WO2007052847A1 - Polymer compound and method of synthesizing the same - Google Patents

Polymer compound and method of synthesizing the same Download PDF

Info

Publication number
WO2007052847A1
WO2007052847A1 PCT/JP2006/322510 JP2006322510W WO2007052847A1 WO 2007052847 A1 WO2007052847 A1 WO 2007052847A1 JP 2006322510 W JP2006322510 W JP 2006322510W WO 2007052847 A1 WO2007052847 A1 WO 2007052847A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
polymer compound
substituted
hydrocarbon group
polymerization
Prior art date
Application number
PCT/JP2006/322510
Other languages
French (fr)
Inventor
Katsuhiro Matsuda
Hirohide Matsuhisa
Hitoshi Horie
Takeshi Komuro
Original Assignee
Canon Kabushiki Kaisha
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 Canon Kabushiki Kaisha filed Critical Canon Kabushiki Kaisha
Priority to EP06832523.2A priority Critical patent/EP1948709B1/en
Priority to US12/092,805 priority patent/US8143355B2/en
Publication of WO2007052847A1 publication Critical patent/WO2007052847A1/en
Priority to US13/402,723 priority patent/US20120207956A1/en
Priority to US14/792,415 priority patent/US11634535B2/en

Links

Classifications

    • 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
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]

