JP2003096193A - Polyester elastomer and its production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester elastomer retaining excellent heat resistance and exhibiting sufficient mechanical strengths such as flexibility, elasticity- restoring properties and the like, and excellent stability to changes with time enough to retain performances such as tensile strength and the like without undergoing changes even in the case of being exposed to a high temperature environment for a long period, and to provide its production method. SOLUTION: The polyester elastomer comprises a block copolymer comprising a polyimide segment (A), which has a number-average molecular weight of 1,000-5,000, and a polyester segment (B), whose constituent gives by polymerization a polyester having a glass transition temperature of 0 deg.C or lower, and having a melting point of 180-330 deg.C and an intrinsic viscosity, as measured in a phenol/tetrachloroethane mixed solvent having a mixing ratio of 1/1 at 25 deg.C, of at least 0.6 dl/g, and is extremely excellent in long-term heat resistance and useful for various industrial materials requiring heat resistance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polyester elastomer having sufficient heat resistance and mechanical strength and hardly changing its physical properties even when exposed to high temperature for a long time, and a method for producing the same.

[0002]

2. Description of the Related Art It is well known that various thermoplastic elastomers have been proposed and put into practical use because of their ease of molding. A general polyester-based elastomer is a block copolymer having polyester and polyether as repeating units, and has excellent mechanical properties, heat resistance, and oil resistance. As described above, since the thermoplastic elastomer has excellent characteristics, it is used for industrial materials such as sheets, films and fibers, automobiles, and electric / electronic parts. However, all of these thermoplastic elastomers are easily deformed even at a temperature of less than 170 ° C. Therefore, an elastomer having further excellent heat resistance is desired. As a method for improving the heat resistance of the thermoplastic elastomer, JP-A-56-14525
In the publication, a method of crosslinking a molecular chain at the time of molding is proposed, but a material excellent in heat resistance has a drawback that it has high hardness and poor flexibility as an elastomer, and a satisfactory result has not been obtained. Therefore, various proposals have been made to solve this drawback. Japanese Unexamined Patent Publication (Kokai) No. 5-239198 proposes a method of increasing the glass transition temperature by using 2,6-naphthalenedicarboxylic acid or the like, but the thermoplastic elastomer obtained here has a temperature range of 100 ° C. or higher. It was not satisfactory to use. Further, JP-A-10-152604 proposes a composition excellent in initial flexibility and mechanical properties by using a silicone compound, but the silicone compound bleeds out with time. There was a problem. Further, JP-A-4-80229 proposes an attempt to improve the heat resistance by introducing a polyimide skeleton into the polyester elastomer having low heat resistance. However, since the copolymer disclosed in JP-A-4-80229 is insufficient in flexibility and elastic recovery performance, it is unsatisfactory, and therefore it is low in cost and has good moldability and heat resistance. Elastomers were desired.

[0003]

The object of the present invention is to maintain excellent heat resistance, to have sufficient mechanical strength such as flexibility and elastic recovery, and to maintain physical properties such as tensile strength at high temperatures for a long period of time. It is an object of the present invention to provide a polyester-based elastomer having stability with respect to changes with time such that it does not easily change even when exposed, and a method for producing the same.

[0004]

The present invention is an elastomer comprising a block copolymer of 10 to 90% by mass of a polyimide segment (A) and 90 to 10% by mass of a polyester segment (B). The number average molecular weight of A) is 1000 to 5000, the glass transition temperature of the polyester obtained by polymerizing the components constituting the polyester segment (B) is 0 ° C. or lower, and the melting point of the block copolymer is 180 to It is a polyester elastomer characterized in that the block copolymer has an intrinsic viscosity of 0.6 dl / g or more at 330 ° C. and measured in a mixed solvent of phenol / tetrachloroethane = 1/1 at 25 ° C. . Further, the present invention is the method for producing a polyester elastomer, wherein an imide bond composed of an aromatic tetracarboxylic dianhydride and a diamino compound is sequentially formed in the step of synthesizing the polyimide segment (A). Is.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The polyester elastomer of the present invention comprises a polyimide segment (A) of 10 to 90% by mass.
And a polyester segment (B) of 90 to 10% by mass. The polyimide segment (A) has the following general formula (1) or (2).
Is a polyimide oligomer residue.

