JPS6178833A - Aromatic polyamide copolymer - Google Patents

Abstract

PURPOSE:The titled thioether bond-containing copolymer excellent in heat resistance and moldability, obtained by polycondensing an aromatic diamine mixture with terephthaloyl chloride or isophthaloyl chloride and comprising specified structural units. CONSTITUTION:An aromatic polyamide copolymer comprising 51-99mol%, based on structural units, recurring units of formula I and 49-1mol%, based on structural units, recurring units of formula II and/or formula III. In the formulae, Ar is a 6-20C aromatic ring, formula IV is residue of terephthalic or isophthalic acid, X is a 1-10C bivalent hydrocarbon group, or the like, a is 0 or 1, Y is a 1-20C alkyl group, or the like, b and c are each 0-4, d is 0-20 and e is 0-4. Said aromatic polyamide copolymer can be produced by polycondensing a diamine mixture comprising 51-99mol% aromatic diamine of formula IV and 49-1mol% aromatic diamines of formula V and/or VI with formula VII (terephthaloyl chloride and/or isophthaloyl chloride).

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the invention] - Industrial field of application The present invention relates to an aromatic polyamide copolymer having thioether bonds. The aromatic polyamide copolymer of the present invention has excellent heat resistance and moldability, and is useful as a fiber film and coating material.

[Conventional technology and its problems]

Aromatic polyamide resins synthesized from aromatic diamines and aromatic dicarboxylic acids or their chlorides have attracted attention for their excellent heat resistance and flame retardancy, and are being actively researched and developed. However, aromatic polyamides generally have a melting point of less than 0.5%, and many have a melting point of more than the thermal decomposition initiation temperature in air, making injection molding or extrusion molding difficult. Also,
It has poor solubility in common organic solvents, which is extremely inconvenient when forming fibers, films, coatings, etc.

Therefore, processability is improved by lowering the melting point as a copolymer or by dissolving it in cutting.

As such an aromatic polyamide with improved processability: i, (a) method of copolymerizing an aliphatic component (%
-109592, JP-A-53-94397), (b)
A method of introducing a connecting functional group into the main chain or imparting flexibility (US Pat. No. 3,505,288, JP-A-52-231)
98, JP-A-53-104695), (C) Method of random copolymerization of aromatic components (JP-A-53-104697)
, JP 56-88427, U.S. Patent No. 4410684
No.) etc. are known stones. However, the polyamides obtained by these techniques cannot be said to have a sufficient balance between processability and heat resistance.

[Configuration of the present invention]

The present invention provides an aromatic polyamide copolymer having a thioether bond that has well-balanced moldability and heat resistance.

That is, in the present invention, 51 to 99 mol% of the constituent units of the copolymer are repeating units of the following formula (I), and 49 to 1 mol% are repeating units of the following formula (B) and/or (B). An aromatic polyamide copolymer is provided.

[In the formula, Ar is an aromatic ring having 6 to 20 carbon atoms.

It is a residue of isophthalic acid. X is a divalent hydrocarbon group having 1 to 10 carbon atoms, -o-, -s-, -5o-1-8O2-
, -Co-1. a is 0 or 1, and when a is 0, it means that aromatic rings are bonded to each other without X. Y is an alkyl group having 1 to 20 carbon atoms, 3 to 20 carbon atoms
20 cycloalkyl group, aryl group having 6 to 20 carbon atoms, )-rogen group, and nitro group, which may be the same or different from each other. bX c represent integers of θ to 4, which are the same or different from each other. Also, d is O
Indicates a number between ~20, and e represents an integer from 0 to 4. ] (Production) Such an aromatic polyamide copolymer has the general formula “
H2N-Ar NH2 (Formula I11) 51 to 99 mol% of an aromatic diamine represented by the general formula %: Manufactured by condensation.

[Ar, X, Y, a, bXc,
d and e are the same as in formulas (I), (rin), and (shi).

