JPH0739493B2 - Method for producing organopolysiloxane resin and method for producing organopolysiloxane resin powder - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing an organopolysiloxane resin by hydrolysis and condensation of silane and its use.

Methods for producing organopolysiloxane resins are already known. For example, US Pat. No. 4605.
No. 446 (Kansai Paint Comp)
(Any, Ltd .; submitted August 12, 1986) describes a method in which a tetraalkoxysilane and a trialkoxysilane are first hydrolyzed in the presence of an acid and then condensed in the presence of a base. Isolation of the formed organopolysiloxane is carried out by adding a water-insoluble solvent and phase separation. U.S. Pat. No. 4,528,390 (Toshiba Silicon Co. Lt).
d. , Filed July 9, 1985), a method for producing an organosilsesquioxane by hydrolyzing and condensing methyltrialkoxysilane in an aqueous solution of ammonium or amine is disclosed. The precipitated resin is isolated. Further, West German Patent Publication No. 3717073 (Wacker-Chemie)
GmbH; filed Dec. 8, 1988) or corresponding U.S. Pat. No. 4,935,484 (19).
(Filed June 19, 1990) describes a method for producing a silicone resin powder by spray drying an aqueous colloidal suspension of organopolysiloxane produced by a special method.

[0003]

SUMMARY OF THE INVENTION There is a problem of providing a method capable of producing an organopolysiloxane resin by a simple method. Another object was to provide a method for obtaining an organopolysiloxane resin powder in a technically simple manner.

[0004]

These problems are solved by the present invention.

The present invention relates to a method for producing an organopolysiloxane resin, which comprises a step of formula: R _a Si (OR ¹ ) _4-a (I) wherein a is 0, 1, 2 Or 3, R may be the same or different and represent a monovalent organic group, and R ¹ may be the same or different and represent a monovalent organic group.]
At least one silane and / or a partial hydrolyzate thereof (provided that at least one silane of formula (I) in which a is 0 or 1 and / or a partial hydrolyzate thereof is used), and R ² ₃ Si—O—SiR ² ₃ (II) [wherein, R ² may be the same or different and represents the one described for R], (R ³ ₂ SiO) _b (III) [formula Wherein R ³ may be the same or different and represents R, and b is an integer of 3 to 8], and an organo (poly) siloxane selected from the group Reacting in the presence of an acid and optionally other substances, in a second step the reaction product obtained in the first step is reacted in the presence of a base and optionally other substances, and in a third step a second step The reaction product obtained in the process is placed in water and Mixed with additives by, it consists in mixing agitation.

Suitable radicals R are monovalent hydrocarbon radicals having 1 to 18 carbon atoms which may have substituents which are inert towards water.

Examples of radicals R are alkyl radicals such as methyl-, ethyl-, n-propyl-, iso-propyl, n-.
Butyl-, iso-butyl-, t-butyl-, n-pentyl-, iso-pentyl-, neo-pentyl-, t-pentyl-group, hexyl group such as n-hexyl group, heptyl group such as n-heptyl. Group, octyl group, for example n-
Octyl and iso-octyl groups such as 2,2,4-
Trimethylpentyl group, nonyl group such as n-nonyl group, decyl group such as n-decyl group, dodecyl group such as n-dodecyl group, octadecyl group such as n-octadecyl group; alkenyl group such as vinyl-, allyl-,
n-5-hexenyl-, 4-vinylcyclohexyl- and 3-norbornenyl groups; cycloalkyl groups such as cyclopentyl-, cyclohexyl-, 4-ethylcyclohexyl-, cycloheptyl groups, norbornyl groups and methylcyclohexyl groups; aryl groups such as Phenyl-,
Biphenylyl-, naphthyl- and anthryl- and phenanthryl groups; alkaryl groups such as o-, m-, p
A tolyl group, a xylyl group and an ethylphenyl group; an aralkyl group such as a benzyl group, an α- and a β-phenylethyl group.

Examples of substituted hydrocarbon radicals as radical R are halogenated hydrocarbon radicals such as chloromethyl-3.
-Chloropropyl-, 3-bromopropyl-, 3,3
3-trifluoropropyl- and 5,5,5,4,4
3,3-heptafluoropentyl group, and chlorophenyl-, dichlorophenyl- and trifluorotolyl groups; mercaptoalkyl groups such as 2-mercaptoethyl- and 3-mercaptopropyl groups; cyanoalkyl groups such as 2-cyanoethyl -And 3-cyanopropyl groups: aminoalkyl groups such as 3-aminopropyl-,
N- (2-aminoethyl) -3-aminopropyl- and N- (2-aminoethyl) -3-amino (2-methyl)
Propyl group; aminoaryl group such as aminophenyl group; acyloxyalkyl group such as 3-acyloxypropyl- and 3methacryloxypropyl group; hydroxyalkyl group such as hydroxypropyl group and formula:

[0009]

[Chemical 1] And _{HOCH 2 CH (OH) CH 2} SCH 2 CH 2 -

It is the basis of

The radicals R are particularly preferably methyl-, n-propyl-, vinyl-, n-5-hexenyl-, 3-norbornenyl-, phenyl- and tolyl radicals.

