JPS6049013A - Polymerization of diethynyl compound - Google Patents

Abstract

PURPOSE:In polymerizing a diethynyl compound containing ethynyl groups directly bonded to benzene ring, etc., to prepare a linear polymer containing ethynyl groups in the molecule in high yield, by using a specific metal carbene compound as a catalyst. CONSTITUTION:A diethynyl compound [e.g., compound shown by the formula I (R1-R4 are H, 1-10C alkyl, etc.)] having two ethynyl groups directly bonded to a benzene ring or a ring wherein 2-5 benzene rings are condensed is polymerized by using a metal carbene compound [e.g., compound shown by the formula II (M' is Nb, or Ta; L' is cyclopentadiene, etc.; R7 and R8 are H, 1-10C alkyl, etc.), etc.] of VB group of periodic table or a metal carbene compound [e.g., compound shown by the formula III (M is W, or Mo; R5 is 1-10C alkoxy, etc.; R6 is 1-10C alkyl, etc.; L is carbonyl, etc.) etc.] of VIB group as a catalyst, to give a polymer (e.g., polymer shown by the formula IV, etc.) containing an ethynyl group in the molecule. USE:A heat-resistant material, electron radiation resist material, etc.

Description

[Detailed Description of the Invention] The present invention provides a heat-resistant material, an electronic cord/distoy, 1'$,
), etc., and relates to a method for producing a polymer having an ethynyl group in the molecule, which is useful for applications such as It relates to the method of polymerizing a jetynyl compound in which the group is directly bonded in the presence of I to obtain an IJ7 compound having an ethynyl group in the molecule. .

Fl-resin developed by Harcules is known as a polymer having an ethynyl group at the end of the molecule.

11 Heresin is Tokko Akira! fll-g, :Z'l. vinegar,
Tokuko Shou 3 Otsu-ri 3 Zo 3 Ri No., JP 419-, /θ7 Gugu, X-Yumi. It is obtained by reacting the group in the presence of an aromatic compound (hereinafter referred to as an aromatic compound) that promotes the formation of an aromatic compound.

IJ, Ninnno 1-compound, Eya as aromatization melting medium
For example, nickel bisacrylic acid, nickel carbonyl bistriphenylphosphine, cyanide yusocurbistriphenylphosphine, and a combination of nickel acetylacetonate and triphenylphosphine are known. In addition, as an aromatization catalyst, Zie
gler) Glass catalysts, such as titanium and monocrylate
A combination Q of r-diethylaluminum is also known. However, when jetynylbenzene is polymerized using the above-mentioned aromatization catalyst, it is difficult to obtain a proper polymerization of sieve molecules, but if ML<reaction≧W is raised too much, a gelled product is produced. The obtained 6m compound is an S-branched borinoenylene compound having an ethynyl group at the end of the molecule.

On the other hand, a number of methods are known for producing aliphatic J-type polymers by arranging monocochinyl compounds. For example, LLlcr
7th spring of omo1c+culeII'aH, issue 7.
Tanges hexachloride 1 or 6, as described in vol. 9 of the same magazine, pages 2g to 73/pages (7776), volume 9 of the same magazine, Method using molynodene chloride as a catalyst, Polymerii, p i; A
,2,,? Volume, July issue, /l, A, 7m, /6
As reported in 1966, there is a method in which a group VIB metal carbonyl compound irradiated with ultraviolet rays in the presence of carbon tetrachloride is used as a catalyst. However, when a jetinyl compound, such as jetinylbenzene, is polymerized using the above VIB group compound as a catalyst, a large number of cross-linked gelled products are generated, and the yield of a solvent-soluble linear polymer useful for electron beam materials etc. is reduced. It gets lower.

The present inventors took note of these problems and, through intensive research and polymerization of jethinyl compounds, came to invent a method for producing linear polymers having ethynyl groups in the molecule with good yield. .

That is, the present invention provides a structure in which two ethynyl groups are directly bonded to a benzene salt or a monkey formed by condensing 2 to 3 benzene rings.
7. A method for obtaining a polymer having an ethynyl group in the molecule by polymerizing a jetynyl compound, which is characterized in that a metal carbene compound of group VB or group VIB of the periodic table is used as a catalyst. It is about the method.

The polymerization method of the present invention is particularly suitable for obtaining a polymer having a structure represented by the following general formula (II) in a high yield from a jetinyl compound represented by the following general formula (I) in a high yield.

(It1 to 1 and 4 in the formula are hydrogen, carbon number/゛ to lθ
an alkyl group, a cycloatkyl group or an aryl group having 6 to 10 carbon atoms, a group selected from the group S1111, and an ethynyl group bonded to the meta or para position relative to Ω on the molecule. It is something. ) The polymer having the structure represented by the above general formula (II) is '
α, X, Shiyu, etc., because it has a high sensitivity and is susceptible to plasma etching resistance.

It is useful as a material such as Kameko υ resist, Also, this polymer is mainly; 34
．． : Since it has a conjugated stop bond, it can also be used as an organic semiconductor material and a 14L material.

In the present invention, the monkeys formed by combining the benzene lattice with the K or S side line refer to Naphtat Nzi, An-1 Rasen monkey, Phenan-Len monkey, 1-Lihuenylene term, etc. As a 7-enanylated @ compound in which Shikei is directly bonded, compounds as shown in Table-/ can be found. It is a group selected from a cycloargyl group or an aryl group or a halogen of 1 to IO. In particular, tungsten compounds, molynodene compounds, ono compounds, and tantalum compounds are effective.

