JPH0347836A - Block copolymer and production thereof - Google Patents

Abstract

PURPOSE:To readily obtain the title copolymer having improved solvent solubility, compatibility with other polymers and excellent handleability by subjecting a polyamide comprising a specific aromatic dicarboxylic acid and aromatic diamine and a specific copolymer to polycondensation. CONSTITUTION:A polyamide shown by formula I (R is bifunctional organic group; R' is phenolic hydroxyl group-containing bifunctional aromatic group; Ar is bifunctional aromatic group shown by formula II to formula VII; l and m are average degree of polymerization, respectively, l+m=2-300 and m/(m+l)>=0.04) prepared by subjecting (A) an aromatic dicarboxylic acid composed of at least 4mol% phenolic hydroxyl group-containing aromatic dicarboxylic acid and (B) an aromatic diamine to polycondensation and (C) a copolymer (shown by formula VIII (x, y and z are each average polymerization degree, x=3-7, y=1-4 and z=5-15) are subjected to polycondensation in the presence of an aromatic phosphorous ester to give the aimed copolymer having 2-20 block units shown by formula IX and 2-20 block units shown by formula X.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a novel block copolymer and a method for producing the same, and more particularly to a crosslinkable polyamide-polybutadiene-acrylonitrile block copolymer and a method for producing the same. .

[Conventional technology]

Polybutadiene has a flexible molecular structure, and polybutadiene-based block copolymers, typified by styrene-butadiene block copolymers, are known to be excellent thermoplastic elastomers.

However, the polystyrene chains of this block copolymer have a low softening temperature, and there is a problem in that the block copolymer does not exhibit satisfactory performance when used at relatively high temperatures. In order to solve this problem, a polyamide-polybutadiene block copolymer using polyamide instead of styrene has been proposed (Japanese Patent Application Laid-Open No.
49026 and Japanese Patent Publication No. 62-3171).

[Problem to be solved by the invention]

However, although the previously proposed polyamide-polybutadiene block copolymers are thermoplastic elastomers with high heat resistance, they have problems such as insufficient solubility in solvents and insufficient compatibility with other polymers. Ta.

The present invention has been made for the purpose of solving the above-mentioned problems in the conventional technology.

The present inventors previously proposed a polyamide-polybutadiene-acrylonitrile block copolymer (Patent Application No.
No. 83493). This block copolymer is a thermoplastic elastomer with high heat resistance, and although it has sufficient solvent solubility and ease of handling before use, it does not meet the requirement for high solvent resistance after use. It turns out that there is a problem of sufficiency.

Therefore, as a result of further research, we have completed the present invention.

Therefore, an object of the present invention is to provide a polymer with good heat resistance, excellent solubility in solvents and compatibility with other polymers, and good handling properties, as well as heat resistance, adhesive properties, and solvent resistance. An object of the present invention is to provide a novel block copolymer that provides an elastic body and a method for producing the same.

[Means to solve the problem]

The first aspect of the present invention relates to a polyamide polybutadiene-acrylonitrile copolymer 4, which has aminoaryl groups at both ends formed by polycondensation of an aromatic dicarboxylic acid and an aromatic diamine. and a polybutadiene-acrylonitrile copolymer having written carboxyl groups at both terminals, the polycondensate is a polycondensate of a polyamide having the following formula (1):
A) and the general formula below (pro-tsuku unit force shown in the old)
(A) 0 (wherein R represents a divalent organic group, R' represents a divalent aromatic group having a phenolic hydroxyl group, and Ar represents the following formula (
1) to (6), where F3 X%Y%ZSρ and m are the average degree of polymerization, respectively, 5-15.1
+m-2~! Indicates an integer of 100, m/(m10g)≧
0.04) and is characterized in that the number of block units (A) and block units (B) are each present in a range of 2 to 20.

