The method of obtaining the sioh-functional dendrimeric of carbosilane

 

(57) Abstract:

Describes how to obtain Si-OH functional dendrimeric of carbosilanes, which consists in the interaction of the Si-Y, where Y is C1, Br, J, dendrimeric of carbosilanes with water in the presence of a base or mixture of bases and organic solvent, with an organic solvent and water is used in a weight ratio of from 0.5 to 1.4. The technical result is ease of processing of the product and obtaining the pure product with a higher yield up to 97%. 5 C.p. f-crystals.

The invention relates to a method for SiOH-functional dendrimeric of carbosilanes.

Under the dendrimers understand highly branched molecules with complex, often three-dimensional, structure, molar mass is the molar mass oligomers or polymers.

However, dendrimers have the advantage that they can build with exactly the same molar mass, while in the case of conventional polymers always have a certain distribution of molar masses. You can also get certain functional dendrimers with a certain number of reactive end groups.

Application DE 19603242 and 19603241 known SiOH-the organic compounds and varnishes (see application DE 19603242), for binding of catalytically active metallovedenie (see application DE 19632700) or as cross-linking agents in slivaushiesia by condensation organopolysiloxane masses (see application DE 19603241).

According to the applications DE 19603242 and DE 19603241 SiOH-functional gendamerie carbosilane produced by interaction of the respective flint-halogen-functional dendrimeric of carbosilanes with water in the presence of a base in an environment of a non-polar solvent. The reason to use triorganotin, preferably trialkylamine, and as a non-polar solvent - aliphatic ethers.

However, this reaction has the disadvantage that the resulting as a by-product hydrochloride trialkylamine precipitates as high volume solids, which then must be removed by complex filtering process. Specified hydrochloride during the reaction hinders or even prevents uniform mixing of the reaction mixture, so that due to gradients of concentration and temperature are encouraged adverse reactions leading to the formation of oligomers.

Therefore, the method described in application DE 19603242 and 19603241 is extremely neprosteno, the complexity of individual process steps and the extremely low output per unit volume/time.

Thus, there is a high need to develop a method of obtaining SiO-functional dendrimeric carbosilanes, not having the disadvantages of the method according to the prior art.

It has been found that these disadvantages can be avoided by using different solubility product and byproduct.

The object of the invention is a method for dendrimeric of carbosilane formula (I)

K[(CH2)nSiXaR3-a]i(I)

in which n is an integer of 2-6, preferably 2, and R is alkyl with 1-18 carbon atoms and/or aryl with 6 to 20 carbon atoms, and n and R may be the same or different in the molecule and with the other symbols and indices have the following meanings:

(A) means [R4-iSi], and i is the integer 3 or 4, preferably 4,

or

B) To mean a group of the formula

< / BR>
in which i is equal to m and denotes an integer of 3-6, preferably 4, and

a) X - band (HE), and

and is an integer 1,

or

b) X is a group [(CH2)nSi(OH)R2], a

and is an integer of 1-3, preferably 3

or

in) occhialino 3,

or

g) X [(CH2)nSiR3-a[(CH2)nSiR3-a[(CH2)nSi(OH)R2]a]a], and

and is an integer of 1-3, preferably 3,

by interacting dendrimeric of carbosilane formula (II)

K[(CH2)nSiYaR3-a]i(II)

in which n denotes an integer of 2-6, preferably 2, and R is alkyl with 1-18 carbon atoms and/or aryl with 6 to 20 carbon atoms, and n and R are the same or different within the molecule, and the other symbols and indices have the following meanings:

(a) means a group [R4-iSi], where i is the integer 3 or 4, preferably 4,

or

B) To mean a group of the formula

< / BR>
in which i is equal to m and denotes an integer of 3-6, preferably 4, and

a) Y represents chlorine, bromine or iodine, and

and is an integer 1,

or

b) Y - [(CH2)nSi(Z)R2] in which Z denotes chlorine, bromine or iodine,

and is an integer of 1-3, preferably 3,

or

in) Y - [(CH2)nSiR3-a[(CH2)nSi(Z)R2]a] in which Z is chlorine, bromine or iodine, and

and is an integer of 1-3, preferably 3,

or

g) Y - [(CH2)nSiR3-a[(CH2)SiR3-a][(CH
with water in the presence of a base or mixture of bases and organic solvent, and the organic solvent and water is used in a weight ratio of from 0.5 to 1.4, preferably from 0.9 to 1.1.

