JPH0873578A - Production of polyester and polyester carbonate - Google Patents

Abstract

PURPOSE: To easily and inexpensively obtain a less colored polyester and polyester carbonate. CONSTITUTION: This manufacturing process comprises reacting a diorganoester of a dicarboxylic acid with a polycarbonate and/or an aromatic diorganodicarbonate substantially in the absence of oxygen.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel method for producing polyesters and polyester carbonates. More specifically, when a polyester or polyester carbonate is produced by reacting a diorganoester of a dicarboxylic acid with a polycarbonate and / or an aromatic diorganocarbonate, the reaction is carried out in the substantial absence of oxygen. The present invention relates to a method for producing a characteristic low-colored polyester and polyester carbonate.

[0002]

2. Description of the Related Art Various methods for producing polyesters and polyester carbonates are known. The general method is to dissolve phosgene and dicarboxylic acid dichloride in an organic solvent and bring them into contact with an alkaline aqueous solution of diphenols. Interfacial polycondensation. This interfacial polycondensation can be carried out at a low temperature, a high molecular weight product is easily obtained, and the resulting polymer is also low in color. However, complicated operations are required for the synthesis and purification of the raw material phosgene and acid chloride. There are problems such as being necessary. Further, since a large amount of a solvent such as methylene chloride is used, there are problems that environmental problems and manufacturing costs increase.

Also known is melt polycondensation in which diphenols and carbonic acid diesters and carboxylic acid esters are polymerized in a molten state by a transesterification method. This melt polycondensation has a characteristic that it does not use a solvent and basically does not use a halogen-based raw material, but it is difficult to obtain a high molecular weight product,
Since the reaction is carried out at a high temperature, there is a problem that the resulting polymer is strongly colored.

As a means for solving such a problem of melt polycondensation, for example, in US Pat. No. 4,360,648, as a method for producing polyester and polyester carbonate, aromatic polycarbonate and dicarboxylic acid diester are reacted in the presence of a transesterification reaction catalyst. A method of transesterification in the molten state is disclosed. When this method is used, it is possible to inexpensively and easily produce high-molecular weight polyesters and polyester carbonates, but there is a problem that the polyesters and polyester carbonates produced by this method are severely colored. From such a background, development of a method for producing a low-colored polyester and a polyester carbonate by an easy and inexpensive production process has been desired.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to overcome the drawbacks of the conventional methods for producing polyesters and polyester carbonates and to provide a novel method for producing low-colored polyesters and polyester carbonates. To do.

[0006]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that the reaction of dicarboxylic acid diorganoester with polycarbonate and / or aromatic diorganodicarbonate is substantially carried out. It was found that polyesters and polyester carbonates with greatly reduced coloration can be produced by carrying out the reaction in the absence of oxygen, and completed the present invention. That is,
The present invention provides that when a diorganoester of a dicarboxylic acid is reacted with a polycarbonate and / or an aromatic diorganodicarbonate to produce a polyester and a polyestercarbonate, the reaction is carried out in the substantial absence of oxygen. A method for producing a characteristic low-colored polyester and polyester carbonate is provided.

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

[0008]

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[In the general formula (I), R ¹ is a divalent aromatic hydrocarbon group, R ² —X—R ³ group (provided that R ² and R ³ 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 a represents a positive integer of 1 to 500. The polycarbonate used in the present invention is particularly preferably a polycarbonate based on bisphenol A from the viewpoint of balance between physical properties and cost.

Examples of the aromatic diorganodicarbonate used in the present invention include compounds represented by the general formula (II).

[0011]

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[R ⁴ in the general formula (II) is a divalent aromatic hydrocarbon group, R ⁶ -X-R ⁷ group (provided that R ⁶ and R ⁷ 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 ⁵ is an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Indicates. ]

Specific examples of the aromatic diorganodicarbonates include the following aromatic diols dimethyl, diethyl and diphenyl carbonate. That is, as a specific example 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-hydroxy) Phenyl) 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, resorcinol, dihydroxynaphthalene, dihydroxyanthracene, phenolphthalein, fluorescein, 2,2'-dihydroxy-
1,1-dinaphthylmethane, 4,4'-dihydroxydinaphthyl and the like can be mentioned. Of these, dimethyl carbonate of bisphenol A is particularly preferable because it is easily available. In the present invention, the above-mentioned polycarbonate and aromatic dialkyl dicarbonate may be used alone or in combination of two or more kinds.

