WO2012148187A2 - Procédé de préparation du poly(ester de 1,4:3,6-dianhydrohexitol) - Google Patents

Procédé de préparation du poly(ester de 1,4:3,6-dianhydrohexitol) Download PDF

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WO2012148187A2
WO2012148187A2 PCT/KR2012/003233 KR2012003233W WO2012148187A2 WO 2012148187 A2 WO2012148187 A2 WO 2012148187A2 KR 2012003233 W KR2012003233 W KR 2012003233W WO 2012148187 A2 WO2012148187 A2 WO 2012148187A2
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dianhydrohexitol
polyester
formula
reaction
carbon atoms
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PCT/KR2012/003233
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WO2012148187A3 (fr
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오광세
김종량
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에스케이케미칼 주식회사
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Publication of WO2012148187A2 publication Critical patent/WO2012148187A2/fr
Publication of WO2012148187A3 publication Critical patent/WO2012148187A3/fr

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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
    • C08G63/78—Preparation processes
    • C08G63/80—Solid-state polycondensation

Definitions

  • the present invention relates to a method for preparing 1,4: 3,6- dianhydrohexitol polyester (poly (1,4: 3,6- dianhydrohexitol ester)), more specifically, acylate (acylated) 1,4: 3,6-dianhydrohexitol (homo) polyester in-situ using 1,4: 3,6-dianhydrohexitol (homo) polyester).
  • 1,4: 3,6-dianhydrohexitol is a renewable resource such as wheat, sugar, corn, etc., which contains polysaccharide as a component.
  • a bio-based raw material derived from biomass which is a renewable resource, it is used in various fields such as polymer materials, pharmaceuticals, and cosmetics.
  • 1,4: 3,6-dianhydrohexitol is an isomannide represented by the following formula 1a (isomannide, mp: 81-85 °C, bp: 123-130 °C / 2 mmHg), represented by the formula 1b Isosorbide (mp: 61-62 ° C, bp: 148-151 ° C / 2 mmHg) and isoidide represented by the following formula (1c) (isoidide, mp: 64 ° C, bp: 159-162 ° C / 2 mmHg)
  • formula 1a isomannide, mp: 81-85 °C, bp: 123-130 °C / 2 mmHg
  • Isosorbide mp: 61-62 ° C, bp: 148-151 ° C / 2 mmHg
  • isoidide represented by the following formula (1c) isoidide, mp: 64 °
  • the polyester produced has an environmentally friendly advantage, in addition to 1,4: 3,6 Excellent thermal and optical properties are due to the rigidity, the molecular structure of dianhydrohexitol, and the chirality due to the presence of asymmetric hydroxyl groups. Due to such a characteristic, the application range of 1,4: 3,6-dianhydrohexitol is used as a representative constituent raw material for the development of environmentally friendly materials.
  • the following Chemical Formulas 1d to 1f represent the molecular structures of isomannide (formula 1d), isosorbide (formula 1e), and isoidide (formula 1f), respectively.
  • isosorbide a representative 1,4: 3,6-dianhydrohexitol, has a central angle between two fused rings of 120 ° and two chemically equivalents
  • C2-OH forms an exo orientation on two fused rings, making it easier to access stericly different compounds.
  • C5-OH has an endo orientation and forms an intramolecular hydrogen bond with an oxygen atom of an adjacent tetrahydrofuran ring.
  • iso sorbitan p K a value of the hydroxyl group of the carbide is because acid is strongly compared with general linear diol to 5.0 ⁇ 7.5, and in the polyester polycondensation reaction, the oxygen lone pair of hydroxyl groups of isosorbide dicarboxylic It is not easy to attack the carbonyl group of carboxylic acid, and it becomes a cause of the reactivity decline.
  • isoidide (0 hydrogen bonds in the molecule; endo 0, exo 2)> isosorb High reactivity in the order of Bide (1 hydrogen bond in the molecule; endo 1, exo 1)> Isomannide (2 hydrogen bonds in the molecule; endo 2, exo 0).
  • melt condensation polymerization of aromatic dicarboxylic acid or dicarboxylic acid esters with isosorbide requires an esterification or transesterification reaction temperature of 250 ° C. or higher, which causes isosorbide to thermally decompose and polymerize. Discoloration of the reactants can be caused, and the reaction time is very slow.
  • linear aliphatic dicarboxylic acid or dicarboxylic acid having 4 to 10 carbon atoms with isosorbide can be used for binders, coatings, toners, and the like which can be produced at a melt polymerization temperature of 250 ° C. or lower. Melt polycondensation is known to be the most effective isosorbide homopolyester to date. In addition, in the commercial plastic field, a small amount of isosorbide is added as a copolymerization monomer to prepare co-polyester, thereby increasing the glass transition temperature (Tg) or reducing the crystallinity.
  • Tg glass transition temperature
  • aromatic dicarboxylic acids or diols having low reactivity during polyester polycondensation may increase reactivity by activating respective carboxylic acid or hydroxyl groups.
  • a method for enhancing the reactivity of the aromatic monomers may include (i) using activated dicarboxylic acid monomers, (ii) using activated dicarboxylic acids and diols, and (iii) activated diols. Is used as a monomer.
  • Dicarboxylic acid dichloride may be typically used as the activated dicarboxylic acid monomer, and in the case of the method (i), dicarboxylic acid dichloride and free diol may be condensation-polymerized.
  • the activated diol monomer a bissilylated diol, an acylated diol, and the like may be used.
  • dicarboxylic acid dichloride and bissilyl may be used.
