KR101491781B1 - Polycarbonate terpolymer, and molded article using the same - Google Patents

Abstract

The present invention relates to a polycarbonate terpolymer having high heat resistance, transparency and excellent processability, a method for producing the same, and a molded article using the same. The polycarbonate ternary copolymer according to the present invention has high transparency, fluidity and thermal stability at the same time while maintaining the characteristics of the existing polycarbonate, and has a high application power in the field of engineering plastics. Further, by controlling the content ratio of each monomer, A polycarbonate having a transition temperature can be easily produced.

Description

TECHNICAL FIELD [0001] The present invention relates to a polycarbonate terpolymer, and a molded article using the polycarbonate terpolymer,

More particularly, the present invention relates to a novel polycarbonate terpolymer having high heat resistance, transparency and excellent processability by organic bonding with the structure of a monomer constituting polycarbonate, and a polycarbonate terpolymer, And a molded article using the same.

Recently, new types of electronic materials are emerging as new applications such as the flat panel display industry appear. The focus of this technology is the simplicity of large area, low cost, and process. Transparent electronic materials have been developed to achieve the goal of eliminating the spatial and visual constraints of existing electronic devices by implementing the functions of information recognition, information processing, information display, and information transfer with transparent electronic equipment. to be.

Transparent electronic materials are generally referred to as optically transparent electronic devices based on transparent oxide semiconductor films, unlike conventional electronic devices made of opaque semiconductor compounds such as Si and GaAs. Transparent electronic devices are electronic devices manufactured on the basis of transparent semiconductors, transparent electrodes and transparent dielectrics. By implementing the functions of information recognition, information processing, and information display with transparent electronic devices, the spatial and visual constraints of existing electronic devices can be solved . This refers to electronic devices and transparent substrates fabricated on transparent substrates based on transparent semiconductors, transparent conductors, and transparent insulators. For example, as a transparent electronic material, opportunities for transparent electronic warfare include parts for information processing such as substrate material, transparent sensor, transparent RFID tag, transparent security electronic device, information processing parts such as transparent digital / analog IC, smart window, It is used for information display parts and so on. Therefore, it is necessary to develop a transparent material including a transparent transistor (TTFT) in order to realize a transparent electronic material.

Smart Window, which is a visually transparent form of window that has functions of information recognition / information processing / information display / information transmission as its application field, is applied to various fields. For example, there is a functional car glass that carries visual information to implement the guidance function, an intelligent display window that can display various displays depending on the surrounding situation or information, a personal goggle that is a display that displays targets and instructions, , A transparent display, a bi-directional information transmission window that can be seen by both users, and an information aquarium. Other applications include real-time or 3-D displays that can be transparent displays as multiple overlaps, transparent sensors or transparent communication devices used in military or security devices, and the ability to eliminate spatial and visual constraints using transparency It is used in various IT equipment such as transparent AMOLED panels, transparent tablets and transparent thin clients.

Because transparent electronic materials are developed and applied at the core of developing transparent electronic materials, these transparent semiconducting materials must have productivity and process suitability that can be readily applied to existing processes. Therefore, in developing transparent electronic material technology, it is necessary to use the know-how accumulated in the process of development of existing materials to shorten the development time as much as possible and reduce trial and error. In particular, in the field of transparent electronic materials, research is relatively new and it is considered that securing of source technology is more likely than other fields, so it is urgent to secure patents in the source technology field.

Polycarbonate is a thermoplastic polymer having an aromatic polycarbonate bond structure. Resin made of polycarbonate has excellent heat resistance, impact resistance, mechanical strength, dimensional stability, transparency, and is widely used in engineering plastics such as compact discs, packaging materials, and automobile bumpers. A typical polycarbonate is composed of bisphenol A as a monomer unit. Although the polycarbonate composed of bisphenol A has excellent mechanical properties, it is difficult to apply it to applications requiring high temperature treatment. have.

In recent years, aromatic polycarbonates having a bulky and easy-to-move structure have been introduced in order to increase the heat resistance while maintaining the existing characteristics of the polycarbonate. Among them, an example in which a polycarbonate composed of a monomer having a fluorene structure is used for an optical lens is disclosed in US-A-2010-0048855. Fluorene-structured polycarbonates have excellent heat resistance, high impact strength, chemical resistance, good permeability and refractive index, and are particularly useful in the field of lenses and high heat-resistant transparent resins. On the other hand, the polycarbonate having a fluorene structure has a difficulty in the production process due to the high melting point of the prepolymer, and it becomes very difficult to handle the molten polymerization mixture having a high viscosity in the process. Polycarbonates having a trimethylcyclohexane (TMC) structure have been developed in order to overcome such disadvantages in the process. The polycarbonate having the trimethylcyclohexane (TMC) structure has excellent heat resistance and high fluidity, There is an insufficient limit to the expected level of high heat resistance for a polycarbonate molded article used in the present invention.

As described above, although polycarbonates using various monomer structures have been developed, there is still a demand for the development of polycarbonate polymers that can sufficiently satisfy both transparency, fluidity and heat resistance.

It is an object of the present invention to provide a polycarbonate terpolymer having improved transparency, fluidity and thermal stability while maintaining the existing polycarbonate properties in order to compensate for the disadvantages of the conventional polycarbonates.

It is another object of the present invention to provide a molded article made from a polycarbonate terpolymer having improved transparency, flowability and thermal stability.

In order to achieve the above object,

A monomer represented by Formula 1 below;

A monomer represented by the following formula (2); And

There is provided a polycarbonate terpolymer comprising a repeating unit derived from one kind of monomer selected from the group consisting of monomers represented by the following formulas (3), (4) and (5).

[Chemical Formula 1]

In Formula 1,

R 1 and R 2 are independently selected from an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms;

a and b are independently integers of from 0 to 4;

에서 선택되는 그룹을 나타내고;X is a chemical bond or an oxygen atom, a sulfur atom, -SO2- group, an aliphatic radical having 1 to 20 carbon atoms, or

≪ / RTI >

R3 and R4 are independently selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, an aryl group having 4 to 20 carbon atoms, or a fused ring having 4 to 20 carbon atoms.

 (2)

In Formula 2,

R12 is a biphenyl derivative.

(3)

In Formula 3,

R5, R6, R7, R8 and R9 are independently selected from the group consisting of an alkyl group having 0 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, an aryl group having 4 to 20 carbon atoms, a halogen atom, a nitro group and a cyano group;

c, d, e, f, m, n and o are independently an integer of 0 to 4;

[Chemical Formula 4]

In Formula 4,

R10 and R11 are independently selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, an aryl group having 4 to 20 carbon atoms, a halogen atom, a nitro group, and a cyano group;

p, q, r and s are independently an integer of 0 to 4;

[Chemical Formula 5]

In Formula 5,

R14 is a biphenyl derivative.

In this case, except that any two or more monomers among the monomers represented by the above formulas (1) to (5) are the same,

X mole of the repeating unit derived from the monomer represented by the formula (1), y mole of the repeating unit derived from the monomer represented by the formula (2), and a monomer represented by the formula (3), And the mole ratio of x, y and z satisfies x: y: z = 1: 0.01-100: 0.01-100.

The present invention also provides a molded article produced using the polycarbonate terpolymer.

The polycarbonate ternary copolymer according to the present invention has high applicability to the engineering plastics field, while maintaining the properties of conventional polycarbonate and having improved flowability and thermal stability at the same time, especially in a molten state. In addition, a molded article produced using the polycarbonate terpolymer has properties suitable for transparent electronic materials due to excellent transparency and heat resistance.

The polycarbonate terpolymer of the present invention can easily obtain a polycarbonate having a necessary glass transition temperature by controlling the content ratio of each monomer.

1 shows the FT-IR spectrum of the polycarbonate terpolymer of Example 19. Fig.
2 shows the FT-IR spectrum of the polycarbonate terpolymer of Example 62. Fig.
3 shows the FT-IR spectrum of the polycarbonate terpolymer of Example 67. Fig.

Hereinafter, the polycarbonate terpolymer of the present invention and a molded article using the polycarbonate terpolymer will be described in detail.

Polycarbonate Terpolymer

The polycarbonate terpolymer of the present invention,

A monomer represented by Formula 1 below;

A monomer represented by the following formula (2); And

And repeating units derived from one kind of monomer selected from the group consisting of monomers represented by the following formulas (3), (4) and (5).

[Chemical Formula 1]

In Formula 1,

R 1 and R 2 are independently selected from an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms;

a and b are independently integers of from 0 to 4;

에서 선택되는 그룹을 나타내고;X is a chemical bond or an oxygen atom, a sulfur atom, -SO2- group, an aliphatic radical having 1 to 20 carbon atoms, or

≪ / RTI >

R3 and R4 are independently selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, an aryl group having 4 to 20 carbon atoms, or a fused ring having 4 to 20 carbon atoms.

 (2)

In Formula 2,

R12 is a biphenyl derivative.

