KR101349711B1 - End-cappled and Branched Polycarbonate Resin and Method for Preparing the Same - Google Patents
End-cappled and Branched Polycarbonate Resin and Method for Preparing the Same Download PDFInfo
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Abstract
The end capped branched polycarbonate resin according to the present invention is prepared by melt polymerizing the end capped linear polycarbonate and the branching agent, and has excellent stability at high temperature, and a process for producing the end capped branched polycarbonate according to the present invention. Silver (1) polymerized aromatic dihydroxy compounds and diaryl carbonates to produce end-capped carbonate oligomers, and (2) melt polymerization of the end-capped carbonate oligomers and linear polycarbonates to produce end-capped linear polycarbonates. And (3) preparing a terminally capped branched polycarbonate by adding a branching agent to the terminally capped linear polycarbonate, and being environmentally friendly and economical.
Description
The present invention relates to an end capped branched polycarbonate resin and a method for producing the same. More specifically, the present invention relates to an end capped branched polycarbonate resin having excellent stability at high temperature and a method for producing an environmentally friendly and economical end capped branched polycarbonate resin.
Polycarbonate resin is a transparent polymer material having excellent heat resistance and impact resistance, and is widely used in compact discs, structures, and optical films due to its excellent physical properties, and the demand for polycarbonate resin is rapidly increasing.
Recently, polycarbonate resins have been used considerably for the manufacture of hollow containers through blow molding, in which case polycarbonate resins require high strength in the molten state.
As a method of imparting high melt strength to the polycarbonate resin, there is a method of introducing an appropriate amount of branching agent into the polycarbonate resin.
U.S. Patent No. 4,959,422 discloses a process for preparing branched polycarbonate resins by introducing a branching agent that has three epoxy functional groups in one molecule. U.S. Patent No. 6,022,941 discloses a process for producing branched polycarbonate resins using a branching agent having several acrylate functional groups. U.S. Patent No. 6,437,083 discloses a process for producing a branched polycarbonate resin using a conventional branching agent and methyl salicyl carbonate together.
On the other hand, production processes used to produce branched polycarbonate resins include interfacial polymerization processes using phosgene, melt polymerization processes without phosgene, and solid phase polymerization processes.
The interfacial polymerization process involves dissolving a branching agent such as 1,1,1-tris (4-hydroxyphenyl) ethane in an appropriate amount in an aromatic hydroxy compound such as bisphenol A, as disclosed in US Pat. No. 3,799,953. An aqueous solution and an organic solvent such as methylene chloride are mixed, and polymerization is carried out using gaseous or liquid phosgene to prepare a branched polycarbonate resin. However, this interfacial polymerization process requires the use of highly toxic phosgene and a toxic solvent such as methylene chloride.
Solid phase polymerization process, as disclosed in US Patent No. 5,710,238, after the low molecular weight of the branched polycarbonate is prepared using a melt polymerization method and crystallized it, and polymerization using a fluidized bed reactor or the like at a temperature lower than the melting temperature Proceed with the reaction. However, this solid phase polymerization process has an uneconomical problem of using a large amount of solvent for crystallization and a large amount of hot nitrogen.
The melt polymerization process is a method of proceeding polymerization in a state in which monomers used as raw materials are melted, and are economical by not using an organic solvent and are a safe and environmentally friendly method of producing phosgene.
U.S. Patent No. 4,888,400 discloses a process for producing branched polycarbonate by injecting and extruding an appropriate amount of branching agent into a linear polycarbonate resin having a weight average molecular weight of 10,000 to 30,000. However, polycarbonate resins, which are not capped at the end, have a problem in that toxic phenol occurs when the product is discolored or exposed to high temperatures during injection or extrusion at high temperatures.
Therefore, in the melt polymerization process, there is a demand for a method for producing a branched polycarbonate resin having a capped end.
It is an object of the present invention to provide end capped branched polycarbonate resins.
Another object of the present invention is to provide an end capped branched polycarbonate resin having excellent stability at high temperatures.
It is another object of the present invention to provide a process for producing the end capped branched polycarbonate resin.
It is another object of the present invention to provide a method for producing an end capped branched polycarbonate resin which is environmentally friendly and economical.
The above and other objects of the present invention can be achieved by the present invention described below.
The end capped branched polycarbonate resin according to the present invention is prepared by melt polymerizing the end capped linear polycarbonate and branching agent, having a weight average molecular weight of 30,000 to 200,000, and a terminal hydroxyl group content of 0 to 8 mol%. .
The process for producing the end capped branched polycarbonate resin according to the present invention comprises (1) polymerizing an aromatic dihydroxy compound and a diaryl carbonate to prepare an end capped carbonate oligomer, (2) the end capped carbonate oligomer and Melt polymerizing the linear polycarbonate to produce an end capped linear polycarbonate, and (3) adding a branching agent to the end capped linear polycarbonate to produce an end capped branched polycarbonate.
In one embodiment of the present invention, the aromatic dihydroxy compound is a compound represented by the following formula (1) or a mixture thereof.
[Formula 1]
In
In one embodiment of the present invention, the diaryl carbonate is a compound represented by the following formula (2) or a mixture thereof.
(2)
In Formula 2, Ar 1 and Ar 2 are each independently an aryl group.
In one embodiment of the present invention, the first step produces 90 to 100 mol% of a compound represented by the following formula (3) or a mixture thereof.
