KR20140127208A - Polycarbonate resin composition - Google Patents
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- KR20140127208A KR20140127208A KR20147016704A KR20147016704A KR20140127208A KR 20140127208 A KR20140127208 A KR 20140127208A KR 20147016704 A KR20147016704 A KR 20147016704A KR 20147016704 A KR20147016704 A KR 20147016704A KR 20140127208 A KR20140127208 A KR 20140127208A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
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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
- 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
- C08G64/307—General preparatory processes using carbonates and phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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Abstract
The present invention relates to a process for producing a phosphite compound and a phosphate compound (hereinafter, referred to as " phosphite compound ") and a phosphate compound And 0.001 to 0.5 parts by mass of at least one kind of organic phosphorus compound selected from the group consisting of:
Description
The present invention relates to a polycarbonate resin composition having excellent heat resistance and good color tone.
Polycarbonate is an engineering plastic excellent in transparency, heat resistance and impact resistance and is widely used in the fields of electric and electronic, automobile, optical parts and other industrial fields. In general, as a production method of a polycarbonate, a method of directly reacting an aromatic dihydroxy compound with phosgene (interfacial polycondensation method), a method of transesterifying an aromatic dihydroxy compound and a carbonic acid diester in a molten state Polymerization method) is known. In the polycondensation method of the polycarbonate, the polycondensation method is advantageous in that poisonous phosgene must be used, the manufacturing apparatus is corroded by by-product chlorine compounds such as hydrogen chloride and sodium chloride, the polymer such as sodium chloride And it is difficult to separate impurities that adversely affect the physical properties of the substrate. On the other hand, although the transesterification (melt polymerization) method has an advantage that polycarbonate can be produced at lower cost than the interfacial polycondensation method, it is usually reacted at a high temperature of 280 to 310 캜 for a long time, There is a major drawback that the polycarbonate can not be avoided from being colored.
As a method for solving the problem of coloring of polycarbonate, it has been proposed to neutralize an inorganic base catalyst of an alkali metal or an alkaline earth metal with a defoaming agent which is an aromatic sulfonic acid compound (for example, see Patent Document 1). Further, there is proposed a method in which an inorganic base catalyst of an alkali metal or an alkaline earth metal is neutralized with a defoaming agent such as a sulfonic acid compound and then a phosphite-based phosphorus antioxidant is added (for example, see Patent Document 2). Further, a method has been proposed in which a quaternary ammonium salt and a quaternary phosphonium salt are used as an organic catalyst in an ester exchange catalyst, and the catalyst is removed by thermal decomposition at the final stage of the reaction without requiring a deactivator (for example, See Patent Document 3).
In the method of neutralizing the inorganic base catalyst proposed in Patent Documents 1 and 2 with a deactivator, the effect of preventing coloring is not satisfactory. On the other hand, in the method using the organic salt catalyst proposed in Patent Document 3 , Since the catalyst can be removed by thermal decomposition, a deactivating agent is not required, and a polycarbonate having excellent quality can be obtained. However, it is desired to further improve the color tone of the polycarbonate.
An object of the present invention is to provide a polycarbonate resin composition having excellent heat resistance and good color tone by using a polycarbonate produced by an ester exchange reaction.
As a result of intensive studies, the present inventors have found that the above problems can be solved by mixing a specific organic phosphorus compound with a polycarbonate obtained by an ester exchange reaction using a specific polymerization catalyst.
That is, the present invention relates to the following 1 to 17.
1. A process for producing a phosphite compound and a phosphate compound, which comprises reacting a phosphite compound and a phosphate compound with 100 parts by mass of a polycarbonate obtained by an ester exchange reaction using a combination of (a) a nitrogen-containing organic basic compound and (b) a quaternary phosphonium salt containing an aryl group And 0.001 to 0.5 parts by mass of at least one kind of organic phosphorus compound selected.
2. The polycarbonate resin composition according to 1 above, wherein the content of sodium, cesium and potassium is 0.1 mass ppm or less, respectively.
3. The polycarbonate resin composition according to 1 or 2, wherein (a) the nitrogen-containing organic basic compound is a quaternary ammonium salt.
4. The polycarbonate resin composition according to the above 1 or 2, wherein the nitrogen-containing organic basic compound (a) is a compound represented by the following general formula (I).
(NR 1 4 ) + (X 1 ) - (I)
[Wherein R 1 represents an alkyl group, an aryl group or an alkylaryl group, four R 1 s may be the same as or different from each other, and two R 1 s may combine to form a cyclic structure. X 1 represents a halogen atom, a hydroxyl group, an alkyloxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, HCO 3 or BR 4 (R represents a hydrogen atom or an alkyl group or an aryl group, They may be the same or different).
5. The polycarbonate resin composition according to any one of (1) to (4), wherein the quaternary phosphonium salt (b) containing an aryl group is a compound represented by the following formula (II).
(PR 2 4 ) + (X 2 ) - (II)
Wherein R 2 represents an alkyl group, an aryl group or an alkylaryl group, at least one of the four R 2 s is an aryl group. In addition, the four R 2 are also the same as or different from each other, or may form a ring structure, and 2 and one R 2 is a bond. X 2 represents a halogen atom, a hydroxyl group, an alkyloxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, HCO 3 or BR 4 (R represents a hydrogen atom or an alkyl group or an aryl group, They may be the same or different).
6. The polycarbonate resin composition according to any one of items 1 to 5, wherein the raw material for the transesterification reaction is (A) a dihydroxy compound and (B) a carbonic acid diester.
7. The polycarbonate resin composition according to 6 above, wherein the dihydroxy compound (A) is 2,2-bis (4-hydroxyphenyl) propane.
8. The polycarbonate resin composition according to 6 or 7, wherein the (B) carbonate diester is diphenyl carbonate.
9. The method according to any one of (1) to (8) above, wherein (a) the nitrogen-containing organic basic compound is tetramethylammonium hydroxide, and (b) the quaternary phosphonium salt containing an aryl group is tetraphenylphosphonium tetraphenylborate. Polycarbonate resin composition.
10. The organic phosphorous compound as claimed in claim 1, wherein the organic phosphorus compound is tris (2,4-di-tert-butylphenyl) phosphite, bis (2,6- Bis (4,6-di-tert-butylphenyl) octyl-phosphite, triphenyl phosphate, bisphenol A bis (diphenylphosphate), and 1,3-phenylene-tetrakis (2,6- And the polycarbonate resin composition according to any one of the above-mentioned items 1 to 9, wherein the polycarbonate resin composition is at least one selected from esters.
