CA1333115C - Process for preparing organopolysiloxanes containing sic-bonded organic radicals having a basic nitrogen - Google Patents
Process for preparing organopolysiloxanes containing sic-bonded organic radicals having a basic nitrogenInfo
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- CA1333115C CA1333115C CA000550908A CA550908A CA1333115C CA 1333115 C CA1333115 C CA 1333115C CA 000550908 A CA000550908 A CA 000550908A CA 550908 A CA550908 A CA 550908A CA 1333115 C CA1333115 C CA 1333115C
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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
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
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Abstract
A process for preparing organopolysiloxanes contain-ing SiC-bonded organic radicals having a basic nitrogen which comprises reacting in a first step, a silane of the formula YSi(CH3)x(OR1)3-x in which R1 represents the same or different alkyl radicals having from 1 to 4 carbon atoms in each radical, and Y repre-sents a monovalent SiC-bonded organic radical having a basic nitrogen, and/or partial hydrolysates of the silane with an organo(poly)siloxane of the formula R3SiO(SiR2O)nSiR3 in which R represents the same or different, monovalent hydro-carbon radicals or monovalent fluorinated hydrocarbon radicals, and n is 0 or an integer having a value of from 1 to 100, in an amount of from 0.1 to 10 parts by weight per part by weight of the above silane and/or partial hydrolysates thereof, in the presence of a basic catalyst and in the absence of water, and in a second step, reacting the organopolysiloxane obtained in the first step, with water in order to hydrolyze groups of the formula -OR1, in which R1 is the same as above, to form silanol groups which are simultaneously and/or subsequently condensed with one another, and thereafter separating the product formed during the condensation from the alkanol and water, and optionally in a third step, reacting the product obtained from the second step with a cyclic organopolysiloxane of the formula (R2SiO)m in which R is the same as above and m is an integer having a value of from 3 to 12, and/or with an organopolysiloxane of `
the formula R3SiO(SiR2O)pSiR3 in which R is the same as above and p is 0 or an integer having a value of at least 1, in the presence of a basic catalyst.
the formula R3SiO(SiR2O)pSiR3 in which R is the same as above and p is 0 or an integer having a value of at least 1, in the presence of a basic catalyst.
Description
133311~
-1- Docket No. Wa-8560 Paper No. 1 A PROCESS FOR PREPARING
ORGANOPOLYSILOXANES CONTAINING
SiC-BONDED ORGANIC RADICALS
HAVING A BASIC NITROGEN
The present invention relates to a process for pre-paring organopolysiloxanes and more particularly to a process for preparing organopolysiloxanes containing SiC-bonded organic radicals having a basic nitrogen atom.
Background of the Invention Organopolysiloxanes containing SiC-bonded organic radicals which have a basic nitrogen atom and processes for preparing the same are described in U. S. Patent No. 2,947,771 to Bailey. The organopolysiloxanes described by Bailey contain units of the formula R3SiO~, R2SiO and YSi(CH3)0, in which R
represents the same or different monovalent hydrocarbon radicals or fluorinated monovalent hydrocarbon radicals and Y represents a monovalent SiC-bonded organic radical having a basic nitrogen.
It is an object of the present invention to provide a process for preparing organopolysiloxanes containing SiC-bonded organic -radicals having a basic nitrogen from readily available organosilicon compounds. Another object of the present invention is to provide a process for preparing organo-polysiloxanes of the type described above, in which at least some of the units of the formula YSi(CH3)0 are replaced by units of the formula YSiO3/2, where Y represents a monovalent SiC-bonded organic radical having a basic nitrogen. Still another object of the present invention is to provide organo-polysiloxanes which are substantially free of groups that are capable of condensation, such as silanol groups or atoms which are capable of condensation, such as Si-bonded hydrogen atoms.
133311~
A further object of the present invention is to provide organopolysiloxanes that are storage stable and are obtained in high yields.
Summary of the Invention The foregoing objects and others which are apparent from the following description are accomplished in accordance with this invention, generally speaking, by providing a process for preparing organopolysiloxanes containing SiC-bonded organic radicals having a basic nitrogen which comprises reacting in a first step, a silane of the formula YSi~CH3)x(oR )3-x in which Rl represents the same or different alkyl radicals having from 1 to 4 carbon atoms in each radical, Y represents a monovalent SiC-bonded organic radical having a basic nitrogen, and x is 0 or 1, or partial hydrolysates of such a silane, or a mixture containing the silane and partial hydrolysates thereof with an organo(poly)siloxane of the formula R3SiO(SiR2O)nSiR3 in which R represents the same or different, monovalent hydro-carbon radicals or monovalent fluorinated hydrocarbon radicals, and n represents 0 or an integer having the value of from 1 to 100, in an amount of from 0.1 to 10 parts by weight per part by weight of the silane having the above formula or partial hydrolysates thereof, in the presence of a basic catalyst and in the absence of water, and in a second step, reacting the organopolysiloxane obtained from the first step, with water in order to hydroly~e groups of the formula -ORl, in which Rl is the same as above, to form an alkanol and silanol groups which are simultaneously and/or subsequently condensed with one another, and the resultant product formed in the condensation is separated from the alkanol and water, and in a third and optional step, reacting the product obtained from the second step with a cyclic organopolysiloxane of the formula (R2sio)m 133~115 in which R is the same as above, and m is an integer having a value of from 3 to 12, or a linear organo(poly)siloxane of the formula R3Sio(SiR2O)pSiR3 in which R is the same as above, and p is 0 or an integer having a value of at least 1, or a mixture containing the linear organo(poly)siloxane and the cyclic organopolysiloxane, in the presence of a basic catalyst.
- Description of the Invention The monovalent hydrocarbon radicals and the monovalent fluorinated hydrocarbon radicals represented by R preferably contain from 1 to 18 carbon atoms in each radical. Examples of hydrocarbon radicals represented by R are the methyl, ethyl, n-propyl, isopropyl, butyl, octyl, tetradecyl and octadecyl radicals; radicals which contain carbon and hydrogen atoms and have aliphatic multiple bonds, such as the vinyl, allyl and hexenyl radicals; cycloaliphatic hydrocarbon radicals, such as the cyclopentyl, cyclohexyl and methylcyclohexyl radicals; aromatic hydrocarbon radicals, such as the phenyl and xenyl radicals; alkaryl radicals, such as the tolyl radicals;
and aralkyl radicals, such as the benzyl radical. An example of a fluorinated hydrocarbon radical is the 3,3,3-trifluoro-propyl radical.
