KR101449127B1 - Polycarbonate resin composition and preparation method thereof - Google Patents

Abstract

The present invention relates to a polycarbonate and a process for producing the polycarbonate. The polycarbonate prepared by the process according to the present invention is excellent in heat resistance and has a high number average molecular weight And polycarbonate with a purity (carbonate linkage of more than 90%) of the carbonate.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate resin composition,

The present invention relates to a polycarbonate composition having a carbonate linkage of more than 90% and a process for its preparation.

The polycarbonate resin is a practically used thermoplastic resin and is a polycarbonate ester compound of bisphenol A. It is an engineering plastic that is transparent and has excellent mechanical properties, especially impact resistance, heat resistance, cold resistance and electrical properties, and is non-toxic and self-extinguishing. It is used for automotive bumpers, packaging materials, switches, hair dryers, Machine parts such as parts, various fans, helmets, fire extinguisher covers, and safety products such as safety glass, apartment windows, bulletproof and soundproof walls.

These polycarbonates are generally prepared by the synthesis of bisphenol A and phosgene. However, the above manufacturing process has caused many environmental problems because volatile organic compounds are used as toxic gas and synthetic solvent for human body such as phosgene.

Accordingly, a method of copolymerizing an epoxy compound with carbon dioxide in the presence of a catalyst is used for the production of polycarbonate. By using a double metal cyanide (DMC) catalyst or the like as the catalyst, only a small amount of chloroform is used as a solvent, Can be easily performed by a simple separation process.

Examples of the conventional double metal cyanide (DMC) catalyst include zinc cobalt cyanide (zinc (Zn)) prepared from K [Co (CN) ₆ ] and zinc halide ZnX ₂ cobalt cyanide). However, the conventional double metal cyanide catalysts contained an excess amount of organic complexing agent. Generally, excessive amount of complexing agent was used after the catalyst preparation step or precipitation. For example, alcohols, aldehydes, ketone ethers, esters, amides, ureas, nitriles, sulphates or mixtures thereof have been used as organic complexing agents, among which ether or water-soluble aliphatic alcohols have been preferred.

Specifically, tertiary butyl alcohol has been used in the preparation of double metal cyanide catalysts.

However, when a catalyst is prepared using an organic complexing agent such as tert-butyl alcohol, the synthesis process is complicated, the production time is prolonged, and environmental pollution is caused by using an excessive amount of organic complexing agent.

In addition, the polycarbonate produced through the conventional double metal cyanide salt has a problem in the physical properties of the polycarbonate obtained by the low number average molecular weight and the carbonate content (the content of the carbonate linkage) and the efficiency of the production process.

Furthermore, when polycarbonate is produced using conventional zinc cobalt cyanide, the carbonate bonding ratio is low, which is economically problematic.

Korean Published Patent 2009-0032086

The present invention is a number average molecular weight in the range of (M _n) is 14,000g / mol to 30,000g / mol, a carbonate bond (linkage) is not less than 85%, to about the polycarbonate composition and a method of manufacturing the same that satisfies the formula (1) A polycarbonate composition having a high number average molecular weight and a carbonate linkage, and a process for producing the polycarbonate composition.

The polycarbonate composition according to the present invention has a number average molecular weight (M _n ) in the range of 14,000 g / mol to 30,000 g / mol, a carbonate linkage of 85% or more, and satisfies the following formula (1).

[Chemical Formula 1]

In Formula (1), A is an aryl having 6 to 30 carbon atoms or a cycloalkyl structure having 3 to 30 carbon atoms,

R is an alkenyl group having 2 to 10 carbon atoms,

l and m are each independently a number of 10 to 200. [

Further, the present invention can provide a process for producing polycarbonate. As an example, carbon dioxide and an epoxy compound may be copolymerized under a double metal cyanide catalyst prepared by mixing an organic complex, a metal salt, a metal cyanide salt, and a polyether compound.

The polycarbonate produced by the process according to the present invention is excellent in heat resistance and has a high number average molecular weight and a high purity of carbonate (carbonate linkage of 85% Or more) of the polycarbonate can be provided.

The present invention provides a polycarbonate composition having a number average molecular weight (M _n ) in the range of 14,000 g / mol to 30,000 g / mol, a carbonate linkage of more than 85%, and satisfying the following formula (1).