The second aspect of the present invention relates to a method for producing a polyamide-polybutadiene-acrylonitrile block copolymer represented by the above general formula (I), which comprises an aromatic dicarboxylic acid having at least 4 mol% of phenolic hydroxyl groups. An aromatic dicarboxylic acid consisting of an aromatic diamine and an aromatic diamine are polycondensed, and further, the following general formula (II) (II) (wherein R, R' Ar [and m have the same meanings as above) is synthesized. ) A polyamide having aminoaryl groups at both ends represented by the following general formula (m) +100C-f(-C112C11-CIl-CIl2
7** -0112C11)-v-3-7-COOI
I (m)N (wherein x'-'/ and 2 have the same meanings as described above.

Polybutadiene-acryloni with carboxyl groups at both ends as shown! - It consists of polycondensation with a lyle copolymer, and is characterized in that each of the above polycondensation reactions is carried out in the presence of an aromatic phosphite and a pyridine derivative.

The present invention will be explained in detail below.

The polyamide-butadiene-acrylonitrile block copolymer of the present invention has a structure represented by the above general formula (I), and first, at least 4 mol% is composed of an aromatic dicarboxylic acid having a phenolic hydroxyl group. By polycondensing aromatic dicarboxylic acid and aromatic diamine,
A polyamide having aminoaryl groups at both ends represented by the above general formula (II) is synthesized, and the resulting polyamide is then co-polymerized with butadiene-acrylonitrile having carboxyl groups at both ends represented by the above general formula (m). It can be produced by polycondensation with a polymer.

In the present invention, the aromatic dicarboxylic acid having a phenolic hydroxyl group used in the synthesis of the polyamide represented by the above general formula (II) is particularly limited as long as it is a compound having a carboxyl group and a hydroxyl group in the aromatic nucleus. For example, 4-hydroxyisophthalic acid, 5
Preferred examples include -hydroxyisophthalic acid and derivatives thereof. Others: 2-hydroxyisophthalic acid, 3-hydroxyphthalic acid, 4-
Hydroxyphthalic acid, 2-hydroxyterephthalic acid, 4
．． Examples include 4'-methylenebis-(3-hydroxy-2-naphthalic acid).

In the present invention, these aromatic dicarboxylic acids having a phenolic hydroxyl group can be used alone, but they may also be used in combination with other aromatic dicarboxylic acids.

In addition, when used together with other aromatic dicarboxylic acids, the aromatic dicarboxylic acid having a phenolic hydroxyl group needs to be at least 4 mol % or more of the total aromatic dicarboxylic acids.

In the present invention, examples of aromatic dicarboxylic acids that can be used in combination with the aromatic dicarboxylic acid having a phenolic hydroxyl group include isophthalic acid, terephthalic acid,
4.4'-biphenyl dicarboxylic acid, 3.3'-methylene nibenzoic acid, 4.4'-methylene nibenzoic acid, 4.4
'-oxynibenzoic acid, 4,4'thiodibenzoic acid, 3.
3'-carbonyl dibenzoic acid, 4.4'-carbonyl dibenzoic acid, 4.4'-sulfonyl dibenzoic acid, ■, 4-
Examples include, but are not limited to, carboxylic acids such as naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, and 2,6-naphthalene dicarboxylic acid, and derivatives thereof.

Further, aromatic diamines that can be used in the present invention include, for example, 3,4'-oxydianiline,
4.4'-oxydianiline, bis(4-a2minophenyl)methane, 3.3'-diaminobenzophenone, 4.4'-diaminobenzophenone, bis(
Examples include 4-aminophenyl) sulfide, bis(4-aminophenyl) sulfone, and 2,2-bis(aminophenyl)hexafluoropropane.

The polycondensation of the aromatic dicarboxylic acid or its derivative and the aromatic diamine is carried out using an excess amount of the aromatic diamine in the presence of the aromatic phosphite and the pyridine derivative.

Aromatic phosphites used include triphenyl phosphite, diphenyl phosphite, and tri-phosphorous acid.
-tolyl, phosphite di0- tolyl, phosphite tri-m-tolyl, phosphite di-m-)lyl, phosphite trily p-)lyl, phosphite di-p-tolyl, phosphite di0-
-chlorophenyl, tri-p-chlorophenyl phosphite, di-p-chlorophenyl phosphite, and the like.

