WO2019093770A1 - Produit moulé fabriqué à partir d'un ester de polycarbonate résistant à la chaleur élevée - Google Patents

Produit moulé fabriqué à partir d'un ester de polycarbonate résistant à la chaleur élevée Download PDF

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Publication number
WO2019093770A1
WO2019093770A1 PCT/KR2018/013491 KR2018013491W WO2019093770A1 WO 2019093770 A1 WO2019093770 A1 WO 2019093770A1 KR 2018013491 W KR2018013491 W KR 2018013491W WO 2019093770 A1 WO2019093770 A1 WO 2019093770A1
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Prior art keywords
reaction
formula
molded article
ester
dianhydrohexitol
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PCT/KR2018/013491
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English (en)
Korean (ko)
Inventor
오광세
Original Assignee
에스케이케미칼 주식회사
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Priority claimed from KR1020180135681A external-priority patent/KR102634462B1/ko
Application filed by 에스케이케미칼 주식회사 filed Critical 에스케이케미칼 주식회사
Priority to US16/757,570 priority Critical patent/US11590682B2/en
Priority to EP18877033.3A priority patent/EP3708601B1/fr
Priority to CN201880070594.XA priority patent/CN111278890A/zh
Priority to JP2020519777A priority patent/JP7279714B2/ja
Priority to ES18877033T priority patent/ES2950732T3/es
Publication of WO2019093770A1 publication Critical patent/WO2019093770A1/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
    • C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

  • the present invention relates to a molded article made from a high-temperature-resistant bio-based polycarbonate ester, and more particularly, to a molded article which is excellent in heat resistance and has a wide variety of properties such as automobile, electric and electronic display, It can be applied to the field.
  • Bio-based polycarbonate esters prepared by melt polycondensation of 1,4: 3,6-dianhydrohexitol with carbonates or 1,4-cyclohexanedicarboxylate are useful as biocide- Bioplastic containing bio-based monomers derived from the sources, namely 1,4: 3,6-dianhydrohexitol.
  • the bio-based polycarbonate ester has a high transparency of PMMA (poly (methyl methacrylate)) and a high heat resistance of bisphenol A (BPA) polycarbonate, which are typical transparent resins.
  • the structural characteristics of such a bio-based polycarbonate ester do not include BPA that induces environmental hormones, and by copolymerizing a 1,4-cyclohexanedicarboxylate monomer having an aliphatic cyclic molecular structure, 1,4: 3,6- Dianhydrohexitol can improve the poor ductility of the molecular structure. Further, the disadvantage of the carbonate bond can be compensated by replacing a part of the carbonate bond with an ester bond.
  • 1,4-cyclohexanedicarboxylic acid (1,4-dimethyl-cyclohexanedicarboxylate, DMCD) or 1,4-cyclohexanedicarboxylic acid (CHDA )
  • DMCD 1,4-dimethyl-cyclohexanedicarboxylate
  • CHDA 1,4-cyclohexanedicarboxylic acid
  • the development of high heat-resistant materials that can be applied to various fields such as automobile, electronic equipment, industrial lighting, and medical treatment has been progressed with a recent glass transition temperature (Tg) of 170 ° C or higher.
  • Tg glass transition temperature
  • the bio-based polycarbonate esters prepared by the melt polycondensation of 1,4: 3,6-dianhydrohexitol and the carbonate or 1,4-cyclohexanedicarboxylate have a Tg of 170 DEG C or lower, It is necessary to improve the heat resistance.
  • an object of the present invention is to provide a polycarbonate resin composition which uses a low-cost raw material that meets heat resistance and economy, and which is capable of maintaining high transparency of a bio-based polycarbonate ester, To provide a molded article.
  • the present invention provides a molded article produced from a high-temperature-resistant bio-based polycarbonate ester,
  • the molded article of the present invention is made from a high-temperature-resistant bio-based polycarbonate ester and is eco-friendly because it does not contain bisphenols, and can be used in various products with an excellent heat resistance at a glass transition temperature of 160 ° C or higher.
  • the present invention relates to a molded article made from a high heat resistant bio-based polycarbonate ester,
  • the high-temperature-resistant bio-based polycarbonate ester comprises repeating units 1 represented by the following formula (1): A repeating unit 2 represented by the following formula (2); And a repeating unit 3 represented by the following formula (3).
