JPS6197330A - Polythiazole resin and its production - Google Patents

Abstract

PURPOSE:To obtain a polythiazole resin which is excellent in heat stability, electrical properties, etc., and soluble in various solvents and can be easily molded, by reacting a specified bis-alpha-halogenoketone with a dithioamide in an organic solvent. CONSTITUTION:A bis-alpha-halogenoketone of formula I (wherein X is a halogen), e.g., 4,4'-bis(phenyl-alpha-bromoacetyl)diphenyl ether, is reacted with a dithioamide of formula II (wherein Ar is benzene, naphthalene or formula III< Y is -SO2, -S-, -O-, -CH2-, -C2H4- or the like, m is 0-1 and l is 0-1), e.g., dithiooxamide or isophthalithioamide) at a temperature of about 0-200 deg.C in an organic solvent (e.g., N,N-dimethylformamide or nitrobenzene). In this way, the purpose polythiazole resin of formula IV (wherein n is 10-200) is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a novel polythiazole resin and a method for producing the same.

BACKGROUND OF THE INVENTION Conventionally, polythiazole resins have been known as excellent heat-resistant resins.

As such polythiazole resin, for example, 5heeh
ann et al., Journal of Polymer 5
scienceSPart A-1, Vol, 3.144
3 (1965), etc.

Problems to be Solved by the Invention However, many of these polythiazole resins are insoluble in various organic solvents and thermally infusible, making it extremely difficult to mold them.

The present invention was made against the background of the above-mentioned conventional technical problems, and an object of the present invention is to provide a polythiazole resin that has good thermal stability and is soluble in various organic solvents.

A means for solving the problem, that is, the first invention of the present invention is to provide a polythiazole resin represented by the following general formula [I]. - (1) (In general formula (1), 8 is a divalent aromatic group represented by the following, Y is 1, l is 0 or 1, and n is an integer of lo to 2oo. ) Furthermore, the second invention of the present invention provides that when producing the polythiazole resin represented by the general formula [2], a bis-α-halogenoketone represented by the following general formula (n) and... ...... [■] (In the general formula [■], X is a halogen atom.) Dithioamide 82 N C represented by the following general formula [I]:,
-(Ar)t g NH2・ ・ ・ ・ ・ [
[Ir) (In the general formula (III), A "and!" represents the general formula N
The present invention provides a method for producing a polythiazole resin, which is characterized by reacting (same as ) in an organic solvent.

First, to explain the polythiazole resin which is the first invention of the present invention, the resin is a phenyl-substituted polythiazole having a phenyl group at the 5-position of the thiazole ring,
Specifically, polythiazole resins having the following repeating units can be mentioned.

In the present invention, among the components constituting the polythiazole resin, preferably the above-mentioned Ar has a polymerization degree (n) of 10 to 200, preferably 10.
~180.

If the degree of polymerization is less than 10, the mechanical properties of the molded product when the resulting polythiazole resin is molded into a coating, film, etc.
Heat resistance etc. are not sufficient, and on the other hand, if it exceeds 200, solubility in organic solvents etc. and moldability deteriorate, which is not preferable.

The polythiazole resin of the present invention can be confirmed by, for example, an infrared absorption spectrum analysis by an absorption band at 1600 cm-' due to >C=N- of the thiazole ring.

The polythiazole resin represented by the general formula [I] of the present invention is soluble in organic solvents, and molded articles such as polythiazole resin coatings and films can be easily obtained from the resulting solution.

Next, the second invention of the present invention provides that when producing the polythiazole resin represented by the general formula [I], a bis-α-halogenoketone represented by the general formula (Il) and a polythiazole resin represented by the general formula It can be obtained by reacting a dithioamide represented by (Ill) in a solvent.

+ n Hz N −(g (A r )1 to t −N Hz − general formula (bis-α represented by IN
- Halogenoketones include 4.4'-bis(phenyl-α-bromoacetyl) diphenyl ether, 4.4'-bis(phenyl-α-chloroacetyl) diphenyl ether, 4.4'-bis(phenyl-α-iodo) Acetyl) diphenyl ether, etc.

These bis-α-halogenoketones represented by the general formula [■] can be produced by halogenation of the corresponding bisgetones.

Further, as the dithioamide represented by the general formula (III), dithiooxamide, isophthalthioamide, terephthalthioamide, 3,3'-biphenyldicarpothioamide, 4,4'-biphenyldicarpothioamide, 3
．． 3'-methylene dibenzothioamide, 4,4'-methylene dibenzothioamide, 4.4'-ethylene dihendithioamide, 4,4'-isopropylidene dibenzothioamide, 3.3'-oxydibenzothioamide, 4.4
-'oxydibenzothioamide, 3.3'-thiodibenzothioamide, 4.4'-thiodibenzothioamide, 3
, 3'-sulfonyldibenzothioamide, 4.4'-,
Sulfonyldibenzothioamide, 3.3'-carbonyldibenzothioamide, 4.4'-carbonyldibenzothioamide, 1.4-natutaledicarbothioamide, 1
, 5-Natsutale dicarbothioamide, 2,6-Natsutalene dicarbothioamide, 2,7-Natsutalene dicarbothioamide, and the like.

These dithioamides represented by the general formula (I[l]) can usually be produced by reacting the corresponding dinitrile with hydrogen sulfide.