Definitions

  • the present invention relates to a novel polymer compound, and to a method of synthesizing the same.
  • polylactic acid has attracted attention as a plastic produced by using a plant as a raw material (hereinafter, referred to as a plant-derived plastic) .
  • Lactic acid to be used as a raw material is obtained by fermenting starch of corn, sweet potato, or the like.
  • polylactic acid often has degraded mechanical strength and heat resistance compared to those of a conventional plastic, and use of polylactic acid has been limited to a packaging material, tableware, and the like.
  • An object of the invention described in Japanese Patent Application Laid-Open No. Hll-140292 is to provide a polylactic acid-based resin composition having maintained characteristics of polylactic acid such as excellent biodegradability, mechanical strength, heat stability, and transparency, and improved brittleness of polylactic acid, and a method of producing the same.
  • Another object. of the invention described in Japanese Patent Application Laid-Open No. 11-140292 is to provide a packaging material or various molded products each formed of the polylactic acid- based resin composition.
  • US Patent No. 2,251,731 describes experimental conditions for synthesis of a polyester having a heterocyclic ring in a skeleton of a polymer compound, and an yield of the polymer compound.
  • US Patent No. 2,251,731 and Y. Hachihama, T. Shono, and K. Hyono, Technol. Repts. Osaka Univ., 8, 475 (1958) each describe the skeleton structure described above, but include no description of the number of units.
  • a polymer compound having the skeleton structure described above by defining a degree of polymerization (DPn, in polymethyl methacrylate equivalent) and have studied mechanical strength.
  • DPn degree of polymerization
  • the inventors of the present invention have found that the polymer compound can be used for applications of electric and electronic components and the like, and have completed the present invention.
  • A represents an aromatic hydrocarbon group which may be substituted, an aliphatic hydrocarbon group which may be substituted, or an alicyclic hydrocarbon group which may be substituted, and n represents a degree of polymerization of 185 or more and 600 or less.
  • composition for a molded product including the above-mentioned polymer compound and an additive.
  • B represents an aromatic hydrocarbon group which may be substituted, an aliphatic hydrocarbon group which may be substituted, or an alicyclic hydrocarbon group which may be substituted, and m is 2 or more.
  • the polymer compound of the present invention has numerical limitation for the degree of polymerization (the number of repeating units) , and is a polymer compound having excellent moldability and mechanical strength (-flexural strength) .
  • such a polymer compound can be provided as a thermoplastic resin containing an additive.
  • Fig. 1 shows polybutylene-2, 5-furandicarboxylate and 1 H-NMR spectrum thereof.
  • Fig. 2 shows polyethylene-2, 5-furandicarboxylate and 1 H-NMR spectrum thereof.
  • Fig. 3 shows polytrimethylene-2, 5- furandicarboxylate and , 1 H-NMR spectrum there.of.'
  • a polymer compound is characterized by having a unit represented by the following formula (2):
  • A represents an aromatic hydrocarbon group which may be substituted, an aliphatic hydrocarbon group which may be substituted, or an alicyclic hydrocarbon group which may be substituted
  • n represents a degree of polymerization (DPn, in polymethyl methacrylate equivalent) of 185 or more and 600 or less.
  • DPn degree of polymerization
  • the polymer compound has low flexural strength and is hardly used for applications of electric and electronic components.
  • n is more than 600, the polymer compound has excessively high viscosity and poor moldability.
  • the polymer compound has a flexural strength of more than 34 MPa, which is a flexural strength of high impact polystyrene (PS Japan Corporation, grade name, 433) as a general-purpose plastic, and thus has favorable mechanical strength.
  • the polymer compound according to the present invention may have one kind of unit represented by the formula (2), or, may be a copolymer having two or more kinds of units having different Rs.
  • the former compound may be referred to as a homopolymer, and the latter compound may be referred to as a copolymer.
  • the polymer compound according to the present invention may be a copolymer with a different monomer unit.
  • the polymer compound of the present invention is obtained from a plant-derived raw material, the polymer compound according to the present invention is often a homopolymer.
  • Examples of the aromatic hydrocarbon group represented by A in the formula (2) include condensed rings such as a naphthalene ring, an indene ring, an anthracene ring, and a phenanthrene ring, in addition to a benzene ring, a biphenyl ring, and a bis (phenyl ) alkane .
  • Examples of the bis (phenyl) alkane include bis (2-hydroxyphenyl) methane and 2,2'- bis (hydroxyphenyl ) propane .
  • heterocyclic ring examples include: a five-membered ring such as furan, thiophene, pyrrole, oxazole, thiazole, or imidaozle; a six-membered ring such as pyran, pyridine, pyridazine, pyrimidine, or pyrazine; and a condensed ring such as indole, carbazole, coumarin, q ⁇ inoline, isoquinoline, acridine, benzothiazole, quinolixane, or purine.
  • a five-membered ring such as furan, thiophene, pyrrole, oxazole, thiazole, or imidaozle
  • a six-membered ring such as pyran, pyridine, pyridazine, pyrimidine, or pyrazine
  • a condensed ring such as indole, carbazole,
  • Examples of the aliphatic hydrocarbon group represented by A in the formula (2) include an ethylene group, a propylene group, an isopropylene group, an n- butylene group, an isobutylene group, an s-butylene group, a t-butylene group, a pentylene group, an isopentylene group, and a neopentylene group.
  • Preferred examples of the aliphatic hydrocarbon group include linear or branched alkylene groups each having 2 to 4 carbon atoms such 1 as an ethylene group, a propylene group, and a butylene group.
  • Examples of the alicyclic hydrocarbon group represented by A in the formula (2) include divalent groups each obtained from a cycloalkylene group or a cycloalkenyl group.
  • Examples of the cycloalkylene group include a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, and a cyclodecylene group.
  • Examples of the cycloalkenyl group include a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, and a cyclooctenyl group.
  • Each of those aromatic hydrocarbon groups, aliphatic hydrocarbon groups, and alicyclic hydrocarbon groups may be substituted.
  • substituents include those each containing a hetero atom such as an oxygen atom, a nitrogen atom, a silicon atom, or a halogen atom.
  • Specific examples of the substituents include an aliphatic oxy group, an aromatic oxy group, a siloxy group, an amino group, a nitro group, a cyano group, a silyl group, and a 'halogeno group.
  • the aliphatic group of the aliphatic oxy group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a cyclohexylmethyl group, a trimethylsiloxyhexyl group, a chloroethyl group, a methoxybutyl group, a dimethylaminomethyl group, a butenyl group, and an octenyl group.
  • An example of the aromatic oxy group is a phenoxy group.
  • the polymer compound having the unit represented by the formula (2) may be obtained by reacting: a furandicarboxylic acid compound represented by the formula (1) (including furandicarboxylic acid and a derivative in which X represents an alkoxy group or a halogen atom) ; and a polyhydric alcohol represented by the formula (3) .
  • a furandicarboxylic acid compound represented by the formula (1) including furandicarboxylic acid and a derivative in which X represents an alkoxy group or a halogen atom
  • a polyhydric alcohol represented by the formula (3) At least one kind of furandicarboxylic acid, a furandicarboxylic acid compound, and a polyhydric alcohol all serving as raw materials for a polymer compound may be produced from biomass .
  • X represents a hydroxyl group, an alkoxy group, or a halogen atom.
  • furandicarboxylic acid examples include: 2,5- furandicarboxylic acid; 2, 4-furandicarboxylic acid; and 3, 4-furandicarboxylic acid.
  • Preferred examples of the alkoxy group in the formula (1) include a methoxy group and an ethoxy group.
  • the furandicarboxylic acid compound represented by the formula (1) can be produced from the so-called plant-derived raw material (biomass) such as cellulose, glucose, or fructose by a known method.
  • B represents an aromatic hydrocarbon group which may be substituted, an aliphatic hydrocarbon group which may be substituted, or an alicyclic hydrocarbon group which may be substituted, and m is 2 or more.
  • reaction path is described by the following general formula.
  • the polymer compound according to the present invention may be referred to as a condensate based on the reaction path.
  • Examples of the aromatic hydrocarbon group represented by B in the formula (3) include various aromatic rings represented by R in the formula (2) such as a benzene ring and a biphenyl ring.
  • the aromatic ring may have various substituents .
  • Examples of the substituent include: a hydrocarbon group such as an alkyl group or an alkenyl group; and various substituents described for A in the formula (2).
  • Examples of the aliphatic hydrocarbon group represented by B in the formula (3) include: a hydrocarbon group such as an alkylene group; and various substituents described for the aliphatic hydrocarbon group represented by A in the formula (2).
  • Preferred examples of the aliphatic hydrocarbon group include linear or branched alkylene groups each having 2 to 4 carbon atoms such as an ethylene group, a propylene group, and a butylene group.
  • Examples of the alicyclic group represented by B in the formula (3) include: a cycloalkylene group; a cycloalkenyl group; and the alicyclic hydrocarbon groups described for A in the formula (2) . Each of those aromatic hydrocarbon groups, aliphatic hydrocarbon groups, and alicyclic hydrocarbon groups may be substituted. Examples of the substituent include various substituents described for A in the formula (2 ) . m in the formula (3) is preferably 2.
  • the formula (3) include an aliphatic or alicyclic diol, a dihydroxybenzene, a bisphenol, glycerin, trimethylolpropane, pentaerithritol, sorbitol, and saccharides. Further, there can be exemplified an etherdiol which is obtained through intermolecular dehydration of " diols, and an oxycarboxylic acid such as hydroxybenzoic acid.
  • aliphatic or alicyclic diol examples include ethylene glycol, 1, 3-propanediol, 1,4- butanediol, and 1, 4-cyclohexanedimethanol .
  • dihydroxybenzene examples include 1, 3-dihydroxybenzene and 1, 4-dihydroxybenzene .
  • bisphenol examples include bis (2- hydroxyphenyl) methane, 2, 2 ' -bis (hydroxyphenyl) propane, and 2, 2 ' -bis (4-hydroxyphenyl) -sulfone .
  • a diol is used as a polyhydric alcohol.
  • the diol represents 1,3- propanediol or 1, 4-butanediol and is produced from a plant-derived raw material.
  • Examples of a polymerization method for obtaining the polymer compound according to the present invention include generally known methods such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization.
  • the polymerization method is arbitrarily selected in accordance with the kind of molded product.
  • a polymerization temperature, a polymerization catalyst, a medium such 1 as a solvent, and the like may be used in accordance with the polymerization method.
  • the method of synthesizing the polymer compound according to the present invention is as follows.' That is, the synthesis method includes the steps of: conducting esterification of a furandicarboxylic acid compound and a polyhydric alcohol in the presence of a catalyst to obtain an ester compound; and conducting polycondensation of the thus-obtained ester compound.
  • a reaction temperature for conducting esterification is HO 0 C to 200 0 C, and more preferably 150 0 C to 18O 0 C.
  • a temperature range for conducting polycondensation is 18O 0 C to 280 0 C, and more preferably 180°C to 230°C.
  • a polymer compound in a molten state formed at an endpoint of this polycondensation process may be used as it is or molded into a required shape to be used for a thermoplastic resin for a molded product.
  • a composition containing the obtained polymer compound and various additives added as required may be used as a raw material for a molded product.
  • the method of producing the polymer compound of the present invention includes two steps.
  • the first- step involves esterification of a dicarboxylic acid and a diol
  • the second step involves polycondensation through an ester exchange reaction.
  • esterification of furandicarboxylic acid and a diol is conducted by gradually heating furandicarboxylic acid, diols, and a catalyst or a catalyst mixture to 110 0 C to 200°C, and more preferably 150 0 C to 180 0 C under stirring. An endpoint of the esterification can easily be confirmed at the time when the reaction mixture becomes transparent. At this time, the reaction mixture is an oligomer, and is not a polymer.
  • a reaction system is heated to a temperature of 18O 0 C to 280°C, and more preferably 180°C to 230 0 C, to thereby cause an ester exchange reaction and start polycondensation for molecular weight increase.
  • the polycondensation step described above is preferably conducted under vacuum.
  • a diol forms as a by-product, and the diol is removed to increase a reaction rate of polycondensation.
  • the heating, stirring, and reducing pressure are continued until a polymer compound has a sufficient molecular weight allowing molding the molded product, or a sufficient molecular weight satisfying specifications of the molded product.
  • an amount of a monomer to be introduced at a start of a reaction is desirably 1 time to 3 times moles of furandicarboxylic acid.
  • the diol in an excessive amount or a diol formed as the polycondensation reaction proceeds may be removed out of the reaction system by: distilling off the diol by bringing the reaction system to reduced pressure; distilling off the diol by boiling with another solvent; or removing the diol by other methods.
  • Synthesis of the polymer compound from a dicarboxylic acid and a diol proceeds without addition of a catalyst because of an autocatalysis action of the dicarboxylic acid.
  • a concentration of the dicarboxylic acid reduces with the progress of polymerization, and thus the catalyst is more preferably added.
  • the synthesis of the polymer compound of the present invention includes two steps of esterification and polycondensation through an ester exchange reaction, and thus preferred catalysts are present for respective steps .
  • Examples of a catalyst preferred for esterification in the first step include: a metal oxide or salt; an organometallic compound of tin, lead, titanium, or the like; and a tetravalent hafnium compound such as hafnium (IV) chloride or hafnium (IV) chloride (THF) 2-
  • Examples of a catalyst most preferred for polycondensation through ester exchange in the second step include: an acetate or carbonate of lead, zinc, manganese, calcium, cobalt, magnesium, or the like; a metal oxide of magnesium, zinc, lead, antimony, or the like; and an organometallic compound of tin, lead, titanium, or the like.
  • a particularly preferred example of a catalyst effective in both steps is titanium alkoxide.
  • the catalysts may be added separately in the first step and the second step, or may be mixed in an arbitrary combination from the above-mentioned catalyst group with a furandicarboxylic acid and a diol from the start of the reaction.
  • the catalysts may obviously be added while a furandicarboxylic acid and a diol are heated, or the catalysts may be added once or more in an arbitrary combination form the above-mentioned catalyst group.
  • solid-state polymerization may be conducted by a known method after the polymer compound is obtained.
  • the thus- obtained polymer has a degree of polymerization (DPn, in polymethyl methacrylate equivalent) of 285, Tm of 170°C, and a 5% weight loss heat decomposition temperature of 338°C.
  • the polymer compound obtained by the above- mentioned method is a thermoplastic resin.
  • the polymer compound has sufficient physical properties satisfying specifications of an optical device, a bottle, or a casing material.
  • the polymer compound may be used as a thermoplastic resin for molding and molded into a desired shape, to thereby obtain a molded product according to the present invention.
  • the molding method is not particularly limited. For example, compression molding, extrusion molding, or injection molding may be used.
  • the polymer compound obtained by the above-mentioned method may contain a required amount of an additive such as a flame retardant, a colorant, an internal releasing agent, an antioxidant, a UV absorber, and various filers added.
  • Preferred application examples of the molded product include: an ink tank of an inkjet printer; a toner container for electrophotography; a packaging resin; and a structural material of a business machine such as a copier or a printer, or a casing of a camera.
  • the following devices and conditions were used for measurement of a molecular weight of the polymer compound, measurement of a glass transition temperature (Tg) , a crystallization temperature (Tc) , and a melting point (Tm) of the polymer compound, and NMR measurement for confirming a structure of the polymer.
  • Tg glass transition temperature
  • Tc crystallization temperature
  • Tm melting point
  • Degree of polymerization A number average molecular weight was determined by using a PMMA standard, and a degree of polymerization was calculated.
  • Example 1 Synthesis of polybutylene-2, 5- furandicarboxylate
  • a 1-L four-necked flask equipped with a nitrogen introducing tube, a fractionating tube-condenser, a thermometer, and a SUS stirring blade was prepared.
  • 2-furandicarboxylic acid 149.9 g
  • 4-butanediol 259.5 g
  • molar ratio 1:3
  • a tin catalyst '(0.059 wt%) a titanium catalyst (0.059 wt%) dissolved in toluene were measured.
  • the fractionating tube was changed to a T-tube, and pressure reduction was started. Inside of the flask was adjusted to full vacuum (5 Pa) over about 1 hour, and the reaction was continued at 180°C for about 390 min under reduced pressure (5 Pa) .
  • the obtained polymer was dissolved in hexafluoroisopropanol, and reprecipitated with methanol. The resultant was dried at 60 0 C under vacuum day and night. Then, solid-state polymerization was conducted at a reaction temperature of 150 0 C for increasing the molecular weight.
  • the thus-obtained polymer had a degree of polymerization (DPn, in polymethyl methacrylate equivalent) of 285, Tm of 170 0 C, Tg of 31°C, Tc of 90 0 C, and a 5% weight loss heat decomposition temperature of 338 0 C.
  • Fig. 1 shows results of identification of the polymer compound by 1 H-NMR. Relative intensities of protons correspond to a theoretical value of
  • Example 2 Synthesis of polyethylene-2, 5- furandicarboxylate '
  • a 1-L four-necked flask equipped with a nitrogen introducing tube, a fractionating tube-condenser, a thermometer, and a SUS stirring blade was prepared.
  • 2-furandicarboxylic acid 149.9 g
  • a tin catalyst 0.05 wt%)
  • titanium catalyst 0.05 wt%) dissolved in toluene
  • the fractionating tube was changed to a T-tube, and pressure reduction was started. Inside of the flask was adjusted to full vacuum (5 Pa) over about 1 hour, and the reaction was continued at 280 0 C for about 390 min under reduced pressure (5 Pa) .
  • the obtained polymer was dissolved in hexafluoroisopropanol, and reprecipitated with methanol. The resultant was dried at 6O 0 C under vacuum day and night. Then, solid-state polymerization was conducted at a reaction temperature of 180°C for increasing the molecular weight.
  • the thus-obtained polymer had a degree of polymerization (DPn, in polymethyl methacrylate equivalent) of 126, Tm of 170 0 C, Tg of 85°C, a crystallization temperature of 156°C, and a heat decomposition temperature of 332°C.
  • a 1-L four-necked flask equipped with a nitrogen introducing tube, a fractionating tube-condenser, a thermometer, and a SUS stirring blade was prepared.
  • the fractionating tube was changed to a T-tube, and pressure reduction was started. Inside of the flask was adjusted to full vacuum (5 Pa) over about 1 hour, and the reaction was continued at 230°C for about 390 min under "reduced pressure (5 Pa). The obtained polymer was dissolved in hexafluoroisopropanol, and reprecipitated with methanol . The resultant was dried at 60°C under vacuum day” and night. Then, solid-state polymerization was conducted at a reaction temperature of 140 0 C for increasing the molecular weight.
  • the obtained polymer had a degree of polymerization (DPn, in polymethyl methacrylate equivalent) of 78, Tm of 150 0 C, Tg of 39°C, a crystallization temperature of 102 0 C, and a heat decomposition temperature of 335°C.
  • Table 1 collectively shows heat decomposition temperatures of Examples.
  • the heat decomposition temperature of this polyester was 279 0 C.
  • the heat decomposition temperature was obtained through TGA measurement (thermogravimetry) of a sufficiently- dried sample under the following conditions and was defined as a 5% weight loss.
  • the obtained polymer compound was subjected to injection molding to produce a rectangular test piece having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm, and the measurement was conducted in accordance with ISO standards .
  • Test method ISO 179/leA (test piece No. 1 A-notch, striking direction of edgewise) Hammer: 0.5 J
  • Table 3 shows the physical properties of the molded product. Table 3 :
  • the polymer compound of the present invention has favorable mechanical strength (flexural strength) and is a polymer compound that can be used for applications of electric and electronic components and the like.
  • the flexural strength is more than 34 MPa, which is a flexural strength of high impact polystyrene (PS Japan Corporation, grade name, 433) as a general-purpose plastic
  • the mechanical strength (flexural strength) of the sample is favorably evaluated.
  • the results shown in Table 3 all indicate favorable results.

