JPH0428719A - Polyamide resin, its production and production of cross-linked polyamide resin - Google Patents

Abstract

PURPOSE:To obtain the subject polyamide resin having a specified structural formula, excellent in solubility in an organic solvent, etc., and suitable for an electron-insulating material, etc., by polycondensing trans-bicyclo(2,2,1)hept-5- ene-2,3-dicarboxylic acid, etc., and an aromatic diamine. CONSTITUTION:Trans-bicyclo(2,2,1)hept-5-ene-2,3-dicarboxylic acid, its dihalide or its diester and an aromatic diamine of formula I (Ar is divalent aromatic ring-containing group) are polycondensed to obtain the objective polyamide resin having a repeating unit of formula II, preferably showing 0.2-5.0dl/g reduced viscosity at 30 deg.C in 0.2g/100ml dimethylformamide solution and soluble in a polar solvent such as N-methyl-2-pyrrolidone. In addition, a cross-linked polyamide resin having resistance to organic solvents can be obtained by heat treating the above-mentioned polyamide resin at 50-300 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a polyamide resin, a method for producing the same, and a method for producing a crosslinked polyamide resin.

(Prior art) Fully aromatic polyamide synthesized from aromatic diamine and aromatic dicarboxylic acid has heat resistance and gas resistance.

Immediately on mechanical properties! It is widely used as an industrial material, such as insulating materials, high-temperature materials, and materials for certain types of protective clothing.

(Problems to be Solved by the Invention) However, conventional aromatic polyamides have poor solubility in ordinary organic solvents, which is extremely inconvenient when forming fibers, films, coatings, etc. Also.

Due to its high melting point and high crystallinity, injection molding or extrusion molding is virtually impossible. The present invention provides a polyamide resin that is soluble in various organic solvents and has excellent heat resistance, and a method for producing the same, as well as a method for producing a crosslinked polyamide resin, which completely solves this problem.

(Problem? Means for solving the problem) The present invention is directed to -Sterial [1] (However, in formula 1, Ar represents a divalent group having an aromatic ring)
The present invention relates to a polyamide resin containing a repeating unit represented by:

9 The present invention also provides trans-biaclo[2,λ1]hept-5-ene-2,3-dicarboxylic acid or its cybalide or diester with the general formula [■] HzN Ar
General formula [l] characterized by polycondensation reaction with an aromatic diamine represented by NH2(Il,] (wherein Ar represents a divalent group having an aromatic ring) (however, in formula 9, Ar is (represents a divalent group having an aromatic ring)
The present invention relates to a method for producing a polyamide resin having a repeating unit represented by:

Further, the present invention relates to a method for producing a crosslinked polyamide resin, which comprises heat-treating a polyamide resin having repeating units represented by the above-mentioned -Katsuri CI] at 150 to 300°C.

This polyamide resin has a reduced viscosity at 30°C of 0.2-5. Octe7'9 is preferred. If the viscosity is too low, the mechanical strength tends to decrease, and if the viscosity is too low, the organic solvent dissolution properties tend to be poor.

In addition, what is the above-mentioned reduced viscosity (ηsp/c)?

(However, η and ηG represent the viscosity of the solution and the solvent, respectively, and when the flow time sound of the solution and solvent when measured using an Ubbelohde dilution capillary viscometer is t and to, respectively, η/ηo ==1/1°, and C is determined by the resin concentration (g/d!, ) of the solution.

The polyamide resin according to the present invention is N-methyl-2-pyrrolidone (NMP) or methylacetamide.

It is soluble in polar solvents such as dimethylformamide (DMF) and dimethyl sulfoxide (DMSO).

Polycondensation reactions include low temperature polycondensation method and direct military condensation method.

All activated esters can be used and there is no limit to 1%.

In the low-temperature polycondensation method, the cibaride gold of the dicarboxylic acid is preferably a 9 to 1.
Use 2 equivalents, triethylamine/, triethylamine,
tertiary amines such as tributylamino and triamylamino;
In a non-reactive polar solvent such as N-methyl-2-pyrrolidone, dimethylamide, etc., in the presence of an acid acceptor such as 1,2-evoquinode, such as propylene, styrene oxide, or cyclohexene oxide. The reaction is carried out at a temperature ranging from -10-odd degrees Celsius to reflux of the organic solvent.

