JPH0353326B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a diacetylene group-containing polyamide, and more specifically to a polymer that exhibits high strength and high elastic modulus not only in the molecular chain direction but also in the vertical direction of the molecular chain by crosslinking with diacetylene groups. This invention relates to diacetylene group-containing polyamide, which is a useful raw material for materials. [Prior Art] In recent years, attempts have been made to apply compounds having diacetylene groups to optical materials, conductive materials, and the like. (Dee Blower, R.R.
Chance, “Polydiacetylene” NATO ASI
Series E, Applied Science 102). In addition, the present inventors have synthesized various compounds having diacetylene groups and have developed high-modulus polymer materials using these as raw materials. [Problems to be solved by the invention] However, amide compounds with diacetylene groups in which the conjugated system spreads throughout the molecule are interesting in that they can exhibit high strength and high elastic modulus in the direction of the molecular chain; Such examples are extremely rare. In addition, fully aromatic polyamide (aramid) has recently attracted attention as a high-strength, high-modulus fiber.
Although it has a number of excellent physical properties, its low strength, elastic modulus, and adhesiveness in the direction perpendicular to the molecular chain, typified by fibrillation, are problems at a practical level. Therefore, the present inventors introduced a diacetylene group with excellent crosslinking properties into the main chain of a wholly aromatic polyamide, thereby making such a wholly aromatic polyamide have high strength and high elastic modulus in the molecular chain direction. It has been found that by maintaining the same properties and crosslinking with diacetylene groups, excellent mechanical properties can be exhibited even in the direction perpendicular to the molecules, and as a result of further intensive studies, the present invention has been achieved. [Means for solving the problem] In other words, the present invention provides, as a repeating unit, (where,
Represents up to 12 divalent aromatic organic groups. ) and a number average degree of polymerization of 3 to 400. In the present invention, X, X', Y, Y' are hydrogen atoms,
Indicates a halogen atom, alkoxide, or a monovalent organic group having 1 to 5 carbon atoms; halogen atoms are Cl, Br, and I; alkoxides are -
OCH ₃ , -OC ₂ H ₅ , -OC ₃ H ₅ , -OC ₆ H ₅ , organic groups having 1 to 5 carbon atoms include -CH ₃ , -C ₂ H ₅ ,
−C ₃ H ₇ , −C ₄ H ₉ , −C ₅ H ₁₁ ,

【formula】 【formula】

[Formula] etc., and some or all of the hydrogen atoms of these organic groups are halogen atoms, nitro groups, amino groups, cyano groups, carbonyl groups, carboxyl groups,
It may be substituted with a functional group such as an ether bond. As these X and X', hydrogen atoms are preferable in order to improve the strength due to the cohesive force of hydrogen bonds.
For Y and Y′, hydrogen atoms are
In addition, methyl groups are used for ease of synthesis and moldability.
preferable. In the present invention, Z is a divalent aromatic group having 4 to 12 carbon atoms, examples of which include:

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] etc., and some or all of the hydrogen atoms of these compounds are halogen atoms, cyano groups,
It may be substituted with a carboxyl group, amide group, ester group, carbonyl group, ether bond, etc. for example,

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] etc. Among these Z, preferable ones are from the viewpoint of tobochemical properties,

Ortho form and meta form of [formula], In terms of rigidity,

It is a loose form of [Formula]. In the present invention, the combinations of X, X', Y, Y', and Z include (X, X', Y, Y', Z), (H,
H, H, H,

[Formula]) (H, H, H, H,

[Formula]) (H, H, H, H,

[Formula]) (H, H, CI, CI,

[Formula]) (H, H, CI, CI,

[Formula]) (H, H, CI, CI,

[Formula]) (H, H, Br, Br,

[Formula]) (H, H, Br, Br,

[Formula]) (H, H, Br, Br,

[Formula]) (CH ₃ , CH ₃ , H, H,

[Formula]) (CH ₃ , CH ₃ , H, H,

[Formula]) (H, H, CH ₃ , CH ₃ ,

[Formula]) (H, H, CH ₃ , CH ₃ ,

[Formula]) (H, H, CH ₃ , CH ₃ ,

[Formula]) (H, H, -OCH ₃ , -OCH ₃ ,

[Formula]) (H, H, H, H,

[Formula]) (H, H, CI, CI,

[Formula]) etc., and due to ease of synthesis and rigidity, (H, H, H, H,

[Formula]) (H, H, H, H,

[Formula]) (H, H, H, H,

[Formula]) (H, H, CI, CI,

[Formula]) etc. are preferred. In the present invention, the degree of polymerization of the diacetylene group-containing polyamide is from 3 to 400, and preferably 50 or more in order to provide sufficient strength and moldability. As a method for producing the diacetylene group-containing polyamide of the present invention, for example, ethynylbenzoic acid chloride

[Formula] (Yn is Y or Y') and diamine

[Formula] is reacted in an organic solvent or in a two-phase system of water and organic solvent. can be synthesized by oxidative coupling polymerization using a metal salt such as CuCl as a catalyst. Ethynylbenzoic acid chloride

Synthesis examples of [Formula] have already been published in Journal of Polymer Science Polymer Chemistry Edition 22, 3011,
(1984), and can be synthesized using this method.