  • the bissilylated diols can be condensation polymerized, and in the case of the method (iii) above, the acylated diols can be condensation polymerized with the free dicarboxylic acid component.
  • P K a value of a representative aromatic diol is hydroquinone (hydroquinone) was 10.35, and also hydroxy acids and p- hydroxy p K a value of the benzene acid (hydroxybenzoic acid) is virtually identical to the p K a value of 3.51 to 4.48 terephthalic acid
  • p-hydroxybenzene acid has a disadvantage in that some decarboxylation occurs under general aromatic liquid crystal polyester melt polycondensation reaction conditions.
  • Aliphatic acid anhydride which is mainly used in the monomer activation process, that is, acylation of aromatic liquid crystalline polyesters, is easy to use commercially, and in particular, the separation or purification of acylated monomers after the activation step It has the advantage of being able to link directly to the melt condensation polymerization step without the process.
  • polycondensation of the acylated diols or hydroxy acids with free dicarboxylic acid components unaffected in the acylation process produces aliphatic acids as by-products, which are condensation of the three activating monomers mentioned above.
  • by-products produced by the reaction commercial application and removal are the easiest.
  • acylate 1,4 which can improve the reactivity and reaction rate during polyester melt condensation polymerization: It is to prepare 3,6- dianhydrohexitol and to use it in-situ to provide a method for producing 1,4: 3,6- dianhydrohexitol polyester.
  • Another object of the present invention is to provide a method for preparing 1,4: 3,6-dianhydrohexitol homopolyester having high polymerizability and excellent mechanical properties and having a rigid polymer repeating unit that can be used for various purposes. To provide.
  • the present invention by acylation reaction of 1,4: 3,6- dianhydrohexitol and aliphatic acid anhydride having 4 to 16 carbon atoms represented by the following formula (1) Preparing the indicated acylate 1,4: 3,6- dianhydrohexitol; And melt condensation polymerization of the acylated 1,4: 3,6- dianhydrohexitol and an aromatic or cycloaliphatic free dicarboxylic acid component having 8 to 14 carbon atoms in-situ.
  • 1,4: 3,6- dianhydrohexitol polyester comprising the step of preparing a 1,4: 3,6- dianhydrohexitol polyester comprising a repeating unit represented by the formula (3) to provide.
  • R 1 are each independently an aliphatic hydrocarbon group having 1 to 7 carbon atoms
  • X is a substituted or unsubstituted aromatic or cycloaliphatic hydrocarbon group having 6 to 12 carbon atoms.
  • 1,4: 3,6- dianhydrohexitol polyester (poly (1,4: 3,6- dianhydrohexitol ester)) according to the present invention is a low reactivity 1,4: 3, 6-dianhydrohexitol is activated via an in-situ acylation reaction. Therefore, it is possible to increase the reaction rate in the polyester melt polycondensation reaction, to activate the reactivity of the non-equivalent hydroxyl groups of 1,4: 3,6- dianhydrohexitol equally, Since the melt condensation polymerization step can be performed immediately without separating or purifying acylated 1,4: 3,6-dianhydrohexitol, there is an advantage in that reaction rate and raw material cost are reduced.
  • 1,4: 3,6-dianhydrohexitol polyester production method is melt condensation polymerization of acylated 1,4: 3,6-dianhydrohexitol using a diol component Increasing the reactivity, (a) 1,4: 3,6- dianhydrohexitol represented by the following formula (1) and substituted or unsubstituted aliphatic acid anhydride having 4 to 16, preferably 4 to 8 carbon atoms To acylation reaction to prepare an acylate 1,4: 3,6- dianhydrohexitol represented by the following formula (2) and (b) the acylate 1,4: 3,6- dianhydrohex A repeating unit represented by the following Chemical Formula 3 is obtained by melt condensation polymerization of a cytol and an aromatic or cycloaliphatic free dicarboxylic acid component having 8 to 14, preferably 8 to 12, carbon atoms in-situ. Preparing a 1,4: 3,6-dianhydrohexitol polyester comprising;
  • wavy lines are wedge lines, ) Or dashed-wedge line, ) And R 1 is each independently an aliphatic hydrocarbon group having 1 to 7 carbon atoms, preferably 1 to 3, and may be substituted with one or more substituents such as halogen as necessary.
  • X is a substituted or unsubstituted aromatic or cycloaliphatic hydrocarbon group having 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms.
  • the wedge line means that the hydroxyl group (-OH) and the like are coupled on the plane (the structure indicated by the normal line), and the point wedge line means the bottom line is coupled.
  • the content of trans cycloaliphatic hydrocarbon group is 0 to 100%.
  • the final attainable intrinsic viscosity (IV) of 1,4: 3,6-dianhydrohexitol polyester comprising a repeating unit represented by Formula 3 prepared by the polyester production method is 0.3 to 1.2 dL / g.
  • dicarboxylic acid component refers to dicarboxylic acids such as terephthalic acid, alkyl esters thereof (lower alkyl esters having 1 to 6 carbon atoms such as monomethyl, monoethyl, dimethyl, diethyl or dibutyl ester) And an acid anhydride thereof, and the like, and the molten polycondensation reaction is a name encompassing esterification and esterification exchange reaction.
  • the step of preparing the acylate 1,4: 3,6- dianhydrohexitol is 1,4: 3,6- dianhydrohexitol (isomanide, isosorbide and
  • the reaction temperature of the acylation reaction is 80 to 180 ° C, preferably 120 to 160 ° C, more preferably 120 to 150 °C