[0006]

[Chemical 1]

[0007]

[Chemical 2] (In the formula, A is a tetracarboxylic acid dianhydride residue,
B is a diamine residue, preferably having 1 to 20 carbon atoms,
More preferably, it is a diamine residue having a linear alkylene group having 1 to 12 carbon atoms, and X is a residue of a compound having one ester-forming functional group and one intramolecular acid anhydride group, or tetracarboxylic acid. A residue of a compound obtained by imide-bonding one molecule of an amine compound having one ester-forming functional group to a dianhydride, Y being a compound having one ester-forming functional group and having an amino group. Is a residue of a compound obtained by binding 1 molecule of imide, and n is an integer of 1 or more, preferably an integer of 1 to 25. )

Specific examples of the residues represented by A, B, X and Y in the above chemical formula include the following. Examples of the residue represented by A in the above chemical formula include pyromellitic dianhydride residue, benzene-1,2,3,4-tetracarboxylic dianhydride residue, 2,3,3 ′, 4'-biphenyltetracarboxylic dianhydride residue, 2,2 ', 3
3'-biphenyltetracarboxylic dianhydride residue,
3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride residue, 2,3,3 ′, 4′-benzophenonetetracarboxylic dianhydride residue, 2,2 ′, 3,3 '-Benzophenone tetracarboxylic acid dianhydride residue, 3,
3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride residue, bis (3,4-dicarboxyphenyl) ether dianhydride residue, bis (3,4-dicarboxyphenyl) methane diacid Anhydrous residue, 1,1-bis (2,3
-Dicarboxyphenyl) ethane dianhydride residue, 1,
1-bis (3,4-dicarboxyphenyl) ethane dianhydride residue, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride residue, 2,2-bis (2,2 Three
-Dicarboxyphenyl) propane dianhydride residue, bis (3,4-dicarboxyphenyl) sulfone dianhydride residue, 3,4,9,10-perylenetetracarboxylic dianhydride residue, 1,2,5,6-naphthalenetetracarboxylic dianhydride residue, 2,3,6,7-naphthalenetetracarboxylic dianhydride residue, 1,2,4,5-naphthalenetetracarboxylic acid Dianhydride residue, 1,4
5,8-naphthalenetetracarboxylic acid dianhydride residue,
2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride residue, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride residue Group, 2,3,6,7-tetrachloronaphthalene-1,
4,5,8-Tetracarboxylic acid dianhydride residue, phenanthrene-1,8,9,10-tetracarboxylic acid dianhydride residue, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldicyclohexane dianhydride residue, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride residue,
2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride residue, p-phenylene bis (trimellitic acid monoester acid anhydride) residue,
1,2- (ethylene) bis (trimellitate anhydride) residue, 1,3- (trimethylene) bis (trimellitate anhydride) residue, 1,4- (tetramethylene) bis (trimellitate anhydride) residue, 1 , 6- (hexamethylene) bis (trimellitate anhydride) residue, 1,8- (octamethylene) bis (trimellitate anhydride) residue, 1,9-
(Nonamethylene) bis (trimellitate anhydride) residue,
Examples thereof include a 1,10- (decamethylene) bis (trimeritate anhydride) residue, a 1,12- (dodecamethylene) bis (trimeritate anhydride) residue, and a mixture thereof.

The residue represented by B in the above chemical formula is 1,4-phenylenediamine residue, 2,3,5,6.
-Tetramethyl-1,4-phenylenediamine residue,
1,3-diaminocyclohexane residue, 1,4-diaminocyclohexane residue, 1,4-bis (aminomethyl)
Cyclohexane residue, 4,4'-diaminodiphenylmethane residue, 4,4'-diaminodiphenylsulfone residue, 4,4'-diaminodiphenyloxide residue,
2,2'-bis (4-aminophenyl) propane residue,
Diethylene glycol (diaminopropyl) ether residue, polyoxypropylene diamine residue, ethylene oxide / propylene oxide copolymer bis (2-aminopropyl) ether residue, and further, for example, having 1 to 2 carbon atoms
Specific examples of the diamine residue having 0, preferably a linear alkylene group having 1 to 12 carbon atoms and having amino groups at both ends are 1,6-diaminohexane residue and 1,7-diaminoheptane residue. , 1,8-diaminooctane residue, 1,
Examples thereof include 9-diaminononane residue, 1,10-diaminodecane residue, 1,11-diaminoundecane residue, 1,12-diaminododecane residue, and mixtures thereof.