11. A polycarbonate is obtained by an ester exchange reaction using a combination of (a) a nitrogen-containing organic basic compound and (b) a quaternary phosphonium salt containing an aryl group, as a polymerization catalyst, and, with respect to 100 parts by mass of the obtained polycarbonate, A phosphite compound and a phosphate compound in an amount of 0.001 to 0.5 parts by mass based on the total amount of the organic phosphorus compound and the phosphorus compound.
12. The process for producing a polycarbonate resin composition as described in 11 above, wherein the polycarbonate is obtained by heat-treating the reaction product at a temperature not lower than the decomposition temperature of the polymerization catalyst after the transesterification reaction.
13. The method for producing a polycarbonate resin composition according to the above 11 or 12, wherein (a) the nitrogen-containing organic basic compound is a quaternary ammonium salt.
14. A process for producing a polycarbonate resin composition according to the above 11 or 12, wherein (a) the nitrogen-containing organic basic compound is a compound represented by the following general formula (I).
(NR 1 4 ) + (X 1 ) - (I)
[Wherein R 1 represents an alkyl group, an aryl group or an alkylaryl group, four R 1 s may be the same as or different from each other, and two R 1 s may combine to form a cyclic structure. X 1 represents a halogen atom, a hydroxyl group, an alkyloxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, HCO 3 or BR 4 (R represents a hydrogen atom or an alkyl group or an aryl group, They may be the same or different).
15. A process for producing a polycarbonate resin composition according to any one of the above 11 to 14, wherein the (b) quaternary phosphonium salt containing an aryl group is a compound represented by the following formula (II).
(PR 2 4 ) + (X 2 ) - (II)
Wherein R 2 represents an alkyl group, an aryl group or an alkylaryl group, at least one of the four R 2 s is an aryl group. In addition, the four R 2 are also the same as or different from each other, or may form a ring structure, and 2 and one R 2 is a bond. X 2 represents a halogen atom, a hydroxyl group, an alkyloxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, HCO 3 or BR 4 (R represents a hydrogen atom or an alkyl group or an aryl group, They may be the same or different).
16. A process for producing a polycarbonate resin composition according to any one of the above items 12 to 15, wherein the temperature for heat-treating the reaction product is 240 占 폚 or more and 350 占 폚 or less.
17. A polycarbonate resin composition produced by the process for producing a polycarbonate resin composition according to any one of 11 to 16 above.
According to the present invention, it is possible to provide a polycarbonate resin composition having excellent heat resistance and excellent color tone.
The polycarbonate resin composition of the present invention can be obtained by obtaining a polycarbonate by an ester exchange reaction using a combination of (a) a nitrogen-containing organic basic compound and (b) a quaternary phosphonium salt containing an aryl group as a polymerization catalyst, And 0.001 to 0.5 part by mass of at least one organic phosphorus compound selected from a phosphite compound and a phosphate compound per 100 parts by mass.
[Polycarbonate]
The polycarbonate contained in the polycarbonate resin composition of the present invention is obtained by an ester exchange reaction using a specific polymerization catalyst. The raw material used in this ester exchange method is not particularly limited and may be produced by a conventional ester exchange method (A) a dihydroxy compound and (B) a carbonic acid diester are preferably used.
The dihydroxy compound (A) includes, for example, an aromatic dihydroxy compound and an aliphatic dihydroxy compound, and is at least one compound selected therefrom.
The aromatic dihydroxy compound used as one of the components (A) includes a compound represented by the following general formula (1).
[Chemical Formula 1]
In the general formula (1), R 4 and R 5 are each a halogen atom of fluorine, chlorine, bromine or iodine, or an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group and an octyl group. R 4 and R 5 may be the same or different from each other. In addition, if a plurality is R 4 it is and even if a plurality of R 4 are the same or different, there may be a plurality of R 5 are the same or different if there is R 5 plurality. m and n are each an integer of 0 to 4; And Z is a single bond, an alkylene group of 1 to 20 carbon atoms, an alkylidene group of 2 to 20 carbon atoms, a cycloalkylene group of 5 to 20 carbon atoms, a cycloalkylidene group of 5 to 20 carbon atoms, -, -SO 2 -, -O-, -CO- or a bond represented by the following formulas (2) and (2 ').
(2)
Examples of the alkylene group having 1 to 20 carbon atoms and the alkylidene group having 2 to 20 carbon atoms include methylene, ethylene, propylene, butylene, pentylene, hexylene, ethylidene, isopropylidene, Examples of the cycloalkylene group having 5 to 20 carbon atoms and the cycloalkylidene group having 5 to 20 carbon atoms include a cyclopentylene group, a cyclohexylene group, a cyclopentylidene group, and a cyclohexylidene group .
Examples of the aromatic dihydroxy compound represented by the general formula (1) include bis (4-hydroxyphenyl) methane; Bis (3-methyl-4-hydroxyphenyl) methane; Bis (3-chloro-4-hydroxyphenyl) methane; Bis (3,5-dibromo-4-hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane; 1,1-bis (2-t-butyl-4-hydroxy-3-methylphenyl) ethane; 1,1-bis (2-t-butyl-4-hydroxy-3-methylphenyl) ethane; 1-phenyl-1,1-bis (3-fluoro-4-hydroxy-3-methylphenyl) ethane; 2,2-bis (4-hydroxyphenyl) propane (collectively bisphenol A); 2,2-bis (3-methyl-4-hydroxyphenyl) propane; 2,2-bis (2-methyl-4-hydroxyphenyl) propane; 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane; 1,1-bis (2-t-butyl-4-hydroxy-5-methylphenyl) propane; 2,2-bis (3-chloro-4-hydroxyphenyl) propane; 2,2-bis (3-fluoro-4-hydroxyphenyl) propane; 2,2-bis (3-bromo-4-hydroxyphenyl) propane; 2,2-bis (3,5-difluoro-4-hydroxyphenyl) propane; 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane; 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane; 2,2-bis (4-hydroxyphenyl) butane; 2,2-bis (4-hydroxyphenyl) octane; 