JPS6399230A - Soluble polyamide - Google Patents

Abstract

PURPOSE:To obtain the titled novel polymer, having a specific structure derived from bis(aminophenyl)fluorenes and phthalic acid derivatives and having improved solubility, heat resistance as well as processability and further chemical resistance, durability, etc. CONSTITUTION:A high-molecular weight polyamide, consisting of a chain member expressed by formula I [R<1> is H, CH3 or C2H5; X is formula II or III; Y is formula IV (R<2> is R<1>; n is the number of repeating units) and having >=0.3dl/g intrinsic viscosity (etainh) measured by using a solution in 0.5g/100ml concentration in dimethylacetamide as a solvent at 30 deg.C and 280-420 deg.C glass transition temperature as well as >=420 deg.C decomposition temperature in air. The above- mentioned polymer is obtained by polymerizing 9,9-bis(4-aminophenyl)fluorene with a terephthaloyl chloride in a solvent, e.g. dimethylacetamide, etc., while cooling.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application This invention relates to a novel aromatic polyamide with improved heat resistance, solubility and processability.

Conventional technology Aromatic polyamide has rigid aromatic rings and intermolecular aggregation failure points,
High thermal decomposition point.

In addition to heat resistance, chemical resistance, mechanical properties,
It has excellent chemical and physical properties such as air bacterium properties. Therefore, aromatic polyamide is an extremely useful material.
It is particularly used in heat-resistant fibers, films, paints, adhesives, and molded products.

Aramids such as Kevlar generally have the above-mentioned properties, and are insoluble in most solvents and have difficulty in pressurization. Therefore, one way to overcome the problem of pressurization is to make it soluble.

Kolshank et al., Journal of Polymer Science (J, Polym, Sci, A-1, 9)
1027 (1971)) reported on soluble polyamides.

Problems to be solved by the invention: Aromatic polyamides, which generally have large rigidity and high symmetry, have excellent mechanical properties, but their melting points are high and close to their decomposition points, so they cannot be used as melting agents. It has the disadvantage that it is not easy to use.

Poly(P-phenylene terephthalamide), a typical aromatic polyamide, is soluble in concentrated sulfuric acid or hexamethylphosphorylamide or N-methylpyrrolidone in which lithium chloride, calcium chloride, etc. are dissolved.
However, it has the disadvantage that it is difficult to use as a solution because of its low solubility.

Means and actions for solving problems The above problems can be solved by improving solubility.

Furthermore, in order to maintain high heat resistance, the present inventor provides an aromatic polyamide represented by general formula (I).

That is, the present invention provides the formula R1O-X (NH-Y-NH-X +n NH-Y-
NH -
A solution of 0.5 g of the polyamide described above in 00op was heated at 30°C.
-c? +I6 constant weight 0.30 d2/g
(7) It has a hard I viscosity (η1nh), with a glass transition temperature of 280℃ and a temperature of 420'C1 decomposition temperature in air of 420''
It is a soluble polyamide exhibiting C or higher.

The aromatic polyamide with the symbol G contains at least one of (a), (b), and (c) in the chain,
As can be seen from the above general formula, the component represented by (a) and the components represented by (b) and (c) are polyamides obtained by reacting with C and the like. In this case, in the present invention, the terminal is stabilized against oxidation and resistant to six colors.
It is characterized by adding a small amount of (b) and (c) L&minutes during the reaction in order to obtain a 1-silacarboxylic acid derivative.

The polyamide of the present invention is synthesized from 9.9-bis(4-aminophenyl)fluorenes and phthalic acid derivatives, such as 9.9-bis(4-aminophenyl)fluorene, 9.9-bis(3-methyl -4-7minophenyl)fluorene or 9.9-bis(3-ethyl-4-aminophenyl)fluorene and either or both of terephthalic acid chloride and inphthalic acid chloride, and cooled in a solvent such as dimethylacetamide. It can be produced by polymerization. Also, the terminal substituent R1
can be changed by the water and alcohol used to purify the polyamide by solidification or reprecipitation. That is, after the completion of the polymerization reaction, the polyamide is reprecipitated for solidification or purification, but the terminal groups can be controlled by the alcohol used at this time.If reprecipitated in tar, methoxy groups, In tanol, it becomes an ethoxy group. Furthermore, in the case of forming a hydroxyl group, reprecipitation in water or direct film formation is possible by adding moisture (moisture) in the air or water to a solvent.

One of the objects of the present invention is to obtain a polyamide that is free from coloration and is less likely to be colored as a polymer. Therefore, the carboxylic acid according to (b) and/or (c) above (
A very slight amount of one of the chloride components is used in the later stages of the reaction to control the end groups, thereby ensuring that the ends of the polyamide are not aniline groups, which are susceptible to oxidation.
It becomes a carboxyl group, making it resistant to oxidation by light, air, etc., and making the polymer itself less likely to be colored.

The physical properties of the polyamide of the present invention include glass transition temperature 2
The temperature is 80°C to 420°C, preferably 300 to 400°C, the decomposition temperature is in the range of 420°C or higher, preferably 450°C or higher in air, and the intrinsic viscosity (η1nh) is:
o, 30 du /g or more, preferably 0,35 du
/g or more.

The intrinsic viscosity was determined using a solution of 0.5 g of the polyamide of the present invention dissolved in 100 IIIi of dimethylacetamide.
It was determined by measuring at °C.

The polyamide of the present invention includes pyridine, m-cresol, 0-
Chlorophenol, N-methylpyrrolidone (NNP)
, dimethylacetamide (I) MAIII:) etc., dissolved in chloroform, methylene chloride, toluene.