Landscapes

  • 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)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Provided is a polymer compound having a furan ring having a degree of polymerization of 185 or more and 600 or less. This polymer compound has excellent mechanical strength (flexural strength).

Description

DESCRIPTION
POLYMER COMPOUND AND METHOD OF SYNTHESIZING THE SAME
TECHNICAL FIELD
The present invention relates to a novel polymer compound, and to a method of synthesizing the same.
BACKGROUND ART" Recently, a technology utilizing renewable resources (biomass) has attracted attention from a viewpoint of suppression " in global warming and in use of depleting resources. As a plastic, polylactic acid has attracted attention as a plastic produced by using a plant as a raw material (hereinafter, referred to as a plant-derived plastic) . Lactic acid to be used as a raw material is obtained by fermenting starch of corn, sweet potato, or the like. However, polylactic acid often has degraded mechanical strength and heat resistance compared to those of a conventional plastic, and use of polylactic acid has been limited to a packaging material, tableware, and the like.
An object of the invention described in Japanese Patent Application Laid-Open No. Hll-140292 is to provide a polylactic acid-based resin composition having maintained characteristics of polylactic acid such as excellent biodegradability, mechanical strength, heat stability, and transparency, and improved brittleness of polylactic acid, and a method of producing the same. Another object. of the invention described in Japanese Patent Application Laid-Open No. 11-140292 is to provide a packaging material or various molded products each formed of the polylactic acid- based resin composition.
Further, US Patent No. 2,251,731 and Y. Hachihama, T. Shono, and K. Hyono, Technol . Repts. Osaka Univ., 8, 475 (1958) each substantially describe the following skeleton structure.
Figure imgf000004_0001
Of the documents, Y. Hachihama, T. Shono, and K. Hyono, Technol. Repts. Osaka Univ., 8, 475 (1958) describes studies in effects of the number of methylene chains of α,ω-glycol on a melting point of a produced polymer compound in polycondensation of 2,5- furandicarboxylic acid and α,ω-glycol by conducting polycondensation with a varying number of methylene chains of α,ω-glycol.
US Patent No. 2,251,731 describes experimental conditions for synthesis of a polyester having a heterocyclic ring in a skeleton of a polymer compound, and an yield of the polymer compound. US Patent No. 2,251,731 and Y. Hachihama, T. Shono, and K. Hyono, Technol. Repts. Osaka Univ., 8, 475 (1958) each describe the skeleton structure described above, but include no description of the number of units.
Such a skeleton structure is described, but physical properties described in Y. Hachihama, T. Shono, and K. Hyono, Technol. Repts. Osaka Univ., 8, 475 (1958) (see Fig. 1 of p. 479, for example), for example, refer to a melting point alone. Mechanical strength is not revealed, and whether the skeleton structure can be used for applications of" electric and electronic components and the like is not clarified.
DISCLOSURE OF THE INVENTION
Therefore, the inventors of the present invention have synthesized a polymer compound having the skeleton structure described above by defining a degree of polymerization (DPn, in polymethyl methacrylate equivalent) and have studied mechanical strength. As a result, the inventors of the present invention have found that the polymer compound can be used for applications of electric and electronic components and the like, and have completed the present invention. Thus, according to one aspect of the present invention, there is provided a polymer compound characterized by having a unit represented by the following formula (2): ,
Figure imgf000006_0001
in the formula (2), A represents an aromatic hydrocarbon group which may be substituted, an aliphatic hydrocarbon group which may be substituted, or an alicyclic hydrocarbon group which may be substituted, and n represents a degree of polymerization of 185 or more and 600 or less.
According to another aspect of the present invention, there is provided a composition for a molded product including the above-mentioned polymer compound and an additive.
Further, according to another aspect of the present invention, there is provided a method of synthesizing a polymer compound, characterized by synthesizing a polymer compound represented by the following formula (2):
Figure imgf000006_0002
including reacting: a furandicarboxylic acid compound represented by the following formula (1):
Figure imgf000007_0001
in the formula (1), X represents a hydroxyl group, an alkoxy group, or a halogen group; and a polyhydric alcohol represented by the following formula (3) :•
B- (0H)m (3) in the formula (3), B represents an aromatic hydrocarbon group which may be substituted, an aliphatic hydrocarbon group which may be substituted, or an alicyclic hydrocarbon group which may be substituted, and m is 2 or more.
The polymer compound of the present invention has numerical limitation for the degree of polymerization (the number of repeating units) , and is a polymer compound having excellent moldability and mechanical strength (-flexural strength) .
Further, such a polymer compound can be provided as a thermoplastic resin containing an additive.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 shows polybutylene-2, 5-furandicarboxylate and 1H-NMR spectrum thereof.
Fig. 2 shows polyethylene-2, 5-furandicarboxylate and 1H-NMR spectrum thereof.- Fig. 3 shows polytrimethylene-2, 5- furandicarboxylate and ,1H-NMR spectrum there.of.'
BEST MODE FOR CARRYING OUT. THE INVENTION -
According to one aspect of the present invention, a polymer compound is characterized by having a unit represented by the following formula (2):
Figure imgf000008_0001
in the formula (2), A represents an aromatic hydrocarbon group which may be substituted, an aliphatic hydrocarbon group which may be substituted, or an alicyclic hydrocarbon group which may be substituted, and n represents a degree of polymerization (DPn, in polymethyl methacrylate equivalent) of 185 or more and 600 or less. In the case where n is less than 185, the polymer compound has low flexural strength and is hardly used for applications of electric and electronic components. In the case where n is more than 600, the polymer compound has excessively high viscosity and poor moldability.
In the case where n is 185 or more and 600 or less, the polymer compound has a flexural strength of more than 34 MPa, which is a flexural strength of high impact polystyrene (PS Japan Corporation, grade name, 433) as a general-purpose plastic, and thus has favorable mechanical strength.
The polymer compound according to the present invention may have one kind of unit represented by the formula (2), or, may be a copolymer having two or more kinds of units having different Rs. The former compound may be referred to as a homopolymer, and the latter compound may be referred to as a copolymer. Alternatively, the polymer compound according to the present invention may be a copolymer with a different monomer unit.
In the case where the polymer compound of the present invention is obtained from a plant-derived raw material, the polymer compound according to the present invention is often a homopolymer.
Examples of the aromatic hydrocarbon group represented by A in the formula (2) include condensed rings such as a naphthalene ring, an indene ring, an anthracene ring, and a phenanthrene ring, in addition to a benzene ring, a biphenyl ring, and a bis (phenyl ) alkane . Examples of the bis (phenyl) alkane include bis (2-hydroxyphenyl) methane and 2,2'- bis (hydroxyphenyl ) propane . On the other hand, examples of the heterocyclic ring include: a five-membered ring such as furan, thiophene, pyrrole, oxazole, thiazole, or imidaozle; a six-membered ring such as pyran, pyridine, pyridazine, pyrimidine, or pyrazine; and a condensed ring such as indole, carbazole, coumarin, qυinoline, isoquinoline, acridine, benzothiazole, quinolixane, or purine.
Examples of the aliphatic hydrocarbon group represented by A in the formula (2) include an ethylene group, a propylene group, an isopropylene group, an n- butylene group, an isobutylene group, an s-butylene group, a t-butylene group, a pentylene group, an isopentylene group, and a neopentylene group. Preferred examples of the aliphatic hydrocarbon group include linear or branched alkylene groups each having 2 to 4 carbon atoms such1 as an ethylene group, a propylene group, and a butylene group.
Examples of the alicyclic hydrocarbon group represented by A in the formula (2) include divalent groups each obtained from a cycloalkylene group or a cycloalkenyl group. Examples of the cycloalkylene group include a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, and a cyclodecylene group. Examples of the cycloalkenyl group include a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, and a cyclooctenyl group. Each of those aromatic hydrocarbon groups, aliphatic hydrocarbon groups, and alicyclic hydrocarbon groups may be substituted. Example of the substituents include those each containing a hetero atom such as an oxygen atom, a nitrogen atom, a silicon atom, or a halogen atom. Specific examples of the substituents include an aliphatic oxy group, an aromatic oxy group, a siloxy group, an amino group, a nitro group, a cyano group, a silyl group, and a 'halogeno group. Specific examples of the aliphatic group of the aliphatic oxy group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a cyclohexylmethyl group, a trimethylsiloxyhexyl group, a chloroethyl group, a methoxybutyl group, a dimethylaminomethyl group, a butenyl group, and an octenyl group. An example of the aromatic oxy group is a phenoxy group. Next, description will be given of synthesis of the polymer compound of the present invention.
The polymer compound having the unit represented by the formula (2) may be obtained by reacting: a furandicarboxylic acid compound represented by the formula (1) (including furandicarboxylic acid and a derivative in which X represents an alkoxy group or a halogen atom) ; and a polyhydric alcohol represented by the formula (3) . At least one kind of furandicarboxylic acid, a furandicarboxylic acid compound, and a polyhydric alcohol all serving as raw materials for a polymer compound may be produced from biomass .
Figure imgf000012_0001
In the formula (1), X represents a hydroxyl group, an alkoxy group, or a halogen atom.
Examples of furandicarboxylic acid include: 2,5- furandicarboxylic acid; 2, 4-furandicarboxylic acid; and 3, 4-furandicarboxylic acid. Preferred examples of the alkoxy group in the formula (1) include a methoxy group and an ethoxy group. The furandicarboxylic acid compound represented by the formula (1) can be produced from the so-called plant-derived raw material (biomass) such as cellulose, glucose, or fructose by a known method.
B- (0H)m (3)
In the formula (3) , B represents an aromatic hydrocarbon group which may be substituted, an aliphatic hydrocarbon group which may be substituted, or an alicyclic hydrocarbon group which may be substituted, and m is 2 or more.
A reaction path is described by the following general formula.
Figure imgf000012_0002
That is, the polymer compound according to the present invention may be referred to as a condensate based on the reaction path.
Examples of the aromatic hydrocarbon group represented by B in the formula (3) include various aromatic rings represented by R in the formula (2) such as a benzene ring and a biphenyl ring. The aromatic ring may have various substituents . Examples of the substituent include: a hydrocarbon group such as an alkyl group or an alkenyl group; and various substituents described for A in the formula (2). Examples of the aliphatic hydrocarbon group represented by B in the formula (3) include: a hydrocarbon group such as an alkylene group; and various substituents described for the aliphatic hydrocarbon group represented by A in the formula (2). Preferred examples of the aliphatic hydrocarbon group include linear or branched alkylene groups each having 2 to 4 carbon atoms such as an ethylene group, a propylene group, and a butylene group.
Examples of the alicyclic group represented by B in the formula (3) include: a cycloalkylene group; a cycloalkenyl group; and the alicyclic hydrocarbon groups described for A in the formula (2) . Each of those aromatic hydrocarbon groups, aliphatic hydrocarbon groups, and alicyclic hydrocarbon groups may be substituted. Examples of the substituent include various substituents described for A in the formula (2 ) . m in the formula (3) is preferably 2.
Specific examples of the formula (3) include an aliphatic or alicyclic diol, a dihydroxybenzene, a bisphenol, glycerin, trimethylolpropane, pentaerithritol, sorbitol, and saccharides. Further, there can be exemplified an etherdiol which is obtained through intermolecular dehydration of" diols, and an oxycarboxylic acid such as hydroxybenzoic acid.
Specific' examples of the aliphatic or alicyclic diol include ethylene glycol, 1, 3-propanediol, 1,4- butanediol, and 1, 4-cyclohexanedimethanol . Examples of the dihydroxybenzene include 1, 3-dihydroxybenzene and 1, 4-dihydroxybenzene .
Examples of the bisphenol include bis (2- hydroxyphenyl) methane, 2, 2 ' -bis (hydroxyphenyl) propane, and 2, 2 ' -bis (4-hydroxyphenyl) -sulfone .
In a preferred embodiment, a diol is used as a polyhydric alcohol. The diol represents 1,3- propanediol or 1, 4-butanediol and is produced from a plant-derived raw material.
Examples of a polymerization method for obtaining the polymer compound according to the present invention include generally known methods such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization. The polymerization method is arbitrarily selected in accordance with the kind of molded product. A polymerization temperature, a polymerization catalyst, a medium such1 as a solvent, and the like may be used in accordance with the polymerization method.
Next, description will be given of a reaction temperature for synthesis of the polymer compound according to the present invention.
As described above, the method of synthesizing the polymer compound according to the present invention is as follows.' That is, the synthesis method includes the steps of: conducting esterification of a furandicarboxylic acid compound and a polyhydric alcohol in the presence of a catalyst to obtain an ester compound; and conducting polycondensation of the thus-obtained ester compound. A reaction temperature for conducting esterification is HO0C to 2000C, and more preferably 1500C to 18O0C. A temperature range for conducting polycondensation is 18O0C to 2800C, and more preferably 180°C to 230°C.
