JPH06122758A - Production of aromatic polyester carbonate - Google Patents

Abstract

PURPOSE:To obtain a high-molecular-weight aromatic polyester carbonate at good efficiency by subjecting a prepolymer of a specified aromatic polycarbonate oligomer with a specified diaryl aryldicarboxylate to solid phase polymerization in a specified manner. CONSTITUTION:This aromatic polyester carbonate is prepared by mixing an aromatic polycarbonate oligomer of formula I with a diaryl aryldicarboxylate monomer of formula II with each other under conditions satisfying formula III, prepolymerizing the obtained mixture to produce an amorphous prepolymer of an Mn in the range of 1000-10000, crystallizing this prepolymer and subjecting the crystalline prepolymer to solid phase polymerization in order to increase its degree of polymerization. In the formulas, Ar<1> and Ar<2> are each an arylene group; X is a single bond or the like; Y and Y<2> are each H or the like; Ar<3> is aryl; Ar<4> and Ar<6> are each aryl; Ar<5> is arylene; (n) is the average degree of polymerization and is equal to or greater than 1; Mn<1> is the number-average molecular weight; and alpha, beta and gamma are the number of moles.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing an aromatic polyester carbonate. More particularly, the present invention relates to a method suitable for industrially producing a high molecular weight aromatic polyester carbonate from an aromatic polycarbonate oligomer and a diaryl ester of an aryl dicarboxylic acid.

[0002]

2. Description of the Related Art Aromatic polycarbonates have excellent transparency and mechanical properties and are used for a wide range of purposes, but they have the drawback of being poor in heat resistance and chemical resistance. on the other hand,
Aromatic polyester has excellent heat resistance and chemical resistance. Therefore, by introducing an ester bond into the aromatic polycarbonate, it can be expected to improve the characteristics of the aromatic polycarbonate, the development of a method for producing such an aromatic polyester carbonate,
is important.

As a method for producing an aromatic polyester carbonate, a method in which a dihydroxydiaryl is reacted with a diarylcarbonate and an aryldicarboxylic acid (Japanese Patent Publication No. 38-26299, JP-A No. 48-113).
94, etc.), a method of reacting a dihydroxydiaryl with a diaryl carbonate and an aryl dicarboxylic acid diester (JP-A-60-186529, etc.),
There is a method of reacting a polycarbonate with an aryl dicarboxylic acid (US Pat. No. 4,338,422, etc.) and a method of reacting a polycarbonate with an aryl dicarboxylic acid ester (US Pat. No. 4,360,648, etc.). Since all of the methods are melt polymerization methods, the viscosity increases in the latter stage of the reaction, high temperature and high vacuum conditions are required to distill off the liberated aromatic monohydroxyl compound, and for high temperature polymerization It had the drawback of being colored.

Therefore, a method has been reported in which bisphenol A, diphenyl carbonate, and terephthalic acid are melt-polymerized, then crystallized and then solid-phase polymerized (Japanese Patent Laid-Open Nos. 55-98224 and 55-55224). -98228
Issue). However, this production method has drawbacks such that it is difficult to obtain a high molecular weight compound and the molecular weight varies.

[0005]

DISCLOSURE OF THE INVENTION The present invention aims to provide a method for efficiently producing a high molecular weight aromatic polyester carbonate by overcoming the drawbacks of the method for producing an aromatic polyester carbonate. It was done for the purpose.

[0006]

Means for Solving the Problems As a result of intensive studies on a method for producing an aromatic polyester carbonate, the present inventors have found that an aromatic polycarbonate having more terminal hydroxyl groups than terminal aryl carbonate groups prepared in advance is used. A method for efficiently producing a high molecular weight aromatic polyester carbonate was found by polymerizing with an aryl dicarboxylic acid diaryl ester and crystallizing the obtained prepolymer, followed by solid phase polymerization. That is, the present invention includes (a) the following [Chemical formula 3]

[0007]

[Chemical 3]

The number average molecular weight (Mn) is 50
An aromatic polycarbonate oligomer having a ratio of 0 to 5,000 and a terminal hydroxyl group in all the terminal groups of 60 to 100 mol%;