(3)

In Formula 3,

R5, R6, R7, R8 and R9 are independently selected from the group consisting of an alkyl group having 0 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, an aryl group having 4 to 20 carbon atoms, a halogen atom, a nitro group and a cyano group;

c, d, e, f, m, n and o are independently an integer of 0 to 4;

[Chemical Formula 4]

In Formula 4,

R10 and R11 are independently selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, an aryl group having 4 to 20 carbon atoms, a halogen atom, a nitro group, and a cyano group;

p, q, r and s are independently an integer of 0 to 4;

[Chemical Formula 5]

In Formula 5,

R14 is a biphenyl derivative.

In this case, except that any two or more monomers among the monomers represented by the above formulas (1) to (5) are the same,

X mole of the repeating unit derived from the monomer represented by the formula (1), y mole of the repeating unit derived from the monomer represented by the formula (2), and a monomer represented by the formula (3), And the mole ratio of x, y and z satisfies x: y: z = 1: 0.01-100: 0.01-100.

The polycarbonate terpolymer of the present invention may, for example, be a terpolymer containing repeating units derived from the general formulas (1), (2) and (3), a repeating unit derived from the general formulas , Or a ternary copolymer containing repeating units derived from the general formulas (1), (2) and (5), respectively.

Herein, the monomers represented by the formulas (1) to (5) are all different and the case where two or more monomers are identical is excluded.

According to an embodiment of the present invention, the monomer represented by Formula 1 may be 1,1-bis- (4-hydroxyphenyl) -methane, 1,1-bis- (4-hydroxyphenyl) 1-bis- (4-hydroxyphenyl) -propane, 1,1-bis- (4-hydroxyphenyl) Bis- (4-hydroxyphenyl) -sulfone, 1,1-bis- (4-hydroxyphenyl) Bis- (4-hydroxyphenyl) -sulfide, 1,1-bis- (4-hydroxyphenyl) Bis- (4-hydroxyphenyl) -sulfoxide, 1,1-bis- (4-hydroxyphenyl) Propane, 2,2-bis- (3-methyl-4-hydroxyphenyl) propane, (3-allyl-4-hydroxyphenyl) propane, 2,2-bis (3-methoxy- Propane, 2,2-bis- (3-phenyl-4-hydroxyphenyl) propane, (3-sec-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxyphenyl) propane, 2,2- Bis (4- hydroxyphenyl) hexafluoropropane, 2,4-bis- (4-hydroxyphenyl) -2-methylbutane, trans- (4-hydroxyphenyl) -2-butene, ethylene glycol-bis (4-hydroxyphenyl) ether,?,? ' Hydroxyphenyl) -p-diisopropylbenzene. ≪ / RTI >

In particular, the monomer represented by Formula 1 may be a compound represented by Formula 1a below.

[Formula 1a]

According to an embodiment of the present invention, the monomers represented by Formula 2 and Formula 5 are each independently 4,4'- (propane-2,2-diallyl) bis (2,6-dimethylphenol) 3,3'-tetramethyl-2,2 ', 3,3'-tetrahydro-1,1'-spiro [indene] -5,5'-diol, 1,6-bis Diazaspiro [4.4] nonane-2,7-dione, 3- (4-hydroxyphenyl) -1,1,3-trimethyl- (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4- (cyclododecane-1,1-dile) biphenol, 4,4-bis (4-hydroxyphenyl) piperidin-1-yl) ethanone, 4,4- 4- (1, 3S, 4S) -3- (4-hydroxyphenyl) -4-methylcyclohexyl) -4- Propane-2-yl) phenol, 4,4'- ((1R, 3R, 4S) -3-isopropyl- 1 -methylcyclohexane- Diol) diphenyl-4-ol, 6,6'-methylenebis (2-cyclohexyl-4-methylphenol), 1,1'-binaphthyl- (4-hydroxyphenyl) -1-phenylmethane, 3,3-bis (4-hydroxyphenyl) -1-naphthylmethane, 1,1- ) Isobenzofuran-1 (3H) -one, 4,4- (2,2-dichloroethene-1,1-dile) biphenol, 1,1,3,4,6-pentamethyl-3- (3,5-dimethyl-4-hydroxyphenyl) -indan- 4,4'- (1,7,7-trimethylbicyclo [2,2,1] heptane-2,2-dile) biphenol, 2,6-dihydroxydibenzo-p-dioxin , 2,7-dihydroxy pyrene, 2,7-dihydroxycarbazole, 4,4'-dihydroxybiphenol, (1-phenylethane-1,1-dile) biphenol, 4,4'- (1-phenylpropane-2,2-dile) biphenol, 4,4'- , 2-dile) biphenol, 4,4'- (4-phenylbutane-2,2-dile) biphenol, 4,4'- (1-p- 4,4'- (9,10-dihydroanthracene-9,9-dile) biphenol, 4,4'- (1- (biphenyl- 4,4'- (biphenylmethylene) biphenol, 4,4'- (2,3-dihydro-1H-indene) -1,1-diallyl) biphenol, 4,4'- (2,2'- (1,4-phenylene) bis (propane-2,2- -2,2-diallyl) bis (2-methylphenol), (4,7,7-trimethylbicyclo [2,2,1] heptane-2,2-dile) biphenol, 4,4'- (propane-2,2-dile) bis (Cyclohexylphenol), 4,4'- (propane-2,2-dile) bis (2-t-butylphenol), 4,4'- (biphenylmethylene) , 4'- (perfluoropropane-2,2-dile) biphenol, 4,4'- (propane-2,2-dile) bis (2-fluorophenol) (4-naphthylphenol), 4,4'- ((4-nitrophenylimino) bis ) Methylene) biphenol, (E) -4,4'-methylenebis (2 - ((E) - (2- (4-nitrophenyl) hydrazano) methyl) phenol) Diol, 4,4'- (pyrazine-2,5-dile) biphenol, 4,4 '- ((1R) -bicyclo [2,2,1] heptane- , 4,3'- (biphenyl-4,4'-diyl bis (phenyl azadiyl)) biphenol, 4,4'- (4,4'- (ethene-1,2-diyl) bis , 1-phenylene)) bis (phenyl azadyl) biphenol, 3,3'-methylenebis (2- D] [1,2,3] triazol-2-yl) phenol), 4,4'- (Cyclododecane-1-yl) -4-hydrobiphenyl) ethane-1,1-diallylbiphenol, 4,4'- (cyclononane- 1-dile) biphenol, 4,4'- (cyclohexane-1,1-dile) biphenol, 4,4'- Hydroxyphenyl-3,5-dimethylphenyl) sulfone, and 4,4 '- (10,10-biphenyl-9,10-dihydroanthracene-9,9-dile) biphenol. It can be all day.

According to another embodiment of the present invention, the monomers represented by the above-mentioned formulas (2) and (5) are each independently and differently selected from the group consisting of 1,1-bis- (4-hydroxyphenyl) 4-hydroxyphenyl) -ethane, 1,1-bis- (4-hydroxyphenyl) -propane, 1,1- (4-hydroxyphenyl) -ketone, 1,1-bis- (4-hydroxyphenyl) (4-hydroxyphenyl) -sulfoxide, 1,1-bis- (4-hydroxyphenyl) -sulfoxide, 1,1- Phenyl) -1-phenylmethane, 1,6-bis- (4-hydroxyphenyl) -1,6-hexanedione, 2,2-bis- (3-methyl Hydroxyphenyl) propane, 2,2-bis (3-ethyl-4-hydroxyphenyl) propane, 2,2- (3-methoxy-4-hydroxyphenyl) propane, 2,2-bis- (3-phenyl-4-hydroxyphenyl) propane, 2,2- (3-sec-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, Propane, 2,2-bis- (3-t-butyl-4-hydroxyphenyl) propane, 2,2- 4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxyphenyl) hexafluoropropane, 2,4-bis- -Bis (4-hydroxyphenyl) -2-butene, ethylene glycol-bis (4-hydroxyphenyl) ether, - (4-hydroxyphenyl) toluene, and α, α'- bis-1 can all be selected from the group consisting of (4-hydroxyphenyl) -p- diisopropylbenzene.

