JPH05271338A - Disubstituted diphenylacetylene polymer - Google Patents

Abstract

PURPOSE:To obtain the subject polymer which has a specific recurring units and is useful as a gas-separation membrane, liquid-separation membrane, a semiconductive material, which are excellent in functions and stability. CONSTITUTION:The objective polymer has the recurring units of formula I [R1 is branched alkyl, trialkylsilyl; R2 is alkyl which may be substituted with halogen atoms, trialkylsilyl, halogen]. It is obtained by polymerization of a compound of formula II, for example, 4-t-butyl-3'-methyldiphenylacetylene.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a disubstituted diphenylacetylene polymer. More specifically, the present invention relates to a novel disubstituted diphenylacetylene polymer useful as a gas separation membrane, a liquid separation membrane, a semiconductor material, a resist material, a chromic material, a biocompatible material and the like.

[0002]

2. Description of the Related Art In recent years, with the rapid expansion of technological applications of polymer chemistry, interest in polymers having new and sophisticated functions has increased, and As a kind of functional polymer, a polyacetylene polymer obtained by synthesizing an acetylene compound as a raw material monmer has been attracting attention.

This polyacetylene polymer has a unique property as, for example, a conductive polymer, and its application to various fields including electronics has been attempted. Further, the diphenylacetylene-based polymer, which is one of them, has been attracting attention for its application to gas separation membranes, electronic materials, optical materials and the like. In particular, this diphenylacetylene polymer is known to be a polymer having a high gas separation ability, and is expected to be applied to applications such as chemical engineering, medical use, and combustion use. It has been reported that this diphenylacetylene polymer is soluble in an organic solvent, can be easily formed into a thin film, and is stable to air.

However, although attention has been paid to its characteristics, at present, the further search for diphenylacetylene-based polymers and the study of their applications have not proceeded unexpectedly. It is considered that the reason is that the acetylene compound as a raw material monomer generally has high reaction activity, is difficult to handle, and has little basic accumulation in chemical research to date.

However, since this diphenylacetylene-based polymer, which is a material leading the next-generation technology, is an extremely important substance, it is desired to break through the present situation. This invention has been made in view of the above circumstances, paying attention to the characteristics of diphenylacetylene-based polymers, and further expected to be applied to conductive polymers, semiconductor materials, resist materials, electrochromic materials, etc. The object is to provide a new diphenylacetylene polymer.

[0006]

In order to solve the above problems, the present invention provides the following general formula:

[0007]

[Chemical 2]

(In the formula, R ₁ represents a branched alkyl group or a trialkylsilyl group, and R ₂ represents an alkyl group which may be substituted with a halogen atom, a trialkylsilyl group or a halogen atom). Provided is a novel disubstituted diphenylacetylene polymer having a repeating unit.

Examples of the branched alkyl group represented by R ₁ include isopropyl group, isobutyl group, tertiary butyl group, 1-methylpropyl group, isopentyl group, 1-methylbutyl group, 2-methylbutyl group,
Examples are 1,1-dimethylpropyl groups and the like, and among them, those having 4 or less carbon atoms are preferable. The trialkylsilyl group for R ₁ and R ₂ includes a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a methyldiethylsilyl group,
Dimethylethylsilyl group, dimethylpropylsilyl group,
Examples thereof include a dimethylisopropylsilyl group, a methylethylisobutylsilyl group and a diethylisopentylsilyl group. Of these, a trialkylsilyl group in which each alkyl group has 3 or less carbon atoms is preferable.

Examples of the alkyl group which may be substituted with a halogen atom of R ₂ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, 2-methylpentyl group, 1,1. -A dimethylpropyl group, or those in which some or all of their hydrogen atoms are replaced with halogen atoms. The latter halogen-substituted alkyl groups include chloromethyl group, chloroethyl group, dichloroethyl group, chloropropyl group, trichloromethyl group, monofluoromethyl group, trifluoromethyl group, monofluoroethyl group, perfluoroethyl group, perfluoro group. Specific examples thereof include a propyl group and a perfluorobutyl group. Among them, carbon number 2
The following chain alkyl groups or their perfluoro-substituted groups are preferable.