Examples of alkyl radicals represented by R are the methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and the tert-butyl radicals, in which the methyl and the ethyl radicals are the preferred radicals.
The monovalent SiC-bonded organic radicals having a basic nitrogen, i.e., the radicals represented by Y, are preferably those of the formula in which R2 represents hydrogen or the same or different alkyl, cycloalkyl or aminoalkyl radicals, and R3 represents a divalent hydrocarbon radical which is free of aliphatic mul-tiple bonds and which contains one carbon atom or 3 or 4carbon atoms in each radical, such as the radical of the formula ( 2)3 -` _4_ 1333115 The specific examples of alkyl radicals represented by R also apply to the alkyl radicals represented by R2.
Examples of aminoalkyl radicals represented by R2 are those of the formulas H2N(CH2)3-H2N(CH2)2NH(CH2)3 H2N(CH2)2-(H3C) 2N(CH2)2 H 2N(CH2)4-H(NHCH 2CH2) 3- and 4 gNHcH2cH2NH(cH2) _ An example of a cycloalkyl radical represented by R2 is the cyclohexyl radical.
The monovalent, SiC-bonded radicals having a basic nitrogen, i.e., the radicals represented by Y may also be, for example, radicals of the formula 2 ~ / 2 ~
O NR3- or \2 ,,,, NR3-in which R3 is the same as above.
Specific examples of silanes of the formula YSi(CH3)x(oR )3-x which can be employed in the first step of the process of this invention are those of the formula 2N(CH2) 3Si(CH3)(0C2H5)2 H2N(CH2)2NH(CH2)3Si(CH3) (0CH3)2 CH~ /cHNH(cH2)3si(cH3)(ocH3)2 ~ CH2CH~
o N(CH2)3Si(CH3)(CH3)2 5~ 1~3Il ~
/ 2 ~
CH~ N(CH2)3Si(cH3)(ocH3)2 H2N(CH2)3Si(OcH3)3 H2N(CH2)3si(oc2 5)3 H2N(CH2)2NH(CH2)3Si(OCH3)3 / 2 ~
CH~ CHNH(CH2)3si(OCH3)3 \ / N(CH2)3Si(OCH3)3 , and / 2 ~
CH ~ N(CH2)3Si(oCH3)3 A specific example of a partial hydrolysate of such a silane is a disiloxane of the formula 2 2)2 H(CH2)3Si(CH3)(OC2H5)] O
In the first step of the process of this invention, it is possible to use one type of silane of the formula YSi(CH3)x(oR )3-x or a partial hydrolysate thereof. However, it is also possible to use a mixture of at least two different types of such silanes or partial hydrolysates thereof in the 1st step of the process of this invention.
In the organo(poly)siloxanes of the formula R3Sio(SiR2o)nSiR3 at least two of the radicals represented by R in the siloxane units of the formula R3SiO%
are preferably methyl radicals. Moreover, it is preferred 13331t~
that at least 50 percent of the radicals represented by R in the units of the formula - SiR2o be methyl radicals because of their availability.
It is possible to employ only one type of organo-(poly)siloxane of the formula R3SiO(SiR2o)nSiR3 in the first step of the process of this invention, or it is possible to use a mixture of at least two different types of such organopolysiloxanes in the first step of the process of this invention.
Any basic catalysts which promote the equilibration of mixtures of organosilicon compounds containing SiC-bonded organic radicals having a basic nitrogen and organo(poly)si-loxanes free of such radicals can be employed in the firststep of the process and also in the optional third step of the process of this invention. Examples of suitable catalysts which may be employed are alkali metal hydrides, alkali metal hydroxides, alkali metal silanolates, alkali metal siloxanolates, quaternary ammonium hydroxides, quaternary ammonium silanolates, quaternary ammonium siloxanolates, quaternary phosphonium hydroxides, quaternary phosphonium silanolates, quaternary phosphonium siloxanolates, alkali metal alkyls, alkali metal alkenyls, alkali metal aryls, base activated montmorillonites and basic ion exchange resins. Specific examples of basic catalysts are sodium hydroxide, potassium hydroxide, caesium hydroxide, potassium methylsilanolate, tetra-n-butylphosphonium hydroxide, products obtained from the reaction of tetramethyl-ammonium hydroxide and octamethylcyclotetrasiloxane, tetra-methylammonium hydroxide, benzyltrimethylammonium hydroxide,naphthalene-potassium, n-butyllithium and amylsodium.
In the first step of the process of this invention, and also in the optional third step of the process of this invention, the basic catalysts can be employed in the same amounts in which they have been employed heretofore for equili-brating mixtures of organosilicon compounds containing SiC-bonded organic radicals having a basic nitrogen and organo-(poly)siloxanes free such radicals. In the case of base 7 133311~i activated montmorillonites, basic ion exchange resins and other basic catalysts which are comparable to these solid, basic catalysts, the amount of catalyst preferably ranges from about 0.1 to 10 percent by weight, based on the total weight of the organosilicon compounds to be reacted with one another in the first step of the process of this invention. In the case of the other basic catalysts and basic catalysts which are comparable to these catalysts, the amount ranges prefer-ably from about 1 to about 1,000 ppm by weight, based on the total weight of the organosilicon compounds to be reacted with one another in the first step of the process of this invention.
The first step of the process of this invention is preferably carried out at from 15 to about 200C, depending on the temperature stability of the basic catalyst used and at atmospheric pressure, i.e., at 1020 hPa (abs.) or about 1020 hPa (abs.). However, higher or lower pressures can also be used, if desired.
If desired, the first step and the optional third step of the process of this invention can be carried out under a protective gas, such as a nitrogen or argon atmosphere.
In the first step of the process of this invention, it is preferred that the contents of the reaction vessel be agitated, for example, by stirring.
The reaction carried out in the first step of the process of this invention is complete when the contents of the reaction vessel are clear, at least after the removal of the catalyst contained therein. Generally, a reaction time of from about 0.1 to 10 hours is sufficient for this reaction.
The organopolysiloxane obtained in the first step of the process of this invention can be stored before carrying out the second step of the process of this invention or the organopolysiloxane obtained from the first step can be pro-cessed further in the second step of the process of this invention, more or less immediately after its preparation without removing or deactivating the basic catalyst present in the organopolysiloxane from the first step of the process of this invention.