According to another embodiment of the present invention, the monomers represented by the formulas (2) and (5) are each independently and differently selected from 1,1-bis- (2- (4-hydroxyphenyl) Hexane, 1,1-bis- (3,5-dimethyl-4-hydroxyphenyl) -methane, 1,1-bis- (3,5- Bis- (3,5-dimethyl-4-hydroxyphenyl) -3,3-dimethyl-5-methylcyclohexane, 1,1- (3,5-biphenyl-4-hydroxyphenyl) -3,3-dimethyl-5-methylcyclohexane, 1,1-bis- Phenyl) -3,3-dimethyl-5-methylcyclohexane, 1,1-bis- (3,5-dibromo-4-hydroxyphenyl) (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis- (4-hydroxyphenyl) sulfone, 1,1- Phenyl) -3,3-dimethyl-5, 5-dimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3-dimethyl-5-methylcyclopentane, 1,1-dichloro-2,2- Dibromo-2,2-bis (4-hydroxyphenyl) ethylene, 1,1-dichloro-2,2-bis Dihydroxynaphthalene, 2,2-bis- (2,3,5,6-tetramethyl-4-hydroxyphenyl) propane (2,6-dibromo-3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis , 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) butane, 2,2-bis Bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,4-bis- (3,5- (4-hydroxyphenyl) -2-methylbutane, 2,2-bis- (4-hydroxy-3-isopropylphenyl) propane, 2- Dihydroxyphenoxy) -propane, 2,6-dihydroxynaphthalene, 2,6-dihydroxyanthracene, 2,7-dihydroxyphenoxazine, 2,7-dihydroxy-9,10-dimethylphenazine , 3,3'-dihydroxybiphenyl ether, 3,3'-dihydroxyphthalide, 3,4'-dihydroxybiphenyl ether, 4,4'-dihydroxybiphenyl ether, Dihydroxybiphenylthioether, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxy-1,1-biphenyl, 4,4'-dihydroxy-3,3 -Dimethyl-1,1-biphenyl, 4,4'-dihydroxy-3,3'-dioctyl-1,1-biphenyl, 6,6'-dihydroxy- , 3'-tetramethyl spiro (bis) indene, benzene-1,4-diol, benzene-1,3-diol, 4-bromo-1,3-dihydroxybenzene, - (hydroxyphenyl) -polysiloxane. ≪ / RTI >

According to an embodiment of the present invention, the monomer represented by Formula 3 may be 1,1-bis- (3-methyl-4-hydroxyphenyl) -3,3-dimethyl-5-methylcyclohexane, 1,1 - (3-ethyl-4-hydroxyphenyl) -3,3-dimethyl-5-methylcyclohexane, 1,1- (3-butyl-4-hydroxyphenyl) -3,3-dimethyl-5-methylcyclohexane, 1,1-bis- Hydroxyphenyl) -3,3-dimethyl-5-methylcyclohexane, 1,1-bis- (3-chloro-4-hydroxyphenyl) Bis- (3-bromo-4-hydroxyphenyl) -3,3-dimethyl-5-methylcyclohexane, 1,1- - (4-hydroxyphenyl) -3,3-dimethyl-5-methylcyclohexane, 1,1-bis- '- (3-methylcyclohexane-1,1-dile) biphenol, 4,4' - (3- (4-tert-butylcyclohexane-1,1-dile) biphenol, 4,4 '- (4-methyl- (Cyclohexane-1,1-dile) biphenol, 4,4 '- (3,5-dimethylcyclohexane-1,1-dyl) biphenol, Bis (2-tert-butylphenol), and 4,4 '- (cyclohexane-1,1-dyl) bis (2-methylphenol).

According to an embodiment of the present invention, the monomer represented by Formula 4 may be 9,9-bis- (4-hydroxyphenyl) fluorene, 9,9-bis- (4-hydroxy- (4-hydroxy-3-ethylphenyl) fluorene, 9,9-bis- (4-hydroxy- (4-hydroxy-2-ethylphenyl) fluorene, 9,9-bis- (4-hydroxy-3-cyclohexylphenyl) fluorene, Fluorene, 9,9-bis- (4-hydroxy-3- (3,5-dimethylcyclohexyl) ) Phenyl) fluorene, 5,5- (9H-fluorene-9,9-dile) bis (3,5-dimethylbiphenyl- Fluorophenyl) fluorene, 9,9-bis- (4-hydroxy-3-bromophenyl) fluorene, and 9,9-bis- Lt; / RTI >

The polycarbonate terpolymer of the present invention can easily obtain a polycarbonate having desired physical properties by controlling the kinds of monomers having different properties and the ratio between the monomers.

The degree of polymerization of the polycarbonate terpolymer of the present invention is 5 to 2,500, preferably 10 to 1,250. More preferably from 10 to 650, even more preferably from 10 to 200,

The weight average molecular weight (Mw) of the polycarbonate terpolymers according to the present invention ranges from about 4,000 to about 3,500,000 g / mole, preferably from about 9,000 to about 200,000 g / mole.

The polycarbonate terpolymer of the present invention may have various glass transition temperatures depending on the molar ratio of the repeating unit compound derived from each monomer. For example, the polycarbonate terpolymers of the present invention may have a glass transition temperature (Tg) of from about 150 to about 360 DEG C, preferably from about 150 to about 340 DEG C, but are not limited thereto.

As described above, the polycarbonate terpolymer of the present invention can provide both high heat resistance and fluidity by complementing the advantages and disadvantages of the above-mentioned repeating unit compounds, and thus can be widely applied to various commercial fields. For example, by extrusion, injection molding or extrusion blow molding to form any desired molded article.

The polycarbonate terpolymer of the present invention can be produced by a polymerization method well known to those skilled in the art.

For example, a melt process by ester exchange or a phosgene polymerization process.

According to one embodiment of the present invention, the polycarbonate terpolymer of the present invention is represented by the following formula (1): x moles of a monomer, y moles of a monomer represented by the following formula (2) And then polymerizing z mol of one kind of monomer selected from the group consisting of monomers to be reacted with aryl carbonate or phosgene.

In this case, the ratio of x: y: z can be optionally set within a range of 1: 0.01 to 100: 0.01 to 100, if necessary, within a range satisfying that x + y + z is 5 to 2,500, May range from 1: 0.01 to 10: 0.01 to 10.

[Chemical Formula 1]

 (2)

 (3)

[Chemical Formula 4]

[Chemical Formula 5]

Examples of the functional groups of the above formulas (1) to (5) and examples of the materials corresponding to the respective formulas are as described above.

According to the process for producing a polycarbonate terpolymer of the present invention, it is possible to easily obtain a polycarbonate having desired physical properties by controlling the kinds of monomers having different characteristics and the ratio between the monomers.

That is, by controlling the content ratio of one monomer selected from the formulas (1), (2) and (3) to (5), a polycarbonate terpolymer having a glass transition temperature (Tg) Can be manufactured.

In the melt polymerization process, one monomer of each of the monomers selected from the above formulas (1), (2) and (3) to (5) is carried out by transesterification with aryl carbonate in molten state with the aid of a suitable polymerization catalyst and optionally further additives.

According to an embodiment of the present invention, the aryl carbonate may be at least one selected from the group consisting of biphenyl carbonate, dicyclopentyl carbonate, dicyclohexyl carbonate, dicycloheptyl carbonate, dibenzyl carbonate, diphenyl carbonate, di (phenylpropyl) Butylphenyl carbonate, tert-butylphenyl-phenyl carbonate, di-tert-butylphenyl carbonate, diisopropylphenyl carbonate, N-hexylphenyl carbonate, di (n-hexylphenyl) carbonate, cyclohexylphenyl-phenyl carbonate, dicyclohexylphenyl carbonate, dicyclohexylphenyl carbonate, Carbonate, phenyl phenol-phenyl carbonate, biphenyl phenol carbonate, isooctyl phenyl-phenyl carbonate, di N-nonylphenyl carbonate, cumylphenyl-phenyl carbonate, dicumylphenyl carbonate, naphthylphenyl-phenyl carbonate, dinaphthylphenyl carbonate, di-tert-butylphenyl carbonate, Di (tert-butylphenyl) carbonate, dicumylphenyl-phenyl carbonate, di (dicumylphenyl) carbonate, 4-phenoxyphenyl-phenyl carbonate, di (4-phenoxyphenyl) carbonate , 3-pentadecylphenyl-phenyl carbonate, di (3-pentadecylphenyl) carbonate, tritylphenyl-phenyl carbonate, and ditolylphenyl carbonate. Diphenyl carbonate is preferred.

The amount of the aryl carbonate is preferably 100 to 120 mol% based on the total amount of each monomer compound selected from the above-mentioned formulas (1), (2) and (3)

Wherein the polymerization catalyst is selected from the group consisting of sodium bicarbonate, potassium hydroxide tetraphenylphosphonium tetraphenylborate, tetramethylammonium hydroxide tetraphenyl, sodium hydrogencarbonate, calcium acetate, lithium acetate, lithium hydride, magnesium chloride, dibutyltin oxide, Sodium phenolate, and hydrogen fluoride, and sodium hydrogencarbonate and potassium hydroxide are preferable.

More specifically, in a process for preparing a polycarbonate terpolymer using a melt polymerization process, the temperature of the reaction system is maintained at from about 150 to about 360 ° C, preferably from about 150 to about 340 ° C, for a period of from about 4 hours to about 6 hours The polycondensation reaction is carried out while the pressure is gradually increased and the pressure is reduced from about 760 torr to about 0 torr.

According to another embodiment of the present invention, there is provided a method for preparing a polycarbonate ternary copolymer, which comprises reacting a monomer x moles represented by Formula 1, y moles of a monomer represented by Formula 2, And z is a number selected from the group consisting of monomers represented by the following formulas (1) and (2), in the presence of a catalyst in an aqueous alkali solution and an organic solvent, and then phosgene is injected thereto.

