organosilicon compounds of the component A comprises Si-bonded hydrogen, (B) at least 0.5 mole of water per mole of alkoxy groups in component A, and (C) optionally a water-miscible solvent, is reacted in the presence of (D) ammonia, a primary or secondary C1-C4-alkylamine or a compound which liberates ammonia or primary or secondary C1-C4-alkylamine on reaction with water to form organopolysiloxanes containing Si-bonded hydroyen.
Description
Docket: WA 9311-S
Paper No. 1 ._ BASE-~T~YZED PRO OESS FOR
PREPARING ~Y~N-CONTAINING ORGANOPOLYSILOXANES
Field of Invention The present invention relates to a process for preparing organopolysiloxanes containing Si-bonded hydrogen using a basic catalyst.
Background of Invention The preparation of organopolysiloxanes containing Si-bonded hydrogen via hydrolysis and condensation of hydrogen-containing organosilanes or hydrolysates thereof has been carried out using acid catalysts, since it was assumed that SiH-bonded hydrogen was reacted to give hydrogen gas under the action of basic catalysts.
EP-A-251 435 Al describes a process for preparing hydrogen-containing organopolysiloxane resins having tetrafunctional siloxane units of alkyl silicate and organosilanes or an oligo-meric organosiloxane compound in the presence of water and acid catalysts. However, the resins have a broad molecular weight distribution.
A process for the base-catalyzed preparation of polysiloxanes not containing hydrogen is known from EP-A-004 2208, published Dec 23,1981.
SummarY of Invention It is an object of the present invention to provide a process by means of which organopolysiloxane oils, elastomers and resins containing hydrogensilyl groups can be prepared in a simple manner and reproducibly with a narrow molecular weight distribution.
The present invention relates to a process for preparing organopolysiloxanes containing Si-bonded hydrogen, which comprises ~133166 - reacting a mixture of the components (A) organosilicon compounds selected from (A1) organosilanes of the general formula RaHbSi(ORl)(4-a-b)~ (1) where R is optionally substituted C1- to C18-hydrocarbon radicals, Rl is optionally substituted C1- to C18-hydrocarbon radicals or hydrogen atoms, a is 0, 1, 2 or 3 and b is 0, 1, 2 or 3, and (A2) organosiloxanes comprising units of the general formula RcHd(oRl)esio(4-c-d-e)/2l (2) where c and e are each 0, 1, 2 or 3, d is 0, 1, 2 or 3 and R and Rl are as defined above, with the proviso that component A has at least 0.01 - 4 mole of alkoxy groups per mole of silicon atoms and that at least a part of the organosilicon compounds of the component A com-prises Si-bonded hydrogen, (B) at least 0.5 mole of water per mole of alkoxy groups in component A, and (C) optionally a water-miscible solvent, in the presence of (D) ammonia, a primary or secondary C1-C4-alkylamine or a com-pound which liberates ammonia or primary or secondary Cl-C4-alkylamine on reaction with water.
The organopolysiloxanes containing Si-bonded hydrogen pre-pared by the process of the invention have a more uniform molecu-lar weight than organopolysiloxanes containing Si-bonded hydrogen prepared by means of acid catalysts.
, Examples of radicals R, wherein each R is independently, alkyl radicals such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl, tert-pentyl radical; hexyl radicals such as the n-hexyl radical;
heptyl radicals such as the n-heptyl radical; octyl radicals such as the n-octyl radical and iso-octyl radicals such as the 2,2,4-trimethylpentyl radical; nonyl radicals such as the n-nonyl radi-cal; decyl radicals such as the n-decyl radical; dodecyl radicals such as the n-dodecyl radical; octadecyl radicals such as the n-octadecyl radical; alkenyl radicals such as the vinyl, allyl, n-5-hexenyl, 4-vinylcyclohexyl and the 3-norbornenyl radical;
cycloalkyl radicals such as cyclopentyl, cyclohexyl, 4-ethylcyclo-hexyl, cycloheptyl radical, norbornyl radicals and methylcyclo-hexyl radicals; aryl radicals such as the phenyl, bipheny, naphthyl and anthryl and phenanthryl radical; alkaryl radicals such as o-, m-, p-tolyl radicals, xylyl radicals and ethylphenyl radicals; aralkyl radicals such as the benzyl radical, the ~, and ~-phenylethyl radical.
Examples of substituted hydrocarbon radicals as radical R are halogenated hydrocarbon radicals such as the chloromethyl, 3-chloropropyl, 3-bromopropyl, 3,3,3-trifluoropropyl and 5,5,5,4,-4,3,3-heptafluoropentyl radical, and also the chlorophenyl, dichlorophenyl and trifluorotolyl radical; mercaptoalkyl radicals such as the 2-mercaptoethyl and 3-mercaptopropyl radical; cyano-alkyl radicals such as the 2-cyanoethyl and 3-cyanopropyl radical;
aminoalkyl radicals such as the 3-aminopropyl, N-(2-aminoethyl)-3-aminopropyl and N-(2-aminoethyl)-3-amino-(2-methyl)propyl radical;
aminoaryl radicals such as the aminophenyl radical; acyloxyalkyl radicals such as the 3-acryloxypropyl and 3-methacryloxypropyl radical; acetoxyalkyl radicals such as the 3-acetoxypropyl radi-cal; diethylphosphonic ester radicals such as the diethylphos-~133I66 phonic ester-ethyl radical; succinic anhydride alkyl radicals such as the 3-succinic anhydride-propyl radical; hydroxyalkyl radicals such as the 3-hydroxypropyl radical and radicals of the formulae O~
CH2-CHCH20(CH2)3- and HOCH2CH(OH)CH2SCH2CH2-.
The radicals R are preferably the methyl, ethyl, n-propyl, vinyl, n-5-hexenyl and phenyl radicals, in particular the methyl and the vinyl radicals.
Examples of the radical Rl are the examples given for R. The radical Rl are preferably alkyl groups having from 1 to 6 carbon atoms which can be substituted by preferably Cl-C6-alkyloxy groups or hydroxy groups.
The radicals Rl are preferably the methyl, ethyl, n-propyl, iso-propyl and hexyl radicals, more preferably the methyl and ethyl radicals.
Examples of the silanes Al of formula (1) used in the process of the invention are tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, vinyltriethoxysilane, dimethyldiethoxy-silane, dimethyldimethoxysilane, trimethylethoxysilane, 3-chloro-propyldimethylmethoxysilane, 3-chloropropyltrimethoxysilane, 3-acetoxypropyldimethylmethoxysilane, 3-mercaptopropyldimethyl-methoxysilane, n-octyldimethylmethoxysilane, 3-methacryloxypropyl-dimethylmethoxysilane, 2-cyclohexenylethyldimethylmethoxysilane, 3-aminopropyldimethylmethoxysilane and 3-cyanopropylmethyldimeth-oxysilane, with preference being given to using tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxy-silane and vinyldimethylethoxysilane, and more preference being given to using tetraethoxysilane, methyltriethoxysilane and dimethyldiethoxysilane.
~1331fi6 - Examples of the hydrogen-containing silanes of formula (1) used in the process of the invention are trihydrogenethoxysilane, dihydrogenmethylethoxySilane, hydrogendimethylethoxysilane, hydro-genmethyldiethoxysilane and hydrogenphenyldiethoxysilane.
The organosiloxanes (A2) used in the process of the invention preferably have at most 15 units of formula (2). Examples of organosiloxanes (A2) are linear organosiloxanes such as disilox-anes, for example hexamethyldisiloxane, 1,3-diphenyltetramethyldi-siloxane, l,3-bis(n-5-hexenyl)tetramethyldisiloxane, 1,3-divinyl-tetramethyldisiloxane, preferably hexamethyldisiloxane and 1,3-di-vinyltetramethyldisiloxane and cyclic organopolysiloxanes compris-ing from 3 to 8, preferably 4 or 5, units of formula (2), such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane and deca-methylcyclopentasiloxane.
Examples of the hydrogen-containing organosiloxanes (A2) used in the process of the invention are dihydrogentetramethyldisilox-ane, tetrahydrogendimethyldisiloxane, dihydrogentetraphenyldisi-loxane, trihydrogentrimethylcyclotrisiloxane, tetrahydrogentetra-methylcyclotetrasiloxane and pentahydrogenpentamethylcyclopenta-siloxane.
The component A can also comprise monomeric and polymeric silicates. This is particularly the case for the preparation of resins. Preferred silicates are methyl orthosilicate, ethyl orthosilicate, methyl polysilicate and ethyl polysilicate, with the silicates comprising alkoxy radicals.
The hydrogen content of the hydrogen-containing organopoly-siloxane final products is preferably 0.0001% to 2% by weight, in particular 0.01% to 0.6~ by weight.
The content of alkoxy groups of the component A is preferably 0.5 to 2 mole, in particular 0.65 to 1.5 mole, per mole of silicon atoms.
21331fi6 -- As component B, use is made of preferably at least 0.5 mole, in particular from 0.5 to 0.8 mole, of water per mole of alkoxy groups of the component A. A higher proportion of water per mole of alkoxy groups of the component A effects an increase in the proportion of gels.