A method for producing a polythiazole resin represented by the above general formula [I] includes a method for producing a polythiazole resin represented by the above general formula [I] and a bis-α-halogenoketone represented by the above general formula [■] in an organic solvent. For example, the reaction temperature is 0 to 200°C and the reaction time is about 10 minutes to 150 hours. If the reaction temperature is less than about 0°C, the polymerization reaction may be difficult to proceed and the degree of polymerization may be less than 10;
If it exceeds this, the polymerization reaction tends to run out of control, resulting in gelation, and the degree of polymerization also exceeds 200, both of which are unfavorable.

In addition, if the reaction time is less than about 10 minutes, polymerization may not proceed sufficiently and the degree of polymerization may be less than 10, and even if the reaction time exceeds 150 hours, the degree of polymerization will not increase proportionally, and in some cases, the degree of polymerization may not increase proportionally. There is also a possibility that the degree of polymerization exceeds 200.

The degree of polymerization (n) of the obtained polythiazole resin can also be adjusted by the amount of the bis-α-halogenoketone represented by the -a formula (II) and the dithioamide represented by the general formula ([11)]. By using approximately equimolar amounts of these reaction components, a high molecular weight polythiazole resin represented by the general formula [I] can be produced.

Examples of organic solvents used in the method for producing polythiazole resin of the present invention include N,N-dimethylformamide, N,
N-dimethylacetamide, N-methyl-2-pyrrolidone, tetramethylsulfone, phenol, cresol,
Examples include nitrobenzene, chlorobenzene, pyridine, formic acid, and acetic acid.

The polythiazole resin represented by the general formula (T) produced in this way is a bis-α-halogenoketone represented by the general formula (II) and/or the general formula (III) used.
The solubility varies depending on the type of dithioamide represented by the dithioamide, but the resulting resin is soluble in methanesulfonic acid, and some resins are soluble in solvents such as cresol, chloroform, nitrobenzene, and pyridine. The resulting polythiazole resin represented by the general formula [I] is
It is extremely stable thermally, and no significant change is observed even when heated to around 500°C.

Function The present invention provides a polythiazole resin with excellent solubility without impairing thermal stability by introducing a phenyl group into the 5-position of the thiazole ring.

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

Example 1 1.5 mmol of 4.4'-bis(phenyl-α-bromoacetyl)diphenyl ether and 1.5 mmol of isophthalthioamide were placed in a flask, and dimethylformamide lQmJ was added thereto to dissolve them. Stir this for 60 minutes
The reaction was carried out at ℃ for 3 days. After the reaction was completed, the reaction mixture was poured into 500 ml of acetone to separate the resulting resin and vacuum-dried. The yield of the resulting resin was 97% and its logarithmic viscosity was 1.14 dIl/g (0.5 g/a, measured at 30° C. in methanesulfonic acid).

The results of the infrared absorption spectrum and elemental analysis of this produced resin were as follows, and it was confirmed that it was a polythiazole resin.

Infrared 1g absorption spectrum (film); 1600cm
An absorption band attributable to the >C=N- bond of the thiazole ring was confirmed at -'.

Elemental analysis calculation value (%), C76,84, H3,94, H4
,98 Actual value (%) i C76, Ol H4,9,
H4,8 The obtained polythiazole resin was soluble in methanesulfonic acid, chloroform, and cresol, and a film could be formed from the solution by a conventional method.

In addition, lO by thermogravimetric measurement of such polythiazole resin
% weight loss temperature is 570°C in air and 580°C in nitrogen.
It was ℃.

Example 2 4.4'-bis(phenyl-α-bromoacetyl)diphenyl ether 1.5 was prepared by the same reaction procedure as in Example 1.
A polythiazole resin was obtained from mmol and 1.5 mmol of terephthalthioamide. The logarithmic viscosity of the produced resin is 1
630d N7g. The obtained polythiazole resin was dissolved in methanesulfonic acid and determined by thermogravimetric measurement.
0% weight loss temperature, 545°C in air, 57°C in nitrogen
It was 0°C.

Effects of the Invention Whereas most conventional polythiazole resins are insoluble in organic solvents and are therefore extremely difficult to mold, the polythiazole resin of the present invention is soluble in organic solvents, easy to mold, and has excellent properties. It has excellent heat resistance and electrical properties, making it extremely valuable as an industrial material.

;, 2 standing'-

Claims (1)

[Claims] 1. A polythiazole resin represented by the following general formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼〔I〕 (In the general formula〔I〕, Ar is,
There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ It is a divalent aromatic group represented by -SO_2-, -S-, -O-, -CH_2-, ▲ Formula , there are chemical formulas, tables, etc. ▼, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ or -C_2H_4-, m is 0 or 1, l is 0 or 1, n represents an integer from 10 to 200. ) 2. When manufacturing polythiazole resin represented by the following general formula [I], there are ▲mathematical formulas, chemical formulas, tables, etc.▼[I] (In the general formula [I], Ar is ▲mathematical formulas, chemical formulas, There are tables, etc. ▼, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ It is a divalent aromatic group represented by -SO_2-, -S-, -O-, -CH_2-, ▲ Formula , there are chemical formulas, tables, etc. ▼, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ or -C_2H_4-, m is 0 or 1, l is 0 or 1, n represents an integer from 10 to 200. ) Bis-α-halogenoketone represented by the following general formula [II], ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [II] (In the general formula [II], X is a halogen atom.) The following general Dithioamide represented by formula [III] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [III] (In general formula [III], Ar and l are the same as in general formula [I] above) in an organic solvent. A method for producing polythiazole resin, which comprises reacting.