JP3022070B2 - Fluorinated organopolysiloxane and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorine-containing organopolypropylene having excellent surface properties and useful as a material for a fiber treatment material, a release agent, a resin modifier, or a solvent-resistant or chemical-resistant rubber material. a process for the production of siloxane and its.

[0002]

2. Description of the Related Art As a method for producing a fluorine-containing organopolysiloxane, a method which is currently industrially used is to react trifluoropropene with methyldichlorosilane to prepare methyl-3,3,3-trifluoropropyl. A dichlorosilane is produced, followed by hydrolysis and cracking to obtain a cyclic monomer, which is subjected to ring-opening polymerization to form a fluorine-containing organopolysiloxane. This manufacturing process can be represented by the following equation.

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Further, Japanese Patent Publication No. 3-75558 discloses a method for producing a fluorinated organopolysiloxane according to a production process represented by the following formula. In this method, the structure of the cyclic monomer produced in the middle is different from the previous method.

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[0004]

However, any of the above-mentioned known methods requires a long reaction step and a high cost. Further, the fluorine content of the obtained polymer is determined by the structure of the cyclic monomer produced in the middle, and it has been difficult to set it arbitrarily.

[0005] Accordingly, an object of the present invention is to provide a method capable of easily producing a fluorinated organopolysiloxane by one-step reaction, and further capable of arbitrarily setting its fluorine content.

[0006]

According to the present invention, in order to solve the problems], following one
General formula (1): Rf-CONH- ( CH 2) n - [- NH- _{(CH 2) 3} -] _m - in (1), Rf is selected from the group consisting monovalent perfluoro 3 to 15 carbon atoms
A polyether group, n is 2 or 3, m is at least one organic is 0 or 1, in the fluorine-containing organic group represented in the molecule
Fluorinated organopolysiloxane is provided.

Further , according to the present invention, the following general formula:
(2): Rf-COOR (2) In the formula, Rf is as described above, and R is an unsubstituted or substituted monovalent hydrocarbon group, and a fluorinated carboxylic acid ester represented by the following general formula:
_{(3): NH 2 - (} CH 2) n - [- NH- _{(CH 2) 3} -] _m - (3) wherein, n and m are, as described above, in the amino group-containing organic group represented At least one in the molecule
Reacting with an organopolysiloxane having
Production of the above-mentioned fluorine-containing organopolysiloxane
A method is provided.

[0008]

That is, in the present invention, a fluorine-containing organopolysiloxane can be produced in one step by a reaction between an organopolysiloxane having an amino group-containing organic group and a fluorinated carboxylic acid ester, and the production efficiency is extremely high. . Moreover, the organopolysiloxane having an amino group-containing organic group used as a reaction raw material has been conventionally industrially produced at low cost, and therefore has a great cost advantage.

Further, the above reactions, the following formula (4): Rf -COOR + NH 2 -Y-Si~ ─────> Rf -CONH-Y-Si~ + ROH (4) ( in the formula, Y is a divalent group interposed between the NH ₂ group and the silicon atom in the general formula (2). Therefore, the fluorine content in the obtained fluorinated organopolysiloxane can be set widely according to the amount of amino groups in the organopolysiloxane to be reacted with the fluorinated carboxylic acid ester. Moreover, this reaction has extremely high selectivity and does not involve a side reaction, and is industrially extremely advantageous.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Fluorine-containing carboxylic acid ester In the production method of the present invention , the fluorine-containing carboxylic acid ester used as a starting material is represented by the general formula (2) : Rf-COOR (2 ) Wherein the fluorine-containing group Rf in the formula is introduced into the organopolysiloxane. The fluorine-containing group Rf is a monovalent perfluoroalkyl ether group having 3 to 15 carbon atoms, linear, may be any branched, and representative examples thereof, but is not limited thereto However, the following can be exemplified.

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In the general formula (2) , the monovalent hydrocarbon group R is a methyl group, an ethyl group, a propyl group, a butyl group,
Alkyl groups such as pentyl group and hexyl group; cycloalkyl groups such as cyclohexyl group; alkenyl groups such as vinyl group, allyl group and hexenyl group; aryl groups such as phenyl group and tolyl group; aralkyl groups such as benzyl group and phenylethyl group. Examples include groups and groups in which part or all of the hydrogen atoms of these groups have been substituted with halogen atoms or the like, such as chloromethyl groups.

Organopoly having an amino group-containing organic group
Siloxane above organopolysiloxane to react with the fluorine-containing carboxylic acid esters of the general formula (3), _{i.e., NH 2 - (CH 2)} n - [- NH- _{(CH 2) 3} -] _m - (3) Wherein the amino group in such an organic group reacts with a fluorinated carboxylic acid ester to introduce a fluorinated group into the organopolysiloxane. is there.

The above amino group-containing organic group is usually bonded to a silicon atom, and the molecular structure of the organopolysiloxane is limited as long as it has at least one organic group. However, any of a chain, a ring, and a branch may be used, but a chain is preferable. The molecular weight and the like may be selected according to the intended fluorine-containing organopolysiloxane. For example, if a high-molecular-weight fluorine-containing organopolysiloxane is intended, a high-molecular-weight organopolysiloxane may be used,
If a low-molecular-weight organopolysiloxane is intended, a low-molecular-weight organopolysiloxane may be used.

In the organopolysiloxane, examples of the silicon-bonded organic group other than the above-mentioned amino group-containing organic group include the same groups as the monovalent hydrocarbon group R in the general formula (2) . Depending on the case, a hydroxyl group, an alkoxy group, a hydrogen atom or the like may be used in addition to these. Generally, alkyl groups, especially methyl groups, are preferred. In the present invention, the following can be illustrated as typical examples of the organopolysiloxane.