In Formula (1), A is an aryl having 6 to 30 carbon atoms or a cycloalkyl structure having 3 to 30 carbon atoms,

R is an alkenyl group having 2 to 10 carbon atoms,

l and m are each independently a number of 10 to 200. [

The polycarbonate composition according to the present invention preferably has a number average molecular weight (M _n ) of 14,000 g / mol to 30,000 g / mol in view of mechanical properties, and has a number average molecular weight (M _n ) of 20,000 g / mol to 25,000 g / mol is more preferable. In addition, the carbonate linkage of the polycarbonate composition according to the present invention is preferably 85% or more, more preferably 88% to 98%, and most preferably 92% to 94%.

The number average molecular weight (M _n ) is excellent in heat resistance, mechanical strength and bending strength in the above range, and can be used again as a reactant, so that it can be a good condition for producing a new polymer. Further, when the carbonate linkage is 85% or less, there is a problem that it is uneconomical.

In the present invention, the number average molecular weight means a number average molecular weight measured by gel permeation chromatography (GPC) after correcting polystyrene of a single molecular weight distribution with a standard material, and a carbonate linkage means a number average molecular weight ≪ / RTI > is meant the ratio of carbonates to carbonates and ethers contained in the mixture.

In Formula 1, A may be an aryl having 6 to 30 carbon atoms or a cycloalkyl structure having 3 to 30 carbon atoms. Of these, cycloalkyl having 3 to 30 carbon atoms is preferably used. Specifically, it may be a structure such as phenyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like. Of these, cyclohexyl More preferable.

R may be an alkenyl group having 2 to 10 carbon atoms and specifically includes a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group and a heptenyl group, and among these, a vinyl group or a propenyl group is preferable .

l and m each independently may be a number of 10 to 200, and l and m are repeating units constituting the polycarbonate. The range of 1 and m is not particularly limited.

The polycarbonate according to the present invention is excellent in heat resistance and can be used in various fields as general engineering plastic through high carbonate purity.

The polycarbonate composition of the present invention satisfying these conditions can be produced through the following process for producing polycarbonate.

To the range of number average molecular weight of the poly (M _n) through the production method of the carbonate is 14,000g / mol to 30,000g / mol, a carbonate bond in the structure of polycarbonate (linkage) is not less than 85% and satisfying the above formula (1) The polycarbonate can be produced.

The present invention can be produced by copolymerizing carbon dioxide and an epoxy compound under a double metal cyanide catalyst prepared by mixing and reacting an organic complex, a metal salt, a metal cyanide salt and a polyether compound in the present invention .

The organic complexing agent used in the present invention may be a compound which satisfies the following general formula (2) or (3).

(2)

(3)

In formulas (2) and (3)

R ₁ and R ₆ each independently represent hydrogen, an aryl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms or R ₄ -NH-,

R ₂ and R ₃ each independently represent hydrogen, a hydroxyl group, a cyanide group, an alkyl group having 1 to 20 carbon atoms or R ₅ -NH-,

R ₄ and R ₅ each independently represent hydrogen or an alkyl group having 1 to 20 carbon atoms,

R ₇ and R ₈ are each independently selected from the group consisting of hydrogen, neopentane, an alkyl group having 1 to 20 carbon atoms, an ester group having 1 to 20 carbon atoms, a ketone group having 1 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, Lt; / RTI &

n ₁ and n ₂ each independently represent a number of 0 to 3;

