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WO2015093525A1 - Elastomère de polyester - Google Patents

Elastomère de polyester Download PDF

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Publication number
WO2015093525A1
WO2015093525A1 PCT/JP2014/083397 JP2014083397W WO2015093525A1 WO 2015093525 A1 WO2015093525 A1 WO 2015093525A1 JP 2014083397 W JP2014083397 W JP 2014083397W WO 2015093525 A1 WO2015093525 A1 WO 2015093525A1
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WO
WIPO (PCT)
Prior art keywords
component
mass
polyester elastomer
acid
soft segment
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2014/083397
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English (en)
Japanese (ja)
Inventor
卓也 下拂
小林　幸治
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyobo Co Ltd
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Toyobo Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyobo Co Ltd filed Critical Toyobo Co Ltd
Priority to JP2015511129A priority Critical patent/JPWO2015093525A1/ja
Publication of WO2015093525A1 publication Critical patent/WO2015093525A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups

Definitions

  • the present invention relates to a polyester elastomer excellent in impact resistance and adhesion to other materials.
  • biodegradable resins and resins using biomass-derived materials have been developed and put to practical use as environmentally friendly or environmentally sustainable materials.
  • these resins are currently inferior in thermal properties and mechanical properties to conventional general-purpose resins and engineering plastics.
  • one of the raw materials derived from biomass has an aliphatic structure, and one of the causes is that a polymer containing them has a disadvantage in thermal properties.
  • furandicarboxylic acid is known as a biomass-derived raw material capable of polymerizing a thermoplastic resin having excellent heat resistance, but sufficient mechanical properties cannot be obtained due to low polymerization degree. That was a challenge.
  • an object of the present invention is to provide a polyester elastomer having a high impact resistance and excellent adhesion to other materials by including a predetermined amount or more of a flange carboxylic acid component in a polyester elastomer comprising a hard segment and a soft segment. It is in.
  • the present invention has the following configuration.
  • a polyester elastomer composed of 20 to 85% by mass of a hard segment component and 80 to 15% by mass of a soft segment component, the hard segment component comprising a dicarboxylic acid component and a glycol component, constituting the hard segment component
  • a polyester elastomer comprising 20% by mass or more of a flanged carboxylic acid component, based on 100% by mass of the total dicarboxylic acid component.
  • the polyester elastomer according to [1] wherein 70% by mass or more of the glycol component constituting the hard segment component is 1,4-butanediol.
  • the soft segment component constituting the polyester elastomer is at least one selected from a polyalkylene ether component, an aliphatic polyester component, and a polyalkylene carbonate component [1] to [2] ]
  • the polyester elastomer in any one of.
  • a polyester elastomer excellent in impact resistance and adhesion to other materials can be obtained.
  • the excellent adhesion is due to the high surface energy, but this can be realized by containing a predetermined amount or more of the flanged carboxylic acid component.
  • the impact resistance can be improved by including a predetermined amount or more of the flanged carboxylic acid component.
  • Impact strength and surface energy depend on the type of soft segment that constitutes the polyester elastomer. Even if any type of soft segment is used, impact resistance is achieved by including a predetermined amount or more of the flanged carboxylic acid component. It becomes possible to improve the adhesiveness between and other materials.
  • the polyester elastomer used in the present invention needs to have a hard segment amount of 20 to 85% by mass and a soft segment amount of 80 to 15% by mass.
  • the soft segment amount is less than 15% by mass, impact resistance is lowered and good surface energy cannot be obtained.
  • the soft segment amount exceeds 80% by mass, the melting point of the polyester elastomer is remarkably lowered, so that heat resistance becomes a problem.
  • the upper limit of the soft segment amount is preferably 75%, more preferably 70% by mass, and the lower limit is preferably 20% by mass, more preferably 25% by mass. It is.
  • the polyester elastomer is a thermoplastic polyester elastomer (block copolymer) composed of a hard segment component and a soft segment component.
  • the hard segment component refers to a high melting point polyester segment composed of a dicarboxylic acid component and a glycol component and having crystallinity as typified by polybutylene terephthalate and polybutylene naphthalate.
  • the soft segment component refers to a low-melting polymer segment such as polyoxyalkylene glycols such as polytetramethylene glycol, poly- ⁇ -caprolactone, and polybutylene adipate.