2,2-bis (4-hydroxyphenyl) phenylmethane; 2,2-bis (4-hydroxy-1-methylphenyl) propane; 1,1-bis (4-hydroxy-t-butylphenyl) propane; 2,2-bis (4-hydroxy-3-bromophenyl) propane; 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane; 2,2-bis (4-hydroxy-3-chlorophenyl) propane; 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane; 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane; 2,2-bis (3-bromo-4-hydroxy-5-chlorophenyl) propane; 2,2-bis (3-phenyl-4-hydroxyphenyl) propane; 2,2-bis (4-hydroxyphenyl) butane; 2,2-bis (3-methyl-4-hydroxyphenyl) butane; 1,1-bis (2-butyl-4-hydroxy-5-methylphenyl) butane; 1,1-bis (2-t-butyl-4-hydroxy-5-methylphenyl) butane; 1,1-bis (2-t-butyl-4-hydroxy-5-methylphenyl) isobutane; 1,1-bis (2-t-amyl-4-hydroxy-5-methylphenyl) butane; 2,2-bis (3,5-dichloro-4-hydroxyphenyl) butane; 2,2-bis (3,5-dibromo-4-hydroxyphenyl) butane; 4,4-bis (4-hydroxyphenyl) heptane; 1,1-bis (2-t-butyl-4-hydroxy-5-methylphenyl) heptane; 2,2-bis (4-hydroxyphenyl) octane; Bis (hydroxyaryl) alkanes such as 1,1- (4-hydroxyphenyl) ethane; 1,1-bis (4-hydroxyphenyl) cyclopentane; 1,1-bis (4-hydroxyphenyl) cyclohexane; 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane; 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane; 1,1-bis (3-phenyl-4-hydroxyphenyl) cyclohexane; Bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) -3,5,5-trimethylcyclohexane; Bis (4-hydroxyphenyl) ether; Bis (hydroxyaryl) ethers such as bis (4-hydroxy-3-methylphenyl) ether; Bis (4-hydroxyphenyl) sulfide; Bis (hydroxyaryl) sulfide such as bis (3-methyl-4-hydroxyphenyl) sulfide; Bis (4-hydroxyphenyl) sulfoxide; Bis (3-methyl-4-hydroxyphenyl) sulfoxide; Bis (hydroxyaryl) sulfoxide such as bis (3-phenyl-4-hydroxyphenyl) sulfoxide; Bis (4-hydroxyphenyl) sulfone; Bis (3-methyl-4-hydroxyphenyl) sulfone; Bis (3-phenyl-4-hydroxyphenyl) sulfone, and 4,4'-dihydroxybiphenyl; 4,4'-dihydroxy-2,2'-dimethylbiphenyl; 4,4'-dihydroxy-3,3'-dimethylbiphenyl; 4,4'-dihydroxy-3,3'-dicyclohexylbiphenyl; And dihydroxybiphenyls such as 3,3'-difluoro-4,4'-dihydroxybiphenyl.
Examples of the aromatic dihydroxy compounds other than the general formula (1) include dihydroxybenzenes, halogen and alkyl-substituted dihydroxybenzenes.
For example, there can be mentioned, for example, resorcin, 3-methylresorcin, 3-ethylresorcin, 3-propylresorcin, 3-butylresorcin, 3- Leucine; 2,3,4,6-tetrafluororesorcin; 2,3,4,6-tetrabromorejorcine; Catechol, hydroquinone, 3-methylhydroquinone, 3-ethylhydroquinone, 3-propylhydroquinone, 3-butylhydroquinone, 3-t-butylhydroquinone, 3-phenylhydroquinone, 3-cumylhydroquinone; 2,5-dichlorohydroquinone; 2,3,5,6-tetramethylhydroquinone; 2,3,4,6-tetra-t-butylhydroquinone; 2,3,5,6-tetrafluorohydroquinone; 2,3,5,6-tetrabromohydroquinone, and ethoxylated or propoxylated products of dihydric alcohols or phenols, such as bis (oxyethyl) bisphenol A, bis (oxyethyl) tetrachlorobisphenol A or Bis (oxyethyl) tetrachlorohydroquinone, and the like.
The aliphatic dihydroxy compound used as one component of the component (A) includes, for example, butane-1,4-diol; 2,2-dimethylpropane-1,3-diol; Hexane-1,6-diol; Diethylene glycol; Triethylene glycol; Tetraethylene glycol; Octaethylene glycol; Dipropylene glycol; N, N-methyldiethanolamine; Cyclohexane-1,3-diol; Cyclohexane-1,4-diol; 1,4-dimethylolcyclohexane; p-xylylene glycol; 2,2-bis (4-hydroxycyclohexyl) -propane, isosorbide; Adamantanediol; Adamantanediol methanol; 1,4-cyclohexanedimethanol, and the like.
In the present invention, as the dihydroxy compound of the component (A), one or more of the above-mentioned compounds are appropriately selected and used, and among them, it is preferable to use bisphenol A which is an aromatic dihydroxy compound Do.
(B) The carbonic acid diester is at least one compound selected from a carbonate diaryl compound, a dialkyl carbonate compound, or an alkylaryl carbonate compound.
The diaryl carbonate compound used as one of the components (B) is a compound represented by the following formula (3): wherein Ar 1 and Ar 2 are each an aryl group and may be the same or different from each other. , Or the following general formula (4): wherein Ar 3 and Ar 4 each represent an aryl group, which may be the same as or different from each other, and D 1 represents a residue obtained by removing two hydroxyl groups from the aromatic dihydroxy compound ].
(3)
The dialkyl carbonate compound is represented by the following general formula (5): wherein R 6 and R 7 each represent an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms, compound, or to shown by the general formula (6) [wherein, R 8 and R 9 are each an alkyl group or a cycloalkyl group of 4 to 20 carbon atoms having 1 to 20 carbon atoms, they are be the same or different from each other, D 2 Is a residue obtained by removing two hydroxyl groups from the aromatic dihydroxy compound.
[Chemical Formula 4]
The alkylaryl carbonate compound is a compound represented by the following general formula (7): wherein Ar 5 represents an aryl group, R 10 represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms, Wherein Ar 6 is an aryl group, R 11 is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms, D 3 is a residue obtained by removing two hydroxyl groups from the aromatic dihydroxy compound, Lt; 2 >
[Chemical Formula 5]
Examples of the diaryl carbonate compound include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, bisphenol A bisphenyl carbonate And the like.
Examples of the dialkyl carbonate compound include diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, bisphenol A bismethyl carbonate, and the like.
Examples of the alkylaryl carbonate compound include methyl phenyl carbonate, ethyl phenyl carbonate, butyl phenyl carbonate, cyclohexyl phenyl carbonate, bisphenol A methyl phenyl carbonate, and the like.
In the present invention, as the carbonic acid diester of the component (B), one or more kinds of the above-mentioned compounds are appropriately selected and used, and among them, diphenyl carbonate is preferably used.
In the present invention, raw materials other than the dihydroxy compound (A) and the carbonic acid diester (B) may be used.
Examples of the diesters of dihydroxy compounds include diacetic acid esters of bisphenol A, dipropionic acid esters of bisphenol A, dibutyl acid esters of bisphenol A, and dibenzoic acid esters of bisphenol A .