Examples of pyridine derivatives include pyridine, 2-picoline, 3-picoline, 4-picoline, 2,4-lutidine, 2,6-lutidine, and 3,5-lutidine.

The polyamide produced by the polycondensation reaction has aminoaryl groups at both ends as shown in the above general formula (II), and has the following repeating unit (C) (wherein R' and Ar are the above-mentioned repeating units). It has the same meaning as

) or consisting of a repeating unit (C) and the following repeating unit (D) (wherein R and Ar have the same meanings as described above). The above polyamide has a repeating unit (
When composed of C) and a repeating unit (D), the repeating unit (C) and the repeating unit (D) may be in the form of a random polycondensate in which they are randomly bonded, or One or both of the repeating units (C) and the repeating units (D) may be combined in the form of a block in which up to 30 units each are combined to form a block copolymer.

Considering the physical properties such as tensile strength and tensile modulus of the block copolymer produced using these polyamides, it is usually preferable that the average degree of polymerization is in the range of m+Ω-2 to 300.

The polyamide represented by the general formula (IT) synthesized by the above polycondensation reaction is then polycondensed by a block copolymerization reaction with a polybutadiene-acrylonitrile copolymer having carboxyl groups at both ends represented by the above general formula (m). let

Polybutadiene with carboxyl groups at both ends
In the acrylonitrile copolymer, the stereochemical structure of the double bond may be a cis structure or a trans structure. The polybutadiene-acrylonitrile copolymer having carboxyl groups at both terminals represented by the above general formula (m) may be produced by any polymerization method that introduces carboxyl groups at both 5 terminals, and usually, It can be produced by anionic or radical polymerization.

In addition, the average degree of polymerization 2 is calculated by considering physical properties such as tensile strength and tensile modulus of normally produced block copolymers.
A range of 5 to 15 is preferred.

The above block copolymerization reaction is also carried out in the presence of an aromatic phosphite and a pyridine derivative, and examples of the aromatic phosphite and pyridine derivative include those listed above. .

In the block copolymerization reaction, a solution polymerization method using a mixed solvent containing a pyridine derivative is usually employed. The organic solvent used as a mixed solvent is limited to a solvent that does not substantially react with both reaction components and the aromatic phosphite, but in addition to this, it must be a good solvent for both reaction components. Moreover, it is desirable that the solvent be a good solvent for the block copolymer as a reaction product. Typical examples of such organic solvents include amide solvents such as 6 N-methyl-2-pyrrolidone and N,N-dimethylacetamide.

In the present invention, in order to obtain a block copolymer with a high degree of polymerization, inorganic salts typified by lithium chloride and calcium chloride can be added to the reaction system.

In the present invention, the above polycondensation reaction and block copolymerization reaction need to be carried out in the presence of the aromatic phosphite and the pyridine derivative.

When the above polycondensation reaction is carried out in the presence of an aromatic phosphite and a pyridine derivative, the phenolic hydroxyl group, which is a functional group, is not protected, and the phenolic hydroxyl group reacts with a carboxyl group or an amino group. Without,
As the polycondensation reaction progresses, in the block copolymerization reaction of polybutadiene-acrylonitrile copolymer having carboxyl groups at both ends and polyamide having aminoaryl groups at both ends, butadiene-acrylonitrile chains are formed without requiring high temperatures. Side reactions such as decomposition reactions and amide exchange reactions can be avoided. Therefore, it has the great advantage that a block copolymer with a controlled structure can be easily produced.

To explain the production method of the present invention in more detail, an excess amount of aromatic diamines is added to the aromatic dicarboxylic acids containing the aromatic dicarboxylic acid having a phenolic hydroxyl group, and the aromatic phosphite and pyridine are mixed together. This can be easily carried out by heating and stirring in the presence of the derivative in an organic solvent typified by N-methyl-2-pyrrolidone under an inert atmosphere such as nitrogen.

This polyamide body and a polybutadiene-acrylonitrile copolymer having carboxyl groups at both ends are further added to the polyamide solution thus obtained, and heated to cause polycondensation through a block copolymerization reaction. The above block copolymer of the invention is obtained.