The residue represented by X in the above chemical formula is a 5-oxyphthalic acid residue, a trimellitic anhydride residue, or a residue of a reactive product of pyromellitic acid and an amine compound shown below ( 3) and (4) are mentioned. In addition, examples of the residue represented by Y in the above chemical formula include 2-aminoethanol residue and 3-aminopropanol residue.

[0011]

[Chemical 3]

[0012]

[Chemical 4]

In the polyimide segment (A) used in the polyester elastomer of the present invention, the reaction ratio of each component is selected so that the above constituents have a desired number average molecular weight in a polar solvent such as N-methylpyrrolidone. The reaction can be carried out, followed by heating and imidization at 150 ° C. or higher to easily synthesize. Examples of the organic solvent used at this time include N-methylpyrrolidone, dimethylacetamide, dimethylformamide, hexamethylphosphoramide, 1,3-dimethyl-3,4,5,6-tetrahydro-2 ( 1H) -pyrimidinone, 1,3-dimethyl-
2-imidazolidinone, sulfolane, dimethyl sulfoxide, γ-butyrolactone, γ-valerolactone, γ-
Caprolactone, α-acetyl-γ-butyrolactone,
ε-caprolactone, dioxane, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, glycerin, diethylene glycol monomethyl ether,
Examples include triethylene glycol monomethyl ether, tetrahydrofuran, phenol, cresol, ethyl acetate, butyl acetate, ethyl cellosolve acetate, butyl cellosolve acetate, toluene, xylene, diethylbenzene, cyclohexane, trichloroethane, tetrachloroethane, monochlorobenzene, and the like, and mixtures thereof. Considering solubility and environmental safety, it is preferable to use dioxane, tetrahydrofuran, N-methylpyrrolidone and the like, particularly N-methyl-2-pyrrolidone.

The number average molecular weight of the polyimide segment (A) thus obtained is in the range of 1,000 to 5,000, more preferably 1,000 to 4,000. When the number average molecular weight of the polyimide segment (A) is less than 1000, the performance as a hard segment cannot be exhibited, and the elastic recovery such as compression set of the obtained polyester elastomer deteriorates. On the other hand, when the number average molecular weight exceeds 5,000, the compatibility with the polyester segment (B) becomes poor, and it becomes impossible to obtain a block copolymer. The number average molecular weight can be measured by a known measuring method. The melting point of the block copolymer described below is
The melting point of the polyimide segment (A) used is slightly higher than that of 220- Three
It is desirable to set the temperature in the range of 50 ° C. Further, the terminal group of the polyimide segment (A) needs to have at least one ester-forming functional group selected from a hydroxyl group, a carboxyl group, a lower alkylcarboxylic acid ester group and the like. Among the above-mentioned polyimide segment (A) having an end group, from the viewpoint of heat resistance and economical efficiency, pyromellitic anhydride / dodecamethylenediamine /
2-aminoethanol (5), pyromellitic anhydride /
Trimellitic anhydride / decamethylenediamine (6) and the like are preferably used.

[0015]

[Chemical 5]

[0016]

[Chemical 6]

As described above, when the number average molecular weight of the polyimide segment (A) used in the polyester elastomer of the present invention is in the range of 1,000 to 5,000, the hard segment is combined with the polyester segment (B). A polyester elastomer having good compatibility and an excellent elastic recovery rate tends to be obtained.

The polyester segment (B), which is another component of the polyester elastomer of the present invention, is a polyester segment (B) having a high melting point, so that a polyester elastomer having a high melting point is easily obtained. (Oxytetramethylene)
Compared with an elastomer containing a polyether compound such as glycol, it is characterized by excellent heat resistance without lowering its elastic performance. As such a polyester segment (B), a substantially non-crystalline material composed of an aromatic dicarboxylic acid such as phthalic acid or isophthalic acid and an α, ω-alkylene diol having 4 to 12 carbon atoms and / or triethylene glycol is used. What can form the polyester of is preferable. When low temperature characteristics are particularly required, the polyester segment (B) has 6 to 2 carbon atoms.
An aliphatic polyester segment composed of an aliphatic dicarboxylic acid having 0 and an aliphatic diol having 2 to 12 carbon atoms or an aliphatic lactone is preferably used.

