WO2009057609A1 - Composition à base d'anhydride d'alcool de sucre présentant une bonne stabilité lors du stockage et procédé de production de polycarbonate avec cette dernière - Google Patents

Composition à base d'anhydride d'alcool de sucre présentant une bonne stabilité lors du stockage et procédé de production de polycarbonate avec cette dernière Download PDF

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WO2009057609A1
WO2009057609A1 PCT/JP2008/069576 JP2008069576W WO2009057609A1 WO 2009057609 A1 WO2009057609 A1 WO 2009057609A1 JP 2008069576 W JP2008069576 W JP 2008069576W WO 2009057609 A1 WO2009057609 A1 WO 2009057609A1
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group
carbon atoms
formula
sugar alcohol
anhydrous sugar
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PCT/JP2008/069576
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English (en)
Japanese (ja)
Inventor
Akimichi Oda
Eiichi Kitazono
Ryuji Nonokawa
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Teijin Limited
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Priority to JP2009539076A priority Critical patent/JP5379016B2/ja
Publication of WO2009057609A1 publication Critical patent/WO2009057609A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65744—Esters of oxyacids of phosphorus condensed with carbocyclic or heterocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6578—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and sulfur atoms with or without oxygen atoms, as ring hetero atoms
    • 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
    • C08G64/02—Aliphatic polycarbonates
    • C08G64/0208—Aliphatic polycarbonates saturated

Definitions

  • the present invention relates to an anhydrous sugar alcohol composition having good storage stability, a method for producing a plant-derived component-containing polycarbonate using the composition as a raw material, and reducing the production of peroxide by adding an antioxidant. And a method for purifying the anhydrous sugar alcohol.
  • anhydrous sugar alcohols are known to be decomposed and denatured depending on the storage conditions, and various studies have been conducted on improving their stability.
  • storage at 40 is achieved by adding a stability improving agent such as a specific reducing agent such as sodium borohydride or an antioxidant at a specific time in the anhydrous sugar alcohol production process. Improvements in stability have been reported.
  • the inventors of the present invention have made it possible to purify commercially available anhydrous sugar alcohols and immediately remove those impurities and use them for melt polycondensation.
  • the quality of the carbonized rice cake was good, but if the anhydrous sugar alcohols after purification were left in an air atmosphere without adding a stability improver, etc., decomposition and deterioration progressed in a few days. It has been found that when such deteriorated anhydrous sugar alcohols are subjected to a polycondensation reaction, the quality of the polymer is lowered.
  • the present inventors obtain a high-purity anhydrous sugar alcohol with a small amount of peroxide in the final purification step in the production of the anhydrous sugar alcohol, and if this can be stabilized, the storage stability is better and the polymer raw material is used. Although it was thought that a suitable one could be obtained, it was not possible to find a publicly known technique regarding the amount of peroxide in anhydrous sugar alcohol and a method for reducing it.
  • Patent Document 1 British Patent No. 1079686
  • Patent Document 2 US Patent No. 4506066
  • Patent Document 3 International Publication No. 2007/013463 Pamphlet
  • Patent Document 4 International Publication No. 2004/1 1 1 106 Panflets
  • Patent Document 5 Pamphlet of International Publication No. 2003 043959 (US Patent Application Publication No. 2003/0097028, JP 2005-5096 67) Disclosure of Invention
  • the present invention contains a stabilizer having a specific structure, has good storage stability and is a polymer.
  • An anhydrous sugar alcohol composition suitable for use as one raw material is provided.
  • the present invention uses a composition of a stabilizer and anhydrosugar alcohol that does not adversely affect the polycondensation reaction or polymer quality as a raw material, and produces a plant-containing component-containing polycarbonate with good reactivity and excellent quality.
  • a method is provided.
  • the present invention provides a purification method capable of obtaining an anhydrous sugar alcohol having a low peroxide content. Means for solving the problem
  • the inventors of the present invention have completed the present invention as a result of intensive studies to solve the above object.
  • the configuration of the present invention is shown below.
  • ( 1 to! ⁇ 4 are each independently a group selected from a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group)
  • R 5 , R 6 , R 8 and R 9 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkyl cyclohexane having 6 to 12 carbon atoms. . alkyl group, a Ararukiru group or phenylene Le group with carbon number.
  • R 7 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms and X is a single bond, a sulfur atom or single CHR 1Q - Group (R 1Q represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms).
  • A represents an alkylene group having 2 to 8 carbon atoms or * one COR 11 — group (R 11 represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents that it is bonded to the oxygen side). .
  • One of Y and ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • R 8 and R 9 are alkyl group having 3 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkyl cycloalkyl group having 6 to 12 carbon atoms, carbon It represents an aralkyl group or a phenyl group of formula 7-12.
  • the two R 5 in the formula (2) may be the same or different.
  • two R 6 in the formula (2) may be the same or different from each other.
  • the two R 7 in the formula (2) may be the same or different ⁇ )
  • At least one auxiliary stabilizer selected from phosphorus stabilizers (except those corresponding to the above formula (2)), phenol stabilizers, thio stabilizers, and hindered amine stabilizers, 2. 5 ⁇ 10- 5 anhydrosugar according claim 1 wherein comprising 10 part by weight alcohol compositions against anhydrosugar alcohol 100 parts by weight of the formula (1) of the preceding claim.
  • the anhydrous sugar alcohol of the formula (1) described in item 1 above has a total content of Na, Fe, and Ca of 2 mass ppm or less, and the purity analysis value by gas chromatography is 99.7 mol%.
  • the total content of the anhydrous sugar alcohol composition as described in 1 above and Na, Fe, and Ca is 2 mass ppm or less, and the purity analysis value in gas chromatography is 99.7 mol% or more
  • RG is an aliphatic group having 2 to 12 carbon atoms
  • the total content of Na, Fe, and Ca is 2 mass p pm or less.
  • R A and R B are groups selected from an alkyl group, a cycloalkyl group, and an aryl group, and R A and R B may be the same group or different groups.
  • a diester is used as a polycondensation catalyst and melt polycondensed in the presence of one or more types of alkali metal compounds, one or more alkaline earth metal compounds, or both of the following formulas (5 ) A method for producing a polycarbonate sheet.
  • ( 1 to! ⁇ 4 are each independently a group selected from a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, RG is an aliphatic group having 2 to 1.2 carbon atoms, and n is 1 or 0. 6 ⁇ n ⁇ 0.9.
  • a molded article comprising the polycarbonate shell described in 7 above.
  • a method for purifying an anhydrous sugar alcohol characterized in that an anhydrous sugar alcohol having a peroxide content of 1 mass ppm or less is obtained by purification after addition of Ppm.
  • an anhydrous sugar alcohol composition having good storage stability can be provided by containing a stabilizer having a specific structure.
  • an anhydrous sugar alcohol composition comprising an anhydrous sugar alcohol and a stabilizer that does not adversely affect the reactivity and polymer quality is used as a raw material. It is possible to produce a polycarbonate with a derived component.
  • the anhydrous alcohol composition of the present invention comprises 0.0005 to 0.5 mass of the cyclic phosphite represented by the formula (2) with respect to 100 mass parts of the anhydrous sugar alcohol represented by the formula (1). Contains. When the added amount is within this range, the storage stability of the anhydrous sugar alcohol composition is improved and long-term storage becomes possible.
  • a more preferable range of the content of the cyclic phosphite per 100 parts by mass of the anhydrous sugar alcohol represented by the formula (1) is 0.003 to 0.5 parts by mass, and a more preferable range is 0.005 to 0.00. 5 parts by mass, and a particularly preferred range is 0.01 to 0.3 parts by mass.
  • the anhydrous sugar alcohol of the above formula (1) used in the present invention is specifically a dianhydride mouth hexitol (hereinafter also referred to as isosorbide or etherdiol).
  • dianhydride hexitols include isomannide, isoidide, and isosorbide (the following formulas (6), (7), (8)).
  • dianhydrohexitols are substances that can be obtained from natural biomass and are one of the so-called renewable resources.
