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JP-7855715-B2 - Polycarbonate copolymer, method for producing the same, and composition containing the same

JP7855715B2JP 7855715 B2JP7855715 B2JP 7855715B2JP-7855715-B2

Inventors

  • イ、ジンソ
  • キム、ドギョン
  • ソ、ドヒョン
  • チョン、ミンジェ
  • ムン、スンファン

Assignees

  • ハンファ ソリューションズ コーポレイション

Dates

Publication Date
20260508
Application Date
20230324
Priority Date
20220325

Claims (11)

  1. Among the units derived from all dihydroxyls, Units derived from primary dihydroxyl compounds are used in amounts of 5 mol% to 45 mol%, A unit derived from the secondary dihydroxyl compound represented by the following chemical formula 4a is used in an amount of 45 mol% to 85 mol%, and This is a polycarbonate copolymer containing 1 mol% to 30 mol% of units derived from a secondary dihydroxyl compound represented by the following chemical formula 4b. [Chemical formula 4a] (In the above chemical formula 4a, R7 is a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms, or a substituted or unsubstituted cycloalkoxylene group having 4 to 20 carbon atoms.) [Chemical formula 4b] (In the above chemical formula 4b, R4 and R6 are each independently a cycloalkylene group or cycloalkoxylene group having 4 to 10 carbon atoms, and R5 is a linear or branched alkylene group having 1 to 10 carbon atoms.) The aforementioned polycarbonate copolymer has a pencil hardness of H or higher when measured by a pencil hardness test (ISO 15184). A polycarbonate copolymer having a glass transition temperature (Tg) of 90 °C to 160°C as measured by ISO 11357.
  2. At least one of the following repeating units represented by chemical formula 1 is present in an amount of 5 mol% to 45 mol%, and The second repeating unit represented by the chemical formula 2a below is present in an amount of 45 mol% to 85 mol%, and A polycarbonate copolymer containing 1 mol% to 30 mol% of the second repeating unit represented by the following chemical formula 2b . [Chemical formula 1] (In the above chemical formula 1, R1 is a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxylene group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms, or a substituted or unsubstituted cycloalkoxylene group having 4 to 20 carbon atoms. ) [Chemical formula 2a] (In the above chemical formula 2a, R7 is a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms, or a substituted or unsubstituted cycloalkoxylene group having 4 to 20 carbon atoms.) [Chemical formula 2b] (In the above chemical formula 2b, R4 and R6 are each independently a cycloalkylene group or cycloalkoxylene group having 4 to 10 carbon atoms, and R5 is a linear or branched alkylene group having 1 to 10 carbon atoms.)
  3. The first repeating unit is ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,15-pentadecanediol, 1,16-hexadecanediol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, nonaethylene glycol, decaethylene glycol, undecaethylene A polycarbonate copolymer according to claim 2, derived from a primary dihydroxyl compound comprising one or more of the following: lenglycol, dodecaethylene glycol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, pentacyclopentadecanedimethanol, decalindimethanol, tricyclotetradecanedimethanol, norbornanedimethanol, adamantanedimethanol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, and bicyclo[ 2.2.2 ]octane-2,3-dimethanol, and at least one or more diester carbonate compounds.
  4. The polycarbonate copolymer according to claim 2, wherein the second repeating unit is derived from a secondary dihydroxyl compound comprising two or more of the following: 1,4:3,6-dianehydrohexitol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-methyl-1,4-cyclohexanediol, tricyclodecanediol, pentacyclopentadecanediol, decalindiol, tricyclotetradecanediol, norbornanediol, adamantanediol, 2,2-bis(4-hydroxycyclohexyl)propane, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol, as well as at least one diester carbonate compound.
  5. The polycarbonate copolymer according to claim 2 , further comprising a third repeating unit derived from at least one tertiary dihydroxyl compound and at least one or more diester carbonate compounds.
  6. The aforementioned polycarbonate copolymer is The pencil hardness of the test specimen measured by the pencil hardness test (ISO 15184) is H or higher, and, The polycarbonate copolymer according to claim 2, wherein, according to ISO 11357, 10 mg of the sample is heated at a rate of 10°C per minute and maintained at 220°C for 1 minute, then cooled at a rate of 10°C per minute, and the glass transition temperature (Tg) at the transition point obtained when the temperature is raised to 220 °C at the same heating rate is 90 °C to 160°C.
  7. The polycarbonate copolymer according to claim 2, wherein the dynamic viscosity of the solution obtained by dissolving 0.5 g of the sample in a mixed solvent of hexafluoroisopropanol and dichloromethane is measured at 25°C using a Brookfield dynamic viscometer to 8.5 cps to 16 cps.
  8. A dihydroxyl compound containing 5 mol% to 45 mol% of at least one primary dihydroxyl compound represented by the following chemical formula 3, 45 mol% to 85 mol% of a secondary dihydroxyl compound represented by the following chemical formula 4a, and 1 mol% to 30 mol% of a secondary dihydroxyl compound represented by the following chemical formula 4b, and at least one diester carbonate compound, is melted to obtain a molten product, and A method for producing a polycarbonate copolymer, comprising condensing the molten material in the presence of a catalyst. [Chemical formula 3] (In the above chemical formula 3, R1 is a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxylene group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms, or a substituted or unsubstituted cycloalkoxylene group having 4 to 20 carbon atoms.) [Chemical formula 4a] (In the above chemical formula 4a, R7 is a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms, or a substituted or unsubstituted cycloalkoxylene group having 4 to 20 carbon atoms.) [Chemical formula 4b] (In the above chemical formula 4b, R4 and R6 are each independently a cycloalkylene group or cycloalkoxylene group having 4 to 10 carbon atoms, and R5 is a linear or branched alkylene group having 1 to 10 carbon atoms.)
  9. The method for producing a polycarbonate copolymer according to claim 8, wherein the dihydroxyl compound may further comprise at least one tertiary dihydroxyl compound, the tertiary dihydroxyl compound comprising one or more of 1,1'-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, bis(4-hydroxyphenyl)cyclohexane, and bis(4-hydroxyphenyl)cyclopentane.
  10. The method for producing a polycarbonate copolymer according to claim 8 , wherein the carbonic acid diester compound comprises one or more of diphenyl carbonate, ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate.
  11. A composition comprising the polycarbonate copolymer according to any one of claims 1 to 7 .