  • the ratio of the hard segment and the soft segment When expressing the ratio of the hard segment and the soft segment, the molecular weight of the different soft segment species is greatly different, or the substantial molecular weight in the polyester elastomer (block copolymer) is not known depending on the soft segment species (or Since it is difficult to calculate, it is necessary to consider in mass% instead of mol%. Therefore, the ratio of the hard segment component and the soft segment component is described in mass%.
  • the mass% of the soft segment component of the polyester elastomer is calculated as follows.
  • the mass% of the polytetramethylene glycol residue in the elastomer is the mass% of the soft segment component.
  • the total of each mass% of the terephthalic acid residue and 1,4-butanediol residue in the elastomer is defined as mass% of the hard segment component.
  • a soft segment component constituting the polyester elastomer one or two types selected from a polyalkylene ether component, an aliphatic polyester component, and a polyalkylene carbonate component are considered in consideration of an improvement effect of mechanical properties and surface energy. The above is desirable.
  • a polyalkylene ether component when low temperature characteristics and hydrolysis resistance are required as characteristics other than mechanical characteristics and surface energy, it is preferable to use a polyalkylene ether component, and when heat resistance is required, an aliphatic polyester component It is preferable to use a polyalkylene carbonate component when heat resistance and hydrolysis resistance are required.
  • a polyalkylene ether component is preferable as a soft segment component.
  • the soft segment component is often composed of a long-chain glycol component
  • the soft segment component is considered as a glycol component for convenience.
  • the soft segment component is made of polylactone, it is considered as a glycol component.
  • polyalkylene ether component examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly (ethylene oxide / propylene oxide) copolymer, poly (ethylene oxide / tetrahydrofuran) copolymer, poly (ethylene oxide / propylene oxide / tetrahydrofuran). ) Copolymers and the like.
  • the polyalkylene ether component is preferably 25% by mass or more, more preferably It is 30% by mass or more, more preferably 35% by mass or more.
  • the upper limit is preferably 95% by mass or less, and more preferably 90% by mass or less.
  • Polytetramethylene glycol is desirable as the polyalkylene ether component.
  • the number average molecular weight of polytetramethylene glycol is preferably 400 or more, more preferably 500 or more, still more preferably 600 or more, particularly preferably 700 or more, and the upper limit is preferably 4000 or less, more preferably 3500 or less, More preferably, it is 3000 or less. If the number average molecular weight of the polytetramethylene glycol is less than 400, it may be difficult to develop the elasticity inherent to the elastomer, and the impact resistance may decrease. On the other hand, when it exceeds 4000, compatibility with the polyester portion constituting the hard segment component may be lowered, and it may be difficult to maintain the block property.
  • the aliphatic polyester component examples include polylactones and polyesters composed of aliphatic dicarboxylic acids having 2 to 10 carbon atoms and aliphatic glycols having 2 to 10 carbon atoms.
  • polylactones are preferred.
  • polylactones include polycaprolactone, polyenane lactone, and polycaprylolactone.
  • the polylactone is preferably 40% by mass or more, more preferably 45% by mass. % Or more, more preferably 50 mass% or more.
  • the upper limit is preferably 80% by mass or less, more preferably 70% by mass or less.
  • These polylactones can be used alone or in admixture of two or more, and poly- ⁇ -caprolactone is most preferred in view of balance between physical properties, handling properties and the like.
  • the polyester elastomer is preferably polymerized using ⁇ -caprolactone as a raw material in consideration of reactivity and productivity.
  • a polyester type block copolymer can be obtained by reacting a crystalline high melting point polyester constituting the hard segment component with the lactone.
  • the reaction is usually carried out by carrying out a melting reaction at a temperature of 200 ° C. to 250 ° C. for 0.5 to 3 hours under a nitrogen atmosphere and then removing unreacted lactones under vacuum.
  • the polyalkylene carbonate component examples include aliphatic polycarbonate diols composed of 1,6-hexanediol, 1,9-nonanediol, and 3-methyl-1,5-pentanediol.
  • the polyalkylene carbonate component is preferably 20% by mass or more, more preferably It is 25% by mass or more, more preferably 30% by mass or more.
  • the upper limit is preferably 80% by mass or less, more preferably 70% by mass or less.
