JP2000154248A - Polyamide block copolymer and preparation thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer which allows melt molding and has a greater heat resistance and low-temperature property compared to those of conventional thermoplastic elastomers, a preparation process of the polymer and a molded part and a fiber made from the polymer. SOLUTION: A polyamide block copolymer is obtained by polymerizing a dicarboxylic acid, a diamine and a polyether diamine and/or polyether dicarboxylic acid, wherein 50 mol% or more of the dicarboxylic acid is terephthalic acid and/or 2,6-naphthalene dicarboxylic acid, and 50 mol% or more of the diamine is an aliphatic alkylene diamine having a carbon number of from 6 to 18. Further, the copolymer has an inherent viscosity of from 0.7 to 3.5 dl/g and a melting point of from 200 to 320 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel polyamide block copolymer, a method for producing the same, and molded articles and fibers made of the polyamide block copolymer. The polyamide block copolymer of the present invention is excellent in heat resistance, cold resistance, oil resistance, elastic recovery and the like, and can be processed into various molded products and fibers having the same properties, and various thermoplastic resins. It is also effective as a modifier for impact resistance. Furthermore, the polyamide block copolymer of the present invention can be melt-molded at a temperature of 250 ° C. or higher, and can be composited by melt-forming or melt-spinning in combination with polyethylene terephthalate or the like which requires heating and melting at a high temperature. Products.

[0002]

2. Description of the Related Art Hitherto, polyetheramides and polyesteretheramides have been known to have heat resistance, oil resistance, mechanical strength and the like. However, for example, JP-A-50-159586 and JP-A-61-24
The polyether amide and polyester ether amide described in JP 7732 and the like have insufficient heat resistance because aliphatic polyamides such as nylon 6, nylon 12, and nylon 66 are used as hard segments, and thus are in the automotive field. However, the heat resistance required for various applications such as the above is not sufficiently satisfied, and the usage is limited. Therefore, when the content of the hard segment is increased for the purpose of increasing the heat resistance and the like of these polymers, there is a strong tendency that the low-temperature characteristics, impact resistance, etc. are inferior, and the balance between the heat resistance and the low-temperature characteristics is poor. Had become. Also, "Polymer", Vol. 38, No. 19, 4891-489
6 (1997) [“Polymer” Vol. 38 No. 19, pp.
4891-4896, 1997] reports a polyester ether amide having a semi-aromatic polyamide composed of 1,4-butanediamine unit and terephthalic acid unit as a hard segment, and the polyester ether amide has a hard segment chain. Short, insufficient heat resistance and mechanical properties. In addition, polyetheramide having a long hard segment chain that satisfies heat resistance and mechanical properties has an excessively high melting point, and polymer is severely deteriorated at a moldable temperature, so that melt molding cannot be substantially performed.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polymer which can be melt-molded and has higher heat resistance and lower temperature characteristics than conventional thermoplastic elastomers in view of the above situation. Another object of the present invention is to provide a method for producing the polymer, and a molded article and a fiber comprising the polymer.

[0004]

The present inventor has made intensive studies to achieve the above object. As a result, high crystallinity, high melting point polyamide as a hard segment,
And it is important that the melting point of the polymer is 320 ° C. or less in ensuring the moldability, and the polyamide block copolymer having the polyamide as a hard segment and a polyether as a soft segment has heat resistance, It was found to be excellent in both cold resistance, good moldability, and exhibit heat resistance higher than that of conventional thermoplastic elastomers.

[0005] The above polyamide block copolymer can not only be used alone for smooth molding or spinning, but also can be used in combination with a polymer which needs to be melted at a high temperature such as polyethylene terephthalate. It has been found that melt molding or melt spinning can be performed at a high temperature together with a polymer requiring such high-temperature molding to provide various products complexed with the polymer.

That is, the present invention relates to a polyamide block copolymer obtained by polymerizing a dicarboxylic acid, a diamine and a polyether diamine and / or a polyether dicarboxylic acid, wherein at least 50 mol% of the dicarboxylic acid is terephthalic acid. And / or 2,6-naphthalenedicarboxylic acid, wherein 50 mol% or more of the diamine is an aliphatic alkylenediamine having 6 to 18 carbon atoms, and the logarithmic viscosity is 0.7 to 3.5 dl / g; 200 melting point
It is a polyamide block copolymer having a temperature of ~ 320 ° C.