In the second step of the process of this invention, water is preferably used in an amount of from about 18 g to 133311~
- 180 g per gram-equivalent of the group of the formula -ORl present in the first step of the process of this invention.
The hydrolysis of the groups of the formula -SiOR1 and the condensation of the silanol groups formed as a result of the hydrolysis in the second step of the process of this invention are preferably carried out at from about 40 to about 200C, and preferably at atmospheric pressure, i.e., at 1020 hPa (abs.) or about 1020 hPa (abs.). If desired, however, higher or lower pressures can be used during the hydrolysis and lower pressures can be used during the condensation of the silanol groups.
The hydrolysis of the groups of the formula -SiOR1 and the condensation of the silanol groups in the second step of the process of this invention are promoted by the catalyst still present from the first step and/or by adding additional catalyst.
The water and alkanol can be removed from the product obtained in the second step of the process of this invention by, for example, distillation.
The contents of the reaction vessel can be agitated, for example by stirring, at least during the hydrolysis of the groups of the formula -SiORl and/or condensation of the silanol groups in the second step of the process of this invention.
In order to obtain a highly storage-stable organo-polysiloxane containing SiC-bonded organic radicals having a basic nitrogen, the catalyst can be removed from the organo-polysiloxane or deactivated after carrying out the second step of the process of this invention. In the case of catalysts such as, for example, quaternary ammonium hydroxides, quater-nary ammonium silanolates and quaternary ammonium siloxanolates,heating the product to a temperature above the decomposition temperature of the catalysts, usually above 150C, is suffi-cient for deactivation.
At least 50 percent of the radicals represented by R
in the units of the formula s iR2o and at least two of the radicals R in the units of the formula R3SiO
are preferably methyl radicals. Likewise, the R radicals in the cyclic organopolysiloxanes having the formula (R2SiO)m and organopolysiloxanes of the formula R3SiO(SiR2O)pSiR3 which are employed in the optional third step of the process of this invention are preferably methyl radicals.
The average value of m is preferably 4 or approxi-mately 4.
There is no upper limit for p since the third and optional step of the process of this invention can be carried out, if necessary, in a solvent which is inert towards the reactants and the catalyst.
It is possible to use only one type of cyclic dior-ganopolysiloxane or linear organopolysiloxane in the third and optional step of the process of this invention. However, it is also possible to employ a mixture of at least two different organopolysiloxanes in this step.
The amount of reactants employed in the third and optional step of the process of this invention are determined merely by the desired proportion of SiC-bonded organic radicals having a basic nitrogen in the organopolysiloxanes produced in the third and optional step of the process according to this invention and by the average chain length desired.
The third and optional step of the process of this invention is preferably carried out at 15 to 200C, depending on the temperature stability of the basic catalyst used, and at atmospheric pressure, i.e., at 1020 hPa (abs.) or about 1020 hPa (abs.). However, higher or lower pressures can also be used, if desired.
The contents of the reaction vessel can also be agitated, for example, stirred in the third and optional step -lo- 133311~
~ of the process of this invention.
Although the third step of the process of this invention is optional, when the third step is carried out, it is complete when the contents of the reaction vessel are clear, at least after the catalyst contained therein has been removed. Generally, from about 0.1 to 10 hours are sufficient for completing the third step of the process.
After carrying out the third step of the process of this invention, the catalyst is preferably either removed from the organopolysiloxane or deactivated.
The various steps of the process of this invention can be carried out successively in one and the same reaction vessel or in separate reaction vessels. The process, accor-ding to this invention, can be carried out batchwise, semi-continuously or continuously.
The organopolysiloxanes or the salts of such organo-polysiloxanes prepared in accordance with this invention with organic or inorganic acids in the second or third step can be used for all purposes for which such organopolysiloxanes con-taining SiC-bonded organic radicals having a basic nitrogen, or salts thereof, can be employed.
They may be employed, for example, as release agents or lubricants, for example, in tire manufacturing or as adhe-sion-repellent finishes for glass and ceramic surfaces, as components of textile treating agents, as lubricating oils, defoamers, foam stabilizers, emulsifiers, antistatic agents and as additives for thermoplastics and elastomers.
In the following examples, all parts and percentages are by weight, unless otherwise specified.
Example 1 First step: A mixture containing 82.5 parts of N-(2-amino-ethyl)-3-aminopropylmethyldimethoxysilane, i.e., a silane of the formula H2N(CH2)2NH(CH2)3Si(CH3)(oCH3)2 59.2 parts of a dimethylpolysiloxane which is endblocked by trimethylsiloxy groups and has an average of 10 siloxane units per molecule, and 0.1 part of a 40 percent solution of benzyl-trimethylammonium hydroxide in methanol is stirred at 80C for 1 hour under dry nitrogen.
Second step: In the reaction vessel used for carrying out the first step, the contents thereof are mixed with 50 parts of water and stirred at 80C for 2 hours, in which a portion of the methanol formed as a result of the hydrolysis of the methoxy groups bonded to the silicon atoms, is removed by distillation. The remaining methanol and water are then removed by distillation at 13 hPa (abs.). The quaternary ammonium hydroxide is deactivated by heating for 60 minutes at 150C at 13 hPa (abs.), and the other components which boil below 150C at 13 hPa (abs.) are simultaneously separated from the organopolysiloxane. About 113 parts of a clear, colorless oil are obtained. The resultant organopolysiloxane has an amine value (number of ml of lN HCL which are necessary to neutralize 1 g of the oil) of 6.6, a viscosity of 205 mm2.s 1 at 25C, and contains less than 0.1 percent of methoxy groups as determined by H nuclear magnetic resonance (NMR) spectrum.
Third step: A mixture containing 4 parts of the organopoly-siloxane obtained in the second step, 500 parts of a mixture of cyclic dimethylpolysiloxanes having from 3 to 10 siloxane units in each molecule and having octamethylcyclotetrasiloxane as the major component, 20 parts of the dimethylpolysiloxane which is endblocked by trimethylsiloxy groups and which has an average of 10 siloxane units in each molecule, and 0.2 parts of a 40 percent solution of benzyltrimethylammonium hydroxide in methanol is stirred at 80C for 2 hours under dry nitrogen.
