JPS61113606A - Copolymer of substituted diethynylbenzene compound and production thereof - Google Patents

Abstract

PURPOSE:To obtain a novel copolymer useful as a material for a separating membrane especially for a mixed gas, by copolymerizing a specific benzene compound with another compound by the use of a metallic carbene compound as a catalyst. CONSTITUTION:A benzene compound shown by the formula I (R1 and R2 are 1-20C alkyl, 3-20C cycloalkyl, or silyl replaced with 1-20C alkyl, etc.; ethynyl group is linked to m- or p-position) is copolymerized with a compound shown by the formula II (X and Y are 6-20C aryl, 7-20C arylalkyl, H, Cl, Br, etc.) and/or a compound shown by the formula III (n is 2-8) by the use of one or more metallic carbene compounds selected from Mo, W, Nb, and Ta, to give a copolymer, a linear polymer comprising a repeating unit shown by the formula IV and a repeating unit shown by the formula V and/or formula VI, 1,000-5,000,000 weight-average molecular weight, and a weight ratio of the unit shown by the formula IV to the unit shown by the formula V and/or formula VI of 1/99-99/1.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention has good separation properties and permeability, especially for gases, and is suitable for the separation of gas mixtures into substance mixtures,% This invention relates to a polymer of substituted jetynylbenzene compounds useful as membrane materials and a method for producing the same.

[Conventional technology and problems]

As materials for mixed gas separation membranes, polydimethylsiloxane, polydimethylsiloxane-polycarbonate block copolymers (U.S. Pat.
11. ♂ No. 6), polydimethylsiloxane copolymer (
JP-A No. 3μ26jOa), poly(≠-methylpentene-1) (JP-A No. 77-No. 3), polyalkynes having an alkyl group or phenyl group as a substituent (JP-A No. 7-7)
/ri No. 0407, Tokukai Shojr-/r3ri□! No., Tokukai Akira! ? -/rijOt etc.), polyalkynes with silyl groups as substituents (J, Amer, Chem, Soa, 1
03 +71173 pages.

(lt3)) etc. are known. However, these did not satisfy all of the requirements of gas permeability, separation performance, film formability, and film durability.

[Means for solving problems]

The inventors of the present invention have conducted intensive studies to obtain materials for gas separation membranes with excellent gas permeability, separation properties, membrane properties, and durability. It has been found that a polymer that satisfies the above-mentioned physical properties can be obtained by introducing the above-mentioned properties.

That is, the polymer of the jetinylbenzene compound in the present invention refers to a repeating unit of the structure represented by the following structural formula (Il and the following structural formula (I) and /i, a structure represented by the following structural formula (1)) A weight average molecular weight of 1000 to zooaoo consisting of repeating units.

A linear polymer in which the weight ratio of the structural unit of formula (I) to the formula value) and/or the structural unit of formula (3) is 1/99 to
It is a copolymer with a ratio of 99/1.

(81 and RS in the formula each have a carbon number of l to co0
having as a substituent an alkyl group having 3 carbon atoms and a cycloalkyl group having 0 carbon atoms, an alkyl group having 7 to 2 o carbon atoms, an aryl group having j and 10 carbon atoms, or an arylalkyl group having 7 to 0 carbon atoms. It is a group selected from silyl groups, and the ethynyl group is bonded to the main chain of the molecule at the meta or para position. ) -C=C- Y (X and yt-t in the formula each have a carbon number of t to 20
aryl group having 7 to λθ carbon atoms, arylalkyl group having 7 to λθ carbon atoms, cycloalkyl group having 3 to RO carbon atoms, 1 carbon number
a silyl group having as a substituent an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a 7-aryl group having 6 to 10 carbon atoms, or a lylalkyl group having 7 to 2 o carbon atoms, element, chlorine, bromine This is a group selected from among.

However, cases where X and Y are hydrogen, chlorine, or bromine, and cases where X and Y consist only of silyl groups are excluded. )−〇M=
CH+C)Iz→,=(Seal) One or more of the hydrogens in formula (III) has a carbon number! or: O's alkyl group or r-alkyl group having 1 to 20 carbon atoms is substituted with an aryl rF having 6 to 0 carbon atoms or a silyl group having an arylalkyl group having 7 to 20 carbon atoms as a substituent; Good too. n is an integer from K to t. ) The alkyl group of R1 and R in the structural formula (R) is, for example, a methyl group, an ethyl group, an n-propyl group, an i-
Examples of the cycloalkyl group include a propyl group, a butyl group, and a methyl group, and a cycloalkyl group includes a cyclohexyl group. In addition, examples of the silyl group for R1 and the island include a trimethylsilyl group, a triethylsilyl group, a tri7enylsilyl group, and among these, a trimethylsilyl group is particularly preferred.

