JP2012046591A - Structure-regulated polyamide and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide block copolymer having excellent crystallinity and mechanical properties, and capable exhibiting high functions and high-performance characteristics by maintaining the molding processability possessed by a random copolymer.SOLUTION: The block copolyamide comprises a repeating unit represented by general formula (1) (wherein, Ar and Ar' are each a 6C-18C divalent aromatic group in which the nuclear may be substituted; R and R' are each a 6C-18C divalent aromatic group in which the nuclear may be substituted, or a 2C-200C divalent aliphatic group; with the proviso that Ar and Ar' are the same group, and R and R' are different groups, or R and R' are the same group and Ar and Ar' are different groups; and m and n are each an integer of 1-150), and has ≥0 and <0.8 of randomness value in the sequence, and ≥0.1 dL/g of the intrinsic viscosity measured by using methanesulfonic acid in a sample concentration of 0.03g/dL at 30°C.

Description

  The present invention relates to a block copolymerized polyamide and a method for producing the same.

  Polyamides containing aromatic dicarboxylic acid residues as dicarboxylic acid residues are excellent in molecular rigidity and chemical stability, and it is relatively easy to select a polymer with any physical properties depending on the purpose by selecting its composition. Therefore, various brands are manufactured and used in a wide range of fields as materials for consumer use, industrial materials or medical devices.

  In particular, polyparaphenylene terephthalamide (PPTA) represented by Twaron (registered trademark), Kevler (registered trademark), and Technora (registered trademark) as wholly aromatic polyamides containing not only dicarboxylic acid residues but also diamine residues as aromatic rings. It is known that copolymerized polyparaphenylene terephthalamide (co-PPTA) such as trademark is useful as a raw material for fibers having excellent heat resistance and mechanical properties and other molded articles.

  In the case of PPTA as a known molding method, after extracting a polymer obtained by polymerization in an organic solvent, a dope having optical anisotropy is prepared by dissolving the polymer at a high concentration in sulfuric acid, and this is directly molded. By doing so, it is known that a highly molecularly distributed material can be obtained without going through a stretch orientation process (see, for example, Patent Document 1).

  In addition, co-PPTA gives an optically isotropic organic solvent moldable dope by polymerizing a polymer in an amide solvent such as NMP without using a strong acid solvent such as sulfuric acid that is difficult to handle. It is known that the molecular orientation control needs to be molded and a super-stretching process needs to be performed (for example, see Non-Patent Document 1).

So far, dope of fully aromatic polyamide that can be molded into an organic solvent so as to become a heat-resisting molded article having a high elastic modulus having molecular orientation by simple molding has not been realized.
On the other hand, semi-aromatic polyamides whose diamines are aliphatic or similar flexible chains have mechanical and physicochemical properties such as elastic modulus and heat resistance while maintaining thermoplasticity and solvent solubility by changing the composition. It can be expressed according to the structure, such as improvement of stretch, recovery of elasticity, elasticity, flexibility, fatigue resistance, etc., so it is widely used for various molded products such as clothing and industrial fibers, films and resins. Has been.

  If these characteristics of a wholly aromatic polyamide and an aliphatic or semi-aromatic polyamide can be regularly incorporated into the same molecule, for example, a material that is soluble in organic solvents but has optical anisotropy, hydrophilic / hydrophobic It is expected that it will be possible to develop highly functional materials that have conflicting properties such as stability and rigidity / flexibility.

  However, this requires a polyamide block structure with a controlled block chain length, and requires an unprecedented precise polyamide polymerization process. Conventionally, it is possible to perform chain control of aliphatic polyamides and depsipeptides by performing condensation reaction and isolation / purification in multiple steps at the monomer stage, and adding additional monomers to the prepared oligomer, as in the peptide synthesis process of amino acids. Although it was known in the laboratory, it was difficult to scale up and continue the process, and in fact it was limited to the production of materials for special purposes such as pharmaceutical intermediates, drug substance synthesis, and medical equipment. It was. On the other hand, polyamide manufacturing technology that controls the block structure in a single polymerization reaction process that can be applied to industrial processes on a large scale in aromatic polyamides, semi-aromatic polyamides and their copolymers that are also useful as industrial materials Was not known about.