The quaternary ammonium hydroxide is then deactivated by warming for 60 minutes at 150C and at 13 hPa (abs.), and the other components which boil below 150C at 13 hPa (abs.) are simultaneously separated from the organopolysiloxane. About 430 parts of a clear, colorless oil are obtained. The organo-polysiloxane has an amine value of 0.06 and a viscosity of 1140 mm2.s 1 at 25C.
Example 2 The procedure described in Example 1 is repeated, except that in the third step, 128 parts of the organopoly-siloxane obtained in the first step are used instead of 4 133~
parts of the organopolysiloxane, 1600 parts of the mixture of cyclic dimethylpolysiloxanes are used instead of 500 parts of the mixture, 27 parts of the dimethylpolysiloxane which is endblocked by trimethylsiloxy groups and which has an average of 10 siloxane units in each molecule are used instead of 20 parts of the endblocked dimethylpolysiloxane, and 0.7 parts of the 40 percent solution of benzyltrimethylammonium hydroxide are used instead of 0.2 parts of the solution.
About 1400 parts of a clear, colorless oil having an amine value of 0.6 and a viscosity of 960 mm2.s 1 at 25C are obtained.
Example 3 First step: A mixture containing 222 parts of N-(2-amino-ethyl)-3-aminopropyltrimethoxysilane, i.e., a silane of the formula H2N(CH2)2NH(CH2)3Si(oCH3)3 296 parts of a dimethylpolysiloxane which is endblocked by trimethylsiloxy groups and which has an average of 10 siloxane units in each molecule, and 0.25 parts of a 40 percent solution of benzyltrimethylammonium hydroxide in methanol is stirred at 80C for 1 hour under dry nitrogen.
Second step: In the reaction vessel used for carrying out the first step, the contents of the reaction vessel are mixed with 125 parts of water and stirred at 80C for 2 hours, in which a portion of the methanol formed as a result of the hydrolysis of the methoxy groups bonded to the silicon atoms, is removed by distillation. The remaining methanol and the water are then removed by distillation at 13 hPa (abs.). About 390 parts of a clear, colorless oil are obtained as a residue after the distillation. This organopolysiloxane has an amine value of 4.6, a viscosity of 614 mm2.s 1 and contains less than 0.1 percent of methoxy groups as determined by the 1HN~R
spectrum.
Third step: A mixture containing 120 parts of the organopoly-siloxane obtained in the second step, 1220 parts of a mixture of cyclic dimethylpolysiloxanes containing 3 to 10 siloxane units in each molecule and having octamethylcyclotetrasiloxane as the major component, 30 parts of the dimethylpolysiloxane which is endblocked by trimethylsiloxy groups and which has an average of 10 siloxane units in each molecule, and 0.5 parts of a 40 percent solution of benzyltrimethylammonium hydroxide in methanol is stirred at 80C for 2 hours under dry nitrogen.
The quaternary ammonium hydroxide is then deactivated by warming for 60 minutes at 150C at 13 hPa (abs.), and the components which boil below 150C at 13 hPa (abs.) are simul-taneously separated from the organopolysiloxane. About 1150 parts of a clear, colorless oil are obtained. The organo-polysiloxane has an amine value of 0.59 and a viscosity of 1174 mm2 s-l
-1- Docket No. Wa-8560 Paper No. 1 A PROCESS FOR PREPARING
ORGANOPOLYSILOXANES CONTAINING
SiC-BONDED ORGANIC RADICALS
HAVING A BASIC NITROGEN
The present invention relates to a process for pre-paring organopolysiloxanes and more particularly to a process for preparing organopolysiloxanes containing SiC-bonded organic radicals having a basic nitrogen atom.
Background of the Invention Organopolysiloxanes containing SiC-bonded organic radicals which have a basic nitrogen atom and processes for preparing the same are described in U. S. Patent No. 2,947,771 to Bailey. The organopolysiloxanes described by Bailey contain units of the formula R3SiO~, R2SiO and YSi(CH3)0, in which R
represents the same or different monovalent hydrocarbon radicals or fluorinated monovalent hydrocarbon radicals and Y represents a monovalent SiC-bonded organic radical having a basic nitrogen.
It is an object of the present invention to provide a process for preparing organopolysiloxanes containing SiC-bonded organic -radicals having a basic nitrogen from readily available organosilicon compounds. Another object of the present invention is to provide a process for preparing organo-polysiloxanes of the type described above, in which at least some of the units of the formula YSi(CH3)0 are replaced by units of the formula YSiO3/2, where Y represents a monovalent SiC-bonded organic radical having a basic nitrogen. Still another object of the present invention is to provide organo-polysiloxanes which are substantially free of groups that are capable of condensation, such as silanol groups or atoms which are capable of condensation, such as Si-bonded hydrogen atoms.
133311~
A further object of the present invention is to provide organopolysiloxanes that are storage stable and are obtained in high yields.
Summary of the Invention The foregoing objects and others which are apparent from the following description are accomplished in accordance with this invention, generally speaking, by providing a process for preparing organopolysiloxanes containing SiC-bonded organic radicals having a basic nitrogen which comprises reacting in a first step, a silane of the formula YSi~CH3)x(oR )3-x in which Rl represents the same or different alkyl radicals having from 1 to 4 carbon atoms in each radical, Y represents a monovalent SiC-bonded organic radical having a basic nitrogen, and x is 0 or 1, or partial hydrolysates of such a silane, or a mixture containing the silane and partial hydrolysates thereof with an organo(poly)siloxane of the formula R3SiO(SiR2O)nSiR3 in which R represents the same or different, monovalent hydro-carbon radicals or monovalent fluorinated hydrocarbon radicals, and n represents 0 or an integer having the value of from 1 to 100, in an amount of from 0.1 to 10 parts by weight per part by weight of the silane having the above formula or partial hydrolysates thereof, in the presence of a basic catalyst and in the absence of water, and in a second step, reacting the organopolysiloxane obtained from the first step, with water in order to hydroly~e groups of the formula -ORl, in which Rl is the same as above, to form an alkanol and silanol groups which are simultaneously and/or subsequently condensed with one another, and the resultant product formed in the condensation is separated from the alkanol and water, and in a third and optional step, reacting the product obtained from the second step with a cyclic organopolysiloxane of the formula (R2sio)m 133~115 in which R is the same as above, and m is an integer having a value of from 3 to 12, or a linear organo(poly)siloxane of the formula R3Sio(SiR2O)pSiR3 in which R is the same as above, and p is 0 or an integer having a value of at least 1, or a mixture containing the linear organo(poly)siloxane and the cyclic organopolysiloxane, in the presence of a basic catalyst.
