JPH0753719A - Preparation of fluorine-containing organopolysiloxane compound - Google Patents

Abstract

PURPOSE:To very easily prepare a fluorine-contg. organopoly-siloxane with high selectivity and conversion as compared with conventional processes. CONSTITUTION:An organopolysiloxane having at least are RSi(H)O2/2 unit (wherein R is a monovalent hydrocarbon group excluding 1-10C unsatd. aliph. groups) per molecule is heat-reacted with a fluorine-contg. olefin of the general formula: R'OaCH2CH=CH2 (wherein R' is a l-10C perfluoroalkyl group or a 2-20C perfluoroalkyl group having an ether bond; and (a) is 0 or 1) in the presence of a catalyst to prepare a fluorine-contg. organopoly-siloxane.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a fluorine-containing organopolysiloxane compound, and more particularly to an organopolysiloxane having a propyl group or an oxypropyl group adjacent to a perfluoroalkyl group or a perfluoroalkyl ether group. The present invention relates to a method for producing a fluorine-containing organopolysiloxane that can extremely easily set the fluorine content arbitrarily.

[0002]

2. Description of the Related Art The following method has been conventionally known as a method for producing a fluorine-containing organopolysiloxane. This one method is currently practiced industrially.

[Chemical 1] , Methyl-3,3,3-trifluoropropyldichlorosilane was prepared from trifluoropropene and dichloromethylsilane, which was then hydrolytically cracked to a cyclic monomer which was then opened. It is a ring-polymerized polymer.

Further, regarding this, the following chemical formula

[Chemical 2] (Here, Rf represents a perfluoroalkyl group) is also known to be carried out (see Japanese Patent Publication No. 3-75558), but all of these methods have long steps. Polymers that are costly and can be obtained
Since the fluorine-containing content of is defined by the structure of the cyclic monomer, it is not easy to set it arbitrarily.

[0004]

In order to produce this fluorine-containing organopolysiloxane, it is also possible to react a fluorine-containing olefin having a vinyl group adjacent to a perfluoroalkyl group with a polysiloxane containing an ≡SiH group. However, the reaction selectivity is low,
There is a disadvantage that only a part of the ≡SiH group can be modified with fluorine by an addition reaction.

[0005]

The present invention relates to a method for producing a fluorine-containing organopolysiloxane which solves the disadvantages of the conventional method and meets the above-mentioned problems, and it relates to at least one RSi () in one molecule. H) O _2/2 unit (R is carbon number 1 ~
An organopolysiloxane having a monovalent hydrocarbon group), except the 10 aliphatic unsaturated group of the general formula ^{_{R 'O a CH 2 CH =}} CH 2 ( wherein the ^R' is from 1 to 10 carbon atoms Pas - fluoroalkyl Group or a perfluoroalkyl group having an ether bond having 2 to 20 carbon atoms, a has an allyl group or an allyloxy group adjacent to the perfluoroalkyl group or the perfluoroalkyl ether group represented by 0 or 1) It is characterized by reacting a fluorinated olefin with heating in the presence of a catalyst.

That is, as a result of various studies on the method for easily producing a fluorine-containing organopolysiloxane, the present inventors have found that an organopolysiloxane having an ≡SiH group has the general formula R'O _a CH ₂ CH = CH ₂ (R ^', a fluorine-containing olefins represented by the as), i.e. Pas - fluoroalkyl group or path - reaction of fluorinated olefins having an allyl or allyloxy group adjacent to the fluoroalkyl ether group, which is very high It was found that a fluorine-containing organopolysiloxane having a substituent represented by ≡SiCH ₂ CH ₂ CH ₂ O _a R ^' can be easily obtained by reacting at a selectivity and a reaction rate, and RfCH = CH is used as this fluorine-containing olefin. ₂
(Rf is a perfluoroalkyl group), the reaction selectivity is low, and it was confirmed that only a part of the ≡SiH groups consumed in the reaction was converted to ≡SiCH ₂ CH ₂ Rf. Completed the invention. This will be described in more detail below.

