JPH07286036A - Production of lowly colored polyester - Google Patents

Abstract

PURPOSE:To produce a very lowly colored polyester by reacting a dialkyl dicarboxylate with a polycarbonate and/or an aromatic dialkyl dicarbonate in the presence of an Sn catalyst. CONSTITUTION:This production process is the one for producing a polyester of a weight-average molecular weight of 3000-150000 by reacting a dialkyl dicarboxylate (A) with a polycarbonate (B) and/or an aromatic dialkyl carbonate (C), which process comprises step 1 of using the raw materials in amounts to give a molar ratio of B and/or C to A in the range of 0.8-1.5, using the Sn catalyst in an amount of 0.001-5.0 pts.wt. per 100 pts.wt. C and heating the mixture to 200-300 deg.C and step 2 of heating the reaction mixture in a vacuum to 280-350 deg.C.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel method for producing polyester. More specifically, when a polyester is produced by reacting a dialkyl ester of dicarboxylic acid with a polycarbonate and / or an aromatic dialkyl dicarbonate, a Sn-based catalyst is used as a transesterification reaction catalyst to produce a low-colored polyester. Regarding the method.

[0002]

2. Description of the Related Art Various methods for producing thermoplastic polyesters are known, but the most general method is a melt polycondensation reaction of a dicarboxylic acid and a diol in the presence of a catalyst. However, although the method is effective for producing a polyester using an aliphatic diol represented by ethylene glycol or the like as a diol, 2,2'-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A is described. In the production of polyester using an aromatic diol represented by
Aromatic diols have poor reactivity and when a polyester having a high degree of polymerization is to be obtained, a reaction under severe conditions is required, resulting in a problem that the resulting polymer is severely colored.

In order to avoid such problems, JP-A-5-262864 discloses a method for producing an aromatic polyester in which a dialkyl ester of an aromatic dicarboxylic acid is reacted with an aromatic polycarbonate and / or an aromatic dialkyl dicarbonate. Is described. However, in the method of the above-mentioned patent, although the reaction conditions are mild, there is a problem in that when the disclosed Ti or Zr-based catalyst is used, the polyester produced is severely colored. Such a problem becomes a serious drawback when the polyester is used for transparent materials such as lenses for automobile lamps. Moreover, the amount of the disclosed Ti or Zr-based catalyst is 0.1-0.1%.
When it is used in a large amount of 5.0% by weight and a large amount of the catalyst remains in the resin, practical problems such as durability and flame retardancy occur. In addition, when a Li-based catalyst is used, coloring is reduced, but there is a problem that it is difficult to increase the molecular weight due to the influence of water and the like. For this reason, it is necessary to control the water content of the raw material / reactor to suppress side reactions, which is a constraint on the manufacturing process.

[0004]

DISCLOSURE OF THE INVENTION The present invention overcomes the drawbacks of the conventional methods for producing polyesters,
The purpose of the present invention is to provide a new method for producing a low-colored polyester.

[0005]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that a Sn-based catalyst is used in a reaction between a dicarboxylic acid dialkyl ester and a polycarbonate and / or an aromatic dialkyl dicarbonate. It has been found that, by using it, it is possible to produce polyesters with greatly reduced coloration. Moreover, generally P
It is said that the Ti-based catalyst is more active than the Sn-based catalyst in the synthesis reaction of ET and PBT [eg, Pilati, etc.
(F.Pilati, A.Murai and P.Manaresi), "Polymer Communication", 25, 187,
(1984)], however, the inventors have found that Sn-based catalysts have higher catalytic activity than Ti or Zr-based catalysts in the present reaction system, and that the present reaction can proceed with a smaller amount of catalyst, thus completing the present invention. As described above, the use of the Sn-based catalyst markedly reduces the coloration, and it is surprising that the activity is higher than that of the Ti-based catalyst.

That is, the present invention is characterized by using a Sn-based catalyst as a transesterification catalyst when a polyester is produced by reacting a dialkyl ester of a dicarboxylic acid with a polycarbonate and / or an aromatic dialkyl dicarbonate. A method for producing a colored polyester is described.

