JPH05105768A - Aramid-polybutadiene-acrylonitrile-based triblock copolymer and its production - Google Patents

Abstract

PURPOSE:To obtain the subject copolymer excellent in heat resistance and solvent solubility, etc., by polycondensation of a specific polybutadiene- acrylonitrile copolymer with an aminoaryl group-contg. aramid under specified conditions. CONSTITUTION:The objective triblock copolymer highly compatible with other polymers, thus capable of composing through a relevant molding processing is obtained by polycondensation of (A) a polybutadiene-acrylonitrile copolymer having 1000-500 number-average molecular weight and carboxyl group at its one end expressed by formula I [(x) and (y) are each composition ratio, satisfying the relationships: x>0, y>0, and y/(x+y)=0.10-0.27; (z) is polymerization degree, being 5-15] with (B) an aramid having aminoaryl groups at its both ends expressed by formula II (Ar is divalent aromatic group; R is divalent organic groups; (n) is means polymerization degree, being 2-100) in the presence of an aromatic phosphorous ester such as triibodotolyl phosphite and pyridine derivative such as 2-picoline.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel structure-regulated triblock copolymer, and more particularly to an aramid-polybutadiene-acrylonitrile triblock polymer and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Polybutadiene has a flexible molecular structure, but styrene-butadiene copolymer is known to be an excellent thermoplastic elastomer. However,
In this copolymer, the polymer chain is softened at low temperature,
There is a problem in that, in a temperature range exceeding 1.0, satisfactory performance is not exhibited in terms of mechanical strength and heat resistance. In order to solve this problem, a polyamide-polybutadiene-based block copolymer in which a styrene component is changed to a polyamide component has been proposed (JP-A-60-49026 and JP-B-62-3).
171). However, this block copolymer is satisfactory in heat resistance, but has a problem in solubility in an organic solvent and compatibility with other polymers. Therefore, the solubility in an organic solvent was improved without impairing heat resistance. As a polymer, a polyamide-acrylonitrile-butadiene-based block copolymer has been proposed (Japanese Patent Application No. 1-63493).

[0003]

However, the previously proposed aramid-polybutadiene-based block copolymers and polyamide-acrylonitrile-butadiene-based block copolymers have heat resistance, solvent solubility, compatibility and the like. However, since the polymer structure and the molecular weight distribution are not regulated, there is a problem that it is difficult to form a composite because the viscosity is abnormally increased during blending with other materials.

The object of the present invention has been made in view of the above problems in the prior art. Therefore,
The object of the present invention is good heat resistance, solubility in a solvent, excellent compatibility with other polymers, and a novel triblock copolymer that does not cause an abnormal viscosity increase during molding and its It is to provide a manufacturing method.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted research to solve the above-mentioned problems in the prior art, and as a result, when producing an aramid-polybutadiene-acrylonitrile block copolymer, By using an acrylonitrile-butadiene copolymer having a carboxyl group only at one end instead of an acrylonitrile-butadiene copolymer having a carboxyl group at both ends, it was found that the above problems can be solved, and the present invention was completed. Came to do.

That is, the aramid-polybutadiene-acrylonitrile triblock copolymer of the present invention has the following formula (I):

[Chemical 5] (In the formula, x and y represent composition ratios, and x> 0, y> 0, y /
(X + y) = 0.10 to 0.27, z represents the degree of polymerization, and is an integer in the range of 5 ≦ z ≦ 15. Further, Ar represents a divalent aromatic group represented by the following general formulas (1) to (6),

[Chemical 6] R represents a divalent organic group, n is an average degree of polymerization, and n
= Indicates an integer of 2 to 100).

The aramid-polybutadiene-acrylonitrile triblock copolymer of the present invention has the following formula (II):
And an acrylonitrile-butadiene copolymer having a carboxyl group at one end having a number average molecular weight of 1000 to 5000 and an aramid having an aminoaryl group at both ends represented by the following general formula (III):

[Chemical 7] (In the formula, x, y, z, Ar, R and n have the same meanings as described above.) It can be produced by polycondensation in the presence of an aromatic phosphite and a pyridine derivative.

