JPS601211A - Polyethynylphenylacetylene and its production - Google Patents

Abstract

PURPOSE:To obtain a polyethynylphenylacetylene suitable for use in electron beam resists, photopolymers, etc., by polymerizing diethynylbenzene in the presence of a specified catalyst in a solvent such as an aromatic hydrocarbon or a halohydrocarbon. CONSTITUTION:The purpose linear polymer represented by formula II (wherein the ethynyl group is m- or p- to the main chain of the molecule, and n is a number corresponding to a weight-average MW of 1,000-100,000) is obtained by polymerizing a compound of formula I (wherein the ethynyl groups are m- or p- to each other) at 0-80 deg.C in a solvent such as an aromatic hydrocarbon or a halohydrocarbon in the presence of a catalyst obtained by exposing tungsten hexacarbonyl or molybdenum hexacarbonyl to light in the presence of an organic halide. In order to obtain the above polymer in good yields, it is preferred that the concentration of the monomer of formula I in the solvent is 10mol/1 or below, and the catalyst is used in an amount 1/10-1/100 time that of the monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polyethynylphenylacetylene which is novel and useful for applications such as electron beam resists, and a method for producing the same.

Polyethynylphenylacetylene in the present invention is a linear polymer represented by structural formula (I).

(In the formula, the ethynyl group is bonded to the meta or para position with respect to the main chain of the molecule, and n is the weight average molecular weight of 100
It is a number ranging from 0 to 100,000. ) A polymer containing an ethynyl group bonded to an aromatic ring was developed by
4'-4ko ao or special public Sho kA-4'! ;De3
9, etc., but since these are polymerized using a catalyst that cyclizes and trimerizes ethynyl groups, the molecular main chain is formed by conjugated double bonds like the polymer in the present invention. It is completely different from the polymer according to the present invention.

The polymer of the present invention is novel, and because the double bond in the main chain and the ethynyl group are conjugated, it is extremely useful in various uses.

The molecular weight of the linear polymer represented by the structural formula (I) in the present invention is from lOθ0 to 1,000,000 in terms of weight average molecular weight, preferably from hoooo to 0,000S.

Those having a weight average molecular weight of 1000 or less have poor physical properties as a polymer, and it is difficult to form a homogeneous coating film for use as an electron beam resist, for example. Moreover, those having a weight average molecular weight of lθ00,000 or more have poor solubility in solvents.

Various methods can be used to obtain the linear polymer represented by structural formula (I), but methods include polymerizing compounds represented by structural formula (U) (hereinafter referred to as monomers) using various catalysts. is preferable because of the simplicity of the process and the ease of purification.

(In the formula, the ethynyl groups are in the para or para positions with respect to each other.) In order to obtain the linear polymer represented by the structural formula (1) in a high yield, the above monomer (II) is polymerized in a solvent. The monomer L concentration at this time is preferably /Om0
It is below V1. Further, in order to obtain the polymer of the present invention, it is desirable to use a catalyst, and the preferred concentration of the catalyst is /rrtrl
/l or less. In addition, the conditions for the polymerization reaction include nitrogen,
Polymerization is preferably carried out at a temperature range of o-go°C, preferably yo-go°C, under an atmosphere of an inert gas that does not react with the monomer and catalyst, such as argon. Generally, it is preferable that the catalyst be 7 to 10%. If the amount of the catalyst used is large, the molecular weight of the polymer will be small, and if the amount of the catalyst used is small, the yield of the polymer will be reduced. Furthermore, the higher the reaction temperature, the faster the polymerization reaction rate, but the shorter the life of the catalyst.

Catalysts used to polymerize the polymers of the invention include:
Catalysts commonly used for polymerizing ethynyl groups can be used, and preferred catalysts include:
Examples include Ziegler-Natsuta type catalysts consisting of a combination of compounds represented by structural formula (m) and structural formula (F/1).