In the present invention, the organic complex agent includes the structure of Formula 2 or Formula 3, for example, 1-hydroxy-2,2,4-trimethyl-3-pentanone (1-hydroxy- 4-trimethyl-3-pentanone, 1-hydroxy-2-butanone, 2- (hexyloxy) ethyl 2-hydroxypropanoate ethyl 2-hydroxypropanoate, 2,6-dihydroxy-2,6-dimethyl-4-heptanone, 2,2,5,5-tetramethyl-4-hydroxynaphthalene Hydroxy-3-methyl-2-butanone, 2-hydroxy-3- butanone, 3-hydroxy-3-methyl-2-hexanone, 3-hydroxy- 3,5-dimethyl-2-hexanone, 4-hydroxy-3-hexanone, 4-hydroxy-3-heptanone, 4-propyl-heptan-3-one, 4-hydroxy-4-methyl-2-pentanone (4-hydroxy-4-methyl-2-pentanone), 5-hydroxy-2,5,6-trimethyl-heptan- 5-hydroxy-4-octanone or 6-hydroxy-5-decanone, methyl 2-hydroxy- Methyl 2-methyl-3-oxopentanoate, ethyl 2-hydroxyhexanoate, ethyl 2-hydroxy-4-methylpentanoate 2-hydroxy-4-methylpentanoate, ethyl 2-ethyl-2-hydroxy-3-oxobutyrate, ethyl 2,2- , 2-diethylglycolate, Ethyl 3-hydroxybutyrate, Ethyl 3-hydroxyhexanoate, Ethyl alpha-hydroxyisobutyrate, Methyl alpha-hydroxyisobutyrate (tert-Butyl alpha-hydroxyisobut) yrate, triethyl citrate, tributyl citrate, diethyl malate, dibutyl malate, methyl 2-hydroxy-2-methyl-3 Methyl 2-methyl-3-oxobutyrate, Methyl-3-hydroxybutyrate, Methyl 3-hydroxyhexanoate, Methyl 3-hydroxy-2,3,4,4-tetramethylvalerate, and 4-hydroxy-4-methyl-2-penta Ethyl 4-methyl-2-pentanone, ethyl 3-hydroxybutyrate, diethyl malate, and ethyl 3-hydroxyhexanoate. hydroxyhexanoate), and among them, 4-hydroxy-4-methyl-2-pentanone, ethyl 3-hydroxybutyrate ( Ethyl 3-hydroxybutyrate, Diethyl malate, and Ethyl 3-hydroxyhexanoate. It is preferable to use at least one selected from the group consisting of 4-hydroxy-4- The use of 4-hydroxy-4-methyl-2-pentanone is more preferable in view of the activity of the catalyst and the economical efficiency of the catalyst production.

The present inventors have found that a double metal cyanide salt having higher catalytic activity can be prepared through the organic complexing agent as described above, thereby increasing the polymerization activity during the preparation of the polycarbonate, thereby improving the number average molecular weight and the carbonate linkage of the finally produced polycarbonate. .

Therefore, the polycarbonate according to the present invention can produce a polycarbonate by a simpler method, and can realize a high carbonate content by using less energy. The polycarbonate thus prepared has excellent heat resistance, mechanical properties This is a universal engineering plastic that can be used in various fields.

In the present invention, the metal salt and the metal cyanide salt contained in the double metal cyanide salt catalyst may be dissolved in water and reacted. Specifically, the double metal cyanide salt catalyst may be a reaction product of a water-soluble metal salt and a water-soluble metal cyanide salt.

For example, the water-soluble metal salt may include the structure of M (X) n. M is at least one element selected from the group consisting of Zn (II), Fe (II), Ni (II), Mn (II) (VI), Al (II), V (V), V (IV), Sr (II), W And may specifically be Zn (II), Fe (II), Co (II) or Ni (II). The X may be a halide, a hydroxide, a sulfate, a carbonate, a cyanide, an oxalate, a thiocyanate, an isocyanate, an isothiocyanate, And may be an anion selected from the group consisting of isothiocyanate, carboxylate, and nitrate. The above-mentioned n is an integer of 1 to 3, and satisfies the valence of M. For example, the metal salt may be at least one selected from the group consisting of zinc chloride, zinc bromide, zinc acetate, zinc acetonylacetonate, zinc benzoate, zinc nitrate, iron bromide (II), cobalt chloride (II), cobalt thiocyanate (II) , Nickel (II) formate, or nickel (II) nitrate.

The water-soluble metal cyanide salt may be potassium hexacyanocobaltate (III), potassium hexacyanoferrate (II), potassium hexacyanoferrate (II), potassium hexacyanoferrate , Potassium hexacyanoferrate (III), calcium hexacyanocobaltate (II), or lithium hexacyanoferrate (II).

For example, the polyether compound contained in the double metal cyanide catalyst may be a compound prepared by ring-opening polymerization of a cyclic ether compound, an epoxy polymer or an oxetane polymer, and the terminal may be a hydroxyl group, an amine group, an ester group or an ether . The number of hydroxyl functional groups may preferably be 1 to 8, and may be, for example, a polyether polyol.

