JPS60226528A - Aromatic polythioether amide polymer and its production - Google Patents

Abstract

PURPOSE:To obtain the titled polymer having excellent heat resistance and moldability and useful as a material of fiber, film and paint, by reacting a specific aromatic diamine having thioether bond with an aromatic dicarboxylic acid (chloride). CONSTITUTION:An aromatic polythioether amide polymer having the recurring unit of formula II (Ar is 6-30C aromatic ring) can be produced either by dispersing an aromatic diamine having a thioether bond and containing >=50mol% diamine of formula I (d is 0-20; Y is 1-20C alkyl, 3-20C cycloalkyl, 6-20C aryl, etc.; e and f are 0-4) in an alkaline aqueous solution, adding a solution obtained by dissolving an aromatic dicarboxylic acid chloride in an organic solvent (e.g. cyclohexane) to the above dispersion, and carrying out the polycondensation of the components, or by dissolving the above aromatic diamine and aromatic dicarboxylic acid in an organic acid amide or organic sulfoxide, adding a condensation agent such as a tertiary amine to the solution, and carrying out the polycondensation of the components.

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the present invention] - Industrial field of application The present invention relates to an aromatic polyamide having 1,000 onythyl bonds and a method for producing the same. The aromatic polyamide of the present invention has excellent heat resistance and moldability, and is useful as a material for fibers, films, and coatings.

[Conventional technology and its problems]

Aromatic polyamide resins synthesized from aromatic diamines, aromatic dicarboxylic acids, and 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 high melting point, and many have a melting point of H higher 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 a solvent.

Such an aromatic polyamide with improved processability is produced by (a) a method of copolymerizing an aliphatic component (JP-A-52-1999
109592, JP-A-53-943973, (b) Method of introducing a connecting functional group into the main chain or imparting flexibility (
U.S. Patent No. 3505288, Japanese Patent Publication No. 52-23198
, JP 53-104695>, (c) Method of random copolymerization of aromatic components (JP 53-104697, JP 56-88427, U.S. Patent No. 4410684)
etc. are known.

However, it is difficult to say that the polyamides obtained by these techniques have a sufficient balance between processability and heat resistance.

[Configuration of the present invention]

The present invention provides an aromatic polyamide having a thioether bond that has a well-balanced moldability and heat resistance, and a method for producing the same.

That is, the first aspect of the present invention provides an aromatic polythioetheramide polymer having the following repeating unit: alkyl group with 3 to 20 carbon atoms, cycloalkyl group with 3 to 20 carbon atoms, aralkyl group with 6 to 200 carbon atoms, 6 to 20 carbon atoms
represents an aryl group, a halogen group, or a nitro group, which may be the same or different from each other, and e and f represent integers of θ to 4, which may be the same or different from each other.

Also, Arld is an aromatic ring having 6 to 30 carbon atoms].

2iJ of the present invention, an aromatic diamine having a thioether bond containing 50 moles or more of the diamine represented by the general formula (1) and an aromatic dicarboxylic acid chloride are reacted to form an aromatic diamine having the following repeating unit. A method for producing a polythioetheramide polymer is provided.

[In the formula, d represents a number between 0 and 200. Yit.

Alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, aralkyl group having 6 to 20 carbon atoms, 6 carbon atoms
~200 represents an aryl group, a halogen group, or a nitro group, and each may be the same or different from each other. e and f are integers of 0 to 4 that are the same or different from each other. Further, k is an aromatic ring having 6 to 30 carbon atoms].

The third aspect of the present invention is to react an aromatic diamine having a thioether bond containing 50 moles or more of a diamine represented by the general formula (1) % formula % () with an aromatic dicarbonyl alcohol, The present invention provides a method for producing an aromatic polythioetheramide polymer having repeating units.

[In the formula, dFio represents an integer of 20. Y is carbon number 1
~20 alkyl group, cycloalkyl group having 3 to 20 carbon atoms, aralkyl group having 6 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, halogen group or monotro group 1, each with the same trapping It may be different or it may be different. e and f
represent integers from θ to 4 that are the same or different from each other.

[Aromatic diamine]

The aromatic diamine having a thioether bond represented by the general formula (1) used in the present invention includes 4,4'-bis(4-aminophenylthio)diphenyl sulfide,
1.4-bis(4-aminophenylthio)benzene, 1
．． 3-bis(4-aminophenylthio)benzene, α,
Examples include ω-diaminopoly(1,4-phenylene) oligo 1-.