  • polyester carbonate components can be used alone or in admixture of two or more, and polyhexamethylene carbonate diol is most preferred in view of balance between physical properties and handling properties.
  • the polyester elastomer is preferably polymerized using a polyalkylene carbonate diol having a molecular weight increased to some extent in order to maintain the block property.
  • the molecular weight of the polyalkylene carbonate diol used as the raw material is preferably 2000 to 80000 in terms of number average molecular weight. The higher the molecular weight, the higher the block property.
  • the polycarbonate diol has a molecular weight of preferably 2000 or more, more preferably 3000 or more, and still more preferably 5000 or more.
  • the upper limit of the molecular weight of the polycarbonate diol is preferably 80000 or less, more preferably 70000 or less, and even more preferably 60000 or less, from the viewpoint of compatibility between the hard segment and the soft segment. If the molecular weight of the polycarbonate diol is too large, the compatibility is lowered and phase separation occurs, which may adversely affect the mechanical properties.
  • the total of the dicarboxylic acid components constituting the hard segment component is 100% by mass, it is necessary to contain 20% by mass or more of the furandicarboxylic acid component.
  • the methyl ester derivative may be used as the dicarboxylic acid component.
  • 2,5-furandicarboxylic acid or its methyl ester derivative is particularly preferable as a furan carboxylic acid as a raw material monomer to be used. More preferably, it is 40 mass% or more, More preferably, it is 60 mass% or more. If it is less than 20% by mass, a good surface energy improvement effect cannot be obtained.
  • the dicarboxylic acid component other than the furandicarboxylic acid component constituting the hard segment component a known copolymerizable component can be used.
  • the component include aromatic dicarboxylic acids having 8 to 22 carbon atoms, aliphatic dicarboxylic acids having 4 to 12 carbon atoms, and carboxylic acids such as alicyclic dicarboxylic acids having 8 to 15 carbon atoms and ester derivatives thereof.
  • one type or two or more types can be copolymerized.
  • terephthalic acid isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, 4,4′-dicarboxybiphenyl, 5-sodium sulfoisophthalic acid and other aromatic dicarboxylic acids
  • 1,4-cyclohexanedicarboxylic acid 1, Alicyclic dicarboxylic acids such as 3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 2,5-norbornenedicarboxylic acid, tetrahydrophthalic acid, oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid
  • aliphatic dicarboxylic acids such as undecanedioic acid, dodecanedioic acid, octadecanedioic acid, fumaric acid, maleic acid, itaconic acid, mesaconic acid, citrac
  • the dicarboxylic acid component other than the furandicarboxylic acid component constituting the hard segment component is preferably an aromatic dicarboxylic acid from the viewpoint of hydrolysis resistance, and in particular, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 4 4′-dicarboxybiphenyl is preferred.
  • the dicarboxylic acid component constituting the hard segment component the total of the furandicarboxylic acid component and the aromatic dicarboxylic acid component is preferably 90% by mass or more, and more preferably 95% by mass or more.
  • p-hydroxybenzoic acid p-hydroxybenzoic acid, m-hydroxybenzoic acid, o-hydroxybenzoic acid, lactic acid, oxirane, ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ - Caprolactone, glycolic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxyisobutyric acid, 2-hydroxy-2-methylbutyric acid, 2-hydroxyvaleric acid, 3-hydroxyvaleric acid, 4-hydroxy Hydroxycarboxylic acids such as valeric acid, 5-hydroxyvaleric acid, 6-hydroxycaproic acid, 10-hydroxystearic acid and their ester-forming derivatives may be used as copolymerization components.
  • 70% by mass or more is preferably 1,4-butanediol from the viewpoints of crystallinity, moldability and heat resistance. More preferably, it is 80 mass% or more, More preferably, it is 90 mass% or more. If it is less than 70% by mass, the mechanical strength and heat resistance tend to decrease.
  • glycol component other than the 1,4-butanediol component constituting the hard segment component examples include aliphatic compounds having 2 to 20 carbon atoms having two hydroxyl groups in the molecule, and those having 6 to 40 carbon atoms.
  • aromatic compound examples include compounds having two hydroxyl groups in the molecule, and one or more of them can be copolymerized.