The present invention will be described in detail below. In the present invention, examples of the polycarbonate used as a raw material include compounds represented by the general formula (I).

[0008]

[Chemical 4]

{R ¹ and R ² in the general formula (I) are the same or different and each is a divalent aromatic hydrocarbon group, R ³ -X
-R ⁴ group (provided that R ³ and R ⁴ are divalent aromatic hydrocarbon groups, and X represents an oxygen atom, a sulfonyl group, a carbonyl group, a hydrocarbon group, an ester group or a direct bond). (However, the hydrogen atom of the aromatic ring may be substituted with a halogen atom, a hydrocarbon group, an alkoxy group, a phenoxy group or the like.), A and b are positive integers from 1 to 500, and c is Indicates a positive integer (however, (ca + cb)
Is 500 or less]. Of the polycarbonates used in the present invention, a polycarbonate based on bisphenol A is preferable from the viewpoint of balance between physical properties and cost.

As the aromatic dialkyl dicarbonate used in the present invention, compounds represented by the general formula (II) can be mentioned.

[0011]

[Chemical 5]

[In the general formula (II), R ⁵ is a divalent aromatic hydrocarbon group, R ⁷ -X-R ⁸ group (provided that R ⁷ and R ⁸ are 2
It is a valent aromatic hydrocarbon group, and X represents an oxygen atom, a sulfonyl group, a carbonyl group, a hydrocarbon group, an ester group or a direct bond. (However, the hydrogen atom of the aromatic ring may be substituted with a halogen atom, a hydrocarbon group, an alkoxy group, a phenoxy group or the like.), And R ⁶ has 1 to 4 carbon atoms.
Is an aliphatic hydrocarbon group or an aromatic hydrocarbon group having 6 to 10 carbon atoms. ]

Specific examples of such compounds include the following aromatic diols dimethyl, diethyl and diphenyl carbonate. That is, as specific examples of the aromatic diol, for example, bisphenol A, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dimethylphenyl) methane, bis (4
-Hydroxy-3,5-dichlorophenyl) methane,
1,1-bis (4-hydroxyphenyl) cyclohexylmethane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) 1-phenylethane, 1,1-bis (4 -Hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,
4'-dihydroxydiphenyl ether, bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, 4,
4'-dihydroxybenzophenone, 2,2-bis (4
-Hydroxy-3,5-dimethylphenyl) propane,
Tetrabromobisphenol A, tetrachlorobisphenol A, dihydroxydiphenyl, hydroquinone,
Examples thereof include resorcinol, dihydroxynaphthalene, dihydroxyanthracene, phenolphthalein, ferulescein, 2,2′-dihydroxy-1,1-dinaphthylmethane, 4,4′-dihydroxydinaphthyl and the like. Of these, bisphenol A is easily available.
Dimethyl carbonate is preferred. In the present invention, the above-mentioned polycarbonate and aromatic dialkyl dicarbonate may be used alone or in combination of two or more kinds, or may be used in combination of one kind or two or more kinds.

In the present invention, the dialkyl ester of dicarboxylic acid used as another raw material is
The compound represented by general formula (III) can be mentioned.

[0015]

[Chemical 6]

[R ⁹ in the general formula (III) has 6 to 1 carbon atoms.
A divalent aromatic hydrocarbon group of 0 (provided that the hydrogen atom of the aromatic ring may be substituted with a halogen atom, a hydrocarbon group, an alkoxy group, a phenoxy group or the like), and a carbon number of 2 to 2.
0 represents an aliphatic or alicyclic hydrocarbon group, and R ¹⁰ represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms. ]