The melt polymerization method of the polyester segment (B) used in the polyester elastomer of the present invention is a generally known method, and the dicarboxylic acid or its lower alkyl ester and the diol are added in the presence of a catalyst. Alternatively, a reaction to obtain a bisdiol ester of dicarboxylic acid or its initial polycondensation reaction product by an esterification reaction or a transesterification reaction in the absence (first-stage reaction)
Then, a polycondensation reaction is performed under reduced pressure or under an inert gas stream to obtain a high-polymerization reaction product (second-stage reaction).

The polyester segment (B) thus obtained needs to have a glass transition temperature of 0 ° C. or lower when it is used as the sole polyester. When this glass transition temperature is higher than 0 ° C, the flexibility of the obtained polyester elastomer is insufficient. As described above, since the glass transition temperature of the polyester segment (B) used in the polyester elastomer of the present invention is 0 ° C. or lower, the flexibility and elastic recovery of the finally obtained polyester elastomer are Are better.

The polyester elastomer of the present invention is
It is a block copolymer composed of the above-mentioned polyimide segment (A) and polyester segment (B), and the amount ratio thereof can be arbitrarily selected depending on the elastic properties required for the obtained polyester elastomer, Usually, the polyimide segment (A) / polyester segment (B) (mass ratio) is 90/10 to 10/9.
0 is desirable, and more preferably 15 / 85-6
It is 0/40. When the proportion of the polyimide segment (A) is out of this range, both flexibility and heat resistance are achieved,
The effects of the present invention such as having sufficient mechanical properties tend to decrease.

To produce the polyester elastomer of the present invention, for example, the polyimide segment (A) is added at a stage before the polycondensation reaction of the ester-forming component constituting the polyester segment (B) is completed, Then, the block copolymer obtained is further polymerized until the intrinsic viscosity reaches a desired viscosity. Hereinafter, the case of producing a polyester by a melt polymerization method which is a general production method will be described as an example. In the present invention, when the ester-forming component constituting the polyester segment (B) is melt-polymerized according to the above, it may be before the completion of the melt-polymerization reaction, preferably after the completion of the esterification reaction or the transesterification reaction. Easily obtained by adding the polyimide segment (A) at the stage before the intrinsic viscosity measured at 25 ° C. in a mixed solvent of phenol / tetrachloroethane = 1/1 reaches 0.2 dl / g and further performing melt polymerization reaction. To be The polyimide segment (A) may exist from the initial stage of melt polymerization of the ester-forming component constituting the polyester segment (B), but if the polyimide segment (A) is added too late, block copolymerization will occur. Does not progress, and the polyimide segment (A) is merely dispersed in the polymer, or the intrinsic viscosity does not tend to rise to a desired value.

Further, the copolymerization reaction in the present invention needs to be carried out under the condition that the polyimide segment (A) is melted.
Composition, degree of polymerization, and ratio with the polyester segment (B). Usually, the reaction temperature is raised, and the reaction is carried out at a temperature at which the reaction system becomes uniform. However, if necessary, an inert medium may be added and the reaction may be carried out in a solution state. When the solubility is not improved even by these methods, it is considered that the compatibility between the polyimide segment (A) and the polyester segment (B) is insufficient, and in this case, the polyimide segment (A It is desirable to lower the molecular weight of (1) or change the constituents of the polyimide segment (A) or the polyester segment (B).

The polyester elastomer of the present invention thus produced has a melting point of 180 to 330 ° C, more preferably 200 to 310 ° C, and particularly preferably 250 to 310 ° C. When the melting point of the polyester elastomer is less than 180 ° C, the heat resistance is poor,
If it exceeds 330 ° C., it tends to be difficult to obtain a high molecular weight block copolymer, and molding tends to be difficult. In addition, the intrinsic viscosity of the block copolymer measured in a mixed solvent of phenol / tetrachloroethane = 1/1 at 25 ° C. is 0.6d.
It is necessary to be 1 / g or more, and more preferably 0.65 dl / g or more. It has an intrinsic viscosity of 0.6 dl / g under the above-mentioned conditions.
If it is less than the above range, mechanical properties (tensile strength, etc.) of the finally obtained molded product, elastic recovery performance, etc. are not preferable.