  • the reaction time is 5 minutes to 10 hours, preferably 10 minutes to 5 hours.
  • Representative examples of the aliphatic acid anhydrides used in the acylation reaction of 1,4: 3,6-dianhydrohexitol include acet anhydride, propionic anhydride, Butyric anhydride, isobutyric anhydride, valeric anhydride, pivalic anhydride, 2-ethylhexanoic anhydride ( 2-ethylhexanoic anhydride, b-bromopropionic anhydride, monochloroacetic anhydride, dichloroacetic anhydride, trichloroacetic anhydride Trichloroacetic anhydride, monobromoacetic anhydride, dibromoacetic anhydride, tribromoacetic anhydride cetic anhydride, monofluoroacetic anhydride, difluoroacetic anhydride, trifluoroacetic anhydride and the like.
  • Two or more aliphatic acid anhydrides may be mixed and used, and R 1 of Chemical Formula 2 is determined according to the aliphatic acid anhydride to be used.
  • R 1 of Chemical Formula 2 is determined according to the aliphatic acid anhydride to be used.
  • the amount of aliphatic anhydride used is 0.9 to 1.2 times the stoichiometric amount of aliphatic anhydride required to acylate all the hydroxyl groups of 1,4: 3,6-dianhydrohexitol, preferably Is 0.97 to 1.13 fold.
  • the reaction rate of the associated polyester melt condensation polymerization may be slowed, or 1,4: 3, including the color of the final polymer, may be caused by mixed anhydride impurities. There is a fear that the physical properties of 6-dianhydrohexitol polyesters are lowered.
  • acylate 1,4 3,6-dianhydrohexitol
  • the inert gas purge is preferably continued in the associated polyester melt polycondensation reaction, and the removal and condensation of the acylation and melt polycondensation by-product aliphatic acids is carried out using conventional methods such as distillation heads and condensers. It can be done easily.
  • acetic acid in the acylation and melt polycondensation reaction by-products is a volatile by-product and is very easy to remove.
  • step (b)) for the preparation of 1,4: 3,6-dianhydrohexitol homopolyester is carried out directly in conjunction.
  • the initiation of the melt polycondensation reaction is achieved by selecting a higher reaction temperature than the acylation reaction.
  • the amount of acyl groups of in-situ prepared acylated 1,4: 3,6-dianhydrohexitol is 0.7 to 1.3 times the equivalent amount of the carboxyl groups of the free dicarboxylic acid component.
  • the temperature increase rate of the melt polycondensation reaction is 0.1 to 60 °C / min, preferably 0.2 to 20 °C / min, more preferably 0.5 to 6 °C / min, the reaction
  • the temperature is from 120 to 320 ° C, preferably from 150 to 290 ° C, more preferably from 170 to 280 ° C, and the reaction time is from 1 to 10 hours, preferably from 3 to 8 hours.
  • the aliphatic acid and unreacted aliphatic acid anhydride produced as reaction by-products during the melt polycondensation reaction must be distilled out of the reaction system in order to shift the reaction equilibrium in the polyester production direction.
  • the acylated 1,4: 3,6-dianhydrohexitol may be vaporized or sublimed together with the aliphatic acid.
  • the 1,4: 3,6- dianhydrohexitol polyester can be prepared by a batch process or by a continuous process.
  • aromatic or cycloaliphatic dicarboxylic acid component may be exemplified by the monomer represented by the following formula (4).
  • R 2 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms
  • X is as defined in Formula 3 above.
  • representative examples of X are , , , , , , , , , Etc. can be illustrated.
  • Y is an oxygen atom (O), a sulfur atom (S), an alkylene group, a carbonyl group or a sulfonyl group.
  • X may be substituted by an alkyl group, an aryl group, an alkoxy group, a halogen group, etc. as needed.
  • 1,4: 3,6-dianhydrohexitol polyester production method according to the present invention may further use a catalyst for improving the reactivity of the melt polycondensation reaction.
  • a catalyst metal catalysts commonly used in polyester melt condensation polymerization may be mainly used.
  • salts of titanium (Ti) or antimony (Sb), lithium (Li), sodium (Na), and the like may be mainly used.
  • an organic catalyst such as methyl imidazole (N-methylimidazole) or dimethylaminopyridine (N, N-dimethylamino pyridine) may also be used.
  • the content of the catalyst is 1 to 500 ppm, preferably 10 to 300 ppm relative to the total reactant weight.
  • the catalyst can be applied irrespective of the melt polycondensation reaction step, but is preferably added before the start of the melt polycondensation reaction.
  • the method for producing 1,4: 3,6-dianhydrohexitol polyester according to the present invention quickly induces by-product removal in a molten state having a high viscosity as the degree of polymerization increases as the melt polycondensation reaction proceeds.
  • Reduced pressure may be applied to accelerate the rate of polymerization.
  • the decompression conditions are 0.2 to 2 Torr, preferably 0.5 to 1 Torr, and the reaction time under reduced pressure may be performed for 1 to 10 hours, preferably 1 to 5 hours.
  • the 1,4: 3,6- dianhydrohexitol polyester manufacturing method which concerns on this invention can further add various additives as needed.
  • antioxidants and heat stabilizers such as hindered phenol, hydroquinone, phosphite, and substituted compounds thereof
  • Additives include UV absorbers such as salicylate, color protection agents such as phosphite and hydrophosphite, lubricants such as montanic acid and stearyl alcohol, and the like.