JP 59-137509 A

Murase Yasuhiro, Polymer Processing, 38 p. 549 (1989)

  The main object of the present invention is to make the conventionally known random copolymerized polyamide chain into a block structure having a regular chain control, thereby overcoming the above-mentioned drawbacks, excellent crystallinity and mechanical properties, and random copolymerization. An object of the present invention is to provide a polyamide block copolymer capable of exhibiting excellent characteristics by maintaining the molding processability of the polymer. Another object of the present invention is to provide a method for easily and efficiently producing such a specific polyamide block copolymer on an industrial scale.

  As a result of intensive studies to solve the above problems, the present inventors have found a block copolymerized polyamide having a specific structure and a method for producing the same, and have completed the present invention. That is, the gist of the present invention is as follows.

1. The following general formula (1)
[In the general formula (1), Ar and Ar ′ are divalent aromatic groups that may be substituted with 6 to 18 carbon atoms, and R and R ′ are substituted with 6 to 18 carbon atoms. And a divalent aromatic group or a divalent aliphatic group having 2 to 200 carbon atoms, and Ar and Ar ′ are the same group and R and R ′ are different from each other, or R And R ′ are either the same group and Ar and Ar ′ are different groups. m and n are each an integer of 1 to 150. ]
The randomness value in the sequence is 0 or more and less than 0.8, and the intrinsic viscosity measured at 30 ° C. at a sample concentration of 0.03 g / dL using methanesulfonic acid is 0.00. A block copolymerized polyamide characterized by being 1 dL / g or more.
2. 1. The average chain length of each block in the repeating unit is 3 or more. The block copolymer polyamide described in the item.
3. In the general formula (1), Ar and Ar ′ are the same group and R and R ′ are different groups. Term or 2. The block copolymer polyamide described in the item.
4). The following general formula (2)
[The definition of Ar in the general formula (2) is the same as the definition in the general formula (1). ]
An aromatic dicarboxylic acid represented by the formula (1) or more and less than 2.5 molar equivalents, and the following general formula (3)
[The definition of R in the general formula (3) is the same as the definition in the general formula (1). ]
Is reacted in a low-polar solvent or in bulk, and then a polar solvent is added. Further, the following general formula (4)
[The definition of R ′ in the general formula (4) is the same as the definition in the general formula (1). ]
2. A diamine represented by the formula (1) or a derivative thereof (1 molar equivalent) is added to cause a polymerization reaction. A process for producing the block copolymerized polyamide according to Item.
5). In the general formula (1), R and R ′ are the same group and Ar and Ar ′ are different groups. Term or 2. The block copolymer polyamide described in the item.
6). The following general formula (3)
[The definition of R in the general formula (3) is the same as the definition in the general formula (1). ]
Represented by the following general formula (2):
[The definition of Ar in the general formula (2) is the same as the definition in the general formula (1). ]
After reacting 1 mol equivalent of the aromatic dicarboxylic acid represented by the following formula in a low polarity solvent or in bulk, a polar solvent is added, and the following general formula (5)
[The definition of Ar ′ in the general formula (5) is the same as the definition in the general formula (1). ]
4. A polymerization reaction is carried out by adding 1 molar equivalent of the aromatic dicarboxylic acid or its derivative represented by the above 5. A process for producing the block copolymerized polyamide according to Item.
7). 4. As the low polarity solvent, one or more selected from hydrocarbon solvents and halogen solvents are used. Term or 6. The production method according to item.
8). The above 4. using an amide solvent as a polar solvent. Term, 6. Term and 7. The manufacturing method in any one of claim | items.

  The block copolymerized polyamide in the present invention has a conventionally known random copolymerized polyamide chain having a regular chain-controlled block structure, thereby overcoming various drawbacks such as low crystallinity derived from the random structure and reduced physical properties, It is a material that has excellent crystallinity and mechanical properties, and can exhibit high-performance and high-performance characteristics by maintaining the molding processability of random copolymers. Mechanical properties can be obtained by melt molding, wet molding, etc. Excellent fiber, film, molded product and the like. In these molded products, there are no problems such as low crystallinity and low impact properties that are found in conventional molded products of random copolymers. In providing the polyamide block copolymer of the present invention, a method for practical production on an industrial scale can be provided without significantly changing the conventional polymerization equipment.

  The block copolymer polyamide of the present invention contains various additives such as stabilizers, colorants, ultraviolet absorbers, mold release agents, reinforcing materials such as glass fibers, and fillers such as inorganic particles and organic particles. It can also be added and used as a resin composition.