The polyether polyols include, for example, poly (propylene glycol) block copolymers, poly (ethylene glycol) block copolymers, polytetramethylene ether glycol block copolymers, block copolymers of ethylene oxide and propylene oxide, Or hyper branched polyglycidol may be included. The block copolymer of ethylene oxide and propylene oxide may be, for example, a poly (ethylene oxide) -poly (propylene oxide) -poly (ethylene oxide) terpolymer, an oxide-capped poly (oxypropylene) Propylene oxide polyol, and the butylene oxide polymer may be a branched glycerol having a butylene glycol and a hydroxyl group having a weight average molecular weight of 1,000 to 50,000, or a copolymer thereof.

In addition, the double metal cyanide salt catalyst used in the present invention can be produced according to the following production method. Preparing a mixed solution 1 comprising an organic complex, a metal salt, and distilled water containing the structure of Formula 2 or 3; Preparing a mixed solution 2 comprising a metal cyanide salt and distilled water; Mixing the mixed solution 1 and the mixed solution 2 to prepare a catalyst slurry; And mixing the catalyst slurry, the organic complex and the polyether mixture.

Specifically, the organic complex, the metal salt and the distilled water may be mixed in a beaker and thoroughly stirred through a mechanical stirrer to prepare the mixed solution 1. Mixed solution 2 can also be prepared by mixing and stirring another cigar metal salt and distilled water with another beaker. Then, the prepared mixed solution 1 was mixed by heating and stirring, and the mixed solution 2 was added dropwise to the thus mixed mixed solution 1 to prepare a catalyst slurry. To the thus prepared catalyst slurry, the organic complexing agent and polyether The mixture can be mixed and stirred, high-speed centrifugation can be used to remove impurities after separation, and the double metal cyanide salt catalyst according to the present invention can be prepared through a washing and drying process.

The polyether compound may be used in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the double metal cyanide catalyst. For example, the content of the polyether compound may be 0.1 to 25, 0.1 to 20, 5 to 25, or 10 to 20. Within the content range of the polyether compound, the double metal cyanide catalyst can achieve high catalytic activity.

In the present invention, a method of copolymerizing carbon dioxide and an epoxy compound under a double metal cyanide salt catalyst comprises: introducing a double metal cyanide salt catalyst into a trap installed inside the reactor; Purging the inside of the reactor using carbon dioxide gas; And an epoxy compound are injected into the reactor to control the internal pressure, the temperature and the stirring speed to copolymerize the carbon dioxide and the epoxy compound to produce the polycarbonate.

Specifically, a method of copolymerizing carbon dioxide with an epoxy compound is as follows. Specifically, a high pressure reactor is used, a double metal cyanide salt catalyst according to the present invention is introduced into a trap installed on the high pressure reactor, The inside can be purged to remove the active gas which is present in the reactor and can cause the explosion. The pressure can then be maintained by injecting the epoxy compound into the reactor, increasing the reactor internal pressure, stirring speed and temperature, and continuously supplying carbon dioxide. This allows the catalyst trapped in the trap located at the top of the reactor to fall to the bottom of the reactor to promote copolymerization of the epoxy compound and carbon dioxide. After the polymerization reaction, the catalyst and the polymerization product may be separated using a vacuum glass filter, and the unreacted epoxy compound may be removed by vacuum drying to obtain the polycarbonate.

The epoxy compound used in the production of the polycarbonate is not particularly limited, but the epoxy compound may be a cyclic epoxide, and the cyclic epoxide may be a cycloalkene having 3 to 30 carbon atoms substituted with an alkenyl group having 2 to 10 carbon atoms Oxide; And an arylene oxide having 6 to 20 carbon atoms, which is substituted or unsubstituted with an alkenyl group having 3 to 12 carbon atoms. Of these, an alkenyl group having 3 to 30 carbon atoms substituted with an alkenyl group having 2 to 10 carbon atoms Of the cycloalkene oxide is more preferably used. For example, the epoxy compound may be selected from the group consisting of 4-vinyl-1-cyclohexene 1,2-epoxide, vinylcyclohexene dioxide, 2- (2-vinylphenyl) oxirane, 1,2-di (oxiran-2-yl) benzene, limonene 1,2-epoxide, among which 4-vinyl-1-cyclohexene It is most preferred to use 1,2-epoxide or limonene 1,2-epoxide.

The molar ratio of the double metal cyanide catalyst to the epoxy compound may range from 5,000: 1 to 50,000: 1. For example, the molar ratio may be 10,000: 1 to 50,000: 1, 10,000: 1 to 30,000: 1, 10,000: 1 to 20,000: 1, or 5,000: 1 to 30,000: 1. Polycarbonate can be produced economically within the above range and can have a high content of carbonate.