A part of these aromatic amines (50 mol % or less, 5 to 30 mol % for good cough) is converted into an aromatic diamine represented by the general formula ([1)] or an aromatic diamine represented by the general formula (m) H2N Ar -NH2(111) may be replaced to improve the solubility and moldability of the resulting aromatic polyamide [wherein, X is a divalent hydrocarbon group having 1 to 10 carbon atoms, -〇-5-8O Indicates -1-5ot-strapping-CO-, a is 0 or Fil, and when a is 0, it represents that the aromatic rings are bonded to each other without TiX.

Y represents an alkyl group having 1 to 200 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a 10-gen group, or a nitro group, respectively. They may be the same or different from each other. Are b and c mutually +t? I-1 or different θ
M17jr represents an integer of ˜4 and is an aromatic ring having 6 to 30 carbon atoms].

The aromatic diamine having a 1,000-onythyl bond represented by L notation (II) and 12 are 2.2-bis(4-(4-aminophenylthio)phenyl)propane, 1.1.1,
3,3.3-hexafluoromethyl-2,2-bis(4
-(4-aminophenylthio)phenyl]propane, 4
, 4'-bis(4-aminophenylthio)diphenyl ether, 4.4'-bis(4-aminophenylthio)benzophenone, 4.4'-bis(4-aminophenylthio)diphenyl sulfoxide, 4.4'- Bis(4-aminophenylthio)diphenylsulfone, 3.3'-
bis(4-aminophenylthio)diphenylsulfone,
4.4'-bis(4-aminophenylthio)biphenyl, 2.2',6.6'-tetramethyl-4,4'-bis(4-aminophenylthio)biphenyl, etc. can be used; As the aromatic diamine represented by the formula Tsukuda), p-
phenylenediamine, m-phenylenediamine, 4-methyl-1,3-phenylenediamine, 5-methyl-1,
3-phenylenediamine, 4r4'-diaminobiphenyl, 4,4-diaminodiphenyl ether, 4,4-diaminodiphenylsulfide, 4,4-diaminobenzophenone, 4,4'-diaminodiphenylsulfoxide, 4,4'-diaminodiphenylsulfone , 4.4'-
Diaminodiphenylmethane, 2.2-bis(4-aminophenyl)propane, 1.4-bis(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'-bis(
4-aminophenoxy)benzophenone, 4.4'-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)be/sophenone, 4,4-bis(4-aminobenzoyl)diphenylsulfoxide, 4.4'-bis(4-aminobenzoyl)diphenylsulfone, 4.4
'-bis(4-aminobenzoyl)diphenylmethane,
2,2-bis(4-(4-aminobenzenesulfonyl)phenyl)furopane, 4.41-bis(4-aminobenzenesulfonyl)diphenyl ether, 4,4'-bis(4-aminobenzenesulfonyl)diphenylsulfi)' , 4
．． 4-bis(4-aminobenzenesulfonyl)benzophenone, 4.4'-bis(4-aminobenzenesulfonyl)diphenylsulfoxide, 4.4'-bis(4-aminebenzenesulfonyl)diphenylsulfone, 4.4
'-Bis(4-aminebenzenesulfonyl)diphenylmethane, 2,2-bis(4-(4-aminebenzenesulfonyl)phenyl)propane, etc. can be used.

[Aromatic dicarboxylic acid chloride]

Aromatic dicarboxylic acid chloride k") used in the present invention
r-f is -m+ terephthalic chloride, isotoric acid chloride, 4,4'-biphenyl dicarboxylic acid chloride, 4,4-diphenyl ether dicarboxylic acid chloride, 4,4'-diphenyl sulfide dicarboxylic acid chloride, 4.4 [Aromatic dicarboxylic acids] Examples include '-benzophenone dicarboxylic acid chloride, 4,4'-diphenylsulfone dicarboxylic acid chloride, 4,4'-diphenylmethane dicarboxylic acid chloride, 1,5-naphthalene dicarboxylic acid chloride, etc. Examples of aromatic dicarboxylic acids used in the invention include terephthalic acid, isophthalic acid, 4,4'-biphenyldicarboxylic acid, a,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenylsulfite dicarboxylic acid,
．． Examples include 4'-benzophenone dicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, and 1,5-naphthalene dicarboxylic acid.

[Method for producing polyamide] Second invention: In the present invention, a known method can be employed as is in the reaction of aromatic diamine and aromatic dicarboxylic acid chloride. For example, for the interfacial polycondensation method, which can be achieved by interfacial polycondensation method, solution polycondensation method, etc., 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 amount of alkali used 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 equivalents.

