JP2005060645A - Polyester-based block copolymer and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ester-ester-based block copolymer excellent in flexibility and thermal aging resistance, and exhibiting stable mechanical characteristics in a wide temperature region, and a method for producing the same. <P>SOLUTION: This ester-ester-based block copolymer excellent in long term thermal aging resistance and high temperature characteristics comprises an aromatic polyester having a specified molecular weight and terminal OH value, which is derived from an aromatic dicarboxylic acid mainly comprising terephthalic acid or its ester-forming derivative and a diol mainly comprising an alkylene glycol, and an aliphatic polyester having a specified molecular weight and terminal OH value, which is derived from a dicarboxylic acid mainly comprising a dimer acid and a diol mainly comprising an alkylene glycol. A method for producing the block copolymer is also provided. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a polyester elastomer having a block structure. More specifically, the present invention relates to an ester-ester block copolymer in which a hard segment is an aromatic polyester and a soft segment is an aliphatic polyester.

Thermoplastic elastomers have been used in recent years due to their good moldability. Among them, elastomers mainly composed of terephthalic acid, butanediol, and polytetramethylene glycol, which are known as polyester elastomers, are heat and cold resistant. It is used for various purposes by taking advantage of such features. However, since this resin contains an ether bond, there is a problem in long-term heat aging resistance, light deterioration resistance, and the like. As a resin that has improved these drawbacks, a copolyester has been proposed in which the composition of the soft segment contains dimer acid as the main component and butanediol as the main glycol component (see, for example, Patent Document 1). However, the above copolyester has a short soft segment molecular length and therefore gives sufficient flexibility, and since it is a random copolymer, it has a low melting point and is not necessarily sufficient in terms of physical properties in a high temperature region. Further, when dimer acid is used for the soft segment, a block copolymer having a long soft segment chain length has been proposed as means for improving physical properties in a high temperature region (see, for example, Patent Document 2). However, in this method, since the soft segment and the hard segment are not sufficiently compatible, a copolyester having two tanδ can be obtained. For this reason, when used as a molded product, the elastic modulus changes in the room temperature region, and it cannot be said that the performance as an elastomer is sufficiently satisfied.
Japanese Patent No. 3110168 (2nd page) International Publication No. 02/02667 Pamphlet (Page 3-4)

  An object of the present invention is an ester-ester copolymer, a high melting point polymer, exhibiting stable mechanical properties in a wide temperature range, and excellent in flexibility, hydrolysis resistance, and heat aging resistance. An ester-ester block copolymer and a method for producing the same are provided.

  Aromatic polyesters derived from terephthalic acid based on terephthalic acid having a specific molecular weight and terminal OH number, or ester-forming derivatives thereof and diols based on alkylene glycol, and specific molecular weight and terminal OH number By using an aliphatic polyester derived from a dicarboxylic acid containing dimer acid as a main component and a diol containing alkylene glycol as a main component, an ester-ester block copolymer having a block structure is obtained. The present invention will be described in more detail below.

  According to the present invention, it is possible to provide an ester-ester block copolymer having a block structure while being an ester-ester copolymer and having excellent physical properties in a high temperature region, and a method for producing the same. The ester-ester block copolymer of the present invention exhibits stable mechanical properties in a wide temperature range, and is excellent in flexibility and heat aging resistance.

  The dicarboxylic acid constituting the aliphatic polyester in the present invention is a fatty acid exemplified by dimer acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, cyclohexanedicarboxylic acid, tetrahydrophthalic anhydride, etc. Dicarboxylic acid, particularly preferably dimer acid.

  The alkylene glycol constituting the aliphatic polyester in the present invention is ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, 1,2-butylene glycol, 1,3- Butylene glycol, 2,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1, 4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, 1,10-decamethylene glycol, 1,12 dodecanedio Le, polyethylene glycol, polytrimethylene glycol, an aliphatic glycol as exemplified such as polytetramethylene glycol, particularly preferably 1,4-butylene glycol. As an aliphatic polyester obtained from a polycondensation reaction between an aliphatic dimer acid and 1,4-butylene glycol, there is a commercial product, PRIPLAST-3195, manufactured by Unikema International. As the aliphatic polyester, two or more types of aliphatic dicarboxylic acids may be copolymerized. A mixture of two or more aliphatic polyesters composed of these alkylene glycols may be used. Furthermore, you may use said aliphatic dicarboxylic acid and alkylene glycol separately as an aliphatic polyester component.

