Polyester elastomer derived from biomass resources

Abstract

To provide a polyester elastomer derived from a biomass resource, which is colorless and can retain excellent mechanical properties, retention stability, water aging resistance, and heat aging resistance of a polyester elastomer derived from a fossil fuel resource.SOLUTION: The polyester elastomer comprises a hard segment comprising a polyester having an aromatic dicarboxylic acid and an aliphatic and / or alicyclic diol as constituent components and a soft segment comprising an aromatic dicarboxylic acid and an aliphatic polyether as constituent components, wherein the aromatic dicarboxylic acid and the aliphatic and / or alicyclic diol are derived from a fossil fuel resource, the aliphatic polyether is derived from a biomass resource, the bio-based degree of the polyester elastomer is 20-85%, and the reduced viscosity of the polyester elastomer is 1.2 dl / g or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a biomass resource-derived polyester elastomer that is free from coloration despite having a high biobased content and that can retain the excellent mechanical properties, residence stability, water aging resistance, and heat aging resistance that are characteristic of fossil fuel resource-derived polyester elastomers. [Background technology]

[0002] Polyester elastomers are excellent in injection and extrusion moldability, and as a material with high mechanical strength, rubber-like properties such as elastic recovery, impact resistance, and flexibility, as well as excellent heat and cold resistance, they are used in a wide range of applications, including automotive parts, electrical and electronic parts, fibers, films, and sports parts.

[0003] In recent years, concerns about the depletion of fossil fuel resources and the increase in atmospheric carbon dioxide have become global environmental issues, and as a result, efforts are being made to convert various polymers from biomass. As biomass resources are renewable, they are expected to become an important design concept in future polymer development from the perspectives of SDGs and carbon neutrality.

[0004] However, biomass-derived raw materials contain impurities that cannot be completely removed during the refining process. Therefore, increasing the proportion of biomass-derived raw materials in an attempt to increase the bio-based content of the polyester increases the amount of impurities. As a result, the reaction is inhibited and the reduced viscosity does not increase, making it difficult to maintain the excellent properties of fossil-fuel-derived polyester.

[0005] To address this issue, it has been proposed to prevent a decline in the mechanical properties of polyesters made from biomass-derived dicarboxylic acids and / or diols by reducing the sulfur atom content and the amount of acid end groups (see Patent Document 1). While this biomass-derived polyester prevents a decline in mechanical properties to some extent, it also causes discoloration of the polyester, which leads to poor appearance of molded products. Furthermore, it fails to maintain the excellent properties of fossil-fuel-derived polyesters in terms of retention stability, water aging resistance, and heat aging resistance. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent No. 5303237 Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention was made in view of the current state of the prior art, and an object of the present invention is to provide a biomass resource-derived polyester elastomer that is free from coloration and can retain the excellent mechanical properties, retention stability, water aging resistance, and heat aging resistance that are characteristic of fossil fuel resource-derived polyester elastomers, even when the proportion of biomass resource-derived raw materials used in the polyester elastomer is increased. [Means for solving the problem]

[0008] As a result of extensive research to achieve this object, the present inventors have found that by using fossil fuel-derived aromatic dicarboxylic acid components and aliphatic and / or alicyclic diols of polyesters constituting the hard segments of a polyester elastomer, and by using aromatic dicarboxylic acid components and aliphatic polyethers constituting the soft segments, the aliphatic polyethers are derived from biomass resources, it is possible to provide a colorless biomass-derived polyester elastomer that can retain the excellent mechanical properties, residence stability, water aging resistance, and heat aging resistance that are characteristic of polyester elastomers derived from fossil fuel resources, and have completed the present invention.

[0009] That is, the present invention comprises the following (1) to (6). (1) A polyester elastomer comprising a hard segment made of a polyester having an aromatic dicarboxylic acid and an aliphatic and / or alicyclic diol as constituent components, and a soft segment made of an aromatic dicarboxylic acid and an aliphatic polyether as constituent components, wherein the aromatic dicarboxylic acid and the aliphatic and / or alicyclic diol are derived from fossil fuel resources, and the aliphatic polyether is derived from biomass resources, the biobased content of the polyester elastomer is 20 to 85%, and the reduced viscosity of the polyester elastomer is 1.2 dl / g or more. (2) The biomass resource-derived polyester elastomer according to (1), wherein the biomass resource-derived aliphatic polyether is polytetramethylene ether glycol. (3) The biomass resource-derived polyester elastomer according to (1) or (2), characterized in that the glass transition temperature (Tg) is −70 to 10° C. (4) A biomass resource-derived polyester elastomer according to (1) or (2), characterized in that the Co-b value of the polyester elastomer is 7 or less. (5) A biomass resource-derived polyester elastomer according to (1) or (2), characterized in that the biobased content of the polyester elastomer is 35 to 85% and the reduced viscosity of the polyester elastomer is 1.8 dl / g or more. (6) A biomass resource-derived polyester elastomer according to (1) or (2), characterized in that the hard segment of the polyester elastomer is a polyester consisting of butylene terephthalate units. [Effects of the Invention]