The carbonyl by ¹³ C-NMR measurement (sample concentration 5 mass%, methanesulfonic acid solvent) of the block copolymerized polyamide obtained in Example 1 in the lower row and the randomly polymerized polyamide obtained in Comparative Example 1 in the upper row. It is a figure which shows the attribution peak and distribution of carbon. The liquid crystal phase observed under crossed nicols of a solution sample obtained by dispersing the block copolymer polyamide obtained in Example 1 in an N-methylpyrrolidone solution of 5% lithium chloride so as to be 15% by mass. It is a photograph figure of a polarization microscope image.

  The copolymerized polyamide of the present invention comprises a repeating unit represented by the general formula (1), has a randomness value in the sequence of 0 or more and less than 0.8, and uses methanesulfonic acid to give a sample concentration of 0.03 g. / DL, intrinsic viscosity measured at 30 ° C. is 0.1 dL / g or more.

In the block copolymer polyamide of the present invention, the average chain length of each block in the repeating unit is preferably 3 or more. Each block in the repeating unit refers to the general formula (1)
And
Each of them.

The randomness value and average chain length in the repeating unit sequence of the copolymerized polyamide can be clarified by ¹ H-NMR measurement and / or ¹³ C-NMR measurement using methanesulfonic acid or the like as a solvent. .

For example, Macromolecules, 36, 6160 (2003) includes a random copolymer of polyparaphenylene terephthalamide (PPTA) and poly 3,4'-phenylenedioxyterephthalamide (P (3,4'-DAPTA)). The knowledge by 13 C-NMR measurement is shown. When p-phenylenediamine, which is a diamine of PPTA portion, is α, and 3,4, -diaminodiphenyl ether, which is a diamine of P3,44′-DAPTA, is β, these In random copolymerization, when terephthalic acid is T, there are the following nine signals derived from the amide carbonylmethylene proton of T.
α-T-α (Peak 1)
α-T- (3) β (α-side peak 2, (3) β-side peak 3)
α-T- (4 ′) β (α-side peak 4, (4 ′) β-side peak 5)
(3) β-T- (3) β (Peak 6)
(3) β-T- (4 ′) β ((3) β-side peak 7, (4 ′) β-side peak 8)
(4 ′) β-T- (4 ′) β (Peak 9)

By comparing the integral ratios of peaks attributed to carbonyls derived from these bonds, the component ratio derived from random copolymerization can be obtained, and the randomness value and average chain length can be evaluated according to the following formula.
- Randomness value _{R αβ = [0.5f αβ / F} α] + [0.5f αβ / F β]
here,
f _αβ : Peak intensity derived from α-T- (3) β and α-T- (4 ′) β F _α : Sum of α component-derived peak intensities F _β : Sum of β component-derived peak intensities · PPTA (α diamine Component block) number average chain length L _α :
_{L α = [f αα + 0.5f} αβ] /0.5f αβ
here,
f _αα : α-T-α-derived peak intensity · Number average chain length L _{β of} P (3,4'-DAPTA) (β-diamine component block):
_{L β = [f ββ + 0.5f} αβ] /0.5f αβ
here,
_fββ : Sum of peak intensities derived from (3) β-T- (3) β, β-T- (4 ′) β and (4 ′) β-T- (4 ′) β

  If the above randomness value is 0, it is a complete block copolymer, and if the randomness value is 0.8 or more, the random structure becomes the main component and it becomes difficult to express the characteristics derived from the block structure. When the randomness value is 1, it is a complete random copolymer. The block copolymer polyamide of the present invention has a randomness value of 0 or more and less than 0.8, preferably 0.7 or less, and more preferably 0.5 or less. Further, the lower limit of the randomness value of the block copolymer polyamide of the present invention is of course preferably 0, but it has sufficient physical properties even if it is not a complete block copolymer, 0.1 or more or 0.2 There are many uses that can be used as described above, which is preferable in terms of ease of preparation.

  In the block copolymer polyamide of the present invention, the average chain length of each block in the repeating unit is preferably 3 or more, more preferably 4 or more, and even more preferably 5 or more. This average chain length is the average length of each copolymer block structure, and if it is too short, the homopolymer-derived physical properties of each chain component in the copolymer disappear, and a difference from the random structure in the polymer properties is recognized. It becomes difficult. On the other hand, the average chain length is preferably as long as it is a high molecular weight and a complete block copolymer, and is preferably as long as possible. The upper limit is not particularly limited, but is preferably 100 or less and more preferably 50 or less because of ease of preparation. Preferably, it is more preferably 20 or less, and particularly preferably 10 or less.

