JP2003268103A - Aromatic copolyamide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymeric material excellent in functions, by controlling the sequence distribution of an aromatic copolyamide. <P>SOLUTION: The aromatic copolyamide has two kinds of aromatic diamine components as the principal components and has a B value to indicate the sequence distribution of 0.75 or less as well as a logarithmic viscosity of the polymer of 0.3 or more; and the method for manufacturing the aromatic copolyamide comprises solution polymerization of an aromatic dicarboxylic chloride with an aromatic diamine having an electron-donating bond and an aromatic diamine having an electron-withdrawing bond in the presence of a tertiary amine. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention provides a polymer material having excellent functionality by controlling the chain distribution of an aromatic polyamide copolymer.

[0002]

2. Description of the Related Art Aromatic polyamides are used as high-performance materials such as fibers, films, and separation membranes by taking advantage of their excellent mechanical properties, heat resistance and solvent resistance. However, with the development of various high-performance polymers having similar characteristics such as polyimide, polybenzimidazole, and polybenzoxazole, it is the current situation that aromatic polyamide materials having more excellent properties are desired.
For example, in the case of polyimide, a high-performance material in which a sulfonic acid group is introduced on the molecular chain to be used as a polymer electrolyte membrane has been studied. However, when a sulfonic acid group is introduced on the polymer molecule, the hydrophilicity increases and the swelling tends to increase especially in high-temperature water. Therefore, when used as a proton exchange membrane for a fuel cell, for example, this form is unstable. Is a problem. For this reason, as a structure that suppresses swelling while having sulfonic acid groups in the polymer, sulfonic acid group-containing units and sulfonic acid group-free units are block-incorporated into the polymer, and the hydrophobicity of sulfonic acid group-free unit chains is improved. Attempts have been proposed to reduce the swelling properties of polymers by utilizing the interaction (eg Pol
ymer, Vol. 42, P.I. 359 (2001)).
In order to obtain such a polymer structure, a method of synthesizing an oligomer from a monomer having a sulfonic acid group or one monomer having no sulfonic acid group and then adding the other monomer to perform polymerization is required. . However, in such sequential addition polymerization, the degree of polymerization is often difficult to increase, and there are problems such that it is difficult to obtain a block copolymer having a desired chain distribution.

On the other hand, in the aromatic component-containing polyamide, the reactivity between the aromatic diamine and the carboxylic acid component of the aliphatic diamine is utilized to bond in a one-step reaction without undergoing the above-described multi-step reaction. A style-controlled synthesis method has also been reported. However, since the heat resistance of a polymer containing an aliphatic diamine is generally inferior to that of a wholly aromatic polyamide system, it is desired to control the bonding mode in such a manner even in a copolymer system in which an aromatic diamine is combined. Polymers with controlled chain distribution have not been reported so far because the difference in reactivity between them is not large.

[0004]

An object of the present invention is to obtain a novel polymer material having particularly excellent functionality by obtaining an aromatic polyamide copolymer whose chain distribution is controlled by a one-step reaction.

[0005]

Means for Solving the Problems As a result of intensive studies conducted by the present inventor, as a result of combining two appropriate aromatic diamine monomers and carrying out solution polymerization with an aromatic dicarboxylic acid chloride in the presence of a tertiary amine, It was found that an aromatic polyamide copolymer having a high block property can be obtained by one-step synthesis, and that the obtained aromatic copolymer polyamide copolymer exhibits excellent functional properties as compared with a normal random copolymer. It is a thing.