  • ethylene glycol 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 2,2 -Diethyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, 2-ethyl-2-methyl-1, 3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 1 , 7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10
  • the glycol component constituting the hard segment component is a total of one or more of 1,4-butanediol and ethylene glycol, 1,2-propanediol, neopentyl glycol, and 1,6-hexanediol, It is preferably 90% by mass or more, and more preferably 95% by mass or more.
  • a tri- or higher functional carboxylic acid component or an alcohol component may be added as a copolymerization component.
  • the trifunctional or higher functional carboxylic acid components include trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, and trimesic acid.
  • examples thereof include aliphatic carboxylic acids such as 1,2,3,4-butanetetracarboxylic acid.
  • tri- or higher functional alcohol component examples include glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, ⁇ -methylglucose, mannitol, and sorbitol. These copolymerization ratios are preferably 0.1% by mass or more and 5% by mass or less in the hard segment component. By copolymerization in this range, the resin skeleton is branched, the terminal is increased, and the reaction The effect which promotes is demonstrated. If the copolymerization ratio of the tri- or higher functional compound is too high, gelation occurs and a problem arises in moldability and the like.
  • the reduced viscosity of the polyester elastomer is not particularly limited, but is preferably 0.5 to 3.5 dl / g. If it is less than 0.5 dl / g, the mechanical strength is significantly reduced. If it exceeds 3.5 dl / g, the melt viscosity becomes high and the handling property becomes worse, and the polymerization time becomes longer, which may adversely affect the productivity. Preferably it is 0.7 to 3.0 dl / g, more preferably 0.8 to 2.8 dl / g.
  • polyester elastomer of the present invention As a method for producing the polyester elastomer of the present invention, known methods can be employed. For example, after the above dicarboxylic acid and glycol components are esterified at 150 to 250 ° C., they are heated at 200 to 280 ° C. under reduced pressure. The desired polyester can be obtained by condensation. Alternatively, a target polyester can be obtained by performing a transesterification reaction at 150 ° C. to 250 ° C. using a derivative such as dimethyl ester of dicarboxylic acid and a glycol component, and then polycondensing at 200 ° C. to 280 ° C. under reduced pressure. Can do.
  • a known catalyst can be used.
  • acetate, carbonate such as lead, zinc, manganese, calcium, cobalt, magnesium, sodium, or metal oxide such as magnesium, zinc, lead, antimony, germanium, or organometallic compound such as tin, lead, titanium, etc. Can be used singly or in combination depending on the reaction system.
  • an antioxidant for the purpose of suppressing thermal deterioration, oxidative deterioration, etc., and it may be added before, during or after the reaction.
  • an antioxidant for example, known hindered phenol-based, phosphorus-based, and thioether-based antioxidants can be used. These antioxidants can be used alone or in combination.
  • the addition amount is preferably 0.1% by mass or more and 5% by mass or less based on the polyester elastomer. If it is less than 0.1% by mass, the effect of preventing thermal deterioration may be poor. If it exceeds 5% by mass, other physical properties may be adversely affected.
  • the method for adding the polyfunctional compound is not particularly limited, and a normal method is used. For example, a method of adding at an arbitrary stage before the end of polycondensation, a method of adding in an inert gas atmosphere after the end of polycondensation, an addition after taking out the copolymer into pellets, flakes, or powders And a method of melt mixing with an extruder or a kneader.
  • polyester elastomer of the present invention have higher performance, generally well-known stabilizers, lubricants, mold release agents, plasticizers, flame retardants, flame retardant aids, ultraviolet absorbers, light stabilizers, Pigments, dyes, antistatic agents, conductivity-imparting agents, dispersants, compatibilizing agents, antibacterial agents, various fillers, and the like can be added alone or in combination of two or more.
  • the polyester elastomer of the present invention has better impact resistance and adhesion to other materials than conventional well-known resins, it is a molded product in a wide range of fields such as fibers, films, sheets, and various molded products.
  • a container such as a bottle, a pipe, a tube, a sheet, a plate, or a film.
  • Particularly preferable molded articles include constituent materials such as an ink tank of an ink jet printer, an electrophotographic toner container, a packaging resin, a copying machine, a business machine such as a printer, or a camera casing.
  • the method for molding the polyester elastomer of the present invention is not particularly limited.
