JPH06263852A - Aromatic polyester or aromatic polyamide and its production - Google Patents

Abstract

PURPOSE:To produce an arom. polyester or polyamide in the absence of a catalyst without heating and without producing a by-product by reacting a specific quinonediketene compd. with a quinone or quinonediimine compd. CONSTITUTION:A quinonediketene compd. of formula I or II is reacted with a quinone compd. (e.g. a compd. of formula I) or a quinonediimine compd. (e.g. a compd. of formula IV) at 0-30 1I) to give an arom. polyester or polyamide respectively of formula V or VI. In those formulae, Ar is a group of formula VII, VIII, or IX; Y is O or NX<1>; R<1> t R<64> are each H, 1-18C alkyl, alkoxy, halogen, etc.; and X<1> is H, 1-18C alkyl, 1-18C alkoxy, 1-18C alkylsulfonyl, halogen, etc. Because of the polymn. conducted at room temp. without using a catalyst, the steps of catalyst removal, heating, and cooling are not necessary and thus a polymer contg. no impurity is obtd.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an aromatic polyester or an aromatic polyamide and a method for producing the same.

[0002]

2. Description of the Related Art Aromatic polyesters and aromatic polyamides are super engineering plastics called polyarylate or aramid, which have excellent heat resistance and mechanical properties.

Conventionally, the production method is by polycondensation. The acid chloride method and the transesterification method (acetate method, phenyl ester method) are used in the case of aromatic polyester, and the acid chloride method is used in the case of aromatic polyamide. The amide exchange method and the isocyanate method are used industrially.

Examples of the acid chloride method in the production of aromatic polyesters include Ind. Eng. Che
m. 51, 147 (1959), J. Macromo
l. Sci. -Chem. , A15,833 (198
1) and J. Appl. Polym. Sci. , 2
No. 3,2409 (1979) and the like are known, but in these methods, a salt is produced as a by-product, and addition of a catalyst or heating at 100 to 200 ° C. is required.

The transesterification method (acetate method, phenyl ester method) is described in J. Polym. Sci. Ch
em. Ed. 14, 2207 (1976), J. Ma
cromol. Sci. -Chem. , A21, 170
5 (1984) and Polymer, 15, 527.
(1974) and the like are known, but in this case, 200-
Heating at 300 ° C. is required, and there are problems such as removal of acetic acid or phenol as a by-product.

As the acid chloride method in the production of aromatic polyamide, for example, Macromol. , 10, 1
396 (1977) is known, but also in this case, the formation of a salt as a by-product is a problem.

Examples of the amide exchange method are described in J. Ap
pl. Polym. Sci. , 25, 1685 (198
0) and Proc. Am. Chem. Soc. Pol
ym. Mater. Sci. Eng. , 60,623
(1989) and the like are known, but removal of acetic acid as a by-product and heating at 200 to 350 ° C. are required.

The isocyanate method is described in Polym.
Eng. Sci. 25, 942 (1985) and J. Polym. Sci. , Part A, Poly
m. Chem. , 27, 1775 (1989) and the like are known. However, these methods require the addition of catalyst and heating at 200 ° C.

On the other hand, C. S. Marvel et al.
We reported the synthesis of polyamide by the addition of amino group to the ketene group in the reaction of 0-dicarbonyl-9,10-anthraquinone with m-phenylenediamine (JP.
olym. Sci. , Part A-1, 8, 2611
(1970)). In this method, the anthracene ring produced is a 9,10-dihydro body, and thereafter, there is no report on the synthesis of polyesters and polyamides using quinone diketene.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide an aromatic polyester or an aromatic polyamide and a method for producing the same, and more specifically, it is a catalyst-free and by-product-free heating. It is intended to provide a novel method for producing an aromatic polyester or an aromatic polyamide by a simple process that does not require

[0011]

Means for Solving the Problems As a result of intensive studies in view of this problem, the present inventors have found a novel aromatic polyester or aromatic polyamide production method using quinone diketene and benzoquinone or benzoquinone diimine as raw materials. They have found the present invention and completed the present invention.

That is, the present invention provides a novel aromatic polyester or aromatic polyamide represented by the general formula (I) or (II) and the general formula (III) or (IV).
And a quinone diketene represented by the general formula (V) to (VI)
Quinones represented by I) or the general formula (VIII)
It relates to a method for producing an aromatic polyester or an aromatic polyamide, which comprises reacting the quinonediimine represented by (X) at 0 to 30 ° C.

The general formula (II) used in the production method of the present invention is
Examples of the quinone diketene represented by I) or (IV) include 9,10-dicarbonyl-9,10-anthraquinone and 1,4-dicarbonyl-1,4-naphthoquinone, which may be used alone or in combination. A combination of two or more species can be used.