  • isosorbide is a diol compound that can be easily made from starch and the like and can be obtained in abundance as a resource.
  • isomannide is superior in ease of manufacture compared to isomannide.
  • the anhydrous sugar alcohol of the formula (1) used in the present invention preferably has an organic impurity content of 0.3 mol% or less of the total amount detected by gas chromatography, and is 0.1 mol% or less. If it is a thing, it is more preferable and it is still more preferable that it is 0.05 mol% or less. Considering the technical limits of the cost of refining, the lower limit of organic impurity content that can be maintained on an industrial scale is about 0.01 mol%. Further, the anhydrous sugar alcohol of the formula (1) used in the present invention is preferably one having a total content of Na, Fe, and Ca detected by ICP emission analysis of 2 mass ppm or less, and 1 mass ppm or less Is more preferable.
  • 6 1 [3- (3-t-petitu 4-hydroxy-5-methylphenyl) propoxy] 1 2, 4, 8, 10 —Tetra _ t-butyldibenz [d, f] [1, 3, 2] Dioxaphosphepine, 6— [3— (3,5-Didi _ t _petite 4-hydroxypropyl) propoxy] 1, 2, 4 , 8, 10-Tetra-t-butyldibenz [d, f] [1, 3, 2] Dioxaphosphepine, 6- [3- (3, 5--di-t-butyl-4-hydroxyphenyl) ) Propoxy] 1,4,8-di-t-petitu 2, 10-dimethyl-12H-dibenzo [d, g] [1, 3, 2] di Oxaphosphocin or 6_ [3— (3,5-di-t-petitu 4-hydroxyphenyl) propiony
  • R 5 , R 6 and R 8 are tertiary alkyl groups having 4 to 8 carbon atoms
  • R 9 is an alkyl group having 1 to 8 carbon atoms
  • X is a single bond
  • A is an alkylene group having 2 to 8 carbon atoms
  • Y is a hydroxyl group
  • Z is a hydrogen atom
  • amines such as trialkanolamines such as triethanolamine, tripropanolamine, tri_i-propanolamine, diethanolamine, dipropanolamine, di-i-propanolamine, Dialkanolamines such as tetraethanolethylenediamine, tetra-i-propanolethylenediamine, monoalkanolamines such as dibutylethanolamine, dibutyl-i-propanolamine, 1, 3 , 5—Trimeru 2, 4, 6—Aromatic amines such as triazine, dibutylamine, piperidine, 2, 2, 6, 6—tetramethylpiperidine, 4 monohydroxy— 2, 2, 6, 6— Alkylamines such as tetramethylpiperidine, hexamethylenetetramine, tri
  • a long-chain aliphatic amine described in JP-A-61-63686 a compound containing a sterically hindered amine group described in JP-A-6-329830, and a hindered piperidinyl-based compound described in JP-A-7-90270
  • Light stabilizers organic amines described in JP-A-7-278164, and the like can also be used.
  • the content ratio of the amine to the cyclic phosphite is usually about 0.01 to 25% by mass.
  • phosphorus stabilizers except for those corresponding to the cyclic phosphites of the above formula (2)
  • phenol stabilizers except for those corresponding to the cyclic phosphites of the above formula (2)
  • thio stabilizers At least one selected from system stabilizers
  • Auxiliary stabilizers can be included.
  • the preferred amount of the co-stabilizer, to the formula 100 parts by weight of anhydrous sugar alcohol (1), 2.
  • a 5X 10- 5 to 1 0 parts by weight, more preferable amount is 5 X 10 one 5 -5 parts by mass, particularly preferably IX 10 4 to 2.5 parts by mass.
  • the phosphorus stabilizer used in the present invention is preferably a phosphorus stabilizer containing a structure represented by the following formula (9).
  • R 12 and R 13 are a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, particularly a hydrogen atom.
  • a methyl group, an isopropyl group, an isobutyl group, a t-butyl group, or a t-pentyl group is preferable.
  • an alkyl group having 1 to 10 carbon atoms is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having carbon atoms 1-10, consequent opening alkyl group having a carbon number of 6-20, cycloalkoxy group having a carbon number of 6-20 ,
  • An alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, the number of carbon atoms? is at least one group selected from the group consisting of an aralkyl group having 20 carbon atoms and an aralkyloxy group having 7 to 20 carbon atoms, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 6 to 10 carbon atoms.
  • An aryl group is preferable, and a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is particularly preferable.
  • the phosphorus-based heat stabilizer used in the present invention is represented by the following formulas (10), (1 1) and (1 2) At least one compound selected from the group consisting of compounds represented by
  • Preferred examples of the above formula (10) include triphenyl phosphite, tris (2-isobutylphenyl) phosphite, tris (2-t-butylphenyl) phosphite, tris (2-t-pentylph).
  • Enyl) phosphite tris (2-cyclohexylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, tris (2 _ t —butyl _ 6-methylphenyl) phosphite, tris (nonylphenyl) phosphite, and tris (2,4-diethyl t-butylphenyl) phosphite is particularly preferable.
  • Preferred examples of the above formula (1 1) include tetrakis (2,4-di-t-butylphenyl) -1,4′-biphenyl dirange phosphonite, tetrakis (2,4-di-t-butylphenyl) — 4, 3 '— biphenyl dirange phosphonite, tetrakis (2, 4 — di-t 1 butyl phenyl) 1 3, 3' — biphenyl dirange phosphonite, tetrakis (2, 6-di _ t 1 butyl phenyl) — 4, 4'-bidiylene phosphonite, tetrakis (2, 6-di-tert-butylphenyl) —4, 3 '— biphenylendiphosphonite, tetrakis (2, 6-di-tert-butylphenyl) —3, 3 '— Biphenyl dirange phosphonite, particularly tetrakis (2, 4-di
  • Ludiphosphite bis (nonylphenyl) pen erythritol diphosphite, bis (2,4-di-t-butylphenyl) Pen erythritol diphosphite, bis (2,6-di-t-butyl) —4—Methylphenyl) Pen erythritol diphosphite, bis (2,4-di-tert-butyl 1-6-methylphenyl) Pen erythritol!
  • Rudiphosphite bis (2,6—di-t-butyl-4-ethylphenyl) pen erythritol 1 ⁇ 1 Rudiphosphite, bis (2,4,6-tri-tert-butylphenyl) pen erythri] Phosphite, etc., especially bis (2,4-di-t-butylphenyl) Pen evening Erisri! Rudiphosphite and bis (2, 6-di-tert-butyl-
  • Penyu erythritol diphosphite is preferred.
  • the phosphorus stabilizer used in the present invention has the following formulas (13), (14), (15
  • a phosphorus stabilizer represented by the formula (1) can also be preferably used.
  • X 2 is an alkyl group having 5 to 18 carbon atoms, preferably an alkyl group having 8 to 18 carbon atoms, and having 10 to 18 carbon atoms. Alkyl groups are particularly preferred.
  • R 14 and R 15 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkylcycloalkyl group having 6 to 12 carbon atoms.
  • R 16 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • X represents a simple bond, a sulfur atom or one CHR 17 — group (R 17 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms).
  • formulas (13), (14) and (15) include distearyl pen erythritol diphosphite, diisodecyl pen erythritol 1 ⁇ l diphosphite, tridecanyl phosphite, trilauryl phosphite, trioctadecyl Phosphate, 2, 2 '—methylenebis (4, 6-di-tert-butylphenol Nyl) 2-ethylhexyl phosphite and the like.
  • tristearyl sorbitol triphosphite 2,2'-ethylidene bis (4,6-diethyl butylphenol) fluorophosphite, bis (2,4 —Di-t-butyl-6-methylphenyl) ethyl phosphite, bis (2,4-di-t-butyl-6-methylphenyl) methyl phosphite, 2 _ (2,4,6-tri-t — Butylphenyl) 1-5-Ethyl_ 5_Butyl-1,3,2-Oxaphosphorinane, 2,2 ', 2', —Liquillyl [Triethyl- ⁇ ris (3,3,, 5,5, — Teller tert-butyl-1,2,1'-biphenyl-2,2'-zyl) Phosphorus stabilizers such as phosphite can also be used.