Specific examples of the dialkyl ester of dicarboxylic acid include dimethyl, diethyl and diphenyl esters of dicarboxylic acid shown below. That is, specific examples of the dicarboxylic acid include terephthalic acid, methoxyterephthalic acid, ethoxyterephthalic acid, fluoroterephthalic acid, chloroterephthalic acid, methylterephthalic acid, isophthalic acid, phthalic acid, methoxyisophthalic acid, diphenylmethane-4,4'-. Dicarboxylic acid, diphenylmethane-3,3'-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, diphenyl-4,
4'-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, adipic acid,
Sebacic acid, azelaic acid, suberic acid, dodecane dicarboxylic acid, 3-methyl azelaic acid, glutaric acid, succinic acid, cyclohexane-1,4-dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid, cyclopentane-
1,3-dicarboxylic acid and the like can be mentioned. These may be used alone or in combination of two or more. Among these, terephthalic acid, isophthalic acid, cyclohexane-1,4-dicarboxylic acid, and cyclohexane-1,3-dicarboxylic acid dimethyl ester are particularly preferably used from the viewpoint of physical properties and cost.

The method for producing a polyester of the present invention is characterized by reacting a polycarbonate and / or an aromatic dialkyl dicarbonate with a dialkyl ester of a dicarboxylic acid in the presence of a Sn-based catalyst. Any Sn-based catalyst used in this reaction can be used as long as it contains a Sn element.

Specific examples of such Sn-based catalysts include tin (II) chloride, tin (II) bromide, tin (II) iodide, etc., dihalogen tin, dibutyltin (II), diphenyltin (II), etc. , Chlorobutyltin (II),
Chlorophenyltin (II) and other halogenated organotins, dimethoxytin (II) and diethoxytin (II) and other tin alkoxides, tin oxide (II) and other tin oxides,
Carboxylic acid salts of tin halides such as monochloro-tin (II) acetate and monochloro-tin (II) octylate, monobutyl-tin (II) acetate, monophenyl-tin (II) acetate.
Such as organotin carboxylate, tin acetate such as tin (II) acetate, tin tetrachloride (IV), tin tetrabromide (IV), tin tetraiodide (IV) tin tetrahalide, Tetramethyltin (IV), Tetraethyltin (I
V), trimethylethyltin (IV), tetraphenyltin (IV), triphenylmethyltin (IV), tetraorganotin such as phenyltrimethyltin (IV), trichloromethyltin (IV), tribromomethyltin (IV) ), Trichloroethyltin (IV), trichlorobutyltin (I
V) and other trihalogenated organotins, dichlorodimethyltin (IV), dichlorodiethyltin (IV), dichlorodibutyltin (IV) and other dihalogendiorganotins, monochlorotrimethyltin (IV), monochlorotriethyltin (IV), monochloro Tributyltin (IV), monohalogenated triorganotin such as monochlorotriphenyltin (IV), tetraethoxytin (IV), tin tetraalkoxide such as tetrabutoxytin (IV), monobutyltrimethoxytin (IV), mono Monoorganotin trialkoxides such as phenyltributoxytin (IV), dibutyldimethoxytin (IV), diorganotin dialkoxides such as diphenyldibutoxytin (IV), tributylmonomethoxytin (IV), triphenylmonobutoxytin (IV) and other triorganotins Dihalogenated tin oxides such as monoalkoxides, dichlorotin (IV) oxide and dibromotin (IV) oxide, dimethyltin (IV) oxide, diethyltin (IV) oxide, dibutyltin (IV) oxide, diphenyltin (IV) oxide, dioctyltin (IV) oxide. , Di-p-methoxyphenyltin (IV) oxide, di-o-methoxyphenyltin (IV) oxide, di-2-phenylethyltin (IV) oxide, etc., diorganotin oxide, monobutylhydroxytin oxide (IV ) Etc., monoorganotin oxide, tin oxide (IV) and other tin oxides, trimethyltin (IV) hydroxide, triphenyltin (IV) hydroxide and other triorganotin hydroxides, dichlorotin diacetate (IV), diacetate Carboxylic acid salts of tin halides such as dibromotin (IV), dibutyltin diacetate (IV), dioctyl dioctylate Organotin carboxylates such as tyltin (IV) and tributyltin acetate (IV), chlorobutyltin diacetate (IV), halogenated organotin carboxylates such as chlorobutyltin dioctylate (IV), tin oxide diacetate (IV) Examples thereof include tin oxide carboxylates such as tin dioctylate oxide (IV) and tin carboxylates such as tin tetraacetate (IV).