Structural formula (X and Y in Ill K include phenyl group, tolyl group, naphthyl group, methyl group, ethyl group,
n- to l-propyl group, butyl group, hexyl group, octyl group, cycloalkyl group, trimethylsilyl group, triethylsilyl group, triphenylsilyl group, hydrogen, chlorine,
Bromine and the like are preferred.

Similarly, substituents in structural formula (1) K include methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, trimethylsilyl group, triethylsilyl group,
Triphenylsilyl group and the like are preferred.

K for obtaining the copolymer of the substituted jetynylbenzene compound in the present invention can be obtained by various methods, but the following structural formula (M
At least one metal carbene compound selected from molybdenum, tungsten, niobium, and tantalum is combined with a compound represented by the following structure (with holes) and/or a compound represented by the following structural formula (VI). It is preferable to copolymerize as a catalyst because of the simplicity of the process. (Compounds (Chrysanthemum, (7) and (6) are hereinafter referred to as monomers.

) (R1% & in the formula is an alkyl group having 1 to 2θ carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms,
A group selected from silyl groups having an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms as a substituent, and the ethynyl groups are mutually metamorphosed. It is attached at the para position or the para position. ) x-c=c-Y (1/) (X and Y of 2M each have from 2 to 20 carbon atoms and are an aryl group of 20,
An arylalkyl group having 7 to 7 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkyl group having 1 to 2θ carbon atoms, an alkyl group having 1 to 7 carbon atoms, or an aryl group having 6 to 7 carbon atoms. or carbon number 7 to 20
A group selected from a silyl group, hydrogen, chlorine, and bromine having an arylalkyl group as a substituent.

However, cases where X and Y consist only of hydrogen, chlorine, or bromine or cases where they consist only of silyl groups are excluded. ) (Formula (VI)
one or more of the hydrogens in is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl group having 7 to 20 carbon atoms
The arylalkyl group may be substituted with a silyl group as a substituent. It is an integer from n to t.

) Compounds represented by the structural formula (g) include 4-bis(propynyl)benzene, i,3-his(fluorovinyl)benzene, 1,! -bis(hexynyl)benzene, 4
Examples include ψ-bis(octynyl)benzene, 43-bis(trimethylsilylethynyl)benzene, 43-bis(triethylsilylethynyl)benzene, 43-bis(triphenylsilylethynyl)benzene, and the structural formula (V
), phenylacetylene,
l-phenylpropyne, l-hexyne, 1-hexy1,
l-octyl-1,2-octyne, 3-octyne, l-phenylhex-7-yne, /-lylophenylacetylene, l-trimethylsilylglobin, /-triphenylsilylpropyne, etc. are also represented by structural formula M). Compounds represented include cyclobutene, cyclopentene, cycloheptene, cyclooctene, 3-methylcyclopente 7, J
, Ir-bistrimethylsilyl octene, l-trimethylsilylbutene, 3-hexylpentene, and the like.

When producing the polymer of the substituted jetynylbenzene compound of the present invention using these compounds, Kd, a catalyst generally used for polymerizing an ethynyl group can be used, but structural formula (2) As the ninth catalyst for selectively polymerizing only one of the ethynyl groups of the jetynyl compound to obtain a linear polymer, for example, a metal carbene catalyst represented by the structural formula (b) is preferable.

Examples of the compound represented by structural formula (2) include methoxyphenylcarbene pentacarbonyltungsten,
Diphenylcarbenepentacarbonyl.

Tungsten, methoxymethylcarbenepentacarbonyltungsten, methoxyphenylcarbenebentacarbonylmolybdenum, diphenylcarbenepentacarbonylmolybdenum, and the like are preferred.