[0007]

The present invention relates to a method for producing a fluorine-containing organopolysiloxane, particularly an organopolysiloxane having a propyl group or an oxypropyl group adjacent to a perfluoroalkyl group or a perfluoroalkyl ether group. As mentioned above, an organopolysiloxane having at least one RSi (H) O _2/2 unit (R is a monovalent hydrocarbon group excluding an aliphatic unsaturated group having 1 to 10 carbon atoms) in one molecule, General formula R'O _a CH ₂ CH = CH ₂ (R ^' is 1 to 1 carbon atoms
A perfluoroalkyl group having 0 or a perfluoroalkyl group having an ether bond having 2 to 20 carbon atoms, and a is 0
Alternatively, it is characterized by reacting the fluorine-containing olefin represented by 1) with heating in the presence of a catalyst. According to this, the general formula R'O _a CH ₂ C can be obtained with high selectivity and reaction rate.
It is possible to obtain an organopolysiloxane having a propyl group or an oxypropyl group adjacent to a perfluoroalkyl group or perfluoroalkyl ether group represented by H ₂ CH _2- (R ', a is as described above). The advantage is that the fluorine content of this polymer can also be set arbitrarily.

The preparation of the fluorine-containing organopolysiloxane according to the present invention is carried out by at least one RSi (H) O _2/2 (R
An organopolysiloxane having organohydrogen diene siloxane unit represented by as) has the general formula ^{_{R 'O a CH 2 CH =}} CH 2 (R', and a fluorine-containing olefin a is represented by the as) To react. This organopolysiloxane contains at least one RS in a molecule.
i (H) O _2/2 units are included, and R is a monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, excluding an aliphatic unsaturated group, For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, hexyl group, cyclohexyl group, alkyl group such as octyl group, phenyl group, tolyl group, aryl group such as xylyl group, benzyl group, Examples thereof include an aralkyl group such as a phenylethyl group. Further, as the substituent bonded to the silicon atom in the siloxane unit other than the RSi (H) O _2/2 unit in the molecule, the same monovalent carbon atom except for the aliphatic unsaturated group having 1 to 10 carbon atoms as described above for R is used. In addition to hydrogen groups, hydroxyl groups, methoxy groups,
Examples thereof include alkoxy groups such as ethoxy group, propoxy group and butoxy group, and hydrolyzable groups such as halogen atom such as chlorine and iodine. The structure of this organopolysiloxane may be linear, cyclic or branched, but is preferably linear or cyclic.

[Chemical 3]

[Chemical 4]

[Chemical 5] (Where L is 1 to 500, m is 0 to 500, and n is 3 to 1)
Those represented by an integer of 0 and x is a hydrolyzable group such as an alkoxy group or a halogen atom are exemplified as preferable ones.

Further, although the fluorine-containing olefin used herein is intended to be represented by ^{_{R 'O a CH 2 CH =}} CH 2 as described above, to this _{C 2 F 5 CH 2 CH =} CH 2 , C ₃ F ₇ CH ₂ CH = CH _2, C ₄ F ₉ CH
₂ CH = CH _2, C ₆ F ₁₃ CH ₂ CH = CH ₂ , C ₈ F ₁₇ CH ₂ CH = CH ₂ , nC ₃ F ₇ OCH ₂
CH = CH ₂ ,

[Chemical 6]

[Chemical 7]

[Chemical 8] (CF ₃₎ such as ₂ CFOCH ₂ CH = CH ₂ are exemplified as preferred.

The compounding ratio of the ≡SiH group-containing organopolysiloxane and the fluorine-containing olefin used in this reaction is ≡
The fluorine-containing olefin may be 0.1 to 1.3 mol per mol of the ≡SiH group of the SiH group-containing organopolysiloxane. When the target ≡SiH group is left in the fluorine-containing organopolysiloxane, When the amount of the fluorinated olefin used is less than 1.0 mol and the ≡SiH group is completely reacted, 1.0 mol or more of the fluorinated olefin may be used.