An aromatic polythioether amide is produced by dispersing an aromatic diamine in an aqueous solution containing the above-mentioned water-soluble neutralizer, and adding a solution of an aromatic dicarboxylic acid dicarboxylic acid dissolved in an organic solvent to the solution and reacting it. Examples of the organic solvent include ketone solvents such as cyclohexanone, diisobutyl ketone, acetophenone, and p-methylacetophenone, methylene chloride, chloroform,
Carbon tetrachloride L 111.1-) +) Tetraethane, 1
, 1,2,2-tetrachloroethane and other halogenated hydrocarbon solvents. In order to obtain a high molecular weight substance, cyclohexanone, p-methylacetophenone, etc. are preferable. Further, the reaction temperature is in the range of Fio to 100°C, preferably 3 to 50°C.

The reaction time ranges from 1 minute to 10 hours, preferably from 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 J pyridine, quinoline, pyrimidine2.
6-lutidine and the like can be mentioned. However, when using these compounds as an organic acid amide as a reaction solvent, F
i) It is not necessarily necessary to add it. If a neutralizing agent is used, the amount used should be 1.0% of the reactive group of the aromatic dicarboxylic acid chloride. Engineering Nl, -t-1°, 3~3. . □□7~yo,
８□ ・）It’s delicious. On the other hand, as the reaction solvent, organic acid amides and organic sulfoxides are preferred. For example, N,N-dimethylformamide, N,N-dimethylacetamide,
N-methylpyrrolidone, N-methyl-ε-caprolactam, hexamethylphosphoramide, tetramethylurea,
Dimethyl sulfoxide and the like can be mentioned.

Aromatic diamine is dissolved in the above reaction solvent, a neutralizing agent is added if necessary, and aromatic dicarboxylic acid chloride is added to this solution and reacted to produce a polyamide having the following repeating unit. be able to.

[wherein the number is between dFiO and 20]. Y is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, or an aralkyl group having 6 to 20 carbon atoms.
represents an aryl group, a halogen group, or a nitro group, which may be the same or different from each other. e and f are integers of 0 to 4 that are the same or different from each other.

Also, Ar　Fi is an aromatic ring having 6 to 30 carbon atoms].

This polyamide may have the following units in the polyamide molecule by using an aromatic diamine represented by formula ([l) or formula]. During the production of polyamide, 5 to 10% by weight of chloride is added. It may be advantageous to add lithium, calcium chloride, rhodan calcium, etc. to the reaction system to significantly increase solubility.

The reaction temperature in this case is in the range of -30°C to 100°C, preferably -20°C to +30°C. Reaction time F15 minutes~
10 hours, preferably in the range of 30 minutes to 5 hours.

[Production method of the third invention] The method of producing polyamide by polycondensing an aromatic diamine and an aromatic dicarboxylic acid can also be a known method as it is, except for the raw materials. It can be achieved by polycondensation method and isobaric method.

The aromatic polythioetheramide polymer of the present invention is produced by dissolving an aromatic diamine and an aromatic dicarboxylic acid in an organic acid amide or an organic sulfoxide, and adding a tertiary amine or the like as a condensing agent to the solution and reacting the same. be able to. Examples of this solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-methyl-1-caprolactam, hexamethylphosphoramide, tetramethylurea, dimethylsulfoxide, and the like. I can do it. As the condensing agent, a phosphorus condensing agent such as triphenyl phosphite is preferred. Examples of tertiary amines include pyridine, quinoline, pyrimidine, 2,6-lutidine, triethylamine,
Examples include tributylamine. The condensing agent is
It is desirable to use 1 to 2 equivalents based on the number of moles of the reactive group of the aromatic dicarboxylic acid. The tertiary amine may be used in excess, and it may be advantageous to add 1 to 10% by weight of lithium chloride, calcium chloride, calcium rhodan, etc., if necessary. Also, the reaction temperature is 0 to 2
00°C, reaction time ranges from 30 minutes to 20 hours.

〔polyamide〕

The polyamide thus produced is an aromatic polythioetheramide polymer having the following repeating units (wherein d represents a number between 0 and 200). Ya, carbon number 1
Represents an alkyl group having ~20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a nitro group spanning a chlorogen group, each of which is the same as the other. It's okay to be different. e and lt are the same or different integers from 0 to 4.

Moreover, Ar is an aromatic ring having 6 to 30 carbon atoms].

