The solution of silicone resin, its production method, containing the bonding composition organopolysiloxane

 

(57) Abstract:

The invention relates to solutions of silicone resins that are free from aromatic hydrocarbons containing C10-14-alkenes. Describes a simple implementation of a well reproducible manner of receiving them. Solutions of silicone resins are very stable, their viscosity does not change during the year at 25oC. 4 c. and 6 C.p. f-crystals, 2 tab.

The invention relates to solutions of silicone resins that are free from aromatic hydrocarbons containing 1-alkenes, method of production thereof and their use in compositions for coating.

Silicone resin, as well as methods of obtaining the silicone resin is widely known. For example, in EP 195936 A (Toray Silicone Co., Ltd., issued October 1, 1986) describes a method for the so-called MQ-resins by hydrolysis of alkylsilane with the monofunctional silane, and the reaction mixture contains at least 5 weight percent hydrogen chloride, and alkylsilanes slowly added dropwise as the last component. Next DE 4216139 A (Wacker-Chemie GmbH, issued November 18, 1993) describes a method of obtaining a silicone resin acid hydrolysis of silanes or, respectively, their chastity toluene, which while removing by distillation the water and the alcohol acts as a so-called entrained additive (Schlepper). The removal of water and alcohol is important, in particular, to obtain a silicone resin with a low content associated with the silicon atom of hydroxyl and CNS groups.

Compositions for coating containing alifaticheskii unsaturated hydrocarbons, are also already known. For example, in EP 108208 B1 (General Electric Co. ; issued April 27, 1988) and EP 216376 A1 (General Electric Co. ; issued April 1, 1987) describes adhesive compositions for coating, designed for the area of contact adhesives and including reactive low viscosity reducers, such as olefins. Cross stitch compositions for coating occurs at the same time, primarily through the reaction of joining catalyzed by platinum. Reactive thinner is introduced into the coating through the so-called anti-adhesion additive. Under these release supplements, which can be adjusted antiadhesive properties for coatings, understood silicone resin, mainly MQ-resins in the respective reactive thinner, which receive the fact that teleology the solvent is then removed by distillation at lower temperatures. Such compositions for coatings contain, as a rule, also aromatic solvent, which incidentally leads to their separation during processing.

The subject invention are solutions of organosilicon (organopolysiloxanes) resins containing 1-alkenes with 10-14 carbon atoms and which are free from aromatic hydrocarbons.

Under organopolysiloxane in the framework of the present invention should be understood also and oligomeric siloxanes.

Solutions of silicone resins according to the present invention have a content of the silicone resin is preferably from 50 to 90 weight%, particularly preferably from 60 to 85 weight percent.

Solutions of silicone resins according to the invention have, in the 25oC the viscosity is preferably from 3 to 10000 mm2/s, particularly preferably from 50 to 3000 mm2/s

Preferably the solutions of silicone resins according to the invention is free from all hydrocarbons except 1-alkenes with 10-14 carbon atoms.

Another object of the present invention is a method of obtaining solutions of silicone resins that are free from aromatic hydrocarbons, characterized in that the SiOSiR3,

where R may be the same or different and denotes a monovalent organic residue,

R1denotes alkyl residue,

and at least one silane of the formula II

Si(OR2)4< / BR>
and/or its partial hydrolyzate,

where R2may be the same or different and denotes an alkyl residue,

and also, if necessary, the organosilicon compound selected from the group consisting of silanes of the formula III

R3aSi (OR4)4-a,

and/or its partial hydrolyzate,

where a = 1 or 2

R3may be the same or different and denotes a monovalent organic residue,

R4may be the same or different and denotes an alkyl residue,

organopolysiloxane formula IV

(R52SiO)b,

where R5may be the same or different and denotes a monovalent organic residue,

b = 3 - 8 integer, preferably 4 or 5,

as well as their mixtures are subjected to contact with water in the presence of acid, and the resulting alcohol is distilled off at least partially; stage 2 obtained in the 1st stage of the homogeneous reaction mass is subjected to usaimage the Eva unsaturation, which is sufficient to obtain a homogeneous reaction mixture, and the water and alcohol are removed by distillation; the 3rd phase obtained in stage 2 of the homogeneous reaction mass is neutralized with acid, optionally partially evaporated aliphatic hydrocarbon with terminal unsaturation, and, if necessary, partially evaporated more water present and the alcohol and remove formed during neutralization, precipitated precipitated salt, and, if necessary, on the 4th stage of the obtained 3-stage homogeneous reaction mass partially allocate aliphatic hydrocarbon with terminal unsaturation.

The residues R, R3and R5denote each independently, preferably monovalent hydrocarbon residues with 1 to 18 carbon atoms.