[0010] The biomass resource-derived polyester elastomer of the present invention can prevent discoloration of the polyester elastomer even when the proportion of biomass resource-derived raw materials used is increased, and can retain the excellent mechanical properties, residence stability, water aging resistance, and heat aging resistance that are characteristic of fossil fuel resource-derived polyester elastomers. Therefore, the biomass resource-derived polyester elastomer of the present invention can significantly contribute to solving global environmental problems such as the depletion of fossil fuel resources. DETAILED DESCRIPTION OF THE INVENTION

[0011] The biomass resource-derived polyester elastomer of the present invention is a polyester elastomer in which hard segments made of a polyester having as its constituent components an aromatic dicarboxylic acid and an aliphatic and / or alicyclic diol are bonded to soft segments made of an aromatic dicarboxylic acid and an aliphatic polyether, and is characterized in that the aromatic dicarboxylic acid and the aliphatic and / or alicyclic diol are derived from fossil fuel resources, and the aliphatic polyether is derived from a biomass resource.

[0012] Typical aromatic dicarboxylic acids are widely used as the aromatic dicarboxylic acid constituting the polyester of the hard segment, and the main aromatic dicarboxylic acid is preferably terephthalic acid or naphthalenedicarboxylic acid (among its isomers, 2,6-naphthalenedicarboxylic acid is preferred). The content of these aromatic dicarboxylic acids is preferably 70 mol% or more, more preferably 80 mol% or more, and even more preferably 90 mol% or more, and may even be 100 mol% of the total dicarboxylic acids constituting the polyester of the hard segment. Examples of dicarboxylic acid components other than terephthalic acid and naphthalenedicarboxylic acid include aromatic dicarboxylic acids such as diphenyldicarboxylic acid, isophthalic acid, and 5-sodium sulfoisophthalic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and tetrahydrophthalic anhydride; and aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid, and hydrogenated dimer acid. These dicarboxylic acids can be used in a range that does not significantly lower the melting point of the resin, and the amount is preferably 30 mol % or less of the total acid components, more preferably 20 mol % or less, and even more preferably 10 mol % or less, and may be 0 mol %. When these dicarboxylic acids are used as raw materials for polyester elastomers, they may be in the form of esters of the dicarboxylic acids. For example, terephthalic acid and dimethyl terephthalate can also be used as raw materials.

[0013] Furthermore, as the aliphatic or alicyclic diol constituting the polyester of the hard segment, general aliphatic or alicyclic diols are widely used and are not particularly limited, but alkylene glycols having 2 to 8 carbon atoms are preferred. Specific examples include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, and 1,4-cyclohexanedimethanol. Of these, either ethylene glycol or 1,4-butanediol is preferred.

[0014] As the component constituting the polyester of the hard segment, those comprising butylene terephthalate units (units consisting of terephthalic acid and 1,4-butanediol) or butylene naphthalate units (units consisting of 2,6-naphthalenedicarboxylic acid and 1,4-butanediol) are preferred in terms of physical properties, moldability, and cost performance.

[0015] Alternatively, when an aromatic polyester suitable for forming the hard segment of the polyester elastomer is prepared in advance and then copolymerized with the soft segment component, the aromatic polyester can be easily obtained by a conventional polyester production method. Preferably, the polyester has a number average molecular weight of 10,000 to 40,000.

[0016] The aromatic dicarboxylic acid constituting the soft segment of the polyester elastomer can be the same as the aromatic dicarboxylic acid constituting the polyester of the hard segment. In a preferred embodiment, the aromatic dicarboxylic acid constituting the soft segment and the aromatic dicarboxylic acid constituting the hard segment are the same.

[0017] The aliphatic polyether constituting the soft segment of the polyester elastomer is preferably a glycol compound because it bonds with the polyester in the hard segment. Specific examples include poly(ethylene oxide) glycol, poly(propylene oxide) glycol, polytetramethylene ether glycol, polytrimethylene ether glycol, poly(hexamethylene oxide) glycol, a copolymer of ethylene oxide and propylene oxide, an ethylene oxide adduct of poly(propylene oxide) glycol, and a copolymer of ethylene oxide and tetrahydrofuran. Among these, polytetramethylene ether glycol and an ethylene oxide adduct of poly(propylene oxide) glycol are preferred in terms of elastic properties.