A polymer compound in a molten state formed at an endpoint of this polycondensation process may be used as it is or molded into a required shape to be used for a thermoplastic resin for a molded product. A composition containing the obtained polymer compound and various additives added as required may be used as a raw material for a molded product.
Next, detailed description will be given of the best mode for carrying out the present invention. In this mode, the method of producing the polymer compound of the present invention includes two steps. The first- step involves esterification of a dicarboxylic acid and a diol, and the second step involves polycondensation through an ester exchange reaction.
In the first step, esterification of furandicarboxylic acid and a diol is conducted by gradually heating furandicarboxylic acid, diols, and a catalyst or a catalyst mixture to 1100C to 200°C, and more preferably 1500C to 1800C under stirring. An endpoint of the esterification can easily be confirmed at the time when the reaction mixture becomes transparent. At this time, the reaction mixture is an oligomer, and is not a polymer. In the second step, a reaction system is heated to a temperature of 18O0C to 280°C, and more preferably 180°C to 2300C, to thereby cause an ester exchange reaction and start polycondensation for molecular weight increase.
The polycondensation step described above is preferably conducted under vacuum. In a polycondensation reaction, a diol forms as a by-product, and the diol is removed to increase a reaction rate of polycondensation. The heating, stirring, and reducing pressure are continued until a polymer compound has a sufficient molecular weight allowing molding the molded product, or a sufficient molecular weight satisfying specifications of the molded product. Next, detailed description will be given of an amount of a monomer to be introduced at a start of a reaction. The amount of a diol to be introduced at the start of the reaction is desirably 1 time to 3 times moles of furandicarboxylic acid. The diol in an excessive amount or a diol formed as the polycondensation reaction proceeds may be removed out of the reaction system by: distilling off the diol by bringing the reaction system to reduced pressure; distilling off the diol by boiling with another solvent; or removing the diol by other methods.
Next, description will be given of a catalyst. Synthesis of the polymer compound from a dicarboxylic acid and a diol proceeds without addition of a catalyst because of an autocatalysis action of the dicarboxylic acid. However, a concentration of the dicarboxylic acid reduces with the progress of polymerization, and thus the catalyst is more preferably added. The synthesis of the polymer compound of the present invention includes two steps of esterification and polycondensation through an ester exchange reaction, and thus preferred catalysts are present for respective steps .
Examples of a catalyst preferred for esterification in the first step include: a metal oxide or salt; an organometallic compound of tin, lead, titanium, or the like; and a tetravalent hafnium compound such as hafnium (IV) chloride or hafnium (IV) chloride (THF) 2- Examples of a catalyst most preferred for polycondensation through ester exchange in the second step include: an acetate or carbonate of lead, zinc, manganese, calcium, cobalt, magnesium, or the like; a metal oxide of magnesium, zinc, lead, antimony, or the like; and an organometallic compound of tin, lead, titanium, or the like. A particularly preferred example of a catalyst effective in both steps is titanium alkoxide.
The catalysts may be added separately in the first step and the second step, or may be mixed in an arbitrary combination from the above-mentioned catalyst group with a furandicarboxylic acid and a diol from the start of the reaction. The catalysts may obviously be added while a furandicarboxylic acid and a diol are heated, or the catalysts may be added once or more in an arbitrary combination form the above-mentioned catalyst group. Further, solid-state polymerization may be conducted by a known method after the polymer compound is obtained.
As a specific preferred example, the thus- obtained polymer has a degree of polymerization (DPn, in polymethyl methacrylate equivalent) of 285, Tm of 170°C, and a 5% weight loss heat decomposition temperature of 338°C. The polymer compound obtained by the above- mentioned method is a thermoplastic resin. The polymer compound has sufficient physical properties satisfying specifications of an optical device, a bottle, or a casing material. Alternatively, the polymer compound may be used as a thermoplastic resin for molding and molded into a desired shape, to thereby obtain a molded product according to the present invention. The molding method is not particularly limited. For example, compression molding, extrusion molding, or injection molding may be used. The polymer compound obtained by the above-mentioned method may contain a required amount of an additive such as a flame retardant, a colorant, an internal releasing agent, an antioxidant, a UV absorber, and various filers added.
Preferred application examples of the molded product include: an ink tank of an inkjet printer; a toner container for electrophotography; a packaging resin; and a structural material of a business machine such as a copier or a printer, or a casing of a camera. EXAMPLES
In Examples 1 to 3, three polymer compounds and respective methods of synthesizing the polymer compounds according to the present invention will be described.
The following devices and conditions were used for measurement of a molecular weight of the polymer compound, measurement of a glass transition temperature (Tg) , a crystallization temperature (Tc) , and a melting point (Tm) of the polymer compound, and NMR measurement for confirming a structure of the polymer. (Molecular weight measurement)
Analytical instrument: Alliance 2695, manufactured by
Waters Corporation
Detector: differential refractometer
Eluant: hexafϊuoroisopropanol solution containing 5 mM sodium trifluoroacetate
Flow rate: 1.0 ml/min
Column temperature: 400C
Degree of polymerization: A number average molecular weight was determined by using a PMMA standard, and a degree of polymerization was calculated.
(Tg, Tc, and Tm measurements)
Device: Differential scanning calorimeter, manufactured by TA Instruments
Pan: platinum pan Sample weight: 3 mg
Temperature increase start temperature: 300C
Temperature increase rate: 10°C/min
Atmosphere: nitrogen
(NMR measurement) Device: JNM-ECA-400, manufactured by JEOL Ltd.
(Example 1) Synthesis of polybutylene-2, 5- furandicarboxylate A 1-L four-necked flask equipped with a nitrogen introducing tube, a fractionating tube-condenser, a thermometer, and a SUS stirring blade was prepared. Into the four-necked flask, 2, 5-furandicarboxylic acid (149.9 g) , distilled 1, 4-butanediol (259.5 g; molar ratio = 1:3), a tin catalyst '(0.059 wt%), and a titanium catalyst (0.059 wt%) dissolved in toluene were measured.
In the four-necked flask, stirring was started while nitrogen was introduced, and the flask was immersed in an oil bath at 15O0C to heat a content of the flask. At about an inner temperature of 1500C, effusion of by-product water started with a condensation reaction, and the content was heated to 1700C over about 4 hours.
The fractionating tube was changed to a T-tube, and pressure reduction was started. Inside of the flask was adjusted to full vacuum (5 Pa) over about 1 hour, and the reaction was continued at 180°C for about 390 min under reduced pressure (5 Pa) . The obtained polymer was dissolved in hexafluoroisopropanol, and reprecipitated with methanol. The resultant was dried at 600C under vacuum day and night. Then, solid-state polymerization was conducted at a reaction temperature of 1500C for increasing the molecular weight. The thus-obtained polymer had a degree of polymerization (DPn, in polymethyl methacrylate equivalent) of 285, Tm of 1700C, Tg of 31°C, Tc of 900C, and a 5% weight loss heat decomposition temperature of 3380C.
Fig. 1 shows results of identification of the polymer compound by 1H-NMR. Relative intensities of protons correspond to a theoretical value of
(a) : (b) : (C) = 1:2:2, indicating that the target polymer compound was' obtained.
(Example 2) Synthesis of polyethylene-2, 5- furandicarboxylate ' A 1-L four-necked flask equipped with a nitrogen introducing tube, a fractionating tube-condenser, a thermometer, and a SUS stirring blade was prepared. Into the four-necked flask, 2, 5-furandicarboxylic acid (149.9 g) , distilled ethylene glycol (186.2 g; molar ratio = 1:3),. a tin catalyst (0.05 wt%), and a titanium catalyst (0.05 wt%) dissolved in toluene were measured.
In the four-necked flask, stirring was started while nitrogen was introduced, and the flask was immersed in an oil bath at 1500C to heat a content of the flask. At about an inner temperature of 15O0C, effusion of by-product water started with a condensation reaction, and the content was heated to 2800C over about 4 hours.
The fractionating tube was changed to a T-tube, and pressure reduction was started. Inside of the flask was adjusted to full vacuum (5 Pa) over about 1 hour, and the reaction was continued at 2800C for about 390 min under reduced pressure (5 Pa) . The obtained polymer was dissolved in hexafluoroisopropanol, and reprecipitated with methanol. The resultant was dried at 6O0C under vacuum day and night. Then, solid-state polymerization was conducted at a reaction temperature of 180°C for increasing the molecular weight. The thus-obtained polymer had a degree of polymerization (DPn, in polymethyl methacrylate equivalent) of 126, Tm of 1700C, Tg of 85°C, a crystallization temperature of 156°C, and a heat decomposition temperature of 332°C.
Fig. 2 shows results of identification of the polymer compound by 1H-NMR. Relative intensities of protons correspond to a theoretical value of (a) : (b) = 1:2, indicating that the target polymer compound was obtained.
(Example 3) Synthesis of polytrimethylene-2, 5- furandicarboxylate
A 1-L four-necked flask equipped with a nitrogen introducing tube, a fractionating tube-condenser, a thermometer, and a SUS stirring blade was prepared.
Into the four-necked flask, 2, 5-furandicarboxylic acid (149.9 g), distilled 1, 3-propanediol (228.3 g; molar ratio = 1:3), a tin catalyst (0.05 wt%), and a titanium catalyst (0.05 wt%) dissolved in toluene were measured. In the four-necked flask, stirring was started while nitrogen was introduced, and the flask was immersed in an oil bath at 1500C to heat a content of the flask. At about an inner temperature of 150°C, effusion of by-product water started with a condensation reaction, and the content was heated to 2300C.over about 4 hours. The fractionating tube was changed to a T-tube, and pressure reduction was started. Inside of the flask was adjusted to full vacuum (5 Pa) over about 1 hour, and the reaction was continued at 230°C for about 390 min under "reduced pressure (5 Pa). The obtained polymer was dissolved in hexafluoroisopropanol, and reprecipitated with methanol . The resultant was dried at 60°C under vacuum day" and night. Then, solid-state polymerization was conducted at a reaction temperature of 1400C for increasing the molecular weight. The obtained polymer had a degree of polymerization (DPn, in polymethyl methacrylate equivalent) of 78, Tm of 1500C, Tg of 39°C, a crystallization temperature of 1020C, and a heat decomposition temperature of 335°C. Fig. 3 shows results of identification of the polymer compound by 1H-NMR. Relative intensities of protons correspond to a theoretical value of (a) : (b) : (C) = 1:2:1, indicating that the target polymer compound was obtained. (Example 4) Measurement of heat decomposition temperature
Table 1 collectively shows heat decomposition temperatures of Examples. As a comparative example, polylactic acid (n=) available from Polymer Source, Inc. was purchased; and TGA measurement was conducted. As a result, the heat decomposition temperature of this polyester was 2790C. The heat decomposition temperature was obtained through TGA measurement (thermogravimetry) of a sufficiently- dried sample under the following conditions and was defined as a 5% weight loss.
Device: 'Thermogravimeter, manufactured by TA Instruments
Pan: platinum pan
Sample weight: 3 mg
Temperature increase start temperature: 300C
Temperature increase rate: 10°C/min Atmosphere: nitrogen
The results revealed that each of the polymer compounds had a higher heat decomposition temperature and excellent heat resistance than those of polylactic acid, which is a conventional plant-derived plastic.
Table 1: Comparison of heat decomposition temperature with polylactic acid
Figure imgf000026_0001
(Example 5)
Mechanical strength of a molded product formed of the synthesized polymer compound is described. The polymer compound of Example 1 was dried under vacuum at 800C for 8 hours before molding. Then, press molding was conducted at 180°C, 170 Kg/cm2, and a pressing time of 2 min. Table 2 shows physical properties of the molded product.
Table 2: Results of physical properties measurement of polybutylene-2, 5-furandicarboxylate
Figure imgf000026_0002
For measurement of flexural strength, flexural modulus, Charpy impact test (notched) , and load- deflection temperature, the obtained polymer compound was subjected to injection molding to produce a rectangular test piece having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm, and the measurement was conducted in accordance with ISO standards .
Respective measurement conditions are described below.
(Measurement conditions for flexural strength and flexural modulus) Test method: ISO 178 Test temperature: 23°C Test speed: 2 mm/min
(Measurement conditions for Charpy impact test (notched) )
Test method: ISO 179/leA (test piece No. 1 A-notch, striking direction of edgewise) Hammer: 0.5 J
(Measurement conditions for load-deflection temperature) Test method: ISO75-2 Load direction: flatwise Flexural stress: 0.45 MPa, 1.80 MPa
Table 3 shows the physical properties of the molded product. Table 3 :
Results of physical properties measurement of polybutylene-2, 5-furandicarboxylate
Figure imgf000028_0001
Table 3 reveals that the polymer compound of the present invention has favorable mechanical strength (flexural strength) and is a polymer compound that can be used for applications of electric and electronic components and the like. In the case where the flexural strength is more than 34 MPa, which is a flexural strength of high impact polystyrene (PS Japan Corporation, grade name, 433) as a general-purpose plastic, the mechanical strength (flexural strength) of the sample is favorably evaluated. The results shown in Table 3 all indicate favorable results.
This application claims priority from Japanese Patent Applications No,.'' £005-322310, filed November 7, 2005 and No. 2006-295938> : filed October 31, 2006, which are hereby incorporate'd • by . reference herein in their entirety.