[0009]

[Chemical 4]

A diaryl ester monomer of aryl dicarboxylic acid represented by the formula (b) below (Formula 2)

[0011]

[Equation 2]

A prepolymerization step for producing an amorphous prepolymer having Mn in the range of 1,000 to 10,000 by mixing so as to satisfy the conditions and preliminarily polymerizing the mixture under heating, (c) crystallizing the amorphous prepolymer. The crystallinity is 5 to 90%
A crystallization step for preparing a crystallized prepolymer in the range of, and (d) above the glass transition temperature of the aromatic polyester carbonate from which the crystallized prepolymer is to be produced, and the crystallized prepolymer is in a solid state The present invention provides a method for producing an aromatic polyester carbonate, which comprises sequentially performing a solid-state polymerization step for further increasing the degree of polymerization by heating to a temperature within a range capable of holding the aromatic polyester carbonate.

In the present invention, the oligomer as a raw material for producing the amorphous prepolymer is represented by the following [Chemical formula 5].

[0014]

[Chemical 5]

The proportion of terminal hydroxyl groups in all the terminal groups is 100 to 60 mol%, the proportion of terminal aryl carbonate groups is 0 to 40 mol%, and the number average molecular weight (Mn) is usually 500 to 5000. Preferably 500-
The aromatic polycarbonate is 4000, more preferably 500 to 3000. When the Mn is 500 terminals, it is difficult to adjust the molar ratio in the prepolymerization, and when it is more than 5000, the ratio of the diaryl ester monomer of the aryl dicarboxylic acid that reacts with the oligomer becomes small, which is not preferable.

The oligomer can be transesterified,
It may also be synthesized by the phosgene method and prepared by a known method. Ar ¹ and Ar ² in the general formula (I) are arylene groups such as phenylene, naphthylene,
Represents a divalent group such as biphenylene, X is a single bond, an alkylene group —O—, —S—, —SO—, —SO ₂ —,
Two or more kinds selected from —CO— may be used.
Y ¹ and Y ² are —H or —CO—O—Ar ³ , and Ar
³ is an aryl group. n is an integer of 1 or more and represents an average degree of polymerization. When X is an alkylene group, X represents an alkylene or substituted alkylene group represented by the following [Chemical Formula 6].

[0017]

[Chemical 6]

(Where R ¹ , R ² , R ³ and R ⁴ are
A hydrogen atom, a lower alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, each of which may be optionally substituted with a halogen atom or an alkoxy group, k
Is an integer of 3 to 11, and hydrogen in the methylene group may be partially substituted with a lower hydrocarbon. ) Preferably, the selected alkylene group is represented by the following [Chemical formula 7].

[0019]

[Chemical 7]

Further, in the arylene groups Ar ¹ and Ar ² in the general formula (1), one or more hydrogen atoms are replaced with other substituents such as a halogen atom, a lower alkyl group, a lower alkoxy group and a lower alkylthiolate. Group, phenyl group,
It may be substituted with a phenoxy group, a cyano group, a silyl group, an amido group, a nitro group or the like. As such Ar ¹ and Ar ² , for example, an arylene group represented by the following [Chemical Formula 8] is preferably used.

[0021]

[Chemical 8]

(Here, R ⁵ and R ⁶ are each a hydrogen atom, a halogen atom, a lower alkyl group having 1 to 4 carbon atoms,
A lower alkoxy group having 1 to 4 carbon atoms, a cycloalkyl group or a phenyl group, which may be the same or different from each other, i and j are integers of 1 to 4, and i is When it is 2 or more, R ⁵ may be different from each other, and when j is 2 or more, R ⁶ may be different from each other. Among these, particularly preferable are the arylene groups represented by the following [Chemical Formula 9].

[0023]

[Chemical 9]

In the general formula (I), Y ¹ and Y ² are -H or -CO-O-Ar ³ . Y ¹ and R ² are −
The case of H is called a terminal hydroxyl group, the case of —CO—O—Ar ³ is called a terminal aryl carbonate group, and particularly when Ar ³ is a phenyl group, it is called a terminal phenyl carbonate group. A
r ³ is an aryl group represented by the following [Chemical Formula 10].