Examples of the dicarbonate esters of the dihydroxy compounds include bismethyl carbonate ester of bisphenol A, bisethyl carbonate ester of bisphenol A, and bisphenyl carbonate ester of bisphenol A, and the like.
Examples of the mono carbonate ester of the dihydroxy compound include bisphenol A monomethyl carbonate ester, bisphenol A monoethyl carbonate ester, bisphenol A monopropyl carbonate ester, and bisphenol A monophenyl carbonate ester.
Further, in the production of the polycarbonate, a terminal terminator may be used if necessary. Examples of the terminating terminator include o-n-butyl phenol; m-n-butyl phenol; p-n-butylphenol; o-isobutylphenol; m-isobutylphenol; p-isobutylphenol; o-t-butylphenol; m-t-butylphenol; p-t-butylphenol; o-n-pentylphenol; m-n-pentylphenol; p-n-pentylphenol; o-n-hexylphenol; m-n-hexylphenol; p-n-hexylphenol; o-cyclohexylphenol; m-cyclohexylphenol; p-cyclohexylphenol; o-phenylphenol; m-phenylphenol; p-phenylphenol; o-n-nonylphenol; m-n-nonylphenol; p-n-nonylphenol; o-cumylphenol; m-cumylphenol; p-cumylphenol; o-naphthylphenol; m-naphthylphenol; p-naphthylphenol; 2,6-di-t-butylphenol; 2,5-di-t-butylphenol; 2,4-di-t-butylphenol; 3,5-di-t-butylphenol; 2,5-dicumylphenol; 3,5-dicumylphenol; A compound represented by the following formula,
[Chemical Formula 6]
And monovalent phenols such as chroman derivatives represented by the following formulas.
(7)
Among such phenols, p-t-butylphenol, p-cumylphenol, p-phenylphenol and the like are preferable, although not particularly limited in the present invention.
A compound represented by the following formula can also be used.
[Chemical Formula 8]
In the present invention, if necessary, fluoroglucine; Trimellitic acid; 1,1,1-tris (4-hydroxyphenyl) ethane; [Alpha] ', [alpha]', [alpha] '- bis (4 "-hydroxyphenyl) ethyl] benzene; Tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene; Isatin bis (o-cresol) or the like may be used as a branching agent.
As the specific polymerization catalyst in the transesterification reaction, a combination of (a) a nitrogen-containing organic basic compound and (b) a quaternary phosphonium salt containing an aryl group is used.
The nitrogen-containing organic basic compound as the component (a) is not particularly limited, and various ones are available. For example, aliphatic tertiary amine compounds such as trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, and dimethylbenzylamine; Aromatic tertiary amine compounds such as triphenylamine; Pyridine, 4-pyrrolidinopyridine, 4-aminopyridine, 2-aminopyridine, 2-hydroxypyridine, 4-hydroxypyridine, 2-methoxypyridine, Or a pharmaceutically acceptable salt thereof, wherein the compound is selected from the group consisting of 4-methoxypyridine, 4-methoxypyridine, imidazole, 2-methylimidazole, 4-methylimidazole, , Diazabicyclooctane (DABCO), and the like.
As the nitrogen-containing organic basic compound of the component (a), quaternary ammonium salts represented by the following general formula (I) may be mentioned.
(NR 1 4 ) + (X 1 ) - (I)
In the general formula (I), R 1 represents an alkyl group, an aryl group or an alkylaryl group, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, An aryl group or an alkylaryl group having 6 to 20 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a biphenyl group and a benzyl group. The four R 1 s may be the same as or different from each other and two R 1 s may combine to form a cyclic structure.
X 1 represents a halogen atom, a hydroxyl group, an alkyloxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, HCO 3 or BR 4 (R represents a hydrogen atom or an alkyl group or an aryl group, May be the same or different from each other).
Examples of such a quaternary ammonium salt include alkyl groups such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide and trimethylbenzylammonium hydroxide; Ammonium hydroxides having an aryl group, an aryl group or the like; And basic salts such as tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, and tetramethylammonium tetraphenylborate.
Among these (a) nitrogen-containing organic basic compounds, quaternary ammonium salts represented by the above-mentioned general formula (I), specifically tetramethylammonium Tetrabutylammonium hydroxide, tetramethylammonium borohydride and tetrabutylammonium borohydride are preferable, and tetramethylammonium hydroxide is particularly preferable. The nitrogen-containing organic basic compound (a) may be used alone or in combination of two or more.
On the other hand, examples of the quaternary phosphonium salt of component (b) include compounds represented by the following general formula (II).
(PR 2 4 ) + (X 2 ) - (II)
The general formula (II) of, R 2 is an alkyl group, an aryl group or alkyl aryl, which may include the same as those exemplified in the explanation of R 1 in the general formula (I), 4 of R 2 Lt; / RTI > is an aryl group. The four R 2 s may be the same as or different from each other, or two R 2 s may combine to form a cyclic structure.
X 2 represents a halogen atom, a hydroxyl group, an alkyloxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, HCO 3 or BR 4 (R represents a hydrogen atom or an alkyl group or an aryl group, Which may be the same or different.