Among the metal carbene compounds of the VTl group and VIB group, when compounds represented by the following general formulas (Ill) and (r) are used as a touch, a spheroidal compound having a cornanyl group can be obtained with a high sieve rate. It is passed through the hemorrhoids to obtain a polymer having the (3) structure of the +1 self formula (II).

(ILi +: 1 kundas 1 in the formula) or molinodene,
R5 is γ no 1 of charcoal blower/muishi t'0. J-hesi group, or charcoal; Homare t/, 1 furino group with f to /θ, circle indicates γ-royal group with carbon number / to /θ, cycloμfurkyl group with 3 to 10 carbon atoms, charcoal A d, 6it to 1
0 aryl group, or hydrogen, carbonyl, cyclopencdiene, or triphenylphosphine. ) (In the formula, M' is niobium or tantalum, L' is cyclopentanene or/and/・p-an, & and R8 are hydrogen, an alkyl group with a carbon number of / to /θ, or a carbon number of t to l
It is a 1-reel group of θ. ) Metal carbene compounds represented by formula (M) include, for example, methoxyphenyl carbene carbonyl tungsten, diphenyl carbene carbonyl tungsten, methoxymethyl carbene carbonyl tungsten, methoxyphenyl carbene pentacarbonyl molybutene. , dienylcarbe)/pentacarbonylated phosphorus “None.

/') xy, dezurcarbene, pentacarbonyldene, etc. are obtained. These M'A may be used in Seidoku or in multiple combinations [7]. .

It is best to polymerize in a solvent, and suitable solvents include benzene, toluene, aromatic hydrocarbons such as carbon tetrachloride, high-IJ anhydride hydrocarbons such as RE-form, and diethyl. Typical examples include ethers, ethers, furan, and dioxane.

In the present invention, the jetinyl compound has 50 mo +/
It is preferable to react once less than /θ+n
+:+l/ is preferably set once below. In addition, the catalyst used is preferably 5"b+ol/ once below, especially /
A limit below moVl is preferred. .

It is preferable that the molar ratio of the sister/jethinyl compound is less than or equal to
(, 4&nii. ~ name...) is preferable.If the amount of catalyst used is too large, the molecular weight of the polymer that rises will become smaller, and if it is too small, the reaction will be delayed. Become slow.

The reaction is preferably carried out under an atmosphere of an inert gas such as υ or argon, and the reaction temperature is 0 to 700°C, preferably 30 to 700°C. The higher the reaction temperature, the faster the reaction rate will be, but the life of the catalyst will be shorter.

L:! In order to obtain the 1116 compound in good yield, it is best to stop the reaction when the reaction rate of the jetynylated metal is within qsi. When the reaction rate approaches ioo@, more products are produced in Ge A1. The polymerization reaction can be terminated using lower alcohols such as methanol, lower alcohols such as acetone, acetonylyl, water, and the like.

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

Example/ Benzene! ; methoxyphenylcarbene for gJ;
Pentacarbonyltungsten/mmol was added to prepare a catalyst solution. To this, p-jethynylbenzene lOnI
A solution prepared by dissolving mDl in benzene/θd was added dropwise to a nitrogen stream -F, and reacted at O<0>C. When the amount of monomer consumed was measured by gas chromatography using xylene as an internal standard, it was found that approximately 3-5 monomers were consumed in S hours. After about 77 tons of 21 tons were added to stop the reaction, the reaction solution was poured into 100 vi of n-hexane to precipitate the pre-coalescence, which was dried once in a humid atmosphere in a room. The yield is approx.

It was Chi. The polymer thus obtained had an average dielectric strength of about 4J/ooo in terms of gel chemistry p-matogosof-f-.

Tsune Jr., bll, 2-10 ri・-1 nigari b mark'' and the other number using pea no no, L person'L,, 1b11 no, and the company also performed a star. Match the result to -1.

Table - Ko

Claims (4)

[Claims] (1) A method of obtaining a polymer having ethynyl groups in the molecule by polymerizing a jetynyl compound in which 5 ethynyl groups are directly bonded to a benzene ring or 5 to 5 benzene rings. Smell °C, periodic table group VB or VIB
1. A method for producing a jetynyl compound, which is characterized by using a group metal carbene compound as a catalyst. (2) A patent claim in which the jetynyl compound is a compound represented by the following general formula (1), and the polymer having an ethynyl group in the molecule has a structure represented by the following general formula (n). A method for polymerizing a jetinyl compound according to scope 1. (R, ~ft4 in the formula is hydrogen, γ of carbon number / to 10
alkyl group, a Schiffle group having 6 to 10 carbon atoms, r) a γ-alkyl group, a γ-lyl group, a group selected from hapgen, and an ethynyl group bonded to the meta-position or the meta-position with respect to the main chain of the molecule. It is. ) (3) The method for combining jetinyl compounds according to claim 1, wherein the VIB group metal carbene compound is a molybdenum or tungsten carbene compound. (4) A carbene compound of molybdenum or tungsten has the general formula (M) Description 0] Di-modunyl compound. (+) Claims j+l in which the VB group gold carbene compound is a niobium, syn, or syl carbene compound
-No' A method for polymerizing a jetinyl compound as described in Jl. (ljl, 21)゛or the carbene compound of tanta-9 is -
A method for polymerizing a compound of the patented cocoon j (3rd shell) represented by IJ formula (1"0).