  • the recurring unit 1 is obtained from the reaction of 1,4: 3,6-dianhydrohexitol and carbonate, and the recurring unit 2 is 1,4: 3,6-dianhydrohexitol and 1,4-cyclo Hexanedicarboxylate, and the repeating unit 3 can be obtained from the reaction of 1,4: 3,6-dianhydrohexitol and terephthalate.
  • the cis / trans ratio of 1,4-cyclohexanedicarboxylate in the repeating unit 2 may be 1/99 to 99/1%, 20/80 to 80/20%, or 30/70 to 70/30% .
  • the 1,4: 3,6-dianhydrohexitol may be isomanide, isosorbide and isoidide, and may be specifically isosorbide.
  • x is a real number of more than 0 and less than 1
  • Y is a real number greater than 0 and less than or equal to 0.7
  • z is a real number greater than 0 and less than or equal to 0.6
  • x + y + z can be 1.
  • x is a real number of more than 0 and not more than 0.9, or not more than 0 and not more than 0.8
  • y is a real number of not less than 0 and not more than 0.6, or not less than 0 and not more than 0.5
  • z is more than 0 and not more than 0.5
  • X + y + z may be a real number.
  • the high temperature resistant biobased polycarbonate ester may have a glass transition temperature (Tg) of 160 to 240 ° C and a melt flow index (MI) at 260 ° C and a load of 2.16 kg of 5 to 150 g / 10 min.
  • the polycarbonate ester may have a Tg of 170 to 220 ⁇ , or 180 to 200 ⁇ , an MI of 10 to 100 g / 10 min, or 15 to 50 g / 10 min at 260 ⁇ and a load of 2.16 kg .
  • the high heat-resistant bio-based polycarbonate ester may have an intrinsic viscosity (IV) of 0.3 to 2.3 dL / g.
  • polycarbonate is superior in heat resistance and mechanical properties to polyesters but relatively insufficient in terms of chemical resistance, residual stress and molding cycle time.
  • polycarbonate esters containing both a carbonate and an ester bond in a single chain have both disadvantages and advantages of each single bond polymer. Accordingly, the molded article produced from the high-temperature-resistant bio-based polycarbonate ester can be used as a material for various fields requiring excellent heat resistance.
  • the molding process of the high-temperature-resistant bio-based polycarbonate ester is not particularly limited.
  • a molding process such as injection molding, extrusion molding, blow molding, extrusion blow molding, inflation molding, calendar molding, foam molding, balloon molding, vacuum molding, and radiation can be applied.
  • the use of the molded article produced from the high heat-resistant bio-based polycarbonate ester is not particularly limited, but it can be used as a substitute for conventional heat resistance and optical molded articles on the basis of its excellent heat resistance and transparency.
  • the molded product may be an automobile component, an electric / electronic component, a display component, an air component, a mechanical component, an illumination component, a medical product, or a food container.
  • the high heat resistant bio-based polycarbonate esters of the present invention can be prepared by the following method.
  • R < 1 > is methyl or hydrogen
  • R 2 and R 3 are each an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, and the aryl group is an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 18 carbon atoms, An alkoxy group having 1 to 18 carbon atoms, a cycloalkoxy group having 4 to 20 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, an alkylsulfonyl group having 1 to 18 carbon atoms, a cycloalkylsulfonyl group having 4 to 20 carbon atoms, A sulfonyl group, and an ester substituent.
  • the ester substituent may be an alkyl ester having 1 to 18 carbon atoms, a cycloalkyl ester having 4 to 20 carbon atoms, or an aryl ester having 6 to 18 carbon atoms
  • the compound represented by the formula (4) is converted into an intermediate reactant having a halogen functional group at the terminal thereof, followed by a nucleophilic reaction with a phenol or phenol substituent, or a phenol or phenol substituent is transesterified Esterification reaction is carried out to prepare a compound represented by the above formula (5).
  • the phenol substituent may be a compound represented by the following general formula (9).
  • R 5 is an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkoxy group having 4 to 20 carbon atoms, An alkylsulfonyl group having 1 to 18 carbon atoms, a cycloalkylsulfonyl group having 4 to 20 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or an ester substituent.
  • the ester substituent may be an alkyl ester having 1 to 18 carbon atoms, a cycloalkyl ester having 4 to 20 carbon atoms, or an aryl ester having 6 to 18 carbon atoms.
  • the intermediate reactant having a halogen functional group at the terminal thereof may be a compound represented by the following formula (8).