The method for producing the aramid-polybutadiene-acrylonitrile type triblock copolymer of the present invention will be further described. First, the aramid represented by the above formula (III) having aminoaryl groups at both ends is produced as follows. To do. That is, using triphenyl phosphite as a condensing agent, a dicarboxylic acid or its derivative and an aromatic diamine in excess of 1 molar amount relative to the dicarboxylic acid or its derivative were added, and the mixture was added in a pyridine solution at 60 to 14%.
Polycondensation is carried out at 0 ° C. for several minutes to several hours to obtain an aramid oligomer having aminoaryl groups at both ends. Next, a polybutadiene-acrylonitrile copolymer having a carboxyl group at one end having a number average molecular weight of 1000 to 5000 represented by the above formula (II) is added to the aramid oligomer thus obtained, and a terminal aminoaryl group possessed by the aramid oligomer, The aramid-polybutadiene-acrylonitrile-based triblock copolymer of the present invention can be produced by adding and reacting the terminal carboxyl groups of the polybutadiene-acrylonitrile copolymer in an equimolar amount.

The polybutadiene having a carboxyl group at one end represented by the above formula (II) used in the present invention
The acrylonitrile copolymer has a number average molecular weight of 1,000.
It is about 5,000, and can be obtained by anionically polymerizing acrylonitrile and butadiene in such a manner that the acrylonitrile has a mole fraction of 10 to 27 mol%. For example, Hycar CT manufactured by Goodrich Co.
BN etc. can be applied.

The aramid having aminoaryl groups at both terminals represented by the above formula (III) used in the present invention is
Divalent aromatic group A represented by the general formulas (1) to (6)
an aromatic diamine represented by the following formula (IV) having r and a dicarboxylic acid represented by the following general formula (V) or a derivative thereof,

[Chemical 8] (In the formula, Ar, R, and n have the same meanings as described above, and X is a hydroxyl group, an alkoxy group such as a methoxy group, an aryloxy group such as a phenoxy group, an alkylthio group such as an ethylthio group, an arylthio group such as a phenylthio group. It represents a group, halogen such as chlorine, etc.) It can be produced by reacting. In this case, the average degree of polymerization of the obtained aramid is 2 to 1 in consideration of mechanical properties such as tensile strength and tensile elastic modulus of the triblock copolymer of the present invention.
The number average molecular weight is in the range of about 00 and the number average molecular weight is in the range of several thousand to 200,000. If the average degree of polymerization exceeds 100, the compound has solvent solubility, but the processability such as complexing is poor, and if it is less than 2, the effect of aramid is not exhibited.

As the aromatic diamine represented by the above formula (IV) used for synthesizing the aramid of the above formula (III) constituting the present invention, a diamine having Ar as defined in claim 1 can be used. Applied, for example, m-phenylenediamine, p-phenylenediamine, 3,4′-oxydianiline, 4,4′-oxydianiline, 3,3′-sulfonyldianiline, bis (4-aminophenyl) sulfone. , 1,4-naphthalenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, 1,3-bis (metaaminophenyl) -1,1,3,3-tetramethyldisiloxane, 4,4 ' -Bis (4-aminophenoxy) diphenyl sulfone, 4,4'-bis (3-aminophenoxy) diphenyl sulfone, 3,3'-diaminobenzophenone, , 4'-bis (4-aminophenoxy) benzophenone, 4,4'-bis (3-aminophenoxy) benzophenone, 4,4'-bis (4-aminophenylmercapto) benzophenone, 4,4'-bis (4 -Aminophenylmercapto) benzophenone,
2,2'-bis (4-aminophenyl) hexafluoropropane, 2,2'-bis (4- (2-trifluoromethyl-4-aminophenoxy) phenyl) hexafluoropropane, 2,2'-bis ( 4- (3-trifluoromethyl-5-aminophenoxy) phenyl) hexafluoropropane, 2,2'-bis (4- (3-trifluoromethyl-4-aminophenoxy) phenyl) hexafluoropropane, 2,2 ′ -Bis (4- (2-trifluoromethyl-5-aminophenoxy) phenyl) hexafluoropropane, 2,2′-bis (4- (4-trifluoromethyl-5-aminophenoxy) phenyl) hexafluoropropane , 2,2'-bis (4- (2-nonafluorobutyl-5-aminophenoxy) phenyl) hexafluoropro Emissions, 2,2'-bis (4- (4-nonafluorobutyl-5-aminophenoxy) phenyl)
Hexafluoropropane, bis- (4-aminophenyl) methane, o-tolidine, o-dianisidine and the like can be mentioned, but the invention is not limited thereto.
In addition, these aromatic diamines may be used alone or in combination.

