JPS61113605A - Polymer of substituted diethynyl benzene compound and production thereof - Google Patents

Abstract

PURPOSE:To obtain a novel polymer useful as a material for a separating membrane especially for a mixed gas, having improved separating properties and permeability, by polymerizing a specific benzene derivative by the use of a metallic carbene compound as a catalyst. CONSTITUTION:A benzene derivative [e.g., 1,4-bis(propenyl)benzene, etc.] shown by the formula I (R1 and R2 are 1-20C alkyl, 3-20C cyclo alkyl, or silyl containing 1-20C alkyl or 6-20C aryl or 7-20C arylalkyl as substituent group; ethynyl group is linked to meta- or para-position) is polymerized by the use of one or more metallic carbene compounds (e.g., methoxyphenylcarbene pentacarbonyl tungstene, etc.) selected from Mo, W, Nb, and Ta as a catalyst in ratio of the catalyst/the compound shown by the formula I of preferably 1/10-1/1,000, to give a linear polymer having a repeating structure unit shown by the the formula II, having 1,000-5,000,000 weight-average molecular weight.

Description

Detailed Description of the Invention [Industrial Application] The present invention has good separation properties and permeability, especially excellent separation properties and permeability for gases, and is suitable for use in substance mixtures, 411 and gas mixtures. A polymer of a substituted jetynylbenzene compound useful as a material for separation membranes and a method for producing the same are disclosed.

[Conventional technology and problems]

Polydimethylsiloxane, polydimethylsiloxane-polycarbonate block copolymer (U.S. Patent No. 10.μj6, U.S. Patent No. 3,1
71/, Rirt No.), polydimethylsiloxane copolymer (41 Kaisho! Otsu-kot J-0 Hiro issue), poly(Hiro-Methyl pair f7-/) (Japanese Patent Kokai Show! 7-Hiro issue 203), Polyalkynes having an alkyl group or phenyl group as a substituent (JP-A No. 7-7-7-0607, JP-A No. 1r Jyor, JP-A No. 1/Pt06, etc.), polyalkynes having a silyl group as a substituent ( J,AffI@r,Chew,
Soc, 10j + 7u'H page (/913')) are known. However, these did not satisfy all of gas permeability, separability, film formability, and membrane durability.

[Means for Solving the Problems] The present inventors have obtained a material for gas separation membranes that has excellent gas permeability, separation performance, membrane σ properties, and durability. It has been found that a polymer satisfying the above physical properties can be obtained by further introducing a crosslinking functional group into the 1-'IJ alkyne having the group.

That is, the polymer used in the present invention is a linear polymer having a weight average molecular weight of 000 to s, ooo, ooo, consisting of repeating structural units represented by the following structural formula.

R.

(R1 and R3 in the formula each have carbon numbers / to 20
Among the silyl groups having an alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkyl group having 1 to 2Q carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms as a substituent. This is a carefully selected group, and the ethynyl group is bonded at the meta or meta position relative to the main chain of the molecule. ) Structural formula (R1 and R2 alkyl groups in INK include, for example, methyl group, ethyl group, n-propyl group,
Examples of the cycloalkyl group include an i-propyl group and a butyl group, but a methyl group is particularly preferred, and a cyclohexyl group is an example of the cycloalkyl group. Also, R1 and R,
Examples of the silyl group include a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group, and among these, a trimethylsilyl group is particularly preferred.

Various methods can be used to obtain the polymer of the substituted jetynylbenzene compound in the present invention. It is preferable to use a metal carpene compound as a catalyst because of the simplicity of the process.

Formula 1 (R1 and R2 in the formula are each an alkyl group having 1 to λ0 carbon atoms, a cycloalkyl group having 3 to 2 o carbon atoms,
A group selected from silyl groups having an alkyl group having 1 to 2 o carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms as a substituent, and the ethynyl groups are in the meta position with respect to each other. 1+ is bonded to the meta position. ) Specific examples of compounds represented by structural formula (If) include:
/, IA-bis(fluorovinyl)benzene, i,3-his()tx vinyl)benzene, /, 3-bis(hexynyl)benzene, 4-bis(octenyl)benzene,
/, 3-bis(trimethylsilylethynyl)benzene,
43-bis(triethylsilylethynyl)benzene, 4
Examples include 3-bis(triphenylsilylethynyl)benzene.