Examples of such quaternary phosphonium salts include tetraphenylphosphonium hydroxide, tetranaphthylphosphonium hydroxide, tetra (chlorophenyl) phosphonium hydroxide, tetra (biphenyl) phosphonium hydroxide Tetraarylphosphonium hydroxides such as a side, tetratalylphosphonium hydroxide and the like; Methyltriphenylphosphonium hydroxide, ethyltriphenylphosphonium hydroxide, propyltriphenylphosphonium hydroxide, butyltriphenylphosphonium hydroxide, amyltriphenylphosphonium hydroxide, heptyltriphenylphosphine Hexyltriphenylphosphonium hydroxide, octyltriphenylphosphonium hydroxide, tetradecyltriphenylphosphonium hydroxide, benzyltriphenylphosphonium hydroxide, ethoxybenzyltriphenylphosphonium < RTI ID = 0.0 > There may be mentioned, for example, hydroxides such as hydroxides, methoxymethyltriphenylphosphonium hydroxides, acetoxymethyltriphenylphosphonium hydroxides, phenacyltriphenylphosphonium hydroxides, chloromethyltriphenylphosphonium hydroxides, bromomethyltri Phenylphosphonium hydroxide, biphenyltriphenylphosphonium hydroxide, naphtyltriphenylphosphonium There may be mentioned, for example, a hydroxide, a chlorophenyltriphenylphosphonium hydroxide, a phenoxyphenyltriphenylphosphonium hydroxide, a methoxyphenyltriphenylphosphonium hydroxide, an acetoxyphenyltriphenylphosphonium hydroxide, a naphthylphenyl Mono (aryl or alkyl) triphenylphosphonium hydroxides such as triphenylphosphonium hydroxide; Monoaryltrialkylphosphonium hydroxides such as phenyltrimethylphosphonium hydroxide, biphenyltrimethylphosphonium hydroxide, phenyltrihexylphosphonium hydroxide, and biphenyltrihexylphosphonium hydroxide; Di (aryl or alkoxy) carbonyl groups such as dimethyldiphenylphosphonium hydroxide, diethyldiphenylphosphonium hydroxide, di (naphthyl) diphenylphosphonium hydroxide and di (biphenyl) Alkyl) diarylphosphonium hydroxides; Further, tetra (biphenyl) phosphonium tetraphenyl borate, tetra (biphenyl) phosphonium tetraphenyl borate, tetra (phenylphenyl) phosphonium tetraphenyl borate, and the like such as tetraphenylphosphonium tetraphenyl borate, tetranaphthylphosphonium tetraphenyl borate, Arylphosphonium tetraphenylborates; Methyltriphenylphosphonium tetraphenylborate, methyltriphenylphosphonium tetraphenylborate, ethyltriphenylphosphonium tetraphenylborate, propyltriphenylphosphonium tetraphenylborate, butyltriphenylphosphonium tetraphenylborate, octyltriphenylphosphonium tetraphenylborate, tetradecyltriphenyl Benzyltriphenylphosphonium tetraphenylborate, ethoxylbenzyltriphenylphosphonium tetraphenylborate, methoxymethyltriphenylphosphonium tetraphenylborate, acetoxymethyltriphenylphosphonium tetraphenylborate, phenacyltriphenylphosphonium tetraphenylborate, Triphenylphosphonium tetraphenylborate, triphenylphosphonium tetraphenylborate, chloromethyltriphenylphosphonium tetraphenylborate, bromomethyltriphenylphosphonium tetraphenylborate, biphenyltriphenylphosphonium tetraphenylborate, naphthyltriphenylphosphonium tetraphenylborate, chloro Phenyltriphenylphosphoniumtetate (Aryl or alkyl) triphenylphosphonium tetraphenylborate such as phenylborate, phenoxyphenyltriphenylphosphonium tetraphenylborate, acetoxyphenyltriphenylphosphonium tetraphenylborate, and naphthylphenyltriphenylphosphonium tetraphenylborate, etc., Ryu; Phenyltrimethylphosphonium tetraphenylborate, biphenyltrimethylphosphonium tetraphenylborate, biphenyltrimethylphosphonium tetraphenylborate, methyltrihexylphosphonium tetraphenylborate, ethyltrihexylphosphonium tetraphenylborate, octyltrihexylphosphonium tetraphenylborate, stearyltrihexylphosphate Monoaryltrialkylphosphonium tetraphenylborates such as phenyltriethylphosphonium tetraphenylborate, phenyltrihexylphosphonium tetraphenylborate, and biphenyltrihexylphosphonium tetraphenylborate; (Aryl or heteroaryl) groups such as dimethyldiphenylphosphonium tetraphenylborate, diethyldiphenylphosphonium tetraphenylborate, di (naphthyl) diphenylphosphonium tetraphenylborate and di (biphenyl) Alkyl) diarylphosphonium tetraphenylborates.
In addition to the above compounds, allyltriphenylphosphonium hydroxide, cinnamyltriphenylphosphonium hydroxide, and the like can also be used.
As the counter anion, an aryloxy group such as phenoxide may be used instead of the above hydroxide or tetraphenylborates. Alkyloxy groups such as methoxide and ethoxide; An alkylcarbonyloxy group such as acetate; Arylcarbonyloxy groups such as benzoate; And quaternary phosphonium salts using halogen atoms such as chloride and bromide.
More preferably, in the production of the polycarbonate, in the transesterification reaction, as a polymerization catalyst, a quaternary phosphonium salt containing (a) a nitrogen-containing organic basic compound and (b) ) Is preferably used in combination.
[Chemical Formula 9]
In the general formula (II-1), R 3 represents an organic group and may be the same or different from each other, and X 3 represents a halogen atom, a hydroxyl group, an alkyloxy group, an aryloxy group, an alkylcarbonyloxy group, group optionally, HCO 3, or BR 4 denotes a (R represents a hydrogen atom or a hydrocarbon group, is also possible to R 4 are the same or different), n represents an integer of 0-4.
Specific examples of such a quaternary phosphonium compound include, for example, tetraphenylphosphonium hydroxide, biphenyltriphenylphosphonium hydroxide, methoxyphenyltriphenylphosphonium hydroxide, phenoxyphenyltriphenyl Phosphonium hydroxide, phosphonium hydroxide, naphthylphenyltriphenylphosphonium hydroxide, tetraphenylphosphonium tetraphenylborate, biphenyltriphenylphosphonium tetraphenylborate, methoxyphenyltriphenylphosphonium tetraphenylborate, phenoxyphenyl tri Phenylphosphonium tetraphenylborate, phenylphosphonium tetraphenylborate, naphthylphenyltriphenylphosphonium tetraphenylborate, tetraphenylphosphonium phenoxide, biphenyltriphenylphosphonium phenoxide, methoxyphenyltriphenylphosphonium phenoxide, phenoxyphenyltriphenylphosphine Naphthylphenyltriphenylphosphonium phenoxide, tetraphenylphosphonium chloride, bis Phenyltriphenylphosphonium chloride, methoxyphenyltriphenylphosphonium chloride, phenoxyphenyltriphenylphosphonium chloride, naphthylphenyltriphenylphosphonium chloride, and the like.
Among the quaternary phosphonium salts (b), from the viewpoint of balance between the activity due to thermal stability during the reaction and the quality of the obtained polycarbonate, tetraarylphosphonium tetraphenylborate, tetraarylphosphonium phenoxide, monoaryl tri Phenylphosphonium borate and monoaryltriphenylphosphonium phenoxide are preferable, and tetraphenylphosphonium tetraphenylborate is particularly preferable.
That is, the quaternary phosphonium salt which does not contain an alkyl group as the component (b) is excellent in thermal stability and is effective for increasing the molecular weight of the latter part of the reaction. These (b) quaternary phosphonium salts may be used alone or in combination of two or more.
The quaternary phosphonium salt (a) containing a nitrogen-containing organic basic compound and (b) an aryl group preferably has a metal impurity content of 50 mass ppm or less, and the content of the alkali metal and alkaline earth metal compound is preferably 30 mass% ppm or less, and particularly preferably 10 mass ppm or less.