Ti (Ql ) 4 Structural formula (It) AI (Q2) 11 Structural formula (In the formula, Ql is an alkoxy group having 20 or less carbon atoms, and Q2 is an alkyl group or aryl group having 20 or less carbon atoms.) As a compound represented by structural formula (N),
For example, titanium tetra-n-butoxide, titanium tetra-1-butoxide, titanium tetra-1-butoxide, etc. are added, and examples of compounds represented by the structural formula (M) include triethylaluminum and the like.

The Ziegler-Natsuta type catalyst has the above structural formula (1)
and Structural Formula (In addition to the combination of compounds represented by O), compounds in which Q1 and Q of Structural Formula (7) to Structural Formula (P/) are halogens, such as TiCl4 or AI (C* H5) CI, etc. combinations are known.

However, the use of a Ziegler-Natsuta type catalyst composed of a compound having a halogen as a substituent,
The ethynyl group tends to be cyclized and trimerized to form a penzene skeleton, which is not preferred as a method for producing the polymer of the present invention.

Other preferred catalysts for polymerizing the polymer in the present invention include, for example, tungsten hexachloride or molybdenum pentachloride alone or in combination with an organotin compound such as teF-raphenyltin or a co-catalyst such as water. It will be done.

More preferred catalysts include, for example, catalysts obtained by irradiating tungsten hexacarbonyl or molybdenum hexacarbonyl with light using a high-pressure water chain lamp or the like in the presence of an organic halide such as carbon tetrachloride. In the case of this catalyst system, the temperature at the time of catalyst preparation (at the time of light irradiation) is preferably lower, and preferably the light irradiation is carried out at a temperature range of 0°C to 30°C. This is because catalysts prepared at high temperatures have a small molecular weight.

In the polymerization reaction to obtain the polymer of the present invention, seven polymers are used.
As the solvent for diluting, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as carbon tetrachloride and chloroform, and ethers such as diethyl ether, tetrahydrofuran and dioxane are used. However, in the case of the Ziegler-Natsuta type catalyst, it is preferable to use an aromatic hydrocarbon as the solvent. It is preferable that the monomer is polymerized while being diluted with these solvents, and lθmo
If polymerization is carried out at a high concentration of 1/1 or more, a three-dimensional crosslinking reaction will proceed and gelation will occur easily.

When using a Ziegler-Natsuta type catalyst and a catalyst obtained by irradiating tungsten hexacarbonyl or molybdenum hexacarbonyl with light in the presence of an organic halogenated proboscis, the polymerization reaction can be terminated by using a small amount of alcohol such as methanol. When tungsten hexachloride or molybdenum pentachloride is used, a small amount of ammoniacal alcohol, such as ammoniacal methanol, is used.

Thereafter, insoluble gelled substances, catalysts, etc. are passed through, and then the desired polymer is precipitated with a large amount of lower alcohol such as methanol or aliphatic hydrocarbon such as hexane.

When using a Ziegler-Natsuta type catalyst, additional hydrochloric acid/
It is preferable to remove the catalyst by washing with a methanol mixture.

The obtained polymer is generally a dark red powder, which is soluble in halogenated hydrocarbons, aromatic hydrocarbons, ketone hydrocarbons, etc., and insoluble in aliphatic hydrocarbons and lower alcohols.

Since the polymer obtained in this way has an ethynyl group, it can be used for electron beam resists, photosensitive resins, thermosetting heat-resistant resins, etc., and is particularly useful as photosensitive resins and electron beam resists. When used, it has high sensitivity, high dry etch resistance, and does not generate gas during curing, so it is useful for producing uniform films.

Furthermore, since the main chain of this polymer is composed of conjugated double bonds, it can also be used as a conductive resin material.

Furthermore, by treating a polymer dissolved in a solvent with a gelling solvent, it can be formed into a film shape, hollow fiber shape, etc., and used as a selectively permeable membrane.

Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto.

Example/ A catalyst solution was prepared under a stream of gin. A 20 tnt toluene solution containing 7 mmol of p-diethynylbenzein was added dropwise to this under an argon stream at room temperature. After the cog time, methanol IO- is added to stop the reaction, and after passing the gelled product, the mother liquor is poured into 100-methanol/concentrated hydrochloric acid (10:l) to precipitate the polymer.