  • dyes and pigments may be used as the coloring agent, and carbon black may be used as the conductive agent, the colorant, or the nucleation agent. Fire retardants, plasticizers, antistatic agents and the like can be used.
  • all the above-mentioned additives should not impair thermal stability, especially among the final polymer properties.
  • a solid-sate polymerization may be further performed after the melt condensation polymerization reaction.
  • the polymer obtained from the melt condensation polymerization is collected in a solid state such as crushed or flakes outside the reactor, and then heated under an inert environment such as nitrogen or argon gas, at a temperature raising rate of 0.1 to 0.5 ° C /.
  • the reaction temperature may be heat-treated at a reaction temperature of 30 to 350 ° C., preferably at 100 to 280 ° C., for a reaction time of 1 to 30 hours, preferably 2 to 24 hours.
  • Solid phase polymerization can be carried out with or without stirring and can be carried out continuously in the same reactor as the melt polymerization. After solid phase polymerization, the obtained polymer can be molded immediately to meet the end purpose according to the application by conventional methods.
  • the final attainable intrinsic viscosity (IV) of the 1,4: 3,6- dianhydrohexitol polyester produced by the solid phase polymerization is from 0.5 to 2.5 dL / g.
  • the flask was emptied with nitrogen and washed five times, and then the flask was equipped with a distillation head, a cooling condenser, a thermometer, a nitrogen input tube, and a mechanical stirrer.
  • 200 g (1.20 mole) of terephthalic acid and 176 g (1.20 mole) of isosorbide were added to the flask, and the temperature was raised to 60 to 70 ° C, followed by stirring for 10 to 20 minutes, followed by a dropping funnel.
  • 250 g (2.45 mole) of acet anhydride were added slowly to a terephthalic acid / isosorbide slurry.
  • Acetic anhydride was all added, then under normal pressure, immediately raised to 120 ° C., and then stirred and maintained for 1 hour. After again raising the temperature to 145 °C, stirred and maintained for 3 hours to 1,4: 3,6- dianhydr-D-glucitol-2,5- diacetate (1,4: 3,6-dianhydro-D -glucitol-2,5-diacetate).
  • the temperature was raised to 200 ° C., and stirred and maintained at 200 ° C. for 1 hour to remove acetic acid which is an acetylation reaction by-product.
  • an additional acetic acid by-product was removed by raising the temperature to 250 ° C. at a rate of 1 ° C./min and then stirring and maintaining at 250 ° C. for 3 hours.
  • 1,4: 3,6-dianhydrohexitol (homo) polyester comprising a repeating unit represented by Formula 3a is amorphous, and glass transition temperature (Tg) is intrinsic viscosity 0.5
  • glass transition temperature Tg
  • the reactivity of 1,4: 3,6-dianhydride-D-glucitol-2,5-diacetate with isosorbide can be compared as follows.
  • the loss rate of 1,4: 3,6- dianhydr-D-glucitol-2,5-diacetate vaporized or sublimed with acetic acid was up to 0.5% of the dose. This loss rate is very low compared to the loss rate of isosorbide.
  • the reactivity of 1,4: 3,6-dianhydride-D-glucitol-2,5-diacetate is markedly improved compared to isosorbide.
  • the same result was obtained in the following examples.
  • step (A) instead of 200 g (1.20 mole) of terephthalic acid and 176 g (1.20 mole) of isosorbide, 250 g (1.45 mole) of 1 having a cis / trans ratio of 77/23%
  • 1,4-cyclohexanedicarboxylic acid manufactured by SK NJC
  • 212 g (1.45 mole) of isosorbide and add 300 g of acet anhydride instead of 250 g (2.45 mole).
  • 1,4: 3,6-dianhydrohexitol (homo) polyester (IV 0.58) containing a repeating unit represented by the following Formula 3b in the same manner as in Example 1 except that )
  • 1,4: 3,6- dianhydrohexitol (homo) polyester comprising a repeating unit represented by the formula (3b) is amorphous, and as a characteristic result is the first monomer 1,4-cyclohexanedica
  • the glass transition temperature of the polymer is affected by the cis / trans ratio in the final polymer, and when the intrinsic viscosity is cis / trans 44/64% at 0.5 or more, the glass transition temperature is 151 to 153 ° C.
  • 1,4: 3,6-dianhydrohexitol (homo) polyester comprising a repeating unit represented by Formula 3c is more than an amorphous polymer structure of a polyester comprising a repeating unit represented by Formula 3a. It is close to linear and exhibits a zig-zag or helical chain conformation with a gentle curve.
  • 1,4: 3,6-dianhydrohexitol (homo) polyester comprising a repeating unit represented by Formula 3d is the same as the result obtained in preparing a polyester including a repeating unit represented by Formula 3b.
  • the cis / trans ratio of the original monomeric 1,3-cyclohexanedicarboxylic acid changed from 46/54% to 5/95%, which was prepared using trans 100% of 1,3-cyclohexanedicarboxylic acid. It has similar properties to the polymers.
  • acylated 1,4: 3,6- dianhydrohexitol (eg, 1,4: 3,6- dianhydrohexitol-2,5-diacetate ) Is prepared in-situ, and when the aromatic or cycloaliphatic 1,4: 3,6-dianhydrohexitol polyester is prepared therefrom, 1,4: 3 Compared to melt polycondensation of, 6-diandianhexitol, the reaction rate is significantly faster and the reactivity is increased. Therefore, the amount of isosorbide (reactant) used can be reduced to be almost equal to the isosorbide content contained in the final polymer. Thus, no complicated process or apparatus for reusing excess isosorbide is required, and 1,4: 3,6-dianhydrohexitol polyester can be economically produced.
  • 1,4: 3,6-dianhydrohexitol polyester can be economically produced.