  • the phenol stabilizer used in the present invention is preferably a phenol stabilizer containing a structure represented by the following formula (16).
  • R 18 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, particularly a methyl group, ethyl Group, isopropyl group, isobutyl group, or t-butyl group is preferred.
  • R 19 is an alkyl group having 4 to 10 carbon atoms, preferably an alkyl group having 4 to 6 carbon atoms, and particularly preferably an isobutyl group, a t-butyl group, or a cyclohexyl group.
  • R 2 Q is a hydrogen atom, an alkyl group having a carbon number of 1 to 1 0, carbon atom number 1 to 1 0 alkoxy group, a cycloalkyl group having a carbon number of 6-2 0, number 6-2 0 carbon atoms A cycloalkoxy group, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and a carbon atom.
  • a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is preferred.
  • p is an integer of 1 to 4, an integer of 1 to 3 is preferable, and 2 is particularly preferable.
  • the stabilizer having a hindered phenol moiety used in the present invention is represented by the following formulas (17), (18) and ( At least one compound selected from the group consisting of compounds represented by 19) is preferred.
  • R 21 is a hydrocarbon group that may contain an oxygen atom having 8 to 30 carbon atoms, more preferably a hydrocarbon group that may contain an oxygen atom having 12 to 25 carbon atoms, In particular, a hydrocarbon group which may contain an oxygen atom having 15 to 25 carbon atoms is preferred.
  • R 22 is a hydrogen atom or an alkyl group having 1 to 25 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, particularly the number of carbon atoms. 1 to 18 alkyl groups are preferred.
  • m is an integer of 1 to 4, an integer of 1 to 3 is preferable, and 2 is particularly preferable.
  • k is an integer of 1 to 4, an integer of 3 to 4 is preferable, and 4 is particularly preferable.
  • R 23 , R 24 , R 25 and R 26 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms. In particular, a methyl group is preferred. 1 is an integer of 1 to 4, an integer of 1 to 3 is preferable, and 2 is particularly preferable.
  • Preferred examples of the above formula (17) include octyldecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, benzenepropanoic acid 3,5-bis (1,1-dimethylethyl) 4-Hydroxyalkyl ester (alkyl has 7 to 9 carbon atoms and side chain), ethylene bis (oxchethylene) bis [3— (5 _ t _ butyl _4-hydroxy-m-tolyl) probione], Hexamethylenebis [3— (3,5—di-tert-butyl _4-hydroxy Ciphenyl) propionate.
  • R 27 is an alkyl group having 4 to 10 carbon atoms, preferably an alkyl group having 4 to 6 carbon atoms, particularly an isobutyl group, t-butyl group, t-pentyl group, or A cyclohexyl group is preferred.
  • R 28 is an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably a methyl group, an ethyl group, an isopropyl group, an isobutyl group, or a t-butyl group.
  • R 29 and R 3Q are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and 7 to 20 carbon atoms. And at least one group selected from the group consisting of aralkyl groups, preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, particularly a hydrogen atom or carbon atom. Number 1-1 Zero alkyl groups are preferred.
  • R 31 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and substituted. Is at least one group selected from the group consisting of a good acryloyl group and an optionally substituted methacryloyl group, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an aralkyl having 7 to 20 carbon atoms. Group, an acryloyl group which may be substituted, or an acryloyl group which may be substituted is preferable.
  • a hydrogen atom, an acryloyl group which may be substituted or a methacryloyl group which may be substituted is preferable.
  • the substituent which may be substituted with an acryloyl group or a methacryloyl group is preferably an alkyl group having 1 to 4 carbon atoms or an aralkyl group having 7 to 10 carbon atoms.
  • Preferred examples of the above formula (20) include 2,2′-methylenebis (6_t-butyl-4-methylphenol, 2,2′-isopropylidenebis (6-tert-butyl-4-methylphenol, 2-t-butyl).
  • _6— (3— t-Butyl-2-hydroxy-5 _methylbenzyl) 1 4 1-methylphenyl acrylate, 2 1 t-pentyl 6— (3-t 1-pentyl 1 2-hydroxy-5-methylbenzyl) 1 4 —Methylphenylacrylate, 2—t _butyl—6— (3-t —butyl-2-hydroxy—5-methylbenzyl) 1—4-methylphenyl acrylate, 2—t—pentyl 6— (3 _ t-pentyl 2-hydroxy-5-methylbenzyl) —4-methylphenyl acrylate, 2_ [1— (2-hydroxy-3, 5 _di-t-butylphenyl) ethyl]
  • phenolic stabilizers include the following compounds: 2, 6-di-tert-butyl-4-methylphenol, 2, 4, 6_tree tert-butyl phenol, 2,4-dioctylthiomethyl-6_methylphenol, 2, 2'-thiobis (6 _ t _butylphenol), 4, 4 '—thiobis (3-methyl-6 _ t-butylphenol), 2, 2' —ethylidenebis (4, 6-di-t-butylphenol), 4, 4 '—butylidenebis (3-methyl-6-t-butylphenol), 1,1 bis (4-hydroxyphenyl) cyclohexane, 1,1 bis (5-tert-butyl-4-hydroxy_2_methylphenol) butane 1, 1, 3—Tris (5-t _butyl—4-hydroxy-2-methylphenyl) butane, 2, 4, 6— ⁇ lith (3,5-di-t _butyl _4_ phenoxy) 3,5-triazin
  • the above phenol-based stabilizer may be one or a mixture of two or more.
  • silicone-based antioxidant include the following. Two or more of these can also be used: dilauryl 3,3 'monothiodiprovionate, tridecyl 3,3'-thiodipropionate, dimyristyl 3,3' monothiodipropionate, distearyl 3,3 ' - Chio dipropionate, stearyl Ariru 3, 3 '- Chio dipropionate, neopentanetetrayl tetrakis (3-lauryl-thio propionate Bok) such ⁇
  • hindered amine light stabilizers include the following: Bis (2, 2, 6, 6-tetramethyl-4-piperidyl) Sebacate, Bis ((2, 2, 6, 6-tetramethyl-4-piperidyl) succinate, bis (1, 2, 2, 6, 6-pentamethyl-4-seperidyl) sebacate, bis ( ⁇ -octoxy-2, 2, 6, 6-tetramethyl 1 4 —Piperidyl) Sebacate, bis ( ⁇ -benzyloxy-1, 2, 6, 6-tetramethyl-4-piperidyl) sebacate, bis ( ⁇ -cyclohexyloxy-1, 2, 2, 6, 6—te Tramethyl _ 4-piperidyl) sebacate, bis (1, 2, 2, 6, 6-pen-methyl 4-piperidyl) 2- (3,5-di-tert-butyl 4-hydroxybenzyl) -2-butyl malonate, bis ( 1-acryloyl — 2, 2, 6, 6 —tetramethyl mono 4 -Piperidyl) 2,2-bis (3
  • Particularly preferred hindered amine light stabilizers include the following, and two or more of these may be used: Bis (2, 2, 6, 6-tetramethyl- 4-piperidyl) Sebagate, Bis (1, 2, 2, 6, 6-Penyu-methyl-4-piperidyl) Sebacate, Bis (N-octoxy-1,2,6,6-tetramethyl-4-piperidyl) Sebagate, Bis (N-benzyloxy-1,2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidyl) Sebake, Bis (1,2 , 2, 6, 6 _Penyu methyl-4-piperidyl) 2_ (3,5-di-tert-butyl-4-hydroxybenzyl) 1-butyl malonate, bis (1-acryloyl _ 2, 2, 6, 6 —Tetramethyl _ 4-piperidyl) 2, 2—Bis (3,5 _d
  • anhydrous sugar alcohol composition of the present invention may further comprise other additives as required, for example, an ultraviolet absorber, a light stabilizer other than hindered amine, a peroxide stabilizer, a polyamide stabilizer, an organic nickel complex.