The polymer was filtered, further washed with methanol/concentrated hydrochloric acid, then methanol, and dried under vacuum.

The obtained polymer is a dark red powder that is soluble in halogenated hydrocarbons such as polyproform, aromatic hydrocarbons such as benzene and toluene, and ketone hydrocarbons such as acetone, and is soluble in low-grade hydrocarbons such as methanol. Insoluble in aliphatic hydrocarbons such as alcohol and hexane.

Gel permeation chromatography (column is 5
According to the results of molecular weight measurement using HODEX AC403+ kC-JOke), the weight average molecular weight was approximately 0.00,000.

FIG. 1 shows the proton nuclear magnetic resonance spectrum (NMR spectrum) of this polymer in deuterated chloroform.

Example cobenzene 0.0 kOd of WCl6. ! r m mo 1
was added to prepare a catalyst solution, and a 30-benzene solution containing 7 mmol of p-jethynylbenzene # was added dropwise thereto under stirring.

The reaction was carried out at 30° C. under a nitrogen stream, and the consumption rate of 7mer was measured by gas chromatography using xylene as an internal standard. The consumption amount of Natsuma reaches equilibrium in 30 minutes to 7 hours, while the precipitation of gelled products becomes more noticeable with time. Therefore, in order to obtain the desired monomer in a good yield, it is preferable to stop the reaction 73 to 30 minutes after the start of the reaction.

The reaction is stopped by adding a small amount of ammoniacal methanol. The gelled product is separated and the p solution is poured into 300% n-hexane to precipitate the desired polymer. The filtered polymer was washed with methanol and dried under vacuum at room temperature. The yield of the obtained polymer was approximately 0%
According to the results of gel permeation chromatography, the weight average molecular weight was approximately 70,000. The NMR spectrum and other physical properties were consistent with the results of the polymer obtained in Example 1.

Example 3 2 mmol of W (CO)a was added to carbon tetrachloride go-, and the mixture was irradiated with light for 7 hours using a 300 W high-pressure mercury lamp to obtain a catalyst solution. This is p-jethynylbenzene/θmm
The mixture was added dropwise to a go-carbon tetrachloride solution of ol at qo°C under a nitrogen stream. After 1 hour, about 10 methanol was added to stop the reaction, and the solid matter was filtered off. Concentrate the p solution to about
-Heavier due to hexane coθθ-.

The coalescence was precipitated. The polymer was filtered, washed with methanol, and dried under reduced pressure at room temperature. The consumption rate of seven sweet potatoes was measured by the same method as in Example 1, and was about 60. According to this method, there is much less gelled material than in Example-
The final polymer yield was SO. Furthermore, the molecular weight determined by gel permeation chromatography is approximately 2.
However, the molecular weight distribution was more uniform than the polymers obtained in Example 1 and Example 2. The NMR spectrum and other physical properties were consistent with the results of Example 1 and Example 2.

The results of elemental analysis were 9 carbon atoms and 9 hydrogen atoms.

Example d A polymer was obtained in the same manner as in Example 3 except that m-jethynylbenzene was used instead of p-jethynylbenzene.

According to gel permeation chromatography, the molecular weight of the obtained polymer was approximately /200θ, and the color and solubility in solvents were similar to those of the polymers obtained in Examples 1 to 3. Ta.

Example S The polymer obtained in Example A was dissolved in dimethylformamide and spin-coded onto a preparation. This material was covered with a mask pattern and irradiated with light for 3 minutes using a 10 OW high pressure mercury lamp.

This product was immersed in methyl ethyl ketone for S minutes, further washed with hexane, and dried to obtain a highly resolved image.

Example 6 Parts by weight of the polymer obtained in Example 3 and parts by weight of polystyrene with a weight average molecular weight of 1 g were dissolved in 1000 parts by weight of toluene, spin-coded onto a silicon wafer, and dried under vacuum at room temperature. did.

