JPS63275614A - Substituted polyacetylene - Google Patents

Abstract

PURPOSE:To obtain a high-MW or solvent-insoluble substituted polyacetylene of a high degree of polymerization, useful as an electroconductive or photoconductive material or for various optical uses, mainly consisting of structural units of specified formulas. CONSTITUTION:A substituted polyacetylene which is solvent-insoluble or has a weight-average MW>=50,000, mainly consisting of structural units of formula I (wherein X is C or N, and when X is C, it must have a substituent Y, while when X is N, it has no substituent Y, said substituent Y being an electron-with drawing or electron-donating group, Z<1>-Z<4> are each H, an electron-withdrawing or electron-donating group, and R is H, alkyl or cycloalkyl). This polymer can be obtained by polymerizing a monomer of formula II (wherein X, Y, Z<1>-Z<4> and R are as defined above) by using a specified catalyst, for example, a compound of formula III (wherein COD is cyclooctadienyl and bipy is bipyridyl). This polymer is moldable into a film and the concentration of radicals in the polymer can be increased by heating. By, e.g. adding a dopant to it, it can be used in various uses as an electroconductive or photoconductive polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel polyacetylene having a substituent group with a high degree of polymerization and useful for conductive forest materials, photoconductive materials, or various optical applications.

[Conventional technology and its problems]

Conventionally, as polyphenylacetylene, unsubstituted polymers and polymers having an electron-donating group at the ortho position have been known. However, polymers having a substituent at the para position are obtained by radical polymerization of polymers substituted with electron-withdrawing groups such as nitro groups, and low polymers with molecular changes from oligomers to about 1,000 are obtained. Not too much.

Furthermore, at present, polyacetylenes having a pyridine ring have not been known until now.

Polyphenylacetylene having a substituent at the para position is considered to be an absolutely necessary polymer for imparting the function of polyphenylacetylene. The above functions include not only the conductivity when dopants are added, but also the conductivity increases even without dopants, and the conductivity is enhanced by forming a charge transfer vEIJ complex rather than a dopant. The electrical conductivity is increased by forming a charge transfer complex with an electron-withdrawing compound or polymer on polyphenylacetylene having a donating substituent at the para-position, or at the para- and ortho-positions. ) is also expected when graded and irradiated with light.

Using these functions, plastic batteries, *
It is expected to be used in a variety of applications such as ni films, sensors, solint switches, and electrochromic displays.

On the other hand, it is expected to be used in optical applications as a non-shaped optical material that utilizes wJ-order and third-order pot harmonics, and as a material for separating gases and liquids.

[Means for solving problems]

The present inventors have arrived at the present invention as a result of intensive studies on polyphenylacetylene having a substituent at the para position or polyacetylene having a pyridine ring, and an effective method for producing the same.

That is, the gist of the present invention is to mainly consist of monomer units represented by the following general formula (I), and have a weight average molecular weight of! 0.0θθ or more, or is insoluble in a solvent, and exists in polyacetylene having a substituent.

(In the formula, does X represent a carbon atom or a substituent atom? When X is a carbon atom, it always has a substituent Y, and when X is a nitrogen atom, there is no substituent Y. The substituent Y is an electron Indicates an attracting or electron donating group.

zl-24 represents a hydrogen atom, an electron-withdrawing group or an electron-donating group, and R represents a hydrogen atom, an alkyl group or a cycloalkyl group. ) Hereinafter, the present invention will be explained in detail.

Based on the general formula (I), Y represents an electron-liquid withdrawing group or an electron-donating group, and 21 to z4 represent a hydrogen atom, an electron-withdrawing group, or an electron-donating group. Typical examples of electron-donating groups include alkoxy groups, aryloxy groups, alkyl groups, cycloalkyl groups, aralkyl groups, aryl groups, amine groups, alkylamino groups, dialkylamino groups, /-piperidino groups, /-piperazino groups. Substituents include, but are not limited to, substituents such as /-pyrrolidino group, acylamino group, halogen, hydroxyl group, mercapto group, alkylthio group, arylthio group, trialkylsilyl group, and trialkylsiloxy group; sex rl
If you are chivalrous, then either is fine.

Examples of electron-withdrawing groups include, but are not limited to, nitro groups, cyano groups, acyl groups, acyloxy groups, carboxamide groups, alkogysis sulfonyl groups, phenylsulfonyl groups, and any electron-withdrawing substituent can be used. But that's fine.

Particularly preferred groups among these are alkoxy, nitrogen, and nitro groups.

The polymer of the present invention has a weight average molecular weight of to, ooθ or more, or is insoluble in a solvent. The molecular weight is determined by the GPO method using tetrahydrofuran as a solvent, and the polymers of the present invention include those that are insoluble in tetrahydrofuran at a temperature of -3°C.