  • an ultraviolet absorber for example, an ultraviolet absorber, a light stabilizer other than hindered amine, a peroxide stabilizer, a polyamide stabilizer, an organic nickel complex.
  • Excitation energy absorbers typified by, UV shielding agents typified by carbon black and titanium oxide, lead-based stabilizers, tin-based stabilizers, metal-based stabilizers, / 3-diketone compound-based stabilization aids, Hydroxylamine, lubricant, plasticizer, flame retardant, nucleating agent, metal deactivator, antistatic agent, pigment, filler, pigment, antiblocking agent, surfactant, processing aid, foaming agent, emulsifier, Neutralizing agents such as brightener, calcium stearate, hydrated talcite, etc., and 9, 10-dihydro-9 monoxa_ 1 0-phosphophenanthrene-10 Coloring improvers and, U.S. Patent 4 3 2 5 8 5 3 Pat, 4
  • Examples of the ultraviolet absorber include the following.
  • salicylate derivatives are phenyl salicylate, 4_t-butylphenyl salicylate, 2,4-di-t-butylphenyl 3,, 5, tert-butyl butyl 4'-hydroxybenzoate, 4 — T —Octylphenyl salicylate, bis (4 _ t _ butylbenzoyl) resorcinol, benzoyl resorcinol, hesisadecyl 3,, 5, zy t-butyl-4, —hydroxybenzoate, octyldecyl 3 ', 5 '--Di-t-butyl-4, -hydroxybenzoate, 2-methyl--4,6-di-t-butylphenyl 3', 5'-di-t-butyl 4 -'- hydroxybenzoate and mixtures thereof.
  • 2-hydroxybenzophenone derivatives examples include 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2, 2'-dihydroxy-4-methoxybenzophenone, bis (5-benzoyl 4-Hydroxy — 2-methoxyphenyl) Methane, 2, 2 ', 4, 4'-tetrahydroxybenzophenone and mixtures thereof.
  • UV absorbers include the following, which can be used in combination of two or more:
  • phenyl silicate 4 tert-butylphenyl salicylate, 2, 4 —di-t-butylphenyl 3 ′, 5, —di-t-butyl-4′-hydroxybenzoate, 4 tert-butylphenyl salicylate, 2, 4-dihydroxy benzophenone, 2-hydroxy 4-methoxybenzophenone, 2-hydroxy 4-octoxybenzophenone, 2, 2, —dihydroxy 4-methoxybenzophenone, bis (5-benzoyl 4-hydroxy 2-methoxyphenyl) methane, 2, 2 ', 4, 4, monotetrahydroxybenzophenone, 2 (2-hydroxy-5-methylphenyl) benzotriazole, 2- (3', 5 'zy-tert-butyl-2' —Hydroxyphenyl) benzotriazole, 2- (5 '— t-butyl-2 ′ —hydroxyphenyl) benzotriazol , 2-(2 '-hydroxy 1 5' _ —
  • Examples of light stabilizers other than hindered amines include the following.
  • Examples of the metal deactivator include the following. N, N '— Diphenyloxamide, N— Salicylarou N ′ — Salicyloylhydrazine, N, ⁇ ′ — Bis (salicyloyl) hydrazine, ⁇ , N ′ One bis (3, 5— Di one t One butyl — 4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1, 2, 4-triazol, bis (benzylidene) oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenyl hydrazide, N, N ' —Bis (salicyloyl) oxalyl dihydrazide, N, N 'monobis (salicyloyl) thiopropionyl dihydrazide, and mixtures thereof.
  • peroxide scavengers include, for example, esters of j8-thiodipropionic acid, mercaptobenzoimidazole, zinc salt of 2_mercaptobenzoimidazole, zinc salt of dibutyldithiocarbamate, dioctyldecyl disulfide, Examples include pen erythritol tetrakis (/ 3-dodecyl mercapto) propionate and mixtures thereof.
  • polyamide stabilizers include iodides or phosphorus compounds such as copper or divalent manganese salts and mixtures thereof.
  • hydroxyamine include N, N-dibenzylhydroxylamine, N, N-jetylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-di Tetradecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, N-dioxydecylhydroxylamine, N Monohexadecyl-N-octyldecylhydroxyamine, N-hedecyldecyl-hydroxydecylhydroxyamine, and mixtures thereof.
  • neutralizing agent examples include calcium stearate, zinc stearate, magnesium stearate, hydrated talcite (basic magnesium, aluminum, hydroxy, carbonate, hydrate), calcium oxide, melamine, ammine, polyamide, polyurethane and A mixture thereof may be mentioned.
  • lubricants include aliphatic hydrocarbons such as paraffin and wax, higher aliphatic acids having 8 to 22 carbon atoms, and higher aliphatic acid metals having 8 to 22 carbon atoms (A l, C a, Mg, Z n) salt, aliphatic alcohol having 8 to 22 carbon atoms, polydaricol, ester of higher fatty acid having 4 to 22 carbon atoms and aliphatic monohydric alcohol having 4 to 18 carbon atoms, and having 8 to 22 carbon atoms Higher aliphatic amides, silicone oils, rosin derivatives and the like.
  • the anhydrous sugar alcohol composition used in the present invention comprises the cyclic phosphites of the above formula (2) and other additives used as necessary, or the cyclic phosphites of the above formula (2) It can be produced by blending at least one auxiliary stabilizer selected from an agent, a phenol stabilizer, a thio stabilizer, a hindered amine stabilizer and other additives used as necessary. In blending, any known method and apparatus for obtaining a homogeneous mixture can be used.
  • the anhydrous sugar alcohol of the formula (1) and the cyclic phosphates of the formula (2) are mixed in the production process, the purification process, or any subsequent process of the anhydrous sugar alcohol. According to the method, the anhydrous sugar alcohol composition is also produced.
  • the anhydrous sugar alcohol, the cyclic phosphites and the auxiliary stabilizer, and the various additives when mixed may be in the form of a solid, a melt, or a solution.
  • the present invention is characterized in that degradation / denaturation of the anhydrous sugar alcohol is suppressed by adding the cyclic phosphates of the above formula (2) to the anhydrous sugar alcohol of the above formula (1). It is also a method for stabilizing alcohol.
  • anhydrous sugar alcohol of the formula (1) generates formic acid by decomposition / denaturation, and the storage of the anhydrous sugar alcohol or the anhydrous sugar alcohol composition under predetermined conditions is started. Sampling is performed as appropriate, and the sample is turned into aqueous The stability of the anhydrous sugar alcohol or its composition can be evaluated by monitoring the change in pH over time.
  • An anhydrosugar alcohol composition having a pH of 5 or more measured by the above method does not progress so much and is suitable as a polymer raw material, and a pH of 6 or more is more preferred. Unless the basic substance is added, the pH of the aqueous solution of the anhydrous sugar alcohol composition sample in the above evaluation method is unlikely to exceed 9. Of anhydrous sugar alcohol after storage for 100 hours in air at 50
  • the pH When the pH is 5 or more, it can be said that it has sufficient stability during storage under normal conditions, that is, at about room temperature.
  • the pH of the anhydrous sugar alcohol or its composition is less than 5, the degree of polymerization of the polymer obtained when the anhydrous sugar alcohol or its composition is used as a polymer raw material does not reach the desired value, Since problems such as deterioration occur, it is not preferable.
  • the present invention uses a composition of a stabilizer and an anhydrous sugar alcohol that does not adversely affect the polycondensation reaction or polymer quality as a raw material, and produces a plant-derived component-containing polycarbonate having excellent reactivity and excellent quality.
  • the present invention also provides a method, a polycarbonate obtained by the production method, and a molded article of the polycarbonate.
  • a polycarbonate is obtained by using the anhydrous sugar alcohol composition comprising the anhydrous sugar alcohol of the formula (1) and the cyclic phosphites of the formula (2) as raw material monomers. Further, two or more kinds of the anhydrous sugar alcohols of the above formula (1) may be combined in the production of the polystrandone.
  • the diol component of the formula (3) may be co-polymerized with the anhydrous sugar alcohol composition.
  • the diol component of the formula (3) (hereinafter, the diol of the formula (3) may be referred to as glycols), ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol.