- Description of the Invention The monovalent hydrocarbon radicals and the monovalent fluorinated hydrocarbon radicals represented by R preferably contain from 1 to 18 carbon atoms in each radical. Examples of hydrocarbon radicals represented by R are the methyl, ethyl, n-propyl, isopropyl, butyl, octyl, tetradecyl and octadecyl radicals; radicals which contain carbon and hydrogen atoms and have aliphatic multiple bonds, such as the vinyl, allyl and hexenyl radicals; cycloaliphatic hydrocarbon radicals, such as the cyclopentyl, cyclohexyl and methylcyclohexyl radicals; aromatic hydrocarbon radicals, such as the phenyl and xenyl radicals; alkaryl radicals, such as the tolyl radicals;
and aralkyl radicals, such as the benzyl radical. An example of a fluorinated hydrocarbon radical is the 3,3,3-trifluoro-propyl radical.
Examples of alkyl radicals represented by R are the methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and the tert-butyl radicals, in which the methyl and the ethyl radicals are the preferred radicals.
The monovalent SiC-bonded organic radicals having a basic nitrogen, i.e., the radicals represented by Y, are preferably those of the formula in which R2 represents hydrogen or the same or different alkyl, cycloalkyl or aminoalkyl radicals, and R3 represents a divalent hydrocarbon radical which is free of aliphatic mul-tiple bonds and which contains one carbon atom or 3 or 4carbon atoms in each radical, such as the radical of the formula ( 2)3 -` _4_ 1333115 The specific examples of alkyl radicals represented by R also apply to the alkyl radicals represented by R2.
Examples of aminoalkyl radicals represented by R2 are those of the formulas H2N(CH2)3-H2N(CH2)2NH(CH2)3 H2N(CH2)2-(H3C) 2N(CH2)2 H 2N(CH2)4-H(NHCH 2CH2) 3- and 4 gNHcH2cH2NH(cH2) _ An example of a cycloalkyl radical represented by R2 is the cyclohexyl radical.
The monovalent, SiC-bonded radicals having a basic nitrogen, i.e., the radicals represented by Y may also be, for example, radicals of the formula 2 ~ / 2 ~
O NR3- or \2 ,,,, NR3-in which R3 is the same as above.
Specific examples of silanes of the formula YSi(CH3)x(oR )3-x which can be employed in the first step of the process of this invention are those of the formula 2N(CH2) 3Si(CH3)(0C2H5)2 H2N(CH2)2NH(CH2)3Si(CH3) (0CH3)2 CH~ /cHNH(cH2)3si(cH3)(ocH3)2 ~ CH2CH~
o N(CH2)3Si(CH3)(CH3)2 5~ 1~3Il ~
/ 2 ~
CH~ N(CH2)3Si(cH3)(ocH3)2 H2N(CH2)3Si(OcH3)3 H2N(CH2)3si(oc2 5)3 H2N(CH2)2NH(CH2)3Si(OCH3)3 / 2 ~
CH~ CHNH(CH2)3si(OCH3)3 \ / N(CH2)3Si(OCH3)3 , and / 2 ~
CH ~ N(CH2)3Si(oCH3)3 A specific example of a partial hydrolysate of such a silane is a disiloxane of the formula 2 2)2 H(CH2)3Si(CH3)(OC2H5)] O
In the first step of the process of this invention, it is possible to use one type of silane of the formula YSi(CH3)x(oR )3-x or a partial hydrolysate thereof. However, it is also possible to use a mixture of at least two different types of such silanes or partial hydrolysates thereof in the 1st step of the process of this invention.
In the organo(poly)siloxanes of the formula R3Sio(SiR2o)nSiR3 at least two of the radicals represented by R in the siloxane units of the formula R3SiO%
are preferably methyl radicals. Moreover, it is preferred 13331t~
that at least 50 percent of the radicals represented by R in the units of the formula - SiR2o be methyl radicals because of their availability.
It is possible to employ only one type of organo-(poly)siloxane of the formula R3SiO(SiR2o)nSiR3 in the first step of the process of this invention, or it is possible to use a mixture of at least two different types of such organopolysiloxanes in the first step of the process of this invention.
Any basic catalysts which promote the equilibration of mixtures of organosilicon compounds containing SiC-bonded organic radicals having a basic nitrogen and organo(poly)si-loxanes free of such radicals can be employed in the firststep of the process and also in the optional third step of the process of this invention. Examples of suitable catalysts which may be employed are alkali metal hydrides, alkali metal hydroxides, alkali metal silanolates, alkali metal siloxanolates, quaternary ammonium hydroxides, quaternary ammonium silanolates, quaternary ammonium siloxanolates, quaternary phosphonium hydroxides, quaternary phosphonium silanolates, quaternary phosphonium siloxanolates, alkali metal alkyls, alkali metal alkenyls, alkali metal aryls, base activated montmorillonites and basic ion exchange resins. Specific examples of basic catalysts are sodium hydroxide, potassium hydroxide, caesium hydroxide, potassium methylsilanolate, tetra-n-butylphosphonium hydroxide, products obtained from the reaction of tetramethyl-ammonium hydroxide and octamethylcyclotetrasiloxane, tetra-methylammonium hydroxide, benzyltrimethylammonium hydroxide,naphthalene-potassium, n-butyllithium and amylsodium.
In the first step of the process of this invention, and also in the optional third step of the process of this invention, the basic catalysts can be employed in the same amounts in which they have been employed heretofore for equili-brating mixtures of organosilicon compounds containing SiC-bonded organic radicals having a basic nitrogen and organo-(poly)siloxanes free such radicals. In the case of base 7 133311~i activated montmorillonites, basic ion exchange resins and other basic catalysts which are comparable to these solid, basic catalysts, the amount of catalyst preferably ranges from about 0.1 to 10 percent by weight, based on the total weight of the organosilicon compounds to be reacted with one another in the first step of the process of this invention. In the case of the other basic catalysts and basic catalysts which are comparable to these catalysts, the amount ranges prefer-ably from about 1 to about 1,000 ppm by weight, based on the total weight of the organosilicon compounds to be reacted with one another in the first step of the process of this invention.