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

[0015]

[Chemical 3]

[R ⁸ in the general formula (III) is a divalent aromatic hydrocarbon group (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). ), An aliphatic or alicyclic hydrocarbon group, and R ⁹ represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group. ]

Specific examples of the diorganoester 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, naphthalene-
2,6-dicarboxylic acid, naphthalene-1,7-dicarboxylic acid, adipic acid, sebacic acid, azelaic acid, suberic acid, dodecanedicarboxylic acid, 3-methylazelaic acid, glutaric acid, succinic acid, cyclohexane-1,4-
Examples thereof include dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid, cyclopentane-1,3-dicarboxylic acid and the like. These may be used alone or in combination of two or more. Among them, terephthalic acid, isophthalic acid, cyclohexane-1,4-dicarboxylic acid, dimethyl ester of cyclohexane-1,3-dicarboxylic acid, or a mixture of two or more kinds thereof is particularly used from the viewpoint of physical properties and cost. preferable.

In the present invention, it is preferable to use an esterification catalyst and / or a transesterification catalyst during the reaction. Examples of esterification catalysts and transesterification catalysts used in this reaction include alkali metals such as Li element, Na element, K element, alkaline earth metals such as Mg element, Ca element, Sr element, Ba element, Sn, and the like. Elements containing at least one element selected from elements generally called esterification catalysts and transesterification catalysts such as elements, Sb elements, Zn elements, Cd elements, Pb elements, Ti elements, Zr elements, Mn elements, and Co elements. Any of them can be used. Also,
The catalyst is not limited to an anhydride, and a hydrate or the like may be used.

Specific examples of the alkali metal catalysts include metallic lithium, lithium hydroxide, lithium hydrogen carbonate, lithium carbonate, lithium acetate, lithium stearate, lithium borohydride, lithium benzoate, dilithium hydrogen phosphate and bisphenol. A lithium salt, sodium metal, sodium hydroxide, sodium hydrogen carbonate, sodium carbonate, sodium acetate, sodium stearate, sodium borohydride, sodium benzoate, disodium hydrogen phosphate, sodium salt of bisphenol A, metal potassium, Examples thereof include potassium hydroxide, potassium hydrogen carbonate, potassium carbonate, potassium acetate, potassium stearate, potassium borohydride, potassium benzoate, dipotassium hydrogen phosphate, and potassium salt of bisphenol A.

Specific examples of the alkaline earth metal-based catalyst include metal magnesium, magnesium hydroxide, magnesium hydrogen carbonate, magnesium carbonate, magnesium acetate,
Magnesium stearate, metallic calcium, calcium hydroxide, calcium hydrogen carbonate, calcium carbonate, calcium acetate, calcium stearate, barium metal,
Barium hydroxide, barium hydrogen carbonate, barium carbonate, barium acetate, barium stearate, strontium metal, strontium hydroxide, strontium hydrogen carbonate,
Examples thereof include strontium carbonate, strontium acetate, and strontium stearate.