The alkali aqueous solution may be water in which alkali metal or alkaline earth metal hydroxides are dissolved. According to one embodiment of the present invention, it is preferable to use sodium hydroxide or potassium hydroxide solution.

As the organic solvent, halogenated hydrocarbons including methylene chloride, chlorobenzene, dichlorobenzene, trichlorobenzene or a mixture thereof, or aromatic hydrocarbons including toluene or xylene are preferable, and methylene chloride is particularly preferable.

Examples of the catalyst include amine compounds such as triethylamine, tripropylamine, triisopropylamine, tributylamine, triisobutylamine, N-methylpiperidine, N-ethylpiperidine and N-propylpiperidine Is preferable, and triethylamine is particularly preferably used.

In the above-mentioned phosgene polymerization reaction, phenols may optionally be used as terminal terminators. As the phenol, phenol or lower alkyl-substituted phenol can be used, and specific examples thereof include p-tert-butylphenol, p-cumylphenol and isooctylphenol.

According to the process for producing a polycarbonate terpolymer of the present invention, it is possible to easily produce a polycarbonate terpolymer having necessary physical properties by controlling the ratio of the respective monomers and the content ratio thereof, and thus can be industrially applicable .

Polycarbonate The terpolymer  Molded product

The polycarbonate terpolymers of the present invention described above can be worked up by known methods, for example, by extrusion, injection molding or extrusion blow molding to form any desired molded article.

According to one embodiment of the present invention, the resulting polycarbonate terpolymer resin can be injection molded into molds of a desired shape at barrel temperatures of from about 200 to about 400 DEG C, at mold temperatures of from about 30 to about 180 DEG C .

Typical additives such as fillers, UV stabilizers, heat stabilizers, antistatic agents and pigments may be added to the polycarbonate terpolymers according to the invention in conventional amounts. Optionally, external release agents, flow agents and / or refractory agents (e.g., alkyl and aryl phosphites, phosphates, phosphazines and low molecular weight carboxylic acid esters, halogen compounds, salts, chalk, quartz powder, Fibers, pigments, and mixtures thereof.

Polycarbonate terpolymers according to the invention, optionally in combination with other thermoplastic materials and / or conventional additives, when processed to form any desired molded article / extrudate, can be used in all fields where already known polycarbonates are used Lt; / RTI >

Particularly, the molded article produced from the polycarbonate terpolymer of the present invention is useful as a display device, a flexible display device, a transparent substrate of an electronic apparatus, an optical film, an optical lens, an information storage device, , An illumination lid device, a prism device, and the like.

Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

Polycarbonate by melt polymerization method Terpolymer  Produce

≪ Example 1 >

0.9 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.05 mol of 9,9-bis (4-hydroxyphenyl) fluorene, 3,3,3 ' , 0.05 mol of 3,3'-tetrahydro-1,1'-spirobi [indene] -5,5'-diol and 1.02 mol of biphenyl carbonate were fed into the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 92.5%).

≪ Example 2 >

0.6 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.17 mol of 9,9-bis (4-hydroxyphenyl) fluorene, 3,3,3 '',3,3'-tetrahydro-1,1'-spirobi [indene] -5,5'-diol and 1.02mol of biphenyl carbonate were added to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 90.2%).

≪ Example 3 >

0.9 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.03 mol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, '-Tetramethyl-2,2', 3,3'-tetrahydro-1,1'-spiro [indene] -5,5'-diol and 1.02 mol of biphenyl carbonate as a polymerization catalyst, potassium hydroxide Were administered to the reactor. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 92.8%).

<Example 4>

0.6 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.16 mol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, Tetramethyl-2,2 ', 3,3'-tetrahydro-1,1'-spiro [indene] -5,5'-diol and 1.02 mol of biphenyl carbonate as a polymerization catalyst, potassium hydroxide Were administered to the reactor. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 89.8%).

&Lt; Example 5 >

0.9 mol of 2,2-bis (4-hydroxyphenyl) propane, 0.03 mol of 9,9-bis (4-hydroxyphenyl) fluorene, 1,6- -Diazaspiro [4.4] nonane-2,7-dione and 1.02 mol of biphenyl carbonate as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 90.2%).

&Lt; Example 6 >

0.6 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.22 mol of 9,9-bis (4-hydroxyphenyl) fluorene, 1,6- -Diazaspiro [4.4] nonane-2,7-dione and 1.02 mol of biphenyl carbonate as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 88.7%).

&Lt; Example 7 >

, 0.07 mol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 0.07 mol of 1,6-bis (4-hydroxyphenyl) Hydroxyphenyl) -1,6-diazaspiro [4.4] nonane-2,7-dione and 1.02 mol of biphenyl carbonate were added to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 92.1%).

&Lt; Example 8 >

Bis (4- hydroxyphenyl) propane, 0.16 mol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 0.16 mol of 1,6- Hydroxyphenyl) -1,6-diazaspiro [4.4] nonane-2,7-dione and 1.02 mol of biphenyl carbonate were added to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 90.3%).

&Lt; Example 9 >

0.8 mol of 2,2-bis- (4-hydroxyphenyl) propane, 3,3,3 ', 3'-tetramethyl-2,2', 3,3'-tetrahydro- 0.12 mol of 1,6-bis (4-hydroxyphenyl) -1,6-diazaspiro [4.4] nonane-2,7-dione and 0.02 mol of biphenyl Potassium carbonate as a polymerization catalyst was added to the reactor in 1.02 mol of carbonate. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 89.1%).

&Lt; Example 10 >

0.9 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.04 mol of 9,9-bis (4-hydroxyphenyl) fluorene, 0.06 mol of trimethyl-2,3-dihydro-1H-inden-5-ol and 1.02 mol of biphenyl carbonate were added to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 94.5%).

&Lt; Example 11 >

(4-hydroxyphenyl) propane, 0.14 mol of 9,9-bis (4-hydroxyphenyl) fluorene, 0.26 mol of trimethyl-2,3-dihydro-1H-inden-5-ol and 1.02 mol of biphenyl carbonate were added to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 91.1%).

&Lt; Example 12 >

0.9 mol of 2,2-bis (4-hydroxyphenyl) propane, 0.03 mol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, ) -1,1,3-trimethyl-2,3-dihydro-1H-inden-5-ol and 1.02 mol of biphenyl carbonate as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 95.6%).

&Lt; Example 13 >

(4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 0.13 mol of 1,1-bis (4-hydroxyphenyl) ) -1,1,3-trimethyl-2,3-dihydro-1H-inden-5-ol and 1.02 mol of biphenyl carbonate were added to the reactor as polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 92%).

&Lt; Example 14 >

0.9 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.07 mol of 9,9-bis (4-hydroxyphenyl) fluorene, -Dimethyladamantane and 1.02 mol of biphenyl carbonate as a polymerization catalyst were fed into the reactor. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 95.2%).

&Lt; Example 15 >

0.6 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.26 mol of 9,9-bis (4-hydroxyphenyl) fluorene, -Dimethyladamantane and 1.02 mol of biphenyl carbonate as a polymerization catalyst were fed into the reactor. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 93%).

&Lt; Example 16 >

, 0.9 mol of 2,2-bis (4-hydroxyphenyl) propane, 0.04 mol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 0.06 mol of hydroxyphenyl) -5,7-dimethyladamantane and 1.02 mol of biphenyl carbonate were added to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 96.1%).

&Lt; Example 17 >

, 0.17 mol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 0.17 mol of 1,3-bis (4-hydroxyphenyl) Hydroxyphenyl) -5,7-dimethyladamantane and 1.02 mol of biphenyl carbonate, potassium hydroxide was supplied to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 94.2%).

&Lt; Example 18 >

0.8 mol of 2,2-bis- (4-hydroxyphenyl) propane and 0.1 mol of 3- (4-hydroxyphenyl) -1,1,3-trimethyl-2,3-dihydro-1H- , 0.09 mol of 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane and 1.02 mol of biphenyl carbonate, potassium hydroxide was supplied to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 90%).

&Lt; Example 19 >

0.9 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.3 mol of 9,9-bis (4-hydroxyphenyl) fluorene and 4 mol of 4,4- (cyclododecane- 0.7 mol of phenol and 1.02 mol of biphenyl carbonate, potassium hydroxide was supplied to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 90.3%).

&Lt; Example 20 >

0.6 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.18 mol of 9,9-bis (4-hydroxyphenyl) fluorene, 0.22 mol of phenol and 1.02 mol of biphenyl carbonate, potassium hydroxide was supplied to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 88.2%).

&Lt; Example 21 >

0.9 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.04 mol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, -1,1-dile) 0.06 mol of biphenol and 1.02 mol of biphenyl carbonate were added to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 93%).

&Lt; Example 22 >

, 0.6 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.15 mol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, -1,1-diallyl) biphenol and 1.02 mol of biphenyl carbonate were fed into the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 89.6%).