In the present invention, the above-mentioned aromatic dicarboxylic acid,
The block copolymer of the present invention can also be obtained by reacting the aromatic diamine and the polybutadiene-acrylonitrile copolymer in a mixed state in a solvent such as N-methyl-28-pyrrolidone. can.

The amount of aromatic phosphite used in these polycondensations is usually equal to or more than an equimolar amount to the carboxyl group, but it is not economically advisable to use more than 30 moles.

Further, the amount of the pyridine derivative needs to be at least equimolar to the carboxyl group, but in reality, it is preferable to use a large excess in order to play a role as a reaction solvent. Furthermore, in the present invention, pyridine derivatives and N
A mixed solvent consisting of an organic solvent typified by -methyl-2-pyrrolidone is preferably used, and the amount of the mixed solvent used is usually preferably such that it contains 5 to 30% by weight of the reaction component.

In the present invention, the reaction temperature is usually 60 to 140
A range of 0.degree. C. is preferred. Further, the reaction time is greatly influenced by the reaction temperature, but in most cases it is between several minutes to 20 hours. In any case, it is desirable to stir the reaction system up to 9°C, which gives the highest viscosity, meaning the highest degree of polymerization.

After the reaction is complete, the reaction mixture is poured into a non-solvent such as methanol or hexane to separate the produced block copolymer.
Further, purification is performed by a reprecipitation method to remove by-products, inorganic salts, etc., and a purified block copolymer can be obtained.

The composition ratio of the polybutadiene-acrylonitrile copolymer and the polyamide polycondensate in the polyamide-polybutadiene-acrylonitrile block copolymer having a phenolic hydroxyl group synthesized as described above is determined by the amount of each charged, but generally polybutadiene - As the composition ratio of the acrylonitrile copolymer increases, the elastic modulus and solvent solubility increase, and the heat resistance decreases. In the block copolymer of the present invention, the block unit (A)
and block unit (B) must exist in the range of 2 to 20, respectively. The number of each block unit is 20
If it exceeds this value, it becomes unfavorable in terms of workability. If the condensation polymerization is carried out using an excess of either of the two reaction components, it becomes possible to reduce the number of block units.

The block copolymer represented by the above general formula (1) of the present invention has a phenolic hydroxyl group contained in the incyana-1
・Isothiocyanate, diketene, ethyleneimine,
Although it can easily react with a compound such as epoxy to give it a crosslinked structure, it is particularly preferable to carry out a crosslinking reaction with an epoxy compound.

This is because the crosslinking reaction proceeds under relatively mild conditions, which is advantageous in terms of further improvement in heat resistance and adhesiveness, selectivity for a wide range of compounds, low cost, and easy handling.

The epoxy compound that can be reacted with the block copolymer of the present invention is not particularly limited as long as it has at least two epoxy groups, and examples include brominated epoxy compounds, epoxy novolac resins, etc. , bisphenol A-epichlorohydrin, polyfunctional epoxy compounds, aliphatic epoxy compounds, alicyclic epoxy compounds, fluorine-containing epoxy compounds, and epoxy-modified resins, as well as numerous other commercially available compounds. Various types can be selected and used depending on the purpose. Furthermore, if necessary, a catalyst, a curing accelerator, etc. may be used in combination.

By reacting the block copolymerization of the present invention with these epoxy compounds, its solvent resistance, adhesiveness, and heat resistance are further improved.

〔Example〕

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 Isophthalic acid 187 mg (l mol), 3,4'-
Oxydianiline 440 mg (2.2 mol), 5
-Hydroxyisophthalic acid 182 mg (l mol)
(approximately 50 mol% based on the total aromatic dicarboxylic acid),
Lithium chloride l [lOmg, calcium chloride 300 m
gSN-methyl-2-pyrrolidone 8+nj! .