Specific examples of Sn-based catalysts include tin (II) fluoride, tin (II) chloride, tin (II) bromide, and tin (II) iodide.
Such as dihalogen tin, dibutyltin (II), diphenyltin (II) and other diorganotin, chlorobutyltin (II), chlorophenyltin (II) and other halogenated organotin, dimethoxytin (II), diethoxytin (II) ), Dipropoxytin (II), dibutoxytin (II) and other divalent tin alkoxides, tin (II) monochloroacetate, tin (II) monochlorooctylate and other divalent tin halide carboxylates, and monomethylacetic acid. Tin (II), Monoethyl tin acetate (II), Monobutyl tin acetate (II), Monophenyl tin acetate (II), Monomethyl octyl tin acetate (II), Monoethyl octyl tin acetate (II), Monobutyl octyl tin acetate ( II), divalent organotin carboxylates such as monophenyloctyltin acetate (II), tin carboxylates of tin (II), tin tetrafluoride (IV), tin tetrachloride (IV) , Tetrabromide (IV), tin tetraiodide and other tetrahalogen halides, tetraphenyltin (IV), butyltriphenyltin (IV), dibutyldiphenyltin (IV), tributylphenyltin (IV) and other tetraorgano Tin (IV), Tribromobutyltin (IV) Trichlorobutyltin (IV), Trichloro-2-methoxyphenyltin (IV), Trichloro-4-methoxyphenyltin (I
V), trichloroethyltin (IV), trichloromethyltin (IV), trichlorophenyltin (IV) and other trihalogenated organotins, dibutyldichlorotin (IV), dibutyldibromotin (IV), dimethyldichlorotin (IV) ), Diethyldichlorotin (IV), diphenyldichlorotin (IV), bis (2-methoxyphenyl) dichlorotin (IV), bis (4)
-Methoxyphenyl) dichlorotin (IV) and other dihalogenated diorganotin, tributylchlorotin (IV), tributylbromotin (IV), trimethylchlorotin (IV), triethylchlorotin (IV), triphenylchlorotin (IV) ), Tris (2-methoxyphenyl) chlorotin (IV), tris (4-methoxyphenyl) chlorotin (IV) and other monohalogenated triorganotin, tetramethoxytin (IV), tetraethoxytin (IV), tetra Tetraalkoxytin such as propoxytin (IV) and tetrabutoxytin (IV), tetraalkyltin such as tetramethyltin (IV), tetraethyltin (IV) and tetrabutyltin (IV), tetraphenyltin, tetrakis (2-) Tetraaryl tin such as methoxyphenyl) tin (IV) and tetrakis (4-methoxyphenyl) tin, monobutyltin trimethoxide Monobutyltin triethanolamine butoxide, monobutyltin tripropoxide side, monomethyl tin tri methoxide, monomethyl tin triethyl butoxide,
Monoalkyl tin trials such as monomethyl tin tripropoxide, monoethyl tin trimethoxide, monoethyl tin triethoxide, monoethyl tin tripropoxide, monophenyl tin trimethoxide, monophenyl tin triethoxide, monophenyl tin tripropoxide Coxide and monoaryl tin trilcoxide, dibutyltin dimethoxide, dibutyltin dietoxide, dibutyltin dipropoxide, dimethyltin dimethoxide,
Dialkyltin dialkoxides and diaryltin dialkoxides such as dimethyltin diethyloxide, dimethyltin dipropoxide, diethyltin dimethoxide, diethyltin diethyloxide, diethyltin dipropoxide, diphenyltin dimethoxide, diphenyltin diethyloxide, diphenyltin dipropoxide and the like. , Tributyltin monomethoxide, tributyltin monoethoxide, tributyltin monopropoxide, trimethyltin monomethoxide, trimethyltin monoethoxide, trimethyltin monopropoxide, triethyltin monomethoxide, triethyltin monoethoxide , Triethyltin monopropoxide, triphenyltin monomethoxide, triphenyltin monoethoxide, triphenyltin monopropoxide, etc. Kill tin mono alkoxide and triaryl tin mono alkoxides, tin tetraacetate,
Tetravalent tetracarboxylates such as tin tetralaurate and tin tetrakis (2-ethylhexanoate), monobutyltin triacetate, monobutyltin tris (2-ethylhexanoate), monobutyltin trilaurate, monomethyltin triacetate, monomethyltin Tris (2-
Ethylhexanoate), monomethyltin trilaurate, monoethyltin triacetate, monoethyltin tris (2-ethylhexaate), monoethyltin trilaurate, monophenyltin triacetate, monophenyltin tris (2-ethylhexanoate), monophenyltin Trilaurate, 2-methoxyphenyltin triacetate, 2-methoxyphenyltin tris (2-ethylhexanoate), 2-methoxyphenyltin trilaurate,
4-methoxyphenyltin triacetate, 4-methoxyphenyltin tris (2-ethylhexanoate), 4-
Monoalkyltin tricarboxylates such as methoxyphenyltin trilaurate and monoaryltin tricarboxylates, dibutyltin diacetate, dibutyltin bis (2-ethylhexanoate), dibutyltin dilaurate, dimethyltin diacetate, dimethyltin bis ( 2-ethylhexanoate), dimethyltin dilaurate, diethyltin diacetate, diethyltin bis (2-ethylhexanoate), diethyltin dilaurate, diphenyltin diacetate, diphenyltin bis (2-ethylhexanoate), Diphenyltin dilaurate, bis (2-methoxyphenyl) tin diacetate, bis (2-methoxyphenyl) tin bis (2-ethylhexanoate), bis (2-methoxyphenyl) tin dilaurate, bis (4-
Dialkyltin dicarboxylates such as methoxyphenyl) tin diacetate, bis (4-methoxyphenyl) tin bis (2-ethylhexanoate), bis (4-methoxyphenyl) tin dilaurate and diaryltin dicarboxylates, tributyltin Acetate, tributyltin (2
-Ethylhexanoate), tributyltin laurate,
Trimethyltin acetate, trimethyltin (2-ethylhexanoate), trimethyltin laurate, triethyltin acetate, triethyltin (2-ethylhexanoate), triethyltin laurate, triphenyltin acetate, triphenyltin (2-ethyl) Hexanoate),
Triphenyl tin laurate, tris (2-methoxyphenyl) tin acetate, tris (2-methoxyphenyl)
Tin (2-ethylhexanoate), tris (2-methoxyphenyl) tin laurate, tris (4-methoxyphenyl) tin acetate, tris (4-methoxyphenyl)
Trialkyltin monocarboxylates such as tin (2-ethylhexanoate) and tris (4-methoxyphenyl) tin laurate, and monoaryltin monocarboxylates, monobutyltin hydroxide oxide, monobutyltin chloride dihydrooxide, etc. Organotin compound, 1,3-diacetoxy-1,1,3,3
Examples thereof include a binuclear complex compound of tin such as tetrabutyl distanoxane, a complex compound of tin, a diorgano tin oxide such as dibutyl tin oxide, tin (II) oxide, tin (IV) oxide and the like. Among these, in particular, tetravalent tri-, di-, mono-alkyl and aryl tin carboxylates, divalent tin carboxylates, tin binuclear complexes, tin dichloride, tin tetrachloride, dibutyltin oxide, tetravalent halogens. Preferred are alkyl tin halides, tetravalent aryl tin halides and the like.