In the present invention, even if the molecular weight cannot be measured because it is insoluble in a solvent, the molecular weight measured by solubilizing it with water is equivalent to the above molecular weight, and even if it is insoluble, it is possible to form a strong film. include.

In addition, in the polymer of the present invention, structural units represented by the following general formulas Jun), (B), ←) and CD) are formed by the monomer, polymerization conditions, or heating after polymerization, and these structural units are The polymers of the present invention also include those having the following.

(General formula), ■), (C) and ■), where X, Y, is ~
z4 and R have the same meanings as in general formula (I) above. ) In particular, when the structural units represented by the general formulas (B), (0) and p) are formed, the electrical conductivity is significantly improved.

In order to produce the polymer of the present invention, the following general formula (general formula (
In I[), X, Y, Z"-Z' and HR have the same meanings as in formula (I).) A monomer represented by the following formula is used.

Specifically, such monomers include p-methoxyphenylacetylene, p-chlorophenylacetylene,
λ,4t,j-)rimethoxyphenylacetylene,
2.4t, 6-) Lichlorophenylacetylene, Hiro-
Methyluco, ≦-dimethoxyphenylacetylene, terdimethylaminophenylacetylene, p-nitrophenylacetylene p-cyanophenylacetylene, λ, 4t
, a-) phosphorus anophenyl acetylene, teracetylenylpyridine, dacetylene 3. j-dimethylpyridine, /-methyl-=-p-fluorophenylacetylene, Z-nitro-comethylphenylacetylene, co,6-dimethyl-e-nitroacetylene, 2,6-cymethoxyternitrophenylacetylene, 9- Methoxy-1-1-2-troacetylene etc. can be used.

As a reaction medium, the following general formula (III) [MLxHn
:1qQp ・・・・・・・・・・・・・・・
...(I[) (wherein, L is a ligand derived from a compound having multiple bonds, H is a ligand derived from a compound having a lone pair of electrons, Q is a depleted ion, M is a d-electron) Indicates transition metals with.

1;0~! , n塙θ~/, p±/~-1q=/In the above general formula (瓜), examples of L include olefin, acetylene, diene, cyclodiene, -carbon oxide, etc., and H
For example, Q is a compound having atoms such as nitrogen, phosphorus, arsenic, oxygen, sulfur, etc.
H°, -1f$E7, cl, -, etc., and M includes metals of VNA and Group 1 of the periodic table.

Among these, specific examples of L include allyl, butadienyl, cyclooctagenyl, -carbon oxide, and phenylacetylenyl, with cyclooctagenyl being particularly preferred.

Further, specific examples of H include pyridine, bipyridyl, ethylenediamine, triethylenediamine, diphenyl ether, diphenylthioether, diethyl ether, triphenylphosphine, trioctylphosphine, triphenylarsine, phenanthroline, etc., but triphenylphosphine is particularly preferable.

In addition, as Q, I'll'6- is particularly preferable, and
Specific examples of M include rhodium, ruthenium, rhenium,
Nickel, platinum, etc. may be used, but rhodium is particularly preferred.

Next, specific examples of hobbies represented by the general formula (I[[) include those listed below.

(Rh(COD)bipy)PF,, (Rh(COD)bipyam'3PF,, (Rh(U
OD) (I')'h3),)PF,,[Rh(NBD
) bipy]PF,,[Rh(OOD)KDA]01
, [uh(con)TKDA]o1, [Rh(COD)C1], Re(Oo),X.

(Re(Co), 01), Re(Co), (PPh,)01, Re(Co), (bipy)04, Re(CO)s (C!OPh), Re(Co),
(PPh,), al, (Re(Co), 01),, Re(Co), (Ph2POH,CH,PPh,)0
1, “1(CO)z(PPhs)t , Rh(PPh, ), 01, N1(PPh,),!,, P t (PPh )a (Os++Ci Ph )t
, Pt(PPh), HOl, Pt(PPh), 01. , i-One product axis f 苓However, COD Nidiclooctagenyl NBD : Norbonadienyl KDM : Ethylenediamine TICDA : ) Liethylenediamine bipy : Bipyridyl bipyam : Bipyran Ph : Phenyl X : Indicates a halogen.

Among these, [Rh(COD)(PPh)! :IPF
It is preferable to use , because it is easy to obtain a polymer with a high degree of polymerization.