Claims

1. A polymer compound having a unit represented by the following formula (2) :
Figure imgf000030_0001
(2) wherein A represents an aromatic hydrocarbon group which may be substituted, an aliphatic hydrocarbon group which may be substituted, or an alicyclic hydrocarbon group which may be substituted, and n represents a degree of polymerization of 185 or more ■and 600 or less.
2. A composition for a molded product comprising the polymer compound according to claim 1, and an additive .
3. A method of synthesizing a polymer compound for synthesizing a polymer compound represented by the following formula (2) :
Figure imgf000030_0002
comprising reacting: a furandicarboxylic acid compound represented by the following formula (1):
Figure imgf000031_0001
wherein X represents a, hydrox-yl group, an alkoxy group, or a halogen group; and a polyhydric alcohol represented by the following formula (3) :
B- (0H)m (3) wherein B represents an aromatic hydrocarbon group which may be substituted, an aliphatic hydrocarbon group which may be substituted, or an alicyclic hydrocarbon group which may be substituted, and m is 2 or more.
PCT/JP2006/322510 2005-11-07 2006-11-06 Polymer compound and method of synthesizing the same WO2007052847A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP06832523.2A EP1948709B1 (en) 2005-11-07 2006-11-06 Polymer compound and method of synthesizing the same
US12/092,805 US8143355B2 (en) 2005-11-07 2006-11-06 Polymer compound and method of synthesizing the same
US13/402,723 US20120207956A1 (en) 2005-11-07 2012-02-22 Polymer compound and method of synthesizing the same
US14/792,415 US11634535B2 (en) 2005-11-07 2015-07-06 Polymer compound and method of synthesizing the same