The total amount of each of the metal impurities in the component (a) and the component (b) is preferably 50 mass ppm or less based on the total amount of the component (a) and the component (b) The content of the alkali metal and the alkaline earth metal compound in the component is more preferably 30 mass ppm or less, particularly preferably 10 mass ppm or less, relative to the total amount of the component (a) and the component (b).
In the present invention, as the polymerization catalyst, the nitrogen-containing organic basic compound of the component (a) is added in an amount of from 10 -1 to 10 -8 mol, preferably from 10 -2 to 10 -8 mol, per mol of the dihydroxy compound, 10 -7 mol, more preferably 10 -3 to 10 -6 mol to use and, (b) 4-level including an aryl phosphonium salt of the component 10 -1 to 10 -8 mol, preferably 10 -2 To 10 -7 moles, and more preferably 10 < -3 > to 10 -6 moles.
If the amount of the component (a) is less than 10 -8 mol, the catalytic activity in the initial stage of the reaction becomes insufficient, and if it exceeds 10 -1 mol, the increase in cost leads to an increase in cost. On the other hand, if the amount of the component (b) is less than 10 -8 mol, the catalytic activity in the latter half of the reaction becomes insufficient, and if it exceeds 10 -1 mol, the increase in cost leads to an increase in cost.
In addition, the polymerization catalyst to the total amount of, (a) component and the (b) component with respect to 1 mol of the dihydroxy compound containing component (A), the starting material for example, typically 2 × 10 -1 ~ 2 × 10 - 8 mol, preferably 2 10 -2 to 2 10 -7 mol, and more preferably 2 10 -3 to 2 10 -6 mol. If the added amount of the catalyst is less than 2 x 10 < -8 > mol, the catalyst effect may not be exhibited. On the other hand, if it exceeds 2 x 10 < -1 > mol, there is a possibility that the physical properties of the polycarbonate as a final product, in particular, heat resistance and hydrolysis resistance are lowered. In addition, none.
Further, in the production of the polycarbonate, the polymerization activity can be increased by using a combination of (a) a nitrogen-containing organic basic compound and (b) a quaternary phosphonium salt containing an aryl group as a polymerization catalyst, Among the finally obtained polycarbonates, it is preferable that the number of metals which adversely affect the hydrolysis resistance and coloring property is minimized. That is, in the production of the polycarbonate in the present invention, the use of the metal catalyst which has been used in the latter half of the reaction by the component (b) is substantially unnecessary.
In the present invention, in the production of the polycarbonate, the raw materials provided for the production of the polycarbonate by the ordinary ester exchange method are used, but preferably the dihydroxy compound of the component (A) and the carbonic acid diester of the component (B) And, if necessary, an ester interchange reaction using an end terminator or a branching agent to obtain a polycarbonate. Specifically, the reaction may be carried out according to a known transesterification method. Hereinafter, the order and conditions of the preferred production method of the present invention are specifically shown.
First, the dihydroxy compound of the component (A) and the carbonic acid diester of the component (B) are transesterified at a ratio of 0.9 to 1.5 times the amount of the carbonic acid diester to the dihydroxy compound. Further, it is preferably 0.98 to 1.20 times, depending on the situation.
In the above transesterification reaction, when the amount of the terminal stopper made of monovalent phenol or the like is in the range of 0.05 to 10 mol% with respect to the dihydroxy compound as the component (A), the hydroxyl group of the obtained polycarbonate Since the end is sealed, a polycarbonate having a sufficiently high heat resistance and water resistance can be obtained. The above-mentioned terminal stopper made of monovalent phenol or the like may be added to the reaction system in its entirety in advance, or may be added in advance to the reaction system, and the remainder may be added along with the progress of the reaction. In some cases, the esterification reaction between the dihydroxy compound of the component (A) and the carbonic acid diester of the component (B) may be partially followed by the total addition to the reaction system.
In carrying out the transesterification reaction, the reaction temperature is not particularly limited and is usually selected in the range of 100 to 330 ° C, preferably 180 to 300 ° C, but more preferably, It is preferable to raise the temperature gradually to 180 to 300 ° C. When the ester exchange reaction temperature is less than 100 ° C, the reaction rate is slowed. On the other hand, when the ester exchange reaction temperature is more than 330 ° C, a side reaction occurs, or a polycarbonate produced is colored.
The reaction pressure is set according to the vapor pressure of the monomer used or the reaction temperature. This is not limitative but may be set so that the reaction is carried out efficiently. (Atmospheric pressure) to a pressure of from 1 to 50 atm (760 to 38,000 torr) at the initial stage of the reaction, and in a reduced pressure state, preferably at a final pressure of 0.01 to 100 torr .
In addition, the reaction time may be set to the target molecular weight, usually 0.2 to 10 hours.
The ester exchange reaction is usually carried out in the absence of an inert solvent, but may be carried out in the presence of 1 to 150% by mass of an inert solvent of the obtained polycarbonate, if necessary. Examples of the inert solvent include aromatic compounds such as diphenyl ether, halogenated diphenyl ether, benzophenone, polyphenyl ether, dichlorobenzene and methylnaphthalene; And cycloalkanes such as tricyclo (5, 2, 10) decane, cyclooctane, and cyclodecane.
The inert gas may be, for example, a gas such as argon, carbon dioxide, dinitrogen monoxide or nitrogen, chlorofluorohydrocarbon, an alkane such as ethane or propane, or an alkane such as ethylene or propylene And the like.
Further, in the production of the polycarbonate, in order to obtain a good quality (coloring) of the obtained polycarbonate after completion of the above-described transesterification reaction, the decomposition temperature of the catalyst is preferably at least 300 deg. C, more preferably 240 deg. Deg.] C to 350 [deg.] C, more preferably 260 [deg.] C to 330 [deg.] C, and particularly preferably 270 to 310 [deg.] C.
[Organophosphorus compound]
The organic phosphorus compound contained in the polycarbonate resin composition of the present invention is at least one selected from a phosphite compound and a phosphate compound.
The inventors of the present invention have found that the active species of the polymerization catalyst (organic basic catalyst) used in the production of the polycarbonate described above can be analyzed by analyzing the residual amount of the active polycarbonate in a trace amount and neutralizing the active species with the organic phosphorus compound Whereby a polycarbonate resin composition having excellent color tone was obtained.