(3)
In Formula 3, Ar 1 and Ar 2 are each independently an aryl group, B 1 is a residue from which two hydroxy groups at both ends of the aromatic dihydroxy compound are removed, and n represents a natural number of 1 to 5 .
In one embodiment of the invention, the molar ratio of the diaryl carbonate / aromatic dihydroxy compound is 1.2 to 2.5.
In one embodiment of the present invention, in the first step, a metal compound catalyst system, a nonmetal compound catalyst system, and mixtures thereof are used as the transesterification catalyst.
In one embodiment of the present invention, the metal compound catalyst system is used in 10 -3 to 10 -8 moles per 1 mole of the aromatic dihydroxy compound, the non-metal compound catalyst system is 10 - per mole of the aromatic dihydroxy compound. It is used in 1 to 10 -6 moles.
In one embodiment of the present invention, the first step is the reaction temperature is 150 to 350 o C, the reaction pressure starts at atmospheric pressure at the beginning of the reaction, gradually maintained a reduced pressure, and finally to 0.01 to 100 mbar , Reaction time is 0.5 to 10 hours.
In one embodiment of the present invention, the weight average molecular weight of the linear polycarbonate is 10,000 to 30,000.
In one embodiment of the present invention, the second step produces 90 to 100 mol% of a compound represented by the following formula (4) or a mixture thereof.
[Chemical Formula 4]
In Formula 4, Ar 1 and Ar 2 are each independently an aryl group, B 1 is a residue from which two hydroxy groups at both ends of the aromatic dihydroxy compound are removed, and m represents a natural number of 40 to 120. .
In one embodiment of the invention, the end capped carbonate oligomer is used in an amount of 1 to 1.05 moles, relative to 1 mole of terminal hydroxyl groups of the linear polycarbonate.
In one embodiment of the present invention, the second step is the reaction temperature is 200 to 380 ° C., the reaction pressure is 0 to 50 mmHg.
In one embodiment of the present invention, an extruder reactor is used in the second step.
In one embodiment of the invention, the branching agent is 1,1,1-tris (4-hydroxy phenyl) ethane, 1,3,5-tris (2-hydroxyethyl) cyanuric acid, 4,6- Dimethyl-2,4,6-tris- (4-hydroxyphenyl) -heptane-2,2,2-bis [4,4 '-(dihydroxyphenyl) cyclohexyl] propane, 1,3,5- Trihydroxybenzene, 1,2,3-trihydroxybenzene, 1,4-bis- (4 ', 4' '-dihydroxytriphenylmethyl) -benzene, 2', 3 ', 4'-tree Hydroxyacetone phenone, 2,3,4-trihydroxybenzoic acid, 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2 ', 4', 6'- Trihydroxy-3- (4-hydroxyphenyl) propiophenone, pentahydroxyflavone, 3,4,5-trihydroxyphenylethylamine, 3,4-trihydroxyphenylethyl alcohol, 2,4, With 5-trihydroxypyrimidyl, tetrahydroxy-1,4-quinone hydrate, 2,2 ', 4,4'-tetrahydroxybenzophenone and 1,2,5,8-tetrahydroxyanthraquinone Lure which is selected from the group.
In one embodiment of the present invention, the end capped branched polycarbonate prepared by the third step has a weight average molecular weight of 30,000 to 200,000, and a terminal hydroxyl group content of 0 to 8 mol%.
In one embodiment of the present invention, the third step is a reaction temperature of 200 to 380 o C, a reaction pressure of 0 to 100 mmHg, the reaction time is 10 to 60 minutes.
In one embodiment of the present invention, an extruder reactor is used in the third step.
In one embodiment of the invention, the second and third stages are run continuously in one extruder reactor.
Hereinafter, the present invention will be described in detail.
The end capped branched polycarbonate resin according to the present invention is excellent in stability at high temperatures, and the process for producing the end capped branched polycarbonate according to the present invention is environmentally friendly and economical.
1 is a process flow diagram of a method for producing an end capped branched polycarbonate resin according to an embodiment of the present invention.
The end capped branched polycarbonate resin according to the present invention is prepared by melt polymerizing the end capped linear polycarbonate and branching agent, having a weight average molecular weight of 30,000 to 200,000, and a terminal hydroxyl group content of 0 to 8 mol%. .
end Capped Branched Polycarbonate Resin
The end capped branched polycarbonate resin according to the invention is prepared by melt polymerizing the end capped linear polycarbonate and branching agent.
In one embodiment of the present invention, the end-capped linear polycarbonate comprises 90 to 100 mol%, preferably 95 to 100 mol% of a compound represented by the following formula (4) or a mixture thereof. In this case, stability at high temperature can be excellent. The content can be calculated by measuring the content of aryl carbonate through NMR analysis.
[Chemical Formula 4]
In Formula 4, Ar 1 and Ar 2 are each independently an aryl group, B 1 is a residue from which two hydroxy groups at both ends of the aromatic dihydroxy compound are removed, and m represents a natural number of 40 to 120. .
