JPS60179420A - Anthracene skeleton-containing polycarbonate - Google Patents

Abstract

PURPOSE:A high-molecular compound having a high MW, solubility in an organic solvent, film-forming property, and applicability to ultraviolet absorbers and display materials, having a structure in which anthracene skeletons and nonanthracene skeletons are alternately arranged through a carbonate linkage. CONSTITUTION:An anthracene skeleton-containing polycarbonate of the formula (wherein R1-R4 are each H, a halogen, an 8C or lower hydrocarbon group, 5C or lower alkoxy, 8C or lower aryloxy, or 10C or lower substituted amino, X is a 2-20C diol residue, and n is a degree of polymerization of 5-400). This compound is soluble in a halohydrocarbon solvent such as chloroform. Its solution can be molded into a flexible film, and its melt molding is also possible. 9,10-Anthraquinone (derivative) in an aqueous caustic alkali solution is reduced in an inert atmosphere. After adding bischloroformate, the reaction solution is agitated at a high speed to obtain a polycarbonate. This polycarbonate can be used as a photoconductive material, photoelectric conversion material, etc., as well as an ultraviolet absorber or a display material.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel single molecule compound, in particular:
The present invention relates to a polycarbonate containing an anthracene skeleton in its main chain.

Polymers with an anthracene skeleton in their main chain are expected to have useful properties such as ultraviolet absorption, fluorescence, photoconductivity, and semiconductor functionality, and there are already many synthetic examples.
Regardless of the percentage, most of them have low molecular weight or are insoluble, so they have poor processability and cannot be put to practical use.

For example, U.S. Patent No. 1,128,896 states:
9. Wurtz-Fit of 10-dizolomuanthracene
Poly(9゜10-anthracenelene) by tig reaction
A synthetic method has been proposed, but only a low yield of tellimer with a low degree of polymerization is obtained. In addition, poly(oxycarzenyl-9,10-anthracenylenecarzenyl) obtained by the dehydration reaction of 9.10-anthracenedicalce/acid is insoluble and its molecular weight cannot be measured (
0. Hinterhofer, Makromol
, Ohem, , vol. 181, pages 83-88, (
1980)).

On the other hand, as a relatively high molecular weight and soluble polymer, 9
．． Polyester, polyether, polyurethane from 10-anthracenediol (Japanese Unexamined Patent Publication No. 57-96010), and poly(9,10-anthraceneylenephenylarsinidene) (UK Percentage No. I1.015.501) ), but there are no examples of polycarbonate.

Generally, aromatic polycarbonates are known to exhibit commercial solubility in organic solvents, and polycarbonate having an anthracene skeleton in its main chain has excellent processability and is considered to be extremely advantageous in practical use. However, poly(oxycarcenyloxy-9,10-anthraquinone ll:, #
! It was insoluble in all kinds of solvents, making it impossible to mold it from a solution, and it also lacked melt moldability because it decomposed without melting when heated (0
．． Hinterhofer, supra cit.).

In view of this situation, the present inventors have developed a material with a simple molecular weight.
Furthermore, the present invention was arrived at as a result of intensive studies aimed at developing a polycarbonate having an anthracene skeleton in its main chain that is soluble in organic solvents and has film-forming properties.

That is, the present invention relates to the general formula (wherein, Itl+ "4* RR+ R4 is a hydrogen atom,
Halogen atom, hydrocarbon group having 8 or less carbon atoms, alkoxy group having 5 or less carbon atoms, aryloxy group having 8 or less carbon atoms,
It is one arbitrarily selected from the group consisting of direct amino groups having 10 or less carbon atoms, X is a diol residue having 2 to 20 carbon atoms, and n indicates the degree of polymerization, which is 5 to 400.) It is an anthracene skeleton-containing polycarbonate represented by:

Examples of the hydrocarbon group having 8 or less carbon atoms in the present invention include a methyl group, an ethyl group, a propyl group, an isozorobyl group,
Lower alkyl groups such as butyl group and t-butyl group; aryl groups such as phenyl group and p-tolyl group; examples of alkoxy groups having 5 or less carbon atoms include methoxy group, ethoxy group, zoropoxy group, inzoloboxy group, cytoxy group, t
Examples of aryloxy groups having 8 or less carbon atoms include phenoxy group, p-methylphenoxy group, p-chlorophenoxy7 group, etc. Substituted amine groups having io or less carbon atoms include, for example. dimethylamino group,
Examples include diethylamino group, diisozolobylamino group, and acetamido group.

