JPH0588853B2 - - Google Patents

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention relates to a method for producing a conjugated polymer stretch molded article. This stretched molded product is useful as a highly conductive polymer and as an electrical/electronic material. <Prior art> Two known methods for producing stretched conjugated polymer bodies include a method of hot stretching a conjugated polymer and a method of thermally decomposing a precursor and hot stretching in parallel with the process of forming a conjugated polymer. It is being Particularly in the latter stretching method, conjugated polymer stretched molded products with high stretching ratios have been reported.
A method of thermally decomposing and hot stretching a polymer sulfonium salt precursor film obtained as a soluble polymer precursor is known (Japanese Patent Laid-Open No. 199746/1983). For example, it is known that it is possible to form a stretched film of poly-p-phenylene vinylene by condensation polymerization of p-xylylene dimethylene bissulfonium salt, followed by desulfonium salt reaction and hot stretching of a cast molded product of the polymer. It is being Likewise, a stretched molded product of substituted poly-p-phenylene vinylene is also known (Japanese Patent Application Laid-open No. 11528/1983). <Problems to be Solved by the Invention> However, since the conjugated polymer is a rigid polymer and is insoluble and infusible, a simple hot stretching method can only yield a stretched molded product with a low magnification. In addition, the method of thermally decomposing and hot stretching the resulting precursor film via a soluble polymer precursor yields a molded product with a higher stretching ratio than the above method, but the conjugated polymer is rigid during stretching. Also occurs, so there is a limit to the stretching ratio. The present inventors have developed a conjugated polymer with a high stretching ratio, which has been virtually difficult to produce using the conventional method of thermally decomposing and hot stretching the obtained precursor film via a soluble polymer precursor. As a result of extensive research into methods for producing molecularly stretched molded bodies, we have arrived at the present invention. An object of the present invention is to provide a method for obtaining a conjugated polymer stretch molded article having an extremely high stretching ratio. <Means for solving the problems> The present invention is based on the general formula ()

[Chemical formula] R ₁ ;> Group that forms a continuous carbon-carbon conjugated system with the vinylene group formed by dehydrogenation of the CH-CH ₂ - group R ₂ ; Bonded to the β-carbon of the CH-CH ₂ - group A molded body of a polymer precursor having a repeating unit represented by a group that is eliminated from a carbon at the α-position is stretched in a solvent that swells the molded body of the polymer precursor, accompanied by the elimination of hydrogen atoms. Provided is a method for producing a conjugated polymer stretch molded article, which comprises performing a treatment to eliminate R ₂ groups after performing the above steps. The present invention will be explained in detail below. The molded body of the polymer precursor used in the present invention has the general formula ()

[Chemical formula] R ₁ :>Group that forms a continuous carbon-carbon conjugated system with the vinylene group formed by dehydrogenation of CH-CH ₂ - group R ₃ , R ₄ : Hydrocarbon group having 1 to 10 carbon atoms X ^- : Obtained by condensation polymerization of a disulfonium salt monomer represented by a counter ion with an alkali. In the polymer precursor molded article of the general formula () used in the present invention or the disulfonium salt monomer of the general formula (), the R ₁ group is an aromatic hydrocarbon having 6 to 14 carbon atoms, a nuclear substituted product thereof, or They are heterocyclic aromatic compounds having 4 to 13 carbon atoms and nuclear substituted compounds thereof. Although there are no particular limitations on these substituents, a hydrocarbon group having 1 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms are preferred. R ₁ group is p-phenylene, 2,5-dimethoxy-p-phenylene, 2,
5-diethoxy-p-phenylene, 2,5-dimethyl-p-phenylene, 2,6-naphthalenediyl, 2,5-thienylene, 3-methyl-2,5-
Examples include thienylene, 3-methoxy-2,5-thienylene, and 2,5-furandiyl. The leaving group R ₂ of the general formula () used in the present invention can be obtained by condensation of a disulfonium salt monomer of the general formula ()