] (Diamine) Examples of aromatic diamines represented by the formula (P/) include P-phnylenediamine, m-phenylenecyamine, 4-methyl-1,3-phnylenediamine, 5-methyl-1, 3
-Fnylerenediamine, 4.4'-diaminobiphenyl, 414'-diaminodiphenyl ether, 4.4'-
Diaminodiphenylsulfide, 414'-diaminobenzophenone, 414'-diaminodiphenylsulfoxide, 4+4'-diaminodiphenylsulfone, 414
'-Diaminodiphenylmethane, 2゜2-bis(4-aminophenyl)propane, 1,4-his(4-aminophenoxy)benzene, 1,4-bis(4-aminobenzoyl)benzene, 1,4-bis( 4-aminebenzenesulfonyl)benzene, 4.4'-bis(4-aminophenoxy)diphenyl ether, 4.4'-bis(4-aminophenoxy)diphenyl sulfide, 4.4'-his(4-ybanophenoxy) Benzophenone, 414'
-bis(4-aminophenoxy)diphenylsulfone,
4.4'-bis(4-aminophenoxy)diphenylmethane, 2.2-bis(4-(4-aminophenoxy)phenyl)propane, 4.4'-bis(4-aminobenzoyl)diphenyl ether, 4.4' -bis(4-aminobenzoyl)benzophenone, 414'-bis(4-
aminobenzoyl) diphenyl sulfoxide, 4.4'
-bis(4-aminobenzoyl)diphenylsulfone,
C4'-bis(4-aminobenzoyl)diphenylmethane, 2.2-bis(4-(4-aminobenzoyl)phenyl)furopane, 4.4'-his(4-aminobenzenesulfonyl)diphenyl ether, 414'-bis( 4
-aminobenzenesulfonyl)diphenylsulfy)”
, 4.4'-bis(4-aminebenzenesulfonyl)
Pentuphenone, 4.4'-his(4-aminobenzenesulfonyl)diphenylsulfoxide, 414'-bis(4-aminobenzenesulfonyl)diphenylsulfone, 4.4'-bis(4-aminobenzenesulfonyl)diphenylmethane, 2.2 -bis(4-(4-aminobenzenesulfonyl)phenyl)furopane and the like can be mentioned.

Next, specific examples of aromatic diamines having a thioether bond represented by formula (V) are shown below. 2,2-bis(4-(4
-aminophenylthio)phenyl)furopane, 1,1.
1,3,3.3-hexafluoromethyl-2,2-bis(4-(4-aminophenylthio)phenyl)propane, 4.4'-his(4-aminophenylthio)diphenyl ether, 4.4' -His(4-aminophenylthio)benzophenone, 414'-bis(4-7mi/phenylthio)diphenylsulfoxide, 4,4'-bis(
4-aminophenylthio)diphenylsulfone, 3.3
'-bis(4-aminophenylthio)diphenylsulfone, 4.4'-his(4-aminophenylthio)biphenyl, 2+2? Examples include L6'-tetramethyl-4,4'-bis(4-aminophenylthio)biphenyl.

In addition, as the extra group diamine represented by the formula (V'O),
4.4'-bis(4-aminophenylthio)diphenyl sulfide, 1.4-bis(4-aminophenylthio)
Benzene, 1,3-bis(4-aminophenylthio)benzene, d,ω-diaminopoly(I,4-phenylene,
) oligomers, etc.

The amount of the aromatic diamine having a thioether bond represented by (V) and/or (vO formula) is 1 to 49 mol%, preferably 15 to 45 mol% of the diamine. If 50 mol% or more is used, It is not preferable because the glass transition degree becomes low and the heat resistance decreases.

The aromatic dicarboxylic acid chloride conveniently used in the present invention is terephthalic acid chloride and/or isophthalic acid chloride.

In the present invention, known methods can be used as they are for the reaction between aromatic diamine and aromatic dicarboxylic acid chloride. For example, this can be achieved by an interfacial polycondensation method, a solution polycondensation method, or the like.

Regarding the interfacial polycondensation method, known water-soluble neutralizing agents are used. Examples include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium hydrogen carbonate. The alkali content is in the range of 0.3 to 3 equivalents, preferably 0.5 to 3 equivalents, based on the number of moles of the reactive group of the aromatic dicarboxylic acid chloride.
It is 1.5 den.

The aromatic polythioetheramide copolymer of the present invention can be produced by dispersing an aromatic diamine in an aqueous solution containing the above water-soluble neutralizing agent, and adding a solution of aromatic dicarboxylic acid chloride dissolved in an organic solvent to the solution to cause a reaction. A combination can be produced. Examples of this solvent include ketone solvents such as cyclohexanone, diisobutyl ketone, acetophenone, and p-methylacetophenone, or methylene chloride, chloroform, tetracarbon monocide, 1,1.1-)lychloroethane, and 1.1.2.2 - Examples include halogenated hydrocarbon solvents such as tetrachloroethane. In order to return a high molecular weight substance, cyclohexanone, p-methylacetophenone, etc. are preferable. Further, the reaction temperature is in the range of 0 to 100°C, preferably 3 to 50°C. Reaction time is 1 minute ~
The time period is 10 hours, preferably 5 minutes to 3 hours.