Further, examples of diol residues having 2 to 20 carbon atoms in the present invention include 1,2-ethanediol residues, 1,3-
Propanediol residue, 1,4-butanediol residue,
1.5-bentanediol residue, 1.6-hexanediol residue, 1.7-hebutanediol residue, l,8-octanediol residue, 1,9-nonanediol residue, 1
．． 10-decanediol residue, 1.12-dodecanediol residue 2,2/-oxygetanol residue, 1
．． 4-cyclohexanediol residue M, 1.4-cyclohexane dimetatool residue, hydroquinone residue, resorcinol residue, 4.4'-isopropylidenediphenol residue, 4.4'-methylenediphenol residue, 4 ,4'
-thiodiphenol residue, p-xylylene diol residue, etc.

The anthracene skeleton-containing polycarbonate of the present invention can be produced by the two-step process shown below.

The first step is a reduction step, in which 9.10-anthraquinone or a substituted derivative thereof is reduced in a caustic alkaline water bath under an inert ambient atmosphere to form an alkali metal of 9.10-anthracenediol or a substituted derivative thereof. Obtain maple salt. As the reducing agent, sodium dithionite is preferred, and the amount used is 1 to 4 mol per 1 mol of anthraquinone.Also, as a dispersant and a phase transfer catalyst in the second step, a small amount of quaternary ammonium salt is used. It is preferable to add and leave at °C, and Cortamine 24P (manufactured by Kao Atlasne L; trade name) can be particularly preferably used.The time required for reduction is 5 to 30 minutes when the reduction temperature is 45 °C.

The second step is an interfacial polymerization step, and polycarzenate is obtained by adding bischloroformate to the reaction solution obtained in the first step and stirring at high speed. Bischloroformate is 0 per mole of 9.10-anthraquinone.
．． It is preferable to use 8 to 1.2 mol of chloroform, 1,1,
2. Halogenated hydrocarbons such as 2-7-trachloroethane can be suitably used. The reaction temperature is 0 to 30°C, and the reaction time is 5 to 20 minutes.

The structure of the polycarzenate of the present invention was confirmed as follows. That is, in the infrared absorption spectrum (hereinafter abbreviated as IR), there are strong absorptions characteristic of carbonate bonds at 1750-1780 ryn-' and 1210-12
It was observed at 20 cm-'. In the ultraviolet absorption spectrum (hereinafter abbreviated as UV), three absorption lines characteristic of the anthracene skeleton were observed in the wavelength range of 350 to 420 nm. These characteristic absorptions were in good agreement with the absorption of a low-molecular model compound (see reference side below).

Furthermore, the elemental analysis values of the polymer were consistent with the calculated values for polycarbonate.

As is clear from the above explanation, l' IJ of the present invention
Carbonate has an alternating copolymer structure in which anthracene skeletons and non-anthracene skeletons are alternately arranged via carbonate bonds, and is a new polymer that is completely different from the existing polycarbonate, which has four homopolymer rows. is. The effect of introducing a non-anthracene skeleton was significantly reflected in the physical properties of the polymer, and the following preferable substances were developed. That is, the polycarzenate of the present invention is soluble in halogenated hydrocarbon solvents such as chloroform, 11213-trichloropropane, and 1°1.2.2-tetrachloroethane, and the high molecular weight polymer can be extracted from these solutions. It can be formed into a transparent and flexible film. Furthermore, since the polycarbonate of the present invention melts in a bath without being decomposed by heating, melt molding is also an option. These properties were not found in the existing polycarbonates, and in this respect as well, the polymer of the present invention can be clearly distinguished from existing polymers.

The polycarbonate of the present invention can be used for various purposes by taking advantage of the above-mentioned excellent processability and functions derived from the anthracene skeleton. For example, it can be used as an ultraviolet absorbing material or a display material.
．． 7-) It is also possible to use it together with an electron-accepting compound such as linitrofluorenone to produce a photoconductive material, a photoelectric conversion material, an organic semiconductor material, etc.