The direct polycondensation method uses the above-mentioned dicarboxylic acid and the above-mentioned aromatic diamide in large or nearly large amounts, and a phosphorus-based catalyst such as triphenyl phosphite, phosphorus trichloride, condensed phosphoric acid ester, etc. The reaction is carried out in a similar non-toxic polar organic solvent at a temperature ranging from room temperature to reflux temperature.

In this case, the phosphorus catalyst is used in an equivalent or approximately equivalent amount to the dicarboxylic acid or the aromatic diamine.

It is preferable to use pyridine or a derivative thereof in an amount of 10 mol or more based on the dicarboxylic acid or aromatic diamino.

In the active ester method, the above dicarboxylic acid dino 1ride and 1
- producing a benzotriazyl ester by reaction with hydroxybenzotriazole, using equivalent or near equivalent amounts of this ester and the aromatic diamine described above, in a non-reactive polar organic solvent similar to that described above, at room temperature or above; This is done by reacting below.

The entire reaction solution obtained as described above is poured into a large excess of a lower alcohol such as methanol and a solvent such as water that is compatible with the above organic solvent and is a poor solvent for the resin to obtain a precipitate. By filtering and drying this, the polyamide resin gold according to the present invention can be recovered.

trans-bicyclo(2411heptane-z3,
It can be obtained solely by the method described in US Pat. No. 4,166,824.

The above-mentioned aromatic diamines represented by "[l]" include metatorso/diamine, 5-talol-m-phenylenediamine, 4,4'-diaminodiphenyl ether, λ3'-dimethyl-44'-diaminodiphenyl ether, 3.3 '-Dimethoxy-4,4'-diaminodiphenyl ether, λ3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 44'-benozidine, 4,4'-diaminodiphenyl thioether, 3,3'-diaminodiphenyl thioether, L
4/-diaminobenzopheno/, λ3'-diaminodiphenylmethane, 4.4'-diaminodiphenylmethane,
2,2/-bis(4-aminophenyl)propane, Z2
'-bis(3-aminophenyl)prop7.4.4'-
Diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfo/3'-diaminodiphenylsulfo/, λ3'-diaminobiphenyl, 1,3-bis(4
-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene/, 4.4'-C1,3-phenylenebis(l-methylethylidene) ], 4.4'
-[1,4-)22dinebis(1-methylethylidene)
],]λ2-bis4-(4-aminophenoxy/)phenyl]propane, 2.2-bis[3-methyl-4-(4-
aminophenoquine) phenyl] propane, Z2-bis [
3-chloro-4-(4-aminophenoxy)phenyl]
Propane, ■, 1-bisC4-<4-aminophenoxy)phenylethane.

Bis[4-(4-aminophenoxy)phenylcomethane, λ3'-dimethoxy4,4'-diaminepiphenyl, bisC4-(4-aminophenoxy)phenyl]sulfono, bis[4-(3-aminophenoxy) Phenyl]
Sulfone, Z2-bisC4-(3-aminophenoxy)
phenyl]propane.

4.4'-bis(4-aminophenox7)biphenyl.

Examples include 2-bis[:4-(4-aminophenoxy)phenyl]hexafluoropuropa 7,9.9-bis(4-aminophenyl)fluorene.

The polyamide resin according to the present invention has an aromatic acid such as terephthalic acid, isophthalic acid, 4,4'-phenyl ether dicarboxylic acid, 14,4'-phenylcarboxylic acid, 1,5-naphthalene dicarboxylic acid, etc. as a carboxylic acid component. It may also contain aromatic dicarboxylic acids such as dicarboxylic acids. When these are used, they are preferably used in an amount of 50 molti or less based on the total carboxylic acid components. If these amounts are too large, the solubility in organic solvents tends to decrease.

-! friend.

The carboxylic acid component may include aliphatic dicarboxylic acids such as adipic acid and sepacic acid. When these are used, they are preferably used in an amount of 50 molti or less based on the total carboxylic acid components. Too much aliphatic dicarboxylic acid tends to reduce heat resistance.