  • R < 4 > are each independently F, Cl or Br.
  • the intermediate reactant containing a halogen functional group at the terminal may be terephthaloyl chloride (TPC) in which R 4 is Cl.
  • the intermediate reactant having a halogen functional group at the terminal may be prepared by reacting the compound of formula (4) (dicarboxylate or dicarboxylic acid) with a halogenated compound.
  • the halogenated compound may be selected from the group consisting of phosgene, triphosgene, thionyl chloride, oxalyl chloride, phosphorus trichloride, phosphorus pentachloride, At least one selected from the group consisting of phosphorus pentabromide and cyanuric fluoride.
  • the halogenated compound may be at least one chlorinating agent selected from the group consisting of phosgene, thionyl chloride, and oxalyl chloride, which facilitates removal of reaction by-products.
  • the halogenated compound may be phosgene.
  • the addition amount of the halogenated compound may be 1 to 10 times, 1.5 to 7.5 times, or 2 to 5 times the number of mols of the total molar amount of the compound of Formula 4 initially introduced.
  • the reaction conditions and time may vary depending on the type of the compound of formula (IV) and the halogenated compound.
  • the conversion to the intermediate reactant can be carried out at atmospheric pressure and a temperature of -30 to 150 ⁇ for 5 minutes to 48 hours. More specifically, the conversion to the intermediate reactant can be carried out at normal pressure and at a temperature of from 20 to 100 DEG C, or from 40 to 80 DEG C for from 10 minutes to 24 hours.
  • an organic solvent may be used to dissolve or disperse the compound of the formula (4).
  • the organic solvent that may be used herein may be, for example, benzene, toluene, xylene, mesitylene, methylene chloride, dichloroethane, chloroform, carbon tetrachloride, monochlorobenzene, o- Dioxane, acetonitrile, and the like.
  • a catalyst may be used depending on the kind of the compound of the formula (4) and the halogenated compound used in the conversion to the intermediate reactant.
  • the type of the catalyst is not particularly limited so long as it is in conformity with this object.
  • Examples of the organic catalyst which can be used herein include dimethylformamide, dimethylacetamide, methylpyrrolidone, dimethyl imidazolidinone, tetramethylurea, tetraethylurea and tetrabutylurea.
  • dimethylformamide, tetramethylurea or dimethylimidazolidinone may be used as the organic catalyst
  • aluminum chloride or titanium tetrachloride may be used as the inorganic catalyst
  • dimethyl formamide may be used as a commercially preferable organic catalyst
  • aluminum chloride may be used as an inorganic catalyst.
  • the amount of the catalyst to be used in the conversion to the intermediate reactant is not particularly limited, but depends on the type of the compound of formula (IV) and the halogenated compound. Specifically, the amount of the catalyst used in the conversion to the intermediate reactant may be in the range of more than 0 to 10 mol%, more than 0 and 5 mol%, or more than 0 and 3 mol% or less based on the total molar amount of the compound of Formula 4 initially introduced have. When the amount of the catalyst used is less than the above range in the conversion to the intermediate reactant, the problem of lowering the reaction rate and causing the runaway reaction and the exothermic reaction can be prevented.
  • the step (1) is a step wherein Terephthalic acid (TPA) in which R 1 is hydrogen or dimethyl terephthalate (DMT) in which R 1 is methyl is reacted with TPC which is an intermediate reactant having a halogen functional group at the terminal Diphenyl terephthalate (DPT) represented by the general formula (5) can be prepared by reacting with phenol or a phenol substituent (see Scheme 1 below).
  • TPA Terephthalic acid
  • DMT dimethyl terephthalate
  • DPT Diphenyl terephthalate
  • the molar ratio of the compound represented by Formula 8 to the phenol or phenol substituent may be 1: 1 to 5. Specifically, in the nucleophilic reaction, the molar ratio of the compound represented by Formula 8 to the phenol or phenol substituent may be 1: 2 to 3.
  • the final yield of the compound (DPT) represented by the formula (5) which is a problem that may occur due to the use of an excessive phenol or phenol substituent Can be prevented.
  • TPA in which R 1 is hydrogen or DMT in which R 1 is methyl is transesterified or esterified with a phenol or phenol substituent in the above formula (4) to prepare a compound represented by the following formula (See Scheme 1 above).