The halogen atom for R ₂ is a fluorine atom,
A chlorine atom, a bromine atom and an iodine atom are shown, and among them, a fluorine atom is preferable. More specific examples of the disubstituted diphenylacetylene compound of the present invention include the following. Two
3'-bistrimethylsilyldiphenylacetylene,
3,3'-bistrimethylsilyldiphenylacetylene, 4,3'-bistrimethylsilyldiphenylacetylene, 4,4'-bistrimethylsilyldiphenylacetylene, 3-trimethylsilyl-3'-triethylsilyldiphenylacetylene, 3-dimethylethylsilyl-
3'-triethylsilyldiphenylacetylene, 3,
3'-bistriethylsilyldiphenylacetylene,
4,4'-bistripropylsilyldiphenylacetylene, 3-trimethylsilyl-3'-methyldiphenylacetylene, 4-trimethylsilyl-3'-ethyldiphenylacetylene, 4-trimethylsilyl-4'-propyldiphenylacetylene, 3-trimethylsilyl-3 '
-Monofluoromethyldiphenylacetylene, 4-trimethylsilyl-3'-trifluoromethyldiphenylacetylene, 4-trimethylsilyl-4'-trifluoromethyldiphenylacetylene, 4-trimethylsilyl-
4'-perchloroethyldiphenylacetylene, 4-trimethylsilyl-3'-perfluoropropyldiphenylacetylene, 3-trimethylsilyl-4'-fluorodiphenylacetylene, 4-trimethylsilyl-4'-
Fluorodiphenylacetylene, 2-triethylsilyl-3'-chlorodiphenylacetylene, 4-trimethylsilyl-3'-bromodiphenylacetylene, 3-isopropyl-4'-trimethylsilyldiphenylacetylene, 4-isobutyl-4'-trimethylsilyldiphenylacetylene, 4 -Tert-butyl-3'-trimethylsilyldiphenylacetylene, 4-tert-butyl-4'-trimethylsilyldiphenylacetylene,
4-Isopentyl-4'-trimethylsilyldiphenylacetylene, 4-tert-butyl-3'-methyldiphenylacetylene, 3-tert-butyl-4'-
Methyldiphenylacetylene, 4-tert-butyl-3'-ethyldiphenylacetylene, 4-tert-butyl-3'-propyldiphenylacetylene, 3-
Tert-Butyl-4'-trifluoromethyldiphenylacetylene, 4-tert-butyl-4'-trifluoroethyldiphenylacetylene, 4-tert-butyl-3'-fluorodiphenylacetylene, 4-
Tertiary butyl-4'-fluorodiphenylacetylene, 4-tert-butyl-4'-bromodiphenylacetylene, 4-tertiarybutyl-4'-iododiphenylacetylene.

For example, the disubstituted diphenylacetylene-based polymer of the present invention exemplified as above can be produced by a conventional method.

[0013]

[Chemical 3]

Obtained by polymerizing the compound of
You can Raw material monomer compound
It For example R₁And R₂Is a trialkylsilyl group
In the case of external compounds, R ₁With substituted phenylacetylene
R₂Substituted halogen benzene in the presence of palladium catalyst
Can be produced by Heck reaction
It

As the palladium catalyst in this case, an appropriate one such as an inorganic acid salt of palladium, an organic acid salt, a palladium complex compound or the like can be used, and a phosphine compound or the like is used as a ligand in the reaction system. May be. A copper (I) compound can also be used as a cocatalyst. It is also effective to use triethylamine or other amine compound as a diluent. The reaction temperature is usually 0
The reaction time can be set to about 30 minutes to 24 hours.

On the other hand, when _one or both of R ₁ and R ₂ is a trialkylsilyl group, the halogen-substituted diphenylacetylene compound is reacted with a lithium reagent such as alkyllithium or a Grignard reagent, and then the trialkylsilyl group is reacted. It can be produced by reacting with a halide and silylating. In this case, a diluent such as ether or tetrahydrofuran may be used.

The reaction temperature can be usually about -70 to 10 ° C, and the reaction time can be about 30 minutes to several hours. For example, the disubstituted diphenylacetylene compound produced by the above method can be polymerized alone or in combination of two or more kinds. As the polymerization initiator, for example, transition metal compounds such as molybdenum, tungsten, niobium, and tantalum are used. Among them, a tantalum compound is particularly preferable, and a tantalum halide such as tantalum pentachloride is used as the method of using it. There are a method of using it, a method of using an initiator containing tantalum halide as a main catalyst and a reducing agent as a second component, and the like. In the latter method, tantalum pentachloride is preferably used as the tantalum halide as the main component, and the reducing agent as the second component usually contains aluminum, boron, silicon, tin, antimony, bismuth, lithium and the like. Organometallic compounds are used.

In any of the above methods, the amount of the polymerization catalyst used can be usually in the range of 0.1 to 25 mol% with respect to the monomer. In the method using the reducing agent, the reducing agent may be used so that the molar ratio of the reducing agent to the main catalyst is about 0.3 to 3. The polymerization reaction is preferably carried out in a solvent, and examples of the solvent include aromatic hydrocarbons such as toluene, aliphatic hydrocarbons such as cyclohexane, halogenated hydrocarbons such as carbon tetrachloride and ethylene dichloride, anisole, and diamine. Examples include ethers such as butyl ether and dioxane, ketones such as acetone and acetophenone, and esters such as ethyl acetate. One of these solvents may be used, or 2
You may mix and use 1 or more types.