In addition, as a diamine component, hecypmethylenediamine,
Aliphatic diamines such as ethyleneamine/1,3-bis(
3-Aminobrohyalonetetramethedisiloxane, l
, 70xanediamine such as 3-bis(4-aminophenyl)tetramethyldisiloxane. When using a siloxane, it is preferably used in an amount of 30 moles or less based on the total diamine. If there are too many components, the heat resistance will decrease. The above-mentioned aromatic dicarboxylic acids and aliphatic dicarboxylic acids are used as they are in the form of diesters of halides and diesters, corresponding to the two-polymerization method.

The polyamide resin according to the present invention has a bicyclo ring in its main chain, and due to its bulk, exhibits extremely superior solubility in organic solvents compared to conventional aromatic polyamide resins.

The polyamide resin according to the invention has excellent film formability and can be made into a film by a casting method (for example, drying at 100°C for 1 hour after casting), and these films have excellent heat resistance and 9 Excellent mechanical properties, electronic insulating material, heat-resistant adhesive.

Suitable for use as a high temperature material.

In addition, the polyamide resin according to the present invention was heated to 150 to 300°C.
A solvent in which the bicyclo ring moiety is decomposed by a reverse Diels-Alder reaction by heat treatment, preferably at 195'C to 275C (treatment time is, for example, 10 minutes to 3 hours), and further crosslinking by Michael addition occurs. It can be a crosslinked polyamide resin that is insoluble in.

(Example) The present invention will be explained below with reference to Examples.

Example 1 2 with Liebig cooling tube, gas introduction tube and stirring device
Trans-bicyclo[:2.2.1]hept-5-ene-2,3-dicarboxylic acid (common name transnadic acid) 3.559 (
19.5 mmol, 2.2-bisC4-(4-aminophenoxy)phenyl]propa/&OOg(19,
5mm07), triphenylphosphite 1119
(39.0mm0/l, Virigiy 6.0g
(75,9 mmoz) and Liteu chloride A0.6 a (
14.1 mmol of N-methyl-2-pyrrolid/(NMP) was added under nitrogen, and after stirring at room temperature for 10 minutes, the temperature was raised and the reaction was carried out at 110°C for 4.5 hours.

After cooling to room temperature, it was poured into 400 g of methanol. The resulting precipitate was filtered off and washed with methanol.

It was dried at 100°C overnight.

Table 1 shows the reduced viscosity, yield, and organic solvent solubility of the thus obtained boriagodo resin.

In addition, the NMP solution of the obtained polyamide resin was cast, 150°C for XIO minutes + 200°C for 10 minutes + 250°C.
Table 1 shows the glass transition temperature, which is an index of the heat resistance of the film prepared by heat treatment for 10 minutes and drying. The infrared absorption spectrum (film method) of the polyamide resin is shown in FIG. In Figure 1, 1655 cm'
absorption of carbonyl of amide bond and 3305 cm
Absorption based on N-H stretching vibration was observed, confirming the formation of an amide bond.

1) (Nuclear Magnetic Resonance Spectrum (Solvent: DMSO-(isl) of the above polyamide resin is shown in FIG. 2. In FIG. 2, 131-3.50. 6.02-6.34
Norbornene ring in ppm, methyl group in 1.59ppm, benzene ring 10.01 to 6.83-7.66ppm
A peak based on the proton of the amide group was observed at 10.20 ppm.

It was confirmed that the polyamide resin obtained above had the desired structure.

Example 2 2 with Liebig cooling tube, gas introduction tube and stirring device
00-separable 40 flasks, trans-bicycloC2111hept-5-dyne-λ3-dicarboxylic acid 4.
00 g (2ZOmmol).

4.47-diamitudiphenyl ether 4.40 g
(zz.

mmo(),) Riphenyl phosphite 117g (44
2 mmoj), pyridine 77.09 (8 & 6 mmol) and lithium chloride 0.7 g (16,5 mmol) 1
There are people.

Add 40 ml of N-methyl-2-bi-01/d under nitrogen.

After stirring at room temperature for 10 minutes, the temperature was raised to 110°C for 3.
The reaction was allowed to proceed for 5 hours. After cooling to room temperature methanol 40
I opened it during the offering. Filter out the formed precipitate.

It was washed with methanol and dried at 100°C overnight.

As in Example 1, various properties of the polyamide resin thus obtained are shown in Table 1. Also.

The infrared absorption spectrum (film method) of the above polyamide resin is shown in FIG. 1659cm' in Figure 3
An absorption of the carbonyl of the amide bond was observed at 3304 cm', and an absorption based on the NH stretching vibration was observed at 3304 cm', confirming that an amide bond was formed.