  • 1,3-propanediol is a polymer having high polymerizability in polymer synthesis and a high glass transition point in the physical properties of the polymer.
  • 1,4-BDO 1,4-butanediol
  • 1,6-HDO 1,6-hexanediol
  • 1,3-propanediol is particularly preferred because it can be obtained from plant raw materials and has a large effect of improving melt fluidity by copolymerization. Further, at least two kinds of these diol components of the formula (3) may be combined.
  • the method for purifying the anhydrous sugar alcohol of the formula (1) and the diol component of the formula (3) used in the present invention is not particularly limited. Preferably, it may be purified by simple distillation, rectification or recrystallization, or a combination of these techniques.
  • the anhydrous sugar alcohol of the formula (1) is particularly preferably subjected to a purification treatment in the presence of the cyclic phosphites of the formula (2) and the like, as will be described later.
  • the anhydrous sugar alcohol of the formula (1) and the diol component of the formula (3) used in the present invention have an organic impurity content detected by gas chromatography of 0.3 mol% or less of the total amount. More preferably, it is 0.1 mol% or less, more preferably 0.05 mol% or less. Considering the technical limits of the purification cost, the lower limit of organic impurities that can be maintained on an industrial scale is usually about 0.1 mol%.
  • the anhydrous sugar alcohol of the above formula (1) and the diol component of the above formula (3) used in the present invention are detected by ICP emission spectrometry.
  • the total content of Na, Fe and Ca is 2 mass ppm or less, more preferably 1 mass ppm or less.
  • the carbonic acid diester used in the present invention is represented by the above formula (4).
  • aromatic carbonic acid diesters particularly aromatic carbonic acid carbonic acid diesters having 13 to 25 carbon atoms, are preferred in view of reactivity and cost, and diphenyl carbonate is preferably used. Further preferred.
  • the method for purifying the carbonic acid diester of the formula (4) used in the present invention is not particularly limited. Preferably, it may be purified by simple distillation, rectification or recrystallization, or a combination of these techniques.
  • the content of organic impurities detected by gas chromatography is not more than 0.3 mol%, preferably not more than 0.1 mol%, Preferably it is 0.05 mol% or less.
  • the total content of Na, Fe, and Ca detected by I CP emission spectrometry is 2 mass ppm or less, and preferably mass 1 ppm or less.
  • Known methods for producing polycarbonate resins include a phosgene method in which an alkaline aqueous solution of a dihydroxy compound and phosgene are reacted in the presence of an organic solvent, or a dihydroxy compound and a carbonic acid diester in the presence of a transesterification catalyst at high temperature and high vacuum.
  • Examples thereof include a melt polycondensation method in which a melt polycondensation reaction is performed.
  • the melt polycondensation method is a process that requires a transesterification catalyst and a high temperature and high vacuum, but is more economical than the phosgene method, and a polycarbonate resin that does not substantially contain chlorine atoms. Since there is an advantage obtained, it is preferable as a production method for obtaining a polycarbonate having a plant-derived component of the present invention.
  • the present invention relates to cyclic phosphites represented by the above formula (2) in an amount of 0.05 to 0.5 parts by mass with respect to 100 parts by mass of the anhydrous sugar alcohol represented by the above formula (1).
  • the polycarbonate represented by the above formula (5) is produced.
  • the total diol component of diester carbonate is the sum of the anhydrous sugar alcohol represented by the formula (2) and the diol component represented by the formula (3). Is preferably used in an amount of 0.90 to 1.30 mol, more preferably in an amount of 0.99 to 1.05 mol, in the production method according to the present invention, the polycondensation catalyst is used. In the presence of one or more kinds of alkali metal compounds, one or more alkaline earth metal compounds, or both, the above raw materials are melt polycondensed.
  • polycondensation catalysts examples include alkali metal or alkaline earth metal (including magnesium) alkoxides, phenoxides, hydroxides, carbonates, bicarbonates, and organic acid salts. Naughty Of these, sodium compounds and barium compounds are preferred, particularly sodium hydroxide, 2,2-bis (4-hydroxyphenyl) propan disodium salt, barium hydroxide, and barium carbonate.
  • the total addition amount as an alkali metal element and an alkaline earth metal element is 1 ⁇ 10— from that preferably in the 1 X 10- 5 mols 9, 1 more preferably to be in the X 10- 9 ⁇ 5 X 10- 6 mols, ranging from 1 X 10- 9 of 4 X 10- 5 moles further to be in preferably, particularly preferably in the range of 1 X 10- 5 mol 1. 2X 10- 6.
  • barium compound catalyst during use 1. More preferably in the range of ⁇ 5 X 10- 6 mol 2 X 10- 6.
  • nitrogen-containing basic compound as a polycondensation catalyst in the present invention.
  • nitrogen-containing basic compounds include tetramethylammonium hydroxide (Me 4 NOH), tetraethylammonium hydroxide (E t 4 NOH), tetraptylammonium hydroxide (Bu 4 NOH), benzyltrimethylammonium.
  • Ammonium hydroxides (C 6 H 5 _CH 2 (Me) 3 NOH), hexadecyltrimethylammonium hydroxide and other alkyl, aryl, and alkylaryl groups, triethylamine, Tertiary amines such as tryptylamine, dimethylpentylamine, hexadecyldimethylamine, tetramethylammonium polyhydride (Me 4 NBH 4 ), tetraptylammonium polo hydride (Bu 4 NBH 4 ) , tetra Petit Luang monitor ⁇ -time tetra-phenylene Lupo rate (Me 4 NBPh 4) Tetra Petit Ruan monitor ⁇ beam tetramethyl phenylene Rupore preparative (Bu 4 NBPh 4) can include basic salts such as, of tetramethylene chill ammonium Niu beam hydroxide are particularly preferably used.
  • Nitrogen basic compound the basic nitrogen atom is the total diol component to 1 mol, is preferably used so that the ratio of IX 1 0_ 5 ⁇ 1 X 1 0- 3 mol, more preferably 2 X 1 0- 5 ⁇ 8 X 1 0—The ratio is 4 mol.
  • the amount of the nitrogen-basic compound, the basic nitrogen atom is the total diol component to 1 mol is preferably used so that the ratio of 1 X 1 0- 5 ⁇ 1 X 1 0- 3 mol, more preferably is a ratio of the 2 X 1 0 one s to 8 X 10- 4 mol.
  • polycondensation catalysts for the production of polycarbonate cake boron compounds, aluminum compounds, zinc compounds, boron compounds, silicon compounds, titanium compounds Products, tin compounds, lead compounds, osmium compounds, antimony compounds, zirconium compounds, manganese compounds, and the like are also known to have catalytic ability for transesterification or esterification reactions.
  • these compounds may be used in combination with the above alkali metal compound or alkaline earth metal compound, but when used in a large amount, in terms of reactivity, influence on the quality of the molded article, and hygiene. Problems may arise.
  • the polycarbonate of the above formula (5) obtained using only a tin compound or a zinc compound as a polycondensation catalyst tends to be inferior in hue and thermal stability.
  • the raw sugar alcohol composition as raw materials, the glycols, and the carbonic acid diester are heated at normal pressure to undergo a pre-reaction, and then under reduced pressure, 2 Stirring while heating at a temperature of 80 or less to distill phenols such as phenol or aliphatic alcohol to be formed.
  • the reaction system is preferably maintained in an atmosphere of a gas inert to the raw materials and reaction mixture such as nitrogen. Examples of inert gases other than nitrogen include argon. It is preferable to carry out the heating reaction at normal pressure at the beginning of the reaction.
  • the reaction can be advanced by appropriately removing phenols or aliphatic alcohols from the system (reactor). For that purpose, it is effective and preferable to reduce the pressure.
  • a low temperature condition is preferable for suppressing the decomposition of the anhydrous sugar alcohol and obtaining a highly viscous resin with little coloration.
  • the polymerization temperature is 180.degree. In the range of 2 80 to the following range, it is more preferable that the highest polymerization temperature is in the range of 2 30 to 2 70.