When producing the polymer of the substituted jetynylbenzene compound of the present invention using these compounds, catalysts that are generally used for polymerizing ethynyl groups can be used. For example, a metal carpene catalyst represented by the structural formula (Ml) is preferable as a catalyst for selectively polymerizing one of the ethynyl groups of the jetynyl compound represented by the following formula to obtain a linear polymer.

Specific examples of compounds represented by the structure (200) include methoxyphenylcarpenpentacarbonyltungsten, diphenylcarpenpentacarbonyltungsten, methoxymethylcarpenpentacarbonyltungsten, and methoxy722carpentacarbonyltungsten. Carbonylmolybten, CyphenylcarpenbentacarbonylmolJ
7'7" etc. are preferred.

Other preferred catalysts for selectively obtaining linear polymers using the compound represented by the structural formula (1) include the general formula (conversion) to tungsten hexachloride or molybdenum pentachloride.
Catalysts in which a monosubstituted acetylene represented by the general formula M is reacted with, or tantalum pentachloride or niobium pentachloride reacted with a disubstituted acetylene represented by the general formula M can be mentioned.

Al-c=c-H(5) (in the formula, human represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, and an arylalkyl group having 3 to 20 carbon atoms; A group selected from a cycloalkyl group of O, a furkyl group having 1 to 20 carbon atoms, an aryl group having 2 to 20 carbon atoms, or a silyl group having as a substituent an arylalkyl group having 7 to λO carbon atoms. There is.) A Tomi-〇 = E C-As ('/
) - (In the formula, Goose and As each represent the number of carbon atoms/fk
Alkyl group having 0 carbon atoms, aryl group having 6 to 20 carbon atoms, arylalkyl group having 7 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, 1 to λ0 carbon atoms
The alkyl group or aryl group having 7 to 20 carbon atoms is a group selected from silyl groups having an arylalkyl group having 7 to 20 carbon atoms as a substituent. However, this excludes the case where A4 and AI are both the above-mentioned silyl groups. ) Examples of compounds represented by the general formula (sub) include phenylacetylene, α- to β-naphthylacetylene, /-7'tin, l-pentyne, l-hexyne, trimethylsilylacetylene, etc. Examples of the compounds represented include 2-hexyne, λ-octyne,
Preferred are x-decyne, l-phenylpropyne, /-phenylhexyne, I-t+)J tylsilylpropyne, and the like.

When a compound represented by general formula (g) or general formula (g) is reacted with large tungsten chloride, molybdenum pentachloride, tantalum pentachloride, or niobium pentachloride, K is equivalent to 1 mole of the corresponding metal chloride, /-10 molar equivalents, preferably 2 to 3 molar equivalents of mono- or disubstituted acetylene are heated at 0 to ioo°C in the polymerization solvent described below.
Preferably, the reaction may be carried out at Fi20 to 10°C for 30 minutes to 2 hours. The subsequent polymerization reaction is carried out by dropping this catalyst solution directly into the monomer solution.

Solvents that can be used when polymerizing the substituted jetynylbenzene compound of the present invention using the catalyst described above include:
Aromatic hydrocarbons such as benzene and toluene, carbon tetrachloride,
Typical examples include hacegenated hydrocarbons such as chloroform, ethers such as diethyl ether, and dioxane, and the appropriate reaction temperature is generally 0 to 10°C, preferably λ0 to 10°C, and even more suitable for reaction temperatures. As for the atmosphere, the reaction is preferably carried out in an inert gas such as nitrogen or argon.