This polyamide may have the following units in its molecule.

or [wherein, X is a divalent hydrocarbon group having 1 to 10 carbon atoms, -0
-1-SO-1-802- or -CO-, a is 0 or 1, and when a is 00, X is absent and the aromatic rings are bonded to each other. Table b-t-, y is
Alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, aralkyl group having 6 to 20 carbon atoms, 6 carbon atoms
~20 aryl groups, halogen groups, or nitro groups, which may be the same or different from each other.

b and C represent integers of θ to 4 that are the same or different from each other.

Moreover, Ar and A'r are aromatic rings having 6 to 30 carbon atoms].

The glass transition temperature of the polyamide thus obtained is approximately 70 to 280°C for the homopolymer and approximately 100 to 350°C for the copolymer.

〔purification〕

A solution containing an aromatic polythioetheramide polymer 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,
The polyamide is isolated by allowing the polymer to settle and then filtering it.

[Processing, usage]

When molding the polymer of the present invention, it may contain various known filler components. Typical examples of filler components include (a) fibrous fillers such as glass fiber, carbon fiber,
Boron fiber, aramid fiber, alumina fiber, silicon carbide m, etc., Cb1 inorganic filler: mica, talc, clay, graphite, carbon black, silica, asbestos, molybdenum sulfide, magnesium oxide,
Examples include calcium oxide.

The polyamide of the present invention can be used for various electrical and electronic parts, housings, military parts, aircraft interior materials, sliding parts,
It can be used in a wide range of applications, including gears, insulating materials, heat-resistant films, heat-resistant panels, and heat-resistant fibers.

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

(Left below) Example 1 A stirring bar, a thermometer, and a dropping funnel were placed in a Mitsuro flask, and 2.02 g of sodium hydroxide was added to 4 Ofg of water.
Dissolve K and put it in a flask. Next, 1.4-bis(4
-aminophenylthio)benzene 8.1Of was added, 5
The mixture was stirred vigorously at ℃ and dispersed in the aqueous solution. On the other hand, 5.98 f of isophthalic acid chloride was added to 1 of cyclohexanone.
The acid chloride solution was poured into the flask from the dropping funnel. At this time, the reaction temperature was set at 15℃.
I kept it below.

After 20 minutes, 100ml of water and 80I11 of cyclohexanone were added to the reaction solution. / was added, and then 200 d of acetone was poured in to precipitate the polymer. Sorting polymers by F,
Wash with hot water and then dry in a vacuum oven.

(100°C, 8 hours). Polymer yield 11.4 f(
yield 100%). The glass transition temperature of this polymer is 25
8°C, and the softening point was 368°C. Also,; intrinsic viscosity keo, a 7 dl/f (o, schi DM80 solution,
30°C).

When the infrared absorption spectrum of this polymer was measured, an absorption derived from the amide was observed at 1640 cm-1, 1505 cE-1, an absorption derived from the thioether at 1 (170 cm), and an absorption derived from the aromatic ring at 805 m''. Ta.

Example 2 Polyamide was produced in the same manner as in Example 1 using raw materials having the following composition.

Polymer yield 11.2t (98%). Glass transition temperature 2
60°C, softening point 388°C. Intrinsic viscosity 0.40dl/f
(osti DMSO solution, 30°C).

IR spectrum (Figure 1): 1640.1515 signal-1
(amide), 1075 cm-” (thioether), 81
0 cm-' (aromatic ring).

Example 3 Polyamide was produced in the same manner as in Example 1 using raw materials having the following composition.

Yield: 14.11F (99%). Glass transition temperature 192℃
, softening point 335℃, intrinsic viscosity (1,51 dl/f (o
, zcIJNMP solution, ao°C).

IR spectrum = 16411.1510i1 (amide)
, 1070cn*-' (thioether), 805cm
-” (Aromatic 3Jl).

Example 4 A polymer was produced in the same manner as in Example 1 using raw materials having the following composition.

Yield: 14°1r (c+91). Glass transition temperature 198℃
, softening point 357°C. Intrinsic viscosity (138di/f(0,2
(NMP solution, 30°C).

IR spectrum (Figure 2 1: 1640, 151.5
cm” (amide), tosO (m-1 (thioether)
, 810-1 (aromatic ring), l Example 5 A polyamide was produced in the same manner as in Example 1 using raw materials having the following composition.

Yield 14.2f(10([1°Glass transition temperature 195°C
, softening point 325°C. Intrinsic viscosity 0.63 dl/f (0.2
(NMP solution, 30°C).