  • the lower limit of the specific viscosity in 2 of a solution obtained by dissolving 0.7 g of the polycarbonate in 10 mL of methylene chloride is 0.20 or more, preferably 0.2. 2 or more, and the upper limit is 0.45 or less, preferably 0.37 or less, and more preferably 0.34 or less.
  • the specific viscosity is lower than 0.20, it becomes difficult to give the molded product obtained from the polycarbonate of the present invention sufficient mechanical strength.
  • the specific viscosity is higher than 0.45, the melt fluidity deteriorates and the fluidity necessary for molding is obtained. The melting temperature becomes higher than the decomposition temperature, which is not preferable.
  • the specific viscosity (7) sp ) above can be converted from the viscosity measured in other solvent systems.
  • N in the formula (5) is the ratio of the number of moles of repeating units derived from the anhydrous sugar alcohol of the formula (1) to the number of moles of repeating units of all diol components in the polymer chain, 6 ⁇ n ⁇ 0.9. Therefore, n-1 is the ratio of the number of moles of repeating units derived from the diol component of formula (3) to the number of moles of repeating units of all diol components in the polymer chain.
  • n in the formula (5) is smaller than 0.6, the glass transition temperature and heat resistance of the resulting resin are lowered, which is not preferable. On the other hand, if it is greater than 0.9, the melt fluidity is high and it may be difficult to ensure the fluidity required for molding.
  • the average degree of polymerization of the polycarbonate of the present invention is generally 10 to 10,000.
  • it is 30 to 5000, more preferably 30 to 1000.
  • the polycarbonate obtained by the production method of the present invention has a Co 1-b value indicating a hue of 5 or less, preferably 3 or less.
  • the polycarbonate of the present invention may be a composition with a cyclic phosphite of the formula (2), a stabilizer such as a phenol stabilizer, other additives, or a mixture thereof.
  • any known method and apparatus for obtaining a homogeneous mixture can be used.
  • it can be added in a molten state.
  • the cyclic phosphites of the above formula (2) When the cyclic phosphites of the above formula (2) are added during the polycondensation reaction, the cyclic phosphites of the above formula (2) contained in the anhydrous sugar alcohol composition of the present invention used as a raw material are used. It is preferable that the total amount with the phytos is 0.0005 to 0.5 parts by mass with respect to 100 parts by mass of the anhydrous sugar alcohol of the formula (1).
  • additives such as the cyclic phosphites of the above formula (2) can be directly mixed with the polycarbonate of the present invention using a dry blend or a mixer such as a Henschel mixer.
  • additives such as the cyclic phosphites of the above formula (2) can be blended with the polycarbonate resin in the form of a masterbatch.
  • the polycarbonate of the present invention is widely used for various applications including optical media, electrical / electronic / OA, automobile / industrial equipment, medical / security, sheet / film / packaging, miscellaneous goods.
  • DVDs, CD-ROMs, CD-Rs, minidiscs for optical media applications mobile phones, personal computer housings, battery pack cases, liquid crystal parts, connectors, automobiles for electrical and electronic applications
  • Headlamps, inner lenses, door handles, bumpers, fenders, roof rails, instrument panels, class boxes, console boxes, cameras, power tools for medical equipment, medical labels, nameplates, carports, LCD diffusers, reflective films, Drinking water tanks and miscellaneous goods include pachinko parts and fire extinguisher cases.
  • injection molding, compression molding, injection compression molding, extrusion molding, blow molding and the like are used as a method for obtaining a molded body by molding polycarbonate for the above-mentioned uses.
  • methods for producing films and sheets include a solvent casting method, a melt extrusion method, and a calendar method.
  • the present invention also provides an anhydrous sugar alcohol with a low peroxide content. It also provides a purification method that can be used.
  • one or more kinds of antioxidants selected from the following (a) to (e) forces are added to the anhydrous sugar alcohol represented by the above formula (1). It is characterized in that an anhydrous sugar alcohol having a peroxide content of 1 mass ppm or less can be obtained by purification after adding ⁇ 1000 mass ppm.
  • the cyclic phosphates of the formula (2) used in the method for purifying anhydrous alcohol of the present invention are preferably the same as those used in the anhydrous sugar alcohol composition, and more preferably those of the formula (2)
  • R 5 , R 6 , and R 8 are tertiary alkyl groups having 4 to 8 carbon atoms
  • R 9 is an alkyl group having 1 to 8 carbon atoms
  • X is a single bond
  • A is 2 to 8 carbon atoms.
  • alkylene group Y being a hydroxyl group, and Z being a hydrogen atom, particularly preferred are 6- [3- (3-tert-butyl 4-hydroxy-5-methylphenyl) propoxy] —2, 4, 8, 10-tetra-t-butyldibenz [d, f] [1, 3, 2] dioxaphosphine.
  • the phosphorus stabilizer used in the method for purifying anhydrous alcohol of the present invention (except for those corresponding to the formula (2)) is preferably the same as that used in the anhydrous sugar alcohol composition, Compounds of the above formulas (10) to (12) having the structure of the above formula (9), compounds of the above formulas (13) to (15), bis (2,6-di-t-butyl_4-monomethylphenyl) pen Erisri in the evening! It is more preferable to use at least one compound selected from compounds such as mono-lujiphosphite and tristearyl sorbitol triphosphite.
  • the phenol stabilizer used in the method for purifying anhydrous alcohol of the present invention is preferably the same as that used in the anhydrous sugar alcohol composition, and the formula having the structure of the formula (16) is used. It is more preferable to use at least one compound selected from the compounds (17) to (19), the compound represented by the formula (20), 3,5-tert-butyl 4-hydroxytoluene and the like.
  • io stabilizer used in the method for purifying anhydrous alcohol of the present invention are preferably the same as those used in the above-mentioned anhydrous sugar alcohol composition, specifically: dilauryl 3, 3′-thiodipropionate, tridecyl 3, 3′-thiodipropionate, etc. Two or more of these can be used.
  • the hindered amine stabilizer used in the method for purifying anhydrous alcohol of the present invention is preferably the same as that used in the above-mentioned anhydrous sugar alcohol composition.
  • bis (2, 2, 6, 6— Examples include tetramethyl-4-piperidyl) sebacate, bis ((2, 2, 6, 6-tetramethyl-4-piperidyl) succinate, etc. Two or more of these may be used.
  • the amount of the antioxidant added in the purification method is 100 to 1000 mass ppm of the antioxidants (a) to (e) with respect to the anhydrous sugar alcohol of the formula (1).
  • the amount is 100 to 500 mass p pm If the addition amount of the antioxidant is not less than the above lower limit amount, an anhydrous sugar alcohol having a low peroxide content can be obtained for safety. Masui. In consideration of the balance of the addition effect and cost of the antioxidant, the addition amount of the antioxidant is at most is sufficient upper limit amount of about above.
  • the amount of peroxide contained in the purified sugar alcohol after purification can be reduced to 1 mass ppm or less, and more preferably, it can be reduced to 0.5 mass ppm or less.
  • Examples of the method for purifying anhydrous sugar alcohol employed in the present invention include batch or continuous distillation, evaporation, extraction, crystallization, thermal filtration, adsorption, etc. Distillation is preferred, and vacuum distillation is particularly preferred in order to suppress degradation of the anhydrous sugar alcohol.
  • the conditions for vacuum distillation are that the pressure is reduced to 120 mm or more, preferably 140 or more, to ImmHg (0.13 kPa) or less, more preferably 0.8 mmHg (0.10 kPa) or less. Is preferred.
  • the distillation apparatus a normal single distillation apparatus, a regular packed tower distillation apparatus, a perforated plate tower distillation apparatus, a bubble bell tower distillation apparatus, or the like can be used.
  • the anhydrous sugar alcohol purified by the method of the present invention is particularly suitable as a raw material for polyester and polycarbonate. If the anhydrous sugar alcohol after purification contains the above-mentioned item (a), that is, the cyclic phosphites of the above formula (2), the period from when the anhydrous sugar alcohol is purified until it is used as a polymer raw material. Degradation and degradation are suppressed, which is very preferable.