Examples of the residues R, R3and R5each time independently of one another, are alkali, such as methyl, ethyl, n-propyl, ISO-propyl, n-butyl, ISO-butyl, tert-butyl, n-pentyl, out-of pentyl, neo-pentyl, tert-pentyl, hexylene residues, such as n-hexyl, heptylene residues, such as n-heptyl, aktalnye residues, such as n-octyl and ISO-aktiline residues, such as 2,2,4-trimethylpentyl, monilinia residues, as n-nonyl, decile remains, such as: and, as vinyl, allyl, n-5-hexenyl, 4-vinylcyclohexane and 3-norbornanyl, cycloalkyl remains, as cyclopentyl, cyclohexyl, 4-ethylcyclohexyl, cycloheptyl, norbornylene residues and methylcyclohexyl residues; aryl residues such as phenyl, biphenylyl, naphthyl and until and tenantry; alkaline residues, such as o-, m -, p-tolyl, xylyl and ethylphenyl; kalkilya residues, such as benzyl, alpha - and beta-phenylethyl.

Examples of substituted hydrocarbon residue as residue R, R3and R5include, each independently of one another, halogenated hydrocarbon residues, such as chloromethyl, 3-chloropropyl, 3-bromopropyl, 3,3,3-cryptochromes and 5,5,5,4,4,3,3-heptadecene, and the chlorophenyl, dichlorophenyl and triptorelin; acyloxyacyl residues, such as 3-acroloxidae and 3-methacryloxypropyl; hydroxyalkyl residues, such as hydroxypropyl and the remnants of the formula

< / BR>
The residues R, R3and R5each time independently of one another particularly preferably represent stands and veniam.

Examples of residues of R1, R2and R4are these for the remainder of R, R3and R5examples of alkyl residues.

Preferred residues R1, R2ih">

Especially preferred residues R1, R2and R4denote, respectively independently of one another methyl and ethyl.

In the method according to the invention are mainly used silanes of formula (I), (II) and, optionally, (III) or (partial) hydrolysates, in which R1, R2and R4have the same value.

If in the method according to the invention are applied partially hydrolyzed silanes of General formula (II) and (III), respectively, any preferred number of silicon atoms to 15.

The examples used in the method according to the invention silanes of the formula (I) or their hydrolysates, hence disiloxane include trimethylaluminium, vinylimidazole, hexamethyldisiloxane, 1,3-diphenyl-tetramethyldisiloxane, 1,3-bis(allyl)tetramethyldisiloxane, 1,3-divinyltetramethyldisiloxane, and hexamethyldisiloxane and 1,3-divinyltetramethyldisiloxane especially preferred.

The examples used in the method according to the invention silanes of the formula (II) include tetramethoxysilane, tetraethoxysilane and Tetra-n-proposition, and tetraethoxysilane and its partial hydrolysate especially predpochtitelnye methyltrimethoxysilane, VINYLTRIMETHOXYSILANE, 3-chloropropionitrile, phenyltrimethoxysilane, o, m,p-tartrate.oxycontin, propyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, 3-chloropropionitrile, phenyltriethoxysilane, o, m,p-tolyltriazole, propyltrimethoxysilane, dimethyldiethoxysilane and dimethyldiethoxysilane, preferably applied methyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, o,m,p-tolyltriazole and propyltriethoxysilane.

The examples used, optionally, in the method according to the invention of organopolysiloxane formula (IV) include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, preferably octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane.

In case, if you apply a silane of the formula (III) or its partial hydrolyzate and/or organopolysiloxane formula (IV), they are mainly used in quantities of up to 15 weight percent, counting on the total weight of the silicon compounds.

The use of silane of the formula (III) or its partial hydrolysate, and organopolysiloxane formula (IV) in the method according to the invention is not so the silane of formula (I) and/or its hydrolyzate, in particular, in which R is methyl or vinyl residue, and the silane of formula (II) and/or its hydrolysate in a molar ratio of believing in Si-units, preferably from 0.4:1 to 2.0:1, particularly preferably from 0.5:1 to 1.5:1, and R1in the formula (I) has the same meaning as R2in the formula (II).

The method according to the invention provides that on the 1st stage to a mixture consisting of silane of the formula (I) and/or its hydrolyzate of silane of formula (II) and/or its partial hydrolysate, and, if necessary, organosilicone compounds of the formula (III) and/or its partial hydrolyzate, or (IV), add water to the acid and the mixture is stirred.

At the 1st stage of the method according to the invention water is used in amounts of preferably from 5 to 30 weight percent, particularly preferably from 5 to 20 percent by weight, in particular from 8 to 18 weight percent, considering respectively the total weight of the reaction mass of 1-St stage before the distillation.

As for the acids used in the 1st stage of the method according to the invention, it may be the same acid, which is still used for the hydrolysis of silanes with alkoxygroup. Examples of such acids include reorganize is, formic, propionic, methansulfonate, triftormetilfullerenov acid, preferably HCl used.

To achieve homogeneity of the reaction mass at the 1st stage of the method according to the invention the acid is used preferably in quantities of from 0.2 to 50 mmol, particularly preferably from 2.5 to 15 mmol, respectively, calculated on 1000 g of the reaction mass of 1-St stage before the distillation. At higher concentrations of acid homogeneity of the reaction mass in General is not achieved. For example, if the use is particularly preferred HCl as acid profitable concentration range from 100 to 500 million-1counting on the total weight of the reaction mass of 1-St stage before the distillation.