  The aromatic dicarboxylic acid constituting the aromatic polyester in the present invention is orthophthalic acid, isophthalic acid, terephthalic acid, 5- (alkali metal) sulfoisophthalic acid, diphenic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalene. Dicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-biphenylsulfonedicarboxylic acid, 4,4 ′ -Biphenyl ether dicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid, aromatic dicarboxylic acid exemplified by pamoic acid, anthracene dicarboxylic acid and the like, and ester-forming derivatives thereof, particularly preferably terephthal Acids or their ester-forming derivatives .

  The alkylene glycol constituting the aromatic polyester in the present invention includes ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, 1,2-butylene glycol, and 1,3-butylene. Glycol, 2,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4 -Cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, 1,10-decamethylene glycol, 1,12 dodecanedi Lumpur, polyethylene glycol, polytrimethylene glycol, an aliphatic glycol as exemplified such as polytetramethylene glycol, particularly preferably 1,4-butylene glycol.

  In the composition of the present invention, known catalysts, stabilizers, modifiers or additives may be used in the polymerization, esterification reaction or transesterification reaction. As the transesterification catalyst, titanium compounds such as tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-tert-butyl titanate, tetracyclohexyl titanate, tetraphenyl titanate, titanium oxalate A magnesium compound, a calcium compound, a zinc compound, a manganese compound, etc. can also be used. Polymerization catalysts include antimony compounds such as antimony trioxide, antimony pentoxide, antimony acetate, and antimony glycoloxide, and titanium compounds such as tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, and tetraisobutyl titanate. , Tetra-tert-butyl titanate, tetracyclohexyl titanate, tetraphenyl titanate, titanium oxalate, etc., germanium compounds as germanium dioxide, germanium tetrachloride, etc., tin compounds as dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethyl Ditin oxide, triethyltin hydroxide, monobutylhydroxytin oxide, triisobutyltin adduct, di E Nils dilaurate, monobutyltin trichloride, dibutyltin sulfide, dibutyl hydroxy tin oxide, methyl Stan non acid, such as ethyl Stan non acid. 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-dicyclohexyl-4-methylphenol, 2 as antioxidant and heat stabilizer , 6-Diisopropyl-4-ethylphenol, 2,6-di-tert-amyl-4-methylphenol, 2,6-di-tert-octyl-4-n-propylphenol, 2,6-dicyclohexyl-4- n-octylphenol, 2-isopropyl-4-methyl-6-tert-butylphenol, 2-tert-butyl-2-ethyl-6-tert-octylphenol, 2-isobutyl-4-ethyl-6-tert-hexylphenol, 2 -Cyclohexyl-4-n-butyl-6-isopropylphenol, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butyl Phenyl) butane, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6 -Hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thiodiethylenebis [3- (3,5-di-tert-butyl-4, 4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 1,3,5-tris (2,6-dimethyl-3- Hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris [(3,5 -Di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tris (4-tert-butyl-2,6-dimethyl-3-hydroxybenzyl) isocyanurate, 2,4-bis (n-octylthio) ) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5-triazine, tetrakis [methylene (3,5-di-tert-butyl-4- Droxy) hydrocinnamate] methane, bis [(3,3-bis (3-tert-butyl-4-hydroxyphenyl) butyric acid) glycol ester, N, N′-bis [3- (3,5-di -tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 2,2′-ogizamide bis [ethyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert- Butyl-4-methyl-6- (3-tert-butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 1,3,5-trimethyl-2,4,6-tris (3,5-di- tert-butyl-4-hydroxybenzyl) benzene, 3,9-bis [1,1-dimethyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2 , 4,8,10-Tetraoxaspiro [5,5] undecane, 2,2-bis [4- (2- (3,5-di-tert-butyl-4-hydroxycinnamoyloxy)) ethoxy Phenyl] propane, β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid alkyl ester, tetrakis- [methyl-3- (3 ′, 5′-di-tert-butyl-4-hydroxy) Phenyl) propionate] methane, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) ) Butane, thiodiethylene-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-) m-tolyl) propionate], hexamethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, triethylene glycol-bis-[-3- (3'-tert-butyl-4 -Hydroxy-5-methylphenyl)] propionate, 1,1,3-tris [2-methyl-4- [3- (3,5-di-tert-butyl-4-hydroxyl) Nyl) propionyloxy] -5-tert-butylphenyl] butane, dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl benzylphosphonate, diethyl benzylphosphonate, diphenylphosphine Acid, methyl diphenylphosphinate, phenyl diphenylphosphinate, phenylphosphinic acid, methyl phenylphosphinate, phenylphenylphosphinate, diphenylphosphine oxide, methyldiphenylphosphine oxide, triphenylphosphine oxide, p-hydroxyphenylphosphonic acid, p-hydroxy Dimethyl phenylphosphonate, diethyl p-hydroxyphenylphosphonate, p-hydroxyphenylphosphone Diphenyl, bis (p-hydroxyphenyl) phosphinic acid, methyl bis (p-hydroxyphenyl) phosphinate, phenyl bis (p-hydroxyphenyl) phosphinate, p-hydroxyphenylphenylphosphinic acid, methyl p-hydroxyphenylphenylphosphinate , P-hydroxyphenylphenylphosphinic acid phenyl, p-hydroxyphenylphosphinic acid, methyl p-hydroxyphenylphosphinate, phenyl p-hydroxyphenylphosphinate, bis (p-hydroxyphenyl) phosphine oxide, tris (p-hydroxyphenyl) Examples include phosphine oxide and bis (p-hydroxyphenyl) methylphosphine oxide.