[0025]

[Chemical 10]

(Here, R ⁷ is a hydrogen atom, a halogen atom, a lower alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cycloalkyl group or a phenyl group, and p is 1 R ⁷ may be different when p is 2 or more.) Particularly preferred A
r ³ is a phenyl group (represented by —Ph). In addition,
A compound having 3 or more phenolic hydroxyl groups may be contained in the oligomer in an amount of about 0.001 to 3% by weight.

Examples of such trihydric or higher polyhydric phenols include phloroglucin: phloroglucid: 4,6
-Dimethyl-2,4,6-tri (4'-hydroxyphenyl) heptene-2: 2,6-dimethyl-2,4,6-
Tri (4'-hydroxyphenyl) heptene-3: 4
6-Dimethyl-2,4,6-tri (4'hydroxyphenyl) heptane: 1,3,5-tri (4'-hydroxyphenyl) benzene: 1,1,1-tri (4'-hydroxyphenyl) ethane : 2,2-bis [4,4-bis (4'-hydroxyphenyl) cyclohexyl] propane: 2,6-bis (2'-hydroxy-5'-methylbenzyl) -4-methylphenol: 2,6- Screw (2 '
-Hydroxy-5'-isopropylbenzyl) -4-isopropylphenol: bis [2-hydroxy-3-
(2'-Hydroxy-5'-methylbenzyl) -5-methylphenyl] methane: tetra (4-hydroxyphenyl) methane: tri (4-hydroxyphenyl) phenylmethane: bis (2,4-hydroxyphenyl) ketone:
1,4-bis (4 ', 4'-dihydroxytriphenylmethyl) benzene: 1,4-dimethyl-1,4-bis (4'-hydroxy-3-methylphenyl) -6-hydroxy-7-methyl- 1,2,3,4-tetralin:
2,4,6-tri (4'-hydroxyphenylamino)
-S-triazine and the like can be mentioned.

The oligomer may be synthesized by the known transesterification method, phosgene method, or other methods.
The number average molecular weight (Mn) is 500 by these methods.
, 5000, and the proportion of terminal aryl carbonate groups in all the terminal groups is 0 to 40 mol%, and the proportion of terminal hydroxyl groups is 100 to 60 mol%.

The diaryl ester monomer of aryl dicarboxylic acid used in the present invention is represented by the following [Chemical Formula 11].

[0030]

[Chemical 11]

(Where Ar^Four, Ar⁶Is the above Ar³
Same as^FiveIs the above Ar ¹Or Ar¹-X¹
-Ar²Is the same as. ) In the following [Chemical 12] [Chemical 13]
The indicated monomers are preferred and also in mixtures of these.
It may be.

[0032]

[Chemical 12]

[0033]

[Chemical 13]

Among the aryl dicarboxylic acid diaryl esters, phthalic acid, isophthalic acid, terephthalic acid,
Diphenyl esters of naphthalene dicarboxylic acids are particularly preferred. In the present invention, in the prepolymerization step of reacting the oligomer and the aryl dicarboxylic acid diaryl ester to produce an amorphous prepolymer, it is preferable to polymerize while releasing the aromatic monohydroxy compound and the diaryl carbonate in a molten state. preferable.

The prepolymer having such a molecular weight range does not have such a high melt viscosity, so that it is easy to carry out industrially. Of course, when carrying out this prepolymerization reaction, a solvent inert to the reaction, such as methylene chloride, chloroform, 1,2-dichloroethane,
Tetrachloroethane, dichlorobenzene, tetrahydrofuran, diphenylmethane, diphenyl ether and the like may be used, but they are usually used in the solvent-free and molten state.

In order to produce a high molecular weight aromatic polyester carbonate, it is necessary to adjust the terminal molar amount ratio of the oligomer and the aryl dicarboxylic acid diaryl ester monomer during the prepolymerization reaction. That is, the following [Equation 3]

[0037]

[Equation 3]

More preferably, the following [Equation 4] is satisfied so as to satisfy the above condition.