In the case of the solution polycondensation method, a known tertiary amine may be used as a neutralizing agent. For example, triethylamine, tributylamine, pyridine, quinoline, pyrimidine, 2
, 6-lutidine and the like. However, these compounds do not necessarily need to be added when an organic acid amide is used as a reaction solvent. When a neutralizing agent is used, the amount used is preferably 0.3 to 3.0 equivalents based on the number of moles of the reactive group of the aromatic dicarboxylic acid chloride. On the other hand, as the reaction solvent, organic acid amides and organic sulfoxides are preferred. Aromatic compounds that may include, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-methyl-6-caprolactam, hexamethylphosphoramide, tetramethylurea, dimethylsulfoxide, etc. The polymer of the present invention can be prepared by dissolving the diamine in the above reaction solvent, adding a neutralizing agent if necessary, and adding aromatic dicarboxylic acid chloride to this solution for reaction.

If necessary, at this time, 5 to 10% lithium chloride,
Synthesis by adding calcium chloride, calcium rhodan, etc. may be advantageous as it significantly increases solubility. Further, the reaction temperature is -30 to +100°C, preferably -20 to +30°C.
℃ range. The reaction time ranges from 5 minutes to 10 hours, preferably from 30 minutes to 5 hours.

A solution containing an aromatic polyamide copolymer produced by any of the methods shown above is diluted with a solvent that does not dissolve the polymer and is easily compatible with the reaction solvent to precipitate the polymer. By this, the polymer of the present invention is isolated.

When molding the polymer of the present invention, various known filler components can be included. Typical filler components include (a) fibrous fillers, glass fibers, carbon fibers;
Boron fiber, aramid fiber, alumina fiber, silicon nicarbide fiber, etc.) Inorganic fillers: silica, asbestos, molybdenum sulfide, magnesium oxide, calcium oxide, etc. can.

The polymer of the present invention can be used for various parts in the electric and electronic fields, housings, automobile parts, aircraft interior materials, sliding parts, gears, insulating materials, heat-resistant films, heat-resistant panels, heat-resistant fibers, etc.
It can be used in a wide range of applications.

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

Example 1 A three-bottle flask was equipped with a stir bar, a thermometer, and a dropping funnel, and then hydroxide was added.8 and Of were dissolved in 7 and 150 ml, and the mixture was charged into the flask. Next, m-phnylenediamine 8.64 f (80 mol%)
and 4,4'-bis(4-aminophenylthio)diphenylsulfone (9.289% by mole) were added into the flask and stirred vigorously at 5°C to disperse in the aqueous solution. On the other hand, 10.15 f of isophthalic acid chloride and 10.152 f of terephthalic acid chloride were mixed with cyclohexanone 500 IR.
1 and poured the acid chloride solution from the dropping funnel. At this time, the reaction temperature was kept below 15°C. After 20 minutes, 100 d of water and 100 d of cyclohexanone were added to the reaction solution.
d was added, and then 400 ml of acetone was poured in to precipitate the polymer.

The polymer was separated, washed with hot water, and then dried in a vacuum oven at 100°C for 8 hours), 30.7? (Yield 99%
) polymer was harvested. The glass transition temperature of this polymer was 270°C. Also, intrinsic viscosity ￥i0.61 d
i/f (0.2% NMP solution, 30°C).

When the IR spectrum of this polymer was measured, it was found that 16
Absorption derived from Akudo at 40X 1510α, 114
Absorption originating from sulfone at 0d', 1070 cm'
absorption derived from thioether, 810.710 cm-
Absorption originating from aromatic rings was observed in '.

In addition, this polymer does not decompose in air up to 380°C,
By compression molding at 320° C., a strong amber film could be obtained.

Furthermore, when measured with a Koka type flow tester under the conditions of 330° C. and 100 Kf load, it showed a flowability of 0.10 CC/min.

Example 2 A test was carried out using the same apparatus and method as in Example 1 using raw materials having the following composition.

Polymer yield 30.5 f (99%). Glass transition temperature 266°C. Intrinsic viscosity 0.59 dt/f (0,2
%NMP solution, 30°C).

IR spectrum (Figure 1): 1640.1510ci'
(amide), 1140crt*-' (sulfone), 1
070bi (thioether), 810.710d1 (aromatic ring) By compression molding these polymers at 320°C, an amber strong film could be obtained.

Example 3 A test was carried out using the same apparatus and method as in Example 1 using raw materials having the following composition.

Polymer yield 29.5 f (99%). Glass transition temperature 243°C. Intrinsic viscosity 0.59 dt/f (0,2
%NMP solution, 30°C).

IR Subscription: 1640.151 oon-” (7
(mido), 1070cPn (thioether), 81o1
710 am-” (aromatic ring).

Example 4 A test was carried out using the same apparatus and method as in Example 1 using raw materials having the following composition.