For example, when tetraphenylphosphonium tetraphenylborate (TPTB) is used as an organic basic catalyst, tetraphenylphosphonium phenoxide in which bisphenol A (BPA) is activated by TPTB is neutralized and deactivated by a phosphite compound and a phosphate compound And is considered to be stabilized, and the effect of making the color tone of the resin composition extremely excellent can be exhibited. On the other hand, when sodium hydroxide which is a strong base is used as the inorganic basic catalyst, sodium phenoxide activated with sodium hydroxide can not be neutralized by the phosphite compound and phosphate compound and becomes like sodium phosphate, Which is considered to act in polycarbonate, and can not exhibit the effect of making the color tone of the resin composition excellent.
Examples of the phosphite compound include triphenylphosphite, trisnonylphenylphosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecylphosphite, trioctylphosphite, Decyl phosphite, dodecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyldiphenyl phosphite, monoctyldiphenyl phosphite, distearyl (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2'-methylenebis (4,6-di-tert- butylphenyl) octylphosphite , Bis (nonylphenyl) pentaerythritol diphosphite and bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite.
Among these, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,6-di-tert- butyl-4-methylphenyl) pentaerythritol diphosphite and 2,2'- 4,6-di-tert-butylphenyl) octyl phosphite is preferable. The phosphite compounds may be used alone or in combination of two or more.
The phosphate compound includes, for example, tributyl phosphate, trimethyl phosphate, trioctyl phosphate, octyldiphenyl phosphate, cresyldiphenyl phosphate, tricresyl phosphate, tri (2-ethylhexyl) phosphate, diisopropylphenyl phosphate, But are not limited to, triphenylphosphine, triphenylphosphate, triethylphosphate, diphenylcresylphosphate, diphenylmonoctalkenylphosphate, tributoxyethylphosphate, dibutylphosphate, dioctylphosphate, diisopropylphosphate, (Diphenylphosphate), hydroquinone bisphosphate, resorcinbisphosphate, resorcinol-diphenylphosphate, trioxylbenzene tri (triphenylphosphine) phosphate, bisphenol A bisphosphate, Phosphate, 1,3-phenylene-tetra Lacquis (2,6-dimethylphenyl) phosphate ester, and the like.
Among them, triphenyl phosphate, bisphenol A bis (diphenylphosphate) and 1,3-phenylene-tetrakis (2,6-dimethylphenyl) phosphoric acid ester are preferable. The phosphate compound may be used alone or in combination of two or more.
In the polycarbonate resin composition of the present invention, the content of the at least one organic phosphorus compound selected from the phosphite compound and the phosphate compound is 0.001 to 0.5 part by mass, preferably 0.003 to 0.2 part by mass based on 100 parts by mass of the polycarbonate Mass part, more preferably 0.003 to 0.1 mass part. If the content is less than 0.001 parts by mass, the effect of improving the color tone of the resin composition can not be exhibited. If the content is more than 0.5 parts by mass, deterioration of the function such as poor moisture resistance of the resin composition occurs.
The phosphite compound and the phosphate compound may be used alone or in combination. The content of the phosphite compound and the phosphate compound when used together indicates the total amount of the phosphite compound and the phosphate compound.
[Polycarbonate resin composition]
The organophosphorus compound may be introduced into the reactor at the completion of the transesterification reaction in the production of the polycarbonate, or may be kneaded by being fed into a twin-screw extruder or the like at the time of granulating the polycarbonate.
In the polycarbonate resin composition of the present invention, well-known additives such as a plasticizer, a pigment, a lubricant, a releasing agent, a stabilizer, an inorganic filler and the like can be blended in addition to the polycarbonate and the organic phosphorus compound. The polycarbonate resin composition of the present invention can be used.
The compounding and kneading are carried out by a commonly used method, for example, a method using a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single screw extruder, a twin screw extruder, a coneizer, a multiaxial screw extruder, can do. The heating temperature in the melt-kneading is usually selected in the range of 220 to 260 占 폚.
In addition, since the polycarbonate resin composition of the present invention uses the above-mentioned polymerization catalyst (organic basic catalyst) in the production of polycarbonate, unlike the case of using an inorganic base catalyst, The content of cesium and potassium may be less than 0.1 mass ppm each as an element.
Therefore, the polycarbonate resin composition of the present invention has excellent heat resistance and excellent color tone.
Example
EXAMPLES The present invention will be described more specifically by the following examples, but the present invention is not limited to these examples.
The quality evaluation in Examples and Comparative Examples was carried out by the following methods.
(1) Quantitative analysis of metal contents (Na, Cs and K)
The obtained polycarbonate pellets were dissolved in N-methylpyrrolidone (NMP) to prepare a 1 mass% solution, and Na, Cs and K were quantitatively determined by standard method of indium using ICP-MS 7500cs manufactured by Agilent.
(2) Hue (absorbance measurement)
The obtained polycarbonate pellets were subjected to a thermal stability test at 360 DEG C for 1 hour under a nitrogen atmosphere and the obtained sample was dissolved in methylene chloride to prepare a 5 mass% solution, which was then added to a 5 cm quartz cell And the absorbance at a wavelength of 420 nm was measured using UV-2450 manufactured by Shimadzu Corporation. The color tone was evaluated by the difference in absorbance before and after the thermal stability test (? Abs 420 ).
(3) Mv (viscosity average molecular weight)
The viscosity of the methylene chloride solution at 20 캜 was measured using a Ubero type viscometer, and the intrinsic viscosity [?] Was determined therefrom. [?] = 1.23 10 -5 Mv 0 . 83 , the viscosity average molecular weight (Mv) was calculated.
[Examples 1 to 6]
The internal volume 200 ㎖ of Ni force flask, bisphenol A (BPA) to 22.8 g (0.10 ㏖), was added to the type and amount of catalyst represents the diphenyl carbonate in 23.5 g (0.11 ㏖), and Table 1, and N 2 After performing the substitution five times, the mixture was heated to 180 DEG C and reacted at normal pressure for 30 minutes. Then, the temperature was raised to 210 DEG C, the degree of vacuum was raised to 100 mmHg, and the reaction was carried out for 30 minutes. Then, the temperature was raised to 240 캜, the degree of vacuum was raised to 10 mmHg, and the reaction was carried out for 30 minutes. Subsequently, the temperature was raised to 270 ° C, the degree of vacuum was raised to 2 mmHg, and the reaction was allowed to proceed for 30 minutes, and then the degree of vacuum was increased to 0.5 mmHg and further reacted for 30 minutes. At this point, polycarbonate was sampled to measure Mv (viscosity average molecular weight).
Thereafter, the organic phosphorus compound in the amount shown in the table was added as a toluene solution into the reaction system and kneaded for 5 minutes to obtain a polycarbonate resin composition, which was then pelletized by an extruder. Table 1 shows the metal amount, color tone and Mv measured by the above method.