Component C, if used, consists preferably of organic solvents which at 20~C are homogeneously miscible with water in the volume ratio 1 : 1. Examples of solvents suitable as component C are monohydric and polyhydric alcohols such as methanol, ethanol, n-propanol, isopropanol and ethylene glycol; ethers such as dioxane and tetrahydrofuran; amides such as dimethylformamide;
dimethyl sulfoxide and sulfolane or mixtures of these solvents.
Preference is given to solvents having a boiling point or boiling range of up to 120~C at 0.1 MPa, in particular the above monohydric alcohols.
Component C is preferably added in an amount such that, depending on the system, the proportion of gel is equal to 0, preferably from 20% to 300% by weight, in particular from 50% to 100% by weight, based on the proportion of silane in component A.
Those compounds of component D which liberate ammonia or primary or secondary C1-C4-alkylamine on reaction with water, are preferably of the formulae R2nSiZ4-n (R23Si)2NH (4), (R22SiNH)X (5), (R23Si)2NR3 (6) and (R22SiNR3)y (7) where R2 is a hydrogen atom or a C1-C4-alkyl radical, R3 is a Cl-C4-alkyl radical, Z is the group -NHR3 or NR32, ~133166 - n is 2 or 3, x is an integer from 3 to 6 and y is an integer from 1 to 12.
Particular preference is given to using compounds of formula (4), in particular hexamethyldisilazane.
In the process of the invention, ammonia or primary or secon-dary C1-C4-alkylamine act as catalyst and are preferably removed after the reaction, in particular by treatment under reduced pressure.
In the process of the invention, use is preferably made of 0.005 to 0.5 mole, in particular 0.05 to 0.3, mole of ammonia or primary or secondary C1-C4-alkylamine or compounds which liberate the above amounts of ammonia or primary Cl-C4-alkylamine on reac-tion with water, per 1 mole of the component A.
The invention can be used to prepare hydrogen-containing organopolysiloxane oils, elastomers and resins by varying the selection of components A through D. Silanes of formula (1) in which (4-a-b) = w and siloxanes of formula (2) in which (4-c-d) =
w are designated as M, D, T and Q units respectively when w = 1, 2, 3 and 4 respectively. The number of M, D, T or Q units used in the process can vary from O up to 100 mole ~. The process of the invention is particularly suitable for the preparation of hydro-gen-cont~ining silicone resins, in particular of MQ resins in which the M/Q ratio is preferably from 0.3 : 1 to 2 : 1, in par-ticular from 0.5 : 1 to 1.25 : 1. For example, it is possible to prepare transparent, monomodally distributed MQ resins which are soluble in organic solvents and whose molecular weights can be set to from 4,000 g/mole to 25,000 g/mole. Such MQ resins have a pro-portion of gel of less than 2% by weight, based on the theoretical yield.
~13316~
The process of the invention is preferably carried out at from 0~C to 100~C, in particular at from 25~C to 75~C. All vola-tile components such as water and solvent, such as ethanol, are preferably removed after the reaction, preferably under reduced pressure. In the process of the invention, the components A and D
are preferably initially charged and B and C are metered in.
Subse~uent to the reaction of the components A to D, the hydrogen-containing organopolysiloxanes obtained, in particular the resins, can be subjected to further condensation under the action of acid or base to lower the content of _oR1 groups, in particular the alkoxy group content. If this is carried out in the absence of water, the hydrogen content can also be kept almost unchanged using strong bases, such as alkali metal and alkaline earth metal hydroxides as condensation catalysts in organic sol-vents such as hydrocarbons.
The further condensation to lower the content of alkoxy groups is also possible with hydrogen-containing organopolysilox-anes which have been prepared in another way and not by the pro-cess of the invention.
The hydrogen-containing organopolysiloxanes prepared by the process of the invention can be used for all purposes for which hydrogen-containing organopolysiloxanes can be used. For example, the MQ resins are suitable as filler, as crosslinker in addition-crosslinking systems and as adhesion promoter.
In the following examples, unless otherwise indicated, (a) all amounts are by weight;
(b) all pressures are 0.10 MPa (abs.);
(c) all temperatures are 25~C.
~133166 - The following abbreviations were used:
AR = analytical reagent dist. = distilled Example 1 To the initially charged mixture, heated to 40~C under protective gas, comprising 125.4 g of tetraethoxysilane (0.6 mole), 9.72 g of hexamethyldisilazane (0.06 mole) and 62.53 g of hydrogendimethylethoxysilane (0.6 mole) were added drop-wise 21.60 g of dist. water (1.2 mole) and 60.00 g of AR
ethanol (1.3 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 2.5 hours at room temperature and atmospheric pressure. The mixture was sub-sequently adjusted to pH 7, freed by filtration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 44.48 g (55.9% yield) of a viscous, transparent oil containing 0.53% by weight of Si-bonded hydrogen.
Example 2 To the initially charged mixture, heated to 40~C under protective gas, comprising 20.90 g of tetraethoxysilane (0.1 mole), 1.62 g of hexamethyldisilazane (0.01 mole) and 6.72 g of 1,1,3,3-tetramethyldisiloxane (0.05 mole) were added drop-wise 3.60 g of dist. water (0.2 mole) and 12.00 g of AR
ethanol (0.26 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 3 hours at room temp-erature and atmospheric pressure. The mixture was subse-quently adjusted to pH 7, freed by filtration of any amounts of gel formed and then evaporated in a high vacuum at 100~C
to constant weight.
~133166 ~ This gave 7.90 g (55.48% yield) of a highly viscous, transparent oil containing 0.56% by weight of Si-bonded hydrogen.
Example 3 To the initially charged mixture, heated to 40~C under protective gas, comprising 20.90 g of tetraethoxysilane (0.1 mole), 2.66 g of hexamethyldisilazane (0.0165 mole), 3.06 g of 1,3-divinyltetramethyldisilazane (0.0165 mole) and 3.44 g of hydrogendimethylethoxysilane (0.033 mole) were added drop-wise 3.60 g of dist. water (0.2 mole) and 10.00 g of AR
ethanol (0.22 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 2.5 hours at 60~C, one hour at room temperature and atmospheric pressure. The mixture was subsequently adjusted to pH 7, freed by filtra-tion of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 11.13 g (84.9% yield) of a highly viscous, transparent oil containing 0.11% by weight of Si-bonded hydrogen and 5.34% by weight of vinyl groups.
Example 4 To the initially charged mixture, heated to 40~C under protective gas, comprising 20.90 g of tetraethoxysilane (0.1 mole), 2.70 g of hexamethyldisilazane (0.0167 mole), 5.55 g of 3-chloropropyldimethylmethoxysilane (0.033 mole) and 2.24 g of 1,1,3,3-tetramethyldisiloxane (0.0167 mole) were added dropwise 3.60 g of dist. water (0.2 mole) and 12.0 g of AR
ethanol (0.26 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 24 hours at room temperature and atmospheric pressure. The mixture was subse-~uently adjusted to pH 7, freed by filtration of any amounts - of gel formed and then evaporate~ ~n a high vacuum at 100~C
to constant weight.
This gave 9.53 g (62.5% yield) of a low-viscosity, trans-parent oil containing 2.84% by weight of chloropropyl groups and 0.038% by weight of Si-bonded hydrogen.
Example 5 To the initially charged mixture, heated to 40~C under protective gas, comprising 10.45 g of tetraethoxysilane (0.05 mole), 1.35 g of hexamethyldisilazane (0.00835 mole), 3.41 g of 3-acetoxypropyldimethylmethoxysilane (0.0167 mole) and 1.12 g of 1,1,3,3-tetramethyldisiloxane (0.00835 mole) were added dropwise 1.80 g of dist. water (0.1 mole) and 6.0 g of AR ethanol (0.13 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 24 hours at room temperature and atmospheric pressure. The mixture was subse-quently adjusted to pH 7, freed by filtration of any amounts of gel formed and then evaporated in a high vacuum at 100~C
to constant weight.
This gave 3.03 g (36.7% yield) of a low-viscosity, trans-parent oil containing 2.36% by weight of acetoxypropyl groups and 0.039% by weight of Si-bonded hydrogen.
Example 6 To the initially charged mixture, heated to 40~C under protective gas, comprising 10.45 g of tetraethoxysilane (0.05 mole), 1.35 g of hexamethyldisilazane (0.00835 mole), 2.75 g of 3-mercaptopropyldimethylmethoxysilane (0.0167 mole) and 1.12 g of 1,1,3,3-tetramethyldisiloxane (0.00835 mole) were added dropwise 1.80 g of dist. water (0.1 mole) and 6.0 g of AR ethanol (0.13 mole), previously mixed in the feed vessel.
~1331 fib The reaction mixture was stirred for 3.5 hours at 75~C and atmospheric pressure and was then cooled to room temperature.
The mixture was subsequently adjusted to pH 7, freed by fil-tration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 6.9 g (90.8% yield) of a transparent oil con-taining 2.55% by weight of mercaptopropyl groups and 0.041%
by weight of Si-bonded hydrogen.
Example 7 To the initially charged mixture, heated to 40~C under protective gas, comprising 10.45 g of tetraethoxysilane (0.05 mole), 1.35 g of hexamethyldisilazane (0.00835 mole), 4.48 g of diethyl 2-(ethoxydimethylsilyl)ethylphosphonate (0.0167 mole) and 1.12 g of 1,1,3,3-tetramethyldisiloxane (0.00835 mole) were added dropwise 1.80 g of dist. water (0.1 mole) and 6.0 g of AR ethanol (0.13 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 3.5 hours at 75~C and atmospheric pressure and was then cooled to room temperature.