Put 1 mp of pyridine into a 50-30 round bottom flask, stir and dissolve, then add 1 mp of pyridine to
g was added thereto, and the mixture was reacted at 90°C for 2 hours to produce a boria 2 amide compound. This is followed by a polybutadiene-acrylonitrile copolymer (Il) having carboxyl groups at both ends.
ycar CTBN, manufactured by BP Goodrlch)
A solution of 810 mg dissolved in 5 ml of pyridine was added, and the mixture was allowed to react for an additional 3 hours, and then cooled to room temperature.

Thereafter, this reaction solution was poured into 500 mil of methanol to precipitate a polyamide-polybutadiene-acrylonitrile block copolymer having phenolic hydroxyl groups and having a polybutadiene-acrylonitrile copolymer content of 50% by weight. This precipitated block copolymer was further purified by methanol washing and methanol reflux. The intrinsic viscosity of the block copolymer thus obtained was 1.251Q/g (N.

N-dimethylacetamide, 30'C). The infrared absorption spectrum of this block copolymer is shown in FIG. At the wave number corresponding to the structure of the block copolymer,
The absorption corresponding to the C-N bond at 2248 cm-' is *
Tal B57cm-'1. Knee NIIC(-0)-(7)
C-01: Corresponding absorption is observed.

Example 2 3 200 mg of the polybutadiene-acrylonitrile copolymer having carboxyl groups at both ends used in Example 1
A polyamide-polybutadiene-acrylonitrile block copolymer having a phenolic hydroxyl group and having a content of 50% by weight of the polybutadiene-acrylonitrile copolymer portion was obtained in exactly the same manner as in Example 1, except that . The intrinsic viscosity of this block copolymer is 0.65 dj)
/ g (N,N-dimethylacetamide, 30°C)
Met. FIG. 2 shows the infrared absorption spectrum of this block copolymer.

At the wave number corresponding to the ISI structure of the block copolymer,
An absorption corresponding to the C-N bond is observed at 2240 cm-', and an absorption corresponding to C-O of mil(C(-0)-) is observed at 1B62 cm-'.

Example 3 The 5-hydroxyisophthalic acid used in Example 1 was
9 mg (0.6 mmol) (approximately 30 mol% based on the total aromatic dicarboxylic acid), 234 m of isophthalic acid
Example 1 except that g (1,4 mmo I) was used.
In exactly the same manner as above, a polyamide-polybutadiene-acrylonitrile block copolymer having phenolic hydroxyl groups and containing 50% by weight of 4 parts of polybutadiene-acrylonitrile copolymer was obtained. The intrinsic viscosity of this block copolymer is 0. [io dΩ/g (N,N-dimethylacetamide, 30°C). The infrared absorption spectrum of this block copolymer is shown in FIG.

At the wavenumber corresponding to the structure of the block copolymer, 22
The absorption corresponding to the C-N bond at 38 cm-' is also 1
An absorption corresponding to C-0 of -NIIC(-0)- is observed at 68Qcm-'.

Example 4 The 5-hydroxyisophthalic acid used in Example 1 was
mg (0.2 mmol) (10 mol% based on the total aromatic dicarboxylic acid), and 301 mg (0.2 mmol) of isophthalic acid (
A polyamide-polybutadiene-acrylonitrile block copolymer having a phenolic hydroxyl group in which the content of the polybutadiene-acrylonitrile copolymer portion was 50% by weight was prepared in exactly the same manner as in Example 1, except that 1.8 mmol) was used. Obtained. The intrinsic viscosity of this block copolymer was 0.80 dΩ/g (N,N-dimethylacetamide, 30°C). The infrared absorption spectrum of this block copolymer is shown in FIG. At the wave number corresponding to the structure of the block copolymer, there is an absorption corresponding to the C-N bond at 2241 am ``'', and -
Absorption corresponding to C-0 of NIIC(-0)- is observed.

Example 5 Isophthalic acid 0.830 g (5 mmol), 5-hydroxyisophthalic acid 0.910 g (5 mmol)
, 2.334 g of 3,3'-diaminobenzophenone (
11 open o1), lithium chloride 1.01g% N-methyl-
2-pyrrolidone 2om, if, pyridine l mIl,
Pour 100 mg into a 30 round bottom flask, stir to dissolve, add 6.2 g of triphenyl phosphite, and add 1.
The reaction was carried out at 00° C. for 2 hours to produce a terminal amine aramid oligomer.