[0018] In the present invention, it is preferable to use a biomass-derived aliphatic polyether, which is a component of the soft segment, particularly polytetramethylene ether glycol (PTMG) derived from a biomass resource. Commercially available PTMGs are available, and preferred examples include BioPTMG1000 and BioPTMG2000 manufactured by Mitsubishi Chemical Corporation.

[0019] The polyester elastomer is preferably a copolymer primarily composed of terephthalic acid, 1,4-butanediol, and polytetramethylene ether glycol. Of the dicarboxylic acid components constituting the polyester elastomer, terephthalic acid preferably accounts for 40 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, and particularly preferably 90 mol% or more. Of the glycol components constituting the polyester elastomer, the total of 1,4-butanediol and polytetramethylene ether glycol is preferably 40 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, and particularly preferably 90 mol% or more.

[0020] The number-average molecular weight of the polytetramethylene ether glycol is preferably 500 to 4000, more preferably 700 to 3000, and even more preferably 800 to 2500. If the number-average molecular weight is below the above range, it may be difficult to exhibit elastomeric properties. On the other hand, if the number-average molecular weight exceeds the above range, compatibility with the hard segment component may decrease, making it difficult to copolymerize in a block form.

[0021] In the present invention, the mass of the hard segment refers to the mass of the component composed of an aromatic dicarboxylic acid and an aliphatic and / or alicyclic diol, and the mass of the soft segment refers to the mass of the component composed of an aromatic dicarboxylic acid and an aliphatic polyether. For example, in the case of a polyester elastomer composed of terephthalic acid, 1,4-butanediol, and polytetramethylene ether glycol (PTMG), the mass of the hard segment is the mass of butylene terephthalate units (condensation units of terephthalic acid and 1,4-butanediol), and the mass of the soft segment is the mass of the condensation units of terephthalic acid and polytetramethylene ether glycol (PTMG).

[0022] The mass ratio of hard segments to soft segments in the polyester elastomer is preferably 5 / 95 to 90 / 10, more preferably 10 / 90 to 85 / 15, and even more preferably 15 / 85 to 80 / 20. If the amount of hard segments is low (the amount of PTMG is high), the polyester elastomer may not have satisfactory heat aging resistance and moldability (crystallinity). Conversely, if the amount of hard segments is high (the amount of PTMG is low), the compatibility between the hard segment components and the soft segment components may decrease, making it difficult to copolymerize them into blocks. The polyester elastomer preferably has a melting point of 150 to 230°C. If the melting point is below 150°C, the polyester elastomer may not have the required heat aging resistance and moldability (crystallinity). Conversely, if the melting point is above 230°C, the polyester elastomer may contain a large amount of hard segments, resulting in a correspondingly high glass transition temperature (Tg), and may not have the required impact resilience, flexibility, and low-temperature mechanical properties.

[0023] To produce the polyester elastomer of the present invention, it is preferable to extend the polycondensation time compared to conventional methods. Typically, the polycondensation time for polyester elastomer production is approximately 50 to 90 minutes. In the present invention, however, the polycondensation time is preferably 100 to 140 minutes, more preferably 105 to 135 minutes. It is also preferable to control the polycondensation temperature within a narrow range. Typically, the polycondensation temperature for polyester elastomer production is approximately 235 to 260°C. In the present invention, however, the polycondensation temperature is preferably 235 to 255°C, more preferably 240 to 250°C. If the polycondensation time is too short or the polycondensation temperature is too low, the reduced viscosity of the polyester elastomer may not increase, and the elongation at break and tensile strength at break may not satisfy the polyester elastomer's functions. Conversely, if the polycondensation time is too long or the polycondensation temperature is too high, the polyester elastomer may become discolored, resulting in a poor appearance and a decrease in reduced viscosity due to thermal degradation.

[0024] The biobased content of the polyester elastomer of the present invention is 20 to 85%, preferably 30 to 85%, and more preferably 35 to 85%. Conventionally, biomass-derived raw materials contain impurities that cannot be completely removed during the refining process. Therefore, increasing the proportion of biomass-derived raw materials to increase the biobased content results in an increase in the amount of impurities, inhibiting the reaction and preventing an increase in reduced viscosity. This leads to problems with prolonged polymerization time and discoloration. Therefore, it has been difficult to obtain a biomass-derived polyester elastomer that can maintain excellent flexibility, low-temperature mechanical properties, heat aging resistance, and water resistance without reducing production efficiency. The present inventors conducted extensive research into the polymerization raw materials for polyester elastomers. By using fossil fuel-derived hard segments and aliphatic polyethers as biomass-derived raw materials for the soft segments, and by adopting appropriate polycondensation reaction times and temperatures, they have succeeded in obtaining a biomass-derived polyester elastomer that is free of discoloration and maintains the excellent properties of fossil fuel-derived polyester elastomers.