Example 3 2 with Liebig cooling tube, gas introduction tube and stirring device
00-separable 40 flasks with trans-bicyclo(
Z2.11 hept-5-2/-Z3-dicarboxylic acid &5
6 g (19,6 mmol, bis(4-(4-aminophenoxy)phenyl)sul*y8.46 g (
19,6mmol), ) Riphenyl phosphite 12
．． ．． 2 B (39.4 mmoz), 6.0 g of pyridine
(75,9 mmoj) and lithium chloride 0.69 (1
4.1 mmo/) and 40 d of N-methyl-2-pyrrolidone were added thereto, and after stirring at room temperature for 10 minutes, the temperature was raised and the reaction was carried out at 110° C. for 4.5 hours. After cooling to room temperature, it was poured into 400 ml of methanol. The resulting precipitate was filtered off, washed with methanol, and dried at 100°C overnight.

As in Example 1, various properties of the polyamide resin thus obtained are shown in Table 1. Also.

The infrared absorption spectrum (film method) of the above polyamide resin is shown in FIG. 1662ao' in Figure 4
absorption of carbonyl of amide bond and 3325 am-
Absorption based on N--H stretching vibration was observed in ', and it was confirmed that an amide bond was formed.

Example 4 Liebig cooling tube, gas introduction tube and stirring device 2
00-separable 40 flasks with trans-bicyclo[
2,Zl) Hepto-5-en/-23-dicarphoya!
3. ．． 95s (21,7m"01)s 1,4-
Bis(4-aminophenoxy)benzene 6.359(2
1,7mm0/),)riphenyl phosphite 13.5
g (43,5 mmol), Pyridy 6.9 g
(87,3 mmoJ) and lithium chloride 0.79 (1
6.5 mmof) was added thereto, 40-N-methyl-2-pyrrolidone was added under nitrogen, and after stirring at room temperature for 10 minutes, the temperature was raised.

The reaction was carried out at 110°C for 4 hours. After cooling to room temperature, it was poured into 400 methanol. The resulting precipitate was filtered off, washed with methanol, and dried at 100°C overnight.

The properties of the nine polyamide resin samples thus obtained are shown in Table 1 in the same manner as in Example 1. In addition, the infrared absorption spectrum (film method) of the above polyamide resin was
The figure shows friend. Figure 5 shows the absorption of the carbonyl of the amide bond at 1659an-' and 3305 all-'K
Absorption based on N--H stretching vibration was observed, and it was confirmed that an amide bond was formed.

Example 5 Liebig cooling tube, gas introduction tube and stirring device? Added 2
Trans-bicyclo 1 in 00 separate separable 40 flasks
12.1) Hept-5-ene-43-dicarboxylic acid3.
95 g (21.7 mmo/), 1.3-bis(4-
aminophenoxy)benzene 6.35g (21.7mm
oI, ) Riphenyl phosphite 13.5 g'
(43,5 mmo/l, viridi; y 6.9 g (8
7,3 mmo/) and lithium chloride 0.7 g (16,
5 mmo/) of N-methyl-2-pyrrolidone was added thereto, and after stirring at room temperature for 10 minutes, the temperature was raised.

The reaction was carried out at 110°C for 4 hours. After cooling to room temperature, it was poured into methanol 400i. The resulting precipitate was filtered off, washed with methanol, and dried at 100°C overnight.

Various properties of the polyamide resin thus obtained are shown in Table 1 in the same manner as in Example 1. In addition, the infrared absorption spectrum (film method) of the above polyamide resin was
Shown in the figure. In FIG. 6, there is an absorption of the carbonyl of the amide bond at 1659an' and an absorption based on the N-H stretching vibration at 3305cm'.

was observed, confirming that an amide bond was formed.

Example 6 2 with Liebig cooling tube, gas introduction tube and stirring device
00 mg separable 40 flasks were charged with 3.95 (2L7 mmof), 4.4'-his(
4-aminophenoxy), biphenyl 8.009 (21
, 7mmol), ) Riphenyl Phosphite 13.5
g (43,5 mmo / ), pyridine 6,9
g (87.3 mmol) and 0.7 g of lithium chloride
(Insert 16.5mm01.