In one embodiment of the present invention, examples of the aromatic dihydroxy compound constituting the main chain of Formula 4 is bis (4-hydroxy phenyl) methane, bis (3-methyl-4- hydroxy phenyl) methane, bis (3 -Chloro-4-hydroxy phenyl) methane, bis (3,5-diburomo-4-hydroxy phenyl) methane, 1,1-bis (4-hydroxy phenyl) ethane, 1,1-bis (2- Tert-butyl-4-hydroxy-3-methyl phenyl) ethane, 2,2-bis (4-hydroxy phenyl) propane (bisphenol A), 2,2-bis (3-methyl-4-hydroxy phenyl Propane, 2,2-bis (2-methyl-4-hydroxy phenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxy phenyl) propane, 1,1-bis (2-3) Tert-butyl-4-hydroxy-5-methyl phenyl) propane, 2,2-bis (3-chloro-4-hydroxy phenyl) propane, 2,2-bis (3-fluoro-4-hydroxy phenyl ) Propane, 2,2-bis (3-bromo-4-hydroxy phenyl) propane, 2,2-bis (3,5-difluoro-4-hydroxy phenyl) propane, 2,2-ratio (3,5-dichloro-4-hydroxy phenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxy phenyl) propane, 2,2-bis (4-hydroxy phenyl) butane , 2,2-bis (4-hydroxy phenyl) octane, 2,2-bis (4-hydroxy phenyl) phenyl methane, 2,2-bis (4-hydroxy-1-methyl phenyl) propane, 1, 1-bis (4-hydroxy-tert-butyl phenyl) propane, 2,2-bis (4-hydroxy-3-bromo phenyl) propane, 2,2-bis (4-hydroxy-3,5 -Dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethyl phenyl) propane, 2,2-bis (4-hydroxy-3-chloro phenyl) propane, 2,2-bis ( 4-hydroxy-3,5-dichloro phenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromo phenyl) propane, 2,2-bis (4-hydroxy-3,5 -Dibromo phenyl) propane, 2,2-bis (3-bromo-4-hydroxy-5-chloro phenyl) propane, 2,2-bis (3-phenyl-4-hydroxy phenyl) propane, 2 , 2-bis (4-hydroxyphenyl) butane, 2,2-bis (3-methyl-4-ha Idoxy phenyl) butane, 1,1-bis (2-butyl-4-hydroxy-5-methyl phenyl) butane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methyl phenyl ) Butane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methyl phenyl) isobutane, 1,1-bis (2-tert-amyl-4-hydroxy-5-methyl Phenyl) butane, 2,2-bis (3,5-dichloro-4-hydroxy phenyl) butane, 2,2-bis (3,5-dibromo-4-hydro phenyl) butane, 4,4-bis (4-hydroxy phenyl) heptane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methyl phenyl) heptane, 2,2-bis (4-hydroxy phenyl) octane, or 1 Bis (hydroxy aryl) alkanes such as, 1- (4-hydroxyphenyl) ethane; 1,1-bis (4-hydroxy phenyl) cyclopentane, 1,1-bis (4-hydroxy phenyl) cyclo hexane, 1,1-bis (3-methyl-4-hydroxy phenyl) cyclo hexane, 1 , 1-bis (3-cyclohexyl-4-hydroxy phenyl) cyclo hexane, 1,1-bis (3-phenyl-4-hydroxy phenyl) cyclo hexane, or 1,1-bis (4-hydroxy phenyl Bis (hydroxy aryl) cyclo alkanes such as) -3,5,5-trimethylcyclohexane; Bis (hydroxy aryl) ethers such as bis (4-hydroxy phenyl) ether or bis (4-hydroxy-3-methyl phenyl) ether; Bis (hydroxyaryl) sulfide such as bis (4-hydroxyphenyl) sulfide or bis (3-methyl-4-hydroxyphenyl) sulfide; Bis (hydroxyaryl) sulfoxide such as bis (hydroxyphenyl) sulfoxide, bis (3-methyl-4-hydroxyphenyl) sulfoxide or bis (3-phenyl-4-hydroxyphenyl) sulfoxide; Bis (hydroxy aryl) sulfones such as bis (4-dihydroxy phenyl) sulfone, bis (3-methyl-4-hydroxy phenyl) sulfone, or bis (3-phenyl-4-hydroxy phenyl) sulfone; 4,4'-dihydroxy phenyl, 4,4'-dihydroxy-2,2'-dimethylbiphenyl, 4,4'-dihydroxy-3,3'-dimethylbiphenyl, 4,4 ' Dihydroxy biphenyls such as -dihydroxy-3,3'-dicyclobiphenyl or 3,3-difluoro-4,4'-dihydroxybiphenyl; Dihydroxy benzene such as resorcinol or hydroquinone; 3-Methyl Resorcinol, 3-Ethyl Resorcinol, 3-Profisorcinol, 3-Butyl Resorcinol, 3-tert-Butyl Resorcinol, 3-Phenyl Resorcinol , 2,3,4,6-tetrafluororesorcinol, 2,3,4,6-tetrabromoresorcinol, catechol, 3-methylhydroquinone, 3-ethylhydroquinone, 3-propyl Hydroquinone, 3-butylhydroquinone, 3-tert-butylhydroquinone, 3-phenylhydroquinone, 3-gyumilhydroquinone, 2,5-dichlorohydroquinone, 2,3,5,6-tetramethylhydroquinone Or halogen such as 2,3,5,6-tetra-tert-butylhydroquinone, 2,3,5,6-tetrafluorohydroquinone, or 2,3,5,6-tetrabromohydroquinone; Alkyl substituted dihydroxy benzene and the like.