[0025] The reduced viscosity (ηsp / c), which is an index of molecular weight, is an extremely important characteristic of the polyester elastomer of the present invention. In the present invention, the reduced viscosity at which the polyester elastomer exhibits long-term durability (heat aging resistance, water resistance) is 1.2 dL / g or more, preferably 1.3 dL / g or more, more preferably 1.4 dL / g or more, and even more preferably 1.8 dL / g or more. If the reduced viscosity (ηsp / c) is low, the molecular weight will be small, and the polyester elastomer may not be able to provide satisfactory long-term durability (heat aging resistance, water resistance) functions.

[0026] The glass transition temperature (Tg), which is an index of low-temperature mechanical properties, is an important characteristic of the polyester elastomer of the present invention. The glass transition temperature varies depending on the soft segment ratio in the polyester elastomer. In the present invention, the glass transition temperature at which the polyester elastomer exhibits its functions of rebound resilience, flexibility, and low-temperature mechanical properties is preferably -70 to 10°C, more preferably -65 to 10°C. If the glass transition temperature is high, it may not be possible to obtain a polyester elastomer that satisfies the functions of rebound resilience, flexibility, and low-temperature mechanical properties.

[0027] The Co-b value, which is an index of the appearance of a molded product, is an important characteristic of the polyester elastomer of the present invention. The Co-b value varies depending on the impurities in the biomass resource-derived raw material and the polymerization conditions. In the present invention, the Co-b value for obtaining a good appearance is preferably 10 or less, more preferably 7 or less, and even more preferably 4 or less. If the Co-b value is too high, the prepared pellets will yellow, significantly impairing the appearance of the molded product, and a satisfactory product may not be obtained.

[0028] The composition and composition ratio of the polyester elastomer of the present invention can be determined by dissolving a sample in a solvent such as deuterated chloroform and measuring the composition. 1 It can also be calculated from the proton integral ratio in H-NMR. [Example]

[0029] The following examples are provided to demonstrate the effects of the present invention, but the present invention is not limited to these examples. The property values ​​were evaluated by the following methods. The raw materials used in the examples, and those not otherwise specified, are derived from fossil fuel resources.

[0030] (1) Reduced viscosity (ηsp / c) 0.05 g of polyester elastomer was dissolved in 25 mL of a mixed solvent (phenol / tetrachloroethane = 60 / 40), and the viscosity was measured at 30°C using an Ubbelohde viscosity tube.

[0031] (2) Melting point (Tm) Using a differential scanning calorimeter "DSC220" manufactured by Seiko Instruments Inc., 5 mg of the measurement sample was placed in an aluminum pan, the lid was pressed down and sealed, and the sample was melted in nitrogen at 250°C for 2 minutes, then the temperature was lowered to 50°C at a rate of 20°C / min, and the temperature was then raised from 50°C to 250°C at a rate of 20°C / min. The endothermic peak due to melting from the obtained thermogram curve was taken as the melting point.

[0032] (3) Glass transition temperature (Tg) A dynamic viscoelasticity measuring device, Rheogel-E4000 (manufactured by UBM Co., Ltd.), was used to measure the sample. A 0.4 mm thick sheet was prepared by pressing the sample with a hot plate heated to 200-250°C using an NF-type single-action compression molding machine (manufactured by Shinto Metal Industries Co., Ltd.). Measurements were performed at a frequency of 11 Hz and a heating rate of 2°C / min, with the peak position of tan δ measured from -150°C to 150°C being taken as Tg.

[0033] (4) Acid value (AV) 0.2 g of sample was accurately weighed, and benzyl alcohol was added and heated to dissolve. It was then dissolved in 20 ml of chloroform and titrated with 0.08 N potassium hydroxide (ethanol solution). The acid value was calculated from the amount of potassium hydroxide required for neutralization. Phenol red ethanol solution was used as an indicator.

[0034] (5) Color difference The Co-b value (the higher the value, the greater the yellowness) was measured using an automatic color difference meter (manufactured by Toyorika Kogyo Co., Ltd.).