The mixture was subsequently adjusted to pH 7, freed by fil-tration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 6.90 g (76% yield) of a low-viscosity, transpar-ent oil containing 2.99% by weight of diethyl ethanephospho-nate groups and 0.041% by weight of Si-bonded hydrogen.
Example 8 To the initially charged mixture, heated to 40~C under protective gas, comprising 10.45 g of tetraethoxysilane (0.05 mole), 1.35 g of hexamethyldisilazane (0.00835 mole), 3.38 g of n-octyldimethylmethoxysilane (0.0167 mole) and 1.12 g of -- 1,1,3,3-tetramethyldisiloxane (0.00835 mole) were added drop-wise 1.80 g of dist. water (0.1 mole) and 6.0 g of AR ethanol (0.13 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 3.5 hours at 75~C and atmospheric pressure and was then cooled to room temperature.
The mixture was subsequently adjusted to pH 7, freed by fil-tration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 5.51 g (67% yield) of a viscous, transparent oil containing 2.32% by weight of n-octyl groups and 0.043% by weight of Si-bonded hydrogen.
Example 9 To the initially charged mixture, heated to 40~C under protective gas, comprising 10.45 g of tetraethoxysilane (0.05 mole), 1.35 g of hexamethyldisilazane (0.00835 mole), 3.61 g of 3-(methacryloxy)propyldimethylmethoxysilane (0.0167 mole) and 1.12 g of 1,1,3,3-tetramethyldisiloxane (0.00835 mole) were added dropwise 1.80 g of dist. water (0.1 mole) and 6.0 g of AR ethanol (0.13 mole), prevlously mixed in the feed vessel.
The reaction mixture was stirred for 5 hours at 60~C and atmospheric pressure and was then cooled to room temperature.
The mixture was adjusted to pH 7, subsequently freed by filtration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 7.52 g (88.9% yield) of a transparent oil con-taining 3.56% by weight of 3-(methacryloxy)propyl groups and 0.037% by weight of Si-bonded hydrogen.
Example 10 To the initially charged mixture, heated to 40~C under ~1331 66 - protective gas, comprising 10.45 g of tetraethoxysilane (0.05 mole), 1.35 g of hexamethyldisilazane (0.00835 mole), 3.31 g of 2-cyclohexenylethyldimethylmethoxysilane (0.0167 mole) and 1.12 g of 1,1,3,3-tetramethyldisiloxane (0.00835 mole) were added dropwise 1.80 g of dist. water (0.1 mole) and 7.0 g of AR ethanol (0.15 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 5 hours at 75~C and atmospheric pressure and was then cooled to room temperature.
The mixture was adjusted to pH 7, subsequently freed by fil-tration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 3.56 g (43.7% yield) of a yellow, transparent oil containing 3.1~ by weight of 2-cyclohexenyl groups and 0.03~ by weight of Si-bonded hydrogen.
Example 11 To the initially charged mixture, heated to 40~C under protective gas, comprising 10.45 g of tetraethoxysilane (0.05 mole), 1.35 g of hexamethyldisilazane (0.00835 mole), 3.48 g of 2-phenylpropyldimethylmethoxysilane (0.0167 mole) and 1.12 g of 1,1,3,3-tetramethyldisiloxane (0.00835 mole) were added dropwise 1.80 g of dist. water (0.1 mole) and 7.0 g of AR
ethanol (0.15 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 5 hours at 75~C and atmospheric pressure and was then cooled to room temperature.
The mixture was adjusted to pH 7, subsequently freed by fil-tration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 5.24 g (63.06% yield) of a viscous, transparent oil containing 2.22% by weight of 2-phenylpropyl groups and 0.039% by weight of Si-bonded hydrogen.
~l33l66 -Example 12 To the initially charged mixture, heated to 40~C under protective gas, comprising 10.45 g of tetraethoxysilane (0.05 mole), 1.35 g of hexamethyldisilazane (0.00835 mole), 3.11 g of 3,3,3-trifluoropropyldimethylmethoxysilane (0.0167 mole) and 1.12 g of 1,1,3,3-tetramethyldisiloxane (0.00835 mole) were added dropwise 1.80 g of dist. water (O.l mole) and 7.0 g of AR ethanol (0.15 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 3.5 hours at 75~C and atmospheric pressure and was then cooled to room temperature.
The mixture was adjusted to pH 7, subsequently freed by fil-tration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 6.88 g (86.5% yield) of a viscous, transparent oil containing 2.86% by weight of 3,3,3-trifluoropropyl groups and 0.035% by weight of Si-bonded hydrogen.
Example 13 To the initially charged mixture, comprising 1.80 g of dist. water (0.1 mole), 6.0 g of AR ethanol (0.13 mole) and 2.46 g of 3-aminopropyldimethylmethoxysilane (0.0167 mole) was added 0.0167 mole of hydrogen chloride in the form of a concentrated aqueous hydrochloric acid and the mixture was adjusted to pH 7.0 using a pH meter. The neutralized initi-ally charged mixture was heated to 40~C under protective gas, and 10.45 g of tetraethoxysilane (0.05 mole), 1.35 g of hexa-methyldisilazane (0.00835 mole) and 1.12 g of 1,1,3,3-tetra-methyldisiloxane (0.00835 mole) were added dropwise.
~13316~
- The reaction mixture was stirred for 3.5 hours at 75~C and atmospheric pressure and was then cooled to room temperature.
The mixture was adjusted to pH 7, subsequently freed by filtration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 6.78 g (85.7% yield) of a yellow solid resin containing 2.5% by weight of 3-aminopropyl hydrochloride groups and 0.029% by weight of Si-bonded hydrogen.
Example 14 To the initially charged mixture, heated to 40~C under protective gas, comprising 62.70 g of tetraethoxysilane (0.3 mole), 8.1 g of hexamethyldisilazane (0.05 mole), 27.49 g of 3-methyldiethoxysilylpropylsuccinic anhydride (0.1 mole) and 6.72 g of 1,1,3,3-tetramethyldisiloxane (0.05 mole) were added dropwise 10.80 g of dist. water (0.6 mole) and 36.0 g of AR ethanol (0.78 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 24 hours at room temperature and atmospheric pressure. The mixture was adjusted to pH 7, subsequently freed by filtration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 44.72 g (88.6% yield) of a yellow solid resin containing 3.2% by weight of propylsuccinic anhydride groups and 0.02% by weight of Si-bonded hydrogen.
The resin was dissolved in a mixture of 50 ml of AR etha-nol, 150 ml of dist. water and 2.0 g of potassium hydroxide (0.036 mole). Using a pH meter and with the addition of a further 1.0 g of potassium hydroxide (0.018 mole), the pH was adjusted to 6.98. The solution was filtered and then evapo-1 b' b' _ rated in a high vacuum at 100~C to constant weight. The product was subsequently dried over diphosphorus pentoxide in a high vacuum at 80~C.
Example 15 To the initially charged mixture, heated to 40~C under protective gas, comprising 20.9 g of tetraethoxysilane (0.1 mole), 2.70 g of hexamethyldisilazane (0.0167 mole), 5.77 g of cyanopropylmethyldimethoxysilane (0.0333 mole) and 2.24 g of 1,1,3,3-tetramethyldisiloxane (0.0167 mole) were added dropwise 3.60 g of dist. water (o.2 mole) and 12.o g of AR
ethanol (0.26 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 3 hours at 75~C and atmospheric pressure and was then cooled to room temperature.
The mixture was adjusted to pH 7, subsequently freed by fil-tration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 8.91 g (61.8% yield) of a low-viscosity, trans-parent oil containing 4.24~ by weight of cyanopropyl groups and 0.044% by weight of Si-bonded hydrogen.
Example 16 To the initially charged mixture, heated to 40~C under protective gas, comprising 10.45 g of tetraethoxysilane (0.05 mole), 1.35 g of hexamethyldisilazane (0.00835 mole), 4.21 g of 2,2-diethoxy-2,3,4,5-tetrahydro-1,2-benzoxasilepine (0.0167 mole) and 1.12 g of 1,1,3,3-tetramethyldisiloxane (0.00835 mole) were added dropwise 1.80 g of dist. water (0.1 mole) and 6.0 g of AR ethanol (0.13 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 24 hours at room temperature and atmospheric pressure. The mixture was - adjusted to pH 7, subsequently freed by filtration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 8.11 g (74.5% yield) of a yellow, highly vis-cous, transparent oil containing ~.19% by weight of ortho-phenoxypropyl groups and 0.039% by weight of Si-bonded hydro-gen.
Example 17 To the initially charged mixture, heated to 40~C under protective gas, comprising 20.9 g of tetraethoxysilane (0.1 mole), 2.70 g of hexamethyldisilazane (0.0167 mole), 6.71 g of dimethyldiethoxysilane (0.05 mole) and 7.42 g of methyldiethoxysilane (0.05 mole) were added dropwise 3.60 g of dist. water (0.2 mole) and 12.0 g of AR ethanol (0.26 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 5 hours at 60OC and atmospheric pressure and was then cooled to room temperature.
The mixture was adjusted to pH 7, subsequently freed by fil-tration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 11.58 g (86.3% yield) of a low viscosity, trans-parent oil containing 0.04% by weight of Si-bonded hydrogen groups.