Examples of radical R ¹ are the examples given for R.

Suitable radicals R ¹ are alkyl radicals having 1 to 6 carbon atoms which may be substituted by alkyloxy or hydroxy radicals.

The radicals R ¹ are particularly preferably methyl-, ethyl-, n-propyl-, iso-propyl- and hexyl radicals, in particular the methyl- and ethyl radicals.

Examples of radical R ² are the examples given for R.

Radicals R ² are preferably methyl-, ethyl-, vinyl-, n-5-hexenyl-, 3-norbornenyl- and phenyl radicals, the methyl-, vinyl- and n-groups being preferred. The -5-hexenyl group is particularly preferred.

Examples of radical R ³ are the examples given for R.

The radical R ³ is preferably methyl-, vinyl-
Phenyl groups are also suitable, the methyl groups being particularly preferred.

When using the partial hydrolysates of the silanes of the general formula (I) in the process according to the invention, those having up to 15 silicon atoms are preferred.

Examples of silanes of formula (I) used in the method of the present invention are tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyl. Trimethoxysilane, 3-chloropropyltrimethoxysilane, phenyltrimethoxysilane, o,
m, p-tolyltrimethoxysilane, propyltrimethoxysilane, methylpolyethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-chloropropyltriethoxysilane, phenyltriethoxysilane, o, m, p Tolyltriethoxysilane, propyltrimeethoxysilane, dimethylethoxysilane, dimethyldimethoxysilane and trimethylethoxysilane, where tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, o, m , P-Tolyltriethoxysilane and propyltriethoxysilane are preferably used.

Examples of organo (poly) siloxanes of the formula (II) optionally used in the process according to the invention are hexamethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, 1,3-bis (n-). 5-hexenyl)
Tetramethyldisiloxane, 1,3-divinyltetramethylsiloxane, wherein hexamethyldisiloxane, 1,3-divinyltetramethylsiloxane and 1,3-bis (n-5-hexenyl) tetramethyldisiloxane are Preference is given to hexamethyldisiloxane.

Examples of organo (poly) siloxanes of formula (III) optionally used in the process according to the invention are hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, where Octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane are preferred.

In a preferred embodiment of the process according to the invention, in the first step, the organo (poly) siloxane of formula (II),
In particular, those in which R ² is a methyl- or vinyl group and a silane of the formula (I) in which a is 0 and / or its partial hydrolysates, in a molar ratio of preferably 1.5: 1 to 1 ．
A mixture of 0: 1.0, particularly preferably 0.6: 1 to 0.9: 1, is used.

In another advantageous embodiment according to the invention:
In the first step, any mixture of the silane of formula (I) and / or its partial hydrolyzate is treated such that at least one silane in which a is 0 or 1 and / or its partial hydrolyzate is present. Under at least 20%, preferably at least 50% of the total number of radicals R are aromatic radicals,
For example, a phenyl- or tolyl group. The remaining radicals R are preferably methyl-, n-propyl- or vinyl radicals. The average value of a is 0.3 in this advantageous embodiment.
~ 2.1, particularly preferably 0.5-1.5.

Another object of the present invention is [R ⁴ ₃ Si
O _1/2 ] _-and [SiO _4/2 ] _-units [wherein R ⁴ may be the same or different and represent those described for R, wherein at least one group R ⁴ is n. Represents an -5-hexenyl group] and has an SiC-bonded n-5-hexenyl group.

Examples of R ⁴ are the examples given for R.

Examples of organopolysiloxane resins having SiC-bonded n-5-hexenyl groups according to the invention are:
Hex is an n-5-hexenyl group, Me is a methyl group, and the ratio of c: d is 0.05 to 0.2 and (c +
The ratio of d): e is 0.5 to 0.9 [HexSiMe
₂ O _1/2 ] c [Me ₃ SiO _1/2 ] d [SiO _4/2 ] e type resin.

Advantageously, the SiC-bonded n according to the invention is
The organopolysiloxane resin having a 5-hexenyl group, Hex is n-5-hexenyl group, Me is a methyl group _{[HexSiMe 2 O 1/2] c [} Me 3 S
Suitable examples are io _1/2 ] d [SiO _4/2 ] e type resins, where the ratio of c: d is 0.08 to 0.15 and (c + d):
Those in which the ratio of e is 0.7 to 0.9 are particularly advantageous.

The organopolysiloxane resin having a SiC-bonded n-5-hexenyl group according to the present invention has at least one formula (II) [wherein at least one group R is
² represents an n-5-hexenyl group] of organo (poly)
Siloxane, especially 1,3-bis- (n-5-hexenyl) tetramethyldisiloxane and a silane of formula (I) in which a is 0 and / or its partial hydrolysates, preferably 0.50: 1. ~ 0.80: 1, particularly preferably 0.6
It can be prepared by the process according to the invention using a molar ratio of 5: 1 to 0.75: 1.

In the process according to the invention, in the first step the silane of formula (I) and / or its partial hydrolysates are optionally mixed with an organo (poly) siloxane of formula (II) and / or (III). Add water and acid and optionally other substances and mix.

In that case, in the first step of the method according to the invention,
Water is preferably 10 to 30% by weight, particularly preferably 10 to 20% by weight, based on the total weight of the reaction products of the first step,
In particular, it is used in an amount of 14 to 17% by weight.

Suitable acids for use in the first step of the process according to the invention are the same acids which have hitherto been used for the hydrolysis of silanes having an organyloxy group. Examples of this type of acid are inorganic acids such as HCl, HClO ₄ ,
H ₂ SO ₄ and H ₃ PO ₄ , organic acids such as formic acid, acetic acid, propionic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, dodecylbenzenesulfonic acid and acidic ion exchangers are applicable. HCl, dodecylbenzene sulfonic acid and p-toluene sulfonic acid are preferably used here.

In the first step of the process according to the invention, the acid is preferably at least 10 ppm (parts per million), each based on the total weight of the reaction products of the first step.
n), particularly preferably in an amount of at least 100 ppm. The upper limit of the acid concentration depends on the one hand on the type of acid and on the other hand on the desired degree of homogeneity of the reaction products. For example, when using HCl as the acid, a concentration range of 100-3000 ppm has proved to be advantageous, based on the total weight of the reaction products of the first step. Higher acid concentrations generally do not achieve reaction product homogeneity.

The pH value of the reaction product in the first step of the process according to the invention is preferably in the range from 0 to 3, particularly preferably in the range from 1 to 2.

In addition, in the first step of the process according to the invention, preferably up to 0.01% by weight, based on the total weight of the reaction products of the first step, of other substances, for example of olefinic use. For example, a polymerization inhibitor that suppresses homopolymerization of 1,3-bis- (n-5-hexenyl) tetramethyldisiloxane can be used.

Examples of optional polymerization inhibitors are:
Hydroquinone, brentscatechin and BTH (2,6-
Di-t-butyl-4-methylphenol).

The compounds of R ¹ OH in which R ¹ formed in the hydrolysis of the first step of the process according to the invention represents the abovementioned compounds can be removed in whole or in part during or after the hydrolysis.

[0038] Particularly R ¹ is advantageously removed by distillation during the hydrolysis of the compound of R ¹ OH is an alkyl group having 1 to 6 carbon atoms. After the start of hydrolysis, the removal by distillation should be carried out 3 times so that the distillation of the used silane is sufficiently prevented.
It is advantageous to start only after 0 minutes to 1 hour.

[0039] The compound of R ¹ OH R ¹ is representative of the ones described above, it is advantageous to distilled off to the extent such that the reaction product is left uniform. R ¹ where R ¹ has generated the above meanings
It is advantageous to remove up to 95% by weight of the compound R ¹ OH by distillation, based on the total weight of the compounds of OH.

The first step of the process according to the invention is preferably at a temperature from 20 ° C. to the boiling point of the reaction product, particularly preferably at the boiling point of the reaction mixture, and preferably from 900 to 1100.
Perform at a pressure of hPa.

The first step of the process according to the invention is preferably completed after 30 minutes to 5 hours, particularly preferably after 2 to 3 hours.

After the end of the first step of the process according to the invention, the amount of base and optionally other substances required to neutralize the reaction product are added. At that time, generally 0.1 to 2.0% by weight based on the total weight of the reaction product of the second step.
Use a range of bases.

In the second step, the pH value is 8.0 to 14.0,
It is advantageous to add an amount of base such that it is preferably in the range 9.0 to 12.0.

As the base, it is possible to use all the bases which have hitherto been used as catalysts in the condensation reaction in the second step of the process according to the invention.

Examples of bases of this kind are alkali hydroxides such as sodium and potassium hydroxide, alkali siliconates such as sodium and potassium siliconates, amines such as methylamine, dimethylamine, ethylamine, diethylamine, Triethylamine and n-butylamine, ammonium compounds such as tetramethylammonium hydroxide, tetra-
n-butylammonium hydroxide and benzyltrimethylammonium hydroxide and basic ion exchangers, sodium hydroxide, methylamine,
Ethylamine, diethylamine and benzyltrimethylammonium hydroxide are preferred, and volatile bases, methylamine, ethylamine and ethylamine are particularly preferred.

If desired, the base can be added in admixture with water and / or a polar, water-soluble organic solvent.
However, the dilution of the base should not be too high so that precipitation of the organopolysiloxane resin formed by the addition of base does not occur.

If desired, polar water-soluble organic solvents can be used in the second step according to the invention, in order to obtain a homogeneous reaction product, depending on the amount and type of solvent used. Be useful.

The concept of polar water-soluble organic solvent is a solvent which is preferably completely miscible with water at room temperature and ambient atmospheric pressure. However, the minimum solubility of organic solvents should be above 300 g per liter of water at room temperature and ambient atmospheric pressure.

Examples of polar water-soluble organic solvents are methanol, ethanol, acetone, dioxane, dimethylformamide, tetrahydrofuran, dimethylsulfoxide and mixtures thereof, preference being given to tetrahydrofuran and dioxane, with tetrahydrofuran being particularly preferred. Is.

If a polar, water-soluble organic solvent is used, it is advantageous to use it in such an amount that a sufficiently homogeneous reaction product is obtained. Preference is given to using up to 30% by weight, particularly preferably up to 20% by weight, of polar, water-soluble organic solvents, each based on the total weight of the reaction products of the second step.

Examples of other substances optionally used in the second step are sensitive organic groups in which R is wholly or partly acid, such as 3-aminopropyl-, N- (2-aminoethyl)-. Silanes of formula (I) representing 3-aminopropyl- and aminophenyl groups.

The second step according to the invention is preferably at 50 ° C.
To a boiling point of the reaction product, particularly preferably the boiling point of the reaction product and preferably a pressure of 900 to 1100 hPa.

The second step according to the invention is preferably 1-5.
It ends after a period of time, particularly preferably from 2 to 4 hours.

After the end of the second step, the reaction product is introduced into water, optionally mixed with additives, in which the organopolysiloxane resin precipitates as hydrophobic particles.

The amount of water used in the third step according to the invention is preferably 500 to 1000% by weight, particularly preferably 600 to 70% by weight, based on the total weight of the reaction products of the second step.
It is 0% by weight.

In order to obtain the base-free organopolysiloxane resin, the reaction product obtained in the second step is neutralized with acid before the precipitation in water after the completion of the second step or the precipitate is acid-containing. Do it in water. At that time, all the acids mentioned in the first step are suitable as the acid. When it is necessary to neutralize, in particular this is the case in the production of organopolysiloxane resins containing phenyl groups, the neutralization of the reaction product obtained in the second step of the process according to the invention is carried out. It is advantageous to do this before precipitation.

It is also possible to add other additives with the acid to the water used in the third step of the process according to the invention, such as coagulants.

Examples of setting aids are polyvinyl acetate,
Polyvinyl alcohol, polyacrylate and polyamine.

If a coagulant is used in the third step of the process according to the invention, it is preferably from 0.01 to 0.05% by weight, based on the amount of water used in the third step. Use in quantity.

However, it is advantageous to use neutral water without any additives in the third step of the process according to the invention in order to avoid any residues in the organopolysiloxane resin prepared according to the invention. To be able to.

The third step of the process according to the invention is preferably a temperature of 0 to 50 ° C., particularly preferably 10 to 25 ° C. and a pressure of 90.
It is carried out at 0 to 1100 hPa. However, higher or lower pressures can be used. If the precipitation is carried out under reduced pressure or vacuum, the readily volatile constituents can still be at least partially removed during the precipitation.

The third step of the process according to the invention can be carried out batchwise in a stirrer. However, a simple waste-reducing continuous implementation of precipitation is also possible. For this purpose, for example, the reaction product of the second step and the water of precipitation are introduced in a loop and the precipitated resin is separated off using a filter.
If the water contains a polar water-soluble organic solvent, the solvent is removed from the water and used again for precipitation. The organic solvent can be reused in the second step according to the invention.

According to a particularly advantageous embodiment of the process according to the invention, the silanes of the formula (I) in which a is 0, in particular tetraethoxysilane and / or its partial hydrolysates and the organo (poly) siloxanes of the formula (II). Is mixed with water and an acid in the first step, reacted at the boiling point of the reaction product, at 78 ° C. in the case of tetraethoxysilane and / or its partial hydrolyzate, and at a pressure of 900 to 1100 hPa, In the process
The reaction product obtained in the first step in the presence of a base and a polar water-soluble organic solvent, in particular tetrahydrofuran, at the boiling point of the reaction product, in the case of tetrahydrofuran at 65 ° C.,
And react at a pressure of 900 to 1100 hPa, and in the third step, the reaction product obtained in the second step is used at room temperature and a pressure of 9
Mix in water at 00 to 1100 hPa.

The process according to the invention can be carried out discontinuously, semicontinuously and continuously. The continuous production of the organopolysiloxane resin is carried out, for example, by adding the reaction product obtained in the first step and the base to produce R ¹
This is possible when the compound of R ¹ OH representing the above is continuously distilled off and the reaction product is introduced into water after completion of the reaction.

The process according to the invention has the advantage that it is very simple to carry out, a high space-time yield is obtained and that no water-insoluble solvent is required to separate the organopolysiloxane resin. The process of the invention results in a resin of high purity which precipitates as a fine powder with high dissolution kinetics. The method according to the invention further has the advantage that the thermal loading of the resin is very low.

The organopolysiloxane resins according to the invention preferably have an average molecular weight of 3,000 to 10,000 and, on average, less than 3 mol% of silicon, based on R ^1, are --OR ¹ groups which represent the above. Have. The organopolysiloxane resin according to the invention is at least partially, but preferably wholly soluble in the liquid organopolysiloxane.

An example of an organopolysiloxane resin according to the present invention has Me as a methyl group and an x: y ratio of 0.6:
1 to 0.9: 1 [Me ₃ SiO _1/2 ] x [SiO
_4/2 ] y and Me are methyl groups, Vi is a vinyl group, the ratio of (x + y): z is 0.6: 1 to 0.9: 1, and the ratio of x: y is 98: 2 to 80:20 [Me
₃ SiO _1/2 ] x [Me ₂ ViSiO _1/2 ] y [Si
O _1/2 ] z.

Another object of the present invention is a process for preparing the organopolysiloxane resin, which comprises in the first step,
At least one silane of the formula: R _a Si (OR ¹ ) _4-a (I) [wherein a, R and R ¹ represent the above] and / or a partial hydrolyzate thereof (where a is 0).
Or at least one silane of formula (I) which is 1 and / or
Or a partial hydrolyzate thereof), and optionally R ² ₃ Si—O—SiR ² ₃ (II) [wherein R ² represents the above] and (R ³ ₂ SiO ) _B (III) [wherein R ³ and b are as defined above] selected from the group of organo (poly) siloxanes and mixtures thereof,
Reacting in water in the presence of an acid and optionally other substances, in a second step the reaction product obtained in the first step is reacted in the presence of a base and optionally other substances,
In the step, the reactants obtained in the second step are mixed in water, optionally with additives, and stirred in, and in the fourth step,
It is characterized in that the precipitated organopolysiloxane resin obtained in the third step is filtered and optionally washed with water.

The drying of the organopolysiloxane resins according to the invention is carried out in conventional dryers, for example fluidized-bed dryers, preferably at temperatures of up to 200 ° C., particularly preferably up to 160 ° C. and pressures of 900 to 1100 hPa. be able to. However, it is also possible to carry out the drying at higher or lower pressures. Drying of the heat-labile organopolysiloxane resin is preferably carried out at reduced pressure, especially in vacuum at a correspondingly low temperature.

The particle size of the organopolysiloxane resin powder according to the present invention depends on many factors, such as the rate of addition of the reaction product of the second step to the water of precipitation, the agitation during precipitation of the third step.
And the flow behavior and the time of movement in the settling bed, the optional additives used and the drying of the fourth step of the process according to the invention.

The process according to the invention for producing organopolysiloxane powders is technically very simple to carry out,
It has the advantage that the use of reproducible and expensive grinding steps can be omitted. The process according to the invention can be used to produce thermally unstable organopolysiloxane resin powders under mild reaction conditions.

The organopolysiloxane resin powders according to the invention thus obtained preferably have an average particle size of 1 to 200 μm. The organopolysiloxane resin powders according to the invention are at least partially, but preferably completely, soluble in liquid organopolysiloxanes and customary organic solvents. The organopolysiloxane resin powders according to the invention are very soluble in organic solvents such as toluene, acetone, hexane and tetrahydrofuran, while they are only partially soluble in lower alcohols such as methanol and ethanol.

The organopolysiloxane resin powder according to the invention precipitates without organic solvents, has good dissolution kinetics and also has good storage stability.

The organopolysiloxane resin according to the invention is suitable for all applications in which conventional organopolysiloxane resins could be used. Thus, the organopolysiloxane resin powders according to the invention can be used, for example, as additives to antifoam agents, toners, paints and other coating systems such as paper coating materials. However, it is also possible to use this resin as a filler instead of hydrophobic highly dispersed silicic acid in plastics, especially in silicone rubber. In particular, organopolysiloxane resin powders according to the invention having SiC-bonded aromatic groups, such as phenyl and / or
Alternatively, the tolyl group-containing organopolysiloxane resin powder is very suitable for the production of weather resistant coatings.

Organopolysiloxane resin powders according to the invention having at least one SiC-5-bonded n-5-hexenyl group are low-temperature vulcanization coating systems, so-called LTC systems (low temperature curable low temperature curi).
ng), especially for fast-crosslinking systems in paper coatings.

Next, the present invention will be described in detail with reference to Examples.
Unless stated otherwise in the examples, "parts" are "parts by weight" and "%" are "% by weight". Unless stated otherwise
The following example is based on the pressure of the surrounding atmosphere, ie about 1000 hP
a and room temperature, ie about 20 ° C. or at a temperature which is adjusted by mixing the reaction components without additional heating or cooling at room temperature. All viscosities mentioned in the examples relate to a temperature of 25 ° C.

[0077]

【Example】

Example 1 Tetraethoxysilane with 40% SiO ₂ (Wa
cker-Chemie GmbH, Muenchen
(Commercially available under the name TES40 in Japan) 900 g and hexamethyldisiloxane 400 g, water 200 g and 10% in water
4 g of HCl are added and heated at reflux at a temperature of 78 ° C. for 2 hours, then 470 g of ethanol are distilled off for 1 hour.
Then add 300 ml of tetrahydrofuran to the homogeneous mixture.
And a 40% solution of methylamine in water (Fa. Mercc
2.5 g of D.K., commercially available from Darmstadt) are added and all are heated under reflux at 65 ° C. for 3 hours. Subsequently, the homogeneous reaction mixture obtained in this way is stirred under strong stirring in water 5
The resulting precipitate is filtered off and dried at 120 ° C. Residual ethoxy content 2.3%, average particle diameter 20.0
μm, residual hydroxy content 0.9% and bulk density 0.35
720 g of a white, non-melting organopolysiloxane resin powder with kg / l are obtained.

The organopolysiloxane resin powder obtained in this way is used in a conventional organic solvent such as toluene, acetone, hexane and tetrahydrofuran and in a liquid organopolysiloxane such as α, ω-trimethylsilylpolydimethylsiloxane having a viscosity of 350 cSt. Soluble up to%.

The viscosity of a 50% solution of the obtained organopolysiloxane resin powder in toluene is 5 cSt.

Example 2 The procedure described in Example 1 was repeated using hexamethyldisiloxane 4
Repeat with the difference that 385 g of hexamethyldisiloxane and 60 g of 1,3-divinyltetramethyldisiloxane are used instead of 00 g. The reaction product is homogeneous in both acidic and basic steps. White non-melting organopolysiloxane resin powder 7 having a residual ethoxy content of 2.5%, an average particle diameter of 20.0 μm, a residual hydroxy content of 0.7% and a bulk density of 0.35 kg / l.
40 g are obtained.

The organopolysiloxane resin powder obtained in this way is used in a conventional organic solvent such as toluene, acetone, hexane and tetrahydrofuran and in a liquid organopolysiloxane such as α, ω-trimethylsilylpolydimethylsiloxane having a viscosity of 350 cSt. Soluble up to%.

The viscosity of a 50% solution of the resulting organopolysiloxane resin powder in toluene is 3.2 cSt.

Example 3 Tetraethoxysilane with 40% SiO ₂ (Wa
cker-Chemie GmbH, Muenchen
Marketed under the name TES40), 400 g of hexamethyldisiloxane, 50 g of 1,3-bis- (n-5-hexenyl) tetramethyldisiloxane, and 20 g of water.
Add 0 g and 8 g of 10% HCl in water and operate as described in Example 1. The reaction product is homogeneous in the acidic process as in the basic process. 735 g of a white, non-melting organopolysiloxane resin powder having a residual ethoxy content of 2.5% and an average particle diameter of 18.0 μm are obtained.

The organopolysiloxane resin powder thus obtained is obtained in a conventional organic solvent such as toluene, acetone, hexane and tetrahydrofuran and in a liquid organopolysiloxane such as α, ω-trimethylsilylpolydimethylsiloxane having a viscosity of 350 cSt. Soluble up to%.

The viscosity of an 80% solution of the resulting organopolysiloxane resin powder in cyclohexane is 84 cSt.

Example 4 Tetraethoxysilane with 40% SiO ₂ (Wa
cker-Chemie GmbH, Muenchen
900 g, hexamethyldisiloxane 385 g, and 1,3-bis-n-norbornenyltetramethyldisiloxane having an endo: exo ratio of 1: 1 to 200 g of water and 3 g of dodecylbenzenesulfonic acid. Add and operate as described in Example 1. The reaction product is homogeneous in the acidic process as in the basic process. Residual ethoxy content 2.5% and average particle diameter 20.
670 g of a white, non-melting organopolysiloxane resin powder having 0 μm are obtained.

The organopolysiloxane resin powder obtained in this way is used in a conventional organic solvent such as toluene, acetone, hexane and tetrahydrofuran and in a liquid organopolysiloxane such as α, ω-trimethylsilylpolydimethylsiloxane having a viscosity of 350 cSt. Soluble up to%.

The viscosity of a 50% solution of the obtained organopolysiloxane resin powder in toluene is 3.5 cSt.

Comparative Example 1 The procedure described in Examples 1 to 4 was repeated, except that the reaction product was mixed in 5 liters of water without addition of methylamine and tetrahydrofuran after the ethanol produced by acidic hydrolysis was distilled off. Repeatedly, the viscous and sticky substance precipitates. The material thus obtained is separated and dried at room temperature to give an organopolysiloxane resin insoluble in all customary organic solvents and liquid organopolysiloxanes.

Example 5 To 240 ml of phenyltriethoxysilane and 116 ml of n-propyltriethoxysilane, 160 g of water and 3.6 g of 10% HCl in water were added, and the temperature was 78 ° C. for 2 hours.
Heat under reflux at 240m ethanol for 1 hour
1 is distilled off. After that, 150 ml of tetrahydrofuran
And diethylamine (Fa. Merck, Darmst
(commercially available as adt) 8.0 g, all at 65 ° C. for 4 hours
Heat under reflux at. After neutralization with acetic acid, the reaction product was added to 3 l of water with vigorous stirring, and the resulting precipitate was collected by filtration, 8
Dry at 0 ° C. and 15 hPa. The reaction product is homogeneous in the acidic process as in the basic process. Residual ethoxy content 1.3%, average particle diameter 17.0 μm and melting range 90
160 g of a white organopolysiloxane resin powder having a ˜120 ° C. are obtained.

The organopolysiloxane resin powder thus obtained is soluble up to 60% in customary organic solvents such as toluene, acetone, hexane and tetrahydrofuran.

The viscosity of a 50% solution of the obtained organopolysiloxane resin powder in toluene is 22 cSt.

COMPARATIVE EXAMPLE 2 The procedure described in Example 5 was changed to that in which the reaction product was mixed in 3 l of water without addition of methylamine and tetrahydrofuran after distilling off the ethanol produced by acidic hydrolysis. Again, a viscous, sticky substance precipitates which, after separation and drying at room temperature, cures to an organopolysiloxane resin which is insoluble in all customary organic solvents.

Example 6 To 400 g of phenyltriethoxysilane, 40 g of tolyltrimethoxysilane, 30 g of dimethyldimethoxysilane and 30 g of hexamethyldisiloxane were added 85 ml of water and 2.0 g of 10% HCl in water, and the temperature was adjusted to 6 hours for 3 hours.
Heat at reflux at 5 ° C and continue for 1 hour with ethanol 45
Distill off 0 g. After that, 100 g of tetrahydrofuran
And a 70% solution of ethylamine in water (Fa. Merc
k, marketed at Darmstadt) 10.0 g,
All are heated at reflux at 65 ° C. for 4 hours. The reaction product thus obtained is subsequently subjected to vigorous stirring with a polyvinyl acetate-based setting aid (Wacker-Ch).
emie GmbH, named Muenchen, PVA4
(Commercially available as 0/140) in 3 l of water containing 0.1%, the precipitate formed is filtered off and dried at 80 ° C. and 15 hPa. The reaction product is homogeneous in the acidic process as in the basic process. Residual ethoxy content 1.8%, average particle diameter 2
200 g of a white organopolysiloxane resin powder with 0.0 μm and a melting range of 100-120 ° C. are obtained.

The organopolysiloxane resin powder thus obtained is soluble up to 60% in conventional organic solvents such as toluene, acetone, hexane and tetrahydrofuran.

Example 7 A solution 86 consisting of 428 g of phenyltrimethoxylane and 10 mmol of dodecylbenzenesulfonic acid in 1 l of water.
g, and heated under reflux at a temperature of 78 ° C. for 3 hours,
At that time, 100 g of ethanol is distilled off as a distillate. Subsequently, diethylamine (Fa. Merck, D
0.6g (commercially available at armstadt), all 1
Heat at reflux at 78 ° C. for hours then carefully neutralize with acetic acid. The reaction product thus obtained is added under vigorous stirring in 3 l of water, the precipitate formed is filtered off and dried at 80 ° C. and 15 hPa. The reaction product is homogeneous in the acidic process as in the basic process. Residual ethoxy content 2.0%
With a white organopolysiloxane resin powder 205
g is obtained.

The organopolysiloxane resin powder thus obtained is soluble up to 60% in conventional organic solvents such as toluene, acetone, hexane and tetrahydrofuran.

Example 8 Tetraethoxysilane (Wa with 40% SiO ₂ content)
cker-Chemie GmbH, Muenchen
Marketed under the name TES40) 800 g, methyltriethoxysilane 50 g, phenyltriethoxysilane 50
g and hexagyldisiloxane 360 g, water 200
g and 10 g of 10% HCl in water were added, and the temperature was adjusted to 7 hours.
Heat at 8 ° C under reflux and continue with ethanol 45 for 1 hour.
Distill off 0 g. Then 200 g of dioxane and a 40% solution of methylamine in water (Fa. Merck, Da.
4.0 g (commercially available in rmstadt) are added and all are heated under reflux at 90 ° C. for 3 hours. The reaction product thus obtained is subsequently added to 5 l of water under vigorous stirring and pressure of 500 hPa, the precipitate formed is filtered off and dried at 80 ° C. and 15 hPa. The reaction product is homogeneous in the acidic process as in the basic process. Residual ethoxy content 2.3%
And 700 g of a white, non-melting organopolysiloxane resin powder having an average particle diameter of 20.0 μm are obtained.