  In the block copolymer of the present invention, the aromatic polyester component is 10 to 70 parts by weight, the aliphatic polyester component is 30 to 90 parts by weight, preferably the aromatic polyester component is 20 to 50 parts by weight, and the aliphatic polyester component is It is important that the amount is 50 to 80 parts by weight. If the aliphatic polyester component is less than this, since the soft segment and the hard segment are not sufficiently compatible, a copolymer polyester showing two tan δ can be obtained. For this reason, when used as a molded product, the elastic modulus changes in the room temperature region, and it cannot be said that the performance as an elastomer is sufficiently satisfied. Further, if the aliphatic polyester component is more than this, it becomes an amorphous viscous body having no deformation recovery property, and cannot be said to be an elastomer.

  It is important that the aromatic polyester in the present invention has a number average molecular weight of 5000 to 30000. When the number average molecular weight is 5000 or less, when a transesterification reaction occurs between the aromatic polyester and the aliphatic polyester, the copolymer tends to be a random copolymer and the melting point is lowered, resulting in poor high temperature characteristics. In addition, when the number average molecular weight is 30000 or more, since the soft segment and the hard segment are not sufficiently compatible, the resulting copolymer undergoes a change in elastic modulus in the room temperature region when used as a molded product, It cannot be said that the performance as an elastomer is sufficiently satisfied.

It is important that the aromatic polyester in the present invention has an OH value of 300 eq / 10 ⁶ g or less. When the OH value is larger than 300 eq / 10 ⁶ g, randomization easily occurs between the aromatic polyester and the aliphatic polyester, the melting point is lowered, and the high temperature property of the copolymer is deteriorated.

  It is important that the aliphatic polyester in the present invention has a number average molecular weight of 2000 to 15000. When the number average molecular weight is 2000 or less, when a transesterification reaction occurs between the aromatic polyester and the aliphatic polyester, the copolymer tends to be a random copolymer and the melting point is lowered, resulting in poor high temperature characteristics. In addition, when the number average molecular weight is 15000 or more, the soft segment and the hard segment are not sufficiently compatible, so that the obtained copolymer undergoes a change in elastic modulus in the room temperature region when used as a molded product, It cannot be said that the performance as an elastomer is sufficiently satisfied.

Further, it is important that the aliphatic polyester in the present invention has an OH value of 1000 eq / 10 ⁶ g or less. When the OH value is larger than 1000 eq / 10 ⁶ g, randomization is likely to occur between the aromatic polyester and the aliphatic polyester, the melting point is lowered, and the high temperature characteristics of the copolymer are deteriorated.