The polymerization reaction temperature is −30 to + 100 ° C.
Is preferable, and a range of 0 to 80 ° C. is particularly preferable.
The polymerization time is selected depending on the types of raw material monomers and catalysts, reaction temperature, desired degree of polymerization, etc., but is usually 0.5 to 100.
It can be about an hour. Furthermore, it is advantageous to carry out the polymerization under a dry nitrogen atmosphere. The obtained polymer has the above repeating unit and has a weight average molecular weight (Mw) of 1
It is a polymer of about 0,000 to 4.5 million (Mw is a polystyrene conversion value determined by a gel permeation chromatography method).

It is a white to brown fibrous or powdery substance, stable to air and soluble in organic solvents. This polymer is a gas separation membrane, liquid separation membrane, adsorbent, resist material, semiconductor material, memory material, radiation resistant material, polymer magnetic material, organic nonlinear material, optical material, photoconductive material, chromic material, biological material. Expected to be used for compatible materials.

For example, the gas separation molded body may be a membrane molded body. Of course, even if it is a sheet shape, a plate-like tubular membrane shape, a hollow fiber shape, etc., the purpose of use,
It can be formed into an appropriate shape depending on the application. Regarding the membrane as a gas separation molded body, a thickness that gives a sufficient gas permeation amount as a gas separation membrane and has practical strength,
For example, 0.01 to 100 μm, particularly 0.05 to 50
It is preferable that the film has a thickness of μm.

When the thin film is used, it is preferably a composite film with a support, and in this case, a non-woven fabric, a woven fabric, a porous body or the like is exemplified as the support. As the porous body, a porous polypropylene film, a porous polyethylene film, a porous polysulfone film, a porous cellulose acetate film, a porous tetrafluoroethylene film,
A porous polyimide film etc. are illustrated.

The method for producing such a film is not particularly limited. For example, a method in which a polymer is dissolved in an organic solvent such as toluene, benzene, carbon tetrachloride, tetrahydrofuran, or cyclohexane to obtain a polymer solution, which is spread on a metal, a glass plate, or a water surface, and then the solvent is evaporated, The composite membrane can be obtained by, for example, immersing the porous body in the polymer solution and then pulling it up, coating the porous body with the solution, and drying.

The polymer of the present invention will be described in more detail below with reference to examples.

[0025]

EXAMPLES Reference Example 1 (Production of 4-tert-butyl-3'-methyldiphenylacetylene) Under a nitrogen atmosphere, 40 mmol of 3-methyliodobenzene, 43 mmol of 4-tert-butylphenylacetylene, and dichlorobis (triphenyl) were placed in a reaction vessel. Phosphine) palladium (II) 0.31 mm
ol, triphenylphosphine 0.8 mmol, copper (I) iodide 0.4 mmol, triethylamine 110 ml
Was added, and the mixture was reacted under reflux for 8 hours. After completion of the reaction, the mixture was filtered, and the filtrate was concentrated under reduced pressure. Ethyl acetate was added to the residue and washed with aqueous hydrochloric acid. The organic layer was concentrated under reduced pressure to obtain 4.0 g of a yellow liquid (yield 84.7%). The structure of this product was confirmed by ¹ H-NMR.

[0026]

[Equation 1]

Reference Example 2 (Production of 4-trimethylsilyl-4'-fluorodiphenylacetylene) Under a nitrogen atmosphere, 25 ml of tetrahydrofuran was added to a reaction vessel, and 15 ml of 1.6 M n-butyllithium-hexane solution was added at -40 ° C. .. Then, 20 ml of a tetrahydrofuran solution of 21 mmol of 4-fluoro-4′-bromodiphenylacetylene was gradually added dropwise to react for 1 hour. Thereafter, 5 ml of a tetrahydrofuran solution containing 25 mmol of chlorotrimethylsilane was gradually added dropwise, and the temperature was raised to room temperature for reaction. After completion of the reaction, saturated aqueous ammonium chloride solution was added, the mixture was extracted with ethyl acetate, the organic layer was concentrated under reduced pressure, and recrystallized from methanol to obtain 2.3 g of white crystals (yield 40.7%). The structure of this product was confirmed by ¹ H-NMR.