Further, the metal is not particularly limited as long as it is a transition metal, and zinc is preferably used.

The inner pressure, the polymerization temperature, and the stirring speed are not particularly limited, and may be, for example, from 10 to 650 psi, and the polymerization temperature may be from 20 to 180 ° C under the conditions of copolymerizing the carbon dioxide and the epoxy compound , And the stirring speed can be adjusted to a maximum of 300 rpm. Specifically, the internal pressure can be gradually increased, and carbon dioxide can be continuously supplied and maintained. In addition, the temperature at the time of polymerization can be gradually increased during the polymerization, and after the completion of the polymerization reaction, it can be gradually cooled. In addition, the stirring speed does not exceed a maximum of 300 rpm, and can be adjusted within a range that promotes stirring and polymerization.

The method of polymerizing the polycarbonate is not particularly limited, and for example, a batch polymerization method, a semi-batch polymerization method or a continuous polymerization method can be used.

The number average molecular weight (Mn) of the polycarbonate according to the present invention may range from 14,000 g / mol to 30,000 g / mol through the above-described production process, and the number average molecular weight (Mn) The mechanical properties of the carbonate can be improved, and particularly excellent heat resistance can be realized.

Hereinafter, the present invention will be described in detail with reference to examples. However, the scope of the present invention is not limited to these examples.

Example  One

(One) Double metal cyanide salt  catalyst( DMC - E01 )

A 250 ml Erlenmeyer flask was equipped with a mechanical stirrer, thermostat and thermometer. To the beaker 1 was added 5.9972 g (44 mmol) of zinc chloride, 23 mL of distilled water and 7.3181 mL (63 mmol) of 4-hydroxy-4-methyl-2-pentanone ) Was added and sufficiently dissolved by stirring to prepare mixed solution 1. In addition, Mixture 2 was prepared by mixing 0.6595 g (2 mmol) potassium cobalt cyanide cyanide and 8 mL of distilled water in Beaker 2. Then, the mixed solution 1 was heated to 80 DEG C, stirred at a stirring speed of 400 rpm for 20 minutes using a mechanical stirrer, and mixed solution 2 was added dropwise to the mixed solution 1 at 80 DEG C for 1 hour while mixing. To the thus prepared catalyst slurry was added 3.7171 mL (32 mmol) of 4-hydroxy-4-methyl-2-pentanone and P123 (poly (ethylene glycol) -block-poly (propylene glycol) 0.485 g (0.008 mmol) of poly (ethylene glycol) -block-poly (ethylene glycol) -block-poly (ethylene glycol) (hereinafter referred to as "P123") and MW = 5800 were mixed and reacted for 10 minutes. The mixture was then separated by high speed centrifugation and washed three times with a mixture of 10 mL of distilled water and 3.7171 mL (32 mmol) of 4-hydroxy-4-methyl-2-pentanone The remaining impurities were removed by separation. Then, the separated catalyst cake was dried at a temperature of 60 DEG C and a vacuum of 30 inHg to prepare a double metal cyanide salt catalyst (hereinafter referred to as "DMC-E01").

(2) Production of polycarbonate

10 mg of the double metal cyanide salt catalyst (DMC-E01) prepared above was introduced into the upper part of a 170 mL high-pressure reactor, and the inside of the reactor was purged with carbon dioxide gas. Then, 20 mL of 4-vinyl-1-cyclohexene 1,2 -Epoxide were introduced into the reactor. At this time, the catalyst is trapped in the trap in the reactor and exists in a state separated from the 4-vinyl-1-cyclohexene 1,2-epoxide. At this time, the internal pressure of the reactor was increased from 16 psi to 620 psi, and the reactor temperature was increased from room temperature to 90 캜. The pressure inside the reactor was maintained at 620 psi by continuously supplying carbon dioxide and the stirrer speed was increased to 300 rpm to drop the catalyst trapped in the trap to the bottom of the reactor to form a 4-vinyl-1-cyclohexene 1,2-epoxide . Then, after the reaction was carried out for 1 hour, the supply of carbon dioxide was stopped, the unreacted carbon dioxide inside the reactor was discharged to the outside, and the reactor temperature was cooled to room temperature. At this time, the viscosity of the product inside the reactor was lowered by using a chloroform solvent, and the catalyst and the polymerization product were separated by a vacuum glass filter. Then, it was dried at a temperature of 80 캜 and a vacuum of 30 inHg to remove unreacted 4-vinyl-1-cyclohexene 1,2-epoxide to prepare a polycarbonate.