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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 procédé de préparation in situ de l'(homo)polyester de 1,4:3,6-dianhydrohexitol utilisant du 1,4:3,6-dianhydrohexitol acylé. Ledit procédé de préparation du polyester de 1,4:3,6-dianhydrohexitol comprend les étapes consistant à : utiliser une réaction d'acylation d'un 1,4:3,6-dianhydrohexitol avec un anhydride d'acide aliphatique ayant de 4 à 16 atomes de carbone dans le but de préparer le 1,4:3,6-dianhydrohexitol acylé ; et utiliser une réaction in situ de polymérisation par condensation à l'état fondu dudit 1,4:3,6-dianhydrohexitol acylé et d'un composant acide dicarboxylique aromatique ou cycloaliphatique libre ayant de 8 à 14 atomes de carbone dans le but de préparer le polyester de 1,4:3,6-dianhydrohexitol.
PCT/KR2012/003233 2011-04-27 2012-04-26 Procédé de préparation du poly(ester de 1,4:3,6-dianhydrohexitol) WO2012148187A2 (fr)

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KR10-2011-0039316 2011-04-27
KR1020110039316A KR20120121477A (ko) 2011-04-27 2011-04-27 단단한 폴리(1,4:3,6-디안히드로헥시톨 에스테르) 제조방법