IR spectrum: 1640.1515m''1 (amide), 1080m-' (thioether), 810ttp
t” (aromatic ring).

Example 6 A stirring rod, a thermometer, a Liebig condenser tube, and a nitrogen gas introduction tube were set in a 5011II four-eye flask, and α,
ω-diaminopoly(1,4-thiophenylene) oligomer (average molecular weight 1000) 1 (1,02, terephthalic acid 2.03 f,) liphenyl phosphite 7. (l Of
, lithium chloride 5.00fz quinoline 40m and N
-Prepare 120 ytl of methylpyrrolidone and 200 t under nitrogen flow? The reaction was carried out for 4 hours.

The reaction solution was poured into water to precipitate the polymer. The polymer was separated, washed with hot water, and then dried in a vacuum oven (100° C., 8 hours). Polymer yield 1.12f (99
Yu). Glass transition temperature 100°C, softening point 280°C. Intrinsic viscosity 0.12 dl/f (o, a chiquinoline solution, 30
℃).

IR, spectrum (Figure 3 1: 1645.1515 tan-
1 (Amido), 1085 Shin-1 (1000 One Chill), 81
0 Shin-1 (aromatic ring).

Example 7 Polyamide was produced in the same manner as in Example 1 using raw materials having the following composition.

Polymer collection! 14.6f (1110 section). Glass transition temperature 227°C. Intrinsic viscosity: 072 di/r (0.2 di NMP solution, 30°C).

IR spectrum: 1640.1510cWL-' (amide), 1145 cm' (sulfone), 1o7-
tube thioether), 805 cWL” (aromatic ring).

Example 8 Polyamide was produced in the same manner as in Example 1 using raw materials having the following composition.

Yield of polymer: 14.21 F (1013 F). Glass transition temperature 237°C. Intrinsic viscosity o, 71 dl/? (o
, s1 ]) M 80 solution, 30 °C).

II (spectrum: 1640.1510r4-" (amide), 1240crIv" (x-chill), 1140c
m' (sulfone), 1 (370 cm' (1,000 onychill)
, 805 mercenary 1 (aromatic ring).

[Brief explanation of drawings]

FIGS. 1, 2 and 3 show embodiment 2.4 of the present invention.
FIG. 6 is an infrared absorption spectrum diagram of the polyphosphoramide obtained in Example 6. Patent Applicant: Mitsubishi Yuka Co., Ltd. Agent: Patent Attorney Hidetoshi Furukawa Agent: Masahisa Hase Figure 1) Growth (cm-1) Figure 2) Growth (cm-1) Figure 3: Wavelength (Cm-) ') Procedural amendment (method) August 7, 1980 Patent Application No. 832.63 of 1988 2, Title of invention Aromatic polythioetheramide polymer and process for producing the same 3, Case of the person making the amendment Related Patent applicant name (605) Mitsubishi Yuka Co., Ltd. 4, Agent

Claims (1)

[Scope of Claims] 1) An aromatic polythioetheramide polymer having a zero-order repeating unit [wherein d represents a number between 0 and 20]. Y is carbon number 1
-20 alkyl group, C3-20 cycloalkyl group, C6-20 aralkyl group, C6-20 alkyl group, halogen group or nitro group, each of which is the same as the other. It's okay to be different. e and f
Indicates an integer from 0 to 4 that is the same or different from each other. Moreover, static is an aromatic ring having 6 to 30 carbon atoms]. (5) An aromatic diamine having a thioether bond containing 50 moles or more of a diamine represented by the general formula (1) is reacted with an aromatic dicarboxylic acid chloride (no change in content) to produce the following repeating unit. A method for producing an aromatic polythioetheramide polymer having the following: [wherein d represents an integer of 0 to 20]. Y has 1 or more carbon atoms
20 alkyl group, cycloalkyl group having 3 to 20 carbon atoms, aralkyl group having 6 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, e and f may be the same or different integers from 0 to 4. In addition, k is an aromatic ring having 6 to 30 carbon atoms [63), an aromatic diamine represented by the general formula (13) is dispersed in an alkaline aqueous solution, and a solution of an aromatic dicarboxylic acid chloride dissolved in an organic solvent is added to this. The method according to claim 1, characterized in that the polymer is produced by polycondensation in addition. Claim 2, characterized in that the polymer is produced by dissolving the same acid diamide or organic sulfoxide, adding aromatic dicarboxylic acid chloride thereto, and polycondensing it.
) The method described in section