That is, the present invention is a copolymerized aromatic polyamide containing two kinds of aromatic diamine components, wherein the B value representing the chain distribution is 0.75 or less. The aromatic polyamide copolymer of the present invention,
It is preferable that at least one aromatic diamine has a functional group. Furthermore, the polyamide copolymer of the present invention preferably has a polymer inherent viscosity of 0.3 or more. Further, the present invention uses an aromatic diamine having an electron-donating bond and an aromatic diamine having an electron-withdrawing bond, and solution polymerization is carried out together with an aromatic dicarboxylic acid chloride in the presence of a tertiary amine compound to obtain the aromatic compound of the present invention. A method of making a group polyamide copolymer is included.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

The copolymerized aromatic polyamide containing two kinds of aromatic diamine components as main components of the present invention means an aromatic polyamide composed of an aromatic diamine component and an aromatic dicarboxylic acid component through an amide bond. At least 1
A copolyamide composed of one aromatic dicarboxylic acid component and at least two aromatic diamine components,
It is a copolyamide comprising 50 mol% or more of the wholly aromatic diamine component with these two types of diamine, and preferably a copolyamide comprising 70 mol% or more. And B showing the chain distribution of these two kinds of copolymerization components
The value must be 0.9 or less. What is B value?
J. Polym. Sci. , Polym. Chem. E
d. , Vol. 5, P.I. 2259 (1967), it is defined as follows. That is, when a bifunctional monomer of A and B reacts with a bifunctional C monomer to form a copolymer having an AB binding unit and a BC binding unit, focusing on the C monomer, two functional groups of C The binding modes are A-C-A and A-C-
There are three types of B (same as B-C-A) and B-C-B. About this copolymer, H-NMR and C-N
When the MR is measured, the three types of binding patterns sometimes show signals at different positions, and the abundance ratio of binding can be determined from the respective signal intensities. The abundance ratios of the respective binding modes are P (A-C-A), P (A
-C-B), P (B-C-B) (P (A-C-A) + P
(A−C−B) + P (B−C−B) = 1), the copolymerization ratio of A unit and B unit is R (A), R (B) (R
(A) + R (B) = 1), when the B unit exists, the probability that the A unit exists with the C unit sandwiched is P (A−C−B) / 2R (B), A unit. Is present, the probability that the B unit is present across the C unit is P (A-C-B) / 2R (A). The B value representing the chain distribution of the present invention means P
(A-C-B) / 2R (B) + P (A-C-B) / 2R
It is defined in (A). Regardless of the copolymerization ratio, B = 1 when the copolymer is a random copolymer, and the B value decreases as the block property of the chain distribution increases, resulting in the ultimate mixture of homopolymers. At this time, the B value becomes 0. On the other hand, when the alternating copolymerization property comes out from the random copolymer, the B value becomes a value larger than 1, and in the ultimate case of the perfect alternating copolymer, the B value shows 2. The B value of the copolymerized aromatic polyamide containing two kinds of aromatic diamine components as main components of the present invention shows a value of 0.75 or less, and is characterized by having many block-like chains. Due to this characteristic bond chain distribution, excellent properties are exhibited as compared with ordinary random copolymers. More preferably, the B value is 0.7 or less. Further, since the copolymer of the present invention is not a blend of homopolymers, the B value does not become substantially 0, and more preferably 0.1 or more.

The copolymerized polyamide of the present invention exhibits excellent properties when the polymer inherent viscosity is 0.3 or more.
If the logarithmic viscosity is less than 0.3, defects such as brittleness and inability to maintain shape retention will start to occur when formed into a film or the like. When the logarithmic viscosity is 0.3 or more, the shape retention property, the toughness, and the like are sufficiently exhibited. More preferably, the logarithmic viscosity is 0.4 or more. The larger the logarithmic viscosity is, the better the above-mentioned properties are, which is preferable. However, the moldability of the polymer may be impaired. Therefore, the upper limit of the logarithmic viscosity is not particularly specified, but it is preferably 10 or less. The logarithmic viscosity will be described in detail in Examples, but when the aromatic polyamide has good solubility, it can be measured using N-methylpyrrolidone as a solvent. Concentrated sulfuric acid may be used when the solubility in N-methylpyrrolidone is poor.