Example  2

(1) Preparation of double metal cyanide catalyst ( DMC - E02 )

Ethyl 3-hydroxybutyrate was added in the same mole number instead of 4-hydroxy-4-methyl-2-pentanone in Example 1 A double metal cyanide catalyst (hereinafter referred to as "DMC-E02") was prepared in the same manner as in Example 1.

(2) Production of polycarbonate

A polycarbonate was prepared in the same manner as in Example 1 except that the double metal cyanide catalyst (DMC-E02) was used instead of the double metal cyanide catalyst (DMC-E01) in Example 1.

Example  3

(1) Preparation of double metal cyanide catalyst ( DMC - E03 )

Except that diethyl malate was added in the same mole number instead of 4-hydroxy-4-methyl-2-pentanone in Example 1 A double metal cyanide catalyst (hereinafter referred to as "DMC-E03") was prepared in the same manner as in Example 1.

(2) Production of polycarbonate

A polycarbonate was prepared in the same manner as in Example 1, except that the double metal cyanide catalyst (DMC-E03) was used in place of the double metal cyanide catalyst (DMC-E01) in Example 1.

Example  4

(1) Preparation of double metal cyanide catalyst ( DMC - E04 )

Ethyl 3-hydroxyhexanoate was used in place of 4-hydroxy-4-methyl-2-pentanone in Example 1, A double metal cyanide catalyst (hereinafter referred to as "DMC-E04") was prepared in the same manner as in Example 1.

(2) Production of polycarbonate

A polycarbonate was prepared in the same manner as in Example 1, except that the double metal cyanide catalyst (DMC-E04) was used instead of the double metal cyanide catalyst (DMC-E01) in Example 1.

Example  5

(2) Production of polycarbonate

A polycarbonate was prepared in the same manner as in Example 1, except that the limonene 1,2-epoxide was used instead of the 4-vinyl-1-cyclohexene 1,2-epoxide in Example 1.

Example  6

(2) Production of polycarbonate

A polycarbonate was prepared in the same manner as in Example 2, except that the limonene 1,2-epoxide was used instead of the 4-vinyl-1-cyclohexene 1,2-epoxide in Example 2.

Example  7

(2) Production of polycarbonate

A polycarbonate was prepared in the same manner as in Example 3, except that the limonene 1,2-epoxide was used instead of the 4-vinyl-1-cyclohexene 1,2-epoxide in Example 3.

Example  8

(2) Production of polycarbonate

A polycarbonate was prepared in the same manner as in Example 4, except that the limonene 1,2-epoxide was used instead of the 4-vinyl-1-cyclohexene 1,2-epoxide in Example 4.

Comparative Example  One

(One) Double metal cyanide salt  catalyst( DMC -5)

A 250 ml Erlenmeyer flask was equipped with a mechanical stirrer, thermostat and thermometer. 30 g of zinc chloride, 69 mL of distilled water and 115.5 mL of t-butanol (t-BuOH) were added to beaker 1 and sufficiently dissolved by stirring to prepare mixed solution 1. In addition, Mixture 2 was prepared by mixing 3.15 g of potassium cobalt cyanide cyanide and 42 mL of distilled water in Beaker 2. In addition, 3.5 g of polytetramethylene ether glycols (hereinafter referred to as "PTMEG"), 20 mL of t-butanol (t-BuOH) and 20 mL of distilled water were mixed with beaker 3 to prepare mixed solution 3 Respectively. Then, the mixed solution 1 was added dropwise with stirring at 50 DEG C for 1 hour, followed by addition of the mixed solution 3, followed by reaction for 3 minutes. Then, the mixed product was separated by high-speed centrifugation, mixed with 46 mL of distilled water and 104 mL of t-butanol (t-BuOH), and reacted at 50 DEG C for 1 hour with stirring. Then, 0.85 g of PTMEG Was added to the reactor and stirred for 3 minutes. The prepared catalyst cake was mixed with 100 mL of distilled water and 50 mL of t-butanol (t-BuOH), and the remaining impurities were removed by centrifugation three times. Then, the separated catalyst cake was dried at a temperature of 60 DEG C and a vacuum of 30 inHg to prepare a double metal cyanide catalyst (hereinafter referred to as "DMC-5").