  • molding methods generally used for thermoplastic resins such as injection molding (including two-color molding, insert molding, etc.), hollow molding (various types) Blow molding), extrusion molding (including coextrusion molding, etc.), vacuum molding, press molding, calendar molding, and the like can be used.
  • these molded articles are provided with chemical functions, electrical functions, magnetic functions, mechanical functions, friction / wear / lubricating functions, optical functions, surface functions such as thermal functions, etc.
  • Various secondary processing can also be performed. Examples of secondary processing include embossing, painting, adhesion, printing, metalizing (plating, etc.), machining, surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, Coating, etc.).
  • the polyester elastomer of the present invention has better impact resistance and adhesion to other materials than other well-known resins, and is useful as a component in the above applications, particularly as a composite material with other materials. It has characteristics.
  • Example 1 In a reaction vessel equipped with a stirrer, a thermometer, and a condenser for distillation, 184 parts by mass of dimethyl 2,5-furandicarboxylate, 175 parts by mass of 1,4-butanediol, polytetramethylene glycol having a number average molecular weight of 1000 60 parts by mass of “PTMG1000” (manufactured by Mitsubishi Chemical Corporation) and 0.25 parts by mass of tetrabutyl titanate were added, and a transesterification reaction was performed at 170 to 220 ° C. for 2 hours. After completion of the transesterification reaction, the temperature was raised to 245 ° C., while the pressure in the system was slowly reduced to 665 Pa at 245 ° C.
  • each component name is represented by the raw material used, but the composition (% by mass) is a value obtained from the residue of each component calculated by the method described below.
  • Examples 2 to 5 Comparative Examples 1 to 6
  • the synthesis was performed in the same manner as in Example 1 except that the raw materials used and the composition were changed.
  • the composition and physical properties were as shown in Table 1.
  • Comparative Examples 1 to 6 are compositions containing no soft segment and / or furandicarboxylic acid.
  • Example 6 In a reaction vessel equipped with a stirrer, a thermometer, and a condenser for distillation, 210 parts by mass of polybutylene furandicarboxylate (PBF: polymer obtained in Comparative Example 2), ⁇ -caprolactone (manufactured by Daicel Chemical Industries, Ltd.) ) 115 parts by mass were charged, and after purging with nitrogen gas, the mixture was melt-reacted for 120 minutes with stirring at 230 ° C. Thereafter, unreacted ⁇ -caprolactone was removed under vacuum to obtain a polyester elastomer whose soft segment component was poly- ⁇ -caprolactone. The composition and physical properties of this polyester elastomer were as shown in Table 2.
  • Example 7 210 parts by weight of polybutylene furandicarboxylate (PBF: polymer obtained in Comparative Example 2) and 115 parts by weight of polyhexamethylene carbonate diol having a number average molecular weight of 10,000 are stirred at 245 ° C. and 130 Pa for 1 hour, and the resin is transparent. The contents were taken out and cooled to obtain a polyester elastomer. The composition and physical properties of this polyester elastomer were as shown in Table 2.
  • Comparative Example 7 The synthesis was performed in the same manner as in Example 6 except that the raw materials used were changed. The composition and physical properties were as shown in Table 2. The polymer obtained in Comparative Example 1 was used as polybutylene terephthalate (PBT).
  • Comparative Example 8 The synthesis was performed in the same manner as in Example 7 except that the raw materials used were changed. The composition and physical properties were as shown in Table 2. The polymer obtained in Comparative Example 1 was used as polybutylene terephthalate (PBT).
  • Comparative Examples 7 and 8 are compositions containing no furandicarboxylic acid.
  • composition The composition of the polyester elastomer was determined by 1 H-NMR measurement (proton nuclear magnetic resonance spectroscopy) with a resonance frequency of 400 MHz.
  • the measuring apparatus used was an NMR apparatus 400-MR manufactured by VARIAN, and deuterated chloroform was used as the solvent.
  • deuterated chloroform / trifluoroacetic acid 85/15 (mass ratio) was used.
  • Reduced viscosity 0.05 g of a sufficiently dried sample was dissolved in 25 ml of a mixed solvent of phenol / tetrachloroethane (mass ratio 6/4) and measured at 30 ° C. using an Ubbelohde viscosity tube.