As described above, when the melting point of the block copolymer composed of the polyimide segment (A) and the polyester segment (B) is 180 to 330 ° C., the heat resistance and the molecular weight of the block copolymer are high. Good in terms of productivity, phenol / tetrachloroethane = 1
When the block copolymer has an intrinsic viscosity of 0.6 dl / g or more measured in a mixed solvent of 25 ° C., a molded product excellent in mechanical properties (tensile strength, etc.) and elastic recovery performance is obtained. Obtainable.

The polyester elastomer of the present invention thus obtained is used alone or by adding various additives as necessary. Additives that can be added include inorganic particles such as silica, talc, kaolin or calcium carbonate; pigments such as titanium oxide and carbon black; other dyes, ultraviolet absorbers, weather resistance stabilizers, lubricants, release agents, and heat. Examples thereof include stabilizers, antioxidants, antistatic agents, flame retardants and the like.

The polyester elastomer of the present invention produced by the above method is molded into a container by injection molding, a sheet or the like by extrusion molding, or a container or the like by blow molding. The molded product thus obtained may be subjected to various conventionally known processing treatments in order to impart more specific performance. Examples of processing include ultraviolet rays, α rays, β
Irradiation with rays, γ rays, electron rays, etc .; treatment with corona treatment, plasma irradiation treatment, flame treatment, etc .; application of resin such as vinylidene chloride, polyvinyl alcohol, polyamide or polyolefin; deposition of metal or laminate, etc. . Further, the polyester elastomer of the present invention can be mixed with a thermoplastic resin as a resin modifier. As the mixing means, various known methods can be used, for example, a method of mixing with a double cone blender, a ribbon blender, etc., and both resins mixed by such a method are a single-screw extruder and a twin-screw extruder. Alternatively, a method of melt-kneading and granulating with an extruder with a vent can be adopted.

[0028]

EXAMPLES The present invention will be described in detail below with reference to examples. The mass% of the polyimide segment (A) in the examples is
The content ratio of the portion excluding the ester-forming group at both ends is shown, and "part" means "part by mass". The number average molecular weight was measured as follows. As a method for measuring the melting point and the heat of fusion, a differential scanning calorimeter (SEIKO INSTRU
MENTS INC. DSC220C),
The measurement was performed in a nitrogen atmosphere at a temperature rising rate of 20 ° C./min, and the peak temperature of the endothermic peak was taken as the melting point. The heat of fusion was calculated from the peak area. As a method for measuring the number average molecular weight, a polyimide oligomer is produced, heated to 160 ° C. in a sealed tube with about 1.5 times the theoretical amount of acetic anhydride in N-methylpyrrolidone, taken out after 30 minutes and cooled. The whole amount was put into distilled water, boiled for 30 minutes, cooled, and titrated to determine the amount of acid. On the other hand, the titration value of a blank that did not contain a polyimide oligomer and was treated in the same manner was determined, and the terminal OH group of the polyimide segment was determined from the difference. The number average molecular weight was calculated assuming that all terminals of the polyimide segment were OH. The polyester elastomer obtained is dried under reduced pressure at 120 ° C. for 5 hours to 320 ° C.
Then, an ASTM D-638 type 1 test piece (hereinafter referred to as a test piece) was obtained by injection molding. For each test piece, Shore A hardness, compression set, heat resistance, mechanical strength, and temporal change evaluation were performed as follows. Shore A hardness is AST
The measurement was performed according to M-K7215 (there is no unit). However, the thickness of 6.4m is obtained by stacking the above two test pieces.
m and measured at 23 ° C. The compression set is JI
It was measured according to SK 6301. However, the above test piece was cut into 13 mm × 13 mm pieces, four sheets were stacked and the initial thickness was accurately measured, and the test conditions were 120 ° C. and 72 hours. After the test, the film was allowed to cool at 23 ° C. for 30 minutes and then the thickness after the test was measured. Regarding heat resistance, JIS K
The Vicat softening temperature measurement test of 7206 was used to measure and evaluate the softening temperature. However, the load was set to 1.5 N, and the above test piece was cut into 10 mm × 10 mm for measurement. The chemical resistance was evaluated by visually observing a change in the appearance of a molded plate surface rubbed with acetone at 23 [° C.]. The appearance and the change in tensile strength with time were evaluated by observing the appearance change such as bleed-out for the sample in which the molded product was left in an environment of 50 [° C] for 120 [hours] and then allowed to stand at 23 [° C] for 24 hours. Visual observation and ASTM
The tensile strength was measured according to D-638. The tensile strength was measured by setting the initial value of the tensile strength to X ₁ , the value after the above 50 [° C] aging test to X _2, and the retention rate Y according to the following formula.
[%] Was calculated. Y = X ₂ / X ₁ x100: Y ≧ 90 is ◯, 90> Y ≧ 80 is Δ, 80> Y
Was designated as X.