Since the copolyamide of the present invention exhibits excellent characteristics due to its structural characteristics, its synthetic method is not particularly limited, but it is complicated by synthesizing by the following solution polymerization. This is preferable because the target copolyamide can be obtained by a one-step polymerization reaction without going through a step. That is, it is a method in which an aromatic diamine having an electron-donating bond and an aromatic diamine having an electron-withdrawing bond are used and solution polymerization is performed with an aromatic dicarboxylic acid chloride in the presence of a tertiary amine compound.

In the case of phenylenediamines, the aromatic diamine having an electron-donating bond as used herein includes an alkyl group, an alkoxyl group, a phenoxy group, a thiophenoxy group and the like. For example, 5-methylmetaphenylenediamine, 5-ethylmetaphenylenediamine, 5-
t-butyl metaphenylenediamine, 5-methoxymetaphenylenediamine, 5-ethoxymetaphenylenediamine, 5-t-butoxymetaphenylenediamine, 5-
Examples thereof include, but are not limited to, phenoxymetaphenylenediamine, 5- (4-methylphenoxy) metaphenylenediamine, 5-thiophenoxymetaphenylenediamine, and 5- (4-methylthiophenoxy) metaphenylenediamine. In the case of the polycyclic diamine, those having an electron donating group or a bond on the aromatic ring containing an amino group may be used. For example, 4,4 '-(diaminodiphenyl) ether, 3,3'-(diaminodiphenyl) ether, 4,4 '-(diaminodiphenyl) thioether, 3,3'-(diaminodiphenyl) thioether, 2,2- Bis (4-aminophenol) propane, 2,2-bis (3-aminophenol) propane, bis (4-aminophenol) methane, 2,2-bis (3-
Aminophenol) methane, bis (4-aminophenoxy-4-phenyl) ether, bis (3-aminophenoxy-4-phenyl) ether, bis (4-aminophenoxy-4-phenyl) sulfone, bis (3-aminophenoxy-) 4-phenyl) sulfone, 3,3′-dimethylbenzidine and the like can be mentioned, but the invention is not limited thereto. The aromatic diamine having an electron-withdrawing bond, in the case of phenylenediamines, contains a nitro group, a cyano group, a carboxyl group, a sulfonic acid group and the like. For example, 5-nitrometaphenylenediamine, 5
-Cyanometaphenylenediamine, 5-carboxymetaphenylenediamine, 3,5-diaminobenzenesulfonic acid, 3,5-diaminobenzenesulfonic acid, 2,4-
Examples thereof include, but are not limited to, diaminobenzenesulfonic acid, 3,3′-disulfobenzidine, and 2,2′-disulfobenzidine. In the case of the polycyclic diamine, any compound having an electron-withdrawing group or a bond in an aromatic ring containing an amino group may be used. For example, 4,4'-
(Diaminodiphenyl) sulfone, 3,3 ′-(diaminodiphenyl) sulfone, 3,3′-dinitrobenzidine, 3,3′-dicyanobenzidine, 3,3′-diamino-4,4′-dinitrobenzene, 3, Examples thereof include 3'-diamino-4,4'-dicyanobenzene, but are not limited thereto. The presence of a functional group on these aromatic diamines is preferable for exhibiting excellent functionality, but examples of the functional group include a nitro group,
Cyano group, amino group, carboxyl group, sulfonic acid group,
Examples thereof include a phosphonic acid group and a phosphinic acid group. These may be present in a form as found in the above aromatic compound examples, but are not particularly limited to them, and may be present at any position on the aromatic diamine molecule included in the present invention. It only needs to exist. When these functional groups are present in at least one of the aromatic diamines, the characteristics of the aromatic copolyamide according to the present invention are particularly preferable, but of course the two main aromatic diamines are Is also preferred. In this case, the functional groups may be the same or different.