This means that the reaction is carried out in two phases, i.e., the hydrolysis takes place at the phase boundary in a mixture of two phases, namely, the organic phase, in which soluble containing silicon and halogen gendarmerie carbosilane formula (II) (educti) and SiOH-functional dendrimer carbosilane formula (I) (products), and the aqueous phase in which is dissolved the base and formed during the reaction of salt.

As a solvent for the organic phase in the framework of the present invention is suitable all organic solvents and/or mixtures thereof, is not completely miscible with water. If necessary, the mixture of solvents can be single phase or multiphase. Preferably use simple aliphatic esters, particularly preferably simple tert.butyl methyl ether.

As a Foundation in the framework of the present invention can be used with all water-soluble bases and mixtures thereof such as, for example, ammonia, hydroxide, alkali metal carbonates, bicarbonates, fo the ISI, carbonates and/or bicarbonates of alkali metals, particularly preferably ammonia.

The base is used in stoichiometric amount, calculated on the amount released by acid hydrolysis or in excess, in the case of ammonia, preferably in a double up tenfold excess.

Preferably the proposed method is carried out at a temperature of 0oWith or higher, particularly preferably at temperatures from 0oWith up to 50oC.

According to the applications DE 19603242 and 19603241 the compounds of formula (II) can be obtained by gidrauxilirovania, i.e. by reacting suitable unsaturated silanes with peridocially, as, for example, halogenosilanes, in the presence of a catalyst.

According to a particularly preferred variant of the invention gendarmerie carbosilane formula (II) are obtained by reacting unsaturated silanes, for example, tetraphenylsilane or cyclo[Tetra(methylvinylsiloxane)], with halogenosilanes, as, for example, chlorodimethylsilane, in the presence of homogeneous catalysts, preferably platinum complexes in the siloxane matrix containing vinyl groups, such as catalyst Silopren U Pt/S, representing 68% of Rastoke implementation of gidrauxilirovania in advance in an environment suitable for the proposed method for the solvent of the resulting product can be used in situ, that is, without further processing.

The proposed method can be carried out or periodically, for example, equipped with a stirrer boiler, or continuously, for example, in a tube reactor. For this purpose, preferably dendrimeric carbosilane formula (II), dissolved in a suitable solvent, preferably in simple aliphatic ether, particularly preferably in a simple tert.butyllithium ether, or product gidrauxilirovania slowly added to the biphasic mixture, preferably intensively mixed aqueous and organic phases. Mixing can be accomplished, for example, in the boiler by means of a stirrer or in a tube reactor by creating a turbulent flow.

Mixing promotes the reaction at the interface. Released during the hydrolysis, the acid reacts with the base or mixture of bases with the formation of a salt or mixture of salts dissolved in the aqueous phase. Get SiOH-functional dendrimers carbosilane formula (I) is dissolved in the organic phase. Due to the different solubility of the components of the reaction and due to the absence of sediment selection and processing of the product is possible in a simple way.

Upon completion of the reaction, the phases are separated, and in a separate the aqueous phase, and the organic phase, if necessary, subjected to a one-time or repeated washing with water or an aqueous solution of salt, base or acid, then remove excess water, for example, by drying over anhydrous sulfate of alkaline or alkaline-earth metal, calcium chloride and/or molecular sieve, or by distillation.

Get SiO-functional dendrimers carbosilane formula (I) can be distinguished by removing volatile components, for example, by condensation or distillation, and it is obtained in the form of solids or oils. If the target product in the form of solids can also select by adding the organic phase drops to the solvent (precipitator) or solvent mixture in which (where) the product is insoluble or soluble only to a small extent, and subsequent filtration. Suitable solvents are, for example, cyclic, aliphatic or aromatic hydrocarbons, such as cyclohexane, pentane, hexane, heptane, toluene and/or xylene. You can also add precipitator to the organic phase.

In that case, if the target product wish in dissolved form suitable for further reaction or IP phase. Alternative processing methods, for example, replacement of the solvent by adding a solvent, preferably having a higher boiling point, followed by distillation of the initial solvent or mixture of solvents or his (her) removing by condensation.

The proposed method is illustrated using the following examples, however, it is not limited to these examples.

Examples of the proposed method

Preliminary remarks

With the exception of the allocation process, after hydrolysis, all reactions were carried out in a protective gas atmosphere (argon).

Simple tert. butyl methyl ether (with a water content below 0.05%), n-hexane, diethyl ether, tetraphenylsilane, cyclo[Tetra(methylvinylsiloxane)], chlorodimethylsilane, NaHCO3, Na2CO3, NaOH, NaCl and Na2SO4purchased on the market, used directly without further processing. Aqueous solutions of ammonia was obtained by dilution of 25% ammonia solution.