  • the transesterification or esterification reaction may be carried out at 20 to 300 < 0 > C. Specifically, the transesterification or esterification reaction is carried out at 50 to 250 ° C or 100 to 200 ° C at normal pressure, or at 50 to 300 ° C under a pressure of 0.1 to 10 kgf / cm 2 or 1 to 5 kgf / cm 2 .
  • the transesterification or esterification reaction may be carried out for 5 minutes to 48 hours, or 10 minutes to 24 hours.
  • the molar ratio of the compound represented by Formula 4 to the phenol or phenol substituent may be 1: 2 to 40. Specifically, in the ester exchange or esterification reaction, the molar ratio of the compound represented by Formula 4 to the phenol or phenol substituent may be 1: 3 to 30, or 1: 4 to 20.
  • the final yield of the compound of the general formula (5) which may be caused by a small amount of phenol or phenol substituent, can be prevented from lowering.
  • a compound represented by the following formulas (5) to (7) and 1,4: 3,6-dianhydrohexitol are subjected to a melt polycondensation reaction to obtain a compound containing the repeating units 1 to 3 represented by the following formulas .
  • R 2 and R 3 are each an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, and the aryl group is an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 18 carbon atoms, An alkoxy group having 1 to 18 carbon atoms, a cycloalkoxy group having 4 to 20 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, an alkylsulfonyl group having 1 to 18 carbon atoms, a cycloalkylsulfonyl group having 4 to 20 carbon atoms, A sulfonyl group, and an ester substituent.
  • the ester substituent may be an alkyl ester having 1 to 18 carbon atoms, a cycloalkyl ester having 4 to 20 carbon atoms, or an aryl ester having 6 to 18 carbon atoms
  • the cis / trans ratio of the compound represented by Formula 6 may be 1/99 to 99/1%, 10/90 to 90/10%, or 20/80 to 80/20%. Also, the cis / trans ratio of 1,4-cyclohexanedicarboxylate in the repeating unit 2 represented by the general formula (2) is 1/99 to 99/1%, 20/80 to 80/20%, or 30/70 to 70 / 30%.
  • the compound represented by the formula (7) may be prepared by reacting a compound represented by the formula (7) with a compound selected from the group consisting of dimethyl carbonate, diethyl carbonate, di-t-butyl carbonate, diphenyl carbonate, ditolyl carbonate ditolyl carbonate or bis (methylsalicyl) carbonate.
  • diphenyl carbonate or substituted diphenyl carbonate may be used as the compound represented by the general formula (7).
  • the substituted diphenyl carbonate may be ditolyl carbonate or bis (methyl salicyl) carbonate.
  • the 1,4: 3,6-dianhydrohexitol may be isomanide, isosorbide and isoidide, and may be specifically isosorbide.
  • the heat resistance, transparency and transparency of the prepared high-temperature biobased polycarbonate ester In order to improve the mechanical properties, it is very important to control the purity of 1,4: 3,6-dianhydrohexitol used in the melt polycondensation reaction.
  • the 1,4: 3,6-dianhydrohexitol can be used in the form of a powder, a flake, or an aqueous solution.
  • the above 1,4: 3,6-dianhydrohexitol is easily oxidized and discolored when exposed to air for a long time, so that the color and molecular weight of the final polymer can not reach the target level Occurs.
  • the 1,4: 3,6-dianhydrohexitol should be exposed to the air in a minimum time, and it is preferably stored together with an oxygen scavenger such as an oxygen absorbent when stored after exposure.
  • an oxygen scavenger such as an oxygen absorbent when stored after exposure.
  • the impurities of the acid liquid component and the metal component may be controlled to 10 ppm or less, 5 ppm or less, or 3 ppm or less, respectively.
  • the high-temperature-resistant bio-based polycarbonate ester may be composed of the repeating units 1 to 3. Specifically, the 1,4: 3,6-dianhydrohexitol and the compound represented by the formula (7) react to form a carbonate bond (repeating unit 1, formula 1), and the 1,4: 3,6 Dianhydrohexitol and the compound represented by Formula 6 react to form an ester bond (Repeating Unit 2, Formula 2), and the 1,4: 3,6-dianhydrohexitol and the compound represented by Formula 5 The displayed compound may react to form an ester bond (repeating unit 3, formula 3).
  • a polycarbonate prepared by melt polycondensation of 1,4: 3,6-dianhydrohexitol and diphenyl carbonate (Formula 7) in which the amount of the compound represented by Formula 5 and Formula 6 is 0, Has a Tg of 163 ⁇ ⁇ .