Other preferred catalysts for selectively obtaining a linear polymer using the compound represented by the structural formula (2) include large tungsten chloride or molybdenum pentachloride with the general formula (to)
Examples include catalysts in which a monosubstituted acetylene represented by the following formula is reacted with, and catalysts in which tantalum pentachloride or niobium pentachloride are reacted with a disubstituted acetylene represented by the general formula:

A, -Cm C-H (2) (wherein A1 is an alkyl group having 7 to λO carbon atoms, an aryl group having t to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a cyclo group having 3 to λO carbon atoms) It is a group selected from an alkyl group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a silyl group having as a substituent an arylalkyl group having 7 to 0 carbon atoms. ) A, -Cffi C-As loose (in the formula, 4.13 each represents an alkyl group having 7 to λO carbon atoms,
Aryl group having 6 to 200 carbon atoms, 7 to 20 carbon atoms
an arylalkyl group having 3 to 0 carbon atoms, a cycloalkyl group having 3 to 0 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 0 carbon atoms, or an arylalkyl group having 7 to 10 carbon atoms as a substituent. This is the most selected group among the silyl groups. However, this excludes the case where A2 and A3 are both the above-mentioned silyl groups. ) Examples of the compound represented by the general formula - include phenylacetylene, α- to β-naphthylacetylene, t
--/tin, l-pentyne, l-hexyne, trimethylsilylacetylene, etc. are represented by the general formula -, for example, 2-hexyne, λ-octyne, λ-decyne, l-phenylpropyne, /-phenyl Hexin,
/-trimethylsilylpropyne and the like are preferred. General formula (
2) Alternatively, in order to cause the compound represented by the general formula (■) to react with tungsten hexachloride, molybdenum pentachloride, tantalum pentachloride, or niobium pentachloride, an amount of . Preferably Ko~j
A molar equivalent of monosubstituted acetylene or disubstituted acetylene is heated at 0 to 100°C, preferably λθ, in the polymerization solvent described below.
The reaction may be carried out at ~to°C for 3θ minutes to 2 hours. The subsequent polymerization reaction is carried out by dropping this catalyst solution directly onto the monomer solution.

Examples of solvents that can be used in the polymerization of the present invention using the catalysts described above include aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as carbon tetrachloride and chloroform, and ethers such as diethyl ether and dioxane. are cited as typical examples, and the reaction temperature is generally 0.
A temperature of 720 DEG C. to 720 DEG C., preferably 20 DEG to 10 DEG C. is suitable, and the reaction atmosphere is preferably an inert gas such as nitrogen or argon.

In the present invention, monomers (IV), (7) and (6)
is the sum total! It is preferable to react at a concentration below OrrmVl. In particular, a concentration of K/Omol/l or less is preferable. Further, the concentration of the catalyst used is preferably 1 ml/l or less, particularly K 2 /moVl or less. The molar ratio of catalyst/monomer is preferably less than ゛//j, and especially K I
/10-//1000 is preferred.

In order to obtain a linear polymer in good yield, the reaction rate of the monomer is important! O
It is better to stop the reaction within

When the reaction rate approaches 100To, 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, or isobaric water.

The obtained polymer is generally an orange powder, and the orange color becomes lighter as the ratio of monomers (intermonomers or monomers) to monomer (2) increases. In addition, it is generally soluble in halogenated hydrocarbons, aromatic hydrocarbons, ketone hydrocarbons, ester hydrocarbons, etc., and insoluble in lower alcohols and aliphatic hydrocarbons.

[For production]

The polymers obtained by K in this manner have essentially high gas permeability due to their bulky substituents, and furthermore, by crosslinking the ethynyl groups in the side chains using heat or electromagnetic waves, they can withstand high temperatures and pressures. The durability of the film can be increased.

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 to these examples.

Example/Toluene! 111tK tantalum pentachloride O0λmmal
After adding t- and stirring for 30 minutes, l-trimethylsilylpsepine/mmol was added, and the mixture was further reacted at room temperature for 1 hour to obtain a catalyst solution. This catalyst solution was added to 10 d of toluene with 43-His(
trimethylsilylethynyl)benzene! mno1 and/
-) was added dropwise to a monomer solution in which jmmol of limethylsilylprobin was dissolved and reacted at 60°C for 2 hours. All reactions up to this point were conducted under a nitrogen stream. After stopping the reaction with a small amount of methanol, the filtered p solution was poured into about 300 methanol to precipitate a copolymer.

According to 130-NMR of the obtained copolymer, the composition ratio of the 43-bis(trimethylsilylethynyl)peazea moiety and the /-)limethylsilylpropyy moiety in the copolymer was approximately 3/co. The weight average molecular weight of GPCK is approximately 3
It was 20,000.

"The spectral position in C-NMR is around -3 to +3P, the carbon of the trimethylsilyl group is around 27P, and the carbon of the ethynyl group is around /20 to /Jjffll+K near the carbon of the methyl group and around 1O6pp. , the carbon of the benzene ring is 73!~/!θPK, and the carbon of the conjugated double bond is observed.