[Formula]. As the monomer () used in the present invention, one obtained by reacting a dimethylene halogen of _R1 group with a sulfide having a hydrocarbon group having 1 to 10 carbon atoms can be used. Sulfide can be a hydrocarbon group having 1 to 64 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-ethylhexyl, phenyl, cyclohexyl, or benzyl group. , particularly preferred are methyl and ethyl groups. As the sulfonium salt monomer of the general formula () and the counter ion X ^- of the leaving group R ₂ of the general formula (), any one can be used in a conventional manner. For example, halogen, hydroxyl, boron tetrafluoride, perchloric acid, carboxylic acid, sulfonate ions, etc. can be used, and among them, halogen and hydroxyl ions such as chlorine, bromine, and iodine are preferred. The polymer precursor can be obtained by condensation polymerization of the sulfonium salt monomer of the general formula () using an alkali in water alone or in a mixed solvent with a water-soluble organic solvent such as an alcohol. Preferably, it is effective to carry out the polymerization in water or a mixed solvent of water and an organic solvent soluble therein, and even more preferably in water or a mixed solvent of water and alcohol. The alkaline solution used in condensation polymerization is preferably a strongly basic solvent with a pH of 11 or higher in water or an organic solvent, such as a mixed solvent of alcohols and water, and includes sodium hydroxide, potassium hydroxide, calcium hydroxide, quaternary hydroxide, etc. Ammonium salt hydroxides, sulfonium salt hydroxides, strongly basic ion exchange resins (OH type), etc. can be used, and sodium hydroxide, potassium hydroxide, and strongly basic ion exchange resins are preferably used. In the condensation polymerization reaction, the resulting polymer precursor is exposed to heat,
Sensitive to light, ultraviolet rays, strong basic conditions, etc.
Gradual elimination of the R ₂ group tends to result in a polymer precursor having a partially conjugated structure, which may result in heterogeneity. Therefore, the condensation polymerization reaction is carried out at relatively low temperatures, i.e. at least below 50°C, especially below 25°C,
Furthermore, it is preferable to carry out the reaction at a temperature of 5° C. or lower. The reaction time is not particularly limited, but is usually 1
Ranges from minutes to 50 hours. In order to obtain a polymer precursor with high stretchability, it is preferable that the molecular weight is sufficiently large. Those having a molecular weight that cannot be dialyzed by dialysis treatment using a dialysis membrane having a fractional molecular weight of 3500 or more are effectively used. According to the method of the present invention, the polymer precursor of the general formula () is swollen and stretched with a leaving group R ₂ in the side chain, and then the R ₂ is eliminated by post-treatment,
It can be a conjugated polymer. It is more effective if a stretching treatment is further used in conjunction with the R ₂ desorption treatment. In the present invention, it is important to stretch the molded article of the polymer precursor in a swollen state. Here, the swollen state refers to a state in which the molded product of the polymer precursor contains a solvent, preferably 3% or more of solvent per dry weight of the molded product, and can maintain its shape even when stretched. The solvent used for swelling and stretching is not particularly limited as long as it is a solvent that swells the polymer precursor used, and may be used alone or as a mixed solvent. However, it is preferable to use at least one good solvent for the polymer precursor used and at least one solvent.
A mixed solvent of more than one type of poor solvent is preferable from the viewpoint of the operability of stretching. The mixing ratio is not particularly limited, but it actually varies depending on the type of solvent used and the structure of the polymer precursor, so it may be determined appropriately taking this into account. When the leaving group in general formula () has a sulfonium salt structure, good solvents are water and alcohol, and poor solvents are other organic solvents, such as water, methyl alcohol, ethyl alcohol, butyl alcohol, etc. , poor solvents include acetone, dimethylacetamide, dimethylformamide, dimethylsulfoxide, N
- Examples include organic solvents that are soluble in good solvents such as methylpyrrolidone. As a method for swelling and stretching, it is preferable to uniaxially or biaxially stretch the molded product of the polymer precursor in a solvent that swells it. There are no particular restrictions on the temperature for swelling and stretching, but at high temperatures
Since the R ₂ group is eliminated, the effect is small, and the solvent freezes at low temperatures, so the temperature may be lower than the temperature at which the R ₂ group is eliminated, but it is generally preferable to use a temperature of 0 to 80°C. A feature of the present invention is that a polymer precursor molded body is stretched while maintaining its molecular structure, and then heat-treated to form a conjugated polymer. Here, the polymer precursor molded article can be made into a molded article of any shape from a polymer precursor solution. Any method can be used to obtain the polymer stretched molded product, but in terms of its form, for example, films, fibers, coatings on stretchable base materials, etc. are effective for the present invention. At this time, it is preferable to use a polymer precursor solution that has been desalted or freed from unreacted substances by dialysis treatment or the like. The R ₂ group is removed from the polymer precursor, and a conjugated polymer can be produced. The elimination treatment of R ₂ groups involves heat, light,
This can be carried out by applying conditions such as ultraviolet rays or strong base treatment, but heat treatment is preferred.
In order to obtain highly conductive compositions, it is necessary to use polymer precursors.
It is important to perform the elimination treatment of the R ₂ group in an inert atmosphere. The inert atmosphere here refers to an atmosphere that does not cause deterioration of the polymer during treatment, and in particular it is necessary to prevent oxidation reactions due to oxygen and air. This is generally carried out using an inert gas such as nitrogen, argon, helium, etc., but it may also be carried out under vacuum or in an inert medium. When performing elimination treatment of _R2 groups by heat, heat treatment at excessively high temperatures will cause decomposition of the conjugated polymer produced, and at low temperatures the production reaction is slow and impractical, so the treatment temperature is usually 50 ° C to 450 ° C. °C, preferably
Suitable temperature is 80℃~400℃. In addition, the processing time can be selected as appropriate depending on the processing temperature, but 1
A range of minutes to 10 hours is industrially practical. The conjugated polymer produced in this way has R ₁
-CH=CH- is included in the main structural unit. According to the production method of the present invention, it is possible to produce a conjugated polymer having only conjugated repeating units of R ₁ -CH=CH-, as well as a non-conjugated polymer.