Aromatic dicarboxylic acids that can be used in the synthesis of the copolyamide of the present invention include those used in the synthesis of ordinary aromatic polyesters and aromatic polyamides,
For example, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenyl sulfone dicarboxylic acid, biphenyl dicarboxylic acid, terphenyl dicarboxylic acid, 2,2-bis (4-carboxyphenyl) hexafluoropropane, and the like, It is not particularly limited to these. The aromatic dicarboxylic acid preferably has an acid chloride structure. Further, in order to react the aromatic diamines with the dicarboxylic acid chloride, an aprotic polar organic solvent such as N-methylpyrrolidone, dimethylacetamide or dimethylformamide can be used. It is advisable to dissolve the diamines in a solvent, cool the mixture to room temperature or below, and then add dicarboxylic acid chloride to react. At this time, it is especially preferable to add hydrogen chloride produced by the reaction together with the aromatic diamine and an equivalent amount or more of the tertiary amine. Examples of tertiary amines include trialkylamines such as triethylamine and tributylamine, aliphatic cyclic tertiary amines such as N-methylmorpholine, aromatic amines such as N, N-diethylaniline and triphenylamine, and pyridine. , Quinoline and other related tertiary amines.

The copolymerized aromatic polyamide obtained in the present invention exhibits excellent properties depending on thermal properties, solvent resistance, and functional groups, as compared with random copolymers obtained by ordinary polymerization, and fibers and films. , A separation membrane material, etc. The ionic group introduced and imparted with hydrophilicity and ion exchange ability can be used for separation membranes, polymer electrolyte membranes, adhesive materials, binder materials and the like.

[0014]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Various measurements were performed as follows. NMR measurement: Dissolve the sample in deuterated DMSO and add Var
It was measured by Unity-500 (measurement temperature: room temperature). Solution viscosity: polymer powder at a concentration of 0.5 g / dl N-
It was dissolved in methylpyrrolidone and the viscosity was measured using a Ubbelohde viscometer in a constant temperature bath at 30 ° C. to obtain a logarithmic viscosity [ln
It was evaluated by (ta / tb)] / c (ta is the number of seconds of dropping the sample solution, tb is the number of seconds of dropping only the solvent, and c is the polymer concentration). Film thickness measurement: micrometer (minimum scale =
0.001 mm).

Example 1 4,4 '-(diaminodiphenyl) ether (ODA)
4.03 g (0.0201 mol), 4,4 '-(diaminodiphenyl) sulfone (DDS) 5.00 g (0.0.
0201 mol), triethylamine 8.15 g (0.
(0805 mol) was dissolved in 150 ml of N-methyl-2-pyrrolidone (NMP) under a nitrogen stream, and after cooling with ice, 8.18 g (0.0403 mol) of isophthalic acid chloride was added and stirring was continued. After reacting for 1 hour under ice-cooling, after reacting for 2 hours at room temperature, the polymerization solution was poured into excess methanol to obtain an aromatic copolyamide. After repeated washing with a household mixer, it was dried. Yield 13.4
g. The inherent viscosity of a 0.5 g / dl NMP solution measured at 30 ° C. was 0.85. A C-NMR spectrum is shown in FIG. B value = 0.61. The obtained polymer is DS
From the C measurement, a glass transition point was shown at 299 ° C.

Example 2 6.37 g (0.
A copolyamide was obtained in the same manner as in Example 1 except that (0805 mol) was used. Yield 12.9g. 0.5
The logarithmic viscosity of the g / dl NMP solution measured at 30 ° C. was 0.65. B value = 0.63. The obtained polymer showed a glass transition point at 300 ° C. by DSC measurement.

Comparative Example 1 A copolyamide was obtained in the same manner as in Example 1 except that triethylamine was not used. Yield 13.0g. 0.5
The logarithmic viscosity of the g / dl NMP solution measured at 30 ° C. was 1.57. A C-NMR spectrum is shown in FIG. B value = 0.90. The obtained polymer showed a glass transition point at 305 ° C. by DSC measurement.