  The block copolymer polyamide of the present invention uses methanesulfonic acid and has a sample concentration of 0.03 g / dL and an intrinsic viscosity measured at 30 ° C. of 0.1 dL / g or more, preferably 0.2 dL / g or more, More preferably, it is 0.3 dL / g or more. A material having an intrinsic viscosity of less than 0.1 dL / g does not have sufficient physical properties as a polymer and is not suitable for use in ordinary applications such as molding. The upper limit of the intrinsic viscosity of the block copolymer polyamide of the present invention is not particularly limited, but is preferably 10 dL / g or less from the viewpoint of ease of handling, and more preferably 5 dL / g or less.

  As a method for producing the block copolymerized polyamide according to the present invention, a polymerization process applying kinetic reaction control can be utilized. Hereinafter, as the copolymerized polyamide of the present invention, in the general formula (1), Ar and Ar ′ are the same group and R and R ′ are different groups, and the block copolymerized polyamide of the present invention is produced. The method is shown.

  Surprisingly, the aromatic dicarboxylic acid represented by the general formula (2) or a derivative thereof is 1.5 mole equivalent or more and less than 2.5 mole equivalent (may be appropriately adjusted according to the reactivity of each raw material). 1.7 mole equivalent or more and 2.3 mole equivalent or less, preferably 1.9 mole equivalent or more and 2.1 mole equivalent or less, more preferably 2 mole equivalent or less, and further preferably 2 mole equivalent or less). After reacting 1 mol equivalent of the diamine represented by (3) or a derivative thereof in a low polarity solvent or in bulk, a polar solvent is added, and the diamine represented by the general formula (4) or By adding 1 molar equivalent of the derivative and carrying out a polymerization reaction, it is possible to obtain a block copolymer polyamide in which Ar and Ar ′ are the same group and R and R ′ are different groups in the general formula (1). Find It was.

In the above description, the aromatic dicarboxylic acid represented by the general formula (2) or a derivative thereof is used as the diamine of the general formula (3), and the diamine of the general formulas (3) and (4) is used as the general formula. Aromatic dicarboxylic acid represented by formula (2) or a derivative thereof and the following general formula (5)
[The definition of Ar ′ in the general formula (5) is the same as the definition in the general formula (1). ]
Is replaced with an aromatic dicarboxylic acid represented by the following formula or a derivative thereof: In the general formula (1), a method for producing a block copolymerized polyamide in which R and R ′ are the same group and Ar and Ar ′ are different groups is obtained. .

  The aromatic dicarboxylic acid of general formula (2) or (5) or a derivative thereof, which can be used as a raw material for the block copolymerized polyamide of the present invention, is substituted with 6-18 carbon atoms in the aromatic ring moiety. Specifically, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,5-pyridinedicarboxylic acid, hydroxyterephthalic acid, 2,5-dihydroxyterephthalic acid, chloroterephthalic acid 2,5-dichloroterephthalic acid, pyrazine dicarboxylic acid, 2,5-furandicarboxylic acid, 4,4′-biphenyldicarboxylic acid, and the like. Among them, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,5-dihydroxyterephthalic acid, 2,5-dichloroterephthalic acid, 2,5-furandicarboxylic acid, 4, Preferable examples include derivatives of 4′-biphenyldicarboxylic acid, acid halides such as acid chlorides of these aromatic dicarboxylic acids, or active ester compounds such as diphenylesters.