The first step of the process of this invention is preferably carried out at from 15 to about 200C, depending on the temperature stability of the basic catalyst used and at atmospheric pressure, i.e., at 1020 hPa (abs.) or about 1020 hPa (abs.). However, higher or lower pressures can also be used, if desired.
If desired, the first step and the optional third step of the process of this invention can be carried out under a protective gas, such as a nitrogen or argon atmosphere.
In the first step of the process of this invention, it is preferred that the contents of the reaction vessel be agitated, for example, by stirring.
The reaction carried out in the first step of the process of this invention is complete when the contents of the reaction vessel are clear, at least after the removal of the catalyst contained therein. Generally, a reaction time of from about 0.1 to 10 hours is sufficient for this reaction.
The organopolysiloxane obtained in the first step of the process of this invention can be stored before carrying out the second step of the process of this invention or the organopolysiloxane obtained from the first step can be pro-cessed further in the second step of the process of this invention, more or less immediately after its preparation without removing or deactivating the basic catalyst present in the organopolysiloxane from the first step of the process of this invention.
In the second step of the process of this invention, water is preferably used in an amount of from about 18 g to 133311~
- 180 g per gram-equivalent of the group of the formula -ORl present in the first step of the process of this invention.
The hydrolysis of the groups of the formula -SiOR1 and the condensation of the silanol groups formed as a result of the hydrolysis in the second step of the process of this invention are preferably carried out at from about 40 to about 200C, and preferably at atmospheric pressure, i.e., at 1020 hPa (abs.) or about 1020 hPa (abs.). If desired, however, higher or lower pressures can be used during the hydrolysis and lower pressures can be used during the condensation of the silanol groups.
The hydrolysis of the groups of the formula -SiOR1 and the condensation of the silanol groups in the second step of the process of this invention are promoted by the catalyst still present from the first step and/or by adding additional catalyst.
The water and alkanol can be removed from the product obtained in the second step of the process of this invention by, for example, distillation.
The contents of the reaction vessel can be agitated, for example by stirring, at least during the hydrolysis of the groups of the formula -SiORl and/or condensation of the silanol groups in the second step of the process of this invention.
In order to obtain a highly storage-stable organo-polysiloxane containing SiC-bonded organic radicals having a basic nitrogen, the catalyst can be removed from the organo-polysiloxane or deactivated after carrying out the second step of the process of this invention. In the case of catalysts such as, for example, quaternary ammonium hydroxides, quater-nary ammonium silanolates and quaternary ammonium siloxanolates,heating the product to a temperature above the decomposition temperature of the catalysts, usually above 150C, is suffi-cient for deactivation.
At least 50 percent of the radicals represented by R
in the units of the formula s iR2o and at least two of the radicals R in the units of the formula R3SiO
are preferably methyl radicals. Likewise, the R radicals in the cyclic organopolysiloxanes having the formula (R2SiO)m and organopolysiloxanes of the formula R3SiO(SiR2O)pSiR3 which are employed in the optional third step of the process of this invention are preferably methyl radicals.
The average value of m is preferably 4 or approxi-mately 4.
There is no upper limit for p since the third and optional step of the process of this invention can be carried out, if necessary, in a solvent which is inert towards the reactants and the catalyst.
It is possible to use only one type of cyclic dior-ganopolysiloxane or linear organopolysiloxane in the third and optional step of the process of this invention. However, it is also possible to employ a mixture of at least two different organopolysiloxanes in this step.
The amount of reactants employed in the third and optional step of the process of this invention are determined merely by the desired proportion of SiC-bonded organic radicals having a basic nitrogen in the organopolysiloxanes produced in the third and optional step of the process according to this invention and by the average chain length desired.
The third and optional step of the process of this invention is preferably carried out at 15 to 200C, depending on the temperature stability of the basic catalyst used, and at atmospheric pressure, i.e., at 1020 hPa (abs.) or about 1020 hPa (abs.). However, higher or lower pressures can also be used, if desired.
The contents of the reaction vessel can also be agitated, for example, stirred in the third and optional step -lo- 133311~
~ of the process of this invention.
Although the third step of the process of this invention is optional, when the third step is carried out, it is complete when the contents of the reaction vessel are clear, at least after the catalyst contained therein has been removed. Generally, from about 0.1 to 10 hours are sufficient for completing the third step of the process.
After carrying out the third step of the process of this invention, the catalyst is preferably either removed from the organopolysiloxane or deactivated.
The various steps of the process of this invention can be carried out successively in one and the same reaction vessel or in separate reaction vessels. The process, accor-ding to this invention, can be carried out batchwise, semi-continuously or continuously.
The organopolysiloxanes or the salts of such organo-polysiloxanes prepared in accordance with this invention with organic or inorganic acids in the second or third step can be used for all purposes for which such organopolysiloxanes con-taining SiC-bonded organic radicals having a basic nitrogen, or salts thereof, can be employed.
They may be employed, for example, as release agents or lubricants, for example, in tire manufacturing or as adhe-sion-repellent finishes for glass and ceramic surfaces, as components of textile treating agents, as lubricating oils, defoamers, foam stabilizers, emulsifiers, antistatic agents and as additives for thermoplastics and elastomers.
In the following examples, all parts and percentages are by weight, unless otherwise specified.
Example 1 First step: A mixture containing 82.5 parts of N-(2-amino-ethyl)-3-aminopropylmethyldimethoxysilane, i.e., a silane of the formula H2N(CH2)2NH(CH2)3Si(CH3)(oCH3)2 59.2 parts of a dimethylpolysiloxane which is endblocked by trimethylsiloxy groups and has an average of 10 siloxane units per molecule, and 0.1 part of a 40 percent solution of benzyl-trimethylammonium hydroxide in methanol is stirred at 80C for 1 hour under dry nitrogen.
Second step: In the reaction vessel used for carrying out the first step, the contents thereof are mixed with 50 parts of water and stirred at 80C for 2 hours, in which a portion of the methanol formed as a result of the hydrolysis of the methoxy groups bonded to the silicon atoms, is removed by distillation. The remaining methanol and water are then removed by distillation at 13 hPa (abs.). The quaternary ammonium hydroxide is deactivated by heating for 60 minutes at 150C at 13 hPa (abs.), and the other components which boil below 150C at 13 hPa (abs.) are simultaneously separated from the organopolysiloxane. About 113 parts of a clear, colorless oil are obtained. The resultant organopolysiloxane has an amine value (number of ml of lN HCL which are necessary to neutralize 1 g of the oil) of 6.6, a viscosity of 205 mm2.s 1 at 25C, and contains less than 0.1 percent of methoxy groups as determined by H nuclear magnetic resonance (NMR) spectrum.