The dicarboxylic acid represented by the general formula (V) used for synthesizing the aramid of the general formula (III) constituting the present invention is a divalent acid represented by R as described above. Any organic group containing aliphatic, alicyclic, aromatic or the like can be applied to the present invention. For example, isophthalic acid, terephthalic acid, 4,4'-biphenyldicarboxylic acid, 3,3'-methylenedibenzoic acid, 4,4'-
Methylene dibenzoic acid, 4,4'-oxydibenzoic acid,
4,4'-thiodibenzoic acid, 3,3'-carbonyldibenzoic acid, 4,4'-carbonyldibenzoic acid, 4,4'-
Sulfonyl dibenzoic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, succinic acid, glutaric acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, 1,
3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, malonic acid, methylmalonic acid, dimethylmalonic acid, adipic acid, 1,10-decanoic acid, phenylmalonic acid, benzylmalonic acid, phenylsuccinic acid, 3- Phenylglutaric acid, homophthalic acid, 1,3-
Phenylenediacetic acid, 1,4-phenylenediacetic acid, 4-carboxyphenylacetic acid, 5-bromo-N- (carbomethyl) anthranilic acid, 2,5-dihydroxy-1,4-
Examples thereof include, but are not limited to, dicarboxylic acids such as benzenediacetic acid and m-carboxycinnamonic acid, and derivatives thereof. Moreover, you may implement these individually or in combination of multiple.

The present invention will be described in more detail below. The aramid-polybutadiene-acrylonitrile-based triblock copolymer of the present invention is produced by polycondensing a polybutadiene-acrylonitrile copolymer having a carboxyl group at one end and an aramid having an aminoaryl group at both ends. The condensation reaction can also be carried out by simply mixing and heating both, but in that case, the polycondensation reaction must be carried out at a high temperature, and as a result, side reactions such as transamidation reactions are unavoidable. It is not preferable.
Therefore, in the present invention, it is necessary to carry out the polycondensation reaction in the presence of the aromatic phosphite and the pyridine derivative. In that case, since high temperature is not required in the polycondensation reaction and side reactions such as transamidation reaction can be avoided, the polybutadiene-acrylonitrile copolymer part (block unit A) and the aramid part (block unit B) are separated from each other. Become A
It has a great advantage that a BA type block copolymer can be easily produced.

Examples of the phosphite-based condensing agent used for producing the triblock copolymer of the present invention include triphenyl phosphite, diphenyl phosphite, tri-o-tolyl phosphite, and phosphorus phosphite. Acid di-o-tolyl, phosphorous acid tri-m-tolyl, phosphorous acid di-m-tolyl, phosphorous acid tri-p-tolyl, phosphorous acid di-p-tolyl, phosphorous acid di-o- Examples thereof include chlorophenyl, tri-p-chlorophenyl phosphite, and di-p-chlorophenyl phosphite, but are not limited thereto. Furthermore,
Examples of the pyridine derivative used with the phosphite in the present invention include pyridine, 2-picoline, 3-picoline, 4-picoline, 2,4-lutidine, 2,6-lutidine, and 3,5-lutidine. it can.

In the present invention, the above polycondensation reaction is carried out in the presence of a phosphite ester and a pyridine derivative. In this reaction, a solution polymerization method using a mixed solvent containing a pyridine derivative is usually adopted. .. The organic solvent used here is limited in that it does not substantially react with the reaction component or the phosphite, but in addition to this, it is a good solvent for the reaction component and is a block product of the reaction product. It is preferably a good solvent for the copolymer. As such an organic solvent, N-methyl-2
Examples include amide solvents such as -pyrrolidone and N, N-dimethylacetamide. In order to obtain a block copolymer having a high degree of polymerization in the present invention, inorganic salts such as lithium chloride and calcium chloride can be added to this reaction system.

In the present invention, the amount of the phosphite-based condensing agent used in the above polycondensation reaction is usually an equimolar amount or more with respect to the carboxyl group, but it is economical to use a 30-fold molar amount or more. Not good to see. Further, the amount of the pyridine derivative needs to be an equimolar amount or more with respect to the carboxyl group, but in practice, it is often used in a large excess including the role as a reaction solvent.

In the present invention, especially pyridine derivative and N
When a mixed solvent of organic solvents such as -methyl-2-pyrrolidone is used, the amount used is 5 to 30% by weight of the reaction components.
It is preferable to include it. The reaction temperature is generally 6
The range of 0 to 140 ° C. is preferable. The reaction time is largely influenced by the reaction temperature, but in any case, the several minutes to 20 hours necessary to stir the reaction system until the maximum viscosity which means the highest degree of polymerization is obtained is preferable.

After completion of the reaction, the reaction mixture is put into a non-solvent such as methanol or hexane to separate the produced polymer, and by-products and inorganic salts of the reaction system are removed by a reprecipitation method to purify the polymer. The aramid of the present invention-polybutadiene-
An acrylonitrile-based triblock copolymer can be obtained.