Heterogeneous catalyst cat. 1 (platinum concentration 1%) according to example 8 application DE 19603242 received by the supply of activated carbon in powder form the shell of the H2PtCl6.

Spectra1H-NMR was shot at 400 MHz.

Example 1

Getting the initial connection Si[(CH2)2Si(CH3)2CL]4< / BR>
The synthesis was carried out according to the method described in the application DE 19603242:

To 75 g (0,550 mol) of tetraphenylsilane in argon atmosphere was added of 234.2 g (2,475 mol) of chlorodimethylsilane, 500 ml simple tert.butyl methyl ether and 1.5 g of catalyst cat. 1. The reaction mixture under vigorous stirring, they were heated at a temperature of 45oWith prior exothermic reaction, the temperature rose to 51oC. then drops slowly added a mixture of 525 g (3,853 mol) of tetraphenylsilane, 1639,4 g (17,327 mol) of chlorodimethylsilane and 940 ml simple tert.butyl methyl ether, and the reaction temperature was not allowed to fall below the 50oC. and Then stirred at a temperature of phlegmy for 1.5 hours, cooled to room temperature, the catalyst was filtered through a Frit, and the resulting clear solution in vacuum freed from volatile components. The target product was obtained as a white solid. Output: 2120,8 g (94% of theory).

Example 2

Synthesis of Si[(CH2)2Si(CH3)2OH]2)2Si(CH2)2Cl]4obtained according to example 1, 800 ml (592) simple dry rubs.butyl methyl ether, and the temperature of the reaction mixture is slowly increased to 38oC. After the addition is continued to stir at room temperature for 1.5 hours, then the phases were separated, the organic phase is twice washed with water, each time using a 3 l, and dried over sodium sulfate. After removal of the drying agent by filtration, the organic phase droplets were applied in 10 l of n-hexane, and the target product was precipitated as a white, fine crystalline solid, which was isolated by filtration and drying at a temperature of 30oWith the vacuum. The weight ratio simple tert.butyl methyl ether and water is 1,04.

Output: of 464.7 (75,4% of theory).

C16H44O4Si5< / BR>
M=440,95 g/mol

So pl.: 142-143oWITH

1N>/P>Example 3

Synthesis of Si[(CH2)2Si(CH3)2OH]4using sodium carbonate as the base

To intensively stir the mixture solution 16,38 g (195 mmol) Panso3in 200 ml of water and 200 ml (148 g) simple tert.butyl methyl ether slowly at room temperature was added dropwise 10 g (to 19.4 mmol) of Si[(CH2)2Si(CH3)2Cl]4obtained according to example 1, dissolved in 50 ml (37 g) simple tert. butyl methyl ether, and the temperature was increased to 28oC. Then further stirred at room temperature for one hour, using a separating funnel separating the organic phase was dried over sodium sulfate. After separating the drying agent by filtration, the organic phase droplets filed in 1 l of n-hexane, and the target product was precipitated as a white, fine crystalline solid, which was separated by filtration and dried in vacuum at a temperature of 30oC.

(The weight ratio simple tert. butyl methyl ether and water is 0.93.)

Output: 5.2 g (60.7% of theory)

So pl.: 141-142oC.

Example 4

Synthesis of Si[(CH2)2Si(CH3)2HE]4using ka CO3in 1000 ml of water and 1000 ml (740 g) simple tert.butyl methyl ether, and with vigorous stirring to the mixture in an argon atmosphere drops were added 50 g (with 97.1 mmol) of Si[(CH2)2Si(CH3)2Cl]4obtained according to example 1, 250 ml (185 g) simple tert.butyl ether. Continued to stir for one hour, the organic phase was separated, dried over sodium sulfate and then drops were added to 5 l of hexane, and the target product was precipitated as a white, fine crystalline solid, which was filtered and dried in vacuum at a temperature of 30oC.

(The weight ratio simple tert. butyl methyl ether and water is 0.93.)

Output: 33.1 g (77,3% of theory)

So pl.: 142-143oC.

Example 5

Synthesis of Si[(CH2)2Si(CH3)2HE]4using sodium carbonate and sodium hydroxide as the base

To intensively stir the mixture solution of 2.34 g (58,5 mmol) of sodium hydroxide and 1.55 g (14.6 mmol) of Na2CO3in 200 ml of water and 200 ml (148 g) simple tert.butyl methyl ether in an argon atmosphere at room temperature drops gave 10 g (to 19.4 mmol) of Si[(CH2)2Si(CH3)2CL]4, or in the course of an hour, the organic phase was separated, dried over sodium sulfate and drops) was added to 1000 ml of n-hexane, and the target product was obtained as a white solid. The latter was filtered and dried at a temperature of 70oC. Yield: 6.3 g (73.5% of theory).