Specific examples of the Sb type catalyst include antimony oxides such as metallic antimony, antimony trioxide and antimony pentoxide, antimony tribromide, antimony trichloride,
Antimony trihalides such as antimony trifluoride, antimony pentabromide, antimony pentachloride, antimony pentahalides such as antimony pentafluoride, trimethoxy antimony, triethoxy antimony, tripropoxy antimony, tributoxy antimony, antimony triacetate, Triorganoantimony such as trimethylantimony, triethylantimony and triphenylantimony, pentoorganoantimony such as pentaethoxyantimony and pentabutylantimony, trivalent halogenated organoantimony such as monochlorodimethylantimony and dichloromethylantimony, monomethyltetramethoxyantimony, Monophenyl tetramethoxy antimony,
Dimethyl trimethoxy antimony, diphenyl trimethoxy antimony, trimethyl dimethoxy antimony, triphenyl dimethoxy antimony, tetraphenyl methoxy antimony and other pentogarano antimony, monophenyl tetrafluoro antimony, diphenyl trifluoro antimony, triphenyl difluoro antimony,
Examples include pentavalent halogenated organoantimony such as tetraphenylfluoroantimony. Of these, trialkoxy antimony such as triethoxy antimony and tributoxy antimony, and antimony trioxide are particularly preferable.

Specific examples of the Zn-based catalyst include zinc chloride,
Examples thereof include zinc halides such as zinc bromide and zinc iodide, zinc carboxylates such as zinc, zinc carbonate, zinc sulfide and zinc acetate, zinc alkoxides and zinc phenoxides. Of these, zinc carboxylate is particularly preferable.