  In producing the block copolymer in the present invention, it is preferable to add the aliphatic polyester to the molten aromatic polyester, and then proceed to a pressure reduction operation after stirring. When the solid aromatic polyester is added to the aliphatic polyester and then the operation is reduced, the soft segment and the hard segment are not sufficiently compatible. Therefore, the obtained copolymer is used in a room temperature region when used as a molded product. A change in elastic modulus occurs, and it cannot be said that the performance as an elastomer is sufficiently satisfied. The aliphatic polyester is preferably used after being heated within a temperature range in which the aliphatic polyester is not denatured.

In producing the block copolymer in the present invention, the aliphatic polyester component is added to the aromatic polyester during the addition time represented by the mathematical formula (1), and the number of stirring rotations is preferably 50 to 500 rpm. .
3.85Ln (x) +0.67>y> 1.29Ln (x) -4.73 (y> 0) (1)
(Where X is the weight (g) of the block copolymer, and y is the time (minutes) required to add the aliphatic polyester component.)
When the addition time of the aliphatic polyester component is not less than the range limited by the mathematical formula (1) or the stirring rotation speed at the time of addition is 500 rpm or more, randomization easily occurs between the aromatic polyester and the aliphatic polyester, and the melting point is The high temperature properties of the falling copolymer are poor. In addition, when the addition time of the aliphatic polyester component is less than the range limited by the formula (1) or the stirring rotation speed at the time of addition is 50 rpm or less, the soft segment and the hard segment are not sufficiently compatible, When used as a molded product, the elastic modulus changes in the room temperature region, and it cannot be said that the performance as an elastomer is sufficiently satisfied.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention does not receive any limitation by this. Various characteristics in the examples were determined as follows.
Reduced viscosity (ηsp / c): The polymer was dissolved at a concentration of 0.1 / 0.25 (g / dl) using a 6/4 (weight ratio) mixed solution of phenol / 1,1,2,2-tetrachloroethane, and the temperature Measure at 30 ° C.
Number average molecular weight (Mn): The number average molecular weight (Mn) is calculated according to the following formula using the value of reduced viscosity. ηsp / c = 1.019 × 10 ⁻⁴ × Mn ^0.8929 −0.0167 (see J.Apply.Polym.Sci.22 2119 (1978))
Acid value (Av): A sample is pulverized and dried under reduced pressure at 120 ° C. for 12 hours or more. About 0.1 g of sample is accurately weighed and 10 ml of benzyl alcohol is added. Boil at reflux to dissolve. After dissolution, add 10 ml of chloroform and allow to cool to room temperature. Titrate with N / 10-NaOH using phenolphthalein as an indicator. Do the same for the blank without the sample. Av (eq / ton) is calculated according to the following equation. Av = (A−B) × 0.1 × f × 1000 / W (A = drop constant (ml), B = blank titer (ml), f = factor of NaOH, W = weight of sample (g ))
OH value (OHv): Calculate the total number of terminals (N) per ton of polymer from the number average molecular weight, and calculate OHv (eq / t) according to the following formula. OHv (eq / ton) = N−Av
Melting point: The temperature was measured at 20 ° C./min using a differential scanning calorimeter (TA Instruments) and determined from the peak of the endothermic peak corresponding to the melting point of the crystal.
tanδ: Sample of 15 mm long, 5 mm wide and 0.2 mm thick molded into a film using a dynamic viscoelasticity meter (UBM Rheogel-E40000) at a vibration of 11 Hz and a heating rate of 5 ° C / min. The temperature was raised to 70 to 250 ° C. and obtained from the top of tan δ.
Soft segment content: Measured using a 500 MHz ¹ H-NMR measuring device (AVANCE500 manufactured by BRUKER) at a room temperature, a deuterated chloroform solvent containing 15 vol% trifluoroacetic acid, a sample solution concentration of 2 to 3 vol / wt%. The soft segment content was calculated from the integral ratio of the hard segment component and the soft segment component in the spectrum diagram 2 according to the following formula.
Soft segment content (wt%) = (B / 4) x S / ((B / 4) x S + (A / 4) x H)
S = Molecular weight per soft segment unit, H = Molecular weight chain length per hard segment unit: 500MHz ¹ Deuterated chloroform solvent containing 15vol% trifluoroacetic acid using 1H-NMR analyzer (BRUKER AVANCE500) The sample solution concentration was 2 to 3 vol / wt% at room temperature. The chain length was calculated from the integral of each butanediol component in the spectrum (FIG. 2) according to the following formula. C = (C + D) −E
PBT chain length = (C + E) / E
Soft segment chain length = (F + E) / E
Heat aging resistance test: Injection molded JIS3 dumbbell specimens in accordance with JIS6251 are allowed to stand in a thermostatic layer at 150 ° C for 360 hours, and in accordance with JIS K6251, the tensile rupture strength and tensile rupture elongation before and after heat treatment are measured. Then, based on JIS6257, the tensile rupture strength residual ratio and the tensile rupture elongation residual ratio were calculated.