  Examples of the diamine of the general formula (3) or (4) that can be used as a raw material for the block copolymerized polyamide of the present invention include p-phenylenediamine, 3,4′-diaminodiphenyl ether, m-phenylenediamine, 4, 4'-diaminodiphenyl ether, 2,6-naphthalenediamine, 2,5-diaminopyridine, 4-chloro-m-phenylenediamine, 2,5-dichloro-4-phenylenediamine, 2,6-dichloro-1,4- Aromatic diamines such as phenylenediamine, 4,4′-diaminobiphenyl, 2,2-bis (4-aminophenyl) propane, ethylenediamine, propylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1, 5-pentanediamine, 1,6-hexanediamine, 1,8-octane 1,9-nonamethylenediamine, 1,10-decanediamine, 1,12-dodecanediamine, 1,4-cyclohexyldiamine, 1,3-cyclohexyldiamine, 1,4-cyclohexanebis (methylamine), 1 , 3-cyclohexanebis (methylamine), etc., a terminally aminated polyethylene oxide in which both ends of a cyclic aliphatic diamine and polyethylene glycol are aminated (trade name Jeffamine (registered trademark), manufactured by Huntsman Corporation) And bis (3-aminopropyl) tetramethyldisiloxane, bis (3-aminobutyl) tetramethyldisiloxane, and α, ω-bis (3-aminopropyl), which are polydimethylsiloxanes aminated at both ends. Special diamines with flexible chains such as polydimethylsiloxane It can be exemplified as preferred.

  Moreover, what made the said diamine into derivatives like active amino compounds, such as an aminosilylation body and phosphoric acid amide, can be used for manufacturing the block copolymerization polyamide of this invention.

  Examples of the low polarity solvent that can be used in producing the block copolymerized polyamide of the present invention include aliphatic, alicyclic or aromatic hydrocarbon solvents such as hexane, heptane, cyclohexane, benzene, toluene, and xylene. Preferred examples include aliphatic and aromatic ether type hydrocarbon solvents such as diethyl ether, dibutyl ether, tetrahydrofuran and anisole, and / or halogen solvents such as methylene chloride, tetrachloromethane, dichloroethane and tetrachloroethane. Of these, cyclohexane, benzene, toluene, xylene, methylene chloride, diethyl ether and the like are preferable. Surprisingly, the aromatic or semi-aromatic amide condensate initially formed by the reaction of the aromatic dicarboxylic acid or derivative thereof as described above with the diamine or derivative thereof is almost quantitatively determined from these solvents. It precipitates and can be continuously separated from the solvent from the bottom of the reaction vessel with a filter and transferred to the next polymerization reaction vessel.

  Depending on the types of various active dicarboxylic acid derivatives and active diamine derivatives, it is also preferable to add a base catalyst such as pyridine and a reaction neutralizing agent at the same time in order to increase the reactivity.

  On the other hand, as the polar organic solvent used in the polymerization reaction, any organic solvent that does not inhibit the reaction can be used, but N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, 1 One or more high-boiling polar organic solvents selected from the group consisting of 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, sulfolane and the like can be mentioned as preferable examples. Of these, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, 1,3-dimethyl-2-phenyl are considered from the viewpoints of solubility of reactants during polymerization and recovery processes after polymerization. It is preferable to use one or more amide solvents selected from the group consisting of imidazolidinone and the like.

  The reaction temperature can be arbitrarily selected from room temperature to a temperature not higher than the boiling point of the solvent. In selecting the temperature, it is preferable to set an optimum temperature range in consideration of the solubility of the raw materials and the reaction activity in addition to the boiling point of the solvent.

  The block copolymer polyamide of the present invention can contain other copolymer components in a range not impairing its properties, that is, in a proportion of less than 10 mol%, preferably less than 5 mol%, more preferably less than 2 mol%. . Other copolymer components include aliphatic dicarboxylic acids such as succinic acid, adipic acid and sebacic acid, aminocarboxylic acids such as 5-aminocaproic acid, 11-aminoundecanoic acid and 4-aminobenzoic acid, lactic acid, Examples thereof include hydroxycarboxylic acids such as glycolic acid, 5-hydroxycaproic acid and 4-hydroxybenzoic acid, alone or in combination.

  The block copolymerized polyamide of the present invention can be adjusted as a polymer having an intrinsic viscosity of 0.1 dL / g or more by the above-described polymerization method, but the purpose is to increase the molecular weight after polymerization. Therefore, it is possible to obtain a polyamide having an increased molecular weight by further solid-phase polymerization. In the method of the present invention, the polymer obtained as described above is pulverized to an average particle diameter of 5 mm or less, dried under vacuum overnight, and then at normal pressure under an inert gas stream or a high vacuum state of 1 mmHg or less. The polymer is crystallized by heating at a temperature not lower than the crystallization temperature (Tc) of the polymer and not higher than the melting point (Tm) for about 0.5 to 1 hour to obtain a solid phase polymerization polymer. As the polymer crystallization means, the above-mentioned heat crystallization is preferable, but a method of treating with a solvent can also be adopted if necessary.