Example 3 4.84 g of 4,4 '-(diaminodiphenyl) ether
(0.0242 mol), 2,2′-disulfobenzidine 5.55 g (0.0161 mol) and triethylamine 11.41 g (0.1128 mol) were dissolved in N-methyl-2-pyrrolidone (NMP) 150 ml under a nitrogen stream. Then, after cooling with ice, 8.18 g (0.
(0403 mol) was added and stirring was continued. After reacting for 1 hour under ice-cooling, after reacting for 2 hours at room temperature, the polymerization solution was poured into excess methanol to obtain an aromatic copolyamide. After repeated washing with a household mixer, it was dried. Yield 17.4g. The inherent viscosity of a 0.5 g / dl NMP solution measured at 30 ° C. was 0.75. B value = 0.69. A film having a thickness of 20 μm was produced from the obtained polymer from an NMP solution by a casting method. The film was heat-treated in hot water at 100 ° C. for 3 hours, but no change was observed in the film shape.

Comparative Example 2 3.26 g (0.0322 mol) of triethylamine
A copolyamide was obtained in the same manner as in Example 3 except that Yield 16.9g. The logarithmic viscosity of a 0.5 g / dl NMP solution measured at 30 ° C. was 0.86. B value = 0.95. A film having a thickness of 20 μm was produced from the obtained polymer from an NMP solution by a casting method. When this film was heat-treated in hot water at 100 ° C. for 3 hours,
Swelling occurred and the shape retention was reduced.

Comparative Example 3 7.77 g (0.0383 mo) of isophthalic acid chloride was used.
A copolyamide was obtained in the same manner as in Example 3 except that the above was changed to l). Yield 11.9g. The logarithmic viscosity of the 0.5 g / dl NMP solution measured at 30 ° C. was 0.24. B
Value = 0.71. A film having a thickness of 20 μm was produced from the obtained polymer from an NMP solution by a casting method.
It was a brittle film.

[0021]

EFFECTS OF THE INVENTION The copolymerized aromatic polyamide obtained by the present invention is superior to the random copolymer obtained by ordinary polymerization,
It exhibits excellent properties depending on thermal properties, solvent resistance, and functional groups.
For example, a sulfonic acid group-containing copolymer has hydrophilicity, but has a characteristic of excellent water resistance as compared with a random copolymer. The aromatic copolyamide of the present invention has excellent properties as a fiber, a film, and a separation membrane material, and those having an ionic group introduced to impart hydrophilicity, ion exchange ability and the like are used as separation membranes and have high properties. It is a material suitable for use in molecular electrolyte membranes, adhesive materials, binder materials, etc.

[Brief description of drawings]

FIG. 1: 4,4′-polymerized with triethylamine
(Diaminodiphenyl) ether / 4,4 ′-(diaminodiphenyl) sulfone / isophthalic acid chloride = 1 /
C-NMR spectrum of 1/2 (molar ratio) copolymer

FIG. 2: 4,4 ′-(diaminodiphenyl) ether / 4,4 ′-(diaminodiphenyl) sulfone / isophthalic acid chloride polymerized in the absence of tertiary amine = 1/1 /
C-NMR spectrum of 2 (molar ratio) copolymer

Claims (4)

[Claims] 1. A copolymerized aromatic polyamide containing two kinds of aromatic diamine components as main components and having a chain distribution B.
A copolymer having a value of 0.75 or less. 2. The aromatic polyamide copolymer according to claim 1, wherein at least one kind of the aromatic diamine has a functional group. 3. The aromatic polyamide copolymer according to claim 1, which has a polymer inherent viscosity of 0.3 or more. 4. An aromatic diamine having an electron-donating bond and an aromatic diamine having an electron-withdrawing bond are used, and solution polymerization is performed with an aromatic dicarboxylic acid chloride in the presence of a tertiary amine compound. 4. The method for producing an aromatic polyamide according to any one of 1 to 3.