In the present invention, monomer (II) is preferably reacted at a concentration of j Omol/1 or less, and 49 K/
(The concentration is preferably 7 mol/l or less. Also, the concentration of the catalyst used is preferably j moVl or less, especially / m
A concentration of ol/l or less is preferred. The molar ratio of catalyst/monomer is preferably below //j, and especially VC//10 to 17ioo
o is preferred.

In order to obtain a linear polymer with a good yield, the reaction rate of the monomers should be
It is better to stop the reaction within

When the reaction rate approaches 100%, more gel-like substances are produced.

The polymerization reaction can be stopped using a lower alcohol such as methanol, a lower ketone such as acetone, water, or the like.

The obtained polymer is generally an orange powder, and is generally soluble in halogenated hydrocarbons, aromatic hydrocarbons, ketone hydrocarbons, ester hydrocarbons, etc., and insoluble in lower alcohols and aliphatic hydrocarbons. It is.

[For production]

The polymer obtained in this way has essentially high gas permeability due to its bulky substituents, and by crosslinking the ethynyl groups in the side chains using heat or electromagnetic waves, it can be used as a membrane under high temperature and high pressure. The one with high durability is K.

Furthermore, since the ethynyl group in this side chain can be crosslinked by electromagnetic waves, it can also be used as an electron beam resist or a photosensitive resist.

〔Example〕

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

Example 1 /, J-k'su()IJ/Tylsilylethynyl)Hensen77mmalt)Dissolved in luene lO-t
,,% Zimmer solution. Separately, 0.2 mtool of large tungsten chloride was added to toluene j-, and after stirring for 30 minutes, phenylacetylene/mmol was added and stirred at room temperature for 1 hour to obtain a catalyst solution. This catalyst solution was added dropwise to the above monomer solution and allowed to react at 30°C for 2 hours with stirring. All operations up to this point were performed under a nitrogen stream. After stopping the reaction by adding about 1,000 g of methanol, the filtered p solution is poured into about 1,000 g of methanol, and a polymer precipitates out. The precipitated polymer is passed through, thoroughly washed with methanol, and dried under vacuum at room temperature. The polymer yield was about 27 cm, an orange powder. According to gel permeation chromatography (hereinafter referred to as GPC) K, the weight average molecular weight was about ZOOO. In C-NMR, the carbon of the trimethylsilyl group is found to overlap with the carbon of the ethynyl group near θ-, and the phenyl and conjugated double-bonded carbons appear in the vicinity of 107yp. Furthermore, in the infrared spectrum, C Mi C is ko / 00elft
“Appears nearby.

Examples λ to t A compound was obtained in the same manner as in Example 1 except that the monomers and catalysts were changed to the compounds shown in Table 1. The weight average molecular weight of the obtained polymer is also shown in Table/.

(Left below) Application example/ A solution of 20% by weight of the polymer obtained in Example 7 dissolved in toluene was filtered using a Millipore membrane filter T.
M-JPK was uniformly impregnated and the permeability of hydrogen and nitrogen was measured using a gas permeation tester.The ilm did not show any weight loss up to about 3℃ and 0℃, and the gas permeation rate changed to the above gas permeation rate after about 100 hours at 100℃. There was no.

Claims (2)

[Claims] (1), consisting of repeating structural units represented by the following structural formula (I), with a weight average molecular weight of 1,000 to 5,0
00,000 linear polymer. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (R_1 and R_2 in the formula are each an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or A group selected from silyl groups having an aryl group having 7 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms as a substituent, and the ethynyl group is at the meta or para position with respect to the main chain of the molecule. (It is a combination.) (2), consisting of repeating structural units represented by structural formula (I), with a weight average molecular weight of 1,000 to 5,000
0,000, a compound represented by the following structural formula (II) is polymerized using at least one metal carpene compound selected from molybdenum, tungsten, niobium, and tantalum as a catalyst. A method for producing characteristic polymers. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (R_1 and R_2 in the formula each have 1 to 20 carbon atoms.
Among the silyl groups having an alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms as a substituent. The ethynyl groups are bonded to each other in the meta or para position. )