[Comparative Example 1]
The procedure of Example 1 was repeated except that the organic phosphorus compound was not added. Table 1 shows the metal amount, color tone and Mv measured by the above method.
[Comparative Examples 2 to 5]
The reaction was carried out at the same temperature and pressure as in Example 1 except that TPTB (b) used as the catalyst in Example 1 was replaced with sodium hydroxide (NaOH). The polycarbonate obtained was sampled and Mv was measured.
Next, the deactivation agent (p-TsOBu: p-toluenesulfonic acid butyl) in the amount shown in the table was added to the reaction system as a toluene solution and kneaded for 15 minutes. Thereafter, the organic phosphorus compound in the amount shown in the table was added as a toluene solution into the reaction system and kneaded for 5 minutes to obtain a polycarbonate resin composition, which was then pelletized by an extruder. Table 1 shows the metal amount, color tone and Mv measured by the above method.
[Comparative Examples 6 to 8]
(P-TsOBu) and the organophosphorus compound were added in place of the cobalt carbonate (Cs 2 CO 3 ) used in the comparative example 2, and the amount of the deactivator (p-TsOBu) Respectively. Table 1 shows the metal amount, color tone and Mv measured by the above method.
From the results of Comparative Examples 2 and 6, it can be seen that the color tone of the resin composition is inferior to that of Examples, when the inorganic basic catalyst of NaOH or Cs 2 CO 3 is used and a deactivator is added. In Comparative Examples 3 to 5, 7 and 8, even when the inorganic basic catalyst is combined with the organophosphorus compound which is a phosphite and a phosphate compound, the effect of improving the color tone is not exhibited.
From the contrast of Comparative Example 1 and Examples 1 to 6, it can be seen that the effect of dramatically improving the color tone is obtained by mixing the organophosphorus compound.
Industrial availability
The polycarbonate resin composition of the present invention is useful in electric / electronic fields, automobile fields, optical parts fields, and other wide industrial fields because of excellent heat resistance and excellent color tone.
Claims (17)
Wherein the content of sodium, cesium and potassium is 0.1 mass ppm or less as an element.
(a) a polycarbonate resin composition wherein the nitrogen-containing organic basic compound is a quaternary ammonium salt.
(a) the nitrogen-containing organic basic compound is a compound represented by the following general formula (I).
(NR 1 4 ) + (X 1 ) - (I)
[Wherein R 1 represents an alkyl group, an aryl group or an alkylaryl group, four R 1 s may be the same as or different from each other, and two R 1 s may combine to form a cyclic structure. X 1 represents a halogen atom, a hydroxyl group, an alkyloxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, HCO 3 or BR 4 (R represents a hydrogen atom or an alkyl group or an aryl group, They may be the same or different).
(b) a polycarbonate resin composition wherein the quaternary phosphonium salt containing an aryl group is a compound represented by the following general formula (II).
(PR 2 4 ) + (X 2 ) - (II)
Wherein R 2 represents an alkyl group, an aryl group or an alkylaryl group, but at least one of the four R 2 s is an aryl group. In addition, the four R 2 are also the same as or different from each other, or may form a ring structure, and 2 and one R 2 is a bond. X 2 represents a halogen atom, a hydroxyl group, an alkyloxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, HCO 3 or BR 4 (R represents a hydrogen atom or an alkyl group or an aryl group, They may be the same or different).
Wherein the raw material for the transesterification reaction is (A) a dihydroxy compound and (B) a carbonic acid diester.
(A) the polycarbonate resin composition wherein the dihydroxy compound is 2,2-bis (4-hydroxyphenyl) propane.
(B) the polycarbonate resin composition in which the carbonic acid diester is diphenyl carbonate.
wherein the nitrogen-containing organic basic compound (a) is tetramethylammonium hydroxide, and (b) the quaternary phosphonium salt containing an aryl group is tetraphenylphosphonium tetraphenylborate.
(2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2'-methylenebis Bisphenol A bis (diphenylphosphate), and 1,3-phenylene-tetrakis (2,6-dimethylphenyl) phosphoric acid ester Wherein the polycarbonate resin composition is at least one selected from the group consisting of a polycarbonate resin and a polycarbonate resin.
A method for producing a polycarbonate resin composition, comprising: heat-treating a reaction product at a temperature not lower than a decomposition temperature of a polymerization catalyst after completion of an ester exchange reaction to obtain a polycarbonate resin composition.
(a) a method for producing a polycarbonate resin composition wherein the nitrogen-containing organic basic compound is a quaternary ammonium salt.
(a) the nitrogen-containing organic basic compound is a compound represented by the following general formula (I).
(NR 1 4 ) + (X 1 ) - (I)
[Wherein R 1 represents an alkyl group, an aryl group or an alkylaryl group, four R 1 s may be the same as or different from each other, and two R 1 s may combine to form a cyclic structure. X 1 represents a halogen atom, a hydroxyl group, an alkyloxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, HCO 3 or BR 4 (R represents a hydrogen atom or an alkyl group or an aryl group, They may be the same or different).
(b) a quaternary phosphonium salt containing an aryl group is a compound represented by the following general formula (II).
(PR 2 4 ) + (X 2 ) - (II)
Wherein R 2 represents an alkyl group, an aryl group or an alkylaryl group, but at least one of the four R 2 s is an aryl group. In addition, the four R 2 are also the same as or different from each other, or may form a ring structure, and 2 and one R 2 is a bond. X 2 represents a halogen atom, a hydroxyl group, an alkyloxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, HCO 3 or BR 4 (R represents a hydrogen atom or an alkyl group or an aryl group, They may be the same or different).
Wherein the temperature at which the reaction product is heat-treated is not less than 240 ° C and not more than 350 ° C.
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| JPJP-P-2012-025213 | 2012-02-08 | ||
| JP2012025213A JP2013159755A (en) | 2012-02-08 | 2012-02-08 | Polycarbonate resin composition |
| PCT/JP2013/052099 WO2013118624A1 (en) | 2012-02-08 | 2013-01-30 | Polycarbonate resin composition |
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| KR (1) | KR20140127208A (en) |
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| EP3911694A1 (en) * | 2019-01-17 | 2021-11-24 | Basf Se | Process for producing porous materials |
| JP2024049857A (en) * | 2022-09-29 | 2024-04-10 | 三菱エンジニアリングプラスチックス株式会社 | Polycarbonate resin composition |
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| US7786195B2 (en) * | 2004-11-05 | 2010-08-31 | Teijin Chemicals Ltd. | Spectacle lens and polycarbonate resin molding material for optical moldings |
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