[Formula] and

〔Effect of the invention〕

Since the diacetylene group-containing polyamide of the present invention has a rigid molecular chain, it exhibits high strength and high elastic modulus in the direction of the molecular chain, and also has high mechanical properties in the direction perpendicular to the molecular chain due to the crosslinking reaction by the diacetylene group. can be expressed. Therefore, the diacetylene group-containing polyamide of the present invention is extremely useful as a raw material for structural materials, conductive materials, optical functional materials, and non-fibril fibers. [Examples] Hereinafter, the present invention will be explained using examples to further clarify the present invention, but it goes without saying that the scope of the present invention is not limited to these examples. Furthermore, the reagents used in the present invention may be purified if necessary, and this is preferable. Example 1 synthesis of

[Formula] 1 mol was dissolved in 400 ml of chloroform, and to this was slowly added 0.5 mol of p-phenylenediamine dispersed in 600 ml of 2N-NaOH aqueous solution at 10°C.
Stir vigorously for a minute. After the reaction, the precipitated solid was isolated by suction filtration, and further recrystallized using hexafluoroisopropanol. thus obtained Dissolve 0.5 mol in 600 ml of N-methylpyrrolidone, and then add 100 ml of tetramethylethylenediamine.
ml and 0.01 mol of copper chloride (1) were added, and the mixture was reacted for 16 hours while blowing oxygen gas. After the reaction, the mixture was poured into a large amount of methanol, and the precipitated white solid was isolated by suction filtration. The yield of the obtained polymer is p-
Starting from phenylenediamine it was 86%.
The polymer also decomposed at 365°C. The number average degree of polymerization of the polymer determined by the terminal group determination method is
It was 3.0. IR (Nujol) 3286cm ^-1 , 3080cm ^-1 , 1647cm ^-1 ,
1602cm ^-1 , 1130cm ^-1 Example 2 Instead of synthesis p-phenylenediamine,

Example 1 was repeated except using the formula: The white solid obtained is 79
% yield and decomposed at 382°C. The number average degree of polymerization of this polymer was 232.9. IR (Nujol) 3286cm ^-1 , 3070cm ^-1 , 1647cm ^-1 ,
1602cm ^-1 , 1132cm ^-1 Example 3 Synthesis of instead of p-phenylenediamine,

Example 1 was repeated except that the formula was used. The white solid obtained was 90% yield and decomposed at 289°C. The number average degree of polymerization of this polymer was 398.6. IR (Nujol) 3078cm ^-1 , 2986cm ^-1 , 1664cm ^-1 ,
1538cm ^-1 , 1140cm ^-1 Example 4 synthesis of

instead of [expression]

Example 1 was repeated except using the formula. The resulting white solid had a yield of 83% and decomposed at 346°C. The number average degree of polymerization of this polymer was 400.0. IR (Nujol) 30286cm ^-1 , 3080cm ^-1 , 1647cm ^-1 ,
1602 cm ^-1 , 1130 cm ^-1 Example 5 0.2 mole of 0.5 mole of p-phenylenediamine

Example 1 was repeated except that [Formula] was replaced. The pale yellow solid obtained is 79%
yield and was decomposed at 350°C. The number average degree of polymerization of this polymer was 276.3. IR (Nujol) 3272cm ^-1 , 1640cm ^-1 , 1530cm ^-1 ,
1332cm ^-1 , 1186cm ^-1 Example 6

[Formula] Instead of 1 mole,

[Formula] 0.5 mol,

Example 1 was repeated except that a 0.5 molar mixture was used. The white solid obtained had a yield of 88%. The number average degree of polymerization of this polymer was 123.6. IR (Nujol) 3286cm ^-1 , 1647cm ^-1 , 1530cm ^-1 ,
1132 cm ^-1 Example 7 When pyridine was used in place of tetramethylethylenediamine in the oxidative coupling polymerization of Example 1, the yield was improved to 93%. The number average degree of polymerization of the obtained polymer was 46.2. Example 8 synthesis of

[Formula] Dissolve 1 mole in anhydrous tetrahydrofuran, add another 1 mole of pyridine, and gradually add

0.5 mol of [Formula] was added and the mixture was reacted for 4 hours in argon. After the reaction, the reaction product was poured into water, and the precipitated white solid was recrystallized from hexafluoroisopropanol. thus obtained were subjected to oxidation coupling assembly according to Example 7. The white solid obtained was 86% yield;
It did not decompose up to 376℃. The number average degree of polymerization of this polymer was 15.3. IR (Nujol) 3286cm ^-1 , 3080cm ^-1 , 1647cm ^-1 ,
1602cm ^-1 , 1130cm ^-1 Example 9 synthesis of

instead of [expression]

Example 1 was repeated except using the formula. The resulting white solid had a yield of 93% and decomposed at 370°C. The number average degree of polymerization of this polymer was 98.7. IR (Nujol) 3286cm ^-1 , 3080cm ^-1 , 1647cm ^-1 ,
1602cm ^-1 , 1100cm ^-1

Claims (1)

[Claims] 1. As a repeating unit, (where,
Represents up to 12 divalent aromatic organic groups. ) having a number average degree of polymerization of 3 to 400.