[0035] (6) Retention stability (ΔMFR) The polyester elastomer composition pellets obtained in the examples and comparative examples were retained at 190°C (Examples 2 to 4, Reference Examples 2 to 4, Comparative Example 4) or 230°C (Examples 1, 5, and 6, Reference Examples 1, 5, and 6, Comparative Examples 1 to 3) for 25 minutes, and then the melt flow rate (MFR: g / 10 min) was measured at 2160 g according to the test method (Method A) described in JIS K7210. Compositions with a moisture content of 0.1% by mass or less were used for the measurement.

[0036] (7) Tensile elongation and strength at break The tensile elongation and strength at break of the polyester elastomer were measured in accordance with JIS K 6251. Test specimens were prepared by injection-molding the resin, which had been dried under reduced pressure at 100°C for 5 hours, into a 100 mm x 100 mm x 2 mm plate using an injection molding machine (Yamashiro Seiki Co., Ltd., model-SAV) at a cylinder temperature of (Tm+20°C) and a mold temperature of 30°C, and then punching out a dumbbell-shaped No. 3 test specimen from the plate.

[0037] (8) Water aging resistance (treatment time at which elongation retention at break after water aging test is 50%) After treating the test pieces in boiling water at 100°C, the elongation at break was measured using the above method. The elongation at break of test pieces that were not treated in boiling water was also measured, and the retention of elongation at break after boiling water treatment was calculated as follows: The initial elongation at break is the elongation at break before boiling water treatment. Elongation retention at break (%) = (elongation at break after boiling water treatment / initial elongation at break) x 100 The boiling water treatment time when the elongation retention at break reached 50% was measured as the elongation half-life.

[0038] (9) Heat aging resistance (treatment time at which elongation retention at break after heat aging test is 50%) The test pieces were exposed to air at 140°C, and then the elongation at break was measured using the method described above. The elongation at break of test pieces that had not been heat-treated was also measured, and the retention of elongation at break after heat treatment was calculated as follows: The initial elongation at break is the elongation at break before heat treatment. Breaking elongation retention rate (%) = (breaking elongation after heat treatment / initial breaking elongation) x 100 The heat treatment time when the elongation retention at break reached 50% was measured as the elongation half-life.

[0039] (10) Bio-based content The bio-based content is the ratio of biomass-derived monomer components to the total mass of all monomer components that make up the polyester elastomer, calculated from the mass of the biomass-derived monomer components. The bio-based content is the ratio of the amount of biomass-derived monomer components contained only in raw materials derived from biomass resources to the total carbon contained in the polyester elastomer. 14 C carbon ( 12 The bio-based content of polyester elastomers is measured using accelerator mass spectrometry (AMS) in accordance with ASTM D6866.

[0040] Example 1 2000 g of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 1360 g of 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical), 750 g of biomass-derived polytetramethylene ether glycol (BioPTMG1000, number average molecular weight 1000, manufactured by Mitsubishi Chemical), 2.4 g of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 g of AO-330 (manufactured by ADEKA) were charged into an autoclave, and the temperature was raised from room temperature to 220 ° C over 150 minutes to carry out a transesterification reaction. The pressure inside the autoclave was then gradually reduced and the temperature was further raised to 245 ° C and 1 Torr or less over 75 minutes to carry out an initial condensation reaction. The polymerization reaction was then carried out for 135 minutes at 245 ° C and 1 Torr or less, and a polymer with a hard segment / soft segment mass ratio of 72 / 28 (mass%) was extracted in pellet form. The resulting polymer was designated as the polyester elastomer of Example 1.

[0041] Example 2 1200 g of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 800 g of 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical), 1780 g of biomass-derived polytetramethylene ether glycol (BioPTMG1000, number average molecular weight 1000, manufactured by Mitsubishi Chemical), 2.4 g of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 g of AO-330 (manufactured by ADEKA) were charged into an autoclave, and the temperature was raised from room temperature to 200 ° C over 165 minutes to carry out a transesterification reaction. The pressure inside the autoclave was then gradually reduced and the temperature was further raised to 245 ° C and 1 Torr or less over 90 minutes to carry out an initial condensation reaction. The polymerization reaction was then carried out for 115 minutes at 245 ° C and 1 Torr or less, and a polymer with a hard segment / soft segment mass ratio of 33 / 67 (mass%) was extracted in pellet form. The resulting polymer was designated as the polyester elastomer of Example 2.