(2) Production of polycarbonate

A polycarbonate was prepared in the same manner as in Example 1 except that the double metal cyanide catalyst (DMC-5) was used in place of the double metal cyanide catalyst (DMC-E01) in Example 1.

Comparative Example  2

(2) Production of polycarbonate

A polycarbonate was prepared in the same manner as in Comparative Example 1, except that the epoxy compound in Comparative Example 1 was replaced by a limonene 1,2-epoxide instead of 4-vinyl-1-cyclohexene 1,2-epoxide .

Comparative Example  3

(2) Production of polycarbonate

A polycarbonate was prepared in the same manner as in Comparative Example 1, except that cyclohexene oxide was used instead of 4-vinyl-1-cyclohexene 1,2-epoxide in Comparative Example 1.

Comparative Example  4

(2) Production of polycarbonate

A polycarbonate was prepared in the same manner as in Example 1 except that cyclohexene oxide was used instead of 4-vinyl-1-cyclohexene 1,2-epoxide in Example 1.

Comparative Example  5

(2) Production of polycarbonate

A polycarbonate was prepared in the same manner as in Comparative Example 4, except that the double metal cyanide catalyst (DMC-E02) was used in place of the double metal cyanide catalyst (DMC-E01) in Comparative Example 4.

Comparative Example  6

(2) Production of polycarbonate

A polycarbonate was prepared in the same manner as in Comparative Example 4, except that the double metal cyanide catalyst (DMC-E03) was used in place of the double metal cyanide catalyst (DMC-E01) in Comparative Example 4.

Comparative Example  7

(2) Production of polycarbonate

A polycarbonate was prepared in the same manner as in Comparative Example 4, except that the double metal cyanide catalyst (DMC-E04) was used in place of the double metal cyanide catalyst (DMC-E01) in Comparative Example 4.

Experimental Example  One

The yield, turnover number (amount of polymer that can be produced per mole of zinc, hereinafter referred to as "TON") of the polycarbonate produced through Examples 1 to 12 and Comparative Examples 1 to 8, (Tm), the number average molecular weight (Mn), and the number average molecular weight (Mn) of each of the impurities (Ether) and carbonate contained in the produced polycarbonate (hereinafter referred to as "TOF" (PDI) and the content of carbonate. The melting points of the impurities and the carbonates were measured using a differential scanning calorimetry (910 DSC) of Du Pont Instrument. The number average molecular weight and the degree of dispersion were measured by GPC and the carbonate content was measured by NMR.

Yield (g) TON TOF T _m GPC Carbonate
content(%) ether carbonate M _n PDI Example 1 20.114 22258.75 22258.75 97.7 150.1 25,000 1.40 91.74 Example 2 21.234 20295.41 20295.41 101.2 148.9 20,200 1.44 90.09 Example 3 21.845 22668.14 22668.14 95.0 144.5 24,100 1.42 92.59 Example 4 20.765 20677.81 20677.81 96.4 148.5 21,500 1.48 91.74 Example 5 15.212 16834.05 16834.05 78.4 134.5 30,300 1.65 93.45 Example 6 16.555 15823.23 15823.23 73.0 129.1 22,900 1.66 91.74 Example 7 16.019 16622.61 16622.61 76.5 140.1 27,800 1.59 91.74 Example 8 15.750 15683.87 15683.87 74.2 128.8 23,300 1.60 90.90 Comparative Example 1 15.875 3651.86 3651.86 79.9 131.1 10,500 1.80 71.42 Comparative Example 2 10.254 2358.81 2358.81 65.8 114.1 8,700 1.95 64.51 Comparative Example 3 14.978 3445.52 3445.52 71.5 138.8 27,100 1.61 60.24 Comparative Example 4 20.154 22303.02 22303.02 90.1 148.5 88,100 1.38 80.00 Comparative Example 5 18.684 17858.13 17858.13 100.5 150.2 70,200 1.41 75.76 Comparative Example 6 20.358 21125.11 21125.11 86.7 134.8 67,500 1.47 75.76 Comparative Example 7 19.658 19575.46 19575.46 86.5 148.8 69,000 1.50 80.00

As a result of the above Table 1, it has been found that a double metal cyanide catalyst prepared by using a lactate compound or an organic complexing agent having the structure of Formula 2 and 4-vinyl-1-cyclohexene 1,2-epoxide as an epoxy compound It was confirmed that the physical properties such as yield, melting point, productivity, and carbonate content were significantly higher than those of Comparative Example 1 using zinc cobalt cyanide as a conventional catalyst. Examples 5 to 8, which are polycarbonates prepared by using limonene 1,2-epoxide, also have remarkably higher physical properties than those of Comparative Example 2. Particularly, the melting point (Tm) of the carbonate is different by about 10 ° C or more, and the carbonate content is also different by 10% or more.