Hereinafter, the present invention will be explained in more detail with reference to Examples.
), and the number average molecular weight (Mn) and weight average molecular weight (molecular weight) were determined by gel permeation chromatography. ■General is measured by KBr tablet method, U■ is 1
．． 1.2. Measured in 2-tetrachloroethane.

Reference example 2.6-cynotoxy9,10-anthraquinone 2.6
8 f, Cortamine 24P (manufactured by Kao Atlas Co., Ltd., the same hereinafter) 1.9 ml, potassium hydroxide 4.21 r, sodium dithionite 2.61 f (i-Water 125 was mixed in 1, and the mixture was heated under a nitrogen atmosphere. The mixture was stirred at 45°C for 15 minutes.

The reaction mixture was cooled to 15°C and stirred at high speed (3000 rpm).
30W of 3.26t of ethyl chloroformate
The Ll chloroform solution was added all at once and allowed to stir for 10 minutes. Add 30 d of chloroform to the reaction mixture and dilute
The chloroform layer was washed with 100 m6 of water, dried over anhydrous magnesium sulfate, and condensed to obtain a yellow powder of 3.731F. This powder is recrystallized from ethanol,
Diethyl 2,6-dimethoxy-9, having the following structure:
1o-Anthracenylene dicarzenate3. aor (yield 8o%) was obtained as yellow needle crystals.

mp: 205.2~205 +8℃IR: 175
5crn' (0=O), 1220cIn-' (0-
0) Uv:λmax 372.392.414 nmN
MR (in 4g ODO, 60MHz): δ1.37(s
,6H.

0H3), 3.90 (s, 6H+0OH3),
4.46 (quadruple line 94HI OOR,), 7.1-8.
0 (m.

6H, aromatic proton) 0 63.76 63.58 H5,355+36 Example 1 9.10-Anthraquinone 2.08 f, Cortamine 2
4 P 1-9 tttls Potassium hydroxide 3.65
f, 2.61 t of sodium dithionite and 125 d of water
and stirred for 15 minutes at 45° C. under nitrogen atmosphere. The reaction mixture was cooled to 15°C and heated at 3500 rpm.
A solution of 2.55 f of -\xamethylene bischloroformate in 30'ml of chloroform was added at once, and stirring was continued for 10 minutes. 20 g of chloroform was added to the reaction mixture to separate the layers, and the chloroform layer was diluted with 0.05N
Wash with m acid 150mJ, then the electrical conductivity of the washing liquid is 10
After washing with water until it became below μS/cm, it was added to a large amount of methanol. The resulting precipitate was filtered, washed with methanol, and dried to obtain polymer 2.89f (yield: 769
b) was obtained.

mp: 181-184℃ ηinh: 0.81'Fr;;: 31,500 VFt: 165;000 IR: 1755an-'' (0=O), 1720ty
n-” (0-0)Uv: λmax 353, 37
1,391 nm elemental analysis bimolecular formula (OuHzoOs)
n Calculated value Analytical value 0 69.46 68.32 H5,305,2,9 Example 2 9.10-ant 2 quinone 2. ．． 2- instead of 08t
The reaction was carried out in the same manner as in Example 1 except that methoxy-9,10-anthraquinone 2.389 was used to obtain a polymer 3.32y (yield: 81%) having the following structure.

Below margin mp: 178-184℃ 17 inh: 0.58 Ml: 32,200 Mw: 133,000 IR: 1760z-' (C=0), 12156n-
'(U-0)Uv: λmax 35B, 38
5,405 nm elemental analysis: Molecular formula (U*5HuOy)
n Calculated value Analytical value 0 67.31 67.04 H5,405,36 Example 3 9.10-Anthraquinone 2.08 2゜6-Simethoxy9.10-Anthraquinone 2.68t instead of f
The amount of chloroform added after polymerization was 701MI! The reaction was carried out in the same manner as in Example 1 except that polymer 3. having the following structure was prepared. x7t (yield 72%) was obtained.