Of these, tin (II) chloride, tin (II) acetate, tin (IV) tetrachloride, tin (IV) tetrabromide, trichlorobutyltin (IV), dichlorodibutyltin (I)
V), dibutyltin oxide (IV), diphenyltin oxide (I
V), dioctyltin oxide (IV), monobutylhydroxytin oxide (IV) and dibutyltin diacetate (IV) are preferred. These are used alone or in combination of two or more. The amount of these Sn-based catalysts used is not particularly limited, but 0.001 to 5.0 parts by weight, preferably 0 to 100 parts by weight of the polycarbonate and / or the aromatic dialkyl dicarbonate is preferred in view of the balance between reactivity and physical properties. .01
˜5.0 parts by weight, more preferably 0.1 to 3.0 parts by weight.

The method for producing the polyester of the present invention may be either a batch method or a continuous method. In the method for producing a polyester of the present invention, the amount of polycarbonate and / or aromatic dialkyl dicarbonate and dialkyl ester of dicarboxylic acid used is 0.
The range from 5: 1 to 1: 2.0 (polycarbonate and / or aromatic dialkyl dicarbonate: dialkyl ester of dicarboxylic acid) is preferred. If the amount of the dialkyl ester of dicarboxylic acid used is equal to or less than the equivalent amount, ester carbonate is produced, and if the amount is equal to or more than the equivalent amount, polyester is produced. From the viewpoint of the balance between the physical properties of the produced polymer and the cost, it is more preferable to use the polymer in a molar ratio of 0.8 to 1.5.

In the present invention, it is preferable to carry out the reaction in two steps at different temperatures. In the first step, 2
The heating is performed at 00 to 300 ° C, more preferably 250 to 300 ° C. In this step, the polycarbonate is depolymerized by a transesterification reaction to produce a dialkyl carbonate. In the second step, heating is performed at 280 to 350 ° C., more preferably 300 to 350 ° C. under reduced pressure (0.05 to 1.0 Torr). In this step, a high molecular weight polyester is obtained by removing the remaining portion of the produced dialkyl carbonate.

In the present invention, suitable cosolvents such as diphenyl ether, substituted cyclohexane,
Decahydronaphthalene or the like may be used. Further, in the present invention, various compounds may be added to impart various properties. For example, it is possible to use a branching agent or the like to adjust the viscosity. Further, in order to obtain a low-colored polyester, for example, an antioxidant may be added.

Generally, the weight average molecular weight of the polyester obtained in the present invention is 3000 to 15 in terms of polystyrene.
The range of 0000 is preferable, and 30,000 to 100,000
Is more preferable. The polyester obtained in the present invention may also contain dyes, pigments, stabilizers, flameproofing agents, flame retardants, fillers, and reinforcing substances such as glass fibers, carbon fibers, or other auxiliaries. The amount added is appropriately determined depending on the intended use. The polyesters obtained according to the invention are preferably used for the production of shaped articles, fibers, filaments and films. The polyester obtained by the present invention has high heat resistance, strength (toughness), hydrolysis resistance, creep resistance,
Since it has stress crack resistance and the like, it is therefore particularly suitable for articles in which these are required, for example, the electric field, the lighting field, and the automobile field.

[0025]

EXAMPLES The present invention will be described in more detail based on the following examples, but the present invention is not limited to the following examples, and various modifications can be made without departing from the scope of the invention. The properties of the polymer were measured according to the methods described below. (1) Weight average molecular weight of polymer [Mw] A 510 type GPC system manufactured by Waters was used, and the column temperature was 3 at a polymer concentration of 2 mg / ml in a chloroform solvent.
It was measured at 5 ° C. The weight average molecular weight was calculated using polystyrene as a standard sample. (2) Glass transition temperature [Tg] of polymer It was measured using a DSC-7 differential scanning calorimeter manufactured by Perkin-Elmer under a nitrogen stream at a temperature rising rate of 20 ° C / min. (3) Yellowness Index [YI] of Polymer Using JIS Z80 color difference meter manufactured by Nippon Denshoku Industries Co., Ltd., JIS K
It was measured by a transmission method based on 7013.