Third step: A mixture containing 4 parts of the organopoly-siloxane obtained in the second step, 500 parts of a mixture of cyclic dimethylpolysiloxanes having from 3 to 10 siloxane units in each molecule and having octamethylcyclotetrasiloxane as the major component, 20 parts of the dimethylpolysiloxane which is endblocked by trimethylsiloxy groups and which has an average of 10 siloxane units in each molecule, and 0.2 parts of a 40 percent solution of benzyltrimethylammonium hydroxide in methanol is stirred at 80C for 2 hours under dry nitrogen.
The quaternary ammonium hydroxide is then deactivated by warming for 60 minutes at 150C and at 13 hPa (abs.), and the other components which boil below 150C at 13 hPa (abs.) are simultaneously separated from the organopolysiloxane. About 430 parts of a clear, colorless oil are obtained. The organo-polysiloxane has an amine value of 0.06 and a viscosity of 1140 mm2.s 1 at 25C.
Example 2 The procedure described in Example 1 is repeated, except that in the third step, 128 parts of the organopoly-siloxane obtained in the first step are used instead of 4 133~
parts of the organopolysiloxane, 1600 parts of the mixture of cyclic dimethylpolysiloxanes are used instead of 500 parts of the mixture, 27 parts of the dimethylpolysiloxane which is endblocked by trimethylsiloxy groups and which has an average of 10 siloxane units in each molecule are used instead of 20 parts of the endblocked dimethylpolysiloxane, and 0.7 parts of the 40 percent solution of benzyltrimethylammonium hydroxide are used instead of 0.2 parts of the solution.
About 1400 parts of a clear, colorless oil having an amine value of 0.6 and a viscosity of 960 mm2.s 1 at 25C are obtained.
Example 3 First step: A mixture containing 222 parts of N-(2-amino-ethyl)-3-aminopropyltrimethoxysilane, i.e., a silane of the formula H2N(CH2)2NH(CH2)3Si(oCH3)3 296 parts of a dimethylpolysiloxane which is endblocked by trimethylsiloxy groups and which has an average of 10 siloxane units in each molecule, and 0.25 parts of a 40 percent solution of benzyltrimethylammonium hydroxide in methanol is stirred at 80C for 1 hour under dry nitrogen.
Second step: In the reaction vessel used for carrying out the first step, the contents of the reaction vessel are mixed with 125 parts of water and stirred at 80C for 2 hours, in which a portion of the methanol formed as a result of the hydrolysis of the methoxy groups bonded to the silicon atoms, is removed by distillation. The remaining methanol and the water are then removed by distillation at 13 hPa (abs.). About 390 parts of a clear, colorless oil are obtained as a residue after the distillation. This organopolysiloxane has an amine value of 4.6, a viscosity of 614 mm2.s 1 and contains less than 0.1 percent of methoxy groups as determined by the 1HN~R
spectrum.
Third step: A mixture containing 120 parts of the organopoly-siloxane obtained in the second step, 1220 parts of a mixture of cyclic dimethylpolysiloxanes containing 3 to 10 siloxane units in each molecule and having octamethylcyclotetrasiloxane as the major component, 30 parts of the dimethylpolysiloxane which is endblocked by trimethylsiloxy groups and which has an average of 10 siloxane units in each molecule, and 0.5 parts of a 40 percent solution of benzyltrimethylammonium hydroxide in methanol is stirred at 80C for 2 hours under dry nitrogen.
The quaternary ammonium hydroxide is then deactivated by warming for 60 minutes at 150C at 13 hPa (abs.), and the components which boil below 150C at 13 hPa (abs.) are simul-taneously separated from the organopolysiloxane. About 1150 parts of a clear, colorless oil are obtained. The organo-polysiloxane has an amine value of 0.59 and a viscosity of 1174 mm2 s-l
Claims (3)
1. A process for preparing organopolysiloxanes con-taining SiC-bonded organic radicals having a basic nitrogen which comprises reacting in a first step, a silane of the formula YSi(CH3)x(OR1)3-x where R1 is an alkyl radical having from 1 to 4 carbon atoms in each radical, Y is a monovalent SiC-bonded organic radical having a basic nitrogen, and x is 0 or 1, or a partial hydroly-sate of said silane, or a mixture containing the silane and a partial hydrolysate thereof with an organo(poly)siloxane of the formula R3SiO(SiR2O)nSiR3 in which R is selected from the group consisting of a mono-valent hydrocarbon radical and a monovalent fluorinated hydro-carbon radical, and n is 0 or an integer having a value of from 1 to 100, in an amount of from 0.1 to 10 parts by weight per part by weight of the silane and the partial hydrolysate thereof, in the presence of a basic catalyst and in the absence of water, and in a second step, reacting the organopolysiloxane obtained in the first step, with water to form an alkanol and silanol groups which are simultaneously and/or subsequently condensed, and thereafter separating the resultant product from the alkanol and water, and optionally in a third step, reacting the product obtained from the second step with an organopolysiloxane selected from the group consisting of a cyclic organopolysiloxane of the formula (R2SiO)m, an organo(poly)siloxane of the formula R3SiO(SiR2O)pSiR3 and mixtures thereof, in which R is the same as above, m is an integer of from 3 to 12 and p is 0 or an integer having a value of at least 1, in the presence of a basic catalyst.