In addition, a polybutadiene-acrylonitrile copolymer (Ilycar CTlN) having carboxyl groups at both ends was added.
3.6 g of N5BF (manufactured by Goodrlch) was added to pyridine 20-20, which was then added into the reactor and reacted for an additional 4 hours.

After cooling to room temperature, the resulting reaction solution was poured into 1 g of 6 methanol to precipitate a polyamide-polybutadiene-acrylonitrile block copolymer containing about 50% by weight of polyacrylonitrile-butadiene moieties.

The intrinsic viscosity of the obtained block copolymer was 0.64dj
? 7 g (in N,N-dimethylacetamide, 30°C
)Met. When the infrared absorption spectrum of this block copolymer was measured, absorption based on the amide carbonyl group was observed at 1657c+n-', and absorption based on the ketone carbonyl group was observed at 1710cm~1.

Further, when the dynamic viscoelasticity of this block copolymer was examined, it was confirmed that the elastic modulus from room temperature to around 200°C has little temperature dependence.

Example 6 8,3'-diaminobenzophenone in Example 5 was converted into bis(3-aminophenyl) sulfide 2.879
A block copolymer was obtained by performing the same operation except that g (Ilmmol) was used instead.

The intrinsic viscosity of the obtained block copolymer was 0.6861
) 7g (in N,N-dimethylacetamide, 30°C
)7. When the infrared absorption spectrum of this block copolymer was similarly measured, it was found to be 1651 (J -
'The absorption based on the amide carbonyl group is 1423 cm
Absorption based on -8- was observed in -'.

Example 7 The 3,3'-diaminobenzophenone in Example 5 was converted to 71 g of bis(4-aminophenyl)sulfone 2J (
A block copolymer was obtained by carrying out the same operation except that the amount of 11 mmol was changed.

The intrinsic viscosity of the obtained block copolymer was 0.70dj
! / g (in N,N-dimethylacetamide, 30
℃). When the infrared absorption spectrum of this block copolymer was similarly measured, it was found to be 2800c1
Absorption based on terminal methyl was observed near 11'', and absorption based on -5O2- was observed at 1215 and 1885 cm-'.

Example 8 3,3'-diaminobenzophenone in Example 5 was mixed with 2.218 g of bis(4-aminophenyl)methane (
A block copolymer was obtained by carrying out the same operation except that 11+nn+ol) was used.

8 The intrinsic viscosity of the obtained block copolymer is 0.41rH
I/g (in N,N-dimethylacetamide, 30
℃). When the infrared absorption spectrum of this block copolymer was similarly measured, it was found that 28,000 m
There is an absorption based on terminal methyl in the vicinity of −', 1684 cm−
Absorption based on the amide carbonyl group was observed in '.

Example 9 The same procedure was carried out except that 3,3'-diaminobenzophenone in Example 5 was replaced with 3.677 g (llmmol) of 2,2-bis(4-aminophenyl)hexafluoropropane, A block copolymer was obtained.

The intrinsic viscosity of the obtained block copolymer was 0.32dj
! / g (in N,N-dimethylacetamide, 30
℃). When the infrared absorption spectrum of this block copolymer was similarly measured, it was found that 18B4 (J
There is an absorption based on the amide carbonyl group in the vicinity of +-'.
Absorption based on 10-P was observed near 300 cm-'.

Application Example Polyamide polybutadiene-acryloni 9 having a phenolic hydroxyl group obtained in Example 1 2 g of tolyl block copolymer and a bisphenol type epoxy compound (Epicote 828, manufactured by Yuka Shell Co., Ltd.) 0
．． 8 g and 6 mil of N,N-dimethylacetamide
After dissolving the mixture, it was applied onto a glass substrate, dried, and then heated at 180° C. for 3 hours to cause a reaction. The membrane of the epoxy-modified polyamide-polybutadiene-acrylonitrile block copolymer thus obtained was insoluble in N,N-dimethylacetamide with only slight swelling.