  • the purified anhydrosugar alcohol is added to the (a)
  • the cyclic phosphites of (a) added at the time of purification may be contained in an appropriate amount in the purified anhydrous sugar alcohol.
  • the anhydrous sugar alcohol obtained by the purification method of the present invention has a low peroxide content, and compared with the anhydrous sugar alcohol not according to the present invention, it is stable due to the addition of the cyclic phosphites of the above (a). Great effect.
  • the isosorbide used in Examples 1 to 4 and Comparative Examples 1 to 6 was purified by vacuum distillation from a rocket company product, and had a purity of 99.9 mol%, and the contents of Na, Ca, and Fe were all 0.1 mass ppm. Less than (measured by ICP emission analysis) and then stored at room temperature (10-35 ° C) in a dry, inert atmosphere protected from light. Acetone manufactured by Wako Pure Chemicals was used.
  • the antioxidant was selected from the following various stabilizers i to i V and used.
  • Example 1 isosorbide and iso The stability of the sorbide composition was evaluated by measuring the pH of a 40% by weight aqueous solution (using a Horiba B-212 type pH meter).
  • Example 1 isosorbide and iso The stability of the sorbide composition was evaluated by measuring the pH of a 40% by weight aqueous solution (using a Horiba B-212 type pH meter).
  • Isosorbide 40 g was dissolved in acetone to make a 200 mL solution. While stirring this solution, 6- [3— (3-tert-butyl 4-hydroxy-5-methylphenyl) propoxy] —2, 4, 8, 10-tetra-t-butyldibenz
  • Example 6 [3- (3- (3-tert-Butyl-4-hydroxy) -5-methylphenyl) propoxy] —2, 4, 8, 10, 10-tetra _ t —Ptyldibenz [d, f] [1, 3, 2]
  • the same procedure as in Example 1 was conducted except that the amount of dioxaphosphepine (1. cyclic phosphites) added was 0.1 parts by mass. The results are shown in Table 1.
  • Example 2 The same procedure as in Example 1 was carried out except that NaBH 4 (iv) was used as a stabilizer and the amount added to 100 parts by mass of isosorbide was 0.0002 parts by mass. Holding at high temperature After 48 hours, the pH of the aqueous sample solution dropped to around 6. The results are shown in Table 1. Comparative Example 5
  • Example 2 The same procedure as in Example 1 was carried out except that NaBH 4 (iv) was used as a stabilizer and the amount added to 100 parts by mass of isosorbide was 0.0033 parts by mass. Holding at high temperature After 48 hours, the pH of the aqueous sample solution dropped to around 6. The results are shown in Table 1. Comparative Example 6
  • Example 1 The same test as in Example 1 was performed using only isosorbide without adding a stabilizer. Holding at high temperature After 48 hours, the pH of the aqueous sample solution dropped to about 5. The results are shown in Table 1.
  • isosorbide used in Examples 5 to 8 and Comparative Examples 7 to 11 was prepared by purifying a Rocket product by distillation under reduced pressure to obtain a purity of 99.9 mol%, Na, Ca, and Fe. The total content was less than 1 mass p pm (measured by ICP emission spectrometry), and then stored at room temperature (10-35) in a dry, inert atmosphere protected from light.
  • Diphenyl carbonate was manufactured by Teijin Chemicals and had a purity of 99.9 mol% and a total content of Na, Ca and Fe of less than 1 mass p pm (measured by ICP emission analysis).
  • Tetramethylammonium hydroxide, methylene chloride, barium hydroxide octahydrate and acetone were manufactured by Wako Pure Chemical Industries.
  • antioxidant (stabilizer) used in ⁇ 11 is selected from the above i to iV.
  • Example 5 to 8 and Comparative Examples 7 to 11 were performed by the methods described below.
  • the amount of various metals in raw materials such as isosorbide and diphenyl carbonate was quantified using the ICP emission analyzer VI STA MP-X (multi type) (manufactured by Varian) (detection limit 0 l ppm) .
  • isosorbide and isosorbide composition were evaluated by preparing a 40 mass% aqueous solution of the sample and measuring its pH (using a Horiba B-212 type pH meter).
  • the specific viscosity of the polymer was determined by measuring the viscosity at 20 of a solution obtained by dissolving 0.7 g of polycarbonate in 10 mL of methylene chloride.
  • UV—VISR ECORD I NG SPECTROPHOTOMETER manufactured by Shimadzu Corporation 4 mL was added and dissolved, and this was confirmed by measuring the Co 1 b value under the conditions of a wavelength of 780 to 380 nm, illumination: C, and visual field: 2 °.
  • Example 5 UV—VISR ECORD I NG SPECTROPHOTOMETER
  • the isosorbide composition obtained here was put into a hot air dryer set to 50, and this time was regarded as a high temperature holding time of zero. Thereafter, sampling was performed at the time when 100 hours had elapsed, and pH measurement was performed. Further, the polycondensation reaction of the polycarbonate cake was carried out as follows by using the obtained isosorbide composition for 50 hours at the obtained 50.
  • Isosorbide 6- [3— (3-tert-Butyl_4-Hydoxy-5-methylphenyl) propoxy] —2, 4, 8, 10, 10-Tetra_t-Iptyldibenz [d, f] [1, 3, 2]
  • the amount of dioxaphosphepine (i. Cyclic phosphites) added is 0.0033 parts by mass, and 2, 2-bis (4-hydroxyphenyl) propan disodium salt in the polycondensation reaction amount of 0. except that the 25mg (0. 9 X 10- 6 mo l) was carried out analogously to example 5. The results are shown in Table 2.
  • Example 8 The catalyst in the polycondensation reaction, 2-bis (4-hydroxyphenyl) rather than prop Nni sodium hydroxide of barium octahydrate (0. 284mg, 0. 9 X 10- 6 mo l) except for using The same operation as in Example 5 was performed. The results are shown in Table 2.
  • Example 8 The catalyst in the polycondensation reaction, 2-bis (4-hydroxyphenyl) rather than prop Nni sodium hydroxide of barium octahydrate (0. 284mg, 0. 9 X 10- 6 mo l) except for using The same operation as in Example 5 was performed. The results are shown in Table 2. Example 8.
  • Example 5 Bis (2,4-di-t-butylphenyl) Penyu erythri] ⁇ Luludiphosphite (iii. Phosphorus stabilizer), which is not a cyclic phosphite, is used as a stabilizer, and 100 parts by mass of isosorbide Example 5 was carried out in the same manner as in Example 5 except that the amount added was 0.001 6 parts by mass. The results are shown in Table 2. Comparative Example 9.
  • Example 5 This was carried out in the same manner as in Example 5 except that NaBH 4 (iv) was used as a stabilizer instead of cyclic phosphite, and the amount of addition to 100 parts by mass of isosorbide was 0.0033 parts by mass. The results are shown in Table 2. Comparative Example 10.
  • isosorbide used in Examples 9 to 15 and Comparative Examples 12 to 16 was purified by distillation under reduced pressure from a rocket company, and had a purity of 99.9 mol%, Na, Ca, and Fe content. The total amount was less than 1 ppm by mass (measured by ICP emission analysis) and then stored at room temperature (10-35 ° C) in a light-shielded, dry inert atmosphere.
  • 1, 3_propanediol, 1,4 monobutanediol, 1,6-hexanediol are manufactured by Wako Pure Chemical Industries, Ltd., purity 99.9 mol%, Na, C a
  • the total Fe content was less than 1 mass p pm (measured by ICP emission analysis).
  • Diphenyl carbonate manufactured by Teijin Chemicals and having a purity of 99.9 mol% and a total content of Na, Ca and Fe of less than 1 mass p pm (measured by ICP emission analysis) was used.
  • Tetramethylammonium hydroxide, methylene chloride, barium hydroxide octahydrate and acetone manufactured by Wako Pure Chemical Industries, Ltd. were used.
  • 2,2-bis (4-hydroxyphenyl) propane disodium salt was prepared from 2,2_bis (4-hydroxyphenyl) propane according to a conventional method.