(The weight ratio simple tert. butyl methyl ether and water is 0.93.)

So pl.: 141-142oC.

Example 6

Synthesis of Si[(CH2)2Si(CH3)2HE]4using ammonia as the base

In a protective gas atmosphere in the reactor filed 200 g (1,468 mol) of tetraphenylsilane, 480 ml (355,2 g) simple tert.butyl methyl ether and 0.1 ml of the catalyst Silopren U Pt/S and at stirring drops added 556 g (5,876 mol) (CH3)2Sil. For transmission of the first reaction at room temperature was rapidly added about 30 ml (CH3)2Sil, and due to the beginning of the exothermic reaction the temperature was increased to about 32oC. the Remaining share (CH3)2Sil drops) was added with speed, providing a constant temperature rise to approximately 60oC. Then further heated at a temperature of phlegmy within two hours. Cooled to room temperature reactionwhen mixture drops added to intensively stir the mixture 473,5 g (27.8 mol) of ammonia in 2900 ml of water and 2600 ml (1924) simple tert.butyl methyl ether. Then additionally stirred for one hour, the aqueous phase was separated, the organic phase is twice washed with water, each time using 1000 ml, and dried over sodium sulfate. After separating the drying agent by filtration, the organic phase drops) was added in 10 l of n-hexane, and the target product was precipitated as a white solid, which was filtered and dried in vacuum at a temperature of 30oC.

(The weight ratio simple tert.butyl methyl ether and water is 0,86.)

Output: 359 g (55,5% of theory, calculated on tetraphenylsilane).

So pl.: 141-143oC.

Example 7

Synthesis of Si[(CH2)2Si(CH3)2HE] 4using ammonia as the base

In the reactor filed 170 ml (for 125.8 g) simple tert.butyl methyl ether and 0.05 ml of palladium-sulfur catalyst Silopren U, then in a protective gas atmosphere by heating at a temperature of phlegmy drops) was added a mixture of 25 g (183 mmol) of tetraphenylsilane and to 69.9 g (739 mmol) (CH3)2Sil. Then was stirred for one hour at a temperature of phlegmy, cooled to room temperature and the reaction mixture drops added to intensively stir the mixture 430 is stirred for one hour, the aqueous phase was separated, the organic phase is washed twice times using 400 ml of water and 400 ml of concentrated aqueous solution of sodium chloride. After this was dried over sodium sulfate and drops were filed in 1100 ml of n-hexane. Saducees this solid substance was separated by filtration and dried in vacuum at a temperature of 30oC.

(The weight ratio simple tert.butyl methyl ether and water is 1.31.)

Output: of 54.8 g (67.8% of theory, calculated on tetraphenylsilane)

So pl.: 142-143oC.

Example 8

Synthesis of cyclo-{OSi(CH3)[(CH2)2Si(CH3)2(HE)]}4using ammonia as the base

To the mixture 689 g (2 mol) of cyclo-{0Si(CH3)(C2H3)}4, 1200 ml (888 d) simple tert.butyl methyl ether and 0.2 ml of palladium-sulfur catalyst Silopren U at temperature 45oC and under stirring drops added 788 g (8,33 mol) (CH3)2Sil. While the reaction temperature was continuously increased to 60oC. after the addition was heated at a temperature of phlegmy for one hour, cooled to room temperature and the reaction mixture is slowly drops) was added to stir intensively two-phase mixture 3000A. Then additionally stirred at room temperature for one hour, the phases were separated, the organic phase is washed once using 3500 ml of water and once using 3500 ml to about 5% sodium chloride solution and dried over sodium sulfate.

After removal of the drying agent by filtration, the volatile components are kept in vacuum at a temperature of 25oC. was Obtained a transparent, light yellow, highly viscous oil, still containing about 5% simple tert.butyl methyl ether.

(The weight ratio simple tert. butyl methyl ether and water is 1.01.)

Output: 1294 g butter (theoretical yield: 1296,4 g).

1H-NMR (DMSO-d6): 0,0 million hours (C, 6N, Si(CH3)2); 0,08 million h (s, 3H, Si(CH3)); 0.43 million hours (m, 4H, Si(CH2)2Si); the 5.25 million h (s, 1H, Si(OH)).