The alcohol formed during the hydrolysis of 1-St stage of the method according to the invention, is removed during or after, especially after hydrolysis, fully or partially. Depending on the type of alcohol or respectively the number of used water distillate may contain certain amounts of water. It is preferable to keep off alcohol after hydrolysis to the extent that the reaction mass remained homogeneous.

Particularly preferably removed by distillation from 50 to 90 weight prnu carried out mainly at a temperature of 20oC to the boiling temperature of the reaction mass, particularly preferably at temperatures from 50oC to the boiling temperature of the reaction mass, and at a pressure of preferably from 900 to 1100 HPa.

the 1st stage of the method according to the invention ends after a period of time preferably from 30 minutes to 5 hours, particularly preferably after 1 to 3 hours.

At the end of the 1st stage of the method according to the invention to add the base in at least such a quantity, which is necessary to achieve the main character of the environment of the reaction mixture, if necessary, also other substances, as well as aliphatic hydrocarbons with a terminal unsaturation. It is, depending on the applicable bases, in General the quantities of base from 0.02 to 2.0 weight percent, counting on the total weight of the reaction mass of 2-nd stage before the distillation.

On the 2nd stage of the method according to the invention the base is added preferably in an amount such that the pH was in the range of from 8.0 to 14.0, preferably from 9.0 to 12.0.

As grounds for the 2nd stage of the method according to the invention can be applied to all bases, which are still used katalov, as sodium hydroxide and potassium hydroxide, siliconate alkali metal, such as siliconate sodium and siliconate potassium, amines, such as methylamine, dimethylamine, ethylamine, diethylamine, triethylamine and n-butylamine, ammonium compounds such as the hydroxide of Tetramethylammonium and hydroxide tert-n-butyl-ammonium, preferably sodium hydroxide, potassium hydroxide, methylamine, ethylamine and diethylamine and particularly preferred sodium hydroxide, potassium hydroxide and methylamine.

When it comes to used according to the invention aliphatic hydrocarbons with a terminal unsaturation, preferably mean 1-alkenes with 10-18 carbon atoms, such as 1-mission 1-dodecene, 1-tetradecene and 1-hexadecene, and particularly preferred 1-alkenes with 10-14 carbon atoms, in particular 1-dodecene and 1-tetradecene.

Used on 2-stage method according to the invention aliphatic hydrocarbon with terminal unsaturation introducing at least in such an amount that is sufficient to obtain a homogeneous reaction mixture. It mainly concerns the quantities of up to 50 percent by weight, especially preferably about quantities of up to 40 weight percent of aliphatic the AI before distillation. In particular adds so much volume parts of aliphatic hydrocarbon with terminal unsaturation, as was distilled alcohol and possibly water on the 1st stage.

When the distillation carried out at stage 2 of the method according to the invention contained in the reaction mixture water and residual alcohol is distilled over completely or almost completely, possibly together with them distills small amounts of aliphatic hydrocarbons with a terminal unsaturation.

Held on the 2nd stage of the method according to the invention the distillation should begin immediately after addition of the base. Distillation is required to obtain a silicone resin, free from alkoxy and/or hydroxy groups, or a silicone resin with a low content of alkoxy and/or hydroxy groups.

With the addition of the base in the 2nd stage to the acidic reaction mass of 1-St stage is formed in small amounts of salt, which can precipitate after distillation in stage 2. However, in the framework of the present invention, the salt may have fallen into the sediment, should not be taken into account in the concept of "homogeneous reaction mass at stage 2".

the 2nd stage of the way collaspe.

the 2nd stage of the method according to the invention ends after a period of time preferably from 0.5 to 5 hours, particularly preferably after 1 to 3 hours.

At the end of the 2nd stage of the method according to the invention, the homogeneous reaction mixture is neutralized at the 3rd stage acid, completely distilled off, if necessary, still present water and alcohol and remove fallen precipitated salt. At this stage of the method can also be partially removed, if desired, aliphatic hydrocarbon with terminal unsaturation. Distillation of the 3rd stage of the method according to the invention is carried out preferably at a pressure of from 5 to 1100 HPa and a temperature of from 80 to 180oC.

To neutralize the acid suit all named to the 1st stage acid, preferably using the same acid as that on the 1st stage.

If the 3rd stage of the method according to the invention are applied acid, diluted with water, and/or distillation of 2-stage was incomplete, 3 stage water is necessary to drive away, and after distillation present in the reaction mass of the salt is completely precipitates.

Precipitated precipitated salt then remove from the reaction mixture preferably filter the assy maybe if necessary, partially allocated to stage 4 aliphatic hydrocarbons with a terminal unsaturation, preferably by distillation, and the distillation is preferably carried out at a pressure of from 5 to 1100 HPa and a temperature of from 100 to 180oC.