  • antioxidants used in Examples 9 to 15 and Comparative Examples 12 to 16 were selected from i to i V described above.
  • Example 9 The analysis and evaluation in Examples 9 to 15 and Comparative Examples 12 to 16 (the amount of metal in various raw materials such as isosorbide, the evaluation of the stability of the isosorbide and isosorbide composition, the specific viscosity of the polymer, and the hue of the polymer) are as described above. It went by the method of. Example 9.
  • Example 1 The same procedure as in Example 9 was performed except that the amount of 2,2-bis (4-hydroxyphenyl) propaninatrium salt added in the polycondensation reaction was changed to 0.25 mg (0.9 X 10 ' 6 mo 1). . The results are shown in Table 3.
  • Example 1 1.
  • Example 13 The catalyst in the polycondensation reaction, 2-bis (4-hydroxyphenyl) rather than prop Nni sodium hydroxide barium octahydrate except for using (0. 284mg, 0. 9 X 10_ 6 mo l) carried Performed as in Example 9. The results are shown in Table 3. Example 13.
  • the catalyst in the polycondensation reaction is not barium hydroxide octahydrate (0.57 mg, 1. 8 X 1 0 1 6 mol) instead of 2,2-bis (4-hydroxyphenyl) propanisodium salt.
  • Example 14 The catalyst in the polycondensation reaction is not barium hydroxide octahydrate (0.57 mg, 1. 8 X 1 0 1 6 mol) instead of 2,2-bis (4-hydroxyphenyl) propanisodium salt.
  • Example 1 The same operation as in Example 10 was carried out except that 1,4-butanediol was used in the same number of moles instead of 1,3-propanediol. The results are shown in Table 3. Example 1 5.
  • Example 12 The same operation as in Example 10 was performed except that 1,6-hexanediol was used in the same number of moles instead of 1,3-propanediol. The results are shown in Table 3. Comparative Example 12.
  • Stabilizers are phenolic stabilizers i) rather than cyclic phosphites i) 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] — 4,6-di-dipentylphenol
  • diluacrylate was used and the addition amount per 100 parts by mass of isosorbide was changed to 0.000029 parts by mass. The results are shown in Table 3. Comparative Example 13.
  • Example 15 This was carried out in the same manner as in Example 9 except that NaBH 4 (iV) was used as a stabilizer instead of cyclic phosphite, and the addition amount per 100 parts by mass of isosorbide was 0.0033 parts by mass. The results are shown in Table 3. Comparative Example 15. Without using isosorbide as a composition with a stabilizer, it was placed in a hot air drier set at 50 ° C. in the same manner as in Example 9, and sampled at a time point of 100 hours to measure pH. The pH of the sample dropped to 4.2. The results are shown in Table 1. Since it was clear from the results of other comparative examples that a polymer of good quality could not be obtained using this isosorbide, the polycondensation reaction was not performed. Comparative Example 1 6.
  • the isosorbide used in Examples 16 to 18 and Comparative Example 17 was a product of Rocket Corporation.
  • As an antioxidant 6 _ [3- (3_ t-butyl-4-hydroxy-5-methylphenyl) propoxy] —2, 4, 8, 10-tetra-t-peptyldibenz [d, f] [1, 3 , 2] — Dioxaphosphepine (Surn i 1 izer (registered trademark) GP, manufactured by Sumitomo Chemical Co., Ltd.), Bis (2, 6-di-tert-butyl-4-methylphenyl) Pen Yu Erisri!
  • Irudiphosphite (Adekastab (registered trademark) PEP-36, manufactured by Ade force Co., Ltd.), 3,5-t-Iptiru 4-hydroxytoluene (BHT) (manufactured by Wako Pure Chemical Industries, Ltd.) was used.
  • the amount of peroxide was measured in accordance with JIS K01 15 (General Absorption Spectrometry Standards, International Standard ICS 7 1.040.50) using the sample solution, standard solution, and blank test side solution prepared by the following procedure. From the absorbance measured at a wavelength of 360 nm and a cell length of 10 mm, the following equation (e q — l) was used.
  • Standard solution Dissolve 1 OmL of water in 5 g of the sample after distillation, add 5 mL of peroxide standard solution (5 mg_H 2 0 2 / L), 1 mL of acetic acid, and 2 mL of 2% potassium iodide solution in this order. Nitrogen was sealed, stoppered, and allowed to stand for 90 minutes in water. Water was added to make the volume 25 mL.
  • Blank test solution Add 1 mL of acetic acid and 2 mL of 2% lithium iodide solution to 1 OmL of water, fill with nitrogen, stopper and leave for 90 minutes, add water to reduce the volume. 25 mL.
  • A is the amount of peroxide (mass p pm) in the sample
  • a is the absorbance (Abs) of the sample solution
  • b is the absorbance (Abs) of the standard solution.
  • Example 18 The same procedure as in Example 16 was performed except that the antioxidant was changed to bis (2,6-di-t-butyl-4-methylphenyl) pen erythritol diphosphite (Adekastab® PEP-36). It was. The results are shown in Table 4. Example 18.
  • Example 16 The same operation as in Example 16 was performed, except that the antioxidant was changed to 3,5-tert-petite 4-hydroxytoluene (BHT). The results are shown in Table 4. Comparative Example 17.
  • Example 16 The same operation as in Example 16 was carried out except that no antioxidant was added. The results are shown in Table 4. Table 4.
  • the anhydrous sugar alcohol composition of the present invention has good storage stability and is suitable for various applications.
  • the anhydrous sugar alcohol composition contains a plant-derived component produced from the anhydrous sugar alcohol composition as a raw material.
  • Polycarbonate has good physical properties such as hue, optical media use, electrical / electronic • OA field, automobile / industrial equipment use, medical use, security use, sheet, film, packaging use, and miscellaneous goods use. Very suitable.

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Abstract

La présente invention concerne une composition à base d'anhydride d'alcool de sucre renfermant 100 parties en masse d'un anhydride d'alcool de sucre représenté par la formule (1) et 0,0005 à 0,5 partie en masse d'un phosphite cyclique représenté par la formule (2). (1) dans laquelle R1 à R4 représentent indépendamment un résidu choisi parmi un atome d'hydrogène, un groupe alkyle, un groupe cycloalkyle et un groupe aryle. (2) dans laquelle R5, R6, R8 et R9 représentent indépendamment un groupe alkyle ayant 1 à 8 atomes de carbone ou analogues ; R7 représente un atome d'hydrogène ou analogues ; A représente un groupe alkylène ayant 2 à 8 atomes de carbone ou analogues ; et l'un ou l'autre de Y et Z représente un groupe hydroxyle ou analogues, et l'autre représente un atome d'hydrogène ou analogues.
PCT/JP2008/069576 2007-10-31 2008-10-22 Composition à base d'anhydride d'alcool de sucre présentant une bonne stabilité lors du stockage et procédé de production de polycarbonate avec cette dernière WO2009057609A1 (fr)

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JP2011219746A (ja) * 2010-03-26 2011-11-04 Mitsubishi Chemicals Corp ポリカーボネート樹脂組成物及び成形品
JP2012207184A (ja) * 2011-03-30 2012-10-25 Mitsubishi Chemicals Corp ポリカーボネート樹脂組成物及びポリカーボネート樹脂組成物の製造方法
JP2018535274A (ja) * 2015-11-30 2018-11-29 サムヤン コーポレイション 安定性を高めた濃縮無水糖アルコール製造用組成物及び無水糖アルコールの濃縮方法
JP2019501960A (ja) * 2015-11-30 2019-01-24 サムヤン コーポレイション 保存安定性を高めた無水糖アルコール組成物及び無水糖アルコールの保存方法
CN109897050A (zh) * 2017-12-07 2019-06-18 中国科学院大连化学物理研究所 一种制备异山梨醇二羧酸酯的方法

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JP2015145353A (ja) * 2014-02-04 2015-08-13 第一工業製薬株式会社 無水糖アルコールの精製方法、無水糖アルコール及び樹脂
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