It was also observed that this film had significantly improved adhesion.

FIG. 5 is a graph showing the infrared absorption spectrum of a film formed from the mixture of the polyamide-polybutadiene acrylonitrile block copolymer and epoxy compound, and FIG.
3 is a graph showing an infrared absorption spectrum when reacting for 3 hours). As is clear from Figures 5 and 6, 1 is the absorption of phenolic hydroxyl groups before the heating reaction.
400 cm-' and 83 (the absorption around 10 Sen-1 is
There is a relative decrease after the heating reaction, which suggests that the phenolic 0 hydroxyl group and the epoxy compound are reacting.

〔Effect of the invention〕

The polyamide-polybutadiene-acrylonitrile block copolymer having a phenolic hydroxyl group of the present invention has good solvent solubility, good compatibility with other polymers, and excellent handling properties. When the polyamide-polybutadiene-acrylonitrile block copolymer having a phenolic hydroxyl group of the present invention is modified with an epoxy compound, an elastic body with high heat resistance, adhesiveness, and solvent resistance can be obtained, and this material has a wide range of applications. It is useful as a wide range of materials.

Furthermore, the method of the present invention does not require the protection of the phenolic hydroxyl group, which is a functional group, or the reaction of this hydroxyl group with a carboxyl group or an amino group. Not only can side reactions such as decomposition and reaction of butadiene chains and transamide reactions be avoided, but also polyamide-polybutadiene-acrylic-tolyl block copolymers with phenolic hydroxyl groups with a controlled structure can be used. Can be easily manufactured.

[Brief explanation of drawings]

1 to 4 are graphs showing the infrared absorption spectra of the polyamide-polybutadiene-acrylonitrile block copolymers of Examples 1 to 4 of the present invention, respectively, and FIG. A graph showing an infrared absorption spectrum when an acrylonitrile block copolymer is mixed with an epoxy compound, and FIG. 6 is a graph showing an infrared absorption spectrum when the acrylonitrile block copolymer is modified by heating.

Claims (1)

[Scope of Claims] (1) A polyamide having aminoaryl groups at both ends formed by polycondensation of an aromatic dicarboxylic acid and an aromatic diamine, and a polybutadiene-acrylonitrile copolymer having carboxyl groups at both ends. A block unit (A) represented by the following general formula (I), which is a polycondensate of
It consists of a block unit represented by the following general formula (II), ▲There are mathematical formulas, chemical formulas, tables, etc.▼(A) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(B) (In the formula, R is a divalent represents an organic group, R' represents a divalent aromatic group having a phenolic hydroxyl group, and Ar represents the following formula (
Indicates the divalent aromatic group shown in 1) to (6). There are chemical formulas, tables, etc. (4) z, l and m are average degrees of polymerization, respectively, x = 3 to 7, y = 1 to 4, z = 5 to 15, l + m = 2
Indicates an integer of ~300, m/(m+l)≧0. 04) and a polyamide-polybutadiene-acrylonitrile block copolymer, characterized in that the block units (A) and block units (B) are each present in a range of 2 to 20. (2) The following general formula (II) synthesized by polycondensing an aromatic dicarboxylic acid consisting of an aromatic dicarboxylic acid having at least 4 mol % of phenolic hydroxyl groups and an aromatic diamine ▲Mathematical formula, chemical formula, table etc.▼(II) (In the formula, R represents a divalent organic group, R' represents a divalent aromatic group having a phenolic hydroxyl group, and Ar represents the following formula (
Indicates the divalent aromatic group shown in 1) to (6). There are chemical formulas, tables, etc. (4) , each having an average degree of polymerization, l+m=2
~300, and m/(m+l)≧0.04) A polyamide having aminoaryl groups at both ends is represented by the following general formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼( III) (where x, y and z are each average degree of polymerization, x=
3 to 7, y = 1 to 4, and z = an integer of 5 to 15). The method for producing a polyamide-butadiene-acrylonitrile block copolymer according to claim 1, which is carried out in the presence of an aromatic phosphite and a pyridine derivative.