[Formula] It is also possible to produce a polymer containing a skeleton as a part of its constituent units. In other words, after insufficient desorption treatment, the polymer is still in an incomplete desorption state.

[Formula] The presence of a structural unit having a skeleton is observed by infrared absorption spectroscopy and the like. In this case, a highly flexible conjugated polymer can be produced. In addition, for R ₁ −CH=CH− unit

[Formula] The proportion of units can be changed by arbitrarily modifying the manufacturing conditions depending on the purpose of use. For purposes such as conductive polymer materials, the ratio of the latter to the former is preferably 1 or less, more preferably 1/20 or less. Further, during the elimination treatment of the R ₂ group of the polymer precursor, it is also possible to further stretch and orient the polymer precursor. By subjecting the swollen and stretched polymer precursor molded product to stretching and heat treatment in this manner, even higher orientation can be imparted. <Effects of the Invention> Compared to a stretched molded product obtained by simply heating and stretching, the polymer stretched molded product obtained through the swelling stretching process of the present invention has a significantly improved degree of stretching, and the molecular chain orientation pattern is different from that of the conventional one. It is considered different. As explained above, according to the present invention, it is possible to obtain a product with a much higher stretching ratio than conventional conjugated polymer stretched molded products, and the present invention also enables application to highly conductive materials. Conjugated polymer stretch molded bodies having various shapes are provided. <Examples> The present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples in any way. Example 1 After dissolving 4.4 g of p-xylylene bis(diethylsulfonium bromide) in 50 ml of distilled water, an aqueous solution of 0.8 g of caustic soda dissolved in 50 ml of distilled water was prepared.
The mixture was added dropwise over 15 minutes, and stirring was continued at 0°C to 5°C for 3 hours. After the reaction, it was neutralized using a 0.66N hydrogen bromide solution. The resulting aqueous solution of a polymeric sulfonium salt having a sulfonium salt in its side chain was dialyzed against water for one day using a dialysis membrane (Cerotube, molecular weight fraction 8000, manufactured by Union Carbide). This dialysate was dried under reduced pressure to obtain a cast film with a thickness of 50 μm. Polymer precursor film 3
It was cut into cm squares and immersed in an acetone mixed solvent containing 10% by weight of water (25°C). The weight increase at this time is 31
It was in weight%. Then, the film was slowly stretched to 18 times the length before dipping, the acetone/water mixed solvent was discharged, and the film was dried under a nitrogen stream. This film was processed using a horizontal tube furnace under a nitrogen atmosphere.
The film was heat treated at 100 to 400°C and stretched to 1.2 times to obtain an orange 22 times uniaxially stretched poly-p-phenylene vinylene film. The thickness of this film was 20 μm. Example 2 4.4 g of p-xylylene bis(diethylsulfonium bromide) was dissolved in 50 ml of ion-exchanged water and then cooled to 3°C. Next, in advance, p-xylylene bis(diethylsulfonium bromide) was
Two equivalents of a strong basic ion exchange resin (Amberlite IRA-401, Rohm and Haas) converted to OH type was gradually added over 10 minutes, and stirring was continued at 0 to 5°C for 3 hours. . After the reaction,
The filtrate is filtered through a dialysis membrane (cellotube, molecular weight fractionation).
3500 (manufactured by Union Carbide) for 2 days at room temperature against water. This obtained polymeric sulfonium salt aqueous solution having sulfonium salt side chains was cast and heated at 30°C for 24 hours.
