JPS59193925A - Polysiloxane containing benzene ring and its preparation - Google Patents

Abstract

PURPOSE:To obtain a compound having the group of formula -CH2Cl, having high molecular weight and reactivity, and useful as a starting material for the synthesis of various derivatives, by reacting a phenyl-containing siloxane oligomer, etc. with a chloromethyl lower alkyl ether in the presence of a Friedel- Crafts catalyst. CONSTITUTION:The objective polysiloxane having the recurring unit of formula (R, R' and R'' and H, alkyl or phenyl; l, m and n are 0 or positive integer provided that l and m are not 0 at the same time) can be prepared by reacting (A) a phenyl-containing siloxane oligomer or a phenyl-containing polysiloxane having low molecular weight with (B) a chloromethyl lower alkyl ether in the presence of (C) a Friedel-Crafts catalyst preferably at -10 deg.C- room temperature for 30min-30hr. USE:Useful as a resist material for high energy radiation such as electron beam, etc., an electrically insulating material, a surface treatment agent such as water repellent, an ion exchange membrane, etc.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention can be used as an electronic component material such as a resist toy A material for high energy beams such as electron beams and soft As a surface treatment agent for water agents, etc., or as a jtHf
This invention relates to a high-molecular-weight Hensen ring-containing 1-borine loki-1 nane that can be used as a base for functional membranes such as ion exchange membranes, and a method for producing the same.

[Prior art]

Compared to organic polymers, borinoloxano exhibits superior heat resistance and cold resistance, and its electrical properties are stable over a wide temperature range, so it is finding many uses as functional film materials and electrical/electronic heavy-duty materials.

In particular, since phenyl group-containing polysoloxane has a high glass transition temperature, it is thought that strong and hard IIK can be obtained.
It is expected that the range of its use will expand significantly. However, it is difficult to obtain a high molecular weight phenyl group-containing polysiloxane using conventional production methods. That is, the conventional method for producing polysiloxane involves hydrolyzing chlorosilane to produce a cyclic silicone oligomer, which is then polymerized in the presence of an acid or alkali catalyst. Polymer methylsiloxanes with molecular weights of 5D or more have been obtained, but phenyl group-containing siloxanes, particularly diphenylsiloxanes, can only yield low molecular weight polymers of about 1000 to 140 degrees and are difficult to separate from oligomers. For this reason, there were drawbacks such as the inability to obtain a uniform and usable polymer membrane, and the inability to take full advantage of the characteristics of the polymer.

Furthermore, since conventional polysiloxanes do not have appropriate reactive groups in their molecules, there has been little effort to introduce functional groups necessary to develop high functionality.

[Purpose of the invention]

The present invention was made in order to solve these drawbacks, and its purpose is to produce a benzene ring-containing polysiloxane and a lolomethyl group-containing polysiloxane that has a high molecular weight and high reactivity, and enables the synthesis of various derivatives. The object of the present invention is to provide a manufacturing method thereof.

, [Structure of the Invention] That is, to summarize the present invention, the first invention of the present invention is an invention of a benzene ring-containing polysiloxane, which has the following general formula I: (wherein L(, R' and RLL are , the same or different groups, hydrogen, alkyl groups and phenyl groups/
It is characterized by containing a repeating unit represented by ζ1, where L, m and n represent U or a positive number, and it is possible for L and m to be 0 at the same time.

Therefore, the second invention of the present invention is an invention of a method for producing a pensen width gauge IJ bossolo+zano containing a repeating unit of the above general formula I, which has a nonunyl group. In the presence of a Friedel Krach type catalyst, chloroIJ medul lower alkyl ether is added to the phenyl group-containing polysiloxane containing 1-carbon molecule or 1-carbon molecule.
It is characterized by being able to be extended.

A low molecular weight polyphenyl group-containing siloxane obtained by polymerizing a pheni #M-containing m-type silicone oligomer, e.g., t-hexaphenylcyclotrisiloxane, octaphenylcyclotetrasiloxane, with acid or alkali, used as a raw material in the above production method. can be mentioned. In addition to 4, phenyl group-containing siloxane oligomers such as polydiphenylsiloxane and polydimethyldiphenylsiloxane can also be used. In addition, Friedel-Crach type catalysts can be used as catalysts for general Friedel-Craf reactions such as aluminum chloride, ferric chloride, boron trifluoride, zinc chloride, stannic chloride, and titanium tetrachloride. Here are the ones that are used. Also, chloromethyl lower alkyl ether,! : Examples include chloromethyl methyl ether and chloromethyl ethyl ether.