&Lt; Example 23 >

0.8 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.12 mol of 9,9-bis (4-hydroxyphenyl) fluorene, 4,4- (tetrahydro- -Dial) 0.08 mol of biphenol and 1.02 mol of biphenyl carbonate were added to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 93.3%).

&Lt; Example 24 >

0.8 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.07 mol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2H-thiopyran-4,4-diallyl) biphenol and 1.02 mol of biphenyl carbonate were added to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 95%).

&Lt; Example 25 >

0.8 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.08 mol of 4,4- (cyclododecane-1,1-dile) biphenol, 4,4- (tetrahydro-2H-thiopyran- 4,4-dile) 0.12 mol of biphenol and 1.02 mol of biphenyl carbonate were added to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 90.2%).

&Lt; Example 26 >

0.8 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.06 mol of 9,9-bis (4-hydroxyphenyl) fluorene, 1- (4,4-bis (hydroxyphenyl) -1-yl) ethanone and 1.02 mol of biphenyl carbonate, potassium hydroxide was supplied to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 94.3%).

&Lt; Example 27 >

0.8 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.06 mol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, (Hydroxyphenyl) piperidin-1-yl) ethanone and 1.02 mol of biphenyl carbonate, potassium hydroxide was supplied to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 95%).

&Lt; Example 28 >

, 0.8 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.06 mol of 9,9-bis (4-hydroxyphenyl) fluorene, 4,4- (1,3-dimethylcyclohexane- -Dial) Potassium hydroxide was added to the reactor as a polymerization catalyst in 0.14 mol of biphenol and 1.02 mol of biphenyl carbonate. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 93.3%).

&Lt; Example 29 >

0.8 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.06 mol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, -Dimethylcyclohexane-1,3-diallyl) biphenol and 1.02 mol of biphenyl carbonate, potassium hydroxide was supplied to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 94.2%).

&Lt; Example 30 >

, 0.07 mol of 1- (4,4-bis (hydroxyphenyl) piperidin-1-yl) ethanone, 0.07 mol of 4,4- (1, 3-dimethylcyclohexane-1,3-diallyl) biphenol and 1.02 mol of biphenyl carbonate, potassium hydroxide was supplied to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 89.6%).

&Lt; Example 31 >

0.12 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.12 mol of 9,9-bis (4-hydroxyphenyl) fluorene, (4-hydroxyphenyl) -4-methylcyclohexyl) propan-2-yl) phenol and 1.02 mol of biphenyl carbonate as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 92.2%).

&Lt; Example 32 >

0.12 mol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 0.12 mol of 4- (2 - ((1S , 0.08 mol of 3S, 4S) -3- (4-hydroxyphenyl) -4-methylcyclohexyl) propan-2-yl) phenol and 1.02 mol of biphenyl carbonate as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 93.4%).

&Lt; Example 33 >

, 0.12 mol of 9,9-bis (4-hydroxyphenyl) fluorene, 0.8 mol of 2,2-bis- (4-hydroxyphenyl) Isopropyl-1-methylcyclohexane-1,4-diallyl) biphenol and 1.02 mol of biphenyl carbonate were added to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 92.5%).

&Lt; Example 34 >

0.8 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.12 mol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, , 3R, 4S) -3-isopropyl-1-methylcyclohexane-1,4-diyl) biphenol and 1.02 mol of biphenyl carbonate as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 94.8%).

&Lt; Example 35 >

(4-hydroxyphenyl) propane, 0.8 mol of 2,2-bis- (4-hydroxyphenyl) propane, (1R, 3R, 4S) -3-isopropyl-1-methylcyclohexane-1,4-diallyl) biphenol and 1.02 mol of biphenyl carbonate in the presence of 0.12 mol of 4,4'- Potassium hydroxide was added to the reactor as a catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 91.5%).

&Lt; Example 36 >

0.9 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.04 mol of 9,9-bis (4-hydroxyphenyl) fluorene, 0.04 mol of 1,1'-binaphthyl- mol and 1.02 mol of biphenyl carbonate, potassium hydroxide was supplied to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 90.8%).

&Lt; Example 37 >

0.6 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.18 mol of 9,9-bis (4-hydroxyphenyl) fluorene, 1,1'-binaphthyl-2,2'- mol and 1.02 mol of biphenyl carbonate, potassium hydroxide was supplied to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 88.2%).

&Lt; Example 38 >

0.9 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.06 mol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 0.02 mol of 2,2'-diol, 0.1 mol of 1,1-bis- (4-hydroxyphenyl) -cyclodecane and 1.02 mol of biphenyl carbonate as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 92.7%).

&Lt; Example 39 >

0.6 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.17 mol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, -2,2'-diol and 1.02 mol of biphenyl carbonate, potassium hydroxide was supplied to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 90.7%).

&Lt; Example 40 >

, 0.9 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.03 mol of 9,9-bis (4-hydroxyphenyl) fluorene, 1,1- And 1.02 mol of biphenyl carbonate, potassium hydroxide was supplied to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 92.6%).

&Lt; Example 41 >

, 0.18 mol of 9,9-bis (4-hydroxyphenyl) fluorene, 1,1-bis- (4-hydroxyphenyl) And 1.02 mol of biphenyl carbonate, potassium hydroxide was supplied to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 90.5%).

&Lt; Example 42 >

0.9 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.04 mol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, -Hydroxyphenyl) -cyclohexane and 1.02 mol of biphenyl carbonate were fed into the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 95.5%).

&Lt; Example 43 >

(4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 0.14 mol of 1,1-bis- (4-hydroxyphenyl) -Hydroxyphenyl) -cyclohexane and 1.02 mol of biphenyl carbonate were fed into the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 92.9%).

&Lt; Example 44 >

0.8 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.15 mol of 1,1-binaphthyl-2,2-diol and 0.05 mol of 1,1-bis- (4-hydroxyphenyl) mol and 1.02 mol of biphenyl carbonate, potassium hydroxide was supplied to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 90.4%).

&Lt; Example 45 >

(4-hydroxyphenyl) propane, 0.12 mol of 9,9-bis (4-hydroxyphenyl) fluorene, 0.12 mol of 1,1-bis- 0.08 mol of naphthylmethane and 1.02 mol of biphenyl carbonate, potassium hydroxide was supplied to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 90.8%).

&Lt; Example 46 >

0.8 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.12 mol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, -Hydroxyphenyl) -1-naphthylmethane and 1.02 mol of biphenyl carbonate were added to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 92%).

&Lt; Example 47 >

0.8 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.1 mol of 9,9-bis (4-hydroxyphenyl) fluorene, 0.1 mol of phenyl methane and 1.02 mol of biphenyl carbonate, potassium hydroxide was supplied to the reactor as a polymerization catalyst. The temperature in the reactor was slowly raised from 180 ° C to 300 ° C, and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 92%).

&Lt; Example 48 >

0.8 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.1 mol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, -Hydroxyphenyl) -1-phenylmethane and 1.02 mol of biphenyl carbonate, potassium hydroxide was supplied to the reactor as a polymerization catalyst. The temperature in the reactor was slowly raised from 180 ° C to 300 ° C, and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 93.6%).

&Lt; Example 49 >

0.8 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.07 mol of 1,1-bis- (4-hydroxyphenyl) -1-naphthylmethane, 1,1- Phenyl) -1-phenylmethane and 1.02 mol of biphenyl carbonate were fed into the reactor as a polymerization catalyst. The temperature in the reactor was slowly raised from 180 ° C to 300 ° C, and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 89.7%).

&Lt; Example 50 >

0.8 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.06 mol of 9,9-bis (4-hydroxyphenyl) fluorene, 4,4 '- (1,7,7-trimethylbicyclo [ 2,2,1] heptane-2,2-diallyl) biphenol and 1.02 mol of biphenyl carbonate were fed into the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 88.3%).

&Lt; Example 51 >

0.8 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.06 mol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, Trimethyl bicyclo [2,2,1] heptane-2,2-diallyl) biphenol and 1.02 mol of biphenyl carbonate were added to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 91%).

&Lt; Example 52 >

0.8 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.05 mol of 9,9-bis (4-hydroxyphenyl) fluorene, 4,4 ' ) 0.15 mol of biphenol and 1.02 mol of biphenyl carbonate, potassium hydroxide was supplied to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 87%).

&Lt; Example 53 >

, 0.8 mol of 2,2-bis (4-hydroxyphenyl) propane, 0.05 mol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, Phenylethan-1,1-diallyl) biphenol and 1.02 mol of biphenyl carbonate were fed into the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 89.5%).

<Example 54>

0.8 mol of 2,2-bis- (4-hydroxyphenyl) propane, 4,4 '- (1,7,7-trimethylbicyclo [2,2,1] heptane-2,2- mol, 0.14 mol of 4,4 '- (1-phenylethane-1,1-dile) biphenol and 1.02 mol of biphenyl carbonate, potassium hydroxide was supplied to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 88.2%).