Methods for synthesizing these quinone diketene compounds are described in, for example, J. Polym. Sci. , Part A-1,
8, 2611 (1970), and since it is highly reactive, it is used as a solution of an inert solvent such as benzene, toluene, xylene, ethylbenzene, cyclohexane, n-pentane, n-hexane and n-heptane. To be

The quinones represented by formulas (V) to (VII) include 1,4-benzoquinone and 2,5-benzoquinone.
Di (t-butyl) -1,4-benzoquinone, 2,6-di (t-butyl) -1,4-benzoquinone, p-chloranil, 1,4-naphthoquinone, 2-chloro-1,4-naphthoquinone, 2,6-naphthoquinone, 1,5-dibromo-
2,6-naphthoquinone and the like can be mentioned, and these can be used alone or in combination of two or more.

Further, the quinonediimines represented by the general formulas (VIII) to (X) include 1,4-benzoquinonediimine, N, N'-dichloro-1,4-benzoquinonediimine and N, N'-. Diphenyl-1,4-benzoquinone diimine, 1,4-naphthoquinone diimine, N,
N'-bis (phenylsulfonyl) -1,4-naphthoquinonediimine, N, N'-bis (phenylsulfonyl)
Examples thereof include 2,6-naphthoquinonediimine, and these can be used alone or in combination of two or more.

The proportion of quinone diketene and quinone or quinone diimine used in the production method of the present invention is not particularly limited, but 0.1 to 20 mol of quinone or quinone diimine is used per 1 mol of quinone diketene. It is particularly preferable to use 0.5 to 10 mol.

As the polymerization solvent used in the reaction of the present invention, benzene, toluene, xylene, ethylbenzene, cyclohexane, n-pentane, n-hexane,
Examples thereof include n-heptane, and benzene is particularly preferable.

The polymerization temperature does not need to be particularly heated and may be 0 to
It can be polymerized at 30 ° C.

The polymerization time is not particularly limited, but since the reaction is instantaneously completed, it is 0.1 to 20 hours, preferably 0.5 to
10 hours.

The characteristic feature of the production method of the present invention is that the quinone diketene represented by the general formula (III) or (IV) and the quinones represented by the general formulas (V) to (VII) or the general formula (VIII) to The use of the quinonediimines represented by (X). That is, in the production method of the present invention, it is considered that the polymerization proceeds by non-catalytic radical alternating copolymerization of quinone diketene and quinone or quinone diimine. Therefore, byproducts such as salts or acetic acid found in the conventional production method by polycondensation are not involved.

Also, J. C. Martin et al., 1,4-
In the reaction of benzoquinone and dimethylketene, the synthesis of mono-β-lactone by the addition reaction of ketene and carbonyl has been reported (J. Org. Chem., 36, 2).
216 (1971)), in the production method of the present invention, benzoquinone diimines, quinones and quinone diimines are
Since the energy difference between the quinoid compound and its triplet excited state, the benzonoid state, is lower than that of the vinyl compound, it is highly reactive, and it is considered that radical alternating copolymerization occurs selectively. Side reactions accompanied by are suppressed. Further, in the production method of the present invention, since the polymerization is carried out at room temperature without a catalyst, the steps of removing the catalyst, heating and cooling, etc. can be simplified, and a pure polymer containing no impurities can be obtained.

[0023]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to the examples.

In this example, the molecular weight of the produced polymer was determined by polystyrene conversion using GPC (HLC-802A manufactured by Tosoh Corporation).

The structure of the produced polymer is NMR
(EX-270 FT-NMR manufactured by JEOL), IR
(JASCO Corporation IR-700 type infrared spectrophotometer), elemental analysis (Yanaco CHN corde)
r MT-3 type).

Example 1 A solution of 0.12 g of 1,4-benzoquinone dissolved in 5 ml of purified and degassed benzene was dissolved in a benzene solution of 9,10-dicarbonyl-9,10-anthraquinone (0.
(2 mol / l) was added to 5 ml with stirring under a nitrogen atmosphere, and the reaction was carried out at room temperature for 5 hours. The precipitated solid was filtered and dried under reduced pressure. As a result, 0.22 g of insoluble and infusible polymer
Got

From the results of elemental analysis of the obtained polymer, the quinone diketene unit in the produced polymer was 50.8 mol%. In addition, IR measurement revealed that lactone ring formation due to side reaction was not observed and a pure polymer was obtained.

Example 2 A solution prepared by dissolving 0.16 g of p-chloranil in 10 ml of purified and degassed benzene was added to 9,10-dicarbonyl-
5 ml of a benzene solution of 9,10-anthraquinone (0.13 mol / l) was added with stirring under a nitrogen atmosphere,
The reaction was carried out at room temperature for 3 hours. The precipitated solid was filtered and dried under reduced pressure to obtain 0.15 g of an insoluble and infusible polymer.

From the results of elemental analysis of the obtained polymer, the quinone diketene unit in the produced polymer was 51.3 mol%. In addition, IR measurement revealed that lactone ring formation due to side reaction was not observed and a pure polymer was obtained.

Example 3 In 6 ml of purified and degassed benzene, 2,6-di (t-
Butyl) -1,4-benzoquinone (0.11 g) was added to a solution of 9,10-dicarbonyl-9,10-anthraquinone in benzene (0.09 mol / l) (5 ml) with stirring under a nitrogen atmosphere. The reaction was carried out at room temperature for 5 hours. The reaction contents were poured into hexane to cause precipitation, which was then filtered and dried under reduced pressure. The yield was 0.03g.