Example 18 To the initially charged mixture, heated to 40~C under protective gas, comprising 17.84 g of methyltriethoxysilane (0.1 mole), 4.035 g of hexamethyldisilazane (0.025 mole) and 5.21 g of hydrogendimethylethoxysilane (0.05 mole) were added dropwise 3.60 g of dist. water (0.2 mole) and 10.00 g of AR ethanol (0.22 mole), previously mixed in the feed vessel.
- The reaction mixture was stirred for 24 hours at room temperature and atmospheric pressure. The mixture was adjusted to pH 7, subsequently freed by filtration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 8.03 g (56.8% yield) of a transparent oil con-taining 0.089% by weight of Si-bonded hydrogen.
Example 19 For the initially charged mixture, 18.48 g of the hydrogen-containing organopolysiloxane resin (ethoxy content: 17.5%
by weight) from Example 1 were dissolved in 200 ml of tolu-ene; 500 ppm of potassium hydroxide (25% strength in AR
methanol) were introduced into the initially charged mixture, the mixture was stirred for 3.5 hours at 80~C and atmospheric pressure and then cooled to room temperature. The mixture was adjusted to pH 7, subsequently freed by filtration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 16.91 g (91.5% yield) of the starting resin having an ethoxy content of 13.99~ by weight. The content of Si-bonded hydrogen did not change.
Example 20 For the initially charged mixture, 4.0 g of the hydrogen-containing organopolysiloxane resin (ethoxy content: 17.5%
by weight) from Example 1 were dissolved in 40 ml of toluene;
500 ppm of aqueous, concentrated hydrochloric acid were introduced into the initially charged mixture, the mixture was stirred for 2.5 hours at 80~C and then cooled to room temperature. The mixture was neutralized by the addition of magnesium oxide, subsequently freed by filtration of any ~ ~ V ~
- amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 3.14 g (78.5% yield) of the starting resin having an ethoxy content of 14.45% by weight. The content of Si-bonded hydrogen did not change.
Example 21 To the initially charged mixture, heated to 40~C under pro-tective gas, comprising 10.45 g of tetraethoxysilane (0.05 mole), 5.91 g of trimethylethoxysilane (0.033 mole) and 1.80 g of dist. water (0.1 mole) and 12.00 g of AR ethanol (0.26 mole), as previously mixed solution, were added dropwise 3.36 g of l,1,3,3-tetramethyldisiloxane (0.025 mole).
The mixture was stirred at this temperature for 5 minutes and the solution was subsequently saturated with gaseous ammonia. The reaction mixture was stirred for an additional 2 hours at room temperature and atmospheric pressure, subse-quently freed by filtration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 2.39 g (22.2% yield) of a viscous, transparent oil containing 0.1% by weight of Si-bonded hydrogen.
Example 22 To the initially charged mixture, heated to 40~C under protective gas, comprising 10.45 g of tetraethoxysilane (0.05 mole), and 1.80 g of dist. water (0.1 mole) and 12.00 g of AR
ethanol (0.26 mole), previously mixed, were added dropwise 6.72 g of 1,1,3,3-tetramethyldisiloxane (0.05 mole).
The mixture was stirred at this temperature for 5 minutes and the solution was subsequently saturated with gaseous ammonia. The reaction mixture was stirred for an additional 2 hours at room temperature and atmospheric pressure, subse-Xl~31 66 - quently freed by filtration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 3.0 g (30.7~ yield) of a low-viscosity, trans-parent oil containing 0.4% by weight of Si-bonded hydrogen.
Example 23 To the initially charged mixture, heated to 40~C under protective gas, comprising 20.90 g of tetraethoxysilane (0.1 mole), 2.66 g of hexamethyldisilazane (0.0165 mole), 4.30 g of 1,3-divinyltetramethyldisilazane (0.033 mole) and 3.44 g of hydrogendimethylethoxysilane (0.033 mole), were added dropwise 3.60 g of dist. water (O.2 mole) and 10.00 g of AR
ethanol (0.22 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 2.5 hours at 60~C and for one hour at room temperature at atmospheric pressure.
The mixture was subsequently freed by filtration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 9.55 g (67.7% yield) of a white solid resin con-taining 5.56% by weight of vinyl groups and 0.099% by weight of Si-bonded hydrogen.
l.o g of solid resin was subsequently dissolved in 9.0 g of toluene and admixed with 100 ppm (based on pure platinum) of a platinum catalyst comprising hexachloroplatinic acid and divinyltetramethyldisiloxane.
This gave 10.0 g of a stable, transparent gel.
Example 24 5.0 g of hydrogen-containing organopolysiloxane resin from Example 2 were mixed with 5.0 g of ~,w-divinylpolydimethyl-siloxane having a viscosity of 500 mPa s, and admixed with 100 ppm (based on pure platinum) of a platinum catalyst ~f 331 66 - comprising hexachloroplatinic acid and divinyltetramethyldi-siloxane.
This gave 10.0 g of a brittle, transparent product.
Example 25 To the initially charged mixture, heated to 40~C under protective gas, comprising 41.8 g of tetraethoxysilane (0.2 mole), 3.24 g of hexamethyldisilazane (0.02 mole) and 13.44 g of 1,1,3,3-tetramethyldisiloxane (0.1 mole), were added drop-wise 7.20 g of dist. water (0.4 mole).
The reaction mixture was stirred for 3 hours at 75~C and atmospheric pressure, and then cooled to room temperature.
The mixture was subsequently evaporated in a high vacuum at 100~C to constant weight.
This gave a white, insoluble powder containing 0.13% by weight of Si-bonded hydrogen.
Paper No. 1 ._ BASE-~T~YZED PRO OESS FOR
PREPARING ~Y~N-CONTAINING ORGANOPOLYSILOXANES
Field of Invention The present invention relates to a process for preparing organopolysiloxanes containing Si-bonded hydrogen using a basic catalyst.
Background of Invention The preparation of organopolysiloxanes containing Si-bonded hydrogen via hydrolysis and condensation of hydrogen-containing organosilanes or hydrolysates thereof has been carried out using acid catalysts, since it was assumed that SiH-bonded hydrogen was reacted to give hydrogen gas under the action of basic catalysts.
EP-A-251 435 Al describes a process for preparing hydrogen-containing organopolysiloxane resins having tetrafunctional siloxane units of alkyl silicate and organosilanes or an oligo-meric organosiloxane compound in the presence of water and acid catalysts. However, the resins have a broad molecular weight distribution.
A process for the base-catalyzed preparation of polysiloxanes not containing hydrogen is known from EP-A-004 2208, published Dec 23,1981.
SummarY of Invention It is an object of the present invention to provide a process by means of which organopolysiloxane oils, elastomers and resins containing hydrogensilyl groups can be prepared in a simple manner and reproducibly with a narrow molecular weight distribution.
The present invention relates to a process for preparing organopolysiloxanes containing Si-bonded hydrogen, which comprises ~133166 - reacting a mixture of the components (A) organosilicon compounds selected from (A1) organosilanes of the general formula RaHbSi(ORl)(4-a-b)~ (1) where R is optionally substituted C1- to C18-hydrocarbon radicals, Rl is optionally substituted C1- to C18-hydrocarbon radicals or hydrogen atoms, a is 0, 1, 2 or 3 and b is 0, 1, 2 or 3, and (A2) organosiloxanes comprising units of the general formula RcHd(oRl)esio(4-c-d-e)/2l (2) where c and e are each 0, 1, 2 or 3, d is 0, 1, 2 or 3 and R and Rl are as defined above, with the proviso that component A has at least 0.01 - 4 mole of alkoxy groups per mole of silicon atoms and that at least a part of the organosilicon compounds of the component A com-prises Si-bonded hydrogen, (B) at least 0.5 mole of water per mole of alkoxy groups in component A, and (C) optionally a water-miscible solvent, in the presence of (D) ammonia, a primary or secondary C1-C4-alkylamine or a com-pound which liberates ammonia or primary or secondary Cl-C4-alkylamine on reaction with water.
The organopolysiloxanes containing Si-bonded hydrogen pre-pared by the process of the invention have a more uniform molecu-lar weight than organopolysiloxanes containing Si-bonded hydrogen prepared by means of acid catalysts.
, Examples of radicals R, wherein each R is independently, alkyl radicals such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl, tert-pentyl radical; hexyl radicals such as the n-hexyl radical;
heptyl radicals such as the n-heptyl radical; octyl radicals such as the n-octyl radical and iso-octyl radicals such as the 2,2,4-trimethylpentyl radical; nonyl radicals such as the n-nonyl radi-cal; decyl radicals such as the n-decyl radical; dodecyl radicals such as the n-dodecyl radical; octadecyl radicals such as the n-octadecyl radical; alkenyl radicals such as the vinyl, allyl, n-5-hexenyl, 4-vinylcyclohexyl and the 3-norbornenyl radical;
cycloalkyl radicals such as cyclopentyl, cyclohexyl, 4-ethylcyclo-hexyl, cycloheptyl radical, norbornyl radicals and methylcyclo-hexyl radicals; aryl radicals such as the phenyl, bipheny, naphthyl and anthryl and phenanthryl radical; alkaryl radicals such as o-, m-, p-tolyl radicals, xylyl radicals and ethylphenyl radicals; aralkyl radicals such as the benzyl radical, the ~, and ~-phenylethyl radical.