Production Example 1 Production of Polyimide Segment (A-1) 1,1 in a reaction vessel under a nitrogen atmosphere in a vessel equipped with a stirrer.
2-dodecamethylenediamine 15.0 parts to 100 parts N
-Methylpyrrolidone (hereinafter referred to as NMP) dissolved in
32.7 parts of pyromellitic dianhydride to 400 parts of NM
The solution dissolved in P was added dropwise over 10 minutes while stirring at room temperature. After gradually raising the reaction temperature and reacting at 80 ° C. for 60 minutes, 500 parts were sampled (S-11).
27.8 parts of 1,12-dodecamethylenediamine was added to 100
(S-11) was added dropwise to 10 parts of the solution dissolved in NMP at room temperature with stirring for 10 minutes, and then reacted at 80 ° C. for 60 minutes to sample 600 parts (S-12). 28.8 parts of pyromellitic dianhydride dissolved in 400 parts of NMP was added to (S-12) at room temperature with stirring.
After dripping for 10 minutes, react for 60 minutes at 80 ℃, 100
0 part was sampled (S-13). Then 1,12
-25.7 parts of dodecamethylenediamine to 200 parts of NM
(S-13) was added dropwise to the one dissolved in P at room temperature with stirring for 10 minutes, and then reacted at 80 ° C. for 60 minutes to give 1
200 parts were sampled (S-14). Furthermore, 27.6 parts of pyromellitic dianhydride were added to 200 parts of NMP.
(S-14) dissolved in 1 while stirring at room temperature
After dropping in 0 minutes, the mixture was reacted at 80 ° C. for 60 minutes, and then 7.7 parts of 2-aminoethanol was added. The reaction temperature was raised to 180 ° C., and a small amount of nitrogen was passed through to remove the water and a part of the solvent, and the reaction was continued for 3 hours. Slurry) was added. The obtained precipitate was filtered off, thoroughly washed with acetone, and dried at 150 ° C. The obtained polyimide segment (A-1) was 132 parts (number average molecular weight 123
0), using a differential scanning calorimeter in a nitrogen atmosphere at 20 ° C.
The melting point (peak temperature of endothermic peak) measured at a heating rate of 1 / min was 299 ° C.

Production Example 2 Production of Polyimide Segment (A-2) In the same manner as in Production Example 1, 8.7 parts of 1,6-hexamethylenediamine was dissolved in 100 parts of NMP to prepare pyromellitic acid. 32.7 parts of dianhydride was dissolved in 400 parts of NMP and added dropwise over 10 minutes while stirring at room temperature. After gradually raising the reaction temperature and reacting at 80 ° C. for 60 minutes, 500 parts were sampled (S-21). Diethylene glycol (diaminopropyl) ether 30.
5 parts dissolved in 100 parts NMP (S-21)
Was added dropwise with stirring at room temperature for 10 minutes, and then reacted at 80 ° C. for 60 minutes to sample 600 parts (S-
22). Add 28.8 parts of pyromellitic dianhydride to 400
(S-22) was added dropwise to 10 parts of NMP dissolved in 10 parts of NMP with stirring at room temperature, and then reacted at 80 ° C. for 60 minutes to sample 1000 parts (S-23). Next, 14.9 parts of 1,6-hexamethylenediamine was added to 20 parts.
(S-23) was added dropwise to 0 parts of NMP while stirring at room temperature for 10 minutes, and then reacted at 80 ° C. for 60 minutes to sample 1200 parts (S-24).
Furthermore, 27.6 parts of pyromellitic dianhydride was added to 200
(S-24) was added dropwise to 10 parts of NMP dissolved in 10 parts of NMP at room temperature with stirring for 10 minutes, and then reacted at 80 ° C. for 60 minutes, and then 7.7 parts of 2-aminoethanol was added. The reaction temperature was raised to 180 ° C., and a small amount of nitrogen was passed through to remove the water and a part of the solvent, and the reaction was continued for 3 hours. Slurry) was added. The precipitate obtained is filtered off,
After thoroughly washing with acetone, it was dried at 150 ° C. The obtained polyimide segment (A-2) was 121 parts (number average molecular weight 1100), and the melting point measured under a temperature rising rate of 20 ° C./min in a nitrogen atmosphere using a differential scanning calorimeter was broad. Was 290 ° C.