  • a sheet sample used for impact strength measurement was prepared using a heat press machine SA-302-I manufactured by Tester Sangyo Co., Ltd. Place a 0.1 mm thick mold frame and polyester elastomer in it between two Teflon (registered trademark) sheets, and sandwich the Teflon (registered trademark) sheet between two stainless steel plates. Installed in the press. After melting for 2 minutes under the temperature condition of the melting point of polyester elastomer + 50 ° C., a load of 50 kgf / cm 2 was applied, and after 1 minute, it was immersed in water and rapidly cooled to obtain a 0.1 mm thick sheet sample. Depending on the level, it may become amorphous at the time of rapid cooling, but in that case, it was allowed to stand for a while at room temperature or near the crystallization temperature, and after confirming whitening due to crystallization, the impact strength was measured.
  • the sheet sample used for contact angle measurement was prepared using a heat press machine SA-302-I manufactured by Tester Sangyo Co., Ltd. Between the two naflon sheets, a 0.2 mm thick mold frame and a polyester elastomer were placed and placed, and the naflon sheet was further sandwiched between two stainless plates and installed in a heat press machine. After melting for 2 minutes under a temperature condition of about + 50 ° C. of the melting point of the polyester elastomer, a load of 50 kgf / cm 2 was applied, and after 1 minute, it was immersed in water and quenched to obtain a sheet sample having a smooth surface of 0.2 mm thickness.
  • the surface energy of the polyester elastomer was calculated from the contact angle.
  • the dripping amount was 1.8 microliters and the contact angle after standing for 1 minute was read.
  • the polyester elastomer of the present invention has particularly excellent impact resistance and surface energy by including a flange carboxylic acid component and a specific soft segment component, compared with a resin outside the scope of the present invention.
  • a resin outside the scope of the present invention.
  • Example 1 dicarboxylic acid component of the hard segment component is furandicarboxylic acid
  • Comparative Example 3 dicarboxylic acid component of the hard segment component is terephthalic acid
  • the polyester elastomer containing the furandicarboxylic acid component has a higher surface energy ⁇ s due to the extremely high surface energy polar term ⁇ sh compared to the polyester elastomer not containing it.
  • the polyester elastomer of the present invention is excellent in impact resistance and adhesion to other materials, and has great industrial utility value.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

La présente invention concerne un élastomère de polyester qui est constitué de 20 à 85 % en masse d'un composant segment dur et de 80 à 15 % en masse d'un composant segment mou. Le composant segment dur comprend un composant acide dicarboxylique et un composant glycol. Quand la totalité du composant acide dicarboxylique constituant le composant segment dur représente 100 % en masse, le composant segment dur contient au moins 20 % en masse d'un composant acide furannedicarboxylique. L'élastomère de polyester présente une excellente résistance au choc et d'excellentes propriétés d'adhérence, par comparaison avec d'autres matériaux.
PCT/JP2014/083397 2013-12-19 2014-12-17 Elastomère de polyester Ceased WO2015093525A1 (fr)

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JP2013-262549 2013-12-19

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107312167A (zh) * 2016-04-26 2017-11-03 中国科学院理化技术研究所 一种基于生物质基2,5-呋喃二甲酸的热塑性聚酯弹性体及其制备方法
CN108586718A (zh) * 2018-03-20 2018-09-28 青岛科技大学 一种石墨烯/聚酯热塑性弹性体复合材料及其制备方法
CN109134835A (zh) * 2018-07-11 2019-01-04 中国科学院宁波材料技术与工程研究所 一种热塑性聚酯弹性体及其制备方法
JP2021531370A (ja) * 2018-08-10 2021-11-18 エルジー・ケム・リミテッド ポリカーボネートおよびその製造方法
WO2023127804A1 (fr) * 2021-12-27 2023-07-06 東洋紡株式会社 Copolyester thermoplastique
CN117843938A (zh) * 2024-03-08 2024-04-09 华东理工大学 一种类聚烯烃的长碳链聚酯弹性体、制备方法及其应用

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CN117843938A (zh) * 2024-03-08 2024-04-09 华东理工大学 一种类聚烯烃的长碳链聚酯弹性体、制备方法及其应用
CN117843938B (zh) * 2024-03-08 2024-05-24 华东理工大学 一种类聚烯烃的长碳链聚酯弹性体、制备方法及其应用

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