Examples of substituted hydrocarbon radicals as radical R are halogenated hydrocarbon radicals such as the chloromethyl, 3-chloropropyl, 3-bromopropyl, 3,3,3-trifluoropropyl and 5,5,5,4,-4,3,3-heptafluoropentyl radical, and also the chlorophenyl, dichlorophenyl and trifluorotolyl radical; mercaptoalkyl radicals such as the 2-mercaptoethyl and 3-mercaptopropyl radical; cyano-alkyl radicals such as the 2-cyanoethyl and 3-cyanopropyl radical;
aminoalkyl radicals such as the 3-aminopropyl, N-(2-aminoethyl)-3-aminopropyl and N-(2-aminoethyl)-3-amino-(2-methyl)propyl radical;
aminoaryl radicals such as the aminophenyl radical; acyloxyalkyl radicals such as the 3-acryloxypropyl and 3-methacryloxypropyl radical; acetoxyalkyl radicals such as the 3-acetoxypropyl radi-cal; diethylphosphonic ester radicals such as the diethylphos-~133I66 phonic ester-ethyl radical; succinic anhydride alkyl radicals such as the 3-succinic anhydride-propyl radical; hydroxyalkyl radicals such as the 3-hydroxypropyl radical and radicals of the formulae O~
CH2-CHCH20(CH2)3- and HOCH2CH(OH)CH2SCH2CH2-.
The radicals R are preferably the methyl, ethyl, n-propyl, vinyl, n-5-hexenyl and phenyl radicals, in particular the methyl and the vinyl radicals.
Examples of the radical Rl are the examples given for R. The radical Rl are preferably alkyl groups having from 1 to 6 carbon atoms which can be substituted by preferably Cl-C6-alkyloxy groups or hydroxy groups.
The radicals Rl are preferably the methyl, ethyl, n-propyl, iso-propyl and hexyl radicals, more preferably the methyl and ethyl radicals.
Examples of the silanes Al of formula (1) used in the process of the invention are tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, vinyltriethoxysilane, dimethyldiethoxy-silane, dimethyldimethoxysilane, trimethylethoxysilane, 3-chloro-propyldimethylmethoxysilane, 3-chloropropyltrimethoxysilane, 3-acetoxypropyldimethylmethoxysilane, 3-mercaptopropyldimethyl-methoxysilane, n-octyldimethylmethoxysilane, 3-methacryloxypropyl-dimethylmethoxysilane, 2-cyclohexenylethyldimethylmethoxysilane, 3-aminopropyldimethylmethoxysilane and 3-cyanopropylmethyldimeth-oxysilane, with preference being given to using tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxy-silane and vinyldimethylethoxysilane, and more preference being given to using tetraethoxysilane, methyltriethoxysilane and dimethyldiethoxysilane.
~1331fi6 - Examples of the hydrogen-containing silanes of formula (1) used in the process of the invention are trihydrogenethoxysilane, dihydrogenmethylethoxySilane, hydrogendimethylethoxysilane, hydro-genmethyldiethoxysilane and hydrogenphenyldiethoxysilane.
The organosiloxanes (A2) used in the process of the invention preferably have at most 15 units of formula (2). Examples of organosiloxanes (A2) are linear organosiloxanes such as disilox-anes, for example hexamethyldisiloxane, 1,3-diphenyltetramethyldi-siloxane, l,3-bis(n-5-hexenyl)tetramethyldisiloxane, 1,3-divinyl-tetramethyldisiloxane, preferably hexamethyldisiloxane and 1,3-di-vinyltetramethyldisiloxane and cyclic organopolysiloxanes compris-ing from 3 to 8, preferably 4 or 5, units of formula (2), such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane and deca-methylcyclopentasiloxane.
Examples of the hydrogen-containing organosiloxanes (A2) used in the process of the invention are dihydrogentetramethyldisilox-ane, tetrahydrogendimethyldisiloxane, dihydrogentetraphenyldisi-loxane, trihydrogentrimethylcyclotrisiloxane, tetrahydrogentetra-methylcyclotetrasiloxane and pentahydrogenpentamethylcyclopenta-siloxane.
The component A can also comprise monomeric and polymeric silicates. This is particularly the case for the preparation of resins. Preferred silicates are methyl orthosilicate, ethyl orthosilicate, methyl polysilicate and ethyl polysilicate, with the silicates comprising alkoxy radicals.
The hydrogen content of the hydrogen-containing organopoly-siloxane final products is preferably 0.0001% to 2% by weight, in particular 0.01% to 0.6~ by weight.
The content of alkoxy groups of the component A is preferably 0.5 to 2 mole, in particular 0.65 to 1.5 mole, per mole of silicon atoms.
21331fi6 -- As component B, use is made of preferably at least 0.5 mole, in particular from 0.5 to 0.8 mole, of water per mole of alkoxy groups of the component A. A higher proportion of water per mole of alkoxy groups of the component A effects an increase in the proportion of gels.
Component C, if used, consists preferably of organic solvents which at 20~C are homogeneously miscible with water in the volume ratio 1 : 1. Examples of solvents suitable as component C are monohydric and polyhydric alcohols such as methanol, ethanol, n-propanol, isopropanol and ethylene glycol; ethers such as dioxane and tetrahydrofuran; amides such as dimethylformamide;
dimethyl sulfoxide and sulfolane or mixtures of these solvents.
Preference is given to solvents having a boiling point or boiling range of up to 120~C at 0.1 MPa, in particular the above monohydric alcohols.
Component C is preferably added in an amount such that, depending on the system, the proportion of gel is equal to 0, preferably from 20% to 300% by weight, in particular from 50% to 100% by weight, based on the proportion of silane in component A.
Those compounds of component D which liberate ammonia or primary or secondary C1-C4-alkylamine on reaction with water, are preferably of the formulae R2nSiZ4-n (R23Si)2NH (4), (R22SiNH)X (5), (R23Si)2NR3 (6) and (R22SiNR3)y (7) where R2 is a hydrogen atom or a C1-C4-alkyl radical, R3 is a Cl-C4-alkyl radical, Z is the group -NHR3 or NR32, ~133166 - n is 2 or 3, x is an integer from 3 to 6 and y is an integer from 1 to 12.
Particular preference is given to using compounds of formula (4), in particular hexamethyldisilazane.
In the process of the invention, ammonia or primary or secon-dary C1-C4-alkylamine act as catalyst and are preferably removed after the reaction, in particular by treatment under reduced pressure.
In the process of the invention, use is preferably made of 0.005 to 0.5 mole, in particular 0.05 to 0.3, mole of ammonia or primary or secondary C1-C4-alkylamine or compounds which liberate the above amounts of ammonia or primary Cl-C4-alkylamine on reac-tion with water, per 1 mole of the component A.
The invention can be used to prepare hydrogen-containing organopolysiloxane oils, elastomers and resins by varying the selection of components A through D. Silanes of formula (1) in which (4-a-b) = w and siloxanes of formula (2) in which (4-c-d) =
w are designated as M, D, T and Q units respectively when w = 1, 2, 3 and 4 respectively. The number of M, D, T or Q units used in the process can vary from O up to 100 mole ~. The process of the invention is particularly suitable for the preparation of hydro-gen-cont~ining silicone resins, in particular of MQ resins in which the M/Q ratio is preferably from 0.3 : 1 to 2 : 1, in par-ticular from 0.5 : 1 to 1.25 : 1. For example, it is possible to prepare transparent, monomodally distributed MQ resins which are soluble in organic solvents and whose molecular weights can be set to from 4,000 g/mole to 25,000 g/mole. Such MQ resins have a pro-portion of gel of less than 2% by weight, based on the theoretical yield.
~13316~
The process of the invention is preferably carried out at from 0~C to 100~C, in particular at from 25~C to 75~C. All vola-tile components such as water and solvent, such as ethanol, are preferably removed after the reaction, preferably under reduced pressure. In the process of the invention, the components A and D
are preferably initially charged and B and C are metered in.
Subse~uent to the reaction of the components A to D, the hydrogen-containing organopolysiloxanes obtained, in particular the resins, can be subjected to further condensation under the action of acid or base to lower the content of _oR1 groups, in particular the alkoxy group content. If this is carried out in the absence of water, the hydrogen content can also be kept almost unchanged using strong bases, such as alkali metal and alkaline earth metal hydroxides as condensation catalysts in organic sol-vents such as hydrocarbons.
The further condensation to lower the content of alkoxy groups is also possible with hydrogen-containing organopolysilox-anes which have been prepared in another way and not by the pro-cess of the invention.
The hydrogen-containing organopolysiloxanes prepared by the process of the invention can be used for all purposes for which hydrogen-containing organopolysiloxanes can be used. For example, the MQ resins are suitable as filler, as crosslinker in addition-crosslinking systems and as adhesion promoter.
In the following examples, unless otherwise indicated, (a) all amounts are by weight;
(b) all pressures are 0.10 MPa (abs.);
(c) all temperatures are 25~C.