Embedded image In the above formula, s, p, and q are 0 to 500, and t is 1 to 5
Is an integer of 00, and m and n are as described above.

As described above, the above-mentioned organopolysiloxane having an amino group-containing organic group has been conventionally produced industrially at low cost, and for example, hexamethylcyclotrisiloxane and octamethylcyclosiloxane. It can be obtained by performing an equilibrium reaction between tetrasiloxane and an amino group-containing organosiloxane as described below in the presence of a catalyst such as an alkali metal hydroxide or silanolate.

[0016]

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This equilibration reaction is represented, for example, by the following formula.

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The reaction between the organopolysiloxane having a reactive fluorine-containing carboxylic acid ester and an amino group-containing organic group are those represented by the formula (4), typically, 200 ° C. or less, preferably 50 to 150 It is performed in a temperature range of ° C. The reaction time can be appropriately selected within a range from several minutes to several tens of hours, but is preferably 5 to 20 hours. The reaction can be carried out in a solvent-free system or in a solvent system. As the solvent, toluene, benzene, hexane, methyl ethyl ketone, methyl isobutyl ketone meta-xylene hexafloride and the like can be suitably used.

The amount of the fluorinated carboxylic acid ester used in the reaction is determined depending on the desired fluorinated content of the fluorinated organopolysiloxane. That is, as is apparent from the above formula (4), when the fluorine-containing carboxylic acid ester is reacted with the same amount of the amino group in the organopolysiloxane, the organopolysiloxane having the maximum fluorine-containing content can be obtained. it can. Therefore, when more fluorine-containing carboxylic acid esters are used, unreacted substances only increase, which is economically disadvantageous.

After completion of the reaction, the desired fluorinated organopolysiloxane can be obtained by distilling off the by-produced alcohol and the solvent.

The organopolysiloxane thus obtained has a fluorine-containing organic group represented by the general formula (1) in the side chain, has excellent surface properties, and has a fiber treatment material, a release agent. It is useful as a resin modifier or a material for a solvent-resistant or chemical-resistant rubber material.

[0022]

EXAMPLES Example 1 The following average structural formula was placed in a 500 ml separa flask equipped with a stirrer:

[0023]

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143.7 g (50 mmol) of the amino group-containing organopolysiloxane represented by the formula is charged, the temperature is raised to 100 ° C., and then the following formula:

[0025]

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Fluorinated methyl carboxylate represented by 5
0.9 g (100 mmol) was added dropwise using a dropping funnel over 30 minutes. After the addition, the mixture was stirred for 1 hour to complete the reaction. still,
By measuring the infrared absorption spectrum of the obtained product, the characteristic absorption (1790 cm ⁻¹ ) of the carbonyl group (> C ＝ O) derived from the fluorinated methyl carboxylate completely disappears, It was confirmed that all the carboxylate was consumed. Next, methanol produced as a by-product was removed by a vacuum strip to obtain 175.5 g (yield: 91.7%) of a fluorinated organopolysiloxane having a viscosity of 166 cSt (25 ° C.). About this, measurement of the infrared absorption spectrum and quantification of the amino group were performed, and the following results were obtained.

Infrared absorption spectrum: The chart is shown in FIG. (Characteristic ^{absorption) 1000~1400cm -1: (C-F} ) 1540,3350cm -1: (NH) 1590cm -1: (NH 2) 1720cm -1: (C = O)

Determination of amino group (indicated by amine equivalent by neutralization titration with hydrochloric acid) Actual value 639 (g / ml) Theoretical value 650 (g / ml)

The organopolysiloxane obtained from the above results has the following formula:

Embedded image It was confirmed to be represented by

[0030]

According to the present invention, solvent resistance, chemical resistance,
Fluorine-containing organopolysiloxane with excellent surface properties such as non-adhesion, water repellency, oil repellency, etc. Since it can be manufactured, it is extremely advantageous industrially. Further, by selecting the amino group content of the amino group-containing organopolysiloxane, it is possible to arbitrarily set the fluorine content of the obtained fluorine-containing organopolysiloxane. Furthermore, the yield and selectivity of the reaction in the production method of the present invention are both extremely high, so that the desired fluorinated organopolysiloxane can be obtained by a simple post-treatment just enough to remove by-product alcohol.

[Brief description of the drawings]

FIG. 1 is a view showing an IR chart of a fluorinated organopolysiloxane produced in Example 1.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Nobuyuki Kobayashi 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture Inside Silicone Electronics Materials Research Laboratory, Shin-Etsu Chemical Co., Ltd. (72) Inventor Koichi Ishida Matsui, Usui-gun, Gunma Prefecture Hitomi Tamachi 1-10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (56) References JP-A-5-156022 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) ) C08G 77/382

Claims (2)

(57) [Claims] 1. A following general formula (1): Rf-CONH- ( CH 2) n - [- NH- _{(CH 2) 3} -] _m - (1) In the formula, Rf is selected from the group consisting -C 3-15 Monovalent perfluoro
A polyether group, n is 2 or 3, m is at least one organic is 0 or 1, in the fluorine-containing organic group represented in the molecule
Fluorinated organopolysiloxanes. 2. A fluorine-containing carboxylic acid represented by the following general formula (2): Rf-COOR (2) wherein Rf is as described above and R is an unsubstituted or substituted monovalent hydrocarbon group. Acid ester and the following general formula
_{(3): NH 2 - (} CH 2) n - [- NH- _{(CH 2) 3} -] _m - (3) wherein, n and m are, as described above, in the amino group-containing organic group represented At least one in the molecule
Reacting with an organopolysiloxane having
Characteristic method of producing fluorine-containing organopolysiloxane
Law.