&Lt; Example 55 >

0.8 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.06 mol of 9,9-bis (4-hydroxyphenyl) fluorene, 4,4 '- (9,10-dihydroanthracene- 9-dile) 0.14 mol of biphenol and 1.02 mol of biphenyl carbonate were added to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 88.2%).

&Lt; Example 56 >

0.8 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.06 mol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 10-dihydroanthracene-9,9-dile) 0.14 mol of biphenol and 1.02 mol of biphenyl carbonate were fed into the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 94.2%).

&Lt; Example 57 >

0.8 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.06 mol of 9,9-bis (4-hydroxyphenyl) fluorene, 4,4 '- (pyrazine- And 1.02 mol of biphenyl carbonate, potassium hydroxide was supplied to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 92.8%).

&Lt; Example 58 >

0.8 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.06 mol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,5-dile) 0.14 mol of biphenol and 1.02 mol of biphenyl carbonate were added to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 93.2%).

<Example 59>

0.8 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.08 mol of 4,4 '- (9,10-dihydroanthracene-9,9-dile) biphenol, 2,5-dile) 0.12 mol of biphenol and 1.02 mol of biphenyl carbonate were added to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 89.4%).

&Lt; Example 60 >

0.9 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.03 mol of 9,9-bis (4-hydroxyphenyl) fluorene and 0.03 mol of 3,3-bis (4-hydroxyphenyl) isobenzofuran- 1 (3H) -one and 1.02 mol of biphenyl carbonate were added to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 91.3%).

&Lt; Example 61 >

(4-hydroxyphenyl) propane, 0.14 mol of 9,9-bis (4-hydroxyphenyl) fluorene, 3,3-bis 1 (3H) -one and 1.02 mol of biphenyl carbonate were added to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 88.7%).

&Lt; Example 62 >

, 0.04 mol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 0.04 mol of 3,3-bis (4-hydroxyphenyl) Hydroxyphenyl) isobenzofuran-1 (3H) -one and 1.02 mol of biphenyl carbonate were added to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 92.2%).

&Lt; Example 63 >

Bis (4-hydroxyphenyl) propane, 0.15 mol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, Hydroxyphenyl) isobenzofuran-1 (3H) -one and 1.02 mol of biphenyl carbonate were added to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 89.8%).

Example 64:

0.8 mol of 2,2-bis (4-hydroxyphenyl) propane, 0.12 mol of 9,9-bis (4-hydroxyphenyl) fluorene, 0.08 mol of sulfone and 1.02 mol of biphenyl carbonate were added to the reactor as a polymerization catalyst. The temperature in the reactor was slowly raised from 180 ° C to 300 ° C, and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 91.5%).

&Lt; Example 65 >

0.8 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.12 mol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, -3,5-dimethylphenyl) sulfone and 1.02 mol of biphenyl carbonate as a polymerization catalyst. The temperature in the reactor was slowly raised from 180 ° C to 300 ° C, and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 92.8%).

&Lt; Example 66 >

(4-hydroxyphenyl) propane, 0.12 mol of 3,3-bis (4-hydroxyphenyl) isobenzofuran-1 (3H) -3,5-dimethylphenyl) sulfone and 1.02 mol of biphenyl carbonate as a polymerization catalyst. The temperature in the reactor was slowly raised from 180 ° C to 300 ° C, and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 88.3%).

&Lt; Example 67 >

(4-hydroxyphenyl) propane, 0.18 mol of 3,3-bis (4-hydroxyphenyl) isobenzofuran-1 (3H) -1,1-diallyl) biphenol and 1.02 mol of biphenyl carbonate were fed into the reactor as a polymerization catalyst. The temperature in the reactor was slowly raised from 180 ° C to 300 ° C, and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 87.5%).

&Lt; Example 68 >

0.8 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.11 mol of 9,9-bis (4-hydroxyphenyl) fluorene, 4,4- (2,2-dichloroethene- -) 0.09 mol of biphenol and 1.02 mol of biphenyl carbonate were added to the reactor as a polymerization catalyst. The temperature in the reactor was slowly raised from 180 ° C to 300 ° C, and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 94.2%).

&Lt; Example 69 >

0.8 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.11 mol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, -Dichloroethene-1,1-) biphenol and 1.02 mol of biphenyl carbonate were added to the reactor as a polymerization catalyst. The temperature in the reactor was slowly raised from 180 ° C to 300 ° C, and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 94.8%).

&Lt; Example 70 >

0.8 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.08 mol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 0.12 mol of 6-pentamethyl-3- (3,5-dimethyl-4-hydroxyphenyl) -indan-5-ol and 1.02 mol of biphenyl carbonate were added to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 91.5%).

&Lt; Example 71 >

0.8 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.08 mol of 9,9-bis (4-hydroxyphenyl) fluorene, 1,1,3,4,6- 3,5-dimethyl-4-hydroxyphenyl) -indan-5-ol and 1.02 mol of biphenyl carbonate were fed into the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 90.7%).

<Example 72>

0.8 mol of 2,2-bis- (4-hydroxyphenyl) propane, 0.06 mol of 4,4- (2,2-dichloroethene-1,1-) biphenol, 0.14 mol of pentamethyl-3- (3,5-dimethyl-4-hydroxyphenyl) -indan-5-ol and 1.02 mol of biphenyl carbonate were added to the reactor as a polymerization catalyst. The temperature in the reactor was slowly increased from 200 ° C to 300 ° C and the pressure was slowly lowered to about 0 torr at about 760 torr to proceed with the polycondensation reaction. After completion of the reaction, a synthesized polycarbonate terpolymer was obtained (yield: 93.2%).

Phosgene  Polycarbonate by polymerization method Terpolymer  Produce

&Lt; Example 73 >

0.8 mol of 2,2-bis (4-hydroxyphenyl) propane, 0.08 mol of 9,9-bis (4-hydroxyphenyl) fluorene, 3,3,3 ' 0.12 mol of 3,3'-tetrahydro-1,1'-spirobi [indene] -5,5'-diol, 0.05 mol of p-cumylphenol, 0.048 mol of triethylamine, 1.5 mol of phosgene, 2 L of methylene chloride , And 2 L of water, and the reaction was carried out by a phosgene polymerization process. Specifically, phosgene was phosgenated by adding phosgene to the mixture at a rate of 10 gram / minute for 71 minutes, and the pH was maintained at 11 to 12 using an aqueous sodium hydroxide solution.

After completion of the reaction, the organic layer was separated and purified with dilute hydrochloric acid and water to obtain a synthesized polycarbonate terpolymer (yield: 91.8%).

&Lt; Example 74 >

0.8 mol of 2,2-bis (4-hydroxyphenyl) propane, 0.08 mol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 0.12 mol of tetramethyl-2,2 ', 3,3'-tetrahydro-1,1'-spirob [indene] -5,5'-diol, 0.05 mol of p-cumylphenol, 0.048 mol of triethylamine , 1.5 mol of phosgene, 2 L of methylene chloride and 2 L of water, and the reaction was carried out by a phosgene polymerization process. Specifically, phosgene was phosgenated by adding phosgene to the mixture at a rate of 10 gram / minute for 71 minutes, and the pH was maintained at 11 to 12 using an aqueous sodium hydroxide solution.

After completion of the reaction, the organic layer was separated and purified with dilute hydrochloric acid and water to obtain a synthesized polycarbonate terpolymer (yield: 93%).

&Lt; Example 75 >

0.8 mol of 2,2-bis (4-hydroxyphenyl) propane, 0.08 mol of 9,9-bis (4-hydroxyphenyl) fluorene, 0.1 mol of dimethyladamantane, 0.05 mol of p-cumylphenol, 0.048 mol of triethylamine, 1.5 mol of phosgene, 2 L of methylene chloride and 2 L of water were charged and the reaction was carried out by the phosgene polymerization process. Specifically, phosgene was phosgenated by adding phosgene to the mixture at a rate of 10 gram / minute for 71 minutes, and the pH was maintained at 11 to 12 using an aqueous sodium hydroxide solution.

After completion of the reaction, the organic layer was separated and purified with diluted hydrochloric acid and water to obtain a synthesized polycarbonate terpolymer (yield: 93.6%).

<Example 76>

0.8 mol of 2,2-bis (4-hydroxyphenyl) propane, 0.08 mol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, Phenylmethylphenyl) -5,7-dimethyladamantane, 0.05 mol of p-cumylphenol, 0.048 mol of triethylamine, 1.5 mol of phosgene, 2 L of methylene chloride and 2 L of water, and the reaction was carried out by the phosgene polymerization process . Specifically, phosgene was phosgenated by adding phosgene to the mixture at a rate of 10 gram / minute for 71 minutes, and the pH was maintained at 11 to 12 using an aqueous sodium hydroxide solution.

After completion of the reaction, the organic layer was separated and purified with diluted hydrochloric acid and water to obtain a synthesized polycarbonate terpolymer (yield: 94.7%).