~133166 - The following abbreviations were used:
AR = analytical reagent dist. = distilled Example 1 To the initially charged mixture, heated to 40~C under protective gas, comprising 125.4 g of tetraethoxysilane (0.6 mole), 9.72 g of hexamethyldisilazane (0.06 mole) and 62.53 g of hydrogendimethylethoxysilane (0.6 mole) were added drop-wise 21.60 g of dist. water (1.2 mole) and 60.00 g of AR
ethanol (1.3 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 2.5 hours at room temperature and atmospheric pressure. The mixture was sub-sequently adjusted to pH 7, freed by filtration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 44.48 g (55.9% yield) of a viscous, transparent oil containing 0.53% by weight of Si-bonded hydrogen.
Example 2 To the initially charged mixture, heated to 40~C under protective gas, comprising 20.90 g of tetraethoxysilane (0.1 mole), 1.62 g of hexamethyldisilazane (0.01 mole) and 6.72 g of 1,1,3,3-tetramethyldisiloxane (0.05 mole) were added drop-wise 3.60 g of dist. water (0.2 mole) and 12.00 g of AR
ethanol (0.26 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 3 hours at room temp-erature and atmospheric pressure. The mixture was subse-quently adjusted to pH 7, freed by filtration of any amounts of gel formed and then evaporated in a high vacuum at 100~C
to constant weight.
~133166 ~ This gave 7.90 g (55.48% yield) of a highly viscous, transparent oil containing 0.56% by weight of Si-bonded hydrogen.
Example 3 To the initially charged mixture, heated to 40~C under protective gas, comprising 20.90 g of tetraethoxysilane (0.1 mole), 2.66 g of hexamethyldisilazane (0.0165 mole), 3.06 g of 1,3-divinyltetramethyldisilazane (0.0165 mole) and 3.44 g of hydrogendimethylethoxysilane (0.033 mole) were added drop-wise 3.60 g of dist. water (0.2 mole) and 10.00 g of AR
ethanol (0.22 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 2.5 hours at 60~C, one hour at room temperature and atmospheric pressure. The mixture was subsequently adjusted to pH 7, freed by filtra-tion of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 11.13 g (84.9% yield) of a highly viscous, transparent oil containing 0.11% by weight of Si-bonded hydrogen and 5.34% by weight of vinyl groups.
Example 4 To the initially charged mixture, heated to 40~C under protective gas, comprising 20.90 g of tetraethoxysilane (0.1 mole), 2.70 g of hexamethyldisilazane (0.0167 mole), 5.55 g of 3-chloropropyldimethylmethoxysilane (0.033 mole) and 2.24 g of 1,1,3,3-tetramethyldisiloxane (0.0167 mole) were added dropwise 3.60 g of dist. water (0.2 mole) and 12.0 g of AR
ethanol (0.26 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 24 hours at room temperature and atmospheric pressure. The mixture was subse-~uently adjusted to pH 7, freed by filtration of any amounts - of gel formed and then evaporate~ ~n a high vacuum at 100~C
to constant weight.
This gave 9.53 g (62.5% yield) of a low-viscosity, trans-parent oil containing 2.84% by weight of chloropropyl groups and 0.038% by weight of Si-bonded hydrogen.
Example 5 To the initially charged mixture, heated to 40~C under protective gas, comprising 10.45 g of tetraethoxysilane (0.05 mole), 1.35 g of hexamethyldisilazane (0.00835 mole), 3.41 g of 3-acetoxypropyldimethylmethoxysilane (0.0167 mole) and 1.12 g of 1,1,3,3-tetramethyldisiloxane (0.00835 mole) were added dropwise 1.80 g of dist. water (0.1 mole) and 6.0 g of AR ethanol (0.13 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 24 hours at room temperature and atmospheric pressure. The mixture was subse-quently adjusted to pH 7, freed by filtration of any amounts of gel formed and then evaporated in a high vacuum at 100~C
to constant weight.
This gave 3.03 g (36.7% yield) of a low-viscosity, trans-parent oil containing 2.36% by weight of acetoxypropyl groups and 0.039% by weight of Si-bonded hydrogen.
Example 6 To the initially charged mixture, heated to 40~C under protective gas, comprising 10.45 g of tetraethoxysilane (0.05 mole), 1.35 g of hexamethyldisilazane (0.00835 mole), 2.75 g of 3-mercaptopropyldimethylmethoxysilane (0.0167 mole) and 1.12 g of 1,1,3,3-tetramethyldisiloxane (0.00835 mole) were added dropwise 1.80 g of dist. water (0.1 mole) and 6.0 g of AR ethanol (0.13 mole), previously mixed in the feed vessel.
~1331 fib The reaction mixture was stirred for 3.5 hours at 75~C and atmospheric pressure and was then cooled to room temperature.
The mixture was subsequently adjusted to pH 7, freed by fil-tration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 6.9 g (90.8% yield) of a transparent oil con-taining 2.55% by weight of mercaptopropyl groups and 0.041%
by weight of Si-bonded hydrogen.
Example 7 To the initially charged mixture, heated to 40~C under protective gas, comprising 10.45 g of tetraethoxysilane (0.05 mole), 1.35 g of hexamethyldisilazane (0.00835 mole), 4.48 g of diethyl 2-(ethoxydimethylsilyl)ethylphosphonate (0.0167 mole) and 1.12 g of 1,1,3,3-tetramethyldisiloxane (0.00835 mole) were added dropwise 1.80 g of dist. water (0.1 mole) and 6.0 g of AR ethanol (0.13 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 3.5 hours at 75~C and atmospheric pressure and was then cooled to room temperature.
The mixture was subsequently adjusted to pH 7, freed by fil-tration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 6.90 g (76% yield) of a low-viscosity, transpar-ent oil containing 2.99% by weight of diethyl ethanephospho-nate groups and 0.041% by weight of Si-bonded hydrogen.
Example 8 To the initially charged mixture, heated to 40~C under protective gas, comprising 10.45 g of tetraethoxysilane (0.05 mole), 1.35 g of hexamethyldisilazane (0.00835 mole), 3.38 g of n-octyldimethylmethoxysilane (0.0167 mole) and 1.12 g of -- 1,1,3,3-tetramethyldisiloxane (0.00835 mole) were added drop-wise 1.80 g of dist. water (0.1 mole) and 6.0 g of AR ethanol (0.13 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 3.5 hours at 75~C and atmospheric pressure and was then cooled to room temperature.
The mixture was subsequently adjusted to pH 7, freed by fil-tration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 5.51 g (67% yield) of a viscous, transparent oil containing 2.32% by weight of n-octyl groups and 0.043% by weight of Si-bonded hydrogen.
Example 9 To the initially charged mixture, heated to 40~C under protective gas, comprising 10.45 g of tetraethoxysilane (0.05 mole), 1.35 g of hexamethyldisilazane (0.00835 mole), 3.61 g of 3-(methacryloxy)propyldimethylmethoxysilane (0.0167 mole) and 1.12 g of 1,1,3,3-tetramethyldisiloxane (0.00835 mole) were added dropwise 1.80 g of dist. water (0.1 mole) and 6.0 g of AR ethanol (0.13 mole), prevlously mixed in the feed vessel.
The reaction mixture was stirred for 5 hours at 60~C and atmospheric pressure and was then cooled to room temperature.
The mixture was adjusted to pH 7, subsequently freed by filtration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 7.52 g (88.9% yield) of a transparent oil con-taining 3.56% by weight of 3-(methacryloxy)propyl groups and 0.037% by weight of Si-bonded hydrogen.
Example 10 To the initially charged mixture, heated to 40~C under ~1331 66 - protective gas, comprising 10.45 g of tetraethoxysilane (0.05 mole), 1.35 g of hexamethyldisilazane (0.00835 mole), 3.31 g of 2-cyclohexenylethyldimethylmethoxysilane (0.0167 mole) and 1.12 g of 1,1,3,3-tetramethyldisiloxane (0.00835 mole) were added dropwise 1.80 g of dist. water (0.1 mole) and 7.0 g of AR ethanol (0.15 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 5 hours at 75~C and atmospheric pressure and was then cooled to room temperature.
The mixture was adjusted to pH 7, subsequently freed by fil-tration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 3.56 g (43.7% yield) of a yellow, transparent oil containing 3.1~ by weight of 2-cyclohexenyl groups and 0.03~ by weight of Si-bonded hydrogen.
Example 11 To the initially charged mixture, heated to 40~C under protective gas, comprising 10.45 g of tetraethoxysilane (0.05 mole), 1.35 g of hexamethyldisilazane (0.00835 mole), 3.48 g of 2-phenylpropyldimethylmethoxysilane (0.0167 mole) and 1.12 g of 1,1,3,3-tetramethyldisiloxane (0.00835 mole) were added dropwise 1.80 g of dist. water (0.1 mole) and 7.0 g of AR
ethanol (0.15 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 5 hours at 75~C and atmospheric pressure and was then cooled to room temperature.
The mixture was adjusted to pH 7, subsequently freed by fil-tration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 5.24 g (63.06% yield) of a viscous, transparent oil containing 2.22% by weight of 2-phenylpropyl groups and 0.039% by weight of Si-bonded hydrogen.
~l33l66 -Example 12 To the initially charged mixture, heated to 40~C under protective gas, comprising 10.45 g of tetraethoxysilane (0.05 mole), 1.35 g of hexamethyldisilazane (0.00835 mole), 3.11 g of 3,3,3-trifluoropropyldimethylmethoxysilane (0.0167 mole) and 1.12 g of 1,1,3,3-tetramethyldisiloxane (0.00835 mole) were added dropwise 1.80 g of dist. water (O.l mole) and 7.0 g of AR ethanol (0.15 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 3.5 hours at 75~C and atmospheric pressure and was then cooled to room temperature.