In one embodiment of the present invention, the aromatic dihydroxy compound constituting the main chain of
In one embodiment of the present invention, the branching agent is a compound having three or more hydroxyl groups, carboxyl groups, carboxyl ester groups or anhydrous carboxyl groups or mixtures thereof.
Examples of the branching agents include 1,1,1-tris (4-hydroxy phenyl) ethane, 1,3,5-tris (2-hydroxyethyl) cyanuric acid, 4,6-dimethyl-2,4, 6-tris- (4-hydroxyphenyl) -heptane-2,2,2-bis [4,4 '-(dihydroxyphenyl) cyclohexyl] propane, 1,3,5-trihydroxybenzene, 1 , 2,3-trihydroxybenzene, 1,4-bis- (4 ', 4' '-dihydroxytriphenylmethyl) -benzene, 2', 3 ', 4'-trihydroxyacetonephenone, 2 , 3,4-trihydroxybenzoic acid, 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2 ', 4', 6'-trihydroxy-3- (4-hydroxyphenyl) propiophenone, pentahydroxyflavone, 3,4,5-trihydroxyphenylethylamine, 3,4-trihydroxyphenylethyl alcohol, 2,4,5-trihydroxypyri Midyl, tetrahydroxy-1,4-quinone hydrate, 2,2 ', 4,4'-tetrahydroxybenzophenone, 1,2,5,8-tetrahydroxyanthraquinone and the like.
In the present invention, the end capped branched polycarbonate resin has a weight average molecular weight of 30,000 to 200,000, and a terminal hydroxy group content of 0 to 8 mol%, preferably 0 to 3 mol%. When the terminal hydroxyl group content is within the above range, stability at high temperature may be excellent.
end Capped Method for producing branched polycarbonate resin
The process for producing the end capped branched polycarbonate resin according to the present invention comprises (1) polymerizing an aromatic dihydroxy compound and a diaryl carbonate to prepare an end capped carbonate oligomer, (2) the end capped carbonate oligomer and Melt polymerizing the linear polycarbonate to produce an end capped linear polycarbonate, and (3) adding a branching agent to the end capped linear polycarbonate to produce an end capped branched polycarbonate.
(1) Preparation of End Capped Carbonate Oligomers
The first step of the process for preparing end-capped branched polycarbonates is to prepare end-capped carbonate oligomers by polymerizing aromatic dihydroxy compounds and diaryl carbonates.
In the first step, a carbonate oligomer is produced by transesterification of the aromatic dihydroxy compound with the diaryl carbonate, and the terminal hydroxy group of the carbonate oligomer is converted into aryl carbonate by transesterification with diaryl carbonate. It is substituted and reaction byproducts such as phenol are released to the outside. 1, diphenyl carbonate (DPC) and bisphenol-A (BPA) react to produce end capped linear oligomers and phenols having a degree of polymerization n of 1 to 5 and phenol is discharged to the outside.
In one embodiment of the present invention, the aromatic dihydroxy compound is a compound represented by the following formula (1) or a mixture thereof.
[Formula 1]
In
Examples of the compound represented by Formula 1 include bis (4-hydroxy phenyl) methane, bis (3-methyl-4-hydroxy phenyl) methane, bis (3-chloro-4-hydroxy phenyl) methane, bis ( 3,5-dibromo-4-hydroxy phenyl) methane, 1,1-bis (4-hydroxy phenyl) ethane, 1,1-bis (2-tert-butyl-4-hydroxy-3-methyl Phenyl) ethane, 2,2-bis (4-hydroxy phenyl) propane (bisphenol A), 2,2-bis (3-methyl-4-hydroxy phenyl) propane, 2,2-bis (2-methyl- 4-hydroxy phenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxy phenyl) propane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methyl phenyl Propane, 2,2-bis (3-chloro-4-hydroxy phenyl) propane, 2,2-bis (3-fluoro-4-hydroxy phenyl) propane, 2,2-bis (3-bromo 4-hydroxyphenyl) propane, 2,2-bis (3,5-difluoro-4-hydroxy phenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxy phenyl) propane , 2,2-bis (3,5- Bromo-4-hydroxy phenyl) propane, 2,2-bis (4-hydroxy phenyl) butane, 2,2-bis (4-hydroxy phenyl) octane, 2,2-bis (4-hydroxy phenyl ) Phenyl methane, 2,2-bis (4-hydroxy-1-methyl phenyl) propane, 1,1-bis (4-hydroxy-tert-butyl phenyl) propane, 2,2-bis (4-hydroxy Oxy-3-bromo phenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethyl phenyl) propane, 2,2-bis (4-hydroxy-3-chloro phenyl) propane, 2,2-bis (4-hydroxy-3,5-dichloro phenyl) propane, 2,2-bis (4-hydroxy-3 , 5-dibromo phenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromo phenyl) propane, 2,2-bis (3-bromo-4-hydroxy-5- Chloro phenyl) propane, 2,2-bis (3-phenyl-4-hydroxy phenyl) propane, 2,2-bis (4-hydroxy phenyl) butane, 2,2-bis (3-methyl-4- hydroxy Hydroxyphenyl) butane, 1,1-bis (2-butyl-4-hydroxy-5-meth Methyl phenyl) butane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methyl phenyl) butane, 1,1-bis (2-tert-butyl-4-hydroxy-5- Methyl phenyl) isobutane, 1,1-bis (2-tert-amyl-4-hydroxy-5-methyl phenyl) butane, 2,2-bis (3,5-dichloro-4-hydroxy phenyl) butane , 2,2-bis (3,5-dibromo-4-hydrophenyl) butane, 4,4-bis (4-hydroxy phenyl) heptane, 1,1-bis (2-tert-butyl-4 Bis (hydroxy aryl) alkanes such as -hydroxy-5-methyl phenyl) heptane, 2,2-bis (4-hydroxy phenyl) octane, or 1,1- (4-hydroxy phenyl) ethane; 1,1-bis (4-hydroxy phenyl) cyclopentane, 1,1-bis (4-hydroxy phenyl) cyclo hexane, 1,1-bis (3-methyl-4-hydroxy phenyl) cyclo hexane, 1 , 1-bis (3-cyclohexyl-4-hydroxy phenyl) cyclo hexane, 1,1-bis (3-phenyl-4-hydroxy phenyl) cyclo hexane, or 1,1-bis (4-hydroxy phenyl Bis (hydroxy aryl) cyclo alkanes such as) -3,5,5-trimethylcyclohexane; Bis (hydroxy aryl) ethers such as bis (4-hydroxy phenyl) ether or bis (4-hydroxy-3-methyl phenyl) ether; Bis (hydroxyaryl) sulfide such as bis (4-hydroxyphenyl) sulfide or bis (3-methyl-4-hydroxyphenyl) sulfide; Bis (hydroxyaryl) sulfoxide such as bis (hydroxyphenyl) sulfoxide, bis (3-methyl-4-hydroxyphenyl) sulfoxide or bis (3-phenyl-4-hydroxyphenyl) sulfoxide; Bis (hydroxy aryl) sulfones such as bis (4-dihydroxy phenyl) sulfone, bis (3-methyl-4-hydroxy phenyl) sulfone, or bis (3-phenyl-4-hydroxy phenyl) sulfone; Or 4,4'-dihydroxy phenyl, 4,4'-dihydroxy-2,2'-dimethylbiphenyl, 4,4'-dihydroxy-3,3'-dimethylbiphenyl, 4,4 Dihydroxy biphenyl such as' -dihydroxy-3,3'-dicyclobiphenyl, or 3,3-difluoro-4,4'-dihydroxybiphenyl.
Aromatic dihydroxy compounds that can be used in addition to the compound represented by
In one embodiment of the present invention, the compound represented by
In one embodiment of the present invention, the diaryl carbonate is a compound represented by the following formula (2) or a mixture thereof.
(2)
In Formula 2, Ar 1 and Ar 2 are each independently an aryl group.
Examples of the compound represented by Formula 2 include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, bis (m-cresyl) carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, or bisphenol A- Bisphenol carbonate and the like. Among them, it is preferable to use diphenyl carbonate which is inexpensive and has good reactivity.
In one embodiment of the present invention, the first step produces 90 to 100 mol%, preferably 95 to 100 mol%, of a compound represented by the following formula (3) or a mixture thereof.
(3)
In Formula 3, Ar 1 and Ar 2 are each independently an aryl group, B 1 is a residue from which two hydroxy groups at both ends of the aromatic dihydroxy compound are removed, and n represents a natural number of 1 to 5 .
In the present invention, in order to synthesize the end capped carbonate oligomer represented by Formula 3, the molar ratio of the diaryl carbonate and the aromatic dihydroxy compound is very important.
In one embodiment of the invention, the molar ratio of diaryl carbonate / aromatic dihydroxy compound is 1.2 to 2.5, preferably 1.2 to 2.0. When the molar ratio of the diaryl carbonate / aromatic dihydroxy compound is within the above range, 90 mole% or more of the end capped carbonate oligomer represented by Chemical Formula 3 may be generated.
As the transesterification catalyst that can be used in the present invention, a metal compound catalyst system and a non-metal compound catalyst system may be used independently or in combination.
The metal compound catalyst system may be alkali or alkaline earth metal hydroxide, acetate, alkoxide, carbonate, or hydride.
Examples of the nonmetallic compound catalyst system include tetramethyl ammonium hydroxide, tetramethyl ammonium acetate, tetramethyl ammonium formate, tetramethyl ammonium carbonate, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide, Quaternary ammonium salts such as tetraphenyl ammonium hydroxide and trimethylphenyl ammonium hydroxide; Tetramethyl phosphonium hydroxide, tetramethyl phosphonium acetate, tetramethyl phosphonium formate, tetramethyl phosphonium carbonate, tetraethyl phosphonium hydroxide, tetrapropyl phosphonium hydroxide, tetrabutyl phosphonium hydroxide Quaternary phosphonium salts such as tetraphenyl phosphonium hydroxide and trimethylphenyl phosphonium hydroxide; Primary, secondary or tertiary amine compounds; Or a compound derivative including nitrogen such as pyridine can be used.
In one embodiment of the present invention, the metal compound catalyst system is preferably used in 10 -3 to 10 -8 moles per 1 mole of the aromatic dihydroxy compound, the non-metal compound catalyst system is in 1 mole of the aromatic dihydroxy compound It is preferably used at 10 -1 to 10 -6 mole relative to. When the metal compound catalyst system and the non-metal compound catalyst system are used within the above range, an appropriate balance of thermal stability and reaction time can be maintained.
In one embodiment of the present invention, the first step is carried out at a reaction temperature of 150 to 350 o C, preferably at a reaction temperature of 180 to 320 o C. When the first step is carried out within the temperature range, the reaction rate is maintained at a certain level or more and there is no problem that side reactions occur or color.