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2005322310 2005-11-07
JP2005-322310 2005-11-07
JP2006295938A JP4881127B2 (en) 2005-11-07 2006-10-31 Polymer compound and synthesis method thereof
JP2006-295938 2006-10-31

Related Child Applications (2)

Application Number Title Priority Date Filing Date
US12/092,805 A-371-Of-International US8143355B2 (en) 2005-11-07 2006-11-06 Polymer compound and method of synthesizing the same
US13/402,723 Continuation US20120207956A1 (en) 2005-11-07 2012-02-22 Polymer compound and method of synthesizing the same

Publications (1)

Publication Number Publication Date
WO2007052847A1 true WO2007052847A1 (en) 2007-05-10

Family

ID=38005988

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2006/322510 WO2007052847A1 (en) 2005-11-07 2006-11-06 Polymer compound and method of synthesizing the same

Country Status (4)

Country Link
US (3) US8143355B2 (en)
EP (1) EP1948709B1 (en)
JP (1) JP4881127B2 (en)
WO (1) WO2007052847A1 (en)

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009104780A1 (en) * 2008-02-20 2009-08-27 Canon Kabushiki Kaisha Polyester resin, method of producing the same, composition for molded article and molded article
WO2009135921A1 (en) 2008-05-08 2009-11-12 Novamont S.P.A. Aliphatic-aromatic biodegradable polyester
US7741389B2 (en) 2007-08-06 2010-06-22 Canon Kabushiki Kaisha Resin composition and molded article
NL2002382C2 (en) * 2008-12-30 2010-07-01 Furanix Technologies Bv A process for preparing a polymer having a 2,5-furandicarboxylate moiety within the polymer backbone and such (co)polymers.
US7863356B2 (en) 2008-02-22 2011-01-04 Canon Kabushiki Kaisha Resin composition and molded article
US7906572B2 (en) 2008-02-22 2011-03-15 Canon Kabushiki Kaisha Resin composition and molded article
US7923494B2 (en) 2007-10-12 2011-04-12 Canon Kabushiki Kaisha Polyester resin composition and molded body thereof
ITMI20091943A1 (en) * 2009-11-06 2011-05-07 Novamont Spa ALYPATIC-AROMATIC BIODEGRADABLE POLYESTER
WO2012005648A1 (en) * 2010-07-07 2012-01-12 Perstorp Ab Unsaturated oligio or polyester
ITMI20102362A1 (en) * 2010-12-22 2012-06-23 Novamont Spa COMPOSITION OF POLYESTERS.
WO2013062408A1 (en) 2011-10-24 2013-05-02 Furanix Technologies B.V. A process for preparing a polymer product having a 2,5-furandicarboxylate moiety within the polymer backbone to be used in bottle, film or fibre applications
WO2013097013A1 (en) 2011-12-29 2013-07-04 Natura Cosméticos S.A. Process for the production of poly (ethylene 2,5- furandicarboxylate) from 2,5-furandicarboxylic acid and use thereof, polyester compound and blends thereof
WO2013144525A1 (en) * 2012-03-30 2013-10-03 Roquette Freres Polymers, the process for the synthesis thereof and compositions comprising same
WO2013120989A3 (en) * 2012-02-17 2013-10-10 Uhde Inventa-Fischer Gmbh Process for preparing a high molecular weight heteroaromatic polyester or copolyester
WO2013158477A1 (en) * 2012-04-16 2013-10-24 The Procter & Gamble Company Plastic bottles for perfume compositions having improved crazing resistance
DE102015205191A1 (en) 2014-04-02 2015-10-08 Basf Se polyester blend
WO2018067007A1 (en) * 2016-10-05 2018-04-12 Furanix Technologies B.V. Process for the production of a solid-state polymerized poly (tetramethylene-2, 5-furan dicarboxylate) polymer and polymer thus produce
EP3011086B1 (en) 2013-06-20 2018-08-08 Furanix Technologies B.V Process for the preparation of a fiber, a fiber and a yarn made from such a fiber
US10189989B2 (en) 2014-04-02 2019-01-29 Basf Se Polyester mixture including polyethylene 2,5-furandicarboxylate
WO2020115221A1 (en) 2018-12-06 2020-06-11 Basf Se Method for preparing a (co)polyester
US11072683B2 (en) 2016-12-22 2021-07-27 Basf Se Furandicarboxylic acid-containing polyesters
US11905362B2 (en) 2016-09-16 2024-02-20 Origin Materials Operating, Inc. Polymers and methods of producing thereof