Specific examples of the Cd-based catalyst include cadmium, cadmium acetate, cadmium formate, cadmium hydroxide, cadmium citrate, cadmium selenide, cadmium stearate, cadmium 4-cyclohexylbutyrate, cadmium carbonate, cadmium chloride, and fluoride. Examples thereof include cadmium, cadmium iodide, cadmium bromide, cadmium nitrate, cadmium oxide, cadmium sulfate, cadmium sulfide, and cadmium phosphate. Of these, cadmium acetate is particularly preferable.

Specific examples of Pb-based catalysts include divalent alkoxy lead such as isopropoxy lead, lead nitrate, lead acetate, lead bromide, lead iodide, lead fluoride, lead chloride, lead carbonate, lead oxide, Lead sulfate, lead thiocyanate, lead perchlorate, lead borate, lead fluoroborate, lead chromate, lead citrate, lead hydroxide, lead phosphate, lead phthalate, lead fluorosilicate, lead stearate, 4 −
Lead cyclohexylbutyrate, lead 2-ethylhexylate, lead naphthenate, lead titanate, lead caprylate, lead maleate,
Examples thereof include divalent lead compounds such as lead octoate, lead oleate, and lead tartrate, tetravalent lead acetate, tetravalent lead oxide, lead trioxide, and lead. Of these, divalent lead acetate is particularly preferable.

Specific examples of the Ti-based catalyst include metallic titanium, titanium oxide (II), titanium oxide (IV), tetramethoxy titanium, tetraethoxy titanium, tetraisopropoxy titanium, tetrabutoxy titanium, tetraphenoxy titanium, titanium chloride. (II), titanium chloride (IV), titanium fluoride (IV), titanium bromide (II), titanium bromide (IV),
Examples thereof include titanium oxyacetylacetonate, potassium titanium fluoride, potassium titanium oxalate, titanium sulfate, titanium nitrate, titanocene dichloride, and dimethyltitanocene. Among these, especially tetramethoxy titanium,
Tetraethoxy titanium, tetraisopropoxy titanium,
Tetraalkoxytitanium such as tetrabutoxytitanium is preferred.

Specific examples of Zr-based catalysts include metallic zirconium, tetramethoxyzirconium, tetraethoxyzirconium, tetraisopropoxyzirconium, tetrabutoxyzirconium, tetraphenoxyzirconium, zirconium (IV) oxide, zirconium chloride (I
V), zirconium (IV) chloride oxide, zirconium naphthenate, zirconium acetylacetonate, potassium zirconium fluoride, zirconium sulfate, zirconyl nitrate, zirconocene dichloride, dimethylzirconocene and the like. Of these, tetraalkoxyzirconium such as tetramethoxyzirconium, tetraethoxyzirconium, tetraisopropoxyzirconium and tetrabutoxyzirconium is particularly preferable.

Specific examples of the Mn-based catalyst include metallic manganese, manganese (II) acetate, manganese (III) acetate, manganese (II) formate, manganese (II) nitrate, manganese (II) oxalate and manganese (II). Acetylacetonate, manganese (II) sulfate, manganese (II) benzoate, manganese (II) salicylate, manganese (II) tartrate, manganese (II) tetrafluoroborate, manganese (II) cyclohexanebutyrate, manganese (II) carbonate , Cyclohexane manganese (II) sulfate, manganese chloride (II), manganese bromide (II)
, Manganese decacarbonyl, manganese (IV) oxide, phthalocyanine manganese, and the like.

Specific examples of Co-based catalysts include metallic cobalt, cobalt (II) acetate, cobalt (II) sulfate, cobalt (II) carbonate, cobalt (II) cyclohexanebutyrate, cobalt (II) diammonium sulfate, and cobalt formate. (II)
, Cobalt naphthenate, cobalt nitrate (II), cobalt oleate, cobalt (II) oxalate, cobalt (III) nitrite, cobalt (II) stearate, cobalt (II) thiocyanate, cobalt (II) chloride, odor Cobalt (II) chloride, hexaamminecobalt chloride, cobalt octacarbonyl, phthalocyaninecobalt and the like can be mentioned.