In the present invention, the reaction pressure of the first step is not particularly limited, but is preferably appropriately adjusted so that the low boiling point reaction by-products generated during the reaction can be extracted out of the reactor. In one embodiment of the present invention, the reaction pressure of the first step may be started at atmospheric pressure in the initial stage of the reaction, to gradually maintain a reduced pressure, and finally to 0.01 to 100 mbar.
In one embodiment of the present invention, the reaction time of the first step is 0.5 to 10 hours. In this case, 90% or more of the end capped carbonate oligomer represented by Chemical Formula 3 may be produced.
There is no particular limitation on the type of reactor that can be used in the first step, but it is preferable to use a vessel-type reactor equipped with a stirrer. In addition, the reactor may be attached to a device for separating and purifying phenols or esters thereof, which are by-products generated by the transesterification reaction.
(2) Preparation of End Capped Linear Polycarbonate
The second step of the process for producing the end capped branched polycarbonate is the step of melt polymerizing the end capped carbonate oligomer and the linear polycarbonate produced in the first step to prepare the end capped linear polycarbonate.
In the second step, by transesterification, the terminal hydroxyl group of the linear polycarbonate is substituted with a residue except for the terminal aryl group of the terminal capped carbonate oligomer to produce a terminal capped linear polycarbonate (condensation polymerization), phenol Reaction byproducts such as these are discharged to the outside. 1, linear polycarbonate and end capped linear oligomer react in end-capping zone in an extruder reactor to produce end capped linear polycarbonate and phenol and phenol to vacuum pump (VAC). Is discharged to the outside.
The reason for reacting the end-capped carbonate oligomer and the linear polycarbonate is, through the end-capping process of replacing the terminal hydroxy group of the linear polycarbonate with residues except the terminal aryl group of the end-capped carbonate oligomer, This is to improve stability to high temperature, and to make the linear polycarbonate easily react with a branching agent containing three or more functional groups such as hydroxy groups in one molecule.
In the present invention, the linear polycarbonate can be prepared using the interfacial polymerization method, melt polymerization method, solid state polymerization method, etc., using the melt polymerization method is economical because no organic solvent, and does not use phosgene is safe And environmentally friendly.
In one embodiment of the present invention, the weight average molecular weight of the linear polycarbonate is 10,000 to 30,000.
In one embodiment of the present invention, the second step produces 90 to 100 mol%, preferably 95 to 100 mol% of a compound represented by the following formula (4) or a mixture thereof.
[Chemical Formula 4]
In Formula 4, Ar 1 and Ar 2 are each independently an aryl group, B 1 is a residue from which two hydroxy groups at both ends of the aromatic dihydroxy compound are removed, and m represents a natural number of 40 to 120. .
In the second step, the content of the end capped carbonate oligomer is determined by the content of the terminal hydroxyl group of the linear polycarbonate resin. The number of moles of the terminal hydroxyl group of the linear polycarbonate can be measured through NMR analysis.
In one embodiment of the invention, the end capped carbonate oligomer is used in an amount of 1 to 1.05 moles, relative to 1 mole of terminal hydroxyl groups of the linear polycarbonate. When the end capped carbonate oligomer is used in less than 1 mole, the end capping reaction may not be sufficient, and when used in excess of 1.05 mole, the amount of unreacted carbonate oligomer is increased to lower the molecular weight of the final product. Can be.
In one embodiment of the present invention, the second step is carried out at a reaction temperature of 200 to 380 o C, preferably at a reaction temperature of 230 to 350 o C. When the second step is carried out within the temperature range, the reaction rate is maintained at a certain level or more, and there is no problem that side reactions occur or color.
In the present invention, the reaction pressure of the second step is not particularly limited, but it is preferable that the low-boiling reaction by-products generated during the reaction are properly adjusted to be extracted out of the reactor. In one embodiment of the present invention, the reaction pressure of the second stage is 0 to 50 mmHg, preferably 0 to 10 mmHg.
In the second step, it is preferable to use an extruder-type reactor capable of sufficient residence time. 1, the linear polycarbonate and the end capped carbonate oligomer react in an end capping zone in an extruder reactor.
Examples of the extruder type reactor include a rotating disk reactor, a rotating cage reactor, and the like.
In one embodiment of the present invention, in the second step, an extruder type reactor capable of maintaining a residence time of about 2 hours may be used even if the melt viscosity of the high molecular weight linear polycarbonate is very high. An example of such a reactor is the Large Volume Process (Reacom) of BUSS, Switzerland.
(3) Preparation of End Capped Branched Polycarbonate
The third step of the process for producing the end-capped branched polycarbonate is to prepare the end-capped branched polycarbonate by adding a branching agent to the end-capped linear polycarbonate produced in the second step.
In the third step, the terminally capped linear polycarbonate is bonded to the branching agent through a process in which the terminal aryl group of the terminally capped linear polycarbonate is substituted with a residue except the functional group of the branching agent (condensation polymerization) This results in end capped branched polycarbonates. Referring to Figure 1, the end capped linear polycarbonate produced in the end capping zone and the branching agent (THPE) reacted in the branching zone in the extruder reactor, the end capped branched polycarbonate (Branched PC). ) And phenol are produced, and the phenol is discharged to the outside by a vacuum pump (VAC).