Example 1 In a glass reaction vessel equipped with a stirring blade, a nitrogen inlet, a pressure reducing port, and a distillation port, 254 g of polycarbonate (manufactured by Teijin Limited, Panlite L-1250W, Mv = 25000) and 97 g of dimethyl terephthalate (0 0.5 mol), dimethyl isophthalate 97 g (0.5 mol), tin (II) acetate
After charging 2.36 g (10 mmol) and purging with nitrogen, the mixture was heated to 280 ° C. in an oil bath under a nitrogen flow. The temperature was maintained as it was for 1 hour, and then the temperature was raised to 300 ° C. over 20 minutes. Dimethyl carbonate produced over 1.5 hours was distilled from the distillation port. Outflow is 4
It was 5 g (50% of theory). The pressure of the reaction system was gradually reduced (1 Torr in 30 minutes), the temperature was raised to 320 ° C., and the temperature was maintained for 3 hours. After the stirring was stopped, the reaction mixture was poured out to obtain 354 g of a pale yellow polymer. The measurement results of the polymer properties are shown in Table 1.

Example 2 Example 2 was repeated except that the catalyst was changed to tin (II) chloride. The measurement results of the polymer properties are shown in Table 1.

Example 3 Example 3 was repeated except that the catalyst was changed to dibutyltin (IV) diacetate. The measurement results of the polymer properties are shown in Table 1.

Example 4 The procedure of Example 1 was repeated except that the catalyst was changed to dibutyltin (IV) dichloride. The measurement results of the polymer properties are shown in Table 1.

Comparative Example 1 Example 1 was repeated except that the catalyst was changed to Ti (OBu) ₄ . The measurement results of the polymer properties are shown in Table 1.

[0031]

[Table 1]

Example 5 In a glass reaction vessel equipped with a stirring blade, a nitrogen inlet, a pressure reducing port, and a distillation port, 344 g (1.0 mol) of dimethyl carbonate of bisphenol A having the following structural formula and 97 g of dimethyl terephthalate (0. 5 mol), 97 g (0.5 mol) of dimethyl isophthalate, tin (II) acetate 2.36.
After charging g (10 mmol) and purging with nitrogen, the mixture was heated to 280 ° C. in an oil bath in a nitrogen flow state. Hold at the same temperature for 1 hour, then 300 ℃ over 20 minutes
The temperature was raised to. Dimethyl carbonate produced over 1 hour was distilled from the distillation port. The amount of outflow was 48 g (53% of theory). Gradually reduce the pressure of the reaction system (1To in 30 minutes)
rr), the temperature was raised to 320 ° C., and the temperature was maintained for 3 hours. After the stirring was stopped, the reaction mixture was poured out to obtain 348 g of a pale yellow polymer. The measurement results of the polymer properties are shown in Table 2.

[0033]

[Chemical 7]

Example 6 Example 6 was repeated except that the catalyst was changed to dibutyltin oxide (IV). The measurement results of polymer properties are shown in Table 2.
Shown in.

Example 7 Example 7 was repeated except that the catalyst was changed to dibutyltin (IV) diacetate. The measurement results of the polymer properties are shown in Table 2.

Example 8 Example 8 was repeated except that the catalyst was changed to diphenyltin (IV) dichloride. The measurement results of the polymer properties are shown in Table 2.

Comparative Example 2 The procedure of Example 5 was repeated except that the catalyst was changed to Ti (OBu) ₄ . The measurement results of the polymer properties are shown in Table 2.

[0038]

[Table 2]

Example 9 In a glass reaction vessel equipped with a stirring blade, a nitrogen inlet, a pressure reducing port and a distillation port, 254 g of polycarbonate (manufactured by Teijin Limited, Panlite L-1250W, Mv = 25000) and 97 g of dimethyl terephthalate (0 0.5 mol), dimethyl isophthalate 97 g (0.5 mol), tin (II) acetate
After charging 79 mg (0.33 mmol) and purging with nitrogen, the mixture was heated to 280 ° C. in an oil bath in a nitrogen flow state. The temperature was maintained as it was for 1 hour, and then the temperature was raised to 300 ° C. over 20 minutes. Dimethyl carbonate produced over 1.5 hours was distilled from the distillation port. Outflow is 4
It was 5 g (50% of theory). The pressure of the reaction system was gradually reduced (1 Torr in 30 minutes), the temperature was raised to 320 ° C., and the temperature was maintained for 3 hours. After the stirring was stopped, the reaction mixture was poured out to obtain 350 g of a pale yellow polymer. Table 3 shows the measurement results of the polymer characteristics.