Further, the present invention is characterized in that a salt is formed from dicarboxylic acid, diamine and polyetherdiamine and / or polyetherdicarboxylic acid, and then a prepolymer is produced, followed by melt polymerization or solid phase polymerization. This is a method for producing the above polyamide block copolymer.

Further, the present invention is a molded article or fiber comprising the above-mentioned polyamide block copolymer.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The diamine unit constituting the polyamide block which is the hard segment of the polyamide block copolymer of the present invention contains 50 to 100 mol% of an aliphatic alkylenediamine unit having 6 to 18 carbon atoms. The content is preferably 75 to 100 mol%, more preferably 90 to 100 mol%. When the content of the aliphatic alkylenediamine unit having 6 to 18 carbon atoms is less than 50 mol%, various properties such as heat resistance of the obtained polyamide block copolymer are decreased, and the moldability is decreased, which is not preferable. . Examples of such aliphatic alkylenediamine units having 6 to 18 carbon atoms include 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, Linear aliphatic alkylenediamines such as 1,11-undecanediamine and 1,12-dodecanediamine; 1-butyl-1,2-ethanediamine, 1,1-dimethyl-1,4-butanediamine, 1-ethyl- 1,4-butanediamine, 1,2-dimethyl-1,4-butanediamine, 1,3-dimethyl-
1,4-butanediamine, 1,4-dimethyl-1,4-
Butanediamine, 2,3-dimethyl-1,4-butanediamine, 2-methyl-1,5-pentanediamine, 3-
Methyl-1,5-pentanediamine, 2,5-dimethyl-1,6-hexanediamine, 2,4-dimethyl-1,
6-hexanediamine, 3,3-dimethyl-1,6-hexanediamine, 2,2-dimethyl-1,6-hexanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4 4-trimethyl-1,6-hexanediamine, 2,4-diethyl-1,6-hexanediamine, 2,2-dimethyl-1,7-heptanediamine,
2,3-dimethyl-1,7-heptanediamine, 2,4
-Dimethyl-1,7-heptanediamine, 2,5-dimethyl-1,7-heptanediamine, 2-methyl-1,8
-Octanediamine, 3-methyl-1,8-octanediamine, 4-methyl-1,8-octanediamine, 1,
3-dimethyl-1,8-octanediamine, 1,4-dimethyl-1,8-octanediamine, 2,4-dimethyl-1,8-octanediamine, 3,4-dimethyl-1,
8-octanediamine, 4,5-dimethyl-1,8-octanediamine, 2,2-dimethyl-1,8-octanediamine, 3,3-dimethyl-1,8-octanediamine, 4,4-dimethyl- 1,8-octanediamine, 5
Examples thereof include units derived from a branched aliphatic alkylenediamine such as -methyl-1,9-nonanediamine, and one or more of these units may be contained.

Among the above aliphatic alkylenediamine units, 1,6-hexanediamine, 1,8-octanediamine, 2-methyl-1,8-octanediamine, 1,9
-Nonanediamine, 1,10-decanediamine, 1,1
Units derived from 1-undecanediamine, 1,12-dodecanediamine and the like are preferred. In particular, 1,9-nonanediamine (NMDA) and 2-methyl-1,8
-Units derived from octanediamine (MODA) are preferred, and a polyamide block copolymer having these units present in an appropriate ratio can sufficiently exhibit heat resistance, cold resistance and moldability. NMDA units and MO
The molar ratio of the DA unit is preferably 100: 0 to 30:70, more preferably 100: 0 to 40:60, and more preferably 100: 0 to 60:40. More preferred.