Further, as the solvent to be used, any solvent that does not react with the catalyst or substrate can be used, and specific examples include ethanol, methanol, diethyl ether, tetrahydro-7rane, dioxane, anisole, etc., but ethanol is the most preferred. The concentration of monomer dissolved in the solvent is 0.
0/~io morti, preferably 0. / -1X/chi. The bile medium concentration is /X/θ-3 to /X/θ-1X/Chi, preferably /X50-' to /X/θ-Yimorti. The polymerization time is IO minutes to ta hours, preferably! ~4t
? The time and temperature are -3θ℃~/0℃, preferably 0-5℃.
00°C, particularly preferably 30 to ro°C.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 The polymerization angle is 0. Oj mmol of Rh (cyclooctagenyl) ("hs)2PFs was taken, and ethanol iow was added. Next, after degassing the system, 6.! mmol
Nor-nitrophenyl acetylene was added and reacted at 4tO°C for a few hours. Since the polymer was insoluble in ethanol, it gradually precipitated as the reaction proceeded. After the polymerization reaction was completed, the mixture was filtered and once dispersed in methanol and washed. The produced polymer was dried under reduced pressure for one day. As a result, a polymer insoluble in tetrahydrofuran (2J°C) was obtained.

The R spectrum of this product is shown in FIG.

Moreover, the ESR spectrum of this product is shown in FIG.

The BBR spectrum of this product is Sing1θt(p-2
,003-±o,oooz, line width;ΔHmslxZ~9
G) was shown. The value is the t value of the free electron, l, 00 J
Since h is larger than Q, this indicates that the hetero atom and the unpaired electron in the molecule interact, that is, some of the unpaired electron flows to the nitro group and causes noise. In other words, the charge separation due to the formation of polarons in the molecule is suppressed.

Example 2 Polymerization was carried out in the same manner as in Example except that Kp-methoxyphenylacetylene was used instead of p-nitrophenylacetylene.

The polymer was dissolved in tetrahydrofuran, and GPO (Toyo 1
G-'4000 manufactured by a different company, using TSKGel column)
When I measured the molecular weight, the heavy electric average molecular weight was 50! ,θ
It was found that poly-p-methoxyphenylacetylene of θθ was obtained, and a cast film could be made from a solution of this polymer in tetrahydrofuran.

The R spectrum of this polymer is shown in FIG. Moreover, the KSR spectrum of this showed 51 mg1et at the temperature (y-2,0032±0,000j).

ΔHms1x? ~/2G). When this sample is heated, the yth
The result is the KEIR spectrum shown in the figure. This spectrum is composed of 2'sL groups of the following formulas (A, (B')).

(A. Hβ, each triplet
It is divided into This is further magnetically equivalent λ H
It is interpreted that it splits into triplets at r, and each splits into triplets again at Ha.

On the other hand, in the group represented by formula (B), since the unpaired electron is on the carbon near the substituted benzene, it splits into a trip'let at Hβ, which becomes H.

It is estimated that the t value of both spectra is f-,2,θQ3.2.
(Observed temperature: 300℃). In this case as well, the value of is larger than that of the free electrons, so as with the nitro group, some of the unpaired electrons are in the methoxy group. It is thought that the polarons flow toward the opposite direction, charge separation occurs, and polarons are generated.

It can be seen that the tetrahydrolyte solution of the polymer produced in Example 1 rises as the cloth becomes thinner. This means that the polymer becomes electrolytically charged and a polaron is generated.

Example 3 Substitute for p-nitrophenylacetylene F) Poly-p-chlorophenylacetylene was obtained in the same manner as in Example except that Itcp-chlorophenylacetylene was used. This R spectrum is shown in FIG.

〔Effect of the invention〕

The polymer of the present invention can be formed into a film, and by applying heat, the radical degree in the polymer can be increased. Furthermore, by adding a dopant or forming a CT complex, it can be used for various purposes as a conductive polymer or as a photoconductive polymer. For example, it can be used as a plastic switch, nonlinear optical material, gas or liquid separation, and the industrial value of the present invention is as follows. 'I'
FIG. 3 is a chart of the E-R spectrum and the IIR spectrum of the K@body. FIG. 3 is a diagram of the R spectrum of the polymer obtained in Example 2. Fig. 7 is an ERR diagram of the polymer of Example 3 at elevated temperature, Fig. 1 is a diagram showing the electrical conductivity of the polymer of Example 30 in tetrahydrofuran at 20°C, and Fig. 6 is a diagram showing the electrical conductivity of the polymer of Example 30 obtained in Example D. FIG.

Applicant Akira Dehata Representative of Shosan-Ken Kasei Kogyo Co., Ltd. Patent attorney For long diameters - (Fi or 7 people) Kou 4 mouth

Claims (1)

[Scope of Claims] A polyacetylene mainly composed of structural units represented by the following general formula (I), having a weight average molecular weight of 50,000 or more, or being insoluble in a solvent and having a substituent. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X represents a carbon atom or a nitrogen atom. If X is a carbon atom, it always has a substituent Y, and if Y is not present. The substituent Y represents an electron-withdrawing group or an electron-donating group. Z^1 to Z^4 represent a hydrogen atom, an electron-withdrawing group, or an electron-donating group, and R is a hydrogen atom, an alkyl group, or a cycloalkyl group. (indicates the group)