A preferred variant of the method according to the invention provides that hexamethyldisiloxane and/or trimethylaluminium, if necessary, in a mixture with 1,3-divinyltetramethyldisiloxane and/or vinylimidazole and tetraethoxysilane and/or its partial hydrolysate of 1-St stage is mixed with water and 0.2-50 mmol acid, counting to 1000 g of the reaction mass of 1-St stage before the distillation, is subjected to the interaction at the boiling temperature of the reaction mass and a pressure of from 900 to 1100 HPa and distilled the resulting ethanol, at stage 2 obtained in the 1st stage of the homogeneous reaction mass is subjected to interaction in the presence of a base selected from the group consisting of sodium hydroxide, potassium hydroxide and methylamine, and aliphatic hydrocarbons with a terminal unsaturation, in particular 1-alkene with 10-18 carbon atoms, at the boiling temperature of the reaction mass and a pressure of from 900 to 1100 HPa, and water, and the ethanol is distilled off completely or post is, fully distilled water and, if necessary, ETANA and, if necessary, partially evaporated 1-alkene, and formed during neutralization, precipitated precipitated salt is filtered off and, if necessary, on the 4th stage obtained in the 3rd stage of the reaction mass is partially freed by distillation from aliphatic hydrocarbon with terminal unsaturation.

Particularly preferred variant of the method according to the invention provides that hexamethyldisiloxane and/or trimethylaluminium, optionally in a mixture with 1,3-divinyltetramethyldisiloxane and/or vinylimidazole and tetraethoxysilane and/or its partial hydrolysate of 1-St stage is mixed with water and 100-500 million-1HCl, counting on the total weight of the reaction mass of 1-St stage before the distillation, is subjected to the interaction at the boiling temperature of the reaction mixture and a pressure of from 900 to 1100 HPa and evaporated to about 70 weight percent of the formed ethanol, considering the total amount of the formed ethanol, 2-stage obtained in the 1st stage of the homogeneous reaction mass is subjected to interaction in the presence of a base selected from the group consisting of sodium hydroxide, potassium hydroxide and methylamine, and 1-alkene with 10-18 the AI from 900 to 1100 HPa, and water and, if necessary, the ethanol is distilled off completely, or almost completely, on the 3rd stage obtained at 2 - phase homogeneous reaction mass is neutralized with HCl, distilled completely water and, if necessary, the ethanol is distilled off, if necessary, partially 1-alkene and filtered precipitated precipitated by neutralization of the salt, and optionally at the 4th stage of the obtained 3-stage reaction mass is partially exempt from aliphatic hydrocarbon with terminal unsaturation.

Obtained according to the invention, the resin solutions have the content of the silicone resin is preferably from 50 to 90 weight%, particularly preferably from 60 to 85 weight percent.

Silicone (organopolysiloxane) resin contained in solutions of silicone resins according to the invention, has an average molecular weight of preferably from 500 to 10000 g/mol and the average does not contain or contains the most up to 6 mole percent of alkoxygroup, counting on tetrafunctional Si-units (SiO4/2), and does not contain or contains most of 0.4 weight percent associated with the silicon atom of hydroxyl groups, counting on the total weight of the silicone resin. Dissolve disiloxane) resin is fully compatible with organopolysiloxane, moreover, the silicone resin at least partially, preferably, however, completely soluble in the liquid organopolysiloxane.

Examples of silicone resins contained in solutions of silicone resins according to the invention include: [Me3SiO1/2]x[SiO4/2]ywhere Me denotes a methyl residue, and the ratio of x : y = 0.5:1 to 1.5:1, and [Me3SiO1/2]x[Me2ViSiO2]y[SiO4/2]zwhere Me denotes a methyl residue, Vi denotes a vinyl residue, the ratio of (x + y) : z is from 0.5:1 to 1.5:1 and the ratio of x : y is from 98:2 to 50:50.

The method according to the invention has the advantage that it is very simple to implement, very well-reproduced and gives high output product per unit volume per unit time. The big advantage was that used according to the invention aliphatic hydrocarbon with terminal unsaturation is not exposed to any chemical transformations, in particular no isomerization, thereby moving the end of the double carbon-carbon connection, which is very important for use in the composition of the coating and in the area of contact adhesives (short times the us. Partially resulting as a by-product of aliphatic hydrocarbons with a terminal unsaturation can be returned into the process. Another advantage is that the method according to the invention does not require separation of liquid phases and thus no loss of yield by the reaction.

Solutions of silicone resins obtained in accordance with the invention have the advantage that they are very stable and their viscosity does not change during the time period at least one year at a temperature of 25oC.

By conducting reactions with homogeneous mass and low concentrations of acids obtained resin with only minor content of low molecular weight resin fractions, which is favourable when used in adhesive compositions for coatings.

According to the method according to the invention are obtained solutions of silicone resins with high purity, containing no associated with the silicon atom CNS and/or hydroxyl groups or containing only small amounts, making these solutions have a high storage stability.

Solutions of silicone resins according to the invention are suitable for, or respectively their solutions in particular, of course, in which the presence of even minor amounts of aromatic hydrocarbons such as toluene, is undesirable.