[Production Example 3] Production of polyimide segment (A-3) 23.6 parts of 1,6-hexamethylenediamine, diethylene glycol (diaminopropyl) ether 30.5
Parts, 89.1 parts pyromellitic dianhydride, and 2-
A polyimide segment was obtained in the same manner as in Production Example 3 with 7.7 parts of aminoethanol. Polyimide segment having no clear melting point (A-3: number average molecular weight of about 130
8) was obtained. [Production Example 4] Production of polyimide segment (A-4) 1400 parts of 1,12-dodecamethylenediamine 68.5 parts, pyromellitic dianhydride 89.1 parts and 2-aminoethanol 15.4 parts. Dissolved in NMP of 8
After reacting at 0 ° C for 60 minutes, the temperature is raised to 18
After the temperature was set to 0 ° C. and a small amount of nitrogen was passed through to remove the water produced together with a part of the solvent, the reaction was performed for 3 hours, and then the reaction product in the form of a slurry was added to about 5 times the amount of acetone.
The precipitate obtained is filtered off and washed thoroughly with acetone, then 150
It was dried at ° C. 95.4 parts of a polyimide segment (A-4: number average molecular weight of about 600) having four peaks at a melting point of 240 to 296 ° C. was obtained.

Example 1 In a reactor equipped with a stirrer capable of high vacuum, 204.7 parts of dimethyl isophthalate and 1,10-
Decanediol 161.8 parts and ethylene glycol 2
0.6 part was charged together with 0.20 part of the catalyst tetrabutyl titanate, and transesterification was carried out while distilling off the methanol produced by heating. After the theoretical amount of methanol (about 64 g) was distilled off, 100 parts of the above polyimide segment (A-1) was added, and the pressure was adjusted to 30 at atmospheric pressure under a nitrogen atmosphere.
The reaction was carried out at 0 ° C. for 30 minutes, and then the temperature was gradually raised, and at the same time, the pressure was reduced to 300 ° C. and 0.2 mmHg to carry out a polycondensation reaction. After reacting for 50 minutes after the start of depressurization, the reaction product was taken out. The intrinsic viscosity of the obtained copolymer in a phenol / tetrachloroethane = 1/1 mixed solvent at 25 ° C. was 0.92, and the melting points measured by a differential scanning calorimeter were 260 ° C. and 290 ° C. (2 peaks). , Heat of fusion 4.0 J / g, heat of crystallization during cooling is 6.0 J / g
Met. In addition, this copolymer was decomposed with methanol to release the glycol component, and the ratio was measured by gas chromatography. The copolymerization ratio (molar ratio)
Is 1,10-decanediol / ethylene glycol =
It was 88/12. When a glass transition temperature was measured by separately synthesizing a polyester composed of glycol and isophthalic acid in this copolymerization ratio, it was -12.9 ° C. The content of the polyimide segment was 25% by weight. The obtained polyester-based elastomer was heated at 80 ° C. for 5
After vacuum drying for an hour, each test sample was injection molded at 290 ° C. For each sample, Shore A hardness, heat resistance,
Each test and evaluation of chemical resistance and change with time were performed. Example 2 As a polyimide segment, (A-1)
Polymerization was performed in the same manner as in Example 1 except that (A-2) was used instead of to obtain a polyester elastomer having an intrinsic viscosity of 1.05. This polyester elastomer had an endothermic peak at 275 ° C. by a differential scanning calorimeter. The heat of fusion was 3.5 J / g, and the heat of crystallization during cooling was 5.0 J / g. The obtained polyester elastomer was evaluated in the same manner as in Example 1.