[0028]

[Equation 2]

Reference Example 3 (Production of 4,3'-bistrimethylsilyldiphenylacetylene) According to Reference Example 1 except that 4,3'-dibromodiphenylacetylene is used instead of 4-fluoro-4'-bromodiphenylacetylene. The reaction was carried out to obtain 1.0 g of white crystals (yield 22.2%).

[0030]

[Equation 3]

Example 1 (Production of 4-tertiarybutyl-3'-methyldiphenylacetylene polymer) 0.27 g of tantalum pentachloride and tetra-tetrahydrofuran in 23.1 ml of toluene under a dry nitrogen atmosphere.
0.50 ml of n-butyltin was added and dissolved at 80 ° C. to prepare a catalyst solution. Next, under a dry nitrogen atmosphere, 5.0 ml of the catalyst solution was added to 5 ml of a 0.8 M toluene solution of 4-tert-butyl-3′-methyldiphenylacetylene monomer, and polymerization was initiated at 80 ° C. After 20 hours, the reaction mixture was poured into a large amount of methanol to precipitate the produced polymer, which was filtered and dried. The yield of the polymer calculated from the yield of the polymer with respect to the charged amount of the monomer was 20%. Weight average molecular weight (Mw) was determined by gel permeation chromatography (Tosoh Corp., HLC-8020).
72 when calculated as polystyrene equivalent by measurement
It was good. The molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) was 3.6. The obtained polymer is yellow and powdery, and is soluble in aromatic hydrocarbons such as toluene, xylene and benzene, halogenated hydrocarbons such as carbon tetrachloride and chloroform, and organic solvents such as ethers such as tetrahydrofuran. there were.

The 5% weight loss temperature in air was measured and found to be 404 ° C. ^The structure was confirmed by ¹ H-NMR. The 5% weight loss temperature of the obtained polymer was measured using a differential thermogravimetric simultaneous measurement apparatus TG / DTA220 manufactured by Seiko Denshi Kogyo Co., Ltd. at a heating rate of 10 ° C.
Calculated as / min.

[0033]

[Equation 4]

Example 2 (Preparation of 4-trimethylsilyl-4'-fluorodiphenylacetylene polymer) 4-tert-butyl-
4'instead of 3'-methyldiphenylacetylene monomer
Polymerization was carried out in the same manner as in Example 1 except that -trimethylsilyl-4'-fluorodiphenylacetylene monomer was used. The yield of the polymer calculated from the yield of the polymer with respect to the charged amount of the monomer was 46%. The weight average molecular weight (Mw) was 3,000,000 and the molecular weight distribution was 8.5.

The polymer was yellow and powdery, and was soluble in an organic solvent as in Example 1. Further, when the 5% weight loss temperature in air was measured, it was 454 ° C. ¹ H
-The structure was confirmed by NMR.

[0036]

[Equation 5]

Example 3 (Production of 4,3'-bistrimethylsilyldiphenylacetylene polymer) 4,3'-in place of 4-tert-butyl-3'-methyldiphenylacetylene monomer
Polymerization was carried out according to Example 1 except that the bistrimethylsilyldiphenylacetylene monomer was used. The yield of the polymer calculated from the yield of the polymer with respect to the charged amount of the monomer was 13%. Weight average molecular weight (Mw) is 3
90,000 and the molecular weight distribution was 2.5.

The obtained polymer was yellow and powdery, and was soluble in an organic solvent as in Example 1. Moreover, when the 5% weight loss temperature in air was measured, it was 411 ° C. ^The structure was confirmed by ¹ H-NMR.

[0039]

[Equation 6]

Reference Example 4 (Evaluation as Gas Separation Membrane) 1 g of each polymer obtained in Examples 1 to 3 was dissolved in 175 ml of toluene, cast on a glass plate, and allowed to stand at room temperature for 3 days. Thus, a polymer film (circle having a diameter of 12 mm and a thickness of 50 μm) was obtained. Each film was measured with a gas permeability measuring device (K-31 manufactured by Rika Seiki Kogyo).
5-N) at 25 ° C. with oxygen and nitrogen gas permeation coefficient (PO ₂ , PN ₂ , unit cm ³ (STP) · cm / cm
² · sec · cmHg) was measured and is shown in Table 1.

[0041]

[Table 1]

[0042]

As described in detail above, the present invention provides a novel diphenylacetylene polymer useful for gas separation membranes, liquid separation membranes, adsorbents, resist materials, semiconductor materials and the like.

Claims (1)

[Claims] 1. The following general formula: (Wherein R ₁ represents a branched alkyl group or a trialkylsilyl group, and R ₂ represents an alkyl group which may be substituted with a halogen atom, a trialkylsilyl group or a halogen atom). A di-substituted diphenylacetylene polymer having.