Especially preferably the use of solutions of silicone resins according to the invention in organopolysiloxane compositions, stitched accession associated with the silicon atom of hydrogen aliphatic double carbon-carbon linkages; such compositions can be produced with a release coating.

Another object of the present invention is stitched organopolysiloxane composition comprising;

(A) organopolysiloxane connection c SiC organic residues with terminal aliphatic double carbon-carbon bond;

(B) organopolysiloxane containing linked with the silicon atom of hydrogen;

(C) a solution of silicone resin according to the invention or obtained according to the invention;

(D) a complex of a metal or compound of a metal of the 8th side groups, as well as, if necessary;

(E) connection, slow connection associated with the silicon atom of hydrogen to aliphatic double bonds.

Components (A), (B), (D) and (E) may be the same as, and possibly used lead-carbon connection.

When talking about organopolysiloxane (A), preferably refers to organopolysiloxane consisting of units of formula V

< / BR>
where R6may be the same or different and denotes alifaticheskii saturated, possibly substituted, associated with SiC hydrocarbon residues with 1 to 18 carbon atoms;

R7may be the same or different and means associated with SiC organic residues with terminal aliphatic double carbon-carbon bond;

e = 0, 1, 2 or 3;

f = 0, 1, 2 or 3; and (e + f) 3 and the siloxane (A) has in the molecule on average at least two residue R7.

Although formula (V) is not expressed, up to 5% of the residues R6in organopolysiloxane (A) may also have value alkoxylate.

Preferably, at least 90% of all related residues organopolysiloxane (A) are methyl residues.

Examples of residues of R6are those indicated above for R examples alifaticheskii remains saturated.

Examples of residues of R7are the vinyl, allyl, 3-butonly, 5-exenergy, 7-octenidine and 9-dartilly residues, and particularly preferred vinyl and 5-exenergy remains.

Princeska balance with terminal aliphatic double carbon-carbon bond.

Particularly preferably, if the siloxane (A) is polydimethylsiloxane with integral dimethylaniline groups.

Used in accordance with the invention, organopolysiloxane (A) have a viscosity at 25oC, preferably from 20 to 5000 mm2/s

Used in accordance with the invention, organopolysiloxane (A) have an iodine number of preferably from 1 to 30, particularly preferably from 2 to 20, and the iodine number indicates expended upon accession to the double bond, the amount of iodine in grams per 100 grams of the material under investigation.

Organopolysiloxane (B) can be known is still linear, branched or cyclic organopolysiloxane containing linked with the silicon atom of hydrogen.

As organopolysiloxane (B) is preferably applied linear, cyclic or branched organopolysiloxane consisting of units of the formula VI

< / BR>
where R8may be the same or different and have the meaning indicated above for R6;

c = 0, 1, 2 or 3;

d = 0, 1, or 2, and (c + d) 3 and on the average molecule at least two associated with the silicon atom of the hydrogen atom.

Although it's not you is about balance.

Organopolysiloxane (B) preferably have an average viscosity of from 5 to 1000 mm2/s, particularly preferably from 10 to 500 mm2/s at 25oC.

Preferably, at least 50% of all related SiC residues organopolysiloxane (B) are methyl residues.

Used in accordance with the invention, organopolysiloxane (B) preferably contains in the molecule on average at least 3 associated with the silicon atom of the hydrogen atom.

Used in accordance with the invention, organopolysiloxane (B) preferably has associated with the silicon atom of hydrogen in the range from 0.1 to 2 weight percent, particularly preferably from 0.8 to 1.7 weight percent, counting on the total weight of organopolysiloxane (B)

In compositions in accordance with the invention, the siloxane (B) is preferably used in quantities of from 0.7 to 5 moles associated with the silicon atom of hydrogen, particularly preferably from 1.1 to 3 mol associated with the silicon atom of hydrogen, respectively, counting on 1 mol of the terminal aliphatic carbon-carbon link siloxane (A).

Solutions of organosilicon (organopolysiloxanes) resin used as component (C) financial interest.

In the composition according to the invention the solution of silicone resin (C) is used preferably in quantities of from 0.5 to 95 percent by weight, particularly preferably from 1 to 90 weight percent, respectively, counting on the total weight of the composition according to the invention.

The amount of silicone resin in the form of an applied component (C) can be adjusted antiadhesive properties of stitched composition according to the invention. So, if you increase the amount of silicone resin is increased adhesive properties.

As (D) facilitating the accession associated with the silicon atom of hydrogen aliphatic double bond, can be used to speed up the process of knitting (education spatial relations), the same catalysts that could be used in the previously known compositions for crosslinking by aliphatic double bonds. Preferably apply the platinum metals or their compounds or complexes, in particular compounds or complexes of platinum.