It was dried under reduced pressure for hours to obtain a cast film with a thickness of 50 μm. The polymer precursor film was cut into 3 cm squares, immersed in an acetone mixed solvent containing 10% water (25°C), slowly stretched to 12.6 times its length before dipping, and then diluted with an acetone/water mixed solvent. It was drained and the film was dried under a stream of nitrogen. This film was heat-treated at 100 to 400° C. and stretched to 1.4 times in a nitrogen atmosphere using a horizontal tube furnace to obtain an orange 17.6 times uniaxially stretched poly-p-phenylene vinylene film.
The thickness of this film was 18 μm. Example 3 After concentrating the polymer precursor aqueous solution obtained in Example 1 to 2 times at 50°C under reduced pressure, 2 mm of the solution was dissolved in acetone.
It was slowly extruded through a nozzle with a diameter of
After drying the generated filament under reduced pressure, it is immersed in an acetone mixed solvent containing 10% water (25°C), slowly stretched to 6 times the length before dipping, and the acetone/water mixed solvent is discharged. The yarn was then dried under a nitrogen atmosphere. This yarn was heat-treated at 100 to 400°C using a horizontal tubular furnace in a nitrogen atmosphere and stretched up to 3 times, to obtain an orange 18 times uniaxially stretched poly-p-phenylene vinylene film. Example 4 4.7 g of 2,5-dimethyl-p-xylylene bis(diethylsulfonium bromide) was dissolved in 50 ml of distilled water and then cooled to 3°C. Then, an aqueous solution in which 0.8 g of caustic soda was previously dissolved in 50 ml of distilled water and cooled to 3°C was added dropwise, and stirring was continued at 0°C to 5°C for 2 hours. After the reaction, it was neutralized using a 0.6N hydrogen bromide solution. The resulting aqueous solution of a polymeric sulfonium salt having a sulfonium salt in its side chain was dialyzed against water for one day using a dialysis membrane (Cerotube, molecular weight fraction 2000, manufactured by Union Carbide). This dialysate was dried under reduced pressure at 30° C. for 24 hours to obtain a cast film with a thickness of 32 μm. Cut the polymer precursor film into 2 cm squares, immerse it in a mixed solvent of acetone and water, slowly stretch it to 5 times the length before dipping, drain the acetone/water mixed solvent, and pass the film through a nitrogen stream. Dry underneath. This film was heat-treated at 100 to 350°C and stretched to 2.2 times in a nitrogen atmosphere using a horizontal tube furnace to obtain an orange 11 times uniaxially stretched poly-2,5-dimethyl-p-phenylene vinylene film. . The thickness of this film was approximately 10 μm. Example 5 After dissolving 3.6 g of 2,5-dimethoxy-p-xylylene bis(dimethylsulfonium bromide) in 50 ml of ion exchange water, 0.3 N NaOH aqueous solution was added.
Drop 50ml over 15 minutes at 0-5℃, and after dropping 0-5℃
Stirring was continued for 30 minutes at 5°C. 0.77 normal after reaction
The mixture was neutralized using an aqueous HBr solution, and 0.77N HBr was added to the equivalent amount of NaOH. This reaction solution was filtered using a dialysis membrane (Cerotube, molecular weight fraction 8000, manufactured by Union Carbide).
Dialysis treatment was performed for several days. Cast this liquid and dry it under reduced pressure at below 40℃.
A 20 μm thick polymer sulfonium salt film having a pale red sulfonium salt in its side chain was obtained. Cut the polymer precursor film into 3 cm squares and add 10% water by weight.
