JPH01234418A - Novel polymer, production thereof, production of conjugated polymer therefrom and highly electrically conductive composition comprising said conjugated polymer - Google Patents

Abstract

PURPOSE:To provide the title polymer having specific recurring unit, useful as a precursor capable of readily giving a di-lower-alkoxy-substituted phenylenevinylene as a conjugated polymer useful for e.g., electronic materials, stable at normal temperature, also excellent in shapeability. CONSTITUTION:The objective novel polymer constituted of recurring unit of formula I (R1 and R2 are each 1-4C alkyl; n is polymerization degree: number >=10). This novel polymer can be obtained by substituting, pref. using a p- toluenesulfonic acid, the A<-> in a polymeric sulfonium salt of formula II (R3 and R4 are each 1-10C-hydrocarbon; A<-> is counter anion except organic acid anion) by an organic acid ion followed by reaction of the resulting product with an alcohol of the formula R2OH (pref. methanol or ethanol). The polymeric sulfonium salt of the formula II can be produced by polycondensation, in the presence of an alkali, of a sulfonium salt monomer such as 2,5-dimethoxy-p- xylenebis(dimethylsulfonium bromide).

Description

Detailed Description of the Invention <Industrial Application Field> The present invention relates to a novel polymer compound that can be converted into poly-2,5-dilower alkoxy-substituted phenylene vinylene, a method for producing the same, and a method for producing a conjugated system from the novel polymer compound. The polymer poly-
The present invention relates to a method for producing 2,5-di-lower alkoxy In phenylene vinylene and a highly conductive composition containing a cough conjugated polymer and a dopant as essential components.

<Prior art> Poly-2,5-di-lower alkoxy-substituted phenylene vinylene is known as a linear conjugated polymer (Japanese Patent Laid-Open No. 60-11
No. 528), the polymer can be doped with various dopants to impart electrical conductivity, and is therefore expected to be used in various applications as electrical and electronic materials.

Further, the above conjugated polymer can be obtained by, for example, condensing and polymerizing 2,5-dialkoxy-p-xylylene bis(dialkylsulfonium halide) in the presence of an alkali to synthesize a polymer sulfonium salt. It is produced by removing the sulfonium salt by heat treatment or the like.

In addition, since the above-mentioned polymeric sulfonium salt is soluble in water, etc., it is formed into a film or thread at the polymeric sulfonium salt stage, and then subjected to a desulfonium salt treatment to form a conjugated polymer in the desired shape. It has the characteristic that it can be obtained.

<The task that the invention is about to solve> However, the above -mentioned polymer polar sulfonium salt is not necessarily stable against heat or light, and is gradually being gradually driven by solution from the phase of polymerization to the desired form. Since the sulfonium salt in the side chain is eliminated, it is necessary to shield from light or carry out the operation at low temperature.

The objects of the present invention are to provide a novel polymer compound that is stable even at room temperature, soluble in F41 solvent, and has excellent shapeability, a method for producing the same, and a conjugated polymer poly-2,5-dilower compound. A method of producing an alkoxy-substituted phenylene vinylene,
Another object of the present invention is to provide a highly conductive composition containing the conjugated polymer and a dopant as essential components.

Means for Solving the Problems> That is, the present invention has the following features: A novel polymeric compound whose main component is a repeating unit represented by the formula (representing a number of 10 or more), -format (2) (wherein R+ and n are the same as above, and R1 and R4 are carbon atoms of 1-10). A of a polymer sulfonium salt represented by a hydrocarbon group, A- is a counter anion excluding the remaining acid anion)
The above formula is characterized in that the product obtained by replacing - with an 8g acid anion is reacted with an alcohol represented by R to σIt (R2 represents an alkyl group having 1 to 4 carbon atoms). (1) Production method of novel polymer compound, above-format (
The operation represented by the general formula (3) (R and n are the same as above), which is characterized by removing -OR and side chains of a polymer compound whose main component is the repeating unit represented by 1). A method for producing poly-2,5-dilower alkoxy-substituted phenylene vinylene containing repeating units as a main component, and poly-2, containing repeating units represented by general formula (3) obtained by the above method as a main component. The present invention provides a highly conductive composition containing 5-di-lower alkoxy-substituted phenylene vinylene and a dopant as essential components.

The novel polymer compound of the present invention has a sulfonium salt side chain of the polymer of the above formula (2) obtained by a specific method described below, and the novel polymer compound is soluble in organic solvents and has excipient properties. We have discovered that this compound has excellent stability and stability compared to those having a sulfonium salt side chain.

The present invention will be explained in detail below.