Collection j'144. of (98%). Glass transition temperature 210
℃. Intrinsic viscosity 0.80 dt/f (0.2%NMP
solution, 30°C).

IR spectrum: 1640, 1510m-' (amide), 1240cts-' (ether), 1140cy
T" (sulfone), 1070 cyn-" (thioether), 805 (?111 (aromatic ring).

Example 5 1. Place a stirring bar, a thermometer, and a dropper in a three-hole flask.
(Ilt, then m-phenylenediamine 3.2
41F (60 mol%), 4,4'-bis(4-aminophenylthio)benzophenone 8.56 t (40 mol%
) was dissolved in 100M/dry N-methylpyrrolidone and placed in a flask.

Under stirring at -5°C, inophthalic acid loli)' 10,15
The dry N-methylpyrrolidone 5Qd solution of No. 2 was poured into the flask from the dropping funnel. At this time, the reaction temperature was set to 0°C.
I kept it below. Stirring was continued at 0° C. for 2 hours, and then the reaction solution was poured into acetone to precipitate the polymer.

The polymer was separated, washed with hot water, and then dried in a vacuum oven (I00°C, 8 hours) to obtain Polymer 18.1? (99%
) was obtained. Polymer glass transition! temperature is 244°C, intrinsic viscosity is 0.51 a/f (0.2% NMP solution, 30
℃).

IR spectrum (Figure 2): 1640.1510crn
-' (amide), 1640 cr' (ketone)
, 1070ci” (thioether), 810.710
cm-” (aromatic ring).

This polymer does not decompose in air up to 380°C and
A yellow strong film could be obtained by compression molding at 0°C.

Further, when measured using a Koka type flow tester under the conditions of 310° C. and a load of 100 Kf, it was found that the polymer of the present invention has a flowability of 2.40 CC/min, indicating that the polymer of the present invention has excellent moldability.

Example 6 A test was carried out using the same apparatus and method as in Example 1 using raw materials having the following composition.

Yield 29.4f (99%). Glass transition temperature 265°C.

Intrinsic viscosity o, s 1tip/t (0.2% NMP solution, 30 °C) and IR spectrum: 1640.1510ci” (amide), 11070c (thioether), 805.710
°CM (aromatic ring).

This polymer did not decompose in air up to 385°C.

Comparative Example 1 A test was carried out using the same apparatus and method as in Example 1 using raw materials having the following composition.

Polymer yield q 23.4!7 (98%). Glass transition temperature 288°C, softening point 438°C. Intrinsic viscosity 1.44dt/
f (0.2% NMP solution, 30°C).

This polymer does not decompose in air up to 380°C, but
It had a high softening point and could not be compression molded into a film. In addition, under the conditions of 340°C and 400 to 9 loads,
Even when measured with a Koka type flow tester, there was no flow at all.

Comparative Example 2 A test was carried out using the same apparatus and method as in Example 1 using raw materials having the following composition.

Polymer yield 111i59.4P (99%). Glass transition temperature 199°C, softening point 284°C. Intrinsic viscosity 0.63dt
/f (0,2% NMP solution, 30 °C).

This polymer does not decompose in air up to 370°C and
Although it is possible to obtain a strong amber film by compression molding at 0°C, the glass transition temperature was lower than that of the polymers of Examples 1 to 6 of the present invention, and the heat resistance was slightly inferior. .

[Brief explanation of the drawing]

FIG. 1 and FIG. 2 are IR spectra of the aromatic polyamide copolymers obtained in Example 2 and Example 5, respectively.

Claims (1)

[Claims] 1) 51 to 99 mol% of the structural units of the copolymer are repeating units of the following formula (I), and 49 to 1 mol% are repeating units of the following formula (I).
An aromatic polyamide copolymer which is a repeating unit of II) and/or (III). ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) [In the formula, Ar has 6 to 20 carbon atoms. is an aromatic ring. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ is a residue of terephthalic acid and/or isophthalic acid. X is a divalent hydrocarbon group having 1 to 10 carbon atoms, -O-, -S-, -SO-, -SO
Indicates _2- or -CO-. a is 0 or 1,
When a is 0, it means that aromatic rings are bonded to each other without X. Y represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a halogen group, or a nitro group, each of which may be the same or different from each other. . b and c represent integers of 0 to 4 that are the same or different from each other. Further, d represents a number between 0 and 20. e represents an integer from 0 to 4. ] 2), -Ar- is ▲There are mathematical formulas, chemical formulas, tables, etc.▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (X in the formula - O-, -S-, -SO-, -SO_2-, -CO- or -C
The aromatic polyamide copolymer according to claim 1, wherein the aromatic polyamide copolymer is H_2-.