&Lt; Example 77 >

0.8 mol of 2,2-bis (4-hydroxyphenyl) propane, 3,3,3 ', 3'-tetramethyl-2,2', 3,3'-tetrahydro- 0.08 mol of [indene] -5,5'-diol, 0.12 mol of 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 0.05 mol of p-cumylphenol, 0.048 mol of triethylamine, 1.5 mol of phosgene, 2 L of methylene chloride and 2 L of water, and the reaction was carried out by the phosgene polymerization process. Specifically, phosgene was phosgenated by adding phosgene to the mixture at a rate of 10 gram / minute for 71 minutes, and the pH was maintained at 11 to 12 using an aqueous sodium hydroxide solution.

After completion of the reaction, the organic layer was separated and purified with dilute hydrochloric acid and water to obtain a synthesized polycarbonate terpolymer (yield: 93.2%).

Polycarbonate From the terpolymer  Molded product to be manufactured

&Lt; Example 78 >

The polycarbonate terpolymer resin obtained in Example 9 was pelletized and extracted. The polycarbonate terpolymer resin was dried at 120 DEG C for 3 hours, and a barrel temperature of 280 to 320 DEG C and a mold temperature of 80 DEG C Lt; / RTI &gt; A rectangular parallelepiped sample having a width of 3 cm, a length of 12 cm, and a thickness of 0.3 cm was prepared from the injection molded article.

The obtained molded article was found to have properties suitable for transparent electronic materials due to excellent transparency and heat resistance.

< Experimental Example >

IR spectrum  Measure

In Examples 19, The infrared spectroscopy (FT-IR) spectra of the polycarbonate terpolymers of Example 62 and Example 67 were measured.

1 shows the FT-IR (KBr) spectrum of the polycarbonate terpolymer of Example 19. Fig. Referring to Figure 1, a polycarbonate terpolymer of Example 19 is ^{_{CH 3 stretch: 2947cm -1, C}} = O stretch: 1771cm -1, Phenol ring stretch: 1508cm -1, CO stretch: 1312cm -1, CC stretch: The band at 1443cm ^{- 1} was shown.

2 shows the FT-IR spectrum of the polycarbonate terpolymer of Example 62. Fig. Polycarbonate terpolymer of Figure 2, according to Example 62 is ^{_{CH 3 stretch: 3053cm -1, C}} = O stretch: 1768cm -1, Phenol ring stretch: 1504cm -1, CO stretch: 1325cm -1, CC stretch: It exhibited a band in the ^{1 -} 1428cm.

3 shows the FT-IR spectrum of the polycarbonate terpolymer of Example 67. Fig. Referring to Figure 3, a polycarbonate terpolymer of Example 67 is ^{_{CH 3 stretch: 3081cm -1, C}} = O stretch: 1758cm -1, Phenol ring stretch: 1511cm -1, CO stretch: 1270cm -1, CC stretch: It exhibited a band in the ^{1 -} 1458cm.

Glass transition temperature ( Tg ) Measure

The glass transition temperatures (Tg) of the polycarbonate terpolymers obtained in Examples 1 to 77 were measured and are shown in Table 1 below.

Example No. 2. Tg value (unit: ° C) One 158 2 187 3 155 4 180 5 156 6 186 7 156 8 185 9 162 10 158 11 190 12 156 13 184 14 159 15 194 16 156 17 182 18 165 19 157 20 190 21 155 22 181 23 177 24 163 25 160 26 164 27 162 28 161 29 158 30 157 31 166 32 161 33 171 34 165 35 160 36 155 37 182 38 152 39 172 40 153 41 177 42 151 43 166 44 154 45 168 46 162 47 162 48 157 49 154 50 170 51 167 52 157 53 154 54 157 55 174 56 171 57 161 58 158 59 163 60 158 61 196 62 156 63 186 64 173 65 167 66 171 67 188 68 166 69 161 70 166 71 170 72 160 73 165 74 163 75 168 76 164 77 163

The polycarbonate ternary copolymer according to the present invention has high applicability to the engineering plastics field, while maintaining the properties of the existing polycarbonate, and especially having good flowability in a molten state and thermal stability with a high glass transition temperature value at the same time. Therefore, it is expected to be widely applied to various electronic circuit substrate materials including displays and transparent substrates, film materials, high-temperature-resistant lenses, information storage / transmission devices, illumination covers, and prisms.

In addition, in the present invention, polycarbonate having a necessary glass transition temperature can be easily controlled by controlling the kind and content ratio of each monomer.

Claims (11)

A monomer represented by Formula 1 below;
A monomer represented by the following formula (2); And
A polycarbonate terpolymer comprising a repeating unit derived from any one of the monomers represented by the following general formula (3), (4), or (5)
[Chemical Formula 1]

In Formula 1,
R 1 and R 2 are independently selected from an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms;
a and b are independently integers of from 0 to 4;
X is a chemical bond or an oxygen atom, a sulfur atom, -SO2- group, an aliphatic radical having 1 to 20 carbon atoms, or

&Lt; / RTI &gt;
R3 and R4 are independently selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, or an aryl group having 4 to 20 carbon atoms.
(2)

In Formula 2,
R12 is a biphenyl derivative.
(3)

In Formula 3,
R5, R6, R7, R8 and R9 are independently selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, an aryl group having 4 to 20 carbon atoms, a halogen atom, a nitro group and a cyano group;
c, d, e, f, m, n and o are independently an integer of 0 to 4;
[Chemical Formula 4]

In Formula 4,
R10 and R11 are independently selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, an aryl group having 4 to 20 carbon atoms, a halogen atom, a nitro group, and a cyano group;
p, q, r and s are independently an integer of 0 to 4;
[Chemical Formula 5]