The mixture was adjusted to pH 7, subsequently freed by fil-tration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 6.88 g (86.5% yield) of a viscous, transparent oil containing 2.86% by weight of 3,3,3-trifluoropropyl groups and 0.035% by weight of Si-bonded hydrogen.
Example 13 To the initially charged mixture, comprising 1.80 g of dist. water (0.1 mole), 6.0 g of AR ethanol (0.13 mole) and 2.46 g of 3-aminopropyldimethylmethoxysilane (0.0167 mole) was added 0.0167 mole of hydrogen chloride in the form of a concentrated aqueous hydrochloric acid and the mixture was adjusted to pH 7.0 using a pH meter. The neutralized initi-ally charged mixture was heated to 40~C under protective gas, and 10.45 g of tetraethoxysilane (0.05 mole), 1.35 g of hexa-methyldisilazane (0.00835 mole) and 1.12 g of 1,1,3,3-tetra-methyldisiloxane (0.00835 mole) were added dropwise.
~13316~
- The reaction mixture was stirred for 3.5 hours at 75~C and atmospheric pressure and was then cooled to room temperature.
The mixture was adjusted to pH 7, subsequently freed by filtration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 6.78 g (85.7% yield) of a yellow solid resin containing 2.5% by weight of 3-aminopropyl hydrochloride groups and 0.029% by weight of Si-bonded hydrogen.
Example 14 To the initially charged mixture, heated to 40~C under protective gas, comprising 62.70 g of tetraethoxysilane (0.3 mole), 8.1 g of hexamethyldisilazane (0.05 mole), 27.49 g of 3-methyldiethoxysilylpropylsuccinic anhydride (0.1 mole) and 6.72 g of 1,1,3,3-tetramethyldisiloxane (0.05 mole) were added dropwise 10.80 g of dist. water (0.6 mole) and 36.0 g of AR ethanol (0.78 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 24 hours at room temperature and atmospheric pressure. The mixture was adjusted to pH 7, subsequently freed by filtration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 44.72 g (88.6% yield) of a yellow solid resin containing 3.2% by weight of propylsuccinic anhydride groups and 0.02% by weight of Si-bonded hydrogen.
The resin was dissolved in a mixture of 50 ml of AR etha-nol, 150 ml of dist. water and 2.0 g of potassium hydroxide (0.036 mole). Using a pH meter and with the addition of a further 1.0 g of potassium hydroxide (0.018 mole), the pH was adjusted to 6.98. The solution was filtered and then evapo-1 b' b' _ rated in a high vacuum at 100~C to constant weight. The product was subsequently dried over diphosphorus pentoxide in a high vacuum at 80~C.
Example 15 To the initially charged mixture, heated to 40~C under protective gas, comprising 20.9 g of tetraethoxysilane (0.1 mole), 2.70 g of hexamethyldisilazane (0.0167 mole), 5.77 g of cyanopropylmethyldimethoxysilane (0.0333 mole) and 2.24 g of 1,1,3,3-tetramethyldisiloxane (0.0167 mole) were added dropwise 3.60 g of dist. water (o.2 mole) and 12.o g of AR
ethanol (0.26 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 3 hours at 75~C and atmospheric pressure and was then cooled to room temperature.
The mixture was adjusted to pH 7, subsequently freed by fil-tration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 8.91 g (61.8% yield) of a low-viscosity, trans-parent oil containing 4.24~ by weight of cyanopropyl groups and 0.044% by weight of Si-bonded hydrogen.
Example 16 To the initially charged mixture, heated to 40~C under protective gas, comprising 10.45 g of tetraethoxysilane (0.05 mole), 1.35 g of hexamethyldisilazane (0.00835 mole), 4.21 g of 2,2-diethoxy-2,3,4,5-tetrahydro-1,2-benzoxasilepine (0.0167 mole) and 1.12 g of 1,1,3,3-tetramethyldisiloxane (0.00835 mole) were added dropwise 1.80 g of dist. water (0.1 mole) and 6.0 g of AR ethanol (0.13 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 24 hours at room temperature and atmospheric pressure. The mixture was - adjusted to pH 7, subsequently freed by filtration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 8.11 g (74.5% yield) of a yellow, highly vis-cous, transparent oil containing ~.19% by weight of ortho-phenoxypropyl groups and 0.039% by weight of Si-bonded hydro-gen.
Example 17 To the initially charged mixture, heated to 40~C under protective gas, comprising 20.9 g of tetraethoxysilane (0.1 mole), 2.70 g of hexamethyldisilazane (0.0167 mole), 6.71 g of dimethyldiethoxysilane (0.05 mole) and 7.42 g of methyldiethoxysilane (0.05 mole) were added dropwise 3.60 g of dist. water (0.2 mole) and 12.0 g of AR ethanol (0.26 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 5 hours at 60OC and atmospheric pressure and was then cooled to room temperature.
The mixture was adjusted to pH 7, subsequently freed by fil-tration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 11.58 g (86.3% yield) of a low viscosity, trans-parent oil containing 0.04% by weight of Si-bonded hydrogen groups.
Example 18 To the initially charged mixture, heated to 40~C under protective gas, comprising 17.84 g of methyltriethoxysilane (0.1 mole), 4.035 g of hexamethyldisilazane (0.025 mole) and 5.21 g of hydrogendimethylethoxysilane (0.05 mole) were added dropwise 3.60 g of dist. water (0.2 mole) and 10.00 g of AR ethanol (0.22 mole), previously mixed in the feed vessel.
- The reaction mixture was stirred for 24 hours at room temperature and atmospheric pressure. The mixture was adjusted to pH 7, subsequently freed by filtration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 8.03 g (56.8% yield) of a transparent oil con-taining 0.089% by weight of Si-bonded hydrogen.
Example 19 For the initially charged mixture, 18.48 g of the hydrogen-containing organopolysiloxane resin (ethoxy content: 17.5%
by weight) from Example 1 were dissolved in 200 ml of tolu-ene; 500 ppm of potassium hydroxide (25% strength in AR
methanol) were introduced into the initially charged mixture, the mixture was stirred for 3.5 hours at 80~C and atmospheric pressure and then cooled to room temperature. The mixture was adjusted to pH 7, subsequently freed by filtration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 16.91 g (91.5% yield) of the starting resin having an ethoxy content of 13.99~ by weight. The content of Si-bonded hydrogen did not change.
Example 20 For the initially charged mixture, 4.0 g of the hydrogen-containing organopolysiloxane resin (ethoxy content: 17.5%
by weight) from Example 1 were dissolved in 40 ml of toluene;
500 ppm of aqueous, concentrated hydrochloric acid were introduced into the initially charged mixture, the mixture was stirred for 2.5 hours at 80~C and then cooled to room temperature. The mixture was neutralized by the addition of magnesium oxide, subsequently freed by filtration of any ~ ~ V ~
- amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 3.14 g (78.5% yield) of the starting resin having an ethoxy content of 14.45% by weight. The content of Si-bonded hydrogen did not change.
Example 21 To the initially charged mixture, heated to 40~C under pro-tective gas, comprising 10.45 g of tetraethoxysilane (0.05 mole), 5.91 g of trimethylethoxysilane (0.033 mole) and 1.80 g of dist. water (0.1 mole) and 12.00 g of AR ethanol (0.26 mole), as previously mixed solution, were added dropwise 3.36 g of l,1,3,3-tetramethyldisiloxane (0.025 mole).
The mixture was stirred at this temperature for 5 minutes and the solution was subsequently saturated with gaseous ammonia. The reaction mixture was stirred for an additional 2 hours at room temperature and atmospheric pressure, subse-quently freed by filtration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 2.39 g (22.2% yield) of a viscous, transparent oil containing 0.1% by weight of Si-bonded hydrogen.
Example 22 To the initially charged mixture, heated to 40~C under protective gas, comprising 10.45 g of tetraethoxysilane (0.05 mole), and 1.80 g of dist. water (0.1 mole) and 12.00 g of AR
ethanol (0.26 mole), previously mixed, were added dropwise 6.72 g of 1,1,3,3-tetramethyldisiloxane (0.05 mole).
The mixture was stirred at this temperature for 5 minutes and the solution was subsequently saturated with gaseous ammonia. The reaction mixture was stirred for an additional 2 hours at room temperature and atmospheric pressure, subse-Xl~31 66 - quently freed by filtration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 3.0 g (30.7~ yield) of a low-viscosity, trans-parent oil containing 0.4% by weight of Si-bonded hydrogen.
Example 23 To the initially charged mixture, heated to 40~C under protective gas, comprising 20.90 g of tetraethoxysilane (0.1 mole), 2.66 g of hexamethyldisilazane (0.0165 mole), 4.30 g of 1,3-divinyltetramethyldisilazane (0.033 mole) and 3.44 g of hydrogendimethylethoxysilane (0.033 mole), were added dropwise 3.60 g of dist. water (O.2 mole) and 10.00 g of AR
ethanol (0.22 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 2.5 hours at 60~C and for one hour at room temperature at atmospheric pressure.
The mixture was subsequently freed by filtration of any amounts of gel formed and then evaporated in a high vacuum at 100~C to constant weight.