Families Citing this family (70)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007270011A (en) * 2006-03-31 2007-10-18 Canon Inc Laminar silicate compound and resin composition containing the laminar silicate compound
JP5446121B2 (en) * 2007-04-24 2014-03-19 三菱化学株式会社 Polyester containing furan structure
JP2009001630A (en) * 2007-06-20 2009-01-08 Canon Inc Polymeric compound and its manufacturing method, and molded product composition
US20090018264A1 (en) * 2007-07-12 2009-01-15 Canon Kabushiki Kaisha Resin composition
JP5213391B2 (en) * 2007-09-06 2013-06-19 キヤノン株式会社 POLYESTER RESIN, PROCESS FOR PRODUCING THE SAME, COMPOSITION FOR MOLDED ARTICLE, AND MOLDED ARTICLE
JP5120944B2 (en) * 2008-04-25 2013-01-16 独立行政法人産業技術総合研究所 Biodegradable high molecular weight aliphatic polyester and method for producing the same
JP5618040B2 (en) * 2009-04-27 2014-11-05 独立行政法人産業技術総合研究所 High molecular weight aliphatic polyester ether using bio-based raw material and process for producing the same
JP5351612B2 (en) * 2009-06-02 2013-11-27 キヤノン株式会社 Polyester, production method thereof, and molded product
JP5517494B2 (en) 2009-06-03 2014-06-11 キヤノン株式会社 Polyester, production method thereof, and molded product
CN102050941B (en) * 2009-11-03 2013-12-11 东丽纤维研究所（中国）有限公司 Macromolecular polymer and production method thereof
US20110124839A1 (en) * 2009-11-25 2011-05-26 Canon Kabushiki Kaisha Flame-retardant polyester copolymer, and production process and molded article thereof
US7985788B2 (en) * 2009-11-27 2011-07-26 Canon Kabushiki Kaisha Flame retardant resin composition and molded article thereof
CN102336906B (en) * 2010-07-20 2014-06-25 东丽纤维研究所（中国）有限公司 Polyesteramide and preparation method thereof
CN102336905B (en) * 2010-07-20 2014-06-25 东丽纤维研究所（中国）有限公司 Polyesteramide and its preparation method
WO2012057233A1 (en) * 2010-10-27 2012-05-03 花王株式会社 Binder resin for toners
JP5794735B2 (en) * 2010-10-27 2015-10-14 花王株式会社 Binder resin for toner
NL2005976C2 (en) 2011-01-10 2012-07-11 Furanix Technologies Bv Process for the depolymerization of a furan dicarboxylate containing polyester.
JP5833409B2 (en) * 2011-03-30 2015-12-16 花王株式会社 Binder resin for toner
JP2012229395A (en) * 2011-04-11 2012-11-22 Canon Inc Plastic film
US20130095271A1 (en) 2011-10-14 2013-04-18 Eastman Chemical Company Polyester compositions containing furandicarboxylic acid or an ester thereof, ethylene glycol and cyclohexanedimethanol
EP2800771A1 (en) * 2012-01-04 2014-11-12 PepsiCo, Inc. 2,5-furan dicarboxylic acid-based polyesters prepared from biomass
JP5955205B2 (en) * 2012-01-23 2016-07-20 キヤノン株式会社 Chemical sealing film
WO2013149157A1 (en) * 2012-03-30 2013-10-03 E. I. Du Pont De Nemours And Company Polyesters and fibers made therefrom
JP5954866B2 (en) * 2012-04-16 2016-07-20 花王株式会社 Binder resin for toner
US8658810B2 (en) 2012-06-22 2014-02-25 Eastman Chemical Company Method for producing purified dialkyl-furan-2,5-dicarboxylate vapor
US8912349B2 (en) 2012-06-22 2014-12-16 Eastman Chemical Company Method for producing purified dialkyl-furan-2,5-dicarboxylate separation and solid liquid separation
US8859788B2 (en) 2012-06-22 2014-10-14 Eastman Chemical Company Esterification of furan-2,5-dicarboxylic acid to a dialkyl-furan-2,5-dicarboxylate vapor with rectification
JP6175501B2 (en) * 2012-08-31 2017-08-02 ソシエテ アノニム デ ゾ ミネラル デヴィアン エ オン ナブレジェ“エス．ア．ウ．エム．ウ” Bottle manufacturing method
JP6021002B2 (en) * 2012-10-29 2016-11-02 国立大学法人 岡山大学 Polyetherketone and method for producing the same
US9068041B2 (en) * 2012-12-18 2015-06-30 Xerox Corporation Polyester EA toner comprising furan
PL2928942T3 (en) * 2013-03-15 2017-08-31 Sulzer Chemtech Ag A process to prepare a polyester polymer composition comprising a polyester polymer having furanic units and a polyester polymer composition obtainable thereby and the use thereof
EP2931784B1 (en) 2013-03-15 2017-01-25 Sulzer Chemtech AG A process to prepare a cyclic oligomer and a cyclic oligomer obtainable thereby
JP6399901B2 (en) * 2013-11-26 2018-10-03 キヤノン株式会社 Flame retardant composition
KR20160102227A (en) * 2013-12-20 2016-08-29 이 아이 듀폰 디 네모아 앤드 캄파니 Furan-based polymeric hydrocarbon fuel barrier structures
JP6168985B2 (en) * 2013-12-24 2017-07-26 花王株式会社 adhesive
JP2015120838A (en) * 2013-12-24 2015-07-02 花王株式会社 Porous sheet
JP6342673B2 (en) * 2014-02-26 2018-06-13 帝人株式会社 Polyester composition and method for producing the same
KR20160127829A (en) 2014-03-11 2016-11-04 퓨라닉스 테크놀러지스 비.브이. Process for enhancing the molecular weight of a polyester
TR201807609T4 (en) 2014-03-11 2018-06-21 Synvina C V Process for the preparation of a polyester under special esterification conditions.
KR20160132947A (en) 2014-03-11 2016-11-21 퓨라닉스 테크놀러지스 비.브이. Polyester and method for preparing such a polyester
CA2941238C (en) * 2014-03-11 2022-05-31 Furanix Technologies B.V. Polyester and method for preparing such a polyester
US9944615B2 (en) 2014-05-08 2018-04-17 Eastman Chemical Company Purifying crude furan 2,5-dicarboxylic acid by hydrogenation and a purge zone
US9504994B2 (en) 2014-05-08 2016-11-29 Eastman Chemical Company Furan-2,5-dicarboxylic acid purge process
US10010812B2 (en) 2014-05-08 2018-07-03 Eastman Chemical Company Furan-2,5-dicarboxylic acid purge process
WO2016032330A1 (en) * 2014-08-25 2016-03-03 Furanix Technologies B.V. Process for producing an oriented film comprising poly(ethylene-2,5-furandicarboxylate)
EP4306569A3 (en) 2015-04-14 2024-04-10 E I Du Pont De Nemours Processes for producing 2,5-furandicarboxylic acid and derivatives thereof and polymers made therefrom
NL2015265B1 (en) 2015-08-04 2017-02-21 Furanix Technologies Bv Polyester composition.
NL2015264B1 (en) 2015-08-04 2017-02-21 Furanix Technologies Bv Masterbatch polyester composition.
NL2015266B1 (en) 2015-08-04 2017-02-21 Furanix Technologies Bv Poly(alkylene furandicarboxylate)-comprising polyester.
JP6440336B2 (en) 2015-09-02 2018-12-19 東洋紡株式会社 Polyester film having a flanged carboxylic acid unit
WO2017038949A1 (en) * 2015-09-04 2017-03-09 三菱化学株式会社 Polyester resin, production method for said polyester resin, and polyester resin composition
EP3350246B1 (en) * 2015-09-14 2022-02-09 Furanix Technologies B.V. Process for the preparation of a polyester
CN108349921A (en) * 2015-09-17 2018-07-31 微麦德斯公司 Polymer and its production method
JP6967455B2 (en) 2015-12-28 2021-11-17 東洋紡株式会社 Laminated polyester film
MX2018007872A (en) 2015-12-28 2019-01-31 Toyo Boseki Laminated polyester film.
US10941244B2 (en) 2016-03-30 2021-03-09 Toyobo Co., Ltd. Polyester film
JP6890587B2 (en) 2016-07-15 2021-06-18 株式会社クラレ Sealant film and its manufacturing method
EP3301091A1 (en) 2016-09-29 2018-04-04 Sulzer Chemtech AG A process to prepare a cyclic oligomer and a cyclic oligomer obtainable thereby and a process to polymerize it
CN110023295B (en) 2016-09-29 2024-03-22 苏尔寿管理有限公司 Method for producing polyester polymers and polyester polymers obtainable therefrom
EP3526272B1 (en) * 2016-10-14 2023-08-23 Covation Inc. Process for preparing poly(trimethylene furandicarboxylate)
US11325363B2 (en) 2017-03-01 2022-05-10 Toyobo Co., Ltd. Laminate including polyester film having furandicarboxylate unit and heat-sealable resin layer, and packaging bag
JP7025402B2 (en) 2017-03-01 2022-02-24 東洋紡株式会社 Method for manufacturing polyester film having flange carboxylic acid unit
US20190023675A1 (en) 2017-07-20 2019-01-24 Eastman Chemical Company Method for producing purified dialkyl-furan-2,5-dicarboxylate
US20190023837A1 (en) * 2017-07-20 2019-01-24 Eastman Chemical Company Production of polyethylene furanoate in a retrofitted polyester plant
CN112512809B (en) 2018-08-03 2023-08-25 三菱化学株式会社 Laminate body
US10526301B1 (en) 2018-10-18 2020-01-07 Eastman Chemical Company Production of purified dialkyl-furan-2,5-dicarboxylate (DAFD) in a retrofitted DMT plant
KR102407792B1 (en) * 2019-09-05 2022-06-10 주식회사 엘지화학 Diol compound, polycarbonate and method for preparing the same
CN111378121B (en) * 2020-03-31 2023-03-10 上海凯赛生物技术股份有限公司 High-viscosity polyamide 56 resin, high-strength polyamide 56 industrial yarn and preparation method and application thereof
CN111411405B (en) * 2020-03-31 2021-09-28 上海凯赛生物技术股份有限公司 High-strength polyamide 56 industrial yarn and preparation method and application thereof
CN112175176A (en) * 2020-10-26 2021-01-05 徐州工程学院 Seawater degradable furan dicarboxylic acid copolyester and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2551731A (en) * 1946-11-12 1951-05-08 Celanese Corp Polyesters from heterocyclic components
JPH05178971A (en) * 1991-05-24 1993-07-20 Hoechst Ag Polycondensate containing tartaric acid derivative, its manufacture, and its use
JP2002505359A (en) * 1998-03-07 2002-02-19 アキシヴァ ゲーエムベーハー Biodegradable polymers based on naturally occurring renewable raw materials, especially isosorbitol
JP2002512268A (en) * 1998-04-23 2002-04-23 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Isosorbide-containing polyester and method for producing the same
JP2002293944A (en) * 2001-03-30 2002-10-09 Dainippon Ink & Chem Inc Method for producing polyarylate

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5283295A (en) * 1992-06-08 1994-02-01 Eastman Kodak Company Polymer blends useful for forming extrusion blow molded articles
JP3783426B2 (en) 1997-08-27 2006-06-07 トヨタ自動車株式会社 Polylactic acid resin composition containing a polycarbonate compound
US6342300B1 (en) 1999-02-20 2002-01-29 Celanese Ventures Gmbh Biodegradable polymers based on natural and renewable raw materials especially isosorbite
US8034866B2 (en) * 2003-12-30 2011-10-11 Sabic Innovative Plastics Ip B.V. Polymer compositions, method of manufacture, and articles formed therefrom

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2551731A (en) * 1946-11-12 1951-05-08 Celanese Corp Polyesters from heterocyclic components
JPH05178971A (en) * 1991-05-24 1993-07-20 Hoechst Ag Polycondensate containing tartaric acid derivative, its manufacture, and its use
JP2002505359A (en) * 1998-03-07 2002-02-19 アキシヴァ ゲーエムベーハー Biodegradable polymers based on naturally occurring renewable raw materials, especially isosorbitol
JP2002512268A (en) * 1998-04-23 2002-04-23 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Isosorbide-containing polyester and method for producing the same
JP2002293944A (en) * 2001-03-30 2002-10-09 Dainippon Ink & Chem Inc Method for producing polyarylate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1948709A4 *