In one embodiment of the present invention, the branching agent is a compound having three or more hydroxyl groups, carboxyl groups, carboxyl ester groups or anhydrous carboxyl groups or mixtures thereof.
Examples of the branching agents include 1,1,1-tris (4-hydroxy phenyl) ethane, 1,3,5-tris (2-hydroxyethyl) cyanuric acid, 4,6-dimethyl-2,4, 6-tris- (4-hydroxyphenyl) -heptane-2,2,2-bis [4,4 '-(dihydroxyphenyl) cyclohexyl] propane, 1,3,5-trihydroxybenzene, 1 , 2,3-trihydroxybenzene, 1,4-bis- (4 ', 4' '-dihydroxytriphenylmethyl) -benzene, 2', 3 ', 4'-trihydroxyacetonephenone, 2 , 3,4-trihydroxybenzoic acid, 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2 ', 4', 6'-trihydroxy-3- (4-hydroxyphenyl) propiophenone, pentahydroxyflavone, 3,4,5-trihydroxyphenylethylamine, 3,4-trihydroxyphenylethyl alcohol, 2,4,5-trihydroxypyri Midyl, tetrahydroxy-1,4-quinone hydrate, 2,2 ', 4,4'-tetrahydroxybenzophenone, 1,2,5,8-tetrahydroxyanthraquinone and the like.
The amount of the branching agent is determined by the weight average molecular weight of the end-capped linear polycarbonate and the weight average molecular weight of the end-capped branched polycarbonate which is the final product.
In one embodiment of the present invention, the number of moles of the branching agent relative to 1 mole of the end-capped linear polycarbonate is calculated by the following formula (1).
[Formula 1]
Wherein n is the number of moles of branching agent per mole of end capped linear polycarbonate, L MW is the weight average molecular weight of the end capped linear polycarbonate, and B MW is the weight of the end capped branched polycarbonate Average molecular weight.
However, since the terminally capped linear polycarbonate has various molecular weight distributions, the number of moles of branching agent calculated in
In one embodiment of the present invention, the end capped branched polycarbonate prepared by the third step has a weight average molecular weight of 30,000 to 200,000, and a terminal hydroxyl group content of 0 to 8 mol%, preferably 0 to 3 Molar%. When the terminal hydroxyl group content is within the above range, stability at high temperature may be excellent.
In one embodiment of the invention, the third step is carried out at a reaction temperature of 200 to 380 o C, preferably 250 to 350 o C. When the third step is performed within the temperature range, the reaction rate is maintained at a certain level or more, and there is no problem that side reactions occur or color.
In the present invention, the reaction pressure of the third step is not particularly limited, but is preferably appropriately adjusted so that the low boiling point reaction by-products generated during the reaction can be extracted out of the reactor. In one embodiment of the invention, the reaction pressure of the third stage is 0 to 100 mmHg, preferably 0 to 50 mmHg.
In one embodiment of the present invention, the reaction time of the third step is 10 to 60 minutes, preferably 20 to 60 minutes. When the reaction time is less than 10 minutes, the reaction may not proceed sufficiently, and when the reaction time exceeds 60 minutes may appear discoloration at high temperatures.
In the third step, it is preferable to use an extruder-type reactor capable of sufficient residence time. 1, the linear polycarbonate and the end capped carbonate oligomer react in an end capping zone in an extruder reactor.
In the third step, it is preferable to use a reactor capable of treating a very high viscosity polycarbonate and extending the residence time in the reactor so that the reaction can occur sufficiently. An example of such a reactor is an extruder reactor with a long residence time, such as Large Volume Process (Reacom) from BUSS, Switzerland.
In one embodiment of the present invention, the second and third steps may be carried out in separate extruder reactors, or may be carried out continuously in one extruder reactor. If one extruder reactor is used, the second step is first followed by a third step by introducing a branching agent into the middle of the extruder reactor. Referring to Figure 1, the linear polycarbonate and the end capped carbonate oligomer is introduced into the initial stage of the extruder reactor, the second step proceeds in the end-capping zone, the branching agent in the middle of the extruder reactor, the third step in the branching zone Proceeds, thereby producing end capped branched polycarbonate.
The method for producing the end-capped branched polycarbonate resin according to the present invention is economical by not using an organic solvent, by using a melt polymerization method, and safe and environmentally friendly by not using phosgene.
The present invention will be further illustrated by the following examples, but the following examples are used for the purpose of illustrating the present invention and are not intended to limit the scope of protection of the present invention.
Example
(1) Preparation of End Capped Carbonate Oligomers
Into a 500 ml stirred glass reactor equipped with a condenser, 89.03 g (0.390 mol) of bisphenol-A (BPA) and 98 g (0.457 mol) of diphenyl carbonate (DPC) were charged and heated to 160 ° C., followed by reaction catalyst. As an example, 0.4 x 10 -5 mol of potassium hydroxide was dissolved in water and injected. After the catalyst injection, the reaction temperature was raised to 250 ° C., the reaction pressure was reduced to 1 mmHg, and phenol, a byproduct generated during the reaction, was evaporated and extracted outside the reactor. The vaporized phenol was liquefied and recovered in a condenser attached to the reactor.
After 120 minutes, the reaction was terminated. The weight average molecular weight of the prepared end capped carbonate oligomer was 5048 g / mol as measured using GPC (gel chromatography), and the content of terminal hydroxyl group was determined by NMR. Analysis showed less than 8 mol%.