The reaction between the ≡SiH group-containing organopolysiloxane and the fluorinated olefin needs to be carried out in the presence of a catalyst, and a known noble metal catalyst may be used as this catalyst. This catalyst may be generally a platinum-based catalyst, and examples thereof include chloroplatinic acid, a complex of chloroplatinic acid with an olefin such as ethylene, and a complex of alcohol or vinylsiloxane. RhCl (PPh ₃ ) ₃ , RhCl (C
_{O) (PPh 3) 2,} RhCl (C 2 H 4) 2, Ru 3 (CO) 12, PdCl 2 (PPh 3) can also be used, such as _2. The amount of this catalyst used is not particularly limited, but is generally 1 × with respect to 1 mol of ≡SiH group.
It may be about 10 ⁻³ to 1 × 10 ⁻⁵ mol.

The reaction of the ≡SiH group-containing organopolysiloxane and the fluorinated olefin according to the present invention
The SiH group-containing organopolysiloxane and the catalyst may be charged, and the fluorinated olefin may be gradually added thereto with stirring over 10 to 60 minutes. The reaction temperature at this time is 4
The temperature may be 0 to 150 ° C., preferably 80 to 130 ° C., and after completion of addition, stirring may be continued at the above temperature for 1 to 24 hours. At this time, a solvent may be used if necessary, and as this solvent, toluene, hexane, trifluoromethylbenzene, 1,3-bistrifluoromethylbenzene and the like are preferable, and the solvent is used after the reaction is completed. The target fluorine-containing organopolysiloxane can be obtained by distilling off the unreacted fluorine-containing olefin added in an equivalent amount or more.

[0013]

EXAMPLES Next, examples and comparative examples of the present invention will be described. Example 1 100 equipped with a thermometer, a Dimroth condenser, and a dropping funnel
ml 3 neck flask type

[Chemical 9] ≡SiH group-containing organopolysiloxane 5.9
3 g, chloroplatinic acid and 1,1,3,3-tetramethyl-
Charge 0.017 g of a 1% toluene solution of the reaction product with 1,3-divinyldisiloxane and 30.0 g of 1,3-bistrifluoromethylbenzene, and heat in an oil bath while stirring with a magnetic stirrer. Then the internal temperature is 1
The temperature was adjusted to 00 to 110 ° C.

Then, using a dropping funnel here, the formula nC ₈
F ₁₇ CH ₂ CH = CH ₂ Fluorine-containing olefin 15.0 g
(1.2 moles with respect to ≡SiH group) was gradually added dropwise over about 20 minutes, and stirring was continued at the above temperature for about 19 hours after completion of the addition. After completion of the reaction, the solvent and unreacted fluorine-containing olefin were When the solvent was distilled off, 18.0 g of a reaction product was obtained. Regarding this, from the weight difference between the ≡SiH group-containing organopolysiloxane used as the raw material and the fluorine-containing organopolysiloxane as the reaction product recovered, 99% of the ≡SiH groups in the raw organopolysiloxane are ≡SiCH ₂ CH ₂ CH ₂ C ₈ F
It has been found that is converted into _17, the 3-path - For organopolysiloxane having perfluorooctyl propyl group because its IR and NMR analysis were at the following result is obtained, the next this thing It was confirmed to be the one represented by the formula.

[Chemical 10]

¹⁹ F-NMR (CF ₃ COOH standard) δ (PPm) -5.1 S, CF ³ --38.2 S, CH ₂ C F ₂ -46.0 to -47.5 m, CF ₂ -51.3 S, CF ₃ -CF ₂ ¹ H-NMR (TMS standard) δ (PPm) 0.26 m, C H 3 - 0.60 ~1.10 m, Si-C H 2 - 1.23 ~2.76 m, CF 2 C H 2 C H 2 IR Figure 1 (900 No absorption peak (2,155 cm ^-1 ) based on 1,300 cm ^-1 C-F, 2,950 cm ^-1 CH ₃ ≡SiH group is observed.)

Example 2 The same three-necked flask as in Example 1 was charged with the formula.