[0019]

The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. Example 1 1.661 g (10 mmol) of isophthalic acid, 3,4 '
-2.202 g (11 mmol) of oxydianiline, 0.33 g of lithium chloride, 1.01 g of calcium chloride, N
-Methyl-2-pyrrolidone 20 ml, pyridine 20 ml
Was placed in a 100 ml three-necked round bottom flask and dissolved with stirring, then 6.2 g of triphenyl phosphite was added and reacted at 100 ° C. for 2 hours to give an aramid oligomer solution having aminoaryl groups at both ends. Got The intrinsic viscosity of the obtained aramid oligomer (in N, N-dimethylacetamide solution, 30 ° C.) was 0.18 dl / g. Next, in the aramid oligomer solution, a polybutadiene-acrylonitrile copolymer having a carboxyl group at one end (y / (x + y) = 0.17, z = 10) 3.
60 g (corresponding to about 1.0 mmol) was dissolved in 20 ml of pyridine, added to the reactor, and further reacted for 2 hours. After cooling to room temperature, the obtained reaction solution was put into methanol 11 to precipitate an aramid-polybutadiene-acrylonitrile-based triblock copolymer. The intrinsic viscosity of the obtained triblock copolymer is 0.44 dl / g
(In N, N-dimethylacetamide, 30 ° C.). Infrared spectrum of this copolymer (F, manufactured by Analect Corp.)
X6160) was measured, in the vicinity of 2800 cm ^-1 polybutadiene - absorption based on C-H acrylonitrile copolymer, absorption corresponding to the nitrile group near 2340cm ^-1 is a carbonyl-based -NHCO to 1658 cm ^-1 Absorption was observed, and it was confirmed that this was the triblock copolymer of the present invention.

Example 2 The same procedure as in Example 1 was repeated except that the 3,4'-oxydianiline was replaced by 2.333 g (10 mmol) of 3,3'-diaminobenzophenone. Got united. The intrinsic viscosity of the obtained triblock copolymer was 0.62 dl / g (in N, N-dimethylacetamide, 30 ° C.). The infrared spectrum (FX6160 manufactured by Analect) of this triblock copolymer was measured to find that the absorption based on C-H of the polybutadiene-acrylonitrile copolymer was 234 at around 2820 cm ^-1.
The absorption corresponding to the nitrile group is around 1657 at around 5 cm ^-1.
The absorption of carbonyl based on -NHCO at cm ^-1 is 17
Absorption based on a ketone carbonyl group was observed at 20 cm ^-1 .

Example 3 The same procedure as in Example 1 was repeated except that the amount of 3,4'-oxydianiline used in Example 1 was changed to 2.730 g (11 mmol) of bis (4-aminosulphenyl) sulfone. A copolymer was obtained. The intrinsic viscosity of the obtained triblock copolymer was 0.68 dl / g (in N, N-dimethylacetamide, 30 ° C.). The infrared spectrum of this triblock copolymer (measured by FX6160 manufactured by Analect) was found to show that the absorption based on C—H of the polybutadiene-acrylonitrile copolymer was 2343 at around 2810 cm ^−1.
Absorption corresponding to nitrile group near cm ^-1 is 1661c
The absorption of carbonyl based on —NHCO at m ⁻¹ is 121
Absorption due to —SO ₂ — was observed around 7 and at 1368 cm ⁻¹ .

Example 4 The same procedure as in Example 1 was carried out except that 3,217 '(11 mmol) of bis (4-aminophenyl) methane was used in place of 3,4'-oxydianiline. A polymer was obtained. The intrinsic viscosity of the obtained triblock copolymer was 0.48 dl / g (in N, N-dimethylacetamide, 30 ° C.). Infrared spectrum of this triblock copolymer (measured by FX6160 manufactured by Analect)
Was measured, polybutadiene near 2812cm ^-1 - absorption based on C-H acrylonitrile copolymer, absorption corresponding to the nitrile group near 2343cm ^-1 is absorption of a carbonyl-based -NHCO to 1664 cm ^-1 Admitted.

Example 5 The 3,4'-oxydianiline of Example 1 was converted to 2,2-bis (4-aminophenyl) hexafluoropropane 3.6.
The same operation was performed except that the amount was changed to 66 g (11 mmol) to obtain the triblock copolymer of the present invention. The intrinsic viscosity of the obtained triblock copolymer was 0.45 dl / g (N,
It was 30 degreeC in N- dimethylacetamide. It was measured an infrared spectrum of the triblock copolymer (measured by Anarekuto Co. FX6160) near 2800 cm ^-1, around 2814cm ^-1 polybutadiene - absorption based on C-H of the acrylonitrile copolymer, 23
Absorption corresponding to nitrile group around 48 cm ^-1 is 130
The absorption corresponding to -C-F near 0 cm ^-1 is 1667c.
Absorption of carbonyl based on -NHCO was observed at m ^-1 .