For production, the raw material phenyl group-containing siloxane oligomer or low molecular weight phenyl group-containing polysiloxane is mixed with chloromethyl lower alkyl ether, a Friedel Krach type catalyst is added, and the reaction is carried out at a reaction temperature of -10'C to room temperature. To do this. The reaction can also be carried out in a bath medium such as charcoal tetrachloride or trichloroethane.

The reaction was completed in 60 minutes to 60 hours, and by repeating precipitation with methanol and reprecipitation with a ketone-alcohol system. lll purify. The molecular weight of the benzene ring-containing polysiloxane obtained in the present invention is 10,000 to 10,000, and can be controlled by the raw material concentration, catalyst concentration, reaction temperature, and reaction time.

The following four points are considered to be the cause of the same molecular weight.

That is, (1) due to the progress of chloromethylation, RIJ
Crosslinking occurs through an intermolecular reaction between the I-methyl group and the unsubstituted phenyl nucleus. (2) Remains at the end. Intermolecular crosslinking occurs due to the reaction between the H group and the chloromethyl group. (3) dehydration condensation of the OHH group at the end using a Friedel-Crafts catalyst; and (4) crosslinking between the OH group and the phenyl group at the end using a Friedel-Crafts catalyst.

The benzene ring-containing polysiloxane of the present invention has a high glass transition temperature and can form a uniform film.

In addition, it contains a chloromethyl group that is highly sensitive to high-energy beams such as electron beams, and has a benzene ring that is resistant to carbon tetrachloride and carbon tetrafluoride gas plasma.
It has a siloxane structure that is highly resistant to oxygen gas plasma, so it can be used as a resist material for high-energy beams. Moreover, the high molecular weight benzene ring-containing siloxane is completely insoluble in water, and can be applied to base materials such as sikaras and ceramics by silicone treatment to impart water repellency to the base materials.

1. However, since the polymer capped benzene ring-containing polysiloxane produced in the present invention contains a chloromethyl group, it is possible to synthesize various derivatives, for example, anion exchange membranes can be obtained by amination treatment. . In addition, it can be used as a highly functional membrane by introducing a functional group from the seed.

〔Example〕

Next, the present invention will be explained with reference to examples, but the present invention is not limited to these examples.

Example 5.2 octaphenyl clotetrasiloxane, 100 ml of tetrahydrofuran, and 250 ml of potassium hydroxide were placed in a glass tube, the tube was degassed and sealed, and reacted at a polymerization temperature of 70 DEG C. for 24 hours. The contents were poured into water-methanol (1:a>my) to obtain a white polymer.The polymer was mixed with methanol-methanol several times.
It was purified by reprecipitation in a kiln system.

The obtained polydiphenylsiloxane has a weight average molecular weight of 1.
j, λi w = 13X10”, dispersion & Mw/Mn =
2.6, power rating: 11, 71p, purity: 150°C.

Next, the polydiphenylsiloxane 205”Q obtained above
Dissolved in 500 nlA of chloromethyl methyl ether,
The reaction was carried out at -5° C. for 10 hours using 20 nrl of stannic chloride as a catalyst. The reaction solution was poured into methanol to obtain a white solid polymer.

Figure 1 shows the infrared absorption spectrum of the polymer.
It is. In FIG. 1, the horizontal axis represents wave number (.7-1) or wavelength (μK), and the vertical axis represents transmittance. As seen in Figure 1, an absorption attributed to di-substituted phenyl was observed at 800on-1, and an absorption attributed to the methylene group of the chloromethyl group was observed at 2200on-1, confirming chloromethylation. did it. From elemental analysis, the chloromethylation rate of this polymer was 20%, and the weight average molecular weight Mw was calculated from gel permey knee chromatography: 1.
2 x 10' and a dispersity Mw/Mn = 1.8, an increase in molecular weight of about 10 times was observed.