The film was immersed in a mixed solvent containing acetone and slowly stretched to four times the length before dipping, the acetone/water mixed solvent was discharged, and the film was dried under a nitrogen stream. This film was heat-treated at 100 to 300°C using a horizontal tube furnace under a nitrogen atmosphere and stretched to 1.5 times to obtain a red 6-fold uniaxially stretched poly-2,5-dimethoxy-p-phenylene vinylene film. .
The thickness of this film was approximately 8 μm. Example 6 1.5 g of 2,5-diethoxy-p-xylylene bis(diethylsulfonium bromide) was dissolved in 50 ml of a mixed solvent of distilled water and ethanol (weight ratio 1:2), and then cooled to 0°C. Next, add 2 equivalents to the sulfonium salt in advance.
A strongly basic ion exchange resin (Amberlite IRA-401, manufactured by Rohm and Haas) converted to OH type was gradually added over 10 minutes, and the mixture was heated at 0 to 5°C.
Stirring was continued for 100 minutes. After the reaction, filtration was performed to remove the ion exchange resin, and the filtrate was dialyzed at 0 to 5°C for one day using a dialysis membrane (Cerotube, molecular weight fraction 10,000 to 20,000, manufactured by Union Carbide). Ivy. Cast this liquid and dry it under reduced pressure at below 40℃.
A pale red polymeric sulfonium salt film with a thickness of 18 μm having a sulfonium salt in its side chain was obtained. Cut the polymer precursor film into 3 cm squares and add 12% water by weight.
The film was immersed in a mixed solvent containing acetone and slowly stretched to 3.2 times the length before dipping, the acetone/water mixed solvent was discharged, and the film was dried under a nitrogen stream. This film was heat-treated and stretched to 1.7 times in a nitrogen atmosphere using a horizontal tube furnace at 100 to 300°C to obtain a red 5.4 times uniaxially stretched poly-2,5-diethoxy-p-phenylene vinylene film. . The thickness of this film was approximately 7 μm. Example 7 After dissolving 7.6 g of 2,5-furandiyl-bis(methylenedimethylsulfonium bromide) in 200 ml of a mixed solvent of ion-exchanged water and methanol (volume ratio 1:1), 20 ml of 1N NaOH and 80 ml of methanol were dissolved. The mixed solution was added dropwise at -30°C over 30 minutes, and after the dropwise addition, stirring was continued at -30°C for 30 minutes. This reaction solution was filtered using a dialysis membrane (Cerotube, molecular weight fraction 8000, manufactured by Union Carbide).
Dialysis treatment was performed at 30°C for 1 day against a water-methanol mixed solvent (1:1). This dialysate was cast and dried under reduced pressure.
A black polymer precursor film having a sulfonium salt in its side chain and having a thickness of 14 μm was obtained. This film was cut into pieces of 2 cm long and 1 cm wide, immersed in an acetone mixed solvent containing 12% water by weight, slowly stretched to 1.8 times the length before dipping, and the acetone/water mixed solvent was drained. The film was dried under a stream of nitrogen. This film was heat-treated at 100 to 200°C in a horizontal tube furnace under a nitrogen atmosphere and stretched to 1.3 times.
A black 2.3 times uniaxially stretched poly-2,5-furandiylvinylene film was obtained. This film thickness is approx.
It was 9μm.

Claims (1)

[Claims] 1 General formula [Formula] R ₁ ;>CH-CH ₂ A group that forms a continuous carbon-carbon conjugated system with the vinylene group formed by dehydrogenation of the group R ₂ ;>CH-CH Molding of a polymer precursor having a repeating unit represented by a group that is eliminated from the α-position carbon with the elimination of the hydrogen atom bonded to the β-position carbon of the ₂ -group. 1. A method for producing a conjugated polymer stretched molded article, which comprises performing a stretching treatment in a solvent that swells the body, and then subjecting the R ₂ group to elimination treatment. 2. The method for producing a conjugated polymer stretched molded article according to claim 1, wherein the molded article is a film or fiber.