Comparative Example 3,4'-oxydianiline 2.00 used in Example 1
2.22 g (11 mmol) of 2 g (10 mmol)
In addition, polybutadiene having a carboxyl group at one end
For comparison, acrylonitrile copolymer 1.80 g (0.5 mmol) was replaced with polybutadiene-acrylonitrile copolymer having carboxyl groups at both ends 3.60 g (1.0 mmol). A block copolymer was obtained. The intrinsic viscosity of the obtained block copolymer was 0.90 dl / g (in N, N-dimethylacetamide, 30 ° C.). The measured infrared absorption spectrum was not significantly different from that of the triblock copolymer of the example.

Mechanical strength and thermal properties of cast films with a thickness of 50 μm formed from the aramid-polybutadiene-acrylonitrile triblock copolymers of the present invention obtained in Examples 1 to 5 and the block copolymer of Comparative Example. Was measured and the results are shown in Table 1. As is clear from Table 1, the triblock copolymer of the present invention is an elastic body having practically sufficient heat resistance. In addition,
The evaluation was performed by the following method. <Mechanical strength> Tensile tester (UCT manufactured by Orientec Co., Ltd.)
-100) with a crosshead speed of 50 mm / min and a load cell of 10 kgf. The test piece is 50 μm x 5
Use mm (width) x 50 mm (thickness). n = 10 <Pyrolysis temperature> Measured in air using a thermobalance (TGA-30 manufactured by Shimadzu Corporation) at a heating rate of 10 ° C./min.

[0026]

[Table 1]

Further, the triblock copolymer 1 of the present invention
0 g and Epicoat 828 (bisphenol A type epoxy resin, epoxy equivalent 190 ± 5, manufactured by Yuka Shell Epoxy Co., Ltd.) were mixed with a mixer and further kneaded with a hot roll set at 170 ° C. to form aramid-polybutadiene-.
An acrylonitrile-based triblock copolymer-epoxy resin composite was obtained. 80 ° C. and 60 of the obtained composite
Viscosity at ℃ was measured by CS rheometer
It was measured using CS-500 manufactured by d. As a comparative example, from the block copolymer obtained by the prior art and the epoxy resin, a composite was molded in the same manner and the viscosity thereof was measured. The results are shown in Table 2. As is clear from Table 2, it is shown that the triblock copolymer of the present invention has a small increase in viscosity upon compounding.

[0028]

[Table 2]

[0029]

The aramid-polybutadiene-acrylonitrile-based triblock copolymer of the present invention is characterized by its properties compared with conventional polyamide-polybutadiene-based block copolymers and polyamide-acrylonitrile-butadiene-based block copolymers. It is a thermoplastic elastic body with high heat resistance that does not impair heat resistance, has excellent compatibility, and does not cause an increase in viscosity when composited with different materials, so it has utility as a material with a wider range of applications. ing.

Claims (3)

[Claims] 1. The following general formula (I): (In the formula, x and y represent composition ratios, and x> 0, y> 0, y /
(X + y) = 0.10 to 0.27, and z represents the degree of polymerization and is an integer in the range of 5 ≦ z ≦ 15. Ar represents a divalent aromatic group represented by the following general formulas (1) to (6): R represents a divalent organic group, n is an average degree of polymerization, and n
An aramid-polybutadiene-acrylonitrile triblock copolymer having a structure represented by the formula: 2. A number average molecular weight of 1,000 to 5,000 having a carboxyl group at one end represented by the following general formula (II).
And a aramid having an aminoaryl group at both ends represented by the following general formula (III): (In the formula, x, y, z, Ar, R and n have the same meanings as described above.) Aramid-polybutadiene-characterized by polycondensation in the presence of an aromatic phosphite and a pyridine derivative. A method for producing an acrylonitrile-based triblock copolymer. 3. The following general formula (III): (In the formula, Ar, R, and n have the same meanings as described above.) In the amount of charge for synthesizing the aramid, polycondensation reaction is performed by adding 1 mol of aromatic diamine to dicarboxylic acid in excess. Then, an aramid oligomer having aminoaryl groups at both ends is produced, and then polycondensation is carried out with the molar ratio of the aminoaryl groups at both ends of the aramid oligomer to the carboxyl group of the polybutadiene-acrylonitrile copolymer being 1: 1. The method for producing an aramid-polybutadiene-acrylonitrile-based triblock copolymer according to claim 2, wherein the reaction is carried out.