In Formula 5,
R14 is a biphenyl derivative.
In this case, except that any two or more monomers among the monomers represented by the above formulas (1) to (5) are the same,
X mole of the repeating unit derived from the monomer represented by the formula (1), y mole of the repeating unit derived from the monomer represented by the formula (2), and a monomer represented by the formula (3), And the mole ratio of x, y and z satisfies x: y: z = 1: 0.01-100: 0.01-100.
The method of claim 1, wherein the monomer represented by Formula 1 is selected from the group consisting of 1,1-bis- (4-hydroxyphenyl) -methane, 1,1-bis- (4-hydroxyphenyl) Bis- (4-hydroxyphenyl) -isobutane, 1,1-bis- (4-hydroxyphenyl) - (4-hydroxyphenyl) -ether, 1,1-bis- (4-hydroxyphenyl) -ketone, 1,1- 4-hydroxyphenyl) -sulfide, 1,1-bis- (4-hydroxyphenyl) -1-phenylmethane, Bis- (4-hydroxyphenyl) -sulfoxide, 1,1-bis- (4-hydroxyphenyl) Propane, 2,2-bis- (3-methyl-4-hydroxyphenyl) propane, (3-allyl-4-hydroxyphenyl) propane, 2,2-bis (3-methoxy- Propane, 2,2-bis- (3-phenyl-4-hydroxyphenyl) propane, (3-sec-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxyphenyl) propane, 2,2- Bis (4- hydroxyphenyl) hexafluoropropane, 2,4-bis- (4-hydroxyphenyl) -2-methylbutane, trans- (4-hydroxyphenyl) -2-butene, ethylene glycol-bis (4-hydroxyphenyl) ether,?,? ' Hydroxyphenyl) -p-diisopropylbenzene. &Lt; / RTI &gt;
[5] The method according to claim 1, wherein the monomers represented by Formula 2 and Formula 5 are each independently 4,4 '- (propane-2,2-dile) bis (2,6-dimethylphenol) , 3'-tetramethyl-2,2 ', 3,3'-tetrahydro-1,1'-spiro [indene] -5,5'-diol, 1,6- (4-hydroxyphenyl) -1,1,3-trimethyl-2,3-dihydro-1H (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4- (cyclododecan-1,1-dyl) biphenol, 4,4 - (tetrahydro-2H-thiopyran-4,4-dile) biphenol, 1- (4,4-bis (4- hydroxyphenyl) piperidin- 1,3-dimethylcyclohexane-1,3-dile) biphenol, 4- (2 - ((1S, 3S, 4S) -3- (4-hydroxyphenyl) (Propane-2-yl) phenol, 4,4 '- ((1R, 3R, 4S) -3-isopropyl-1-methylcyclohexane- 2-dile) diphenyl 4-ol, 6,6'-methylenebis (2-cyclohexyl-4-methylphenol), 1,1'-binaphthyl-2,2'-diol, 1,1- 1-naphthylmethane, 1,1-bis- (4-hydroxyphenyl) -1-phenylmethane and 3,3-bis (4-hydroxyphenyl) isobenzofuran- 4,4- (2,2-dichloroethene-1,1-dile) biphenol, 1,1,3,4,6-pentamethyl-3- (3,5-dimethyl-4-hydroxyphenyl) -indan- 4,4 '- (1,7,7-trimethylbicyclo [2,2,1] heptane-2,2-dile) biphenol, 2,6-dihydroxydibenzo-p-dioxin , 2,7-dihydroxy pyrene, 2,7-dihydroxycarbazole, 4,4'-dihydroxybiphenol, (1-phenylethane-1,1-dile) biphenol, 4,4 '- (1-phenylpropane-2,2-dile) biphenol, 4,4' Biphenol, 4,4 '- (4-phenylbutane-2,2-dile) biphenol, 4,4' - (1-p-tolyloethane- 4,4'- (9,10-dihydroanthracene-9,9-dile) biphenol, 4,4 '- (1- (biphenyl- (Biphenylmethylene) biphenol, 4,4 '- (2,3-dihydro-1H-indene) -1,1-diallylbiphenol, 4,4 '- (2,2' - (1,4-phenylene) bis (propane-2,2- -2,2-diallyl) bis (2-methylphenol), 4,4 '- (4,7,7-trimethylbicyclo [2,2,1] heptane-2,2-dile) biphenol, 4,4' - (propane- (Cyclohexylphenol), 4,4 '- (propane-2,2-dile) bis (2-t-butylphenol) , 4 '- (perfluoropropane-2,2-dile) biphenol, 4,4' - (propane-2,2-diallyl) bis (2-fluorophenol) (4-aminophenol), 4,4'- (propane-2,2-dile) bis (2-nitrophenol) ) Methylene) biphenol, (E) -4,4'-methylenebis (2 - ((E) - (2- (4-nitrophenyl) hydrazano) methyl) phenol) Diol, 4,4 '- (pyrazine-2,5-dile) biphenol, 4,4' - ((1R) -bicyclo [2,2,1] heptane- , 4,3 '- (biphenyl-4,4'-diyl bis (phenyl azadiyl)) biphenol, 4,4' - , 1-phenylene)) bis (phenyl azadyl) biphenol, 3,3'-methylenebis (2- (2H-benzo [d] [1,2,3] Yl) phenol), 4,4 '- (1- (3- (2H-benzo [d] [1,2,3] triazol- 1,1-dile) biphenol, 4,4 '- (cyclononane-1,1-dile) biphenol, 4,4' - (cyclodecane- (Cyclohexadecane-1,1-dile) biphenol, 4,4 '- (cyclotridecan-1,1-dyl) biphenol, bis- (4-hydroxyphenyl-3,5-dimethylphenyl) sulfone , And 4,4 '- (10,10-biphenyl-9,10-dihydroanthracene-9,9-dile) biphenol.
The method according to claim 1, wherein the monomers represented by the general formulas (2) and (5) are each independently and differently selected from 1,1-bis- (4-hydroxyphenyl) -methane, 1,1- (4-hydroxyphenyl) -propane, 1,1-bis- (4-hydroxyphenyl) -butane, 1,1-bis- (4-hydroxyphenyl) - ether, 1,1-bis- (4-hydroxyphenyl) -ketone, 1,1-bis- Sulfone, 1,1-bis- (4-hydroxyphenyl) -sulfide, 1,1-bis- (4-hydroxyphenyl) - phenylmethane, 1,6-bis- (4-hydroxyphenyl) -1,6-hexanedione, 2,2-bis- (3-methyl Hydroxyphenyl) propane, 2,2-bis (3-ethyl-4-hydroxyphenyl) propane, 2,2- (3-methoxy-4-hydroxyphenyl) propane, 2,2-bis- (3-phenyl-4-hydroxyphenyl) propane, 2,2- (3-sec-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, Propane, 2,2-bis- (3-t-butyl-4-hydroxyphenyl) propane, 2,2- 4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxyphenyl) hexafluoropropane, 2,4-bis- -Bis (4-hydroxyphenyl) -2-butene, ethylene glycol-bis (4-hydroxyphenyl) ether, - (4-hydroxyphenyl) toluene, and α, α'- bis (4-hydroxyphenyl) -p- diisopropyl one selected from the group consisting of benzene polycarbonate terpolymer.
The method according to claim 1, wherein the monomers represented by the general formulas (2) and (5) are each independently differently selected from 1,1-bis- (2- (4-hydroxyphenyl) (3,5-dimethyl-4-hydroxyphenyl) -ethane, 1,1-bis- (3,5- (3,5-dimethyl-4-hydroxyphenyl) -3,3-dimethyl-5-methylcyclohexane, 1,1-bis - (3,5-biphenyl-4-hydroxyphenyl) -3,3-dimethyl-5-methylcyclohexane, 1,1- 3-dimethyl-5-methylcyclohexane, 1,1-bis- (3,5-dibromo-4-hydroxyphenyl) (4-hydroxyphenyl) sulfone, 1,1-bis- (4-hydroxy-3-methylphenyl) cyclohexane, 1,1- 3-dimethyl-5, 5-dimethylcyclohexane, 1,1-bis- (4-hydroxy Phenyl) -3,3-dimethyl-5-methylcyclopentane, 1,1-dichloro-2,2-bis (4-hydroxyphenyl) ethylene, 1,1-dibromo-2,2- Hydroxyphenyl) ethylene, 1,1-dichloro-2,2-bis (5-phenoxy-4-hydroxyphenyl) ethylene, 1,3- Dihydroxynaphthalene, 2,2-bis- (2,3,5,6-tetramethyl-4-hydroxyphenyl) propane, 2,2-bis- (2,6- Dimethyl-4-hydroxyphenyl) propane, 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2- (3,5-dimethyl-4-hydroxyphenyl) sulfone, 2,2-bis (3,5-dichloro- ) Propane, 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) propane, 2,4-bis- (3,5- , 2 - ((4-hydroxyphenyl) -2 -) - 3-hydroxyphenyl) -propane, Dihydroxynaphthalene, 2,6-dihydroxyanthracene, 2,7-dihydroxyphenoxazine, 2,7-dihydroxy-9,10-dimethylphenazine, 3,3 ' Dihydroxybiphenyl ether, 3,3'-dihydroxyphthalide, 3,4'-dihydroxybiphenyl ether, 4,4'-dihydroxybiphenyl ether, 4,4'-dihydro Hydroxybiphenylthioether, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxy-1,1-biphenyl, 4,4'-dihydroxy-3,3'-dimethyl- , 1-biphenyl, 4,4'-dihydroxy-3,3'-dioctyl-1,1-biphenyl, 6,6'-dihydroxy-3,3,3 ' Dihydroxybenzene, and?,? '- bis- (hydroxyphenyl) benzene-1,3-diol, 4-bromo- ) -Polysiloxane. &Lt; / RTI &gt;
2. The composition of claim 1, wherein the monomer represented by Formula 3 is selected from the group consisting of 1,1-bis- (3-methyl-4-hydroxyphenyl) -3,3-dimethyl- (3-ethyl-4-hydroxyphenyl) -3,3-dimethyl-5-methylcyclohexane, 1,1- Methyl cyclohexane, 1,1-bis- (3-butyl-4-hydroxyphenyl) -3,3-dimethyl- ) -3,3-dimethyl-5-methylcyclohexane, 1,1-bis- (3-chloro-4-hydroxyphenyl) (3-bromo-4-hydroxyphenyl) -3,3-dimethyl-5-methylcyclohexane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, (4-hydroxyphenyl) -3,3-dimethyl-4-methylcyclohexane, 4,4 '- 3-methylcyclohexane-1,1-dile) biphenol, 4,4 '- (3-tert- (4-tert-butylcyclohexane-1,1-dile) biphenol, 4,4- (4-methyl-4-phenylcyclohexane- 1,1-dile) biphenol, 4,4 '- (3,5-dimethylcyclohexane-1,1-dile) biphenol, 4,4' - (cyclohexane- -Tart-butylphenol), and 4,4 '- (cyclohexane-1,1-dyl) bis (2-methylphenol).
The polymerizable composition according to claim 1, wherein the monomer represented by Formula 4 is 9,9-bis- (4-hydroxyphenyl) fluorene, 9,9-bis- (4-hydroxy- , 9,9-bis- (4-hydroxy-3-ethylphenyl) fluorene, 9,9-bis (4-hydroxy-2-ethylphenyl) fluorene, 9,9-bis- (4-hydroxy-3-cyclohexylphenyl) fluorene, 9,9- (3-methylcyclohexyl) phenyl) fluorene, 9,9-bis- (4-hydroxy- Fluorene, 9,9-bis- (4-hydroxy-3-chlorophenyl) fluorene, 9,9- - (4-hydroxy-3-nitrophenyl) fluorene, and a polycarbonate terpolymer.
The polycarbonate terpolymer of claim 1 prepared by a melt process or a phosgene process.
The polycarbonate terpolymer of claim 1, wherein the monomer represented by Formula 1 is a compound represented by Formula 1a:
[Formula 1a]

A molded article produced from the polycarbonate terpolymer of any one of claims 1 to 9.
The method according to claim 10, wherein the molded article is a display device, a flexible display device, A transparent substrate of an electronic device, an optical film, an optical lens, an information storage device, an information transfer device, an illumination cover device or a prism device.

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