[Chemical 11] ≡SiH group-containing organopolysiloxane 1.8
0 g, chloroplatinic acid and 1,1,3,3-tetramethyl-
Charge 0.017 g of a 1% toluene solution of the reaction product with 1,3-divinyldisiloxane and 30 g of 1,3-bistrifluoromethylbenzene, and use a magnetic star.
The mixture was heated with an oil bath while stirring with a slurry, and the internal temperature was adjusted to 102 to 108 ° C.

Then, using a dropping funnel, the formula n-
C ₈ F ₁₇ CH ₂ CH = CH ₂ Fluorine-containing olefin 15.0
g (1.2 times mol relative to ≡SiH group) was gradually added over about 20 minutes, and stirring was continued at the above temperature for about 19 hours after completion of the dropping. After completion of the reaction, solvent and unreacted fluorine-containing olefin were When the solvent was distilled off, 13.9 g of a reaction product was obtained. Regarding this, 96% of the ≡SiH groups in the raw material were ≡SiCH ₂ CH ₂ CH ₂ C _{8 due} to the weight difference between the ≡SiH group-containing organopolysiloxane used as the raw material and the recovered fluorine-containing organopolysiloxane as the reaction product. it has been found that is converted to F _17, the 3-path - was the IR and NMR analysis for organopolysiloxane having perfluorooctyl propyl group, so the following result is obtained,
It was confirmed that this is represented by the following formula.

[Chemical 12]

¹⁹ F-NMR (CF ₃ COOH standard) δ (PPm) -5.1 S, CF ₃ -37.5 S, CH ₂ C F ₂ -45.0 to -47.0 m, -C F ₂ --50.1 S, CF ₃ -C F ₂ ¹ H-NMR (TMS standard) δ (PPm) 0.25 m, C H ₃ 0.61 to 1.12 m, SiC H ₂ 1.24 to 2.76 m, CF ₂ C H ₂ C H ₂ 4.86 m, Si H IR diagram 2 (2.155cm ^-1 Si-H)

Comparative Example 1 The same SiH group-containing organopolysiloxane as in Example 1 was used and the addition amount was 5.9 g, and the fluorine-containing olefin was represented by the formula nC ₈ F ₁₇ CH = CH ₂ . 6g (≡Si
A fluorine-containing organopolysiloxane treated in the same manner as in Example 1 except that the amount was 1.2 times the molar amount of H 2 group) was obtained. As a result, 9.5 g of a reaction product was obtained. ≡SiCH ₂ CH ₂ C among the ≡SiH groups in the raw materials from the weight difference between the SiH group-containing organopolysiloxane and the recovered fluorine-containing organopolysiloxane as the reaction product.
It was found that only about 30% were converted to ₈ F ₁₇ .

Further, regarding the organopolysiloxane having the 2-perfluorooctylethyl group, I
R and NMR analyzes showed that no ≡SiH groups remained. Other than the addition reaction to the olefin, the side reaction in which the ≡SiH group is consumed is unknown.
It is considered that the reduction reaction of the fluorinated olefin represented by the following formula is involved. C ₇ F ₁₅ CF ₂ CH = CH ₂ → C ₇ F ₁₅ CF = CHCH ₃

¹⁹ F-NMR (CF ₃ COOH standard) δ (PPm) -5.2 S, CF ₃ -38.5 S, CH ₂ CF ₂ -44.5 to -47.5 m, -CF ₂ --50.0 S, CF ₃ CF ₂ ^-1 H-NMR (TMS standard) δ (PPm) 0.26 m, CH ₃ 0.96 〜 1.23 m, SiC H ₂ 1.57 〜 2.76 m, CF ₃ C H ₂ IR Fig. 3 (The absorption peak based on ≡SiH group is unacceptable.)