Example 10 Example 10 was repeated except that the catalyst was changed to tin (II) chloride. Table 3 shows the measurement results of the polymer characteristics.

Example 11 Example 11 was repeated except that the catalyst was changed to dibutyltin (IV) diacetate. Table 3 shows the measurement results of the polymer characteristics.

Example 12 Example 12 was repeated except that the catalyst was changed to dibutyltin (IV) dichloride. Table 3 shows the measurement results of the polymer characteristics.

Comparative Example 3 The procedure of Example 9 was repeated except that the catalyst was changed to Ti (OBu) ₄ . Table 3 shows the measurement results of the polymer characteristics.

[0044]

[Table 3]

Example 13 In a glass reaction vessel equipped with a stirring blade, a nitrogen inlet, a pressure reducing port and a distillation port, 254 g of polycarbonate (manufactured by Teijin Limited, Panlite L-1250W, Mv = 25000) and 107 g of dimethyl terephthalate (0 0.55 mol), 107 g (0.55 mol) of dimethyl isophthalate, and 2.36 g (10 mmol) of tin (II) acetate were charged, and after nitrogen substitution, the mixture was heated to 320 ° C. in an oil bath in a nitrogen flow state. After stirring for 1 hour, dimethyl carbonate produced over 1 hour was distilled from the distillation port. Outflow amount is 54g
(60% of theory). Then, while maintaining the temperature of the oil bath at 320 ° C, the reaction system was gradually depressurized (30
It was set to 1 Torr in minutes and reacted for 3 hours. After the stirring was stopped, the reaction mixture was poured out to obtain 355 g of a pale yellow polymer. Table 4 shows the measurement results of the polymer characteristics.

Example 14 Example 14 was repeated except that the catalyst was changed to dibutyltin (IV) diacetate. Table 4 shows the measurement results of the polymer characteristics.

Comparative Example 4 The procedure of Example 13 was repeated except that the catalyst was changed to Ti (OBu) ₄ . Table 4 shows the measurement results of the polymer characteristics.

[0048]

[Table 4]

[0049]

As described above, according to the present invention,
A polyester having a low degree of coloring can be manufactured by a simple method.

Claims (18)