  In the solid-phase polymerization of a crystallized polymer, the polymer is supplied to a solid-phase polymerization tank, and the glass transition of the polymer is performed in the solid-phase polymerization tank at normal pressure under an inert gas stream or in a high vacuum state of 1 mmHg (133 Pa) or less. The polymerization degree of the polymer is increased by heating to a temperature not lower than the temperature (Tg) and lower by 5 to 20 ° C. than the melting point (Tm) to cause solid phase polymerization. Thus, finally, a block copolymer polyamide having an intrinsic viscosity in the range of 0.1 dL / g or more is obtained. In solid phase polymerization, it is preferable to heat while increasing the temperature continuously or stepwise.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated, an Example is for description and this invention is not limited to this. In the examples, “part” means “part by mass” unless otherwise specified.

Various evaluation items given in the examples were determined as follows.
(1) Measurement of intrinsic viscosity The intrinsic viscosity was measured at 30 ° C by preparing a sample solution having a polyamide sample concentration of 0.03 g / dL using a methanesulfonic acid solvent.
(2) ¹³ C-NMR measurement
^The measurement by ¹³ C-NMR was performed using JEOL JNR-EX270 at 100 ° C. in deuterated dimethyl sulfoxide in methanesulfonic acid under magnetic field lock.

[Example 1]
The inside of the three-necked flask equipped with a nitrogen introduction tube and a discharge tube was dried at 250 ° C. for 1 hour under a nitrogen stream. After returning the temperature in the flask to room temperature, 50 parts by mass of toluene and 20.302 parts by mass of terephthalic acid chloride were added, and the mixture was stirred and dissolved at room temperature and ice-cooled. Separately, 10.12 parts by mass of 3,4'-diaminodiphenyl ether, 50 parts by mass of toluene, and 7.91 parts by mass of pyridine were added to a well-dried dropping funnel and mixed well to obtain a homogeneous solution. Toluene of terephthalic acid chloride The solution was dropped and stirred for 1 hour. Since the reaction active condensation mixture as an intermediate was precipitated after the reaction in the system, the toluene solvent was discharged from the other outlet of the three-necked flask under a nitrogen stream, and N-methyl-2-pyrrolidinone (NMP) was used instead. 100 parts by mass was added and stirred under ice cooling to obtain a homogeneous solution again. While stirring this, a solution prepared by dissolving 5.407 parts by mass of p-phenylenediamine in 100 parts by mass of NMP was added from a dropping funnel, and stirred for 30 minutes at ice-cooling, then stirred for 30 minutes at room temperature, and then stirred at 50 ° C for 60 minutes. Then, the polymerization reaction was carried out, and finally 3.71 parts by mass of calcium hydroxide was added to complete neutralization.
The whole was added to 2000 mL of ion-exchanged water while stirring with a mixer, and the resulting copolymerized polyamide was precipitated and collected by filtration. Further, after washing with ethanol and acetone, it was vacuum dried at 80 ° C. for 12 hours. The intrinsic viscosity of this copolymerized polyamide was measured and found to be 3.8 dL / g.

Furthermore, ¹³ C-NMR measurement was performed on this copolymerized polyamide (the chart is shown in the lower chart of FIG. 1). From the result, p-phenylenediamine (α-component diamine) linking unit and 3,4′-diaminodiphenyl ether were obtained. For the (β component diamine) linking unit, the randomness value R _αβ , the average chain length L _α of the α component diamine, and the average chain length L _β of the β component diamine were determined, and R _αβ was 0.34, and L _α was 5.5 and _Lβ were 6.2, confirming that the block structure was regularly formed. Further, when this block copolymerized polyamide was dispersed and dissolved in a 5% lithium chloride NMP solution at a concentration of 15% by mass, it became a very viscous solution. Anisotropy was observed. A photomicrograph is shown in FIG.