The polymeric sulfonium salt used in the production of the precursor of the present invention is represented by the general formula (2), where R1 is methyl, ethyl,
It is an alkyl group having 1 to 4 carbon atoms such as propyl, isopropyl, n-butyl, 1-butyl, and isobutyl. Also,
n is as described above, and R1 and R4 are hydrocarbon groups having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, and octyl groups, with methyl and ethyl groups being preferred.

These can be produced, for example, by the method described in JP-A-60-11528.

That is, it can be obtained by condensation polymerization of a sulfonium salt monomer represented by the following formula (4) in the presence of an alkali.

As the counter anion A- of the sulfonium salt, any one except an organic acid anion can be used, for example, i, , C
Halogen anions such as I and Br are preferred.

As the solvent for condensation polymerization, water, a mixed solvent of water and alcohol, etc. are used, but a solvent mainly composed of water is preferred in order to increase the solubility of the alkali.

The alkaline solution used for condensation polymerization is preferably a strongly basic solution with a pH of 11 or higher, and sodium hydroxide, potassium hydroxide, calcium hydroxide, strongly basic ion exchange resins (OH type), etc. can be suitably used as the alkali. .

The condensation polymerization reaction is usually preferably carried out at a temperature of 25°C or lower, particularly 10°C or lower. The reaction time may be determined as appropriate depending on the polymerization temperature, and is not particularly limited, but is usually 5
It is within the range of minutes to 20 hours.

After polymerization, the reaction solution is neutralized by adding an acid such as HCI or HBr.

The produced polymer sulfonium salt represented by the following formula (2) is dissolved in the reaction solution after neutralization.

Next, the counter anion ^- of the polymeric sulfonium salt is replaced with an organic acid ion. In the substitution reaction, the alkali salt is removed from the neutralized solution of the polymeric sulfonium salt solution or from this solution by dialysis, reverse osmosis separation, etc. Water solution removed? This can be done by adding and mixing an organic acid salt to &.

The organic acid ion is an aromatic sulfonic acid ion represented by the following formula (5) (where R2 is an alkyl group having 1 to 18 carbon atoms, M is an alkali metal, and L is an integer of O to 3). For example, Hensensulfonic acid, m
or P-) luenesulfonic acid, p-ethylbenzenesulfonic acid, 2,4-dimethylbenzenesulfonic acid, 2!
, 4.6-) dimethylbenzenesulfonic acid, 2.4-
dimethylbenzenesulfonate ion, etc.), carbon number 1-2
Alkyl sulfate ions with 0 alkyl groups (e.g.
lauryl sulfate, ■-eicosyl sulfate ion, etc.) and carboxylic acid ions having an alkyl group having 2 to 20 carbon atoms (
For example, propionic acid, butyric acid, stearate ions, etc.)
It is preferable to use these in the form of salts such as sodium and potassium, and it is particularly preferable to use them in the form of salts such as sodium and potassium.
-Toluenesulfonate.

The amount of organic acid ion used may be at least the equivalent of the ion contained in the polymer sulfonium salt solution, but in particular 2 to 5
It is preferable to use twice the equivalent amount. If the amount is less than the equivalent, substantially all of the A- in the polymer sulfonium salt will not be replaced by organic acid ions, while if the amount is more than necessary, there is no point.

The reaction temperature is preferably 10°C or lower, particularly 5°C or lower. In addition, the reaction time is not particularly limited, but
Usually about 10 minutes to 5 hours is selected.

As the reaction progresses, a compound in which the 8-terminus of the polymeric sulfonium salt is substituted with the aromatic sulfonic acid ion used is produced and precipitated.

Next, this precipitate is added to an alcohol represented by one type of RZOII (R2 is an alkyl group having carbon number] to 4),
By stirring and reacting, the precipitate is dissolved and becomes a homogeneous solution, but after a while the liquid becomes cloudy and a precipitate forms. This precipitate is a precursor of a conjugated polymer represented by the following formula (1) % formula % (R+-Rz, n is as described above).

The alcohol used here is preferably an alcohol having 1 to 4 carbon atoms, and methanol and ethanol are particularly preferred. Furthermore, the alkoxy group in the side chain of the precursor corresponds to the alkoxy group of the alcohol used.

The precursor of the present invention is insoluble in water, dimethylformamide,
It is soluble in aqueous solvents such as dimethylacetamide, dimethylsulfoxide, dioxane, and chloroform, and can be shaped into any shape, such as films and fibers, from the solution by known methods. It has excellent properties and is more stable than conventional polymeric sulfonium salts, and no desorption of alkoxy groups was observed in the resulting cast film even when it was left at room temperature.