  • increasing the amount of the compound represented by Chemical Formula 5 and Chemical Formula 6 increases the ester bond in the polymer chain.
  • polyester having a Tg of 215 ° C is produced.
  • polyester having a Tg of 132 ° C is produced.
  • the content of the repeating units 2 and 3 represented by the above formulas (2) and (3) and the number of carbonate and ester bonds existing in the polymer chain depend on the amount of the compound represented by the above formulas (5) and (6).
  • the polymer chain includes a carbonate and an ester bond together (including the above recurring units 1 to 3)
  • polymers having excellent heat resistance, transparency and processability Can be provided.
  • polycarbonate is superior in heat resistance and mechanical properties to polyesters but relatively insufficient in terms of chemical resistance, residual stress and molding cycle time.
  • polycarbonate esters containing both a carbonate and an ester bond in a single chain have both disadvantages and advantages of each single bond polymer.
  • melt polycondensation reaction can induce rapid removal of by-products from the molten reactant having a high viscosity, and the temperature increase and the decompression can be applied stepwise to promote the polymerization reaction rate.
  • (2-1) a step of subjecting to a primary reaction at a reduced pressure of 50 to 700 torr and at 130 to 250 ° C, 140 to 240 ° C, or 150 to 230 ° C for 0.1 to 10 hours, or 0.5 to 5 hours;
  • phenol may be generated as a reaction by-product during the melt polycondensation reaction.
  • the phenol as the reaction by-product is preferably discharged out of the reaction system.
  • the rate of temperature increase during the melt polycondensation reaction is within the above range, it is possible to prevent the reaction starting material from being vaporized or sublimated together with phenol as a reaction by-product.
  • the polycarbonate ester can be prepared by a batch process or a continuous process.
  • melt polycondensation reaction using 1,4: 3,6-dianhydrohexitol in order to produce a polymer having a high transparency, a relatively low reaction temperature is suitable. Further, in order to ensure the mechanical properties of the produced polymer, it is preferable that the above-mentioned melt polycondensation reaction proceeds to a high polymerization degree. For this purpose, it is effective to use a high viscosity polymerization reactor for the melt polycondensation reaction.
  • the target viscosity of the melt polycondensation reaction may be 10,000 to 1,000,000 poise, 20,000 to 500,000 poise, or 50,000 to 200,000 poise.
  • reaction product of step (2) (compound represented by the above formulas 5 to 7 and 1,4: 3,6-dianhydrohexitol)
  • a compound may be added, and the kind thereof is not limited.
  • the additional diol compound may be a primary, secondary, or tertiary diol compound, depending on the target properties.
  • the input amount of 1,4: 3,6-dianhydrohexitol is 1-q.
  • the bio-based carbon content ASTM-D6866
  • q may be 0 ⁇ q < 0.99. That is, the additional diol compound may be contained in an amount of less than 99 mol% based on 100 mol% of 1,4: 3,6-dianhydrohexitol.
  • the additional diol compound may be a diol compound having a single aliphatic ring or condensed heterogeneous ring at the center of the molecule.
  • the ring size and the heat resistance increase proportionally, but the optical properties do not depend on the ring size and the hydroxyl group position but depend on the characteristics of each raw material. Commercial manufacture and use become difficult.
  • the additional diol compound is selected from the group consisting of 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol (1 , 4-cyclohexanedimethanol), tricyclodecanedimethanol, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane (2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 2,2-bis (4-hydroxycyclohexyl) propane But are not limited to, 2,2-bis (4-hydroxycyclohexyl) propane, pentacyclopentadecanedimethanol, decalindimethanol, tricyclotetradecanedimethanol, norbornanedimethanol, Adamantanedimethanol, bicyclo [2.2.2] octane-2,3-dimethanol,
  • 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 2,2,4,4-tetramethyl-1,3-cyclobutanediol which can be prepared from biologically based raw materials, and tetrahydrofuran- 5,5 '- (1-methylethylidene) bis (2-furanmethanol), 5,5' - (1-methylethylidene) 2,4-di-o-methylene-D-mannitol, and 2,4: 3,5-di-o-methylene-D-mannitol.
  • the additional diol compound is selected from the group consisting of 1,4-cyclohexanedimethanol, 2,2-bis (4-hydroxycyclohexyl) propane, 2,2,4,4-tetramethyl- Or tetrahydrofuran-2,5-dimethanol.