2. The process of claim 1, wherein R is a methyl radical.
3. The process of claim 1, wherein in the third step, the product obtained from the second step is reacted with an organopolysiloxane selected from the group consisting of a cyclic organopolysiloxane of the formula (R2SiO)m, an organopolysiloxane of the formula R3SiO(SiR2O)pSiR3 and mixtures thereof, in which R is selected from the group consisting of a monovalent hydrocarbon radical and a monovalent fluorinated hydrocarbon radical, m is an integer of from 3 to 12 and p is an integer having a value of at least 1, in the presence of a basic catalyst.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3637837.2 | 1986-11-06 | ||
| DE19863637837 DE3637837A1 (en) | 1986-11-06 | 1986-11-06 | METHOD FOR PRODUCING ORGANOPOLYSILOXANES WITH SIC-BONDED ORGANIC REMAINS CONTAINING NITROGEN |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1333115C true CA1333115C (en) | 1994-11-15 |
Family
ID=6313308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000550908A Expired - Fee Related CA1333115C (en) | 1986-11-06 | 1987-11-03 | Process for preparing organopolysiloxanes containing sic-bonded organic radicals having a basic nitrogen |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0269886B1 (en) |
| JP (1) | JPS63135427A (en) |
| AT (1) | ATE91294T1 (en) |
| AU (1) | AU590993B2 (en) |
| BR (1) | BR8705951A (en) |
| CA (1) | CA1333115C (en) |
| DE (2) | DE3637837A1 (en) |
| ES (1) | ES2056806T3 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3808200A1 (en) * | 1988-03-11 | 1989-09-21 | Wacker Chemie Gmbh | AT ROOM TEMPERATURE TO COMPATIBLE TO PAINTABLE ELASTOMER CROSSLINKING ORGANOPOLYSILOXANES |
| JP2799637B2 (en) * | 1991-02-27 | 1998-09-21 | 信越化学工業株式会社 | Method for producing high molecular weight organopolysiloxane |
| DE4208447C1 (en) * | 1992-03-17 | 1993-06-03 | Th. Goldschmidt Ag, 4300 Essen, De | Silicone(s) with silicon-carbon linked residues contg. basic N and alkoxy gps. - by reacting silicone(s) contg. hydroxy-alkyl gps. with amino:alkyl-alkoxy-silane(s) in presence of non-equilibrating acid catalyst |
| FR2714402B1 (en) * | 1993-12-27 | 1996-02-02 | Rhone Poulenc Chimie | Non-yellowing textile softening process in which a composition comprising a polyorganosiloxane is used. |
| DE19649183A1 (en) * | 1996-11-27 | 1998-06-04 | Fraunhofer Ges Forschung | Antistatic agent, process for its preparation and its use for the production of antistatic coatings |
| EP0927735A1 (en) * | 1998-01-02 | 1999-07-07 | Hüls Aktiengesellschaft | Process for the production of non-reactive aminosilicone oils |
| JP4399066B2 (en) * | 1999-10-29 | 2010-01-13 | 東レ・ダウコーニング株式会社 | Process for producing amino group-containing organopolysiloxane |
| BRPI0509870A (en) * | 2004-04-16 | 2007-10-23 | Procter & Gamble | liquid laundry detergent compositions with mixtures of silicones as tissue treatment agents |
| DE102007020569A1 (en) * | 2007-05-02 | 2008-11-06 | Wacker Chemie Ag | Process for the preparation of aminoalkylpolysiloxanes |
| DE102007020568A1 (en) * | 2007-05-02 | 2008-11-06 | Wacker Chemie Ag | Process for the continuous preparation of aminoalkyl-containing organopolysiloxanes |
| DE102007036069A1 (en) * | 2007-08-01 | 2009-02-05 | Wacker Chemie Ag | Multi-stage process for the preparation of aminoalkyl-containing organopolysiloxanes |
| KR101677255B1 (en) * | 2015-03-25 | 2016-11-17 | 건솔루션(주) | Apparatus and method for setting position of workpiece |
| DE102020118717B4 (en) | 2020-07-15 | 2024-02-08 | Humbaur Gmbh | Lashing device for a commercial vehicle, commercial vehicle with such a lashing device and manufacturing method |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1120145B (en) * | 1956-10-12 | 1961-12-21 | Union Carbide Corp | Process for the preparation of end-blocked organopolysiloxanes |
| US2947771A (en) * | 1956-10-12 | 1960-08-02 | Union Carbide Corp | Aminoalkylpolysiloxanes and process for their production |
| US2921950A (en) * | 1957-08-15 | 1960-01-19 | Union Carbide Corp | Method for preparing copolymeric organopolysiloxanes |
| JPS5629691B2 (en) * | 1972-08-11 | 1981-07-10 | ||
| US4496705A (en) * | 1984-01-04 | 1985-01-29 | General Electric Company | Synthesis of zwitterionic siloxane polymers |
| DE3523206A1 (en) * | 1985-06-28 | 1987-01-02 | Bayer Ag | METHOD FOR PRODUCING POLY (DIORGANOSILOXANES) WITH ALKOXY END GROUPS |
| US4661577A (en) * | 1985-10-01 | 1987-04-28 | General Electric Company | Aminofunctional polysiloxanes |
| JP2588724B2 (en) * | 1987-09-08 | 1997-03-12 | 東レ・ダウコーニング・シリコーン株式会社 | Method for producing organopolysiloxane having alkenyl group in side chain at center of molecular chain |
| DE3742069A1 (en) * | 1987-12-11 | 1989-06-22 | Wacker Chemie Gmbh | METHOD FOR PRODUCING DIORGANOPOLYSILOXANS WITH TRIORGANOSILOXY GROUPS AS FINAL UNITS |
-
1986
- 1986-11-06 DE DE19863637837 patent/DE3637837A1/en not_active Withdrawn
-
1987
- 1987-11-02 EP EP87116116A patent/EP0269886B1/en not_active Expired - Lifetime
- 1987-11-02 ES ES87116116T patent/ES2056806T3/en not_active Expired - Lifetime
- 1987-11-02 DE DE8787116116T patent/DE3786443D1/en not_active Expired - Fee Related
- 1987-11-02 AT AT87116116T patent/ATE91294T1/en not_active IP Right Cessation
- 1987-11-03 CA CA000550908A patent/CA1333115C/en not_active Expired - Fee Related
- 1987-11-05 JP JP62278415A patent/JPS63135427A/en active Granted
- 1987-11-05 BR BR8705951A patent/BR8705951A/en not_active IP Right Cessation
- 1987-11-05 AU AU80808/87A patent/AU590993B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63135427A (en) | 1988-06-07 |
| DE3786443D1 (en) | 1993-08-12 |
| AU590993B2 (en) | 1989-11-23 |
| ES2056806T3 (en) | 1994-10-16 |
| EP0269886A2 (en) | 1988-06-08 |
| AU8080887A (en) | 1988-05-12 |
| BR8705951A (en) | 1988-06-14 |
| ATE91294T1 (en) | 1993-07-15 |
| JPH0238604B2 (en) | 1990-08-31 |
| EP0269886B1 (en) | 1993-07-07 |
| DE3637837A1 (en) | 1988-05-19 |
| EP0269886A3 (en) | 1990-05-02 |
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