Insoluble in benzene.

The heat resistance and solubility can be adjusted by changing the ratio of the components (b) and (c).

From the viewpoint of heat resistance and solubility, it is preferable to set the molar ratio of components (b)/(C) to 90,710 to 90, more preferably 70/30 to 20,780. In addition, when the amount is about equimolar, the film hardness softens, making it easier to use as an industrial material.

The present invention can provide a polyamide with good mechanical properties and electrical insulation properties, and the obtained polyamide is suitable for the electrical insulation field.

Further, the polyamide of the present invention can be made into a thin film with a thickness of about 0.005 to 0.20+e layer without any coloring by a conventionally known method, and can be used for various purposes.

A more detailed explanation will be given below based on examples.

Example 1 9.9-
Bis(4-7minophenyl)fluorene (mp 234
~235°C) 34.8g and 20.8g of triethylamine.
2 g was dissolved in 500 g of dimethylacetamide.

Terephthalic acid chloride 10.15. was added while stirring the solution in the flask while maintaining the temperature in the flask at 5 to 10°C. and 10.15 g of inphthalic acid chloride
The mixture was gradually added as a solid.

After stirring for 4.5 minutes, 5 mg of terephthalic chloride was added and stirred for an additional 30 minutes, and the precipitated triethylamine salt was filtered through a glass filter to obtain a polymer solution.

This was cast onto a glass plate and dried under reduced pressure at 100°C for 5 hours to obtain a polyamide film.

The intrinsic viscosity (η1nh) of the obtained polyamide was 0.41
d'l/g, glass transition temperature of 320°C, and decomposition temperature of 485°C in air.

In addition, the tensile strength of the film was 10.1 kgf/am2. Tensile modulus: 590 kgf/mm2. Volume resistivity 3X10
16Ω-cffI (23℃), 4.8X 10'Ω-
cm (200℃), dielectric constant 4.38 (I MHz)
, water absorption rate 7.6%, total light transmittance 90.3%, yellowness 4
．． It was 8%.

The infrared absorption spectrum of this polyamide is 3300c'1
NH, 1880cm-' amide C=O13100~
It showed aromatic absorption at 2900 cm-' and 1810.1520 cm-'.

Example 2 In the same manner as in Example 1, 9.9-bis(4-aminophenyl)fluorene (mp231-234.5°C) 3.4
8 g of triethylamine and 2.02 g of triethylamine were dissolved in 50 g of dimethylacetamide, and 2.03 g of a mixture of terephthalyl chloride and isophthalic acid chloride was added in powder form.

The mixing ratio of terephthalic acid chloride and isophthalic acid chloride was changed as shown in Table 1. A viscous solution was obtained several hours after the start of the reaction. Add 5 mg of a mixture of terephthalic acid chloride and isophthalic acid chloride in the same manner as in Example 1.
Stirred for 0 minutes. This solution was poured into methanol and washed with water and methanol. After that, it was dried at 100℃ for 8 hours.
Polyamide powder (11) was easily dissolved in dimethylacetamide and the like. Table 1 shows the solubility, glass transition point, and decomposition temperature of the obtained polyamide.

The solubility indicates the solubility in various solvents at a c degree of 15 wt%, ■ indicates easily soluble, 0 indicates soluble, and X indicates insoluble.

The intrinsic viscosity (η1nh) was measured by dissolving 0.5 g of polyamide in 100% dimethylacetamide and using an Ostwald viscometer in a constant temperature water bath at 30°C.

Effects of the Invention Heat-resistant polymers are expected to be in increasingly high demand in the space, aircraft, electrical, steel, and other industries. In these applications, #thermal polymers are used in the form of paints, adhesives, films, molded products, etc., and are required to have high heat resistance and appropriate solubility.

As seen in the above examples, the present invention has a decomposition temperature of 450° C. or higher, and the glass transition temperature (Tg) can be changed as necessary, making it easy to obtain processability that meets the requirements.

Moreover, while it has a wide range of solubility, it has chemical resistance to general-purpose solvents such as benzene, toluene, methylene chloride, and chloroform, and has a wide range of applications, making it useful as an industrial material.

In particular, it can be used for electrical and electronic parts such as resistance boards, front plates for printed circuit boards, pulleys, microwave ovens, etc., and mechanical parts such as turbo fans.

Furthermore, metal materials coated with the polyamide solution paint of the present invention have chemical resistance to benzene, toluene, methylene chloride, chloroform, etc.
Durable.

Claims (4)

[Claims] (1) Formula R^1O-X-(NH-Y-NH-X)-_n
NH-Y-NH-X-OR^1...(I) (In the formula, X is at least a member of the group consisting of ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Yes, Y represents the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R^1 and R^2 are either H, CH_3, C_2H_5, and n indicates the number of repeating units). A high molecular weight polyamide consisting essentially of 280℃～4
Soluble polyamide exhibiting a decomposition temperature of 420°C or higher in air at 20°C. (2) Intrinsic viscosity (ηinh) 0.35 dl/g or more, glass transition temperature 300-400°C, decomposition temperature 450 in air
℃ or higher, the soluble polyamide according to claim (1). (3) The soluble polyamide according to claim (1), which is soluble in at least pyridine, m-cresol, and o-chlorophenol. (4) The composition ratio of X in the formula is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ The former is 90 to 10 mol% and the latter is 10 to 10
The soluble polyamide according to claim (1), which has a content of 90 mol%.