  • step (2) the compound represented by the above Chemical Formulas 5 to 7 and 1,4: 3,6-dianhydrohexitol
  • An additional diphenyl ester compound may be further added in addition to the compound represented by the general formula (6).
  • the input amount of the additional diphenyl ester compound is p
  • the amount of the compound represented by the general formulas (5) to (7) is 1-p.
  • p satisfies 0? P ⁇ 1.
  • the additional diphenyl ester compound may be one kind or a mixture of two or more kinds.
  • the additional diphenyl ester can be prepared by reacting a primary, secondary or tertiary dicarboxylate or dicarboxylic acid (hereinafter additional dicarboxylate or dicarboxylic acid) with a phenol or phenol substituent.
  • additional dicarboxylate or dicarboxylic acid a primary, secondary or tertiary dicarboxylate or dicarboxylic acid
  • the additional diphenyl esters may be further dicarboxylates or dicarboxylic acids having a single aliphatic ring or condensed hetero- Can be prepared by reacting a carboxylic acid with a phenol or phenol substituent.
  • the additional dicarboxylate compound may be selected from the group consisting of dimethyl tetrahydrofuran-2,5-dicarboxylate, 1,2-dimethyl-cyclohexanedicarboxylate, , 1,3-dimethyl-cyclohexanedicarboxylate, dimethyl decahydro-2,4-naphthalene dicarboxylate, dimethyldecahydro-dicarboxylate, Dimethyl decahydro-2,5-naphthalene dicarboxylate, dimethyl decahydro-2,6-naphthalene dicarboxylate and dimethyl decahydro-2-naphthalene dicarboxylate. Dimethyl decahydro-2,7-naphthalene dicarboxylate, and the like.
  • the additional dicarboxylic acid compound may be selected from the group consisting of tetrahydrofuran-2,5-dicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, decahydro-2,4-naphthalenedicarboxylic acid, decahydro-2,5-naphthalene, Decahydro-2,5-naphthalenedicarboxylic acid, decahydro-2,6-naphthalenedicarboxylic acid and decahydro-2,7-naphthalenedicarboxylic acid (decahydro-2,7-naphthalenedicarboxylic acid).
  • the additional diphenyl esters may be dimethyltetrahydrofuran-2,5-dicarboxylate or tetrahydrofuran-2,5-dicarboxylic acid, or dimethyldecahydro-2,6- Naphthalene dicarboxylate or decahydro-2,6-naphthalene dicarboxylic acid.
  • a catalyst may be used for improving the reactivity.
  • the catalyst may be added to the reaction step at any time, but it is preferably added before the initiation of the reaction.
  • the catalyst is not particularly limited as long as it is an alkali metal and / or an alkaline earth metal catalyst commonly used in polycondensation polycondensation reaction.
  • the catalyst may be used in combination with a basic ammonium or amine, a basic phosphorus, or a basic boron compound, or may be used alone.
  • the alkali metal catalyst is lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), cesium hydroxide (CsOH), lithium carbonate (Li 2 CO 3), sodium carbonate ( Na 2 CO 3 ), potassium carbonate (K 2 CO 3 ), cesium carbonate (Cs 2 CO 3 ), lithium acetate (LiOAc), sodium acetate (NaOAc), potassium acetate (KOAc) or cesium acetate .
  • the alkaline earth metal catalyst may be at least one selected from the group consisting of calcium hydroxide (Ca (OH) 2 ), barium hydroxide (Ba (OH) 2 ), magnesium hydroxide (Mg (OH) 2 ), strontium hydroxide (OH) 2 ), calcium carbonate (CaCO 3 ), barium carbonate (BaCO 3 ), magnesium carbonate (MgCO 3 ), strontium carbonate (SrCO 3 ), calcium acetate (Ca (OAc) 2 ), barium acetate ) 2 ), magnesium acetate (Mg (OAc) 2 ), or strontium acetate (Sr (OAc) 2 ).
  • the catalyst may be an oxide, hydride, amide, or phenolate of an alkali metal and / or an alkaline earth metal, for example, magnesium oxide (MgO) Barium oxide (BaO), sodium aluminate (NaAlO 2 ), and the like.