[0039]

[Equation 4]

The oligomer and the aryl dicarboxylic acid diaryl ester monomer are mixed so as to satisfy the above condition, and a prepolymerization reaction is carried out under heating to produce an amorphous prepolymer. Mn of the amorphous prepolymer produced in this prepolymerization step is usually 1000 to 10000, preferably 150.
It is selected in the range of 0 to 8000, more preferably 2000 to 6000. If this Mn is less than 1000, the reaction time of solid phase polymerization becomes long, which is not preferable.
If it is made larger, the next crystallization time becomes longer, which is not preferable.

Further, if the prepolymerization is carried out under the condition that the mixing ratio of the oligomer and the diaryl carbonate monomer of the dihydroxydiaryl compound is out of the above range, the number of moles of the terminal hydroxyl group in the reaction system and the (terminal aryl carbonate group The ratio of (the number of moles of + the number of moles of the terminal ester group) is significantly different. The degree of polymerization will not increase. In the amorphous prepolymer obtained in the present invention, regarding the ratio of the number of moles of the terminal hydroxyl groups present and the number of moles of the terminal aryl carbonate group + the number of moles of the terminal ester group, the physical properties of the aromatic polyester carbonate of the final product In order to improve the, it is necessary to reduce the amount of terminal hydroxyl groups at the stage when the target molecular weight is reached.

Therefore, it is preferable to produce the amorphous prepolymer in which the amount of (terminal aryl carbonate group + terminal ester group) is larger than the amount of terminal hydroxyl group. Further, the reaction temperature and reaction time for realizing the prepolymerization step are as follows: kind and amount of the starting material oligomer and aryl dicarboxylic acid diaryl ester, kind and amount of the catalyst used if necessary, and the obtained amorphous prepolymer. Is usually 50 to 350 ° C., preferably 100 to 35, though it depends on the required amount of polymerization of the above or other reaction conditions.
It is selected at a temperature in the range of 0 ° C., usually for 1 minute to 100 hours, preferably for 2 minutes to 10 hours.

In order to prevent the prepolymer from being colored, it is desirable to carry out the prepolymerization reaction at a temperature as low as possible and in a short time. Therefore, particularly preferable conditions are a reaction temperature in the range of 150 to 320 ° C. and a reaction time. It is selected in the range of minutes to hours. In the method of the present invention, since a prepolymer having a relatively low molecular weight may be produced by this prepolymerization, a colorless and transparent prepolymer having a required degree of polymerization can be easily obtained under the above-mentioned conditions.

In this prepolymerization reaction, an aromatic monohydroxy compound and a diaryl carbonate are produced as the reaction proceeds, but the rate is increased by removing them from the reaction system, so that the effect is obtained. At the same time as the agitation, an inert gas such as nitrogen, argon, helium or carbon dioxide or a lower hydrocarbon gas is introduced to generate the aromatic monohydroxy compound and diaryl carbonate produced by these gases. It is preferable to use a method of removing it by entraining it, a method of performing the reaction under reduced pressure, a method of using these in combination, and the like.