Add 40 g of N-methyl-2-pyrrolidone under nitrogen.

After stirring at room temperature for 10 minutes, the temperature was raised and the reaction was carried out at 110° C. for 25 hours. After cooling to room temperature, methanol 40O
The mixture was poured into rrkl and the resulting precipitate was filtered off.

It was washed with methanol and dried at 100°C overnight.

Various properties of the polyamide resin thus obtained are shown in Table 1 in the same manner as in Example 1. In addition, the infrared absorption spectrum (film method) of the above polyamide resin
Shown in the figure. In Figure 7, 1659CI+ is a (
Absorption of carbonyl of bond and N in 3305an-1
-H stretching vibration-based absorption was observed, and an amide bond was formed (effects of the invention) The polyamide resin according to the invention has extremely excellent solubility in organic solvents. Further, mechanical properties such as heat resistance and flexibility, and film formability are also good. The crosslinked polyamide resin according to the present invention obtained by heat treating the polyamide resin with gold retains mechanical properties such as flexibility, has good heat resistance, and has excellent solvent resistance.

These polyamide resins and crosslinked polyamide resins can be preferably applied to electronic insulating materials, heat-resistant adhesives, high-temperature materials, and the like.

[Brief explanation of the drawing]

Figures 1, 3, 4, 5, 6 and 7 show the infrared absorption of the polyamide resins obtained in Examples 1, 2, 3, 4.5° and 6, respectively. The spectrum and FIG. 2 are IH-nuclear magnetic resonance spectra of the polyamide resin obtained in Example 1. Agent Patent Attorney Kuni Wakabayashi Hikomitsu P4+e Sori &! Procedural amendment (voluntary) Name of the amendment for non-disclosure of the case Polyamide resin and its manufacturing method, and its relationship to the case of the person correcting the manufacturing method of crosslinked polyamide resin Patent application Name +445) Agent for Nichizu Kasei Kogyo Co., Ltd. 163 Address No. 5, Nishi-Shinjuku 2-chome Il1, Shinjuku-ku, Tokyo, Claims column of the specification to be amended\Second appendix Claims 1, - Killing (1) (Just in case, Ar in formula 1 represents a divalent group having an aromatic ring)
A polyamide resin containing a repeating unit represented by 2 Polyamide resin No. 0.2 is dissolved in dimethylformamide and the reduced viscosity at 30°C of a 100-100% solution is 0.2 to 5. The polyamide resin according to claim 1, which is Od(/I. General formula CI) (In formula 1, ArFi represents a divalent group having an aromatic ring) is subjected to a polycondensation reaction with an aromatic diamine represented by A method for producing a polyamide resin containing a repeating unit represented by (indicating a group). 4. The polyamide resin according to claim 1 at 150 to 300°C.
A method for producing a cross-linked polyamide resin, which is characterized by heat treatment. Procedural amendment (method) % formula % 2. Name of the invention Polyamide resin and its manufacturing method and manufacturing method of crosslinked polyamide resin 4. Agent address: Hitachi Chemical Co., Ltd. 2-1-1 Nishi-Shinjuku, Shinjuku-ku, Tokyo 163 Within the company 6, Detailed explanation of the invention column 7 of the reference specification of the amendment, Line 14 of page 2 of the statement of contents of the amendment: ``Method for producing amide resin.'' 3. Line J of the detailed explanation of the invention. The next line after "I'm joining."

Claims (1)

[Claims] 1. General formula [I] ▲ Includes mathematical formulas, chemical formulas, tables, etc. ▼ [I] (However, in the formula, Ar represents a divalent group having an aromatic ring)
A polyamide resin containing repeating units represented by 2. The polyamide resin according to claim 1, wherein 0.2 g of the polyamide resin is dissolved in dimethylformamide to make 100 ml, and the reduced viscosity at 30° C. is 0.2 to 5.0 dl/g. 3. Trans-bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic acid or its dihalide or diester and general formula [II] H_2N-Ar-NH_2[II] (However, in the formula Ar indicates a divalent group having an aromatic ring)
[I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [I] (However, in the formula, Ar is a divalent group having an aromatic ring. )
A method for producing a polyamide resin containing a repeating unit represented by 4. The polyamide resin according to claim 1 at 150 to 300°C.
A method for producing a cross-linked polyamide resin, which is characterized by heat treatment.