Preparation of (2) End Capped Linear Polycarbonate and (3) End Capped Branched Polycarbonate
The second and third stages were run continuously using one rotated reactor. 187 g of the end capped carbonate oligomer and the general linear polycarbonate prepared in the first step were added to the reactor inlet to proceed to the second step, and 2.5 g (0.0082 mol) of branching agent (THPE) was added to the reactor stop. Step 3 was progressed. The reaction temperature was 280 ° C., the reaction pressure was 1 mmHg, and the total residence time of the second and third reactions was 2 hours.
After completion of the reaction, the weight average molecular weight of the end capped branched polycarbonate was about 31,000 as measured using GPC, and the terminal hydroxyl group content was 5.1 mol% when analyzed by NMR.
In the following comparative example, a branching agent was added in the first step, and diphenyl carbonate was used in a smaller amount than the example.
Comparative Example
(1) Preparation of Low Molecular Weight Branched Polycarbonate Prepolymer
In a 500 ml stirred stainless reactor equipped with a condenser, 89.03 g (0.390 mol) of bisphenol-A (BPA), 91.06 g (0.425 mol) of diphenyl carbonate (DPC) and 1,1,1-tris ((4- 2.5 g (0.0082 mol) of hydroxy) phenyl) ethane was injected and heated to 160 ° C., and then 0.4 x 10 -5 mol of potassium hydroxide was dissolved in water as a reaction catalyst. After the catalyst injection, the reaction temperature was raised to 270 ° C., the reaction pressure was reduced to 1 mmHg, and phenol, a byproduct generated during the reaction, was evaporated and extracted outside the reactor. The vaporized phenol was liquefied and recovered in a condenser attached to the reactor.
The reaction was terminated after 120 minutes. The weight average molecular weight of the prepared branched polycarbonate prepolymer was 8012 g / mol as measured by GPC (gel chromatography), and the terminal hydroxyl group content was determined by NMR. As a result, it was 15 mol% or more.
(2) Preparation of High Molecular Weight Branched Polycarbonate
High molecular weight branched polycarbonate was prepared using one rotated reactor. High molecular weight branched polycarbonate was prepared by adding 187 g of the low molecular weight branched polycarbonate prepolymer and the general linear polycarbonate prepared in the first step to the reactor inlet. The reaction temperature was 280 ° C., the reaction pressure was 1 mmHg, and the total residence time of the reactants was 2 hours.
After completion of the reaction, the weight average molecular weight of the high molecular weight branched polycarbonate was about 31,000 as measured using GPC, and the terminal hydroxyl group content was 30 mol% as determined by NMR.
In the comparative example, when the branching agent was added in the first step and the diphenyl carbonate was used in a smaller amount than the example, the weight average molecular weight was kept similar, but the content of the terminal hydroxyl group increased sharply, thereby increasing the temperature at high temperature. It is expected that stability will be degraded.
It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (22)
[Chemical Formula 4]
In Formula 4, Ar 1 and Ar 2 are each independently an aryl group, B 1 is a residue from which two hydroxy groups at both ends of the aromatic dihydroxy compound are removed, and m represents a natural number of 40 to 120. .
(2) melt polymerizing the end capped carbonate oligomer and linear polycarbonate to produce end capped linear polycarbonate; And
(3) preparing a terminally capped branched polycarbonate by introducing a branching agent into the terminally capped linear polycarbonate;
Process for producing end-capped branched polycarbonate resin, comprising the step.
[Chemical Formula 1]
In Formula 1, R 1 and R 2 are each independently a halogen atom or an alkyl group having 1 to 12 carbon atoms, a and b are each independently an integer of 0 to 4, Z is a single bond, alkyl having 1 to 8 carbon atoms A ethylene group, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, -S-, -SO-, -SO 2- , -O-, or -CO- Indicates.
(2)
In Formula 2, Ar 1 and Ar 2 are each independently an aryl group.
(3)
In Formula 3, Ar 1 and Ar 2 are each independently an aryl group, B 1 is a residue from which two hydroxy groups at both ends of the aromatic dihydroxy compound are removed, and n represents a natural number of 1 to 5 .
[Chemical Formula 4]
In Formula 4, Ar 1 and Ar 2 are each independently an aryl group, B 1 is a residue from which two hydroxy groups at both ends of the aromatic dihydroxy compound are removed, and m represents a natural number of 40 to 120. .
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| KR100862243B1 (en) | 2007-12-26 | 2008-10-09 | 제일모직주식회사 | Branched polycarbonate resin which can control molecular structure effectively and method for producing the same |
| KR20100017703A (en) * | 2007-05-07 | 2010-02-16 | 사빅 이노베이티브 플라스틱스 아이피 비.브이. | Neutral static polycarbonates, methods of making, and articles formed therefrom |
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| US20080081860A1 (en) | 2006-09-29 | 2008-04-03 | Sabic Innovative Plastics Ip Bv | Thermoplastic compositions, methods of making, and articles formed therefrom |
| KR20100017703A (en) * | 2007-05-07 | 2010-02-16 | 사빅 이노베이티브 플라스틱스 아이피 비.브이. | Neutral static polycarbonates, methods of making, and articles formed therefrom |
| KR100862243B1 (en) | 2007-12-26 | 2008-10-09 | 제일모직주식회사 | Branched polycarbonate resin which can control molecular structure effectively and method for producing the same |
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