[0042] Example 3 680 g of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 430 g of 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical), 2330 g of biomass-derived polytetramethylene ether glycol (BioPTMG2000, number average molecular weight 2000, manufactured by Mitsubishi Chemical), 2.4 g of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 g of AO-330 (manufactured by ADEKA) were charged into an autoclave. The temperature was raised from room temperature to 200°C over 200 minutes to carry out a transesterification reaction. The pressure inside the autoclave was then gradually reduced and the temperature was further raised to 245°C and 1 Torr or less over 90 minutes to carry out an initial condensation reaction. A polymerization reaction was then carried out at 245°C and 1 Torr or less for 115 minutes, and a polymer with a hard segment / soft segment mass ratio of 17 / 83 (mass%) was extracted in pellet form. The resulting polymer was designated the polyester elastomer of Example 3.

[0043] Example 4 840 g of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 560 g of 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical), 2150 g of biomass-derived polytetramethylene ether glycol (BioPTMG2000, number average molecular weight 2000, manufactured by Mitsubishi Chemical), 2.4 g of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 g of AO-330 (manufactured by ADEKA) were charged into an autoclave. The temperature was raised from room temperature to 200°C over 200 minutes to carry out a transesterification reaction. The pressure inside the autoclave was then gradually reduced and the temperature was further raised to 245°C and 1 Torr or less over 90 minutes to carry out an initial condensation reaction. A polymerization reaction was then carried out at 245°C and 1 Torr or less for 120 minutes, and a polymer with a hard segment / soft segment mass ratio of 24 / 76 (mass%) was extracted in pellet form. The resulting polymer was designated the polyester elastomer of Example 4.

[0044] Example 5 1790 g of dimethyl 2,6-naphthalenedicarboxylate (NDC, manufactured by SK Petrochemical), 1020 g of 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical), 1130 g of biomass-derived polytetramethylene ether glycol (BioPTMG1000, number average molecular weight 1000, manufactured by Mitsubishi Chemical), 2.4 g of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 g of AO-330 (manufactured by ADEKA) were charged into an autoclave, and the temperature was raised from room temperature to 220 ° C over 90 minutes to carry out a transesterification reaction. The pressure inside the autoclave was then gradually reduced and the temperature was further raised to 245 ° C and 1 Torr or less over 90 minutes to carry out an initial condensation reaction. The polymerization reaction was then carried out for 110 minutes at 245 ° C and 1 Torr or less, and a polymer with a hard segment / soft segment mass ratio of 56 / 44 (mass%) was extracted in pellet form. The resulting polymer was designated as the polyester elastomer of Example 5.

[0045] Example 6 1920 g of dimethyl 2,6-naphthalenedicarboxylate (NDC, manufactured by SK Petrochemical), 1120 g of 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical), 960 g of biomass-derived polytetramethylene ether glycol (BioPTMG1000, number average molecular weight 1000, manufactured by Mitsubishi Chemical), 2.4 g of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 g of AO-330 (manufactured by ADEKA) were charged into an autoclave, and the temperature was raised from room temperature to 220 ° C over 90 minutes to carry out a transesterification reaction. The pressure inside the autoclave was then gradually reduced and the temperature was further raised to 245 ° C and 1 Torr or less over 90 minutes to carry out an initial condensation reaction. The polymerization reaction was then carried out for 105 minutes at 245 ° C and 1 Torr or less, and a polymer with a hard segment / soft segment mass ratio of 62 / 38 (mass%) was extracted in pellet form. The resulting polymer was designated as the polyester elastomer of Example 6.

[0046] Reference example 1 2000 g of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 1360 g of 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical), 750 g of polytetramethylene ether glycol (PTMG1000, number average molecular weight 1000, manufactured by BASF), 2.4 g of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 g of AO-330 (manufactured by ADEKA) were charged into an autoclave, and the temperature was raised from room temperature to 220°C over 150 minutes to carry out an ester exchange reaction. The pressure inside the autoclave was then gradually reduced, and the temperature was further raised to 245°C and 1 Torr or less over 75 minutes to carry out an initial condensation reaction. A polymerization reaction was then carried out at 245°C and 1 Torr or less for 90 minutes, and a polymer with a hard segment / soft segment mass ratio of 72 / 28 (mass%) was extracted in pellet form. The resulting polymer was designated the polyester elastomer of Reference Example 1.

[0047] Reference example 2 1200 g of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 800 g of 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical), 1780 g of polytetramethylene ether glycol (PTMG1000, number average molecular weight 1000, manufactured by BASF), 2.4 g of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 g of AO-330 (manufactured by ADEKA) were charged into an autoclave, and the temperature was raised from room temperature to 220°C over 90 minutes to carry out an ester exchange reaction. The pressure inside the autoclave was then gradually reduced, and the temperature was further raised to 245°C and 1 Torr or less over 90 minutes to carry out an initial condensation reaction. A polymerization reaction was then carried out for 105 minutes at 245°C and 1 Torr or less, and a polymer with a hard segment / soft segment mass ratio of 33 / 67 (mass%) was extracted in pellet form. The resulting polymer was designated the polyester elastomer of Reference Example 2.