Further, from the viewpoint of reaction activity and color reduction,
Among these transesterification catalysts, Sn-based catalysts are particularly preferable. The amount of the esterification catalyst and / or transesterification catalyst used is not particularly limited, but 0.0001 to 100 parts by weight of the polycarbonate and / or the aromatic diorganodicarbonate is used in view of the balance between reactivity and physical properties.
10 parts by weight, preferably 0.001 to 5 parts by weight, more preferably 0.005 to 2 parts by weight are used.

The method for producing the polyester and polyester carbonate of the present invention may be either a batch method or a continuous method.

In the method for producing polyesters and polyester carbonates of the present invention, the use amount of polycarbonate and / or diorganoester of aromatic diorganodicarbonate and dicarboxylic acid is 100: 5 or more and 100: 200 or less (polycarbonate) in a molar ratio. And / or aromatic diorganocarbonates: diorganoesters of dicarboxylic acids) are preferred. More preferably 1
The range is 00: 5 to 100: 140. The molar ratio is 1
If it is 00:05 or more and less than 100: 100, polyester carbonate is produced, and if it is 100: 100 or more, polyester is produced. Further, some dicarboxylic acid diorganodiesters have sublimation properties, and therefore, when a polyester is produced, the addition amount of the dicarboxylic acid diorganodiester is compared with that of the polycarbonate and / or the aromatic diorganocarbonate. The polyester can be easily produced by slightly increasing the amount. Furthermore, if the above molar ratio is less than 100: 5, the characteristics of polyester carbonate cannot be effectively exhibited, and if it exceeds 100: 200, the diorganoester of dicarboxylic acid is used in a large excess. In addition, there is a problem that the cost is too high.

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 the transesterification reaction to produce diorganocarbonate. In the second step, heating is performed under reduced pressure at 250 to 350 ° C, more preferably 270 to 350 ° C. In this step, high molecular weight polyester and polyester carbonate are obtained by removing the remaining portion of the produced diorganocarbonate. However, the present invention is not limited to the reaction in the above two-step process.
The reaction may be carried out at multiple stages of temperature and reduced pressure, or may be carried out under the same temperature condition throughout the reaction.

In the present invention, when a polyester and a polyester carbonate are produced by reacting a diorganoester of a dicarboxylic acid with a polycarbonate and / or an aromatic diorganocarbonate, the reaction is carried out in the substantial absence of oxygen. A method for producing a low-coloring polyester and a polyester carbonate, which are characteristic. As a method for producing a polyester and a polyester carbonate by reacting a diorganoester of a dicarboxylic acid with a polycarbonate and / or an aromatic diorganodicarbonate in the presence of a transesterification catalyst, the above-mentioned US Pat. A method is described in which the cycle of reduced pressure-nitrogen purge in the reaction system is performed three times. However, when nitrogen in a commonly used nitrogen cylinder (industrial nitrogen) is used to carry out decompression-nitrogen purging in the reaction system, a yellowish brown color similar to the result described in US Pat. No. 4,360,648 is obtained. A polymer is formed and a low-colored product cannot be obtained.

The following methods can be mentioned as specific examples of the method of the present invention in which the reaction is carried out in the substantial absence of oxygen. A method of performing a degassing-nitrogen (or inert gas) purging cycle of the reaction system 10 times or more before starting the reaction, and a degassing-nitrogen (or inert gas) purging cycle of the reaction system before starting the reaction. At this time, a method of performing deaeration for a long time, and when performing a cycle of deaeration-nitrogen (or inert gas) purging of the reaction system before starting the reaction, use nitrogen or an inert gas whose oxygen concentration is suppressed to an extremely low concentration. Method, degassing-nitrogen (or inert gas) purging cycle of the reaction system before starting the reaction, degassing-purge cycle with the reaction system heated, diorganoester of dicarboxylic acid and polycarbonate, /
Or a filter composed of a component having an ability to take in oxygen such as a reducing agent, as a reaction raw material or a reaction product containing an aromatic diorganodicarbonate and an esterification catalyst, a transesterification catalyst, and other additives which are optionally added. Examples include a method of reducing the oxygen concentration by passing through. Oxygen concentration of nitrogen and inert gas used for purging is 2
It is below ppm, preferably below 1 ppm. The temperature in the reaction system during purging is 0 to 200 ° C., preferably 50 to 1
It is 80 ° C. However, the present invention is not limited to the specific examples described above, and any method may be used as long as the reaction is carried out in the substantial absence of oxygen.