  • the catalyst may also be a catalyst such as zinc oxide (ZnO), lead oxide (PbO), dibutyltin oxide ((C 4 H 9 ) 2 SnO), antimony trioxide (Sb 2 O 3 )
  • the amount of catalyst used in the melt polycondensation reaction may be more than 0 mmol, not more than 0 mmol, not more than 3 mmol, or not more than 0 mmol but not more than 1 mmol, per 1 mol of the total diol compound.
  • the amount of the catalyst used is within the above range, it is possible to prevent a problem that the degree of polymerization falls below the target degree of polymerization, and a problem that a side reaction or the like occurs and the target physical property such as transparency is lowered.
  • additives may be further added to the reactant, if necessary.
  • additives include, for example, antioxidants and heat stabilizers such as hindered phenols, hydroquinone, phosphites, and substituted compounds thereof; UV absorbers such as resorcinol and salicylate; Color protectants such as phosphites and hydro phosphites; Lubricants such as montanic acid and stearyl alcohol; And the like.
  • dyes and pigments can be used as colorants, carbon black can be used as a conductive agent, a coloring agent, or a nucleation agent.
  • all of the above-mentioned additives can be used within the range of properties of the final polymer, in particular, the transparency is not impaired.
  • DPT was synthesized in the same manner as in Preparation Example 1, except that 1.27 g (0.017 mol) of dimethylformamide was added as an organic catalyst. As a result of synthesis, the reaction yield was 84%, and the purity of DPT was 99.7% by GC analysis.
  • the toluene was removed from the separated toluene solution using an evaporator, and the obtained crude DPT was recrystallized and purified. Thereafter, the purified DPT was vacuum-dried at 90 DEG C for 24 hours to obtain 106 g of DPT, and the reaction yield was 65%.
  • Example 1 Production of polycarbonate ester based on a high-temperature bio
  • Polycarbonate esters were prepared in the same manner as in Example 1 except that the compositions of the polymer samples were used in the amounts shown in Table 1 below.
  • DPCD DPCD was not used, and DPT obtained in Preparation Example 1, 2549 g (11.9 mol) of DPC (Changfeng), 1988 g (13.6 mol) ISB (Roquette Freres) and 490 g
  • a polycarbonate ester was prepared in the same manner as in Example 1, except that 1,4-cyclohexane dimethanol (CHDM, manufactured by SK Chemicals) was used.
  • Polymerization Polycarbonate ester had a Tg of 155 ⁇ ⁇ and an IV of 0.55 dL / g.
  • Polycarbonate esters were prepared in the same manner as in Comparative Example 1, except that the compositions of the polymer samples were used in the amounts shown in Table 1 below.
  • the glass transition temperature was measured using a differential scanning calorimeter (Q20, TA INSTRUMENTS) according to ASTM D3418.
  • the light transmittance of a specimen having a thickness of 4 mm was measured using a spectrophotometer (CM-3600A, Konica Minolta) according to ASTM D1003.
  • MI Melt flow index
  • the melt flow index was measured using a melt indexer (G-01, TOYOSEIKI) according to ASTM D1238 under conditions of 260 ° C and 2.16 kg load.
  • Example 1 One 0 0.8 0.1 0.1 168 92 72
  • Example 2 One 0 0.7 0.2 0.1 164 92 100
  • Example 3 One 0 0.6 0.2 0.2 172 92 71
  • Example 4 One 0 0.5 0.2 0.3 180 91 41
  • Example 5 One 0 0.4 0.3 0.3 178 92 70
  • Example 6 One 0 0.3 0.4 0.3 174 92 99
  • Example 7 One 0 0.2 0.4 0.4 182 91 69
  • Example 8 One 0 0.1 0.4 0.5 190 91 39
  • Example 9 One 0 0.3 0.3 0.4 185 91 42
  • Example 10 One 0 0.2 0.3 0.5 193 90 14 Comparative Example 1 0.8 0.2 0.7 0 0.3 155 90 35 Comparative Example 2 0.8 0.2 0.6 0.1 0.3 152 91 65 Comparative Example 3 0.7 0.3 0.6 0 0.4 154 89 37
  • the diphenyl terephthalate (DPT) represented by the formula (5) was prepared according to the production method of the present invention, and the high heat resistant biocarbon based polycarbonate esters of Examples 1 to 10 prepared using the same Based polycarbonate ester copolymerized only with conventional DPC and 1,4-diphenyl-cyclohexanedicarboxylate (DPCD), the glass transition temperature was high and it was suitable for applications requiring high heat resistance.