A film having a thickness of approximately 10 μm was prepared by casting a solution of 201 parts of the obtained polymer dissolved in ethyl cellosolve. The hydrogen and nitrogen permeability of this film was measured and it was found to be a highly durable film that showed no weight loss at 3 ROCT.

Example 2 1,4C-bisprovinylbenzene (
A copolymer was obtained in the same manner as in Example 1, except that CH3-=-()-=-CH3) and l-phenylpropyne were used, and a combination of tantalum pentabromide and /-7 erglobin was used as a catalyst. Ta. The weight average molecular weight of the obtained copolymer was determined by GPC to be approximately 210,000, and the weight average molecular weight to be determined by 13C-NMRK was approximately 4 h.
The composition ratio of the bisprovinylbenzene moiety and the l~phenylglobin moiety was approximately j/II.

Example 3 Cyclopentene ioom polishing IK 1.4cm screw (
trimethylsilylethynyl)benzene/<7yy1mo
1 was added to prepare a monomer solution. As a solution catalyst, 0.2 mInol of methoxyphenylcarbenpentacarbonyltungsten was added, and the reaction was carried out at 10° C. for 2 hours under nitrogen. The subsequent recovery of the polymer was carried out in Examples 1 and 2.
This was done in accordance with.

The composition ratio of the moiety derived from 4≠-bis(trimethylsilylethynyl)benzene and the moiety derived from cyclopentene in the obtained copolymer was approximately j// according to H-NMRK.The weight average molecular weight according to GPCVc was It was about 130,000.

Example A copolymer was obtained in the same manner as in Example 3, except that j,t-ditrimethylsilylcyclooctene was used instead of a-pentene. The weight average molecular weight of the obtained nine copolymer by GPC was /lr million. 1, tl in the copolymer,
The composition ratio of the moiety derived from -bis(trimethylsilylethynyl)benzene and the moiety derived from j,r-ditrimethylsilylcyclooctene was approximately r7i according to 13C-NMRK.

Claims (2)

[Claims] (1), a weight average molecular weight of 1,000 or more consisting of a repeating unit of the structure represented by the following structural formula (I) and a repeating unit of the structure shown by the following structural formula (I) and/or the following structural formula (2). 5,000,000 linear polymer in which the weight ratio of the structural unit of formula (I) to the structural unit of formula (II) and/or formula (III) is 1/99 to 1/99.
A copolymer with a ratio of 99/1. ▲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 Carbon number 6
-20 aryl group or silyl group having 7-20 carbon atoms as a substituent, and the ethynyl group is bonded to the meta or para position to the main chain of the molecule. It is. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (X and Y in the formula are each an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms,
cycloalkyl group having 3 to 20 carbon atoms, alkyl group having 1 to 20 carbon atoms, alkyl group having 1 to 20 carbon atoms, aryl group having 2 to 20 carbon atoms, or 7 carbon atoms
or a group selected from a silyl group having 20 arylalkyl groups as a substituent, hydrogen, chlorine, and bromine. However, when X and Y consist only of hydrogen, chlorine, and bromine,
Or except when it consists only of silyl groups. )-CH=C
H-(CH_2)-_n(III) (One or more of the hydrogens in formula (III) has 1 to 2 carbon atoms
0 alkyl group or a C1 to C20 alkyl group or a C6 to C20 aryl group or a C7
It may be substituted with a silyl group having 1 to 20 arylalkyl groups as substituents. n is an integer from 2 to 8. ) (2) When producing a linear polymer consisting of a repeating unit of the structure represented by the structural formula (I) and a structural unit represented by the structural formula (II) and/or the structural formula (III), molybdenum, tungsten, Using at least one metal carbene compound selected from niobium and tantalum as a catalyst, a compound represented by the following structural formula (IV), a compound represented by the following structural formula (V) and/or the following structural formula (
A method for producing a copolymer, comprising copolymerizing a compound represented by VI). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) (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. ) X-C≡C-Y(V) (X and Y in formula (V) each have 6 to 20 carbon atoms
aryl group having 7 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, 1 carbon number
selected from a silyl group having an alkyl group having 1 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, hydrogen, chlorine, and bromine; It is a basic group. However, when X and Y consist only of hydrogen, chlorine, and bromine,
and excluding cases consisting only of silyl groups. )▲Mathematical formulas, chemical formulas, tables, etc.▼(VI) (One or more of the hydrogens in formula (VI) has 1 to 20 carbon atoms
an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl group having 7 carbon atoms;
It may be substituted with a silyl group having 1 to 20 arylalkyl groups as substituents. n is an integer from 2 to 8. )