Example 1
A reactor was charged with 13.5 g of dimethyl terephthalate, 12.3 ml of 1,4 butanediol, and 11 mg of tetrabutoxytitanate, and the mixture was purged with nitrogen. Then, stirring was started at 185 ° C. under normal pressure. The temperature was gradually raised to 230 ° C. and a transesterification reaction was carried out for 100 minutes. Subsequently, the temperature was reduced to 1 mmHg or lower at 250 ° C. over 50 minutes, and a polycondensation reaction was performed for 90 minutes under high vacuum to produce 15 g of polybutylene terephthalate having a number average molecular weight of 6300 and an OH value of 290 eq / 10 ⁶ g. While stirring this molten polybutylene terephthalate at 125 rpm, an aliphatic polyester composed of dimer acid and butanediol having a number average molecular weight of 9,300, an OH number of 214 eq / 10 ⁶ g, a number average molecular weight of 7,500, and an OH number of 13 eq / 10 ⁶ g Was mixed in a ratio of 1: 2 (wt) and 15 g was added over 2 minutes. After stirring for 20 minutes, the pressure was reduced to 1 mmHg or less over 30 minutes, and a polycondensation reaction was performed at 250 ° C. under a high vacuum for 2 hours. The properties of the obtained copolymer are as described in the table.

Example 2
In Example 1, an aliphatic polyester composed of 12 g of polybutyterephthalate, number average molecular weight 9300, OH number 214 eq / 10 ⁶ g, number average molecular weight 7500, OH number 13 eq / 10 ⁶ g and dimer acid and butanediol was 1: 2. A copolymer was produced in the same manner as in Example 1 except that the amount mixed with (wt) was 18 g.

Comparative Example 1
In Example 1, an aliphatic polyester consisting of dimer acid and butanediol having a polybutyterephthalate content of 24 g, a number average molecular weight of 9,300, an OH number of 214 eq / 10 ⁶ g, a number average molecular weight of 7,500, and an OH number of 13 eq / 10 ⁶ g is 1: 2. A copolymer was produced in the same manner as in Example 1 except that the amount mixed with (wt) was 6 g.

Comparative Example 2
A copolymer was produced in the same manner as in Example 1 except that the number average molecular weight of polybutyterephthalate was 32000 and the OH value was 0 eq / t in Example 1.

Comparative Example 3
A copolymer was produced in the same manner as in Example 1 except that the aliphatic polyester composed of dimer acid and butanediol in Example 1 had a number average molecular weight of 1860 and an OH value of 1070 eq / t.

Comparative Example 4
A reactor was charged with 18.5 g of dimethyl terephthalate, 17 ml of 1,4 butanediol, and 11 mg of tetrabutoxytitanate, and after sufficient nitrogen substitution, stirring was started at 185 ° C. under normal pressure. The temperature was gradually raised to 230 ° C. and a transesterification reaction was carried out for 100 minutes. Subsequently, the temperature was reduced to 1 mmHg or lower at 250 ° C. over 50 minutes, and a polycondensation reaction was performed under high vacuum for 150 minutes to produce 21 g of polybutylene terephthalate having a number average molecular weight of 35000 and an OH value of 0eq / 10 ⁶ g. While stirring this molten polybutylene terephthalate at 125 rpm, 9 g of an aliphatic polyester composed of dimer acid and butanediol having a number average molecular weight of 2000 and an OH value of 1000 eq / 10 ⁶ g was added in one minute. After the addition, the pressure was reduced to 1 mmHg or less over 7 minutes, and a polycondensation reaction was performed at 250 ° C. under a high vacuum for 2 hours. The properties of the obtained copolymer are as described in the table.