Description

This invention relates to a polycarbonate copolymer, a method for producing the same, and a composition containing the same. More specifically, this invention relates to a polycarbonate copolymer with excellent heat resistance, scratch resistance, moldability, light resistance, weather resistance, transparency, mechanical strength, etc., a method for producing the same, and a composition containing the same. Polycarbonate refers to a thermoplastic polymer that contains carbonate esters (-COO-) as repeating units in its main chain. Existing polycarbonates are mainly produced through the reaction of bisphenol-A (BPA) and phosgene ( COCl₂ ). While such polycarbonates exhibit excellent heat resistance, impact resistance, and flame retardancy, they have relatively poor light resistance, transparency, and scratch resistance. Furthermore, existing polycarbonates, due to their repeating aromatic ring structure, are susceptible to yellowing caused by sunlight containing ultraviolet rays, resulting in reduced transmittance to certain wavelengths and breakage of polymer chains. Therefore, they are difficult to apply to fields requiring weather resistance. On the other hand, it is known that if monomeric BPA remains in polycarbonate, it can act as an endocrine disruptor in living organisms. Therefore, various regulations have been strengthened regarding the use of existing polycarbonates in products that come into contact with the human body, such as infant products, and in medical supplies. Furthermore, phosgene gas is a highly toxic substance subject to environmental regulations, and its storage and management present challenges, such as the need for separate cooling equipment. Therefore, there is a demand for polycarbonate that overcomes the shortcomings of existing polycarbonates and possesses superior heat resistance, scratch resistance, moldability, light resistance, weather resistance, transparency, and mechanical strength. The present invention will be described in detail below. In this specification, the numerical range "a to b" is defined as "greater than or equal to a and less than or equal to b." (Polycarbonate copolymer) A specific example of the present invention is a polycarbonate copolymer produced from three or more dihydroxyl compound monomers that have an aromatic ring structure, fewer double bonds and triple bonds, and preferably none of these, excluding bisphenol-A which inhibits eco-friendliness and other properties. A polycarbonate copolymer according to one specific example of the present invention comprises units derived from at least one primary dihydroxyl compound and units derived from at least two secondary dihydroxyl compounds, and may have a pencil hardness of H or higher as measured by the pencil hardness test (ISO 15184) and a glass transition temperature (Tg) of approximately 90°C to approximately 160°C as measured by ISO 11357. In a specific example, the polycarbonate copolymer may contain approximately 1 mol% to approximately 30 mol% of units derived from a secondary dihydroxyl compound represented by the following chemical formula 4b, within the total units derived from dihydroxyl. [Chemical formula 4b] In chemical formula 4b, R4 and R6 are independently cycloalkylene or cycloalkoxylene groups having 4 to 10 carbon atoms, and R5 is a linear or branched alkylene group having 1 to 10 carbon atoms. In a specific example, the polycarbonate copolymer may contain, among the total units derived from dihydroxyl compounds, approximately 5 mol% to approximately 45 mol%, units derived from primary dihydroxyl compounds, approximately 45 mol% to approximately 85 mol%, units derived from secondary dihydroxyl compounds represented by the following chemical formula 4a, and approximately 1 mol% to approximately 30 mol%, units derived from secondary dihydroxyl compounds represented by the following chemical formula 4b. [Chemical formula 4a] In the chemical formula 4a, R7 is a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms, or a substituted or unsubstituted cycloalkoxylene group having 4 to 20 carbon atoms. [Chemical formula 4b] In the aforementioned chemical formula 4b, R4 and R6 are each independently a cycloalkylene group or cycloalkoxylene group having 4 to 10 carbon atoms, and R5 is a linear or branched alkylene group having 1 to 10 carbon atoms. In a specific example, the molar ratio of the secondary dihydroxyl compound represented by chemical formula 4a to the secondary dihydroxyl compound represented by chemical formula 4b can be approximately 2:1 to approximately 8.5:1, for example, approximately 5:1 to approximately 8.2:1, and specifically approximately 6:1 to approximately 8:1. In specific examples, the primary dihydroxyl compound may be present in an amount of approximately 5 mol% to approximately 45 mol%, for example, approximately 8 mol% to approximately 40 mol%, specifically approximately 10 mol% to approximately 35 mol%, of 100 mol% of the total dihydroxyl