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3086663A1 (fr) * 2018-10-02 2020-04-03 Roquette Freres Procede de preparation d'un polyester de type poly(1,4:3,6-dianhydrohexitol-cocyclohexylene terephtalate)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101995907B1 (ko) 2013-07-24 2019-07-03 에스케이케미칼 주식회사 고내열 고투명 폴리카보네이트 에스테르 및 그 제조방법
CA2946080C (fr) * 2014-04-30 2020-11-10 Stichting Wageningen Research Polyesters et copolyesters thermoplastiques de furanoate de polyisoidide et utilisation associee dans le conditionnement par remplissage a chaud
KR102083053B1 (ko) 2016-08-09 2020-02-28 주식회사 엘지화학 폴리에스테르 및 이의 제조방법

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003064170A (ja) * 2001-08-24 2003-03-05 Polyplastics Co 芳香族ポリエステルの製造方法
KR20050089743A (ko) * 2002-12-19 2005-09-08 이 아이 듀폰 디 네모아 앤드 캄파니 에스테르 변성 디카르복실레이트 중합체
US20090105377A1 (en) * 2005-03-18 2009-04-23 Battelle Memorial Institute Resins, low temperature formulations, and coatings derived therefrom
US20110040004A1 (en) * 2009-08-12 2011-02-17 Andjelkovic Dejan D Formulations comprising isosorbide-modified unsaturated polyester resins and low profile additives which produce low shrinkage matrices

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003064170A (ja) * 2001-08-24 2003-03-05 Polyplastics Co 芳香族ポリエステルの製造方法
KR20050089743A (ko) * 2002-12-19 2005-09-08 이 아이 듀폰 디 네모아 앤드 캄파니 에스테르 변성 디카르복실레이트 중합체
US20090105377A1 (en) * 2005-03-18 2009-04-23 Battelle Memorial Institute Resins, low temperature formulations, and coatings derived therefrom
US20110040004A1 (en) * 2009-08-12 2011-02-17 Andjelkovic Dejan D Formulations comprising isosorbide-modified unsaturated polyester resins and low profile additives which produce low shrinkage matrices

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3086663A1 (fr) * 2018-10-02 2020-04-03 Roquette Freres Procede de preparation d'un polyester de type poly(1,4:3,6-dianhydrohexitol-cocyclohexylene terephtalate)
WO2020070445A1 (fr) * 2018-10-02 2020-04-09 Roquette Freres Procédé de préparation d'un polyester de type poly(1,4:3,6-dianhydrohexitol-cocyclohexylène téréphtalate)
CN112955491A (zh) * 2018-10-02 2021-06-11 罗盖特公司 用于制备聚(1，4:3，6-双脱水己糖醇-共亚环己基对苯二甲酸酯)类型的聚酯的方法
US20220002476A1 (en) * 2018-10-02 2022-01-06 Roquette Freres Method for preparing a polyester of the poly(1,4:3,6-dianhydrohexitol-cocyclohexylene terephthalate) type

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