Examples of catalysts (D) are compounds or complexes of platinum, such as PtCl4H2PtCl66H2O, Na2PtCl44H2O, platings, platinum-aldehyde complexes, platinum-ketone complexes, including reaction products of H2PtCl66H2O and cyclohexanone, platinum-vinylsilane complexes, in particular platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complexes, dichloride, bis-(gamma-picoline)-platinum dichloride trimethylenetrinitramine, dichloride dicyclopentadienyliron, dichloride dimethylsulfoxidecopper-(11), the reaction products of platinum tetrachloride with olefin and primary amine or secondary amine, the reaction product is dissolved in 1-octene of platinum tetrachloride with Deut.-- butylamine, dichloride cyclooctatetraene and dichloride norbornadiene.

In the composition according to the invention the catalyst is used mainly in number from 10 to 1000 weight ppm (parts per million), particularly preferably from 50 to 200 million-1accordingly comprises the specified amount to the full weight of the composition according to the invention and counting on elemental platinum.

Examples of means (E), slowing down the accession associated with the silicon atom of hydrogen to aliphatic multiple connections, so-called inhibitors, include Akinola, fumaric acid, maleic acid, fumaric esters and male the communities from 0.05 to 2 weight percent, particularly preferably from 0.1 to 1.0 weight percent, counting on the total weight of the composition according to the invention.

In addition, stitched organopolysiloxane composition according to the invention may contain other additives target.

Stitched organopolysiloxane composition according to the invention can be obtained by known methods, such as simple mixing of the individual components.

Preferably silicon solutions (C) according to the invention are used in a mixture with the inhibitor (E) and possibly organopolysiloxane as a so-called anti-adhesive additives.

Another object of the present invention is an antiadhesive additive containing solution (C) silicone resins according to the invention or obtained according to the invention, the compound (E), slowing down the accession associated with the silicon atom of hydrogen to aliphatic double bonds and, possibly, organopolysiloxane selected from the group consisting of organopolysiloxane associated with SiC organic remains, with a double carbon-carbon end-aliphatic bond, and organopolysiloxane containing hydrogen associated with atomo is respectfully from 0.1 to 1.5 weight percent, particularly preferably from 0.1 to 1.0 weight percent, considering respectively the weight of the solution (C) resin.

If antiadhesive additive according to the invention contains organopolysiloxane, mainly refers to the siloxanes of the unit formula (V) with a viscosity of from 30 to 100 000 mm2/s, and particularly preferred polymethylsiloxane with terminal vinyl groups in the named range of viscosity.

If antiadhesive additive according to the invention contains organopolysiloxane, preferably refers to the number of from 1 to 40 weight percent, particularly preferably from 2 to 30 weight percent, respectively, considering the weight of the solution (C) resin.

Antiadhesive additive according to the invention, in addition to solution (C) resin, the inhibitor (E), and possibly organopolysiloxane, preferably do not contain any more components.

Antiadhesive additive can be mixed in a known manner with other components (A), (B) and (D) to obtain structured organopolysiloxane compositions from which can be derived antiadhesive coating.

Stitched organopolysiloxane composition according sobrecalentarse formulations as for example, to get a release on a sticky products coatings. They are suitable, for example, to obtain a separation, covering and lining paper, including the lining paper applied to obtain irrigation or decorative films or foams, including those of polyurethane. The compositions according to the invention are suitable further, for example, to obtain a separation, covering and lining paper, lining films and sukonik for finishing the reverse side of adhesive tapes and self-adhesive films or facial labeled side of self adhesive labels. The compositions according to the invention is also suitable for finishing packaging material as the packaging material of paper, cardboard boxes, metal foils and containers, such as cardboard, plastic, wood or iron, designed or intended for storage and/or transport of adhesive materials, such as adhesives, sticky food products such as cake, honey, sweets and meat, bitumen, asphalt, covered with fat materials and raw rubber. Another example of application of the compositions according to the invention is finishing media for transferring layers of contact adhesive in so nasyscyennoi paper self-adhesive materials as a stand-alone way, and during the main process.

The coating compositions according to the invention on the surface that needed to make the property repulsive adhesive substances may occur by any known method suitable for the production of coatings from liquid materials, for example, dipping, smearing, watering, spraying, rolling, pitaniem for example by offset engraving device coating with a knife or doctor blade, or by pneumatic brushes.

Surface, which is reported property repulsive adhesive substances by applying a composition according to the invention can be a surface of any substance that is solid at room temperature and a pressure of from 900 to 1100 HPa. Examples of such surfaces are the surfaces of paper, wood, cork and plastic films, for example polyethylene films or polypropylene films, woven or non-woven fabric of natural or synthetic fibers or glass fibers, ceramic objects, glass, metals, polyethylene coated paper or paperboard, including the surface of the asbestos. The above-mentioned polyethylene may be respectively polyethylene of high, medium or low dateline not treated with chemicals and/or natural polymer substances, Kraft paper weighing from 60 to 150 g/m2, unsized paper, paper with a low degree of grinding paper pulp, paper, containing wood pulp, niesatynowany or uncalendered paper, paper, which is due to the use of machine calender during its production without further time-consuming activities turns out smooth on one side and is therefore referred to as "one-sided masinagudi paper, uncoated paper or paper made from waste paper, in a word, the so-called worthless paper. But the paper is processed according to the invention, can be, needless to say, high quality paper, as, for example, low-absorption paper, coated paper, paper with a high beating degree of the pulp, paper not containing mechanical pulp, calendered or satin paper or paper with pre-applied coating. Cardboard can also be high - and low-quality.

Stitched organopolysiloxane composition according to the invention may in a known manner be crosslinked during storage, and aliphatic hydrocarbons with a terminal unsaturation used according to the invention component (C) in the formation of a mesh which occurs mainly at temperatures from 50 to 200oC, particularly preferably at a temperature of from 60 to 150oC and a pressure of from 900 to 1100 HPa.

As energy sources for thermoscience used primarily furnace, such as convection ovens, warming the channels, heated rollers, heated plates or thermal infrared region.

The composition according to the invention has the advantage that it is free from aromatic hydrocarbons, and thus to be excluded unwanted emissions in the above applications, especially at elevated temperatures. In addition, the composition according to the invention has the advantage that it is very stable and gives coatings with reproducible release values.

In the following examples, all data related to fractions and percentages are, unless otherwise stated, to the weight. Unless otherwise stated, the following examples are carried out under normal pressure, i.e. at about 1000 HPa, and at room temperature, i.e. approximately at 20oC, i.e., at a temperature, which upon mixing of reagents is installed without additional heating or cooling. All of these examples, the viscosity data relate to Niem TES 40 firm Wacker-Chemie GmbH, Munich), 730 g hexamethyldisiloxane and 116 g of 1,3-divinyltetramethyldisiloxane add 420 g of water and 3.8 g of 20% hydrochloric acid and heated for 2.5 hours at a temperature of 78oC under reflux. Then for one hour away 970 g of distillate. The obtained distillate contains 10% water and 90% ethanol. A homogeneous mixture is mixed with 990 g of 1-dodecene (sold by the firm Chevron Chemical Houston, Geneva) and 8 g of a 25% aqueous solution of NaOH in distilled water and 560 g of volatile components. The resulting distillate is 56% of ethanol, 42% water and 2% of 1-dodecene. Then neutralize the homogeneous reaction mixture is five (5) milliliters of 20% hydrochloric acid and 15 g distilled volatile components. This distillate contains 61% ethanol; 27% water and 12% of 1-dodecene. Completely precipitated precipitated sodium chloride is then filtered off.

Thus obtained resin solution concentrate in the next stage of the process distillatively removing 568 g of volatile components at a temperature of 130oC and a pressure of 30 HPa. Received destillat is 1% of ethanol and 99% of the 1-dodecene, which can again be used upon receipt of the resin solution.

Get 1745 solution of silicone resin with a resin content of 78% and nascosti">

Measurements with1H-NMR show that during the process of obtaining resin isomerization does not occur on the terminal double bond of carbon-carbon 1-dodecene. Not found no one (-CH=CH)-group.

Upon dilution of the obtained resin solution 1-dodecanol to a resin content of 50% of the resulting solution shows a viscosity of 7.8 mm2/with the content associated with the silicon atom of hydroxyl groups of 0.09% and a residual acidity of 3 h/million

Comparative example 1

50 g of the solution of MQ resin containing groups [Me3SiO1/2]-[(CH2= CH)Me2SiO1/2] and [SiO4/2], where Me denotes a methyl residue in toluene to a solids content of 70%, obtained as described in example 3 of the above patent DE 4216139 A method specified in example 1 according to the present invention the ratio of the original substances, are mixed with 100 g of 1-dodecene and distilled 152 g of volatile components at a temperature of 75oC and a pressure of 30 HPa. As the remainder receive 448 g 78% solution of MQ resin in 1-dodecene with a residual content of toluene and 0.9% (defined using the1H-NMR measurements) and viscosity 721 mm2/s

Example 2

With that obtained in example 1, 78% of rasooly according to example 1, 20 parts - dimethylpolysiloxane with a viscosity of 500 mm2/s, 10 parts of dimethylpolysiloxane with a viscosity of 20 000 mm2/with that 5.3 parts - trimethylsilyltrifluoroacetamide with a viscosity of 25 mm2and content associated with the silicon atom of hydrogen of 1.62%, and 0.25 part ethynylcyclohexanol, and platinum in the form of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in such quantity that the mixture has a content of platinum 100 million-1counting on elemental platinum.

Thus prepared mixture is applied using a metal spatula, the so-called manual squeegee, Pergamino paper weight 65 g/m2getting the weight of the coating of 1.5 g/m2.

Covered so the paper utverjdayut in a drying Cabinet with air circulation within 12 seconds at 150oC. Accordingly, one part of the paper coated with the coating layer is then coated with rubber adhesives brands of T-4154" and "7476", and acrylic adhesive stamps "7475" (respectively sold by the company Beiersdorf, D - Hamburg). The laminates are then subjected to aging and experience in accordance with the method FINAT Test No. 10. The test results are summarized in table. 1.