From the NMR measurement and elemental analysis results of the obtained polymer, the quinone diketene unit in the produced polymer was 50.6 mol%, and the molecular weight (Mw) was 430.
It was 0. It was confirmed by NMR measurement and IR measurement that a pure polymer was obtained.

Example 4 A solution of 0.17 g of N, N'-diphenyl-1,4-benzoquinonediimine dissolved in 10 ml of purified and degassed benzene was used to prepare a solution of 9,10-dicarbonyl-9,10-anthraquinone. Benzene solution (0.11mol / l) 6m
It was added to 1 with stirring under a nitrogen atmosphere and reacted at room temperature for 5 hours. The reaction contents were poured into hexane to cause precipitation, which was then filtered and dried under reduced pressure. The yield was 0.11 g.

From the results of NMR measurement and elemental analysis of the obtained polymer, the quinone diketene unit in the produced polymer was 50.4 mol%, and the molecular weight (Mw) was 160.
It was 0. It was confirmed by NMR measurement and IR measurement that a pure polymer was obtained.

Example 5 A solution prepared by dissolving 0.06 g of 1,4-benzoquinonediimine in 3 ml of purified and degassed benzene was used as 9,10-.
13 ml of a benzene solution of dicarbonyl-9,10-anthraquinone (0.04 mol / l) was added with stirring under a nitrogen atmosphere, and the reaction was carried out at room temperature for 5 hours. The precipitated solid was filtered and dried under reduced pressure. The yield was 0.16 g.

From the results of elemental analysis of the obtained polymer, the quinone diketene unit in the produced polymer was 51.0 mol%. In addition, IR measurement revealed that lactone ring formation due to side reaction was not observed and a pure polymer was obtained.

[0036]

EFFECTS OF THE INVENTION According to the production method of the present invention, since the polymerization is carried out at room temperature without a catalyst, the steps of removing the catalyst, heating and cooling, etc. are simplified, and a pure polymer containing no impurities is obtained. be able to.

Claims (2)

[Claims] 1. An aromatic polyester or aromatic polyamide represented by the following general formula (I) or (II). [Chemical 1] [Chemical 2] (Here, Ar may be the same or different, and , Y is —O— or —NX ¹ —, R ^{1 to} R ¹⁴ are each independently hydrogen, an alkyl group having 1 to 18 carbon atoms, and 1 to 1 carbon atoms.
18 alkoxyl groups, halogen or phenyl groups, R
^{15 to} R ³⁰ are each independently hydrogen, an alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, a halogen, a cyano group, a phenyl group or a nitro group, and X ¹ may be the same or different. , Hydrogen, an alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, and 1 to 1 carbon atoms
18 represents an alkylsulfonyl group, halogen, cyano group, phenyl group, phenylsulfonyl group or toluenesulfonyl group) 2. A quinone diketene represented by the following general formula (III) or (IV) and a quinone represented by the following general formulas (V) to (VII) or the following in producing an aromatic polyester or an aromatic polyamide: A method for producing an aromatic polyester or an aromatic polyamide, which comprises reacting the quinonediimines represented by the general formulas (VIII) to (X) at 0 to 30 ° C. [Chemical 4] (Here, R ^{31 to} R ³⁸ each independently represent hydrogen, an alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, a halogen, or a phenyl group.) (Here, R ^{39 to} R ⁴⁴ each independently represent hydrogen, an alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, a halogen or a phenyl group.) (Here, R ^{45 to} R ⁴⁸ each independently represent hydrogen, an alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, a halogen, a cyano group, a phenyl group or a nitro group) ] (Here, R ^{49 to} R ⁵⁴ each independently represent hydrogen, an alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, a halogen, a cyano group, a phenyl group or a nitro group) ] (Here, R ^{55 to} R ⁶⁰ each independently represent hydrogen, an alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, a halogen, a cyano group, a phenyl group or a nitro group) ] (Here, R ^{61 to} R ⁶⁴ are each independently hydrogen, an alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, a halogen, a cyano group, a phenyl group or a nitro group,
X ^{2 to} X ³ are each independently hydrogen, an alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, and 1 carbon atom.
~ 18 alkylsulfonyl group, halogen, cyano group,
A phenyl group, a phenylsulfonyl group or a toluenesulfonyl group) (Here, R ^{65 to} R ⁷⁰ are each independently hydrogen, an alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, a halogen, a cyano group, a phenyl group or a nitro group,
X ^{4 to} X ⁵ are each independently hydrogen, an alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, and 1 carbon atom.
~ 18 alkylsulfonyl group, halogen, cyano group,
A phenyl group, a phenylsulfonyl group or a toluenesulfonyl group) (Here, R ^{71 to} R ⁷⁶ are each independently hydrogen, an alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, a halogen, a cyano group, a phenyl group or a nitro group,
X ^{6 to} X ⁷ are each independently hydrogen, an alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, and 1 carbon atom.
~ 18 alkylsulfonyl group, halogen, cyano group,
Indicates a phenyl group, a phenylsulfonyl group or a toluenesulfonyl group)