The organopolysiloxane resin powder thus obtained is soluble up to 40% in common organic solvents such as toluene, acetone, hexane and tetrahydrofuran.

Example 9 Tetraethoxysilane with 40% SiO ₂ (Wa
cker-Chemie GmbH, Muenchen
Marketed under the name TES40), 450 g, hexamethyldisiloxane 166 g, BHT (Fa. Fluka, N
eu-Ulm) 28 mg and 1,3-bis- (n)
-5-Hexenyl) tetramethyldisiloxane 42g
Is added with 100 g of water and 3.8 g of 10% HCl in water and heated under reflux for 3 hours, a clear solution being formed after 30 minutes. Subsequently, 300 ml of distillate is removed for 1 hour. Then a 40% solution of methylamine in water (commercially available from Fa. Merck, Darmstadt) 3.
4 g are added to 150 ml tetrahydrofuran and the clear solution is heated under reflux for 3 hours. The reaction product thus obtained is subsequently admixed with 2.5 l of water. Three
After stirring for 0 minutes, the precipitated resin is filtered off, washed with water and washed with 1
Dry at 60 ° C. until constant weight. 365 g of a white, non-melting organopolysiloxane resin powder having a residual ethoxy content of 2.5% are obtained.

The organopolysiloxane resin powder obtained in this way is used in a conventional organic solvent such as toluene, acetone, hexane and tetrahydrofuran and in a liquid organopolysiloxane such as α, ω-trimethylsilylpolydimethylsiloxane having a viscosity of 350 cSt. Soluble up to%.

The viscosity of a 50% solution of the obtained organopolysiloxane resin powder in toluene is 9 cSt.

Comparative Example 3 500 g of water and 50 g of ammonia water (28%) were added at 10 ° C.
Cool to. Within 40 minutes, a mixture of 147 g of methyltrimethoxysilane and 54 g of phenyltrimethoxysilane is added dropwise, the temperature rising to 33 ° C. The mixture is subsequently heated under reflux for 1 hour, cooled to room temperature, the precipitated powder is filtered off, washed again with water and at 120 ° C.
Dry until constant weight. This gives a white powder which is insoluble in all customary organic solvents with a yield of 95%.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Helmut Oswaldbauer Stubenberg Berg Hartstraße 1

Claims (2)

[Claims] 1. In the first step, the formula: R _a Si (OR ¹ ) _4-a (I) [wherein, a is 0, 1, 2 or 3 and R is the same or different. Often has a substituent that is inert to water.
And represents a monovalent hydrocarbon group has may 1 to 18 carbon atoms and, R ¹ may be the same or different, alkyl
Carbon optionally substituted with oxy- or hydroxy group
Represents an alkyl group having 1 to 6 atoms ] and / or a partial hydrolyzate thereof (at least one silane of the formula (I) in which a is 0 or 1 and / or a partial hydrolyzate thereof). by) and, if the conditions _{^{used, 2 3 (II) R 2}} 3 Si-O-SiR [ wherein, ^{R 2} can be identical or different, represent a material obtained by <br/> described R] , (R ³ ₂ SiO) _b (III) [wherein, R ³ may be the same or different and represents R , and b is an integer of 3 to 8]. An organo (poly) siloxane selected from the group and mixtures thereof are reacted in water in the presence of an acid and optionally other substances, and in a second step the reaction product obtained in the first step is added to a base and React in the presence of other substances by In the reaction product obtained in the second step in water and mixed with additives optionally wherein the mixing撹拌, preparation of organopolysiloxane resin. 2. In the first step, the formula: R _a Si (OR ¹ ) _4-a (I) [wherein, a is 0, 1, 2 or 3 and R is the same or different. Often has a substituent that is inert to water.
Optionally monovalent hydrocarbon group having 1 to 18 carbon atoms
The stands, R ¹ may be the same or different, A
May be substituted with a rukyloxy- or hydroxy group
Represents an alkyl group having 1 to 6 carbon atoms ] and / or a partial hydrolyzate thereof (a is 0 or 1)
With the proviso that at least one silane of formula (I) and / or its partial hydrolysates is used), and optionally R ² ₃ Si—O—SiR ² ₃ (II) [wherein R ² May be the same or different and represent those described for R], (R ³ ₂ SiO) _b (III) [wherein R ³ may be the same or different and those described for R] And b is an integer from 3 to 8] and an organo (poly) siloxane selected from the group of: and a mixture thereof are reacted in water in the presence of an acid and optionally other substances, and in a second step, The reaction product obtained in the first step is reacted in the presence of a base and optionally other substances, and in the third step the reaction product obtained in the second step is mixed in water, optionally with additives. to, mixed撹拌, in the fourth step Obtained in the third step, it is filtered off the precipitated organopolysiloxane resin, optionally washed with water, and wherein the drying, preparation of organopolysiloxane resin powder.