In the present invention, suitable cosolvents such as diphenyl ether, substituted cyclohexane, decahydronaltalene and the like may be used. Further, in the present invention, various compounds may be added in order to impart desired properties. For example, it is possible to use a branching agent or the like to adjust the viscosity. Further, for example, an antioxidant may be added to obtain a low-colored polyester and polyester carbonate. Generally, the weight average molecular weight of the polyester and polyester carbonate according to the present invention is 3000 to 15000 in terms of polystyrene.
The range of 0 is preferable, and the range of 3000 to 100000 is more preferable.

The polyesters and polyester carbonates obtained by the present invention are dyes, pigments, stabilizers, flame retardants, flame retardants, fillers, and reinforcing substances such as glass fibers, carbon fibers, and other auxiliaries. You may include 1 type (s) or 2 or more types. The amount added is appropriately determined depending on the intended use. The polyester and polyester carbonate obtained by the present invention are shaped articles,
It is preferably used for producing fibers, filaments, films and the like. The polyester and polyester carbonate obtained by the present invention have high heat resistance and strength (toughnes).
s), hydrolysis resistance, creep resistance, stress crack resistance, etc., it is particularly suitable for articles requiring these physical properties, for example, electrical fields, lighting fields, and automobile fields.

[0038]

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 measured in a chloroform solvent at a polymer concentration of 2 mg / ml at a column temperature of 35 ° C. The weight average molecular weight was calculated using polystyrene as a standard sample. (2) Glass transition temperature [Tg] of polymer Using a DSC-7 differential scanning calorimeter manufactured by Perkin-Elmer, measurement was performed under a nitrogen stream at a temperature rising rate of 20 ° C / min. (3) Polymer yellowness index [YI] JIS-K70 using a Z-Σ80 color difference meter manufactured by Nippon Denshoku Industries Co., Ltd.
It was measured by the transmission method based on No. 13.

Example 1 A glass reaction vessel equipped with a stirring blade, a nitrogen inlet, a pressure reducing port, and a distillation port was charged with polycarbonate (manufactured by Teijin Chemicals Ltd., Panlite L-1250W, Mv = 25000) 254.
g, dimethyl terephthalate 97 g (0.5 mol), dimethyl isophthalate 97 g (0.5 mol) and dibutyltin diacetate 3.51 g (0.33 mmol) were charged, and ultra-high purity nitrogen (oxygen concentration: 1 ppm or less) After performing a degassing (0.5 Torr) -nitrogen purging cycle three times using the above, it 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 hour was distilled from the distillation port. Distillation amount is 58g
(64% of theory). The reaction system is gradually depressurized (3
It was set to 1 Torr in 0 minutes, and the temperature was raised to 320 ° C.
Held for hours. After the stirring was stopped, the reaction mixture was discharged and 3
03 g of a pale yellow polymer was obtained. The molecular weight (weight average molecular weight) of the obtained polymer was 50,000 as measured by GPC.
The glass transition temperature (in terms of polystyrene) was 191 ° C. according to the DSC measurement. In addition, 1 of the obtained polyester
The yellowness index (Y.I.) of the / 8 inch molded product was 15.

Comparative Example 1 As a purge gas for degassing and purging, industrial nitrogen gas (oxygen concentration: 5 ppm) was used instead of ultra-high purity nitrogen gas.
The same procedure as in Example 1 was performed except that was used. The molecular weight (weight average molecular weight) of the obtained polymer was 49 by GPC measurement.
000 (polystyrene equivalent), glass transition temperature DSC
It was 190 ° C. from the measurement. The yellowness index (Y.I.) of the 1/8 inch molded product of the obtained polyester is 3
It was 5.