[0048] Reference example 3 680 g of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 430 g of 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical), 2330 g of polytetramethylene ether glycol (PTMG2000, number average molecular weight 2000, manufactured by BASF), 2.4 g of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 g of AO-330 (manufactured by ADEKA) were charged into an autoclave, and the temperature was raised from room temperature to 220°C over 90 minutes to carry out a transesterification reaction. The pressure inside the autoclave was then gradually reduced, and the temperature was further raised to 245°C and 1 Torr or less over 90 minutes to carry out an initial condensation reaction. A polymerization reaction was then carried out for 100 minutes at 245°C and 1 Torr or less, and a polymer with a hard segment / soft segment mass ratio of 17 / 83 (mass%) was extracted in pellet form. The resulting polymer was designated the polyester elastomer of Reference Example 3.

[0049] Reference example 4 840 g of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 560 g of 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical), 2150 g of polytetramethylene ether glycol (PTMG2000, number average molecular weight 2000, manufactured by BASF), 2.4 g of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 g of AO-330 (manufactured by ADEKA) were charged into an autoclave, and the temperature was raised from room temperature to 220°C over 90 minutes to carry out a transesterification reaction. The pressure inside the autoclave was then gradually reduced, and the temperature was further raised to 245°C and 1 Torr or less over 90 minutes to carry out an initial condensation reaction. A polymerization reaction was then carried out at 245°C and 1 Torr or less for 95 minutes, and a polymer with a hard segment / soft segment mass ratio of 24 / 76 (mass%) was extracted in pellet form. The resulting polymer was designated the polyester elastomer of Reference Example 4.

[0050] Reference example 5 1790 g of dimethyl 2,6-naphthalenedicarboxylate (NDC, manufactured by SK Petrochemical), 1020 g of 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical), 1130 g of polytetramethylene ether glycol (PTMG1000, number average molecular weight 1000, manufactured by BASF), 2.4 g of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 g of AO-330 (manufactured by ADEKA) were charged into an autoclave, and the temperature was raised from room temperature to 220°C over 90 minutes to carry out an ester exchange reaction. The pressure inside the autoclave was then gradually reduced, and the temperature was further raised to 245°C and 1 Torr or less over 90 minutes to carry out an initial condensation reaction. A polymerization reaction was then carried out for 90 minutes at 245°C and 1 Torr or less, and a polymer with a hard segment / soft segment mass ratio of 56 / 44 (mass%) was pelletized. The resulting polymer was designated the polyester elastomer of Reference Example 5.

[0051] Reference example 6 1920 g of dimethyl 2,6-naphthalenedicarboxylate (NDC, manufactured by SK Petrochemical), 1120 g of 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical), 960 g of polytetramethylene ether glycol (PTMG1000, number average molecular weight 1000, manufactured by BASF), 2.4 g of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 g of AO-330 (manufactured by ADEKA) were charged into an autoclave, and the temperature was raised from room temperature to 220°C over 90 minutes to carry out an ester exchange reaction. The pressure inside the autoclave was then gradually reduced, and the temperature was further raised to 245°C and 1 Torr or less over 90 minutes to carry out an initial condensation reaction. A polymerization reaction was then carried out for 85 minutes at 245°C and 1 Torr or less, and a polymer with a hard segment / soft segment mass ratio of 62 / 38 (mass%) was extracted in pellet form. The resulting polymer was designated the polyester elastomer of Reference Example 6.

[0052] Comparative Example 1 2000 g of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 1360 g of 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical), 750 g of biomass-derived polytetramethylene ether glycol (BioPTMG1000, number average molecular weight 1000, manufactured by Mitsubishi Chemical), 2.4 g of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 g of AO-330 (manufactured by ADEKA) were charged into an autoclave, and the temperature was raised from room temperature to 220°C over 150 minutes to carry out an ester exchange reaction. The autoclave was then gradually depressurized and further heated to 245°C and 1 Torr or less over 75 minutes to carry out an initial condensation reaction. A polymerization reaction was then carried out at 245°C and 1 Torr or less for 90 minutes, and a polymer with a hard segment / soft segment mass ratio of 72 / 28 (mass%) was extracted in pellet form. The resulting polymer was designated the polyester elastomer of Comparative Example 1.