Comparative example 1 (according to the application DE 19603242)

Synthesis of Si[(CH2)2Si(CH3)2HE]4< / BR>
94,3 g (183,4 mmol) of Si[(CH2)2Si(CH3)2Cl]4dissolve in 100 ml (70,8 g) in diethyl ether at room temperature under strong stirring drops are added to a solution 110,3 ml (729,3 mmol) of triethylamine, and 15.3 g (850 mmol) and water 3630 ml (2686,2 g) simple t of sediment. The addition was carried out with speed, providing a reaction temperature in the region of 25-30oC. after the addition was continued to stir for one hour, the precipitate was filtered through a Frit and washed twice, each time using 500 ml simple tert.butyl methyl ether. After removal of volatile components under vacuum at a temperature of approximately 35oFrom filter was obtained the crude product as a white solid. The latter was dissolved in 120 ml of tetrahydrofuran, and under strong stirring drops were applied in 3 l of hexane. Thus obtained thin white precipitate was separated by filtration, washed with hexane and dried in vacuum.

(The weight ratio mixture of simple tert.butyl methyl ether, diethyl ether and water is 180,2.)

Output: 40,5 g (50.2% of theory).

So pl.: 139-141oC.

Comparative example 2 (according to the application DE 19603241)

Synthesis of cyclo-{OSi(CH3)[(CH2)2Si(CH3)2(HE)]}4< / BR>
To the mixture is 87.4 ml (63,3 g; 628,3 mmol) of triethylamine, 12.1 ml (12.1 g, 672,2 mmol) of water and 2850 ml (2109 g) simple tert.butyl methyl ether for one hour drops) was added 105 g (RUR 145.2 mmol) of cyclo-{ OSi(CH3)[(CH2)2SiCl(CH3)2

(The weight ratio mixture of simple tert.butyl methyl ether, diethyl ether and water is 180,1.)

Output: 64,3 g butter (theoretical yield: 94,1 g).

1. The method of obtaining dendrimeric of carbosilane formula (I)

K[(CH2)nSiXaR3-a]i(I)

in which n is an integer of 2-6;

R is alkyl with 1-18 carbon atoms and/or aryl with 6 to 20 carbon atoms,

moreover, the values of n and R may be the same or different in the molecule and with the other symbols and indices have the following meanings:

(A) means [R4-iSi] , and i is the integer 3 or 4, or (B) To mean a group of the formula

< / BR>
in which i is equal to m and denotes an integer of 3-6,

and (a) X - band (HE), and is an integer 1,
<)nSiR3-a[(CH2)nSi(OH)R2] a] , and a is an integer 1-3,

or g) X [(CH2)nSiR3-a[(CH2)nSiR3-a[(CH2)nSi(OH)R2] a]a] , and a is an integer 1-3,

by interacting dendrimeric of carbosilane formula (II)

K[(CH2)nSiYaR3-a]i(II)

in which n denotes an integer of 2-6 and R is alkyl with 1-18 carbon atoms and/or aryl with 6 to 20 carbon atoms,

moreover, the values of n and R are the same or different within the molecule, and the other symbols and indices have the following meanings:

(A) means a group [R4-iSi] , where i is the integer 3 or 4,

or (B) To mean a group of the formula

< / BR>
in which i is equal to m and denotes an integer of 3-6, and

a) Y represents chlorine, bromine or iodine, and a is an integer of 1

or b) Y - [(CH2)nSi(Z)R2] in which Z denotes chlorine, bromine or iodine, and a is an integer 1-3,

or) Y - [(CH2)nSiR3-a[(CH2)nSi(Z)R2]a] in which Z is chlorine, bromine or iodine, and a is an integer 1-3,

or g) Y - [(CH2)nSiR3-a[(CH2)SiR3-a] [(CH2)nSi(Z)R2]a]a] ,

in which Z denotes chlorine, bromine Iles, characterized in that the organic solvent and water is used in a weight ratio of from 0.5 to 1.4.

2. The method according to p. 1, characterized in that as a reason to use ammonia, hydroxide, alkali metal carbonates, bicarbonates, phosphates, hydrogenphosphate and/or acetates, ammonia or an alkali metal.

3. The method according to p. 1 or 2, characterized in that the organic solvent used simple aliphatic esters.

4. The method according to one or more of the paragraphs. 1-3, characterized in that the base used in stoichiometric amount or in excess, calculated on the amount of acid released during the hydrolysis.

5. The method according to one or more of the paragraphs. 1-4, characterized in that dendrimeric carbosilane formula (II) previously obtained by the interaction of unsaturated silanes with halogenosilanes in the presence of homogeneous catalysts.

6. The method according to p. 5, characterized in that as homogeneous catalysts use platinum complexes in containing vinyl groups of the siloxane matrix.

 

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