Example 2 344 g (1.0 mol) of dimethyl carbonate of bisphenol A (a compound represented by the following structural formula IV) was placed in a glass reaction vessel equipped with a stirring blade, a nitrogen inlet, a pressure reducing port, and a distillation port. Dimethyl terephthalate 97 g (0.5 mol),
Charge 97 g (0.5 mol) of dimethyl isophthalate and 3.51 g (0.33 mmol) of dibutyltin diacetate, and degas using ultra high purity nitrogen (oxygen concentration: 1 ppm or less) (0.5 Torr) -nitrogen. After performing the purging cycle three times, it 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 hour was distilled from the distillation port. Distillation amount is 56
g (62% 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 300 g of a pale yellow polymer. The molecular weight (weight average molecular weight) of the obtained polymer was 480 by GPC measurement.
00 (in terms of polystyrene), the glass transition temperature was 188 ° C. from DSC measurement. The yellowness index (Y.I.) of the 1/8 inch molded product of the obtained polyester is 16
Met.

[0043]

[Chemical 4]

Example 3 A glass reaction vessel equipped with a stirring blade, a nitrogen inlet, a pressure reducing port and a distillation port was charged with polycarbonate (manufactured by Teijin Chemicals Ltd., Panlite L-1250W, Mv = 25000) 254.
g, dimethyl terephthalate 48.5 g (0.25 mol), dimethyl isophthalate 48.5 g (0.25 mol), and dibutyltin diacetate 3.51 g (0.33 mmol) were charged, and ultra-high purity nitrogen (oxygen concentration Degassing (0.5 Torr) -nitrogen purging cycle 3 times with 1 ppm or less), and then 2 with oil bath under nitrogen flow.
Heated to 80 ° C. 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 hour was distilled from the distillation port.
The amount of distillate was 30 g (66% 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 301 g of a pale yellow polymer. The molecular weight (weight average molecular weight) of the obtained polymer was 49000 (converted to polystyrene) by GPC measurement, and the glass transition temperature was 165 ° C. by DSC measurement. The yellowness index (Y.I.) of the 1 / 8-inch molded product of the obtained polyester carbonate was 13.

Example 4 A glass reaction vessel equipped with a stirring blade, a nitrogen inlet, a pressure reducing port and a distillation port was charged with polycarbonate (manufactured by Teijin Chemicals Ltd., Panlite L-1250W, Mv = 25000) 254.
g, dimethyl terephthalate 97 g (0.5 mol), dimethyl isophthalate 97 g (0.5 mol) and dibutyltin diacetate 3.51 g (0.33 mmol) were charged, and ultra-high purity nitrogen (oxygen concentration: 1 ppm or less) After performing a degassing (0.5 Torr) -nitrogen purging cycle three times using the above, the mixture was heated to 320 ° C. in an oil bath in a nitrogen flow state. The temperature was maintained for 1 hour. Thereafter, the dimethyl carbonate produced over 1 hour was distilled from the distillation port. The amount of distillate was 61 g (68% of theory). Gradually reduce the pressure of the reaction system at a temperature of 320 ° C (1 Torr in 30 minutes)
And kept for 3 hours. After the stirring was stopped, the reaction mixture was poured out to obtain 303 g of a pale yellow polymer. The molecular weight (weight average molecular weight) of the obtained polymer was 51,000 (in terms of polystyrene) by GPC measurement, and the glass transition temperature was 191 ° C. by DSC measurement. In addition, the yellowness index (Y.
I. ) Was 25.

Example 5 As a purge gas at the time of degassing and purging, ultra high purity argon gas (oxygen concentration: 1 was used instead of ultra high purity nitrogen gas.
The same procedure as in Example 1 was performed except that (ppm or less) was used. The molecular weight (weight average molecular weight) of the obtained polymer was 50000 (calculated as polyethylene) by GPC measurement, and the glass transition temperature was 191 ° C. by DSC measurement. In addition, the yellowness index (Y.
I. ) Was 14.

[0047]

As described above, according to the present invention, polyester and polyester carbonate having a low degree of coloring can be produced by a simple and inexpensive method.

Claims (1)

[Claims] 1. A diorganoester of a dicarboxylic acid,
A method for producing a polyester and a polyester carbonate, which comprises reacting a polycarbonate and / or an aromatic diorganodicarbonate to produce a polyester and a polyester carbonate, wherein the reaction is carried out substantially in the absence of oxygen.