This prepolymerization reaction can also be carried out without the addition of a catalyst, which is a particularly preferred embodiment.
However, a polymerization catalyst can be used to accelerate the polymerization rate, if necessary. Such a polymerization catalyst is not particularly limited as long as it is a polycondensation catalyst used in this field, lithium hydroxide, sodium hydroxide,
Hydroxides of alkali metals and alkaline earth metals such as potassium hydroxide and calcium hydroxide: lithium hydroxide,
Alkali metal and alkaline earth metal hydroxides such as sodium hydroxide and calcium hydroxide: Alkali metal salts of hydrides of boron and aluminum such as lithium aluminum hydroxide, sodium borohydride and tetramethylammonium borohydride. , Alkaline earth metal salts, quaternary ammonium salts: alkali metal and alkaline earth metal alkoxides such as lithium methoxide, sodium ethoxide, calcium methoxide: lithium phenoxide, sodium phenoxide, magnesium phenoxide, LiO-Ar- OLi, NaO-Ar-O
Alyl oxides of alkali metals and alkaline earth metals such as Na (Ar is an aryl group): Organic acid salts of alkali metals and alkaline earth metals such as lithium acetate, calcium acetate and sodium benzoate: zinc oxide, zinc acetate, zinc Zinc compounds such as phenoxide: boron oxides, boric acid, sodium borate, trimethyl borate, tributyl borate, triphenyl borate and other boron compounds: silicon oxide, sodium silicate, tetraalkyl silicon, tetraaryl silicon , Compounds of silicon such as diphenyl-ethyl-ethoxysilicon: germanium compounds such as germanium oxide, germanium tetrachloride, germanium ethoxide, germanium phenoxide: tin oxide, dialkyltin oxide, diaryltin oxide, dial Dibutyltin carboxylate, tin acetate, tin compounds bound to an alkoxy group or an aryloxy group such as ethyl tin tributoxide, tin compounds such as organotin compounds: lead oxide, lead acetate, lead carbonate,
Lead compounds such as basic lead carbonate, lead and organic lead alkoxides or aryloxides: quaternary ammonium salts,
Onium compounds such as quaternary phosphonium salts and quaternary arsonium salts: Antimony compounds such as antimony oxide and antimony acetate: Manganese compounds such as manganese acetate, manganese carbonate and manganese borate: titanium oxide, titanium Titanium compounds such as alkoxides or aryl oxides: Catalysts such as zirconium acetate, zirconium oxide, zirconium alkoxides or aryl oxides, zirconium compounds such as zirconium acetylacetone can be used.

When a catalyst is used, these catalysts may be used alone or in combination of two or more. The amount of these catalysts used is usually 0.000001 to 1% by weight, preferably 0.000005 to 0.5% by weight, based on the raw material oligomer. Such catalysts usually remain intact in the final product aromatic polyester carbonate. Since such a residual catalyst may adversely affect the polymer physical properties, it is preferable that the amount of the catalyst used is as small as possible.

In the method of the present invention, since the prepolymerization step only needs to produce an amorphous prepolymer having a relatively low molecular weight, it can be carried out substantially without a catalyst without adding such a catalyst. Is advantageous. The method for crystallizing the amorphous prepolymer obtained in the prepolymerization step is not particularly limited, but in the present invention, the solvent treatment method and the heat crystallization method are preferably used. The former solvent treatment method is
It is a method of crystallizing the amorphous prepolymer using a suitable solvent, specifically, a method of dissolving the amorphous prepolymer in a solvent and then precipitating the crystallized prepolymer from this solution, or an amorphous prepolymer. The time required for the solvent to permeate into the amorphous prepolymer and crystallize the amorphous prepolymer using a solvent having a low dissolving power for the polymer,
A method of bringing the amorphous prepolymer into contact with a liquid solvent or solvent vapor is preferably used.

As the method for precipitating the crystallized prepolymer from the amorphous prepolymer solution, for example, a method of removing the solvent from the solution by means such as evaporation of the solvent, or a method of adding a poor solvent for the amorphous prepolymer is used. However, the method of simply removing the solvent is simple and preferable. Further, the time required to crystallize the amorphous prepolymer by infiltrating the solvent into the amorphous prepolymer depends on the type and molecular weight of the amorphous prepolymer, the shape, the type of solvent used, the processing temperature, etc. However, it is usually selected in the range of several seconds to several hours. The processing temperature is usually -10.
It is selected in the range of 200 ° C.

Preferred solvents which can be used for solvent treatment of such an amorphous prepolymer include, for example, chloromethane, methylene chloride, chloroform, carbon tetrachloride,
Chloroethane, dichloroethane (various), trichloroethane (various), trichloroethylene, tetrachloroethane (various) and other fatty acid halogenated hydrocarbons: chlorobenzene, dichlorobenzene and other aromatic halogenated hydrocarbons: tetrahydrofuran, dioxane and other ethers: Esters