This gave 9.55 g (67.7% yield) of a white solid resin con-taining 5.56% by weight of vinyl groups and 0.099% by weight of Si-bonded hydrogen.
l.o g of solid resin was subsequently dissolved in 9.0 g of toluene and admixed with 100 ppm (based on pure platinum) of a platinum catalyst comprising hexachloroplatinic acid and divinyltetramethyldisiloxane.
This gave 10.0 g of a stable, transparent gel.
Example 24 5.0 g of hydrogen-containing organopolysiloxane resin from Example 2 were mixed with 5.0 g of ~,w-divinylpolydimethyl-siloxane having a viscosity of 500 mPa s, and admixed with 100 ppm (based on pure platinum) of a platinum catalyst ~f 331 66 - comprising hexachloroplatinic acid and divinyltetramethyldi-siloxane.
This gave 10.0 g of a brittle, transparent product.
Example 25 To the initially charged mixture, heated to 40~C under protective gas, comprising 41.8 g of tetraethoxysilane (0.2 mole), 3.24 g of hexamethyldisilazane (0.02 mole) and 13.44 g of 1,1,3,3-tetramethyldisiloxane (0.1 mole), were added drop-wise 7.20 g of dist. water (0.4 mole).
The reaction mixture was stirred for 3 hours at 75~C and atmospheric pressure, and then cooled to room temperature.
The mixture was subsequently evaporated in a high vacuum at 100~C to constant weight.
This gave a white, insoluble powder containing 0.13% by weight of Si-bonded hydrogen.
Claims (7)
1. A process for preparing organopolysiloxanes containing Si-bonded hydrogen, which comprises reacting a mixture of (A) organosilicon compounds selected from (A1) organosilanes of the general formula RaHbSi(OR1)(4-a-b), (1) where R is optionally substituted C1- to C18-hydrocarbon radicals, R1 is optionally substituted C1- to C18-hydrocarbon radicals or hydrogen atoms, a is 0, 1, 2 or 3 and b is 0, 1, 2 or 3, and (A2) organosiloxanes comprising units of the general formula RcHd(OR1)esio(4-c-d-e)/2, (2) where c and e are each 0, 1, 2 or 3, d is 0, 1, 2 or 3 and R and R1 are as defined above, with the proviso that component A has at least 0.01 - 4 mole of alkoxy groups per mole of silicon atoms and that at least a part of the organosilicon compounds of the component A comprises Si-bonded hydrogen, (B) at least 0.5 mole of water per mole of alkoxy groups in component A, and (C) optionally a water-miscible solvent, in the presence of (D) ammonia, a primary or secondary C1-C4-alkylamine or a compound which liberates ammonia or primary or secondary C1-C4-alkylamine on reaction with water.
2. The process as claimed in claim 1, wherein the radical R1 is alkyl groups having from 1 to 6 carbon atoms and is optionally substituted with C1-C6-alkyloxy groups or hydroxy groups.
3. The process as claimed in claim 1, wherein component (A) further comprises silicates.
4. The process as claimed in claim 1, wherein the hydrogen content of the Si-bonded hydrogen containing organopolysiloxane final products is 0.0001% to 2% by weight.
5. The process as claimed in claim 1, wherein compounds of (D) which liberate ammonia or primary or secondary C1-C4-alkylamine by reaction with water, are of the formulae R2nSiZ4-n (3), (R23Si)2NH (4), (R22SiNH) X (5), (R23Si)2NR3 (6) and (R22SiNR3)y (7) where R2 is a hydrogen atom or a C1-C4-alkyl radical, R3 is a C1-C4-alkyl radical, Z is the group -NHR3 or NR32, n is 2 or 3, x is an integer from 3 to 6 and y is an integer from 1 to 12.
6. The process as claimed in claim 1, wherein subsequent to the reaction of the components (A) to (D), the hydrogen-containing organopolysiloxanes obtained are subjected to further condensation by addition of acid or base.
7. The process as claimed in claim 6, wherein the process is carried out in the absence of water and alkali metal, or alkaline earth metal hydroxides, in organic solvents are present.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4337695.9 | 1993-11-04 | ||
| DE4337695A DE4337695A1 (en) | 1993-11-04 | 1993-11-04 | Base-catalyzed process for the production of hydrogen-containing organopolysiloxanes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2133166A1 CA2133166A1 (en) | 1995-05-05 |
| CA2133166C true CA2133166C (en) | 1998-09-29 |
Family
ID=6501817
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002133166A Expired - Fee Related CA2133166C (en) | 1993-11-04 | 1994-09-28 | Base-catalyzed process for preparing hydrogen-containing organopolysiloxanes |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0652246B1 (en) |
| JP (1) | JP2693388B2 (en) |
| KR (1) | KR0152309B1 (en) |
| AT (1) | ATE157108T1 (en) |
| CA (1) | CA2133166C (en) |
| DE (2) | DE4337695A1 (en) |
| ES (1) | ES2105468T3 (en) |
| FI (1) | FI945160A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108137812A (en) * | 2015-10-16 | 2018-06-08 | 信越化学工业株式会社 | The manufacturing method of Silicon Containing Hydrogen alkyl organic siliconresin |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6218497B1 (en) | 1997-04-21 | 2001-04-17 | Alliedsignal Inc. | Organohydridosiloxane resins with low organic content |
| US6143855A (en) | 1997-04-21 | 2000-11-07 | Alliedsignal Inc. | Organohydridosiloxane resins with high organic content |
| US6043330A (en) * | 1997-04-21 | 2000-03-28 | Alliedsignal Inc. | Synthesis of siloxane resins |
| US6743856B1 (en) | 1997-04-21 | 2004-06-01 | Honeywell International Inc. | Synthesis of siloxane resins |
| US6177199B1 (en) | 1999-01-07 | 2001-01-23 | Alliedsignal Inc. | Dielectric films from organohydridosiloxane resins with low organic content |
| US6218020B1 (en) | 1999-01-07 | 2001-04-17 | Alliedsignal Inc. | Dielectric films from organohydridosiloxane resins with high organic content |
| US6472076B1 (en) | 1999-10-18 | 2002-10-29 | Honeywell International Inc. | Deposition of organosilsesquioxane films |
| US6440550B1 (en) | 1999-10-18 | 2002-08-27 | Honeywell International Inc. | Deposition of fluorosilsesquioxane films |
| DE102011078544A1 (en) * | 2011-07-01 | 2013-01-03 | Wacker Chemie Ag | Process for the preparation of organopolysiloxanes |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE538417A (en) * | ||||
| US2628213A (en) * | 1948-04-16 | 1953-02-10 | Montclair Res Corp | Copolymers, including siliconols and hydrogen bonded to silicon |
| US2637718A (en) * | 1948-04-16 | 1953-05-05 | Montclair Res Corp | Copolymers containing hydrogen bonded directly to silicon |
| NL124484C (en) * | 1964-05-20 | |||
| JPS5966422A (en) * | 1982-10-08 | 1984-04-14 | Japan Synthetic Rubber Co Ltd | Preparation of silicone resin |
-
1993
- 1993-11-04 DE DE4337695A patent/DE4337695A1/en not_active Withdrawn
-
1994
- 1994-09-28 CA CA002133166A patent/CA2133166C/en not_active Expired - Fee Related
- 1994-10-27 KR KR1019940027725A patent/KR0152309B1/en not_active IP Right Cessation
- 1994-10-28 JP JP6265545A patent/JP2693388B2/en not_active Expired - Lifetime
- 1994-11-02 FI FI945160A patent/FI945160A/en unknown
- 1994-11-03 DE DE59403783T patent/DE59403783D1/en not_active Expired - Fee Related
- 1994-11-03 EP EP94117342A patent/EP0652246B1/en not_active Expired - Lifetime
- 1994-11-03 AT AT94117342T patent/ATE157108T1/en not_active IP Right Cessation
- 1994-11-03 ES ES94117342T patent/ES2105468T3/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108137812A (en) * | 2015-10-16 | 2018-06-08 | 信越化学工业株式会社 | The manufacturing method of Silicon Containing Hydrogen alkyl organic siliconresin |
| US20180298148A1 (en) * | 2015-10-16 | 2018-10-18 | Shin-Etsu Chemical Co., Ltd. | Method for producing hydrosilyl group-containing organic silicon resin |
| US10590242B2 (en) * | 2015-10-16 | 2020-03-17 | Shin-Etsu Chemical Co., Ltd. | Method for producing hydrosilyl group-containing organic silicon resin |
| CN108137812B (en) * | 2015-10-16 | 2021-05-28 | 信越化学工业株式会社 | Method for producing hydrosilyl-containing silicone resin |
Also Published As
| Publication number | Publication date |
|---|---|
| KR950014184A (en) | 1995-06-15 |
| ES2105468T3 (en) | 1997-10-16 |
| FI945160A0 (en) | 1994-11-02 |
| KR0152309B1 (en) | 1998-10-15 |
| DE59403783D1 (en) | 1997-09-25 |
| DE4337695A1 (en) | 1995-05-11 |
| ATE157108T1 (en) | 1997-09-15 |
| JP2693388B2 (en) | 1997-12-24 |
| EP0652246B1 (en) | 1997-08-20 |
| JPH07188415A (en) | 1995-07-25 |
| CA2133166A1 (en) | 1995-05-05 |
| EP0652246A1 (en) | 1995-05-10 |
| FI945160A (en) | 1995-05-05 |
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