mp: 188-192℃ ηinh: 0.64 Mn: 26,900 Mw: 146,000 IR: 1760cm' (U=0), 1210cn
1'((J-0)Uv:λmax 372.393.4
15 nm elemental analysis: Molecular formula (0*4Hz40s) n Calculated value Analysis value 0 65.45 64.88 H5,495,45 Example 4 9.10-Anthraquinone 2.08 2゜6-Simethoxy 9, instead of r 10-anthraquinone 2.689
using 1.1.2.2-tetrachloroethane instead of chloroform, and the amount of potassium hydroxide was 4.21.
The reaction was carried out in the same manner as in Example 1 except that 1F was used, and 1limer-3,04y having the structure shown in Example 3 (yield 69%
) was obtained.

mp: 182-191tll: vinh: 0.34 ■: 27,000 Tri;: 73,000 Example 5 9.10-anthraquinone 2.08 2°6-dimethoxy-9,10-anthraquinone instead of r2. 6Fl
Using -\xamethylene bischloroformate 2.5
The reaction was carried out in the same manner as in Example 1, except that 2.2'-oxydietherbischloroforme) 2.439 was used in place of 5t, and a polymer 2.7af having the following structure was prepared.
(yield: 64%).

mp: 171-173℃ ηInh: 0.24 M stone: 20,300 Mw: 55,700 ■ru: 1760tn' (0=0), 1215cr
n-” ((J-0)Uv: λmax 372,
393, 415cm' Elemental analysis: Molecular formula (022H + O
s) Calculated value Actual value 0 61.68 60.94 Hto, '71 4.84 Example 6 2.6-Simethoxy9,1o-anthraquinone 2.6
8 W, Kotami 724P 1.9+yl? , potassium hydroxide 4.21 ? , sodium dithionite 2.61
f was mixed in 125 d of water and stirred at 45° C. for 15 minutes under nitrogen atmosphere. The reaction mixture was cooled to 15°C and stirred at 3500 rpm, and a solution of 4,4'-isopropylidene diphenylpischloroformate 3.71F in 30d1,1,2,2-tetrachloroethane was added all at once. and continued stirring for 10 minutes. Separate the reaction mixture,
The first layer was washed with 0.05N sulfuric acid (TSOI), then washed with water until the electrical conductivity of the washing solution became 10 μS/z or less, and then added to a large amount of methanol. The resulting precipitate was filtered, washed with methanol, and dried to obtain a polymer 3.8 with the following structure.
49 (yield 7o%) was obtained.

mp: 178-185°C W inh: 0.15 Mn: 24,200 Mw: 42,600 IR: 1780crn-' (0=O), 12203
'(0-0)UV: λmax 372, 392, 4
14 nm elemental analysis bimolecular formula (0ssHuOs) Calculated value Analysis value 0 71.99 71.94 H4,765+14 Example 7 9.10-Anthraquinone 2.08 2- instead of F
Dimethylamino-9,10-anthraquinone 2.51
The reaction was carried out in the same manner as in Example 1 except that t was used, and polymers a and aof (yield 78%) having the following structures were obtained.

mp 2 152-157℃ ηinh: 0.53 Mn: 29,800 Mw: 115,700 IR: 1760cm'' (0=O), 1215c
m-” (0-0)UV: λmax 350, 37
0. 400 nm elemental analysis: Molecular formula (U24H2SN
O6) n total A transparent film with a thickness of 14 μm was obtained by casting on a plate. When this film was irradiated with light at a wavelength of 366 nm, it emitted strong blue-white fluorescence, proving that this polymer would be an excellent display material.

Example 9.10 Films of the polymers obtained in Examples 3 and 5 were formed in the same manner as in Example 8, and when irradiated with 366 nm light, both films emitted strong green fluorescence.

Patent applicant: Asahi Kasei Industries, Ltd.

Claims (1)

[Claims] General formula (in the formula, 几1+"2+几3.R4 is a hydrogen atom), rogene atom, hydrocarbon group having 8 or less carbon atoms, alkoxy group having 5 or less carbon atoms, 8 or less carbon atoms is one arbitrarily selected from the group consisting of an aryloxy group, a substituted amino group having 10 or less carbon atoms, X is a diol residue having 2 to 20 carbon atoms, n indicates the degree of polymerization, 5 to 400) Anthracene skeleton-containing polycarzenate represented by