Examples of the diamine unit which can coexist in addition to the aliphatic alkylenediamine unit having 6 to 18 carbon atoms include aliphatic diamines such as ethylenediamine, propylenediamine and 1,4-butanediamine;
Alicyclic diamines such as cyclohexanediamine, methylcyclohexanediamine, isophoronediamine, norbornanedimethylamine, and tricyclodecanedimethylamine; p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 4, 4'-diaminodiphenylmethane, 4,4'-
Examples thereof include units derived from aromatic diamines such as diaminodiphenyl sulfone and 4,4′-diaminodiphenyl ether, and one or more of these units can coexist.

The carboxylic acid unit constituting the above polyamide block must contain at least 50 to 100 mol% of a terephthalic acid unit and / or 2,6-naphthalenedicarboxylic acid unit, and 70 to 100 mol%.
It is preferably contained, more preferably 90 to 100 mol%. Terephthalic acid units and / or
Alternatively, when the content of the 2,6-naphthalenedicarboxylic acid unit is less than 50 mol%, various properties such as heat resistance and chemical resistance of the polyamide block copolymer deteriorate, which is not preferable.

The dicarboxylic acid units other than the terephthalic acid unit and the 2,6-naphthalenedicarboxylic acid unit include, for example, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, Dimethylmalonic acid, 3,3-diethylsuccinic acid,
2,2-dimethylglutaric acid, 2-methyladipic acid,
Aliphatic dicarboxylic acids such as trimethyladipic acid;
Alicyclic dicarboxylic acids such as 3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; isophthalic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid 1,3-phenylenedioxydiacetic acid, diphenic acid,
Aromatic dicarboxylic acids such as 4,4'-biphenyldicarboxylic acid, 4,4'-oxydibenzoic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid; or any of these Mention may be made of units derived from mixtures. Among these, a unit derived from an aromatic dicarboxylic acid is preferred. Further, a unit derived from a polycarboxylic acid such as trimellitic acid, trimesic acid, and pyromellitic acid may be contained in a range in which the obtained polyamide block copolymer can be melt-molded.

In the above polyamide block, when the diamine unit is NMDA unit and / or MODA unit and the dicarboxylic acid unit is terephthalic acid unit, various properties such as heat resistance and cold resistance of the polyamide block copolymer are obtained. In addition, both moldability and formability are good, which is most preferable.

The polyether diamine unit and / or polyether dicarboxylic acid unit constituting the soft segment of the polyamide block copolymer of the present invention is derived from the corresponding polyether diamine and / or polyether dicarboxylic acid, respectively. The polyether diamine and the polyether dicarboxylic acid may have an amino group or a carboxyl group at both ends of the polyether. As polyether diamine, for example, α,
ω-bis (3-aminopropyl) poly (ethylene glycol), α, ω-bis (2-aminopropyl ether)
Poly (propylene glycol), α, ω-bis (3-aminopropyl) poly (oxytetramethylene), α, ω
-Bis (3-aminopropyl) poly (3-methyltetrahydrafuran) and the like. Examples of the polyether dicarboxylic acid include α, ω-bis (carboxymethyl ether) poly (ethylene glycol), α, ω −
Bis (carboxymethyl ether) poly (propylene glycol), α, ω-bis (carboxymethyl ether) poly (tetrahydrafuran), α, ω-bis (carboxymethyl ether) poly (3-methyltetrahydrafuran) and the like No. When α, ω-bis (3-aminopropyl) poly (oxytetramethylene) unit and / or α, ω-bis (carboxymethyl ether) unit is used as a soft segment,
Various physical properties such as heat resistance of the polyamide block copolymer are particularly excellent. One or more polyether diamine units or polyether dicarboxylic acid units can be contained.

The number average molecular weight of each of the polyether diamine unit and the polyether dicarboxylic acid unit is 40
It is preferably in the range of 0 to 4000. The number average molecular weight is more preferably in the range of 600 to 2,000, and even more preferably in the range of 700 to 1500. When the number average molecular weight of the polyether diamine unit or the polyether dicarboxylic acid unit is less than 400, characteristics such as cold resistance of the polyamide block copolymer deteriorate, which is not preferable. If the number average molecular weight is more than 4000, the polyamide block copolymer tends to be brittle, which is not preferable.