[Claims] 1. A dialkyl ester of dicarboxylic acid,
A method for producing a low-colored polyester, which comprises using an Sn-based catalyst as a transesterification catalyst in producing a polyester by reacting a polycarbonate and / or an aromatic dialkyl dicarbonate. 2. The method according to claim 1, wherein the Sn-based catalyst is at least one divalent tin compound selected from the group consisting of tin halide, diorganotin, organotin halide, tin dialkoxide and tin oxide. 3. The production according to claim 1, wherein the Sn-based catalyst is at least one divalent tin compound selected from the group consisting of tin halide carboxylates, organotin carboxylates and tin carboxylates. Method. 4. The Sn-based catalyst is tetrahalogen tin, tetraorganotin, trihalogenated monoorganotin,
At least one 4 selected from the group consisting of dihalogenated diorganotin and monohalogenated triorganotin
The method according to claim 1, which is a valent tin compound. 5. The Sn-based catalyst is tin tetraalkoxide,
The method according to claim 1, which is at least one tetravalent tin compound selected from the group consisting of monoorgano tin trialkoxide, diorgano tin dialkoxide and triorgano tin monoalkoxide. 6. The Sn-based catalyst is at least one tetravalent tin compound selected from the group consisting of dihalogenated tin oxides, diorganotin oxides, monoorganotin oxides, tin oxides and triorganotin hydroxides. Manufacturing method. 7. The Sn-based catalyst is at least one selected from the group consisting of a tin halide carboxylate, an organotin carboxylate, a halogenated organotin carboxylate, a tin oxide carboxylate and a tin carboxylate. The method according to claim 1, which is a tetravalent tin compound. 8. The Sn-based catalyst is dibutyltin (IV) diacetate.
The manufacturing method according to claim 1, wherein 9. The method according to claim 1, wherein the Sn-based catalyst is used in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the polycarbonate and / or aromatic dialkyl dicarbonate. 10. The amount of the Sn-based catalyst used is 100% or more of polycarbonate and / or aromatic dialkyl dicarbonate.
The manufacturing method according to claim 9, which is 0.01 to 5 parts by weight with respect to parts by weight. 11. The reaction consists of two steps, the first step consisting of two steps.
The second step is performed at 280 to 350 ° C.
The manufacturing method according to claim 1, wherein 12. A polycarbonate is represented by the following general formula (I):
The manufacturing method of Claims 1-11 shown by. [Chemical 1] {R ¹ and R ² in the general formula (I) are the same or different and each is a divalent aromatic hydrocarbon group, R ³ -X-R ⁴ group (provided that R ³ and R ⁴ are divalent aromatic groups). A hydrocarbon group, X
Represents an oxygen atom, a sulfonyl group, a carbonyl group, a hydrocarbon group, an ester group or a direct bond. ) (However,
The hydrogen atom of the aromatic ring may be substituted with a halogen atom, a hydrocarbon group, an alkoxy group, a phenoxy group or the like. ), A and b are positive integers from 1 to 500, and c is a positive integer [where (ca + cb) is 50].
It is 0 or less. ]. } 13. The production method according to claim 1, wherein the aromatic dialkyl dicarbonate is represented by the following general formula (II). [Chemical 2] [R ⁵ in the general formula (II) is a divalent aromatic hydrocarbon group, R 5
⁷ -X-R ⁸ group (wherein, R ⁷ and R ⁸ is a divalent aromatic hydrocarbon group, X represents an oxygen atom, a sulfonyl group, a carbonyl group, a hydrocarbon group, an ester group or a direct bond. (However, the hydrogen atom of the aromatic ring may be substituted with a halogen atom, a hydrocarbon group, an alkoxy group, a phenoxy group or the like.), And R ⁶ is an aliphatic hydrocarbon group having 1 to 4 carbon atoms. Alternatively, it represents an aromatic hydrocarbon group having 6 to 10 carbon atoms. ] 14. The production method according to claim 1, wherein the dialkyl ester of dicarboxylic acid is represented by the following general formula (III). [Chemical 3] [R ⁹ in the general formula (III) is a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms (provided that the hydrogen atom of the aromatic ring is substituted with a halogen atom, a hydrocarbon group, an alkoxy group, a phenoxy group or the like). may be.), represents an aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, R ¹⁰ is an aromatic having from 6 to 10 carbon aliphatic hydrocarbon group or C 1 to 4 carbon atoms carbide Indicates a hydrogen group. ] 15. The aromatic hydrocarbon group (R ¹ and R ² ) of the polycarbonate is 2,2′-bis (4-hydroxyphenylpropane) (bisphenol A) and / or 1,
1'-bis (4-hydroxyphenyl) -3,3,5-
The production method according to claim 12, which is trimethylcyclohexane. 16. The aromatic hydrocarbon group (R ⁵ ) of the aromatic dialkyl dicarbonate is 2,2′-bis (4-hydroxyphenylpropane) (bisphenol A) and / or 1,1′-bis (4-). Hydroxyphenyl) -3,
The method according to claim 13, which is 3,5-trimethylcyclohexane. 17. The method according to claim 1, wherein the dialkyl ester of dicarboxylic acid is dimethyl terephthalate and / or dimethyl isophthalate. 18. The method according to claim 1, wherein the dialkyl ester of dicarboxylic acid is dimethyl 1,4-cyclohexanedicarboxylate and / or dimethyl 1,3-cyclohexanedicarboxylate.