Sravnitelnaia instead of 70 parts of 78%-aqueous resin solution according to example 1 take 70 parts 78% solution of the resin according to comparative example 1. The results are shown in table. 2.

During curing of the composition for coating a toluene evaporates.

Example 3.

Obtained according to example 1 78% resin solution are mixed in a weight ratio of 1:1 ,- dimethylpolysiloxane with a viscosity of 500 mm2/C. Even after several days of storage at 25oC and the pressure of the surrounding atmosphere, the mixture is completely transparent and homogeneous; opacity missing.

1. The solution organopolysiloxane resin, characterized in that it contains 50 to 90 wt.% organopolysiloxane resin and 1-alkenes with 10 to 14 carbon atoms and is free from aromatic hydrocarbons.

2. A method of obtaining a solution organopolysiloxane resin by reacting silane with water in the presence of an acid, characterized in that on the 1st stage of at least one silane of the formula I

R3SiOR1< / BR>
and/or its hydrolysate R3SiOSiR3,

where R, same or different, and represents C1- C18is a hydrocarbon radical;

R1- C1- C4is an alkyl radical,

and at least one silane of the formula II

Si(OR2)4< / BR>
and/or its partial hydrolyzate,

and R2ical connection, selected from the group consisting of silanes of the formula III

Ra3Si(OR4)4-a< / BR>
and/or its partial hydrolyzate,

where a = 1 or 2;

R3identical or different, denotes a C1- C18is a hydrocarbon radical;

R4the same or different, - C1- C4is an alkyl radical,

and organopolysiloxane formula IV

(R25SiO)b,

and R5identical or different, denotes a C1- C18is a hydrocarbon radical;

b = 3 - 8, integer

as well as their mixtures are subjected to contact with water in the presence of acid, and the resulting alcohol is at least partially evaporated, the 2nd stage is subjected to interaction obtained in the 1st stage of the reaction mixture in the presence of a base at pH values of 8 to 14, and at least such a quantity of 1-alkenes with 10 to 14 carbon atoms, which is sufficient to obtain a homogeneous reaction mixture, remove the water and alcohol by distillation, 3-stage neutralize the reaction mixture obtained in stage 2, acid and remove fallen precipitated salt formed by neutralization.

3. The method according to p. 2, characterized in that the 3rd stage of the reaction mixture is yildirimakin and/or trimethylaluminium optionally in a mixture with 1,3-divinyltetramethyldisiloxane and/or vinylimidazole and tetraethoxysilane and/or its partial hydrolysate of 1-St stage is mixed with water and 100 500 million-1HCl of the total weight of the reaction mixture of the first stage before the distillation, conduct the reaction at the boiling temperature of the reaction mixture and a pressure of 900 to 1100 HPa and distilled approximately 70% of the formed ethanol from the total amount of the formed ethanol, 2-stage obtained in the 1st stage of the reaction mixture in the presence of a base selected from the group consisting of sodium hydroxide, potassium hydroxide and methylamine, and 1-alkene with 10 to 14 carbon atoms is subjected to interaction at the boiling temperature of the reaction mixture and a pressure of 900 to 1100 HPa, and distilled off completely or almost completely water and ethanol, on the 3rd phase obtained in stage 2, the reaction mixture was neutralized with HCl, fully distilled water and filtered precipitated precipitated salt formed by neutralization.

5. The method according to p. 4, characterized in that on the 3rd stage also distilled ethanol and partially 1-alkene.

6. The method according to PP.4 and 5, characterized in that the 3rd stage of the reaction mixture is partially freed by distillation from 1-alkenes with 10 to 14 carbon atoms.

7. Stitched organopolysiloxane composition, characterized in that it contains: (a) organopolysiloxane with Si-related organicheskoi number 1 - 30; (B) organopolysiloxane containing Si-bonded hydrogen, with a viscosity of 5 to 1000 mm2/s at 25oC and a content of Si-bound hydrogen of 0.1 - 2.0 wt.%, and siloxane (B) is contained in an amount of 0.7 to 5.0 mol of Si-bound hydrogen per 1 mol of the terminal double carbon-carbon link siloxane (A), (C) 0.5 to 95,0 % calculated on the total weight of the composition solution organopolysiloxane resin under item 1 or received by one or more paragraphs.2 to 6, and (D) 10 - 1000 million-1complex or compound of a metal of the 8th side of the group calculated on the total weight of the composition and calculated the elemental metal.

8. The composition according to p. 7, characterized in that it further comprises (E) 0.05 to 2% of the total weight of the composition of connection, slow connection Si-bound hydrogen to the double bond.

9. Antiadhesive additive, characterized in that it contains a solution of polysiloxane resin under item 1 or obtained according to any one of paragraphs.2 - 7 and the connection, slow connection Si-bonded hydrogen to aliphatic double bonds.

10. Additive under item 9, characterized in that it further comprises organopolysiloxane selected from the group consisting of organopolysiloxane with Si-bound organicheskimim.

 

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