The polyamide block copolymer of the present invention comprises:
It is necessary that the melting point is 200-320 ° C. Its melting point is preferably from 220 to 300 ° C,
290 ° C. is more preferable. Melting point is 320 ° C
If the ratio exceeds the above, thermal decomposition starts when molding the polyamide block copolymer of the present invention, which is not preferable. When the melting point is lower than 200 ° C., the heat resistance of the polyamide block copolymer is poor, which is not preferable.

The composition ratio of the polyamide unit which is a hard segment constituting the polyamide block copolymer of the present invention to the polyether unit which constitutes the soft segment is such that the weight ratio of the polyamide unit / polyether unit is 90%.
/ 10 to 10/90, preferably 80/20 to 2
0/80, more preferably 70/30 to 25/75. When the constituent ratio of the polyamide unit is more than 90% by weight, the cold resistance, impact resistance and the like are inferior, which is not preferable. On the other hand, when the composition ratio of the polyamide unit is less than 10% by weight, heat resistance, mechanical properties, and the like are insufficient, which is not preferable.

The polyamide block copolymer of the present invention comprises:
The logarithmic viscosity measured at 30 ° C. in a mixed solvent of phenol / 1,1,2,2-tetrachloroethane (weight ratio 50/50) must be in the range of 0.7 to 3.5 dl / g. , Preferably in the range of 1.0 to 3.0 dl / g, and more preferably in the range of 1.2 to 2.5 dl / g. When the logarithmic viscosity is less than 0.7 dl / g, the heat resistance and mechanical properties of the polyamide block copolymer are poor, which is not preferable. On the other hand, if the logarithmic viscosity is larger than 3.5 dl / g, the flow characteristics of the polyamide block copolymer at the time of melting will be reduced, and molding will be defective, which is not preferable.

Next, the method for producing the polyamide block copolymer of the present invention will be specifically described. First, a dicarboxylic acid, a diamine, a polyether diamine and / or a polyether dicarboxylic acid are added all at once to a system in which a catalyst and an end capping agent are present, and a nylon salt is produced. When the logarithmic viscosity is 0.1 to 0.6 dl / g when measured at 30 ° C. in a mixed solvent of phenol / 1,1,2,2-tetrachloroethane (weight ratio 50/50) at a temperature of not more than 0 ° C. A polyamide block copolymer is produced by forming a prepolymer and then subjecting the prepolymer to melt polymerization or solid phase polymerization.

As the above-mentioned catalyst, for example, phosphoric acid, phosphorous acid, hypophosphorous acid or a salt or ester thereof is used. As such salts and esters, specifically, potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, metal salts such as antimony, ammonium salts, ethyl esters, isopropyl esters, Examples thereof include butyl ester, hexyl ester, isodecyl ester, octadecyl ester, decyl ester, stearyl ester, and phenyl ester.

The above terminal capping agent is not particularly limited as long as it is a monofunctional compound having reactivity with the amino group or carboxyl group of the polyamide terminal. From the viewpoint, monocarboxylic acid or monoamine is preferable, and from the viewpoint of easy handling, monocarboxylic acid is more preferable. In addition, acid anhydrides such as phthalic anhydride, monoisocyanates, monoacid halides, monoesters, and monoalcohols can also be used.

The monocarboxylic acid used as the terminal blocking agent is not particularly limited as long as it has reactivity with an amino group. For example, acetic acid, propionic acid, butyric acid,
Valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid,
Aliphatic monocarboxylic acids such as pivalic acid and isobutylic acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, phenylacetic acid Such as aromatic monocarboxylic acids; or an arbitrary mixture thereof. Among them, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid are preferred from the viewpoints of reactivity, sealed terminal stability, and price. And benzoic acid are particularly preferred.

The monoamine used as the terminal blocking agent is not particularly limited as long as it has reactivity with a carboxyl group. Examples thereof include methylamine, ethylamine, propylamine, butylamine, hexylamine,
Aliphatic monoamines such as octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine; Alternatively, an arbitrary mixture thereof can be mentioned. Among them, butylamine, hexylamine, octylamine,
Decylamine, stearylamine, cyclohexylamine, aniline are particularly preferred.

The polyamide block copolymer of the present invention comprises
If necessary, stabilizers such as copper compounds, coloring agents, flame retardants, ultraviolet absorbers, antioxidants, hydrolysis stabilizers, fungicides, sulfonates, internal mold release agents, crystallization accelerators Various additives such as glass fibers, various fibers such as organic fibers, talc, silica, other inorganic fillers, various coupling agents, and the like can be appropriately added during or after the production of the polyamide block copolymer. .

Since the polyamide block copolymer of the present invention is thermoplastic and has excellent melt moldability, it can be smoothly processed into various molded articles and fibers by melt molding, melt spinning and the like. Further, the polyamide block copolymer of the present invention is used in combination with polyethylene terephthalate and other high melting point polymers that need to be melted at a high temperature, and melted and mixed at a high temperature to obtain a polyamide block copolymer of the present invention and a high melting point. A composition comprising a polymer can be produced,
Also, a composite molded article of the polyester block copolymer of the present invention and a high melting point polymer, a composite fiber, and the like can be produced by melt molding or melt spinning at a high temperature.

The polyamide block copolymer of the present invention comprises:
Alone or in combination with other polymers, mechanical parts, automotive parts, electrical and electronic parts, sheets, films, belts,
Rolls, curled cords, hoses, tubes, packing materials, vibration damping materials, vibration damping materials, cushioning materials, shoe soles, sports shoes, sports goods, various molded products, various plastic modifiers, elastic fibers, adhesives It can be effectively used for a wide range of uses such as raw materials for When producing the above-mentioned molded article or the like from the polyamide block copolymer of the present invention, various melt molding methods conventionally used for thermoplastic resins and thermoplastic elastomers, for example, extrusion molding, injection molding, etc. Molding, extrusion blow molding,
Various molding methods such as injection blow molding, calender molding, and press molding can be adopted, and the production of fibers can be performed by melt spinning.

[0028]

EXAMPLES The present invention will be described below in more detail with reference to examples and the like, but the present invention is not limited thereto.
In Examples and Comparative Examples, measurements of the logarithmic viscosity, melting point, heat resistance, cold resistance, and tensile strength of the polyamide block copolymer were performed as follows.

[Logarithmic viscosity] In a mixed solvent of phenol / 1,1,2,2-tetrachloroethane (weight ratio 50/50), the concentration of the polyamide block copolymer was 0.5 g /
dl and measured at 30 ° C.

[Melting point] The melting point of the polyamide block copolymer was determined by sequentially performing the steps 1 to 3 shown in Table 1 under a nitrogen stream using a differential scanning calorimeter (DSC) manufactured by Mettler. Was determined as the melting peak temperature.

[0031]

[Table 1]

[Tensile strength and tensile elongation] The polyamide block copolymer was hot-pressed at a temperature of 300 ° C to a thickness of 1
After the production of a 00 μm film, the film
A test piece of cm × 0.5 cm was collected, and the test piece was used for the test, at a pulling speed of 200 mm / min, a temperature of 23 ° C., and a humidity of 65%
A tensile test was performed under the condition of RH, and its tensile strength and tensile elongation were measured.

[Heat resistance] The polyamide block copolymer was hot-pressed at a temperature of 300 ° C. to produce a film having a thickness of 100 μm, and then 3 cm × 0.5 cm from the film.
And the dynamic viscoelasticity of the test piece was measured at a frequency of 11 Hz using an apparatus [DVE-V4FT Rheospectral, manufactured by Rheology Co., Ltd.] to determine the temperature at the end point of the rubbery flat region. Then, the heat resistance was evaluated.

[Cold resistance] The polyamide block copolymer was hot-pressed at a temperature of 300 ° C. to produce a film having a thickness of 100 μm, and then 3 cm × 0.5 cm from the film.
And the dynamic viscoelasticity of the test piece was measured at a frequency of 11 Hz using an apparatus [DVE-V4FT Rheospectral, manufactured by Rheology Co., Ltd.], and the dynamic loss modulus E ″ peaked. Was determined, and the cold resistance was evaluated accordingly.

Tables 2 and 3 show the relationship between the compounds used in the examples and comparative examples and their abbreviations.

[0036]

[Table 2]

[0037]

[Table 3]

Example 1 1100 g of α, ω-bis (3-aminopropyl) poly (oxytetramethylene), 498 g of terephthalic acid, and 2 parts of water
79 g and 1.9 g of sodium diphosphite at room temperature,
After stirring to make the mixture uniform, 316 g of 1,9-nonanediamine and 200 g of water were added, and the mixture was further stirred to obtain a uniform salt. The obtained salt was transferred to an autoclave, and the temperature was set so that the resin temperature was 245 ° C. The internal pressure at this time was 32 kg / cm ² . After the resin temperature reached 245 ° C., the reaction was continued for 2 hours, and then cooled, and the oligomer was taken out of the autoclave and dried. The dried oligomer was crushed and transferred to a reactor capable of melt polymerization. Thereafter, the temperature was set so that the resin temperature became 300 ° C., and the pressure of the reaction system was reduced (3 mmHg). After the resin temperature reached 300 ° C., the reaction was continued for 3 hours, and the polymer was taken out. A film having a thickness of 100 μm was prepared from the obtained polymer, and the logarithmic viscosity, melting point, heat resistance, cold resistance, tensile strength and tensile elongation were evaluated by the methods described above. Table 4 shows the evaluation results. The moldability by hot pressing was good, and the heat resistance, cold resistance, tensile strength and tensile elongation were all excellent values.

Example 2 1100 g of α, ω-bis (3-aminopropyl) poly (oxytetramethylene), 498 g of terephthalic acid, water 2
79 g and 1.9 g of sodium diphosphite at room temperature,
After stirring so as to be uniform, 1,9-nonanediamine / 2-methyl-1,8-octanediamine (molar ratio: 7 /
316 g of the mixture of 3) and 200 g of water were added, and the mixture was further stirred to obtain a uniform salt. The obtained salt was transferred to an autoclave, and the temperature was set so that the resin temperature was 245 ° C. The internal pressure at this time was 32 kg / cm ² . After the resin temperature reached 245 ° C., the reaction was continued for 2 hours, and then cooled, and the oligomer was taken out of the autoclave and dried. The dried oligomer was crushed and transferred to a reactor capable of melt polymerization. Then, when the resin temperature is 280
° C, and the reaction system was decompressed (3 mmH
g). After the resin temperature reached 280 ° C., the reaction was continued for 4 hours, and the polymer was taken out. A film having a thickness of 100 μm was prepared from the obtained polymer, and the logarithmic viscosity, melting point, heat resistance, cold resistance, tensile strength and tensile elongation were evaluated by the methods described above. Table 4 shows the evaluation results.
The moldability by hot pressing was good, and the heat resistance, cold resistance, tensile strength and tensile elongation were all excellent values.

Example 3 600 g of α, ω-bis (carboxymethyl ether) poly (ethylene glycol), 332 g of terephthalic acid, 152 g of water and 1.4 g of sodium diphosphite were stirred at room temperature so as to be uniform. Then, 474 g of 1,9-nonanediamine and 200 g of water were added, and the mixture was further stirred to obtain a uniform salt. The obtained salt was transferred to an autoclave, and the temperature was set so that the resin temperature was 245 ° C. The internal pressure at this time was 32 kg / cm ² .
After the resin temperature reached 245 ° C., the reaction was continued for 2 hours, and then cooled, and the oligomer was taken out of the autoclave and dried. The dried oligomer was crushed and transferred to a reactor capable of melt polymerization. Thereafter, the temperature was set so that the resin temperature became 300 ° C., and the pressure of the reaction system was reduced (3 mmHg). After the resin temperature reached 300 ° C., the reaction was continued for 4 hours, and the polymer was taken out. A film having a thickness of 100 μm was prepared from the obtained polymer, and the logarithmic viscosity, melting point, heat resistance, cold resistance, tensile strength and tensile elongation were evaluated by the methods described above. Table 4 shows the evaluation results. The moldability by hot pressing was good, and the heat resistance, cold resistance, tensile strength and tensile elongation were all excellent values.

Comparative Example 1 α, ω-bis (3-aminopropyl) poly (oxytetramethylene) 1100 g, adipic acid 438 g, water 24
After uniformly stirring 3 g and 1.8 g of sodium diphosphite at room temperature, 232 g of 1,6-hexamethylenediamine and 200 g of water were added, and the mixture was further stirred to obtain a uniform salt. The obtained salt was transferred to an autoclave, and the temperature was set so that the resin temperature was 245 ° C. The internal pressure at this time was 32 kg / cm ² . After the resin temperature reached 245 ° C., the reaction was continued for 2 hours, and then cooled, and the oligomer was taken out of the autoclave and dried. The dried oligomer was crushed and transferred to a reactor capable of melt polymerization. Then, the resin temperature is 300 ° C
The temperature was set so that the pressure became
g). After the resin temperature reached 270 ° C., the reaction was continued for 4 hours, and the polymer was taken out. A film having a thickness of 100 μm was prepared from the obtained polymer, and the logarithmic viscosity, melting point, heat resistance, cold resistance, tensile strength and tensile elongation were evaluated by the methods described above. Table 4 shows the evaluation results.
Both heat resistance and cold resistance were insufficient.

Comparative Example 2 1100 g of α, ω-bis (3-aminopropyl) poly (oxytetramethylene), 664 g of terephthalic acid, water 3
28 g and 1.9 g of sodium diphosphite at room temperature,
After stirring so as to be uniform, 348 g of 1,6-hexamethylenediamine and 200 g of water were added, and the mixture was further stirred to obtain a uniform salt. The obtained salt was transferred to an autoclave, and the temperature was set so that the resin temperature was 245 ° C. The internal pressure at this time was 32 kg / cm ² . After the resin temperature reached 245 ° C., the reaction was continued for 2 hours, and then cooled, and the oligomer was taken out of the autoclave and dried. The obtained oligomer had a tacky rubber-like portion and a hard resin portion, and was non-uniform. When the melting point of the hard part was measured, it was 3
70 ° C. The obtained oligomer was transferred to a reactor capable of melt polymerization, and the pressure was reduced to 3 mmHg, and the temperature was gradually raised.

[0043]

[Table 4]

[0044]

The polyamide block copolymer of the present invention has a high crystallinity and a polyamide block having a high melting point as a constituent unit, so that it has excellent heat resistance and cold resistance, and further has mechanical properties and elasticity. Excellent recoverability. Further, the polyamide block copolymer of the present invention is not only capable of smooth molding or spinning alone, but also can be used in combination with a polymer that needs to be melted at a high temperature such as polyethylene terephthalate. By performing melt molding or melt spinning at a high temperature together with a polymer requiring such high-temperature molding, various products complexed with the polymer can be provided.

Claims (4)

[Claims] 1. A polyamide block copolymer obtained by polymerizing a dicarboxylic acid, a diamine and a polyether diamine and / or a polyether dicarboxylic acid, wherein at least 50 mol% of the dicarboxylic acid is terephthalic acid and / or 2 , 6-naphthalenedicarboxylic acid,
50 mol% or more of the diamine is an aliphatic alkylenediamine having 6 to 18 carbon atoms, and has a logarithmic viscosity of 0.7 to 0.7.
A polyamide block copolymer having a viscosity of 3.5 dl / g and a melting point of 200 to 320 ° C. 2. The method according to claim 1, wherein the aliphatic alkylenediamine having 6 to 18 carbon atoms is 1,9-nonanediamine and / or 2-alkyldiamine.
The polyamide block copolymer according to claim 1, which is methyl-1,8-octanediamine. 3. The method according to claim 1, wherein after forming a salt from the dicarboxylic acid, diamine and polyetherdiamine and / or polyetherdicarboxylic acid, a prepolymer is produced, followed by melt polymerization or solid state polymerization. 3. The method for producing a polyamide block copolymer according to 1.). 4. A molded article or fiber comprising the polyamide block copolymer according to claim 1 or 2.