  • DPT diphenyl terephthalate
  • DPCD 1,4-diphenyl-cyclohexanedicarboxylate
  • the glass transition temperature is decreased as the content of the aliphatic cyclic monomer increases, but the melt flow rate is increased Respectively.
  • Example 10 when the content of DPT repeating units was increased (Examples 2 to 4 and Examples 6 to 8), it was confirmed that the glass transition temperature was increased but the melt flow index was decreased. Particularly, it can be seen that the melt flow index is similar in Example 3, even though the glass transition temperature is higher than that in Example 1, and the melt flow index is similar in Example 7, even though the glass transition temperature is higher than in Examples 1 and 3. Also, in Example 10, the glass transition temperature had the maximum value among the examples, but the melt flow index was relatively low due to the low content of DPCD repeating units.
  • the light transmittances of Examples 1 to 10 were all 90% or more, which is equal to or higher than 90% of maximum light transmittance of BPA polycarbonate products having the same level of heat resistance, And the light transmittance was more than 91%.
  • the bio-based polycarbonate esters of Comparative Examples 1 to 3 using 1,4-cyclohexane dimethanol (CHDM) had low glass transition temperatures and were not suitable for high heat resistance applications, The melt flow index was not high.
  • the light transmittance was decreased as the content of the DPT repeating unit was increased.
  • the highly heat-resistant bio-based polycarbonate ester thus prepared is excellent in heat resistance, transparency and fluidity, and can be used for various high heat resistance applications.

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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 produit moulé fabriqué à partir d'un ester de polycarbonate biologique résistant à la chaleur élevée. Plus spécifiquement, le produit moulé présente une excellente résistance à la chaleur, et peut ainsi être appliqué à divers domaines tels que ceux des automobiles, de l'électronique électrique, des affichages, de l'aviation, des machines, de l'éclairage, des médicaments ou des aliments.
PCT/KR2018/013491 2017-11-09 2018-11-08 Produit moulé fabriqué à partir d'un ester de polycarbonate résistant à la chaleur élevée WO2019093770A1 (fr)

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US16/757,570 US11590682B2 (en) 2017-11-09 2018-11-08 Molded product manufactured from high heat resistant polycarbonate ester
EP18877033.3A EP3708601B1 (fr) 2017-11-09 2018-11-08 Produit moulé fabriqué à partir d'un ester de polycarbonate résistant à la chaleur élevée
CN201880070594.XA CN111278890A (zh) 2017-11-09 2018-11-08 由高度耐热的聚碳酸酯制成的模制品
JP2020519777A JP7279714B2 (ja) 2017-11-09 2018-11-08 高耐熱性ポリカーボネートエステルから製造される成形物
ES18877033T ES2950732T3 (es) 2017-11-09 2018-11-08 Producto moldeado fabricado a partir de éster de policarbonato con alta resistencia al calor

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WO2021254894A1 (fr) * 2020-06-19 2021-12-23 Covestro Deutschland Ag Carbonates de polyester constitués de différents diols dans un rapport défini
WO2021254892A1 (fr) 2020-06-19 2021-12-23 Covestro Deutschland Ag Carbonates de polyester obtenus à partir de diacides cycloaliphatiques, de 1,4 : 3,6-dianhydrohexitol et d'un autre composé dihydroxy aliphatique
WO2021254893A1 (fr) 2020-06-19 2021-12-23 Covestro Deutschland Ag Polyestercarbonates à base de diacides cycloaliphatiques, de 1,4 : 3,6-dianhydrohexitol et de quantités spécifiques d'un composé dihydroxy aliphatique supplémentaire

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WO2021254894A1 (fr) * 2020-06-19 2021-12-23 Covestro Deutschland Ag Carbonates de polyester constitués de différents diols dans un rapport défini
WO2021254892A1 (fr) 2020-06-19 2021-12-23 Covestro Deutschland Ag Carbonates de polyester obtenus à partir de diacides cycloaliphatiques, de 1,4 : 3,6-dianhydrohexitol et d'un autre composé dihydroxy aliphatique
WO2021254893A1 (fr) 2020-06-19 2021-12-23 Covestro Deutschland Ag Polyestercarbonates à base de diacides cycloaliphatiques, de 1,4 : 3,6-dianhydrohexitol et de quantités spécifiques d'un composé dihydroxy aliphatique supplémentaire
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