[Comparative Example 1] As a polyimide segment, (A-3) was used instead of (A-1).
Polymerization was performed in the same manner as in Example 1 to obtain a polyester elastomer having an intrinsic viscosity of 0.85. No endothermic peak was observed with a differential scanning calorimeter for this polyester elastomer. The obtained polyester elastomer was evaluated in the same manner as in Example 1. [Comparative Example 2] As a polyimide segment, (A-1)
Polymerization was performed in the same manner as in Example 1 except that (A-4) was used instead of to obtain a polyester elastomer having an intrinsic viscosity of 0.88. This polyester elastomer has an endothermic curve of 260 ° C. to 290 ° C. measured by a differential scanning calorimeter.
Had four endothermic peaks. Furthermore, the heat of fusion was 9.7 J / g, and the heat of crystallization during cooling was 6.6 J / g. The obtained polyester elastomer was evaluated in the same manner as in Example 1. [Comparative Example 3] 271.6 parts of dimethyl isophthalate,
The intrinsic viscosity was adjusted to 0.1 in the same manner as in Example 1 except that 99.2 parts of 1,4-butanediol, 29.2 parts of ethylene glycol, and 0.21 part of catalyst tetrabutyl titanate were charged.
71 polyester elastomers were obtained. This polyester elastomer had an endothermic peak at 290 ° C. by a differential scanning calorimeter. Furthermore, the heat of fusion is 4.
The amount of heat of crystallization at the time of cooling was 0 J / g and 6.0 J / g.
Moreover, when this copolymer was decomposed with methanol to release the glycol component, and the ratio thereof was measured by gas chromatography, the copolymerization ratio (molar ratio) was 1,4-
Butanediol / ethylene glycol = 80/20. A polyester composed of glycol and isophthalic acid in this copolymerization ratio was separately synthesized and the glass transition temperature was measured to be 6.5 ° C. The content of the polyimide segment was 25% by weight. The obtained polyester elastomer was evaluated in the same manner as in Example 1.

[0034]

[Table 1]

As shown in Table 1, it can be seen that in Comparative Example 1, the polyimide segment has no clear melting point and thus has insufficient heat resistance. Further, in Comparative Example 2, since the molecular weight of the polyimide segment is low and the cohesive force as a hard segment is insufficient, not only heat resistance cannot be obtained, but also deterioration with time and solvent resistance are affected. further,
In Comparative Example 3, since the glass transition temperature of the polyester segment exceeds 0 ° C., it is found that the flexibility is insufficient. On the other hand, it is apparent that the polyester elastomer of the present invention exhibits excellent flexibility and heat resistance.

[0036]

EFFECT OF THE INVENTION The polyester elastomer of the present invention is thermoplastic and can be molded in the same manner as a usual thermoplastic resin, and has the advantage of maintaining its shape even at a high temperature of over 200 ° C. When a polyester segment composed of an aromatic dicarboxylic acid such as isophthalic acid and a long-chain diol is used as the polyester segment, compared to polyurethane and polyether ester, which have good durability at relatively high temperatures among thermoplastic elastomers. Also,
A sheet that has properties such as extremely excellent long-term heat resistance, is used for electrical and electronic applications, automobile parts, and requires heat resistance,
It is useful for various industrial materials such as films, tubes and packings. Further, according to the production method of the present invention, it is possible to use the conventionally used melt polymerization apparatus for polyester as it is, and since it can be produced almost in the same manner as the polymerization of polyester, there is an advantage that facility cost is not required. Is.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Masaharu Fujimoto             20-1 Miyuki-cho, Otake-shi, Hiroshima Mitsubishi Rayo             Central Technology Research Institute F-term (reference) 4J031 AA49 AA57 AB04 AC03 AD01                       AF10 AF14 AF19 AF23

Claims (2)

[Claims] 1. Polyimide segment (A) 10-90
An elastomer comprising a block copolymer of 90% by mass and 90% by mass of a polyester segment (B), wherein the number average molecular weight of the polyimide segment (A) is 1000.
The glass transition temperature of the polyester obtained by polymerizing the components constituting the polyester segment (B) is 0 ° C. or lower, the melting point of the block copolymer is 180 to 330 ° C., and phenol / A polyester elastomer, wherein the intrinsic viscosity of the block copolymer measured in a mixed solvent of tetrachloroethane = 1/1 at 25 ° C. is 0.6 dl / g or more. 2. The polyester system according to claim 1, wherein an imide bond composed of an aromatic tetracarboxylic dianhydride and a diamino compound is sequentially formed in the step of synthesizing the polyimide segment (A). Method for producing elastomer.