Comparative Example 2 The same organopolysiloxane containing .tbd.SiH groups as in Example 2 was used and the amount added was 3.6 g, and the fluorine-containing olefin was represented by the formula n-C ₈ F ₁₇ CH = CH _2. 29.2g
Example 2 except that (1.2 moles with respect to ≡SiH group)
When a fluorine-containing organopolysiloxane was prepared in the same manner as described above, 15.0 g of a reaction product was obtained, which was obtained as a reaction product recovered from the ≡SiH group-containing organopolysiloxane used as a raw material. From the weight difference of the fluorine-containing organopolysiloxane, among the ≡SiH groups in the raw material,
It was found that only about 46% was converted to ≡SiCH ₂ CH ₂ C ₈ F ₁₇ .

IR and NMR analyzes of the fluorine-containing organopolysiloxane revealed that
It was found that no ≡SiH group remained.

¹⁹ F-NMR (CF ₃ COOH standard) δ (PPm) -5.2 S, CF ₃ -38.5 S, CH ₂ CF ₂ --44.1 to -47.4 m, -CF ₂ --50.1 S, CF ₃ C F ₂ ¹ H-NMR (TMS standard) δ (PPm) 0.26 m, CH ₃ 0.95 〜 1.23 m, SiC H ₂ 1.58 〜 2.77 m, CF ₂ C H ₂ IR Fig. 4 (Absorption peak based on ≡SiH group) It is not allowed.)

[0025]

The present invention relates to a method for producing a fluorine-containing organopolysiloxane, particularly an organopolysiloxane having a propyl group or an oxypropyl group adjacent to a perfluoroalkyl group or a perfluoroalkyl ether group. As mentioned above, an organopolysiloxane having at least one RSi (H) O _2/2 unit (R is a monovalent hydrocarbon group excluding an aliphatic unsaturated group having 1 to 10 carbon atoms) in one molecule, formula R'OaCH ₂ CH = CH ₂ (wherein the R ^'is from 1 to 10 carbon atoms Pas - fluoroalkyl group, or d 2 to 20 carbon atoms, - path having ether bond - fluoroalkyl group, a is 0 Alternatively, it is characterized by reacting the fluorinated olefin represented by 1) with heating in the presence of a catalyst. According to this, ≡Si-CH ₂ CH ₂ CH _{2 has a} very high selectivity and reaction rate. ₂ Indicated by OaR ' It is possible to easily obtain a fluorine-containing organopolysiloxane having a substituent, and it is possible to arbitrarily set the fluorine content of the polymer.

[Brief description of drawings]

1 is an IR diagram of an organopolysiloxane having a 3-perfluorooctylpropyl group obtained in Example 1 of the present invention.

FIG. 2 shows an IR diagram of an organopolysiloxane having a 3-pa-fluorooctylpropyl group obtained in Example 2 of the present invention.

FIG. 3 is an IR diagram of the fluorine-containing organopolysiloxane obtained in Comparative Example 1 of the present invention.

FIG. 4 is an IR diagram of the fluorine-containing organopolysiloxane obtained in Comparative Example 2 of the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasuro Tarumi 1 1 Hitomi, Osamu Matsuida-cho, Usui-gun, Gunma Prefecture Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (72) Noriyuki Koike Matsui Matsui, Usui-gun, Gunma Prefecture Tamachi Oji Hitomi 1-10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (72) Inventor Koichi Ishida Matsuda-cho, Gunma Prefecture Usui-gun 1 Hitomi 10 Shin-Etsu Chemical Industrial Silicone Electronic Materials Research Institute

Claims (1)

[Claims] 1. An organopolysiloxane having at least one RSi (H) O _2/2 unit (R is a monovalent hydrocarbon group excluding an aliphatic unsaturated group having 1 to 10 carbon atoms) in one molecule. , General formula
^{_{R 'O a CH 2 CH =}} CH 2 ( wherein the ^R' is path 1 to 10 carbon atoms - Pas having ether bond - - d fluoroalkyl group or 2 to 20 carbon atoms, a fluoroalkyl group, a is 0 Alternatively, a method for producing a fluorine-containing organopolysiloxane compound, which comprises reacting the fluorine-containing olefin represented by 1) with heating in the presence of a catalyst.