Comparative Example 5
A reactor was charged with 13.5 g of dimethyl terephthalate, 12.3 ml of 1,4 butanediol, and 11 mg of tetrabutoxytitanate, and the mixture was purged with nitrogen. Then, stirring was started at 185 ° C. under normal pressure. The temperature was gradually raised to 230 ° C. and a transesterification reaction was carried out for 100 minutes. Subsequently, the temperature was reduced to 1 mmHg or lower at 250 ° C. over 50 minutes, and a polycondensation reaction was performed for 60 minutes under high vacuum to produce 15 g of polybutylene terephthalate having a number average molecular weight of 4300 and an OH value of 440 eq / 10 ⁶ g. While stirring this molten polybutylene terephthalate at 125 rpm, 15 g of an aliphatic polyester consisting of dimer acid and butanediol having a number average molecular weight of 2000 and an OH number of 1000 eq / 10 ⁶ g was added over 2 minutes. After stirring for 20 minutes, the pressure was reduced to 1 mmHg or less over 30 minutes, and a polycondensation reaction was performed at 250 ° C. under a high vacuum for 2 hours. The properties of the obtained copolymer are as described in the table.

Comparative Example 6
Dimethyl terephthalate 15.8g, 1,4 butanediol 14.7ml, polytetramethylene glycol (Mn = 2000) 16.8g Tetrabutoxy titanate (100ppm as Ti) was charged into the reactor, purged with nitrogen, and stirred at 185 ° C under atmospheric pressure. Started. The temperature was gradually raised to 230 ° C. and a transesterification reaction was carried out for 100 minutes. Subsequently, the temperature was reduced to 250 ° C. and 1 mmHg or less over 50 minutes, and a polycondensation reaction was performed for 120 minutes under high vacuum. The properties of the obtained copolymer are as described in Table 1.

  According to the present invention, it is possible to provide an ester-ester block copolymer having a block structure while being an ester-ester copolymer and having excellent physical properties in a high temperature region, and a method for producing the same. The ester-ester block copolymer of the present invention exhibits stable mechanical properties in a wide temperature range, and is excellent in flexibility and heat aging resistance.

3 is a dynamic viscoelasticity measurement chart of a copolymer after completion of polycondensation in Example 1 and Comparative Example 4. 2 is a ¹ H-NMR chart of a copolymer after completion of polycondensation in Example 1. FIG.

Claims (7)

  An aromatic polyester derived from a dicarboxylic acid having an aromatic dicarboxylic acid as a main component or an ester-forming derivative thereof and a diol having an alkylene glycol as a main component; a dicarboxylic acid having a dimer acid as a main component; and an alkylene glycol as a main component. A block copolymer comprising an aliphatic polyester derived from a diol.   2. The block copolymer according to claim 1, wherein the aromatic polyester component in the block copolymer is 70 to 10 parts by weight and the aliphatic polyester component is 30 to 90 parts by weight.   3. The block copolymer according to claim 1, wherein the aromatic polyester is polybutylene terephthalate.   4. The block copolymer according to claim 1, wherein the aliphatic polyester comprises dimer acid and butanediol.   The block copolymer according to claim 1, wherein the melting point is 175 ° C. to 215 ° C. Aromatic polyester derived from diol based on diols based on aromatic dicarboxylic acid or its ester-forming derivatives based on terephthalic acid with number average molecular weight 5000-30000 and OH number 300eq / 10 ⁶ g or less 6. The method for producing a block copolymer according to claim 1, wherein the block copolymer is produced. The block copolymer according to claim 1, wherein the block copolymer is produced using an aliphatic polyester composed of dimer acid and butanediol having a number average molecular weight of 2000 to 15000 and an OH value of 1000 eq / 10 ⁶ g or less. Method.

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