It was confirmed that TOF which can be used as an index of catalytic activity in Examples 1 to 8 according to the present invention is about 6 times higher than TOF of Comparative Example 1. [

Further, in Comparative Examples 4 to 7, cycloalkene oxide unsubstituted as an epoxy compound was used. Compared with Examples 1 to 8 in which cycloalkene oxide substituted with an alkenyl group was used as an epoxy compound, a carbonate content of 10% There is a difference of up to 30%.

Furthermore, Comparative Example 3 using zinc cobalt cyanide as a double metal cyanide catalyst and using cycloalkene oxide as an epoxy compound differed substantially in physical properties compared to Examples 1 to 8 of the present invention.

Claims (11)

A polycarbonate composition having a number average molecular weight (M _n ) in the range of 14,000 g / mol to 30,000 g / mol, a carbonate linkage of 85% or more, and
[Chemical Formula 1]

In Formula (1), A is an aryl having 6 to 30 carbon atoms or a cycloalkyl structure having 3 to 30 carbon atoms,
R is an alkenyl group having 2 to 10 carbon atoms,
l and m are each independently a number of 10 to 200. [
The method according to claim 1,
Wherein the polycarbonate composition has a number average molecular weight (M _n ) of 20,000 g / mol to 25,000 g / mol.
The method according to claim 1,
Wherein the carbonate linkage is 88 to 98%.
The method according to claim 1,
Wherein R in the general formula (1) is a vinyl group or an isopropenyl group.
An organic complexing agent, a metal salt, a metal cyanide salt and a polyether compound,
Carbon dioxide and an epoxy compound,
The organic complex agent preferably satisfies the following formula (2) or (3)
Wherein the epoxy compound is a cyclic epoxide.
(2)

(3)

In formulas (2) and (3)
R ₁ and R ₆ each independently represent hydrogen, an aryl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms or R ₄ -NH-,
R ₂ and R ₃ each independently represent hydrogen, a hydroxyl group, a cyanide group, an alkyl group having 1 to 20 carbon atoms or R ₅ -NH-,
R ₄ and R ₅ each independently represent hydrogen or an alkyl group having 1 to 20 carbon atoms,
R ₇ and R ₈ are each independently selected from the group consisting of hydrogen, neopentane, an alkyl group having 1 to 20 carbon atoms, an ester group having 1 to 20 carbon atoms, a ketone group having 1 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, Lt; / RTI &
n ₁ and n ₂ each independently represent a number of 0 to 3;
delete 6. The method of claim 5,
The polycarbonate is a polycarbonate having a number average molecular weight (M _n ) in the range of 14,000 g / mol to 30,000 g / mol, a carbonate linkage of 85% or more in the structure of the polycarbonate, Gt;
[Chemical Formula 1]

In Formula (1), A is an aryl having 6 to 30 carbon atoms or a cycloalkyl structure having 3 to 30 carbon atoms,
R is an alkenyl group having 2 to 10 carbon atoms,
l and m are each independently a number of 10 to 200. [
6. The method of claim 5,
The organic complex agent may be selected from the group consisting of 4-hydroxy-4-methyl-2-pentanone, ethyl 3-hydroxybutyrate, Wherein the polycarbonate is at least one selected from the group consisting of diethyl malate and ethyl 3-hydroxyhexanoate.
delete 6. The method of claim 5,
Wherein the epoxy compound is a cycloalkene oxide having 3 to 30 carbon atoms substituted with an alkenyl group having 2 to 10 carbon atoms.
6. The method of claim 5,
The epoxy compound is preferably selected from the group consisting of 4-vinyl-1-cyclohexene 1,2-epoxide, vinylcyclohexene dioxide, 2- (2-vinylphenyl) oxirane, (1, 2-di (oxiran-2-yl) benzene).