Cited By (58)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7741389B2 (en) 2007-08-06 2010-06-22 Canon Kabushiki Kaisha Resin composition and molded article
US7923494B2 (en) 2007-10-12 2011-04-12 Canon Kabushiki Kaisha Polyester resin composition and molded body thereof
US9102793B2 (en) 2008-02-20 2015-08-11 Canon Kabushiki Kaisha Polyester resin, method of producing the same, composition for molded article and molded article
US8420769B2 (en) 2008-02-20 2013-04-16 Canon Kabushiki Kaisha Polyester resin, method of producing the same, composition for molded article and molded article
WO2009104780A1 (en) * 2008-02-20 2009-08-27 Canon Kabushiki Kaisha Polyester resin, method of producing the same, composition for molded article and molded article
US7863356B2 (en) 2008-02-22 2011-01-04 Canon Kabushiki Kaisha Resin composition and molded article
US7906572B2 (en) 2008-02-22 2011-03-15 Canon Kabushiki Kaisha Resin composition and molded article
US10526442B2 (en) 2008-05-08 2020-01-07 Novamont S.P.A. Aliphatic-aromatic biodegradable polyester
WO2009135921A1 (en) 2008-05-08 2009-11-12 Novamont S.P.A. Aliphatic-aromatic biodegradable polyester
US11345779B2 (en) 2008-05-08 2022-05-31 Novamont S.P.A. Aliphatic-aromatic biodegradable polyester
US10316139B2 (en) 2008-05-08 2019-06-11 Novamont S.P.A. Aliphatic-aromatic biodegradable polyester
US9567431B2 (en) 2008-12-30 2017-02-14 Furanix Technologies B.V. Process for preparing a polymer having a 2,5-furandicarboxylate moiety within the polymer backbone and such (co)polymers
EP2370496B1 (en) 2008-12-30 2020-06-24 Furanix Technologies B.V A process for preparing a polymer having a 2,5-furandicarboxylate moiety within the polymer backbone and such (co)polymers
US9765183B2 (en) 2008-12-30 2017-09-19 Furanix Technologies B.V. Process for preparing a polymer having a 2,5-furandicarboxylate moiety within the polymer backbone and such (co)polymers
WO2010077133A1 (en) 2008-12-30 2010-07-08 Furanix Technologies B.V. A process for preparing a polymer having a 2,5-furandicarboxylate moiety within the polymer backbone and such (co)polymers
NL2002382C2 (en) * 2008-12-30 2010-07-01 Furanix Technologies Bv A process for preparing a polymer having a 2,5-furandicarboxylate moiety within the polymer backbone and such (co)polymers.
CN102597050A (en) * 2009-11-06 2012-07-18 诺瓦蒙特股份公司 Biodegradable aliphatic-aromatic polyester
US10174157B2 (en) 2009-11-06 2019-01-08 Novamont S.P.A. Biodegradable aliphatic-aromatic polyester
WO2011054926A1 (en) * 2009-11-06 2011-05-12 Novamont S.P.A. Biodegradable aliphatic-aromatic polyester
ITMI20091943A1 (en) * 2009-11-06 2011-05-07 Novamont Spa ALYPATIC-AROMATIC BIODEGRADABLE POLYESTER
WO2012005647A1 (en) * 2010-07-07 2012-01-12 Perstorp Ab Branched polyester
WO2012005645A1 (en) * 2010-07-07 2012-01-12 Perstorp Ab Alkyd resin
WO2012005648A1 (en) * 2010-07-07 2012-01-12 Perstorp Ab Unsaturated oligio or polyester
ITMI20102362A1 (en) * 2010-12-22 2012-06-23 Novamont Spa COMPOSITION OF POLYESTERS.
RU2587167C2 (en) * 2010-12-22 2016-06-20 НОВАМОНТ С.п.А. Polyester composition
WO2012085238A1 (en) * 2010-12-22 2012-06-28 Novamont S.P.A. Polyester composition
US10968345B2 (en) 2010-12-22 2021-04-06 Novamont S.P.A. Polyester composition
WO2013062408A1 (en) 2011-10-24 2013-05-02 Furanix Technologies B.V. A process for preparing a polymer product having a 2,5-furandicarboxylate moiety within the polymer backbone to be used in bottle, film or fibre applications
EP3327061A1 (en) 2011-10-24 2018-05-30 Synvina C.V. Polymer product having a 2,5-furandicarboxylate moiety within the polymer backbone to be used in bottle, film or fibre applications
KR102250679B1 (en) 2011-10-24 2021-05-11 퓨라닉스 테크놀러지스 비.브이. A process for preparing a polymer product having a 2,5-furandicarboxylate moiety within the polymer backbone to be used in bottle, film or fibre applications
CN104024301A (en) * 2011-10-24 2014-09-03 福兰尼克斯科技公司 A process for preparing a polymer product having a 2,5-furandicarboxylate moiety within the polymer backbone to be used in bottle, film or fibre applications
US9527954B2 (en) 2011-10-24 2016-12-27 Furanix Technologies B.V. Process for preparing a polymer product having a 2,5-furandicarboxylate moiety within the polymer backbone to be used in bottle, film or fibre applications
KR102134237B1 (en) 2011-10-24 2020-07-16 퓨라닉스 테크놀러지스 비.브이. A process for preparing a polymer product having a 2,5-furandicarboxylate moiety within the polymer backbone to be used in bottle, film or fibre applications
KR20140110845A (en) * 2011-10-24 2014-09-17 퓨라닉스 테크놀러지스 비.브이. A process for preparing a polymer product having a 2,5-furandicarboxylate moiety within the polymer backbone to be used in bottle, film or fibre applications
KR20180132940A (en) * 2011-10-24 2018-12-12 퓨라닉스 테크놀러지스 비.브이. A process for preparing a polymer product having a 2,5-furandicarboxylate moiety within the polymer backbone to be used in bottle, film or fibre applications
US10030097B2 (en) 2011-10-24 2018-07-24 Furanix Technologies B.V. Polyester-containing object made from melt-processing poly(ethylene-2,5-furandicarboxylate)
WO2013097013A1 (en) 2011-12-29 2013-07-04 Natura Cosméticos S.A. Process for the production of poly (ethylene 2,5- furandicarboxylate) from 2,5-furandicarboxylic acid and use thereof, polyester compound and blends thereof
WO2013120989A3 (en) * 2012-02-17 2013-10-10 Uhde Inventa-Fischer Gmbh Process for preparing a high molecular weight heteroaromatic polyester or copolyester
KR20140138163A (en) * 2012-02-17 2014-12-03 우데 인벤타-피셔 게엠바하 Process for preparing a high molecular weight heteroaromatic polyester or copolyester
US9714320B2 (en) 2012-02-17 2017-07-25 Uhde Inventa-Fischer Gmbh Process for preparing a high molecular weight heteroaromatic polyester or copolyester
KR102085389B1 (en) 2012-02-17 2020-03-05 우데 인벤타-피셔 게엠바하 Process for preparing a high molecular weight heteroaromatic polyester or copolyester
EP2814864B1 (en) 2012-02-17 2020-09-16 Uhde Inventa-Fischer GmbH Process for preparing a high molecular weight heteroaromatic polyester or copolyester
WO2013144525A1 (en) * 2012-03-30 2013-10-03 Roquette Freres Polymers, the process for the synthesis thereof and compositions comprising same
US9217056B2 (en) 2012-03-30 2015-12-22 Roquette Freres Polymers, the process for the synthesis thereof and compositions comprising same
FR2988724A1 (en) * 2012-03-30 2013-10-04 Roquette Freres POLYMERS, PROCESS FOR THEIR SYNTHESIS AND COMPOSITIONS COMPRISING SAME
WO2013158477A1 (en) * 2012-04-16 2013-10-24 The Procter & Gamble Company Plastic bottles for perfume compositions having improved crazing resistance
CN104271633A (en) * 2012-04-16 2015-01-07 宝洁公司 Plastic bottles for perfume compositions having improved crazing resistance
US9622563B2 (en) 2012-04-16 2017-04-18 The Procter & Gamble Company Plastic packages for dispensing aerosol products having improved crazing resistance and sustainability
EP3011086B1 (en) 2013-06-20 2018-08-08 Furanix Technologies B.V Process for the preparation of a fiber, a fiber and a yarn made from such a fiber
DE102015205191A1 (en) 2014-04-02 2015-10-08 Basf Se polyester blend
US10189989B2 (en) 2014-04-02 2019-01-29 Basf Se Polyester mixture including polyethylene 2,5-furandicarboxylate
US11905362B2 (en) 2016-09-16 2024-02-20 Origin Materials Operating, Inc. Polymers and methods of producing thereof
CN109952335A (en) * 2016-10-05 2019-06-28 福兰尼克斯科技公司 Method for preparing solid state polymerized poly (tetramethylene-2, 5-furandicarboxylate) polymer and polymer prepared thereby
WO2018067007A1 (en) * 2016-10-05 2018-04-12 Furanix Technologies B.V. Process for the production of a solid-state polymerized poly (tetramethylene-2, 5-furan dicarboxylate) polymer and polymer thus produce
CN109952335B (en) * 2016-10-05 2021-11-05 福兰尼克斯科技公司 Method for preparing solid state polymerized poly (tetramethylene-2, 5-furandicarboxylate) polymer and polymer prepared thereby
US11174344B2 (en) 2016-10-05 2021-11-16 Furanix Technologies B.V. Process for the production of a solid-state polymerized poly (tetramethylene-2, 5-furan dicarboxylate) polymer and polymer thus produced
US11072683B2 (en) 2016-12-22 2021-07-27 Basf Se Furandicarboxylic acid-containing polyesters
WO2020115221A1 (en) 2018-12-06 2020-06-11 Basf Se Method for preparing a (co)polyester

Also Published As

Publication number Publication date
US8143355B2 (en) 2012-03-27
US11634535B2 (en) 2023-04-25
EP1948709A1 (en) 2008-07-30
US20090124763A1 (en) 2009-05-14
EP1948709A4 (en) 2010-09-22
JP2007146153A (en) 2007-06-14
EP1948709B1 (en) 2013-05-29
JP4881127B2 (en) 2012-02-22
US20160002395A1 (en) 2016-01-07
US20120207956A1 (en) 2012-08-16

Similar Documents

Publication Publication Date Title
US11634535B2 (en) Polymer compound and method of synthesizing the same
JP5517494B2 (en) Polyester, production method thereof, and molded product
US8420769B2 (en) Polyester resin, method of producing the same, composition for molded article and molded article
JP5351612B2 (en) Polyester, production method thereof, and molded product
JP5213391B2 (en) POLYESTER RESIN, PROCESS FOR PRODUCING THE SAME, COMPOSITION FOR MOLDED ARTICLE, AND MOLDED ARTICLE
JP6235067B2 (en) Polyorganosiloxane compound, production method and copolycarbonate resin containing the same
EP2800771A1 (en) 2,5-furan dicarboxylic acid-based polyesters prepared from biomass
Feng et al. A designed synthetic strategy toward poly (isosorbide terephthalate) copolymers: a combination of temporary modification, transesterification, cyclization and polycondensation
JP2008308578A (en) Process for preparing polyarylate resin containing furan ring
Hussain et al. Structure–property relationship of poly (cyclohexane 1, 4‐dimethylene terephthalate) modified with high trans‐1, 4‐cyclohexanedimethanol and 2, 6‐naphthalene dicarboxylicacid
KR20160055564A (en) Copolymeric polycarbonate resin and molded product of the same
JP5114993B2 (en) Polyester resin
Wang et al. Synthesis and properties of biodegradable aliphatic–aromatic polyesters derived from 4‐hydroxybenzaldehyde
WO2013180215A1 (en) Method for producing polyester resin
KR102576369B1 (en) Multiblock polymers synthesized using oligocarbonate polyols
Wang et al. Synthesis and characterization of copolymeric aliphatic–aromatic esters derived from terephthalic acid, 1, 4‐butanediol, and ε‐caprolactone by physical, thermal, and mechanical properties and NMR measurements
Zamora et al. Polyesters analogous to PET and PBT based on O‐benzyl ethers of xylitol and l‐arabinitol
KR102700346B1 (en) Biodegradable polyester resin with remarkably improved marine biodegradability and method for preparing the same
AU2015271988B2 (en) 2,5-furan dicarboxylic acid-based polyesters prepared from biomass
WO2024204727A1 (en) Polycarbonate resin composition
JP3732753B2 (en) Biodegradable copolyester and method for producing the same
JPH09241359A (en) Biodegradable aliphatic polyester copolymer and its production
JP2023149984A (en) Polyalkylene glycol copolymerized polyester
JPS63225625A (en) Aromatic polyester
JP2010018766A (en) Resin composition and method for producing it

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2006832523

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 12092805

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE