JP2000309633A - Polyalkylene terephthalate-polymide block copolymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyalkylene terephthalate-polyamide block copolymer useful as an engineering plastic in extremely high efficiency by making the copolymer include respectively specific polyalkylene terephthalate block and polyamide block. SOLUTION: This copolymer contains (A) a polyalkylene terephthalate block having a repeating unit expressed by formula I (X is a 2-20C alkylene; (m) is 5-200) and (B) a polyamide block having a repeating unit expressed by formula II (Y is a bivalent organic group composed of a 2-20C aliphatic hydrocarbon group, an aromatic hydrocarbon group or an alicyclic hydrocarbon group; (n) is 5-200) wherein the block A is bonded to the block B through an amide bond. The block B is preferably derived from a polyamide produced by reacting a polyalkylene terephthalate resin with a diamine compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polyalkylene terephthalate polyamide block copolymer and a method for producing the same. More particularly, the present invention relates to a polyalkylene terephthalate polyamide block copolymer obtained from a polyalkylene terephthalate resin as a raw material. And a method for advantageously producing it.

[0002]

BACKGROUND ART Conventionally, polyalkylene terephthalate resins such as polyethylene terephthalate (hereinafter abbreviated as PET) resin and polybutylene terephthalate resin as polyester resins have excellent mechanical and electrical properties and good moldability. Today, it is produced in large quantities as an engineering plastic having However, depending on the intended use, further improvement is desired in terms of heat resistance.

On the other hand, poly-p-phenylene terephthalamide, polyethylene terephthalamide, polyhexamethylene terephthalamide, and the like have excellent heat resistance.
As compared with PET resin or the like, there is a problem that the moldability is inferior and the product cost is increased.

[0004] Therefore, in order to obtain a material that complements the disadvantages of both the polyester resin and the polyamide resin, that is, the low heat resistance of the polyester resin and the poor moldability of the polyamide resin, in other words, Research on a polyester-polyamide block copolymer having both a polyester structure and a polyamide structure, which has excellent heat resistance and good moldability, has been conducted for a long time.

For example, (1) a method of melt-kneading a polyester such as PET and a polyamide such as polycaproamide and obtaining a polyester polyamide block copolymer by a partial polyester polyamide exchange reaction (US Pat. No. 337)
8602), (2) a method of conducting a polymerization reaction of a polyester in the presence of a relatively low-molecular-weight polyamide having a carboxyl group or an ester-forming functional group at both terminals (Japanese Patent Publication No. 49-13638); (3) A method of mixing a polyamide having an amino group at both ends and a polyester having a diol ester group at both ends and reacting them by solid-phase polymerization (Japanese Patent Publication No. 49-13640). A method in which a polyamide having a molecular weight of 1,000 to 10,000 having an ester or carboxyl group and a polyester having a molecular weight of 500 to 5,000 having a terminal hydroxyl group are melt-polycondensed in the presence of an esterification catalyst (JP-B-55-48412); ) Polyester having carboxyl groups at both ends and aminoaryl group at both ends (6) a method of polycondensing liamide in the presence of an aromatic hypophosphite and a pyridine derivative (Japanese Patent Application Laid-Open No. 4-85326), (6) a method of using a polyalkylene terephthalate solution and a specific poly p-phenylene terephthalamide solution A method of performing solid phase polymerization after mixing and removing the solution (JP-B-63-13445), (7)
There are many methods such as a method in which an ester-forming component and an amide-forming component are mixed together and polycondensed (Japanese Patent Publication No. 63-45690).

However, in such a method, in the melt-kneading of the simple polyester and the polyamide as described in (1) above, it is difficult to obtain a satisfactory block copolymer due to poor compatibility of both. It is not possible, and when a different component is introduced at the stage of polycondensation to obtain a polyester amide at a stroke as in the above methods (2) to (7), in other words, a polyamide polymerization system is used. When an ester-forming compound is present, or when a polyamide-forming compound is present in a polyester polymerization system, hydrolysis of the ester or the like occurs, so that a high polymer cannot be obtained or the reactivity is low. It was extremely difficult to obtain a useful polyester polyamide block copolymer, for example, due to poor polymer production efficiency.

[0007]

Therefore, the present inventor has previously proposed a novel method for obtaining a polyamide resin from a polyester resin (Japanese Patent Application Laid-Open No. 9-1990).
No. 324037) was proposed, but as a result of further study of the technology, it was found that a high-molecular-weight polyester-polyamide block copolymer could be produced extremely efficiently according to a similar method, and the present invention was completed. That's what happened.

Here, the present invention has been made in view of such circumstances, and a problem to be solved is to provide a high molecular weight polyalkylene terephthalate polyamide block copolymer and a polyalkylene terephthalate block copolymer. It is an object of the present invention to provide a method for producing a terephthalate resin as a raw material extremely efficiently.

[0009]

In order to solve such a problem, the present invention has a polyalkylene terephthalate block having a repeating unit represented by the following formula (6) and a repeating unit represented by the following formula (7). A polyalkylene terephthalate polyamide block copolymer, comprising a polyamide block, and wherein the polyalkylene terephthalate block and the polyamide block are linked via an amide bond. Is what you do.

Embedded image [However, X represents an alkylene group having 2 to 20 carbon atoms, and m is an integer of 5 to 200.] ]

Embedded image [However, Y represents a divalent organic group comprising an aliphatic hydrocarbon having 2 to 20 carbon atoms, aromatic or alicyclic hydrocarbon, and the like, and n is an integer of 5 to 200. ]

According to a preferred embodiment of the polyalkylene terephthalate polyamide block copolymer according to the present invention, the polyamide block is provided by a polyamide obtained by reacting a polyalkylene terephthalate resin with a diamine compound. In this manner, the desired block copolymer can be advantageously obtained.

In the polyalkylene terephthalate polyamide block copolymer according to the present invention, a predetermined polyalkylene terephthalate block and a polyamide block are linked via an amide bond. A higher molecular weight block copolymer could be realized, and since the polyester structure and the polyamide structure were introduced in the molecule, the properties that could be exhibited by each structure were both obtained by the block copolymerization. It is advantageously given to the union.

In the present invention, in order to obtain such a polyalkylene terephthalate polyamide block copolymer advantageously, a polyalkylene terephthalate resin and a double-ended aminopolyamide represented by the following formula 8 or A gist of the present invention is also a production method characterized by reacting an aminopolyamide represented by Chemical formula 9 or Chemical formula 10 at one end.

Embedded image [However, Y represents a divalent organic group comprising an aliphatic hydrocarbon having 2 to 20 carbon atoms, aromatic or alicyclic hydrocarbon, and the like, and n is an integer of 5 to 200. ]

Embedded image Wherein Y represents a divalent organic group comprising an aliphatic hydrocarbon having 2 to 20 carbon atoms, an aromatic or alicyclic hydrocarbon, n represents an integer of 5 to 200, and R ₁ represents a carbon atom. The number represents an alkylene group of 2 to 20. ]

Embedded image [However, Y represents a divalent organic group composed of an aliphatic hydrocarbon having 2 to 20 carbon atoms, aromatic or alicyclic hydrocarbon, etc., n is an integer of 5 to ₂₀₀ , and R ₂ is hydrogen. Or an alkylene group having 1 to 20 carbon atoms. ]

In one preferred embodiment of the method of the present invention, the polyalkylene terephthalate resin and the aminopolyamide at both ends or the aminopolyamide at one end are composed of a hydrocarbon solvent, a halogenated hydrocarbon. A system solvent, an ether solvent, an acetal solvent, and a reaction medium comprising one or more solvents selected from the group consisting of aprotic phophophobic polar solvents, The both-terminal aminopolyamide or one-terminal aminopolyamide is formed by reacting a polyalkylene terephthalate resin with a diamine compound,
preferable. Furthermore, it is desirable that the polyalkylene terephthalate resin has an intrinsic viscosity of 0.2 g / dl or more.

By employing such a method of the present invention, the desired polyalkylene terephthalate polyamide block copolymer can be efficiently produced with a high molecular weight.

[Detailed Description of the Invention] The present invention will be described in more detail below.

According to the present invention, the above formula 1 (formula 6)
The polymer having a polyalkylene terephthalate block structure having a repeating unit represented by the general formula (I) is generally composed of
It is obtained from a polyhydric alcohol compound (diol component) by a polycondensation reaction. Here, as the dihydric alcohol compound, ethylene glycol, butane-1,
Examples thereof include alkylene glycols such as 3-diol and butane-1,4-diol (tetramethylene glycol). As a part of the dicarboxylic acid component, various aliphatic, aromatic or alicyclic dicarboxylic acids and derivatives thereof other than terephthalic acid or a derivative thereof may be used without departing from the gist of the present invention. As the diol component, a dihydric phenol compound can be used in addition to the dihydric alcohol. However, it is desirable that all of the other dicarboxylic acid components and diol acid components used partially be in a proportion of 50 mol% or less in each component.

Specific examples of the polymer having a polyalkylene terephthalate structure in the present invention include a polyethylene terephthalate resin and a polybutylene terephthalate resin. In particular, a polyethylene terephthalate (PET) resin, in particular, a recycled (recovered) polyethylene terephthalate resin is preferable.

The polyamide having a polyamide block structure having a repeating unit represented by the above formula (2) according to the present invention is reacted with a polyalkylene terephthalate resin by reacting a diamine compound in a specific solvent. The obtained one is preferably used.

Specific examples of the diamine compound used for forming such a polyamide include ethylenediamine, trimethylenediamine, tetramethylenediamine,
Aliphatic diamine compounds such as pentamethylenediamine, hexamethylenediamine, octamethylenediamine, dodecamethylenediamine, trimethylene-1,6-hexamethylenediamine; p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, m-trimethylenediamine Diamine, p-xylylenediamine, m-xylenediamine, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodibiphenyl, 3,3 '
-Dichloro-4,4'-diaminobiphenyl, 4,
4'-diaminodiphenyl ether, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 4,4'-diaminobenzanilide, 3,3'-dimethyl- 4,4'-diaminodiphenylmethane, 3,
3'-diethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminoanthraquinone, 3,3'-dimethoxybenzidine, α, α'-bis (4-aminophenyl) -p-isopropylbenzene, Aromatic diamine compounds such as 5-diaminonaphthalene and 2,6-diaminonaphthalene; 1,3-diaminocyclohexane,
4-diaminocyclohexane, 1,3-bis (aminomethyl) cyclohexane, isophoronediamine, piperazine, 2,5-dimethylpiperazine, bis (4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) propane, 4,4 ′ -Diamino-3,3'-dimethyldicyclohexylmethane, α, α'-bis (4-aminocyclohexyl) -p-diisopropylbenzene,
alicyclic diamine compounds such as α, α′-bis (4-aminocyclohexyl) -m-diisopropylbenzene and menthanediamine; These diamine compounds may be used alone or in combination of two or more. The diamine compound is preferably used in a proportion of 0.5 to 1.5 mol per 1 mol of the repeating unit of the polyalkylene terephthalate resin.

Further, as the specific solvent, for example, n-butane, iso-butane, n-pentane, 2-
Methylbutane, 2,2'-dimethylpropane, n-methylpentane, 3-methylpentane, 2,2'-dimethylbutane, n-hexane, 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane, n -Heptane,
2-methylhexane, 3-methylhexane, 2,3-dimethylpentane, n-octane, n-nonane, n-decane, n-tridecane, benzene, toluene, xylene,
Ethylbenzene, cumene, n-propylbenzene, n-
Aliphatic, aromatic, aliphatic-aromatic or alicyclic such as butylbenzene, n-octylbenzene, dodecylbenzene (linear, branched), cyclopentane, cyclohexane, decalin, tetralin, methylcyclopentane, methylcyclohexane, etc. Hydrocarbon solvent; 1,2-dichloroethane, 1,1,1-trichloroethane, chlorobenzene, p-chlorotoluene, o-dichlorobenzene, m-
Halogenated hydrocarbon solvents such as dichlorobenzene, p-dichlorobenzene, 3,4-dichlorotoluene, 1,2,3-trichlorobenzene; diethyl ether, dipropyl ether, dibutyl ether, dihexyl ether, ethyl vinyl ether, butyl vinyl ether , Anisole, phenetole, butyl phenyl ether, pentyl phenyl ether, methoxytoluene, benzyl ethyl ether, diphenyl ether, dibenzyl ether, trioxane, 2-methylfuran, tetrahydrofuran, tetrahydropyran, 1,2-dimethoxyethane, 1,2-di Ethoxyethane, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, Triethylene glycol diethyl ether, ethers such as diethyl acetal, acetal solvents; acetonitrile, sulfolane, 3-sulfolene, N- methylpyrrolidone, 2-aprotic, such as pyrrolidone sparse protonic polar solvents and the like. These solvents may be used alone or in combination of two or more. Therefore, the solvent in the present invention includes petroleum ether, petroleum benzine, gasoline, kerosene, and solvent naphtha.

Specific examples of the polyamide having a polyamide structure obtained by the above-mentioned reaction include a polyethylene terephthalate resin as a polyalkylene terephthalate resin and an ethylene diamine or hexamethylene diamine as a diamine compound. And polyalkylene terephthalamides such as polyethylene terephthalamide and polyhexamethylene terephthalamide, and poly p-phenylene terephthalamide obtained by using p-phenylenediamine as a diamine compound.

The ratio of the polyalkylene terephthalate structure to the polyamide structure in the polyalkylene terephthalate polyamide block copolymer according to the present invention is as follows:
Generally, the polyalkylene terephthalate structure is 95 to 1
0% by weight (polyamide structure 5 to 90% by weight), preferably 90 to 20% by weight (polyamide structure 10 to 80% by weight), more preferably 85 to 30% by weight (polyamide structure 15 to 70% by weight) It is. When the polyalkylene terephthalate structure exceeds 95% by weight, the heat resistance of the polyalkylene terephthalate polyamide block copolymer does not improve even if the polyamide structure is introduced into the molecule, and the polyalkylene terephthalate structure has a polyalkylene terephthalate structure of 10% or less.
If the amount is less than 10% by weight, the moldability of the polyamide is not improved.

Meanwhile, the method for obtaining the polyalkylene terephthalate polyamide block copolymer according to the present invention includes the following steps: (i) reacting a polyalkylene terephthalate resin with a diamine compound in a specific solvent;
A polyamide having an amino group at both terminals or one terminal represented by Chemical Formula 5 (Chemical Formula 8 to Chemical Formula 10) is first formed, and then, a polyalkylene terephthalate resin is newly added to the same reaction system, and the above both are reacted. A method of continuously reacting with a polyamide having a terminal or one terminal amino group,
(Ii) A polyalkylene terephthalate resin and a diamine compound are reacted in a specific solvent to obtain a polyamide having amino groups at both terminals or one terminal represented by the above-mentioned chemical formulas 3 to 5 (chemical formulas 8 to 10). And then reacting the polyalkylene terephthalate resin with the polyamide having amino groups at both terminals or one terminal in another reaction system. In the method according to the above (i) and (ii), first, the above-mentioned polyamide having an amino group at both terminals or one terminal is formed from a terephthalic acid and a diamine compound by a usual polycondensation reaction, and thereafter, Also a method of reacting the polyalkylene terephthalate resin and the generated polyamide in a specific solvent,
It should be understood that they are included in the method of the present invention.

In each of the above methods (i) and (ii), a polyamide having a predetermined amino group at both terminals or one terminal is produced in the first step, and the produced polyamide is produced in the second step. It consists of reacting a polyamide having a terminal or one terminal amino group with a polyalkylene terephthalate resin, but as described in more detail below, in both steps, a reaction vessel having a normal heating and stirring device Will be performed using

That is, in the case of (i), as a first step, a polyalkylene terephthalate resin, a diamine compound and a specific solvent as raw materials are charged into a reaction vessel, and the mixture is heated and agitated. A polyamide having an amino group is obtained, and then, as a second step, a polyalkylene terephthalate resin is newly added to the same reaction system and reacted with the polyamide having an amino group at both terminals or one terminal obtained earlier. Thus, the intended polyalkylene terephthalate polyamide block copolymer is obtained. The polyalkylene terephthalate resins in the first and second stages may be the same or different. In both the first and second stages, the reaction temperature depends on various factors such as the polyalkylene terephthalate resin used, the diamine compound, the type, amount, and shape of the specific solvent, as well as the reaction pressure, reaction time, and stirring state. Although different, generally at least 100 ° C., preferably 1 ° C.
20 ° C. or higher. When the reaction temperature is equal to or higher than the boiling point or the sublimation temperature of the solvent or diamine compound to be used, it is desirable to close or pressurize the reaction vessel. On the other hand, if the reaction temperature is lower than 100 ° C., it takes too much time to produce polyamide or to react polyamide with polyalkylene terephthalate resin, which is not preferable. Furthermore, the reaction time depends on many factors as in the case of the reaction temperature.
0.2 to 100 hours, respectively, preferably 0.5 to 5 hours
0 hours. If the reaction time is less than 0.2 hours, the reaction is insufficient and a good polyalkylene terephthalate polyamide block copolymer cannot be obtained, and if the reaction time exceeds 100 hours, the reaction time becomes longer. This is because, even if it is extended, the effect obtained thereby is small.

In the method (ii), the reaction in the first step is carried out in the same manner as in the method (i), but in the second step, the unreacted diamine compound is removed. In the removed state, a reaction between a predetermined aminopolyamide at both terminals or one terminal and a polyalkylene terephthalate resin can be carried out, so that a copolymer having a large molecular weight is easily obtained. In the second step in the case of the method (ii), the reaction can be allowed to proceed by using a solvent and reaction conditions different from those in the first step.

After completion of the reaction according to the present invention, the polyalkylene terephthalate polyamide block copolymer as a reaction product present in the reaction solvent is separated and recovered. As, when the reaction product is dispersed in a slurry state in the reaction solvent, is separated as it is, when the reaction product is dissolved, employs a solvent spray method,
Alternatively, the reaction product is precipitated by adding an appropriate precipitant, and then separated by a conventional method such as filtration or centrifugation. Further, the obtained separated product is dried by a usual drying method such as a hot air drier or a vacuum drier, whereby an intended polyalkylene terephthalate polyamide block copolymer is obtained. The intrinsic viscosity of the polyalkylene terephthalate polyamide block copolymer thus obtained is usually about 0.3 to 2.5 dl / g.

When it is necessary to further increase the molecular weight of the polyalkylene terephthalate polyamide block copolymer as a reaction product obtained according to the method of the present invention, a so-called solid phase polymerization method or melt polymerization method is used. It is also possible to implement

Here, the solid phase polymerization method is a method in which a polycondensation reaction is carried out while maintaining a solid state to increase the degree of polymerization, that is, to increase the molecular weight. In the case of the present invention, The reaction temperature ranges from 80 ° C. higher than the glass transition temperature of the polyalkylene terephthalate polyamide block copolymer as the reaction product to 20 ° C. lower than the flow start temperature of the copolymer.
The solid-phase polymerization is carried out by performing the polycondensation reaction under a reduced pressure of 00 Pa or less, preferably 300 Pa or less or in an inert gas atmosphere. The reaction time at this time varies depending on the reaction temperature, the amount of the reaction product, the shape of the apparatus used, and the like.
It is 20 hours, preferably about 0.5 to 10 hours.

In the melt polymerization method, a reaction product is heated and melted under reduced pressure or an inert gas, and a polycondensation reaction is advanced while maintaining the state to increase the degree of polymerization, that is, the molecular weight. Method. The melting temperature at the time of this heating and melting is higher than the flow starting temperature of the polyalkylene terephthalate polyamide block copolymer as the reaction product and lower than the decomposition temperature as the reaction product, preferably 20 ° C. or higher than the flow starting temperature of the reaction product. In addition, a temperature lower than the thermal decomposition temperature by 30 ° C. or more is employed. In addition, as a time for allowing such a reaction to proceed,
0.2 to 15 minutes, preferably 0.5 to 10 minutes
Desirably less than a minute.

Further, as an apparatus used for performing such a melt polycondensation, any apparatus capable of kneading a high-viscosity polymer under heating conditions may be employed. For example, rolls, extruders, kneaders and the like are preferable. Among them, a vented extruder and a kneader, which can be easily kneaded at a high temperature, can realize a high molecular weight in a short time, and can easily collect the produced polymer, are preferable. As such an extruder, a single-screw or multi-screw extruder is used, and since reaction by-products can be removed from a vent under reduced pressure, pellets can be easily and quickly obtained. This makes it possible to obtain a high-molecular-weight polyalkylene terephthalate polyamide block copolymer having a shape. In addition,
The degree of pressure reduction of the vent at that time is generally 1000 Pa or less,
Preferably it is 300 Pa or less.

The polyalkylene terephthalate polyamide block copolymer obtained according to the method of the present invention may further contain, if necessary, a known heat stabilizer, light stabilizer, coloring agent, lubricant, reinforcing agent, Various compounding agents such as fillers can be compounded singly or in combination, and the desired polyalkylene terephthalate polyamide block can be mixed by a known melt molding method such as compression molding, injection molding, or extrusion molding. A polymer molded article is formed. It is also possible to dissolve such a polyalkylene terephthalate block copolymer in a solvent and form a film or a coating layer by a casting method.

[0033]

EXAMPLES Hereinafter, some examples of the present invention will be described to clarify the present invention more specifically. However, the present invention imposes some restrictions by the description of such examples. It goes without saying that you don't receive anything. In addition, the present invention, in addition to the following examples, and in addition to the above-described specific description, various changes, modifications, and modifications based on the knowledge of those skilled in the art without departing from the spirit of the present invention. It should be understood that improvements can be made.

Both ends aminopolyhexamethylene terephthalate
First, a commercially available polyethylene terephthalate resin (Mitsui Pet Co., Ltd. ) was vacuum-dried at a temperature of 130 ° C. for 5 hours in order to obtain an aminopolyamide at both ends to obtain a polyalkylene terephthalate polyamide block copolymer according to the present invention. Resin Co., Ltd., J120) 160 g,
Hexamethylenediamine (manufactured by Wako Pure Chemical Industries, Ltd.) 106
g, molecular sieve (4A, manufactured by Wako Pure Chemical Industries, Ltd.)
And then purified by distillation under reduced pressure.
000 g each in a 1 L autoclave,
After pressurizing to ² kg / cm ² , the reaction was performed at 180 ° C. for 10 hours. Next, the obtained reaction solution was cooled to room temperature, a large amount of acetone was added, and the reaction product was precipitated and washed,
It was separated by filtration and collected. Thereafter, the obtained recovered product was dried under reduced pressure at 120 ° C. and 1 Torr to obtain 205 g of a white powdery reaction product.

With respect to the reaction product thus obtained, F
When T-IR, titration of terminal amine and intrinsic viscosity ([η]) were measured, [η] = 0.51 dl / g, glass transition temperature (Tg) 142 ° C., melting point (Tm) 350 ° C. It was confirmed to be polyhexamethylene terephthalamide. The measurement of the intrinsic viscosity ([η]) was performed using an Ubbelohde viscometer, using hexafluoroisopropanol as a solvent, at a temperature of 30 ° C., and measuring the glass transition temperature (Tg) and melting point (Tm). The measurement was performed using a DSC / SII6200 manufactured by Seiko Institute under a nitrogen atmosphere at a heating rate of 20 ° C./min.

Examples 1-3 Preparation of various polyethylene terephthalate polyhexamethylene terephthalamide block copolymers was attempted according to the above-mentioned production method (ii). That is, first, similarly to the above, a commercially available polyethylene terephthalate resin (manufactured by Mitsui Pet Resin Co., Ltd., J120) dried at 130 ° C. for 5 hours under vacuum and a molecular sieve (manufactured by Wako Pure Chemical Industries, Ltd., 4A) After drying in, using a sulfolane purified by distillation under reduced pressure, and both ends amine polyhexamethylene terephthalamide prepared by the method described above,
A 300 ml autoclave was charged at a rate shown in Table 1 below, pressurized to ² kg / cm ^2, and then heated to 180 ° C.
For 10 hours. Thereafter, the reaction solution was cooled to room temperature, a large amount of acetone was added, and the obtained reaction product was collected by precipitation, washing, filtration and separation. Next, the obtained recovered product was dried under reduced pressure at 120 ° C. and 1 Torr to obtain a white powdery reaction product.

The reaction product thus obtained was measured for FT-IR, intrinsic viscosity, glass transition temperature and melting point (DSC), respectively. As a result, polyethylene terephthalate and the above-mentioned both-terminal amine polyhexamethylene terephthalamide were measured. It was confirmed that it was a high molecular weight polyethylene terephthalate polyhexamethylene terephthalamide block copolymer having a clearly divided glass transition temperature (Tg) and melting point (Tm) corresponding to each of the above. For reference, the measurement results of polyethylene terephthalate and polyhexamethylene retephthalamide at both ends are also shown in Table 1 below.

[0038]

[Table 1] *: Polyhexamethylene terephthalamide at both ends

Example 4 In order to obtain a target block copolymer according to the production method (i) as described above, first, a dried polyethylene terephthalate resin (the same as that used in Example 2) was used. Mitsui Pet Resin Co., Ltd., J120) 16
g, 10.6 g of hexamethylenediamine, and 100 g of purified sulfolane were charged into a 300 ml autoclave, pressurized to ² kg / cm ² , and reacted at 180 ° C. for 10 hours.

Next, the temperature of the resulting reaction solution was lowered to room temperature, the lid of the autoclave was opened, 20.5 g of dried polyethylene terephthalate resin (J120, manufactured by Mitsui Pet Resin Co., Ltd.) was added, and the lid was closed again. , 2k
g / cm ² and reacted at 180 ° C. for 10 hours. Thereafter, the temperature of the reaction solution was lowered to room temperature, a large amount of acetone was added, and the obtained reaction product was recovered by precipitation washing, filtration and separation. Then, the obtained collected product is
The reaction product was dried under reduced pressure at 20 ° C. and 1 Torr to obtain 39.6 g of a reaction product as a white powder.

The FT-IR, intrinsic viscosity and DSC of the thus obtained reaction product were measured. The intrinsic viscosity ([η]) = 0.68 dl / g and the glass transition point (Tg) = 77. ° C and 147 ° C, melting point (Tm) = 25
It was confirmed that the copolymer was a polyethylene terephthalate polyhexamethylene terephthalamide block copolymer at 5 ° C. and 357 ° C.

One end aminopolyethylene terephthalamide
A commercially available polyethylene terephthalate resin (Mitsui Pet Resin Co., Ltd.) vacuum-dried for 5 hours at a temperature of 130 ° C. in order to obtain a polyalkylene terephthalate polyamide block copolymer which is used to obtain a polyalkylene terephthalate polyamide block copolymer intended for preparing After drying with 160 g of ethylene-diamine (manufactured by Wako Pure Chemical Industries, Ltd.) and 50 g of molecular sieve (manufactured by Wako Pure Chemical Industries, Ltd., 4A),
1000 g of sulfolane purified by distillation under reduced pressure was charged into a 1 L autoclave, pressurized to ² kg / cm ² , and reacted at 180 ° C. for 10 hours. Thereafter, the reaction solution in the autoclave was cooled to room temperature, a large amount of acetone was added, and the obtained reaction product was collected by precipitation, washed, separated by filtration, and collected. Next, the obtained recovered product was dried under reduced pressure at 120 ° C. and 1 Torr to obtain 157 g of a light yellow powdery reaction product.
I got

The reaction product thus obtained was subjected to FT-IR, titration of terminal amine, and measurement of intrinsic viscosity in the same manner as described above. [Η] = 0.61
dl / g, glass transition temperature (Tg) = 225 ° C, and it was confirmed to be a one-terminal amine polyethylene terephthalamide. Since the melting point (Tm) was higher than the decomposition temperature, measurement was impossible.

Example 5 A dried polyethylene terephthalate resin similar to that used in Examples 1 to 4 (manufactured by Mitsui Pet Resin Co., Ltd.)
J120) 15 g, the above-obtained one-terminal amine polyethylene terephthalamide 15 g and purified sulfolane 10
Each 0 g was charged into a 300 ml autoclave, pressurized to ² kg / cm ² , and reacted at 180 ° C. for 10 hours. Thereafter, the reaction solution was cooled to room temperature, a large amount of acetone was added, and the obtained reaction product was subjected to precipitation washing, filtration separation, and collection. Next, the obtained recovered product was dried under reduced pressure at 120 ° C. and 1 Torr to obtain a pale yellow powdery reaction product.

The FT-IR, intrinsic viscosity, and DSC of the reaction product thus obtained were measured. [Η] = 0.75 dl / g and the glass transition temperature (T
g) = It was confirmed that the copolymer was a polyethylene terephthalate polyethylene terephthalamide block copolymer at two places near 78 ° C and 224 ° C.

[0046]

As is apparent from the above description, according to the present invention, a high molecular weight polyalkylene terephthalate polyamide block copolymer is advantageously provided with a property based on a polyester structure and a property based on a polyamide structure. Is also provided, such a block copolymer,
It can be obtained efficiently using polyalkylene terephthalate resin as a raw material.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J001 DA03 DB05 DC03 DC13 DC14 EB37 EC04 EC05 EC06 EC07 EC08 EC09 EC13 EC14 EC16 EC29 EC44 EC45 EC46 EC47 EC48 EC55 EC56 EC65 EC66 EC67 EC69 EC70 EC75 ED05 ED07 FA01 FB03 FC03 GA12 GA13 GA15 JA01 JC01 4J029 AA03 AB01 AB04 AC03 AD01 AE01 AE11 BA03 BA05 BA09 CB06A KH01 4J031 AA49 AA55 AB04 AC07 AD01 AF10

Claims (6)

[Claims] 1. A polyalkylene terephthalate block comprising a polyalkylene terephthalate block having a repeating unit represented by the following chemical formula (1) and a polyamide block having a repeating unit represented by the following chemical formula (2): A polyalkylene terephthalate polyamide block copolymer, wherein the polyamide block and the polyamide block are linked via an amide bond. Embedded image [However, X represents an alkylene group having 2 to 20 carbon atoms, and m is an integer of 5 to 200.] [Chemical formula 2] [However, Y represents a divalent organic group comprising an aliphatic hydrocarbon having 2 to 20 carbon atoms, aromatic or alicyclic hydrocarbon, and the like, and n is an integer of 5 to 200. ] 2. The polyalkylene terephthalate polyamide block copolymer according to claim 1, wherein the polyamide block is provided by a polyamide obtained by reacting a polyalkylene terephthalate resin with a diamine compound. 3. A method for producing a polyalkylene terephthalate polyamide block copolymer according to claim 1, comprising: a polyalkylene terephthalate resin, a double-ended aminopolyamide represented by the following chemical formula 3, or a chemical formula 4 or With one-terminal aminopolyamide represented by Chemical Formula 5:
A method for producing a polyalkylene terephthalate polyamide block copolymer, characterized by reacting. Embedded image [However, Y represents a divalent organic group comprising an aliphatic hydrocarbon having 2 to 20 carbon atoms, aromatic or alicyclic hydrocarbon, and the like, and n is an integer of 5 to 200. [Formula 4] Wherein Y represents a divalent organic group comprising an aliphatic hydrocarbon having 2 to 20 carbon atoms, an aromatic or alicyclic hydrocarbon, n represents an integer of 5 to 200, and R ₁ represents a carbon atom. The number represents an alkylene group of 2 to 20. [Chemical formula 5] [However, Y represents a divalent organic group composed of an aliphatic hydrocarbon having 2 to 20 carbon atoms, aromatic or alicyclic hydrocarbon, etc., n is an integer of 5 to ₂₀₀ , and R ₂ is hydrogen. Or an alkylene group having 1 to 20 carbon atoms. ] 4. The method according to claim 1, wherein the polyalkylene terephthalate resin and the aminopolyamide at both terminals or the aminopolyamide at one terminal are formed of a hydrocarbon solvent, a halogenated hydrocarbon solvent, an ether solvent, an acetal solvent, and an aprotic hydrophobic solvent. 1 selected from the group consisting of proton polar solvents
The method for producing a polyalkylene terephthalate polyamide block copolymer according to claim 3, wherein the reaction is carried out in a reaction medium comprising one or more kinds of solvents. 5. The polyalkylene terephthalate polyamide block copolymer according to claim 3 or 4, wherein the both-terminal aminopolyamide or one-terminal aminopolyamide is formed by reacting a polyalkylene terephthalate resin with a diamine compound. Manufacturing method of coalescence. 6. The method for producing a polyalkylene terephthalate polyamide block copolymer according to claim 3, wherein the polyalkylene terephthalate resin has an intrinsic viscosity of 0.2 g / dl or more. .