[0053] Comparative Example 2 2030 g of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 1460 g of 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical), 840 g of biomass-derived dimer diol (C36DiOH, manufactured by Croda Pripol 2033), 2.4 g of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 g of AO-330 (manufactured by ADEKA) were charged into an autoclave, and the temperature was raised from room temperature to 220 °C over 110 minutes to carry out an ester exchange reaction. The pressure inside the autoclave was then gradually reduced and the temperature was further raised to 245 °C and 1 Torr or less over 75 minutes to carry out an initial condensation reaction. A polymerization reaction was then carried out for 55 minutes at 245 °C and 1 Torr or less, and a polymer with a hard segment / soft segment mass ratio of 65 / 35 (mass%) was extracted in pellet form. The resulting polymer was designated the polyester elastomer of Comparative Example 2.

[0054] Comparative Example 3 1815 g of dimethyl terephthalate (DMT, manufactured by SK Petrochemical), 1665 g of 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical), 860 g of biomass-derived dimer acid (C36DiCOOH, manufactured by Croda Propol 1009), 2.4 g of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 g of AO-330 (manufactured by ADEKA) were charged into an autoclave. The temperature was raised from room temperature to 220 °C over 120 minutes to carry out transesterification and esterification reactions. The pressure inside the autoclave was then gradually reduced and the temperature was further raised to 245 °C and 1 Torr or less over 75 minutes to carry out an initial condensation reaction. A polymerization reaction was then carried out at 245 °C and 1 Torr or less for 60 minutes, and a polymer with a hard segment / soft segment mass ratio of 66 / 34 (mass%) was extracted in pellet form. The resulting polymer was designated the polyester elastomer of Comparative Example 3.

[0055] Comparative Example 4 2110 g of biomass-derived dimethyl furandicarboxylate (FDME, manufactured by BASF), 1540 g of 1,4-butanediol (1,4-BDO, manufactured by Mitsubishi Chemical), 1780 g of polytetramethylene ether glycol (PTMG1000, number average molecular weight 1000, manufactured by BASF), 2.4 g of tetrabutyl titanate (TBT, manufactured by Nacalai Tesque), and 6.0 g of AO-330 (manufactured by ADEKA) were charged into an autoclave. The temperature was raised from room temperature to 180°C over 120 minutes to carry out a transesterification reaction. The pressure inside the autoclave was then gradually reduced and the temperature was further raised to 245°C and 1 Torr or less over 75 minutes to carry out an initial condensation reaction. A polymerization reaction was then carried out at 245°C and 1 Torr or less for 46 minutes, and a polymer with a hard segment / soft segment mass ratio of 71 / 29 (mass%) was extracted in pellet form. The resulting polymer was designated the polyester elastomer of Comparative Example 4.

[0056] Table 1 shows the compositions and evaluation results of the polyester elastomers of Examples 1 to 6, Reference Examples 1 to 6, and Comparative Examples 1 to 4.

[0057] [Table 1]

[0058] As is clear from Table 1, Examples 1 to 6, in which biomass-derived raw materials were used for the aliphatic polyether of the soft segment, all maintained the excellent flexibility, low-temperature mechanical properties, heat aging resistance, and water resistance of the fossil fuel-derived polyester elastomers of Reference Examples 1 to 6, in which only the same fossil fuel-derived raw materials were used. On the other hand, Comparative Example 1, which has the same composition as Example 1, used a conventional polycondensation time, resulting in a low reduced viscosity and making it impossible to maintain the various excellent properties unique to fossil fuel-derived polyester elastomers. Furthermore, Comparative Examples 2 to 4, in which biomass-derived raw materials were used for portions other than the aliphatic polyether of the soft segment, failed to maintain the various excellent properties unique to fossil fuel-derived polyester elastomers. [Industrial Applicability]

[0059] The biomass-derived polyester elastomer of the present invention is free from coloration and retains the excellent flexibility, low-temperature mechanical properties, heat resistance, and water resistance of fossil fuel-derived polyester elastomers. Therefore, the biomass-derived polyester elastomer of the present invention will greatly contribute to solving environmental problems such as the depletion of fossil fuel resources, and is extremely useful in this industry.

Claims

[Claim 1] 1. A biomass resource-derived polyester elastomer comprising a hard segment made of a polyester having, as constituent components, an aromatic dicarboxylic acid and an aliphatic and / or alicyclic diol, and a soft segment made of, as constituent components, an aromatic dicarboxylic acid and an aliphatic polyether, wherein the aromatic dicarboxylic acid and the aliphatic and / or alicyclic diol are derived from fossil fuel resources, and the aliphatic polyether is derived from a biomass resource; the biobased content of the polyester elastomer is 20 to 85%; and the reduced viscosity of the polyester elastomer is 1.2 dl / g or more.

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