In addition, the degree of polymerization n of the above precursor is preferably sufficiently large in consideration of obtaining a conjugated polymer that provides high conductivity, and is usually 10 or more, preferably 20 to 50,000. It can be obtained by dialyzing an aqueous solution of a polymeric sulfonium salt using a dialysis membrane with a high molecular weight cutoff.

Furthermore, by removing the alkoxy group side chain (R, o-) from this precursor by heat treatment or the like, poly-2,5-dialkoxy group-substituted phenylene vinylene, which is a conjugated polymer, can be obtained. Further, it is preferable that the elimination treatment of the alkoxy groups (R, O-) of the polymer precursor is performed in an inert atmosphere. A suitable treatment temperature is usually 100 to 350°C, preferably 150 to 300'C. Furthermore, when the precursor contains an acid such as HCI, IIBr, etc., the elimination reaction of the alkoxy group (R, o-) is promoted during heat treatment.

The treatment time can be appropriately selected depending on the treatment temperature, and is usually in the range of 10 minutes to 10 hours, although it is not particularly limited.

Alternatively, the polymer precursor may be shaped into a film, fiber, etc., then stretched and oriented, and then subjected to the above heat treatment. The stretching orientation can be performed before or simultaneously with the treatment for eliminating the alkokene group (R20-).

Poly-2,5- which is a conjugated polymer obtained by the treatment
Dialkoxy group-substituted phenylene vinylene can be made into a highly conductive composition by acting with an electron acceptor or an electron donor (referred to as a dopant). Here, the dopant used is a known conductive polymer compound such as polyacetylene doping, or a compound that has been found to have an effect of improving conductivity by forming an interlayer compound of graphite. Although the composition can be obtained by any method, doping is preferably carried out by conventionally known techniques such as chemical doping, electrolytic doping, optical doping, and ion implantation.

Specifically, electron acceptors include fluorine, chlorine, bromine,
Halogens or interhalogen compounds such as iodine, iodine chloride, iodine trichloride, iodine bromide, phosphorus pentafluoride, arsenic pentafluoride, antimony pentafluoride, boron difluoride, boron trichloride, boron tribromide, sulfur dioxide Lewis acids such as hydrogen fluoride, hydrogen chloride, nitric acid, sulfuric acid, perchloric acid, fluorosulfonic acid, chlorinated sulfonic acid, protonic acids such as trifluoromethanesulfonic acid, titanium tetrachloride, zirconium tetrachloride, tetrachloride Hafnium, niobium pentachloride, tantalum pentachloride, molybdenum pentachloride, tungsten hexachloride, iron trichloride, etc.'a
Organic compounds such as transfer metal chlorides tetracyanoethylene, tetracyanoquinodimethane, chloranil, dichlorodicyanohenzoquinone, and electron donors such as lithium,
Examples include alkali metal salts such as sodium, potassium, rubidium, and cesium, and quaternary ammonium salts such as tetraalkylammonium, and particularly preferred are sulfur dioxide, sulfuric acid, and iodine.

The preferred content of the doping reagent varies depending on the type of doping reagent, but can be arbitrarily changed depending on -m and doping conditions, such as doping time and doping reagent concentration. -The most preferable content is that the number of moles of dopant per repeating unit of the conjugated polymer is 0.
It is 1 to 2.0 moles of O, and if the number of moles is small, high conductivity will not be achieved, and if the number of moles is too large, the conductivity will tend to be saturated, which is not economical.

<Effects of the Invention> As explained above, the novel polymer compound of the present invention is more stable than its polymer sulfonium salt and is soluble in organic solvents, so it has excellent monomorphism. In addition, the polymerized compound of the present invention can be easily converted into a conjugated polymer by heat treatment as a precursor of a conjugated polymer, and can also be used to form molded products such as conjugated polymer films and fibers with a high stretching ratio. By doping them, a composition having high conductivity can be obtained.

<Example> The present invention will be described in more detail with reference to Examples.

Example 1 3.1 g of 2.5-dimethoxy-p-xylylene bis(dimethylsphonium bromide') was added to ion-exchanged water for 50 s.
After dissolving in O1, 0.14 normal N a OIt
Add 50ml of aqueous solution dropwise at 0-5°C over 15 minutes,
After dropping, the mixture was allowed to react at 0 to 5°C for 7 hours. Then It
A Br aqueous solution was added to neutralize.

Next, sodium P-toluenesulfonate powder in an amount equivalent to about 3 times the amount of Br contained in the neutralized reaction solution was added to the reaction solution and stirred, resulting in the formation of a precipitate. This precipitate was collected and poured into a large amount of methanol at 20°C.
Upon stirring, the precipitate was uniformly dissolved. When stirring was continued, the liquid began to become cloudy and the precipitate obtained after 1 hour was collected.