When this material was irradiated with an electron beam using an electron microscope (manufactured by JASCO Corporation, type 3S-!) and the sensitivity was measured, it was found that lo-5
The sensitivity was ~10"C/cdl.The development was performed at lo
This was done by immersing the sample in methyl ethyl ketone containing methanol for 3 minutes.

[Brief explanation of the drawing]

FIG. 1 shows the NMR spectrum (1100M7) of the polymer obtained in Example 1. Patent Applicant: Asahi Kasei Industries Co., Ltd. Representative Patent Attorney Toru Hoshino No. 1! i Procedural amendment (voluntary) October 11, 1988 Patent Application No. 109321 2, Name of the invention Polyethynylphenylacetylene and its manufacturing method 3, Relationship with the person making the amendment Case Patent applicant Osaka Prefecture 1-2-6 Dojimahama, Kita-ku, Osaka (003) Teru Miyazaki, President and Representative Director of Asahi Kasei Industries Co., Ltd. 4, Agent: Gashin Building 586, 3-7 Yotsuya, Shinjuku-ku, Tokyo, Number of inventions increased by amendment None 7, "Detailed Description of the Invention Jr. Brief Explanation of Drawings" column of the specification to be amended, and Drawing 8, Contents of the amendment (as attached) Contents of the amendment ■, Description of the amended specification of the specification shall be corrected as follows. (1) Consistent with the rNMR spectrum on page 13, lines 7 to 9. Figure 2 shows the rNMR spectrum of ``. The color and solubility of the obtained polymer in solvents were the same as in Examples 1 and 2. ” he corrected. (2) Add the following statement between lines 18 and 19 on page 14. Example 7 A polymer was obtained in the same manner as in Example 3 except that a 50:50 mixture of p-jethynylbenzene and 1-diethynylbenzene was used in place of p-jethynylbenzene. The weight average molecular weight determined by chromatography was approximately 11,000, and the color and solubility in solvents were similar to those of the polymers obtained in Examples to Example 4.'' (3) Page 15, line 1 Add the following statement after the eye. "Figure 2 shows the proton NMR (100MllzNMR) spectrum of the polymer obtained in Example 3." ■Patent applicant Asahi Kasei featuring Figure 2 of 0 Correction Attachment A1 of the drawing Kogyo Co., Ltd. Agent Patent Attorney Toru Sahono

Claims (1)

[Scope of Claims] (1) A linear polymer represented by the following structural formula (1). (In the formula, the ethynyl group is bonded to the meta or para position with respect to the main chain of the molecule, and n is the weight average molecular weight of 10
It is a number from 00 to 1 million. ) (2) A compound represented by the structural formula (ff) is converted into an aromatic hydrocarbon or a halogenated compound using a catalyst obtained by irradiating tungsten hexacarbonyl or molybdenum hexacarbonyl with light in the presence of an organic halide. A method for producing a linear polymer represented by structural formula (I), which comprises polymerizing in a hydrocarbon solvent in a temperature range of θ°C to gO°C. HCmiC (In the formula, the ethynyl groups are in the meta or para position with respect to each other.) (B) The compound represented by the structural formula (ff) is replaced with either large tungsten chloride or molybdenum pentachloride. alone or in combination with an organotin compound, water, or other co-catalyst, in a solvent such as an aromatic hydrocarbon, a hegesified hydrocarbon, or a cyclic ether at a temperature of θ°C to 0°C. 1. A method for producing a linear polymer represented by structural formula (1), which is characterized in that the linear polymer is polymerized within a range. (4), @The compound represented by the structural formula (I[) is converted into a compound represented by the structural formula (I[)
1) and the structural formula (θ) in an aromatic hydrocarbon solvent using a catalyst consisting of a combination of compounds represented by
A method for producing a linear polymer represented by structural formula (1), which is characterized in that the polymerization is carried out in a temperature range of 0.degree. C. to gO 0 C. Ti (Ql )4 (2)) AI ((h)3 (N) (wherein, Ql is an alkoxy group with a carbon number of 0 or less, and Q2 is a fulkyl group or an aryl group with a carbon number of -θ or less.)