Example 2 Polydiphenylsiloxane 25F obtained in Example 1 was dissolved in chloromethyl methyl ether 500- and reacted with stannic chloride 25mj+ as a catalyst at -5°C for 12 hours.

The reaction solution was poured into methanol to obtain a white solid polymer. From elemental analysis, the chloromethylation rate of this polymer was 17%, and the weight average molecular weight calculated from gel permeation chromatography was Mw = 4.7X 10'
, Mvr/Mn = 5.5, an approximately 40-fold increase in molecular weight was observed.

Person's Ji YuN's I + 6 Real A11i ■ 1 young talent, octaphenyl no cloteto, horn 1 JX-rire (1), tei fuphenyltetonomeno I ledge untrasilochirin and octaphenyl Tsuku・J nodotsuno ['' Mixture of xane
Jωh·, 'de-C, +·su, . I'-<11/This phenylme L! , 3-1 ryotun and 7 no, 7s transition temperature, divided'J↓Bonta.

Table 1 Application Example 1.2 The chloromethylated polydiphenylsoloxane obtained in Example 1.2 was dissolved in methyl isobutyl solution, applied to a thickness of about 0.5 μm on a soric wafer, and heated with nitrogen at 100°C for 20 minutes. Brykhetsk was in the air current. After prebaking, electron beam irradiation was performed at an accelerating voltage of 20 KV. After irradiation, the wafer was rinsed with isopropyl alcohol for development using a mixed solvent of methyl ethyl ketone: isopropyl alcohol = 4:1.

Table 2 shows the electron beam irradiation amount at which 50% of the initial film thickness remained. Each has a sensitivity of 1 μm, which is useful for practical use.
It showed the following high resolution.

Table 2 t7Th Table 31c shows the etching rate of chloromethylated polydiphenyl loxane when reactive ion etching was performed using ○3, CF, , CC1, and C'04F. It is understood that it has a high resistance due to its siloxane structure and phenyl group.

Table 3 Application Example 6 By reacting the chloromethylated polydiphenylsoloxane obtained in Example with trimethylamine, converting it to chloride, and treating it with acid, it can be used as an ion exchange resin or an ion exchange membrane. did it.

〔Effect of the invention〕

As explained above, by using the polysiloxane containing one bag of high molecular weight benzene of the present invention, a uniform film with excellent heat resistance and weather resistance can be obtained. In addition, the production method of the present invention allows the synthesis of various derivatives with high reactivity and the introduction of lolomethyl groups at the same time as polymer b (condensation). It has the advantage that it can be used as a base material for functional membranes.

[Brief explanation of the drawing]

FIG. 1 is a graph of the infrared absorption spectrum of the compound obtained in Example 1 of the present invention. Patent Applicant: Nippon Telegraph and Telephone Public Corporation Agent Hirotoshi Nakamoto Benjo: 162 Shirakata Shirane, Oaza Shirakata, Tokai-mura, Naka-gun, Ibaraki Prefecture, Nippon Telegraph and Telephone Public Corporation, Ibaraki Telecommunications Research Institute, Akira Kogure, Tokai-mura, Naka-gun, Ibaraki Prefecture 162 Oaza Shirakata Shirane Nippon Telegraph and Telephone Public Corporation Ibaraki Telecommunications Research Institute

Claims (1)

[Claims] 11. General formula 1: (In the formula, 1(,)(' and R1/ are the same or different, one selected from the group consisting of hydrogen, an alkyl group, and a phenyl group) A benzene ring-containing polysiloxane characterized by having a repeating unit represented by the following formula: t, m and n are 0 or a positive integer, and t and m are never 0 at the same time. 2 F general formula ■: (In the formula, R, R' and R'' are the same or different groups, hydrogen,
represents one type of group selected from the group consisting of an alkyl group and a phenyl group, L, m and n represent 0 or a positive integer,
In a method for producing a benzene ring-containing polysiloxane containing a repeating unit represented by (t and m are never 0 at the same time), Friedelclay is added to a phenyl group-containing siloxane oligomer or a low molecular weight phenyl group-containing polysiloxane. The method for producing the benzene ring-containing polysiloxane described above, which comprises reacting chloromethyl lower alkyl ether in the presence of a fluorine-type catalyst.