[Comparative Example 1]
The inside of the three-necked flask equipped with a nitrogen introduction tube and a discharge tube was dried at 250 ° C. for 1 hour under a nitrogen stream. After returning the temperature in the flask to room temperature, 10.12 parts by mass of 3,4'-diaminodiphenyl ether, 5.407 parts by mass of p-phenylenediamine, and 100 parts by mass of N-methyl-2-pyrrolidinone (NMP) were once added. In addition, the mixture was stirred well under ice cooling to obtain a uniform solution. While stirring this, a solution in which 20.302 parts by mass of terephthalic acid chloride was completely dissolved in 100 parts by mass of NMP was added in a dropping funnel over 10 minutes, followed by stirring for 30 minutes with ice cooling and then for 30 minutes at room temperature. The mixture was stirred at 60 ° C. for 60 minutes for polymerization reaction, and finally 3.71 parts by mass of calcium hydroxide was added to complete neutralization.

Thereafter, the operation was carried out in the same manner as in Example 1, and the intrinsic viscosity of the obtained copolymerized polyamide was measured and found to be 4.2 dL / g. Further, ¹³ C-NMR measurement was carried out in the same manner as in Example 1 (results are shown in the upper chart of FIG. 1), whereby p-phenylenediamine (α-component diamine) linking unit and 3,4′-diaminodiphenyl ether ( β component diamine) For the linking unit, the randomness value R _αβ , the average chain length L _α of the α component diamine, and the average chain length L _β of the β component diamine were determined. R _αβ was 1.03, and L _α was 2. .0, L _beta is 1.9, a copolymer consisting of substantially completely random structure, that does not has a regular block structure was confirmed. Further, when the obtained copolyamide was dispersed and dissolved in a 5% lithium chloride NMP solution at a concentration of 15% by mass, it became a highly viscous solution, which was observed under a crossed Nicol with a microscope. Anisotropy was not confirmed.

  The block copolymer polyamide of the present invention is suitable for various uses such as fibers, films and molded articles.

Claims (8)

The following general formula (1)
[In the general formula (1), Ar and Ar ′ are divalent aromatic groups that may be substituted with 6 to 18 carbon atoms, and R and R ′ are substituted with 6 to 18 carbon atoms. And a divalent aromatic group or a divalent aliphatic group having 2 to 200 carbon atoms, and Ar and Ar ′ are the same group and R and R ′ are different from each other, or R And R ′ are either the same group and Ar and Ar ′ are different groups. m and n are each an integer of 1 to 150. ]
The randomness value in the sequence is 0 or more and less than 0.8, and the intrinsic viscosity measured at 30 ° C. at a sample concentration of 0.03 g / dL using methanesulfonic acid is 0.00. A block copolymerized polyamide characterized by being 1 dL / g or more.   The block copolymer polyamide according to claim 1, wherein the average chain length of each block in the repeating unit is 3 or more.   The block copolymer polyamide according to claim 1 or 2, wherein in the general formula (1), Ar and Ar 'are the same group and R and R' are different groups. The following general formula (2)
[The definition of Ar in the general formula (2) is the same as the definition in the general formula (1). ]
An aromatic dicarboxylic acid represented by the formula (1) or more and less than 2.5 molar equivalents, and the following general formula (3)
[The definition of R in the general formula (3) is the same as the definition in the general formula (1). ]
Is reacted in a low-polar solvent or in bulk, and then a polar solvent is added. Further, the following general formula (4)
[The definition of R ′ in the general formula (4) is the same as the definition in the general formula (1). ]
The method for producing a block copolymerized polyamide according to claim 3, wherein 1 mole equivalent of the diamine represented by the formula (1) or a derivative thereof is added to cause a polymerization reaction.   The block copolymer polyamide according to claim 1 or 2, wherein, in the general formula (1), R and R 'are the same group and Ar and Ar' are different groups. The following general formula (3)
[The definition of R in the general formula (3) is the same as the definition in the general formula (1). ]
Represented by the following general formula (2):
[The definition of Ar in the general formula (2) is the same as the definition in the general formula (1). ]
After reacting 1 mol equivalent of the aromatic dicarboxylic acid represented by the following formula in a low polarity solvent or in bulk, a polar solvent is added, and the following general formula (5)
[The definition of Ar ′ in the general formula (5) is the same as the definition in the general formula (1). ]
6. The process for producing a block copolymerized polyamide according to claim 5, wherein 1 mole equivalent of an aromatic dicarboxylic acid represented by the formula (1) or a derivative thereof is added to cause a polymerization reaction.   The production method according to claim 4 or 6, wherein at least one selected from a hydrocarbon solvent and a halogen solvent is used as the low polarity solvent.   The production method according to claim 4, wherein an amide solvent is used as the polar solvent.