Elemental analysis of the powder sample obtained by washing this precipitate with methanol and drying revealed that hydrogen 7.25χ
, carbon 67.61χ, and It in the above formula (1).

It was in good agreement with the theoretical values of 7.27χ and 6B, 02χ for the precursor of poly-2,5-dimethoxyphenylenevinylene in which R2 corresponds to 8 times the methyl group.

In addition, this sample was dissolved in deuterium-substituted chloroform, and H
-N gate R was measured and found to be 6.9.6°6.4.9°3.8.3.7.3.2. A proton signal was observed around 2.9 and 2.9. The infrared absorption spectrum is the first
As shown in the figure, absorption of ether bond was observed at 1100 cm −'. From these analysis results, it was confirmed that the precursor polymer had a methoxy group in its side chain. In addition, when the degree of polymerization was measured by gel permeation chromatography using chloroform as a solvent, the degree of polymerization determined from the number average molecule (■) in terms of polystyrene was 850.
Met.

Example 1''?: Obtained film (length 2 cm, width 2 cm)
) was heat-treated at 200'C for 1 hour in a nitrogen atmosphere using an electric furnace to obtain a red film. This structure was confirmed to be poly-2,5-dimethoxyphenylenevinylene since the elemental analysis values and the characteristic absorption in the infrared absorption spectrum coincided with the characteristic absorption of a sample obtained by a known method.

The film obtained above was doped by exposing it to an iodine atmosphere overnight at room temperature. When the electrical conductivity of the film was measured by a four-terminal method, it showed an electrical conductivity of 187 S/cm.

Example 2 2.5-dimethoxy-p-xylylene bis(dimethylsphonium bromide) was replaced with 2.5-dimethoxy-p-xylylene bis(dimethylsphonium bromide).
A precursor polymer was obtained in the same manner as in Example 1 except that -xylylene bis(dimethylsphonium bromide) was used in equal moles. When analysis was performed in the same manner as in Example 1,
It was confirmed that it was a precursor of poly-2,5-jethoxyphenylene vinylene having an ethoxy group in the side chain. This precursor film was then subjected to side chain elimination treatment at +50°C to produce a poly-2,5-jethoxyphenylene vinylene film. This film is L+c+o4. /
After performing electrolytic doping in Autonitrile, the conductive dust was measured in the same manner as in Example 1 (p), and the result was 1133
It showed a conductivity of /cm.

Example 3 A conjugated polymer precursor film having a methoxy group in the side chain was obtained in the same manner as in Example I. 10 of that film
When the methoxy group side chain was removed while uniaxially stretching at a temperature of 0 to 200°C under various conditions, the stretching ratio was 3 to 3.
A 5x poly-2,5-dimethoxophenylene vinylene film was obtained. - On the other hand, a cast film of a polymeric sulfonium salt was uniaxially stretched and desulfonium salt treated at a temperature of 100 to 200°C under various conditions, but poly-2,5-dimethquinphenylene with a stretching ratio of less than 2 times. Only vinylene film was obtained. A uniaxially stretched poly 2,5-dimethoxyphenylene vinylene film obtained by the method of the present invention with a stretching ratio of 3.2 times was doped in the same manner as in Example 1, and the conductive dust was measured. It showed a conductivity of /cm.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing an infrared absorption spectrum of the novel polymer compound of the present invention obtained in Example 1.

Claims (4)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 is an alkyl group with 1 to 4 carbon atoms, R_2 is an alkyl group with 1 to 4 carbon atoms, and n is the degree of polymerization, a number of 10 or more. A new polymer compound whose main component is a manipulation unit represented by (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 is an alkyl group with 1 to 4 carbon atoms, R_3 and R_4 are hydrocarbon groups with 1 to 10 carbon atoms, and A^- is an organic acid. A-
The product obtained by replacing R_2OH with an organic acid ion and R_2OH
(R_2 represents an alkyl group having 1 to 4 carbon atoms.) There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (R_1, R_2 and n are the same as above) ) A method for producing a novel polymeric compound whose main component is a repeating unit. (3) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 is an alkyl group with 1 to 4 carbon atoms, R_2 is an alkyl group with 1 to 4 carbon atoms, and n is the degree of polymerization, a number of 10 or more. A general formula characterized by eliminating the -OR_2 side chain of a polymer compound whose main component is a repeating unit represented by A method for producing poly-2,5-di-lower alkoxy-substituted phenylene vinylene containing repeating units represented by (the same) as a main component. (4) A highly conductive composition containing as essential components poly-2,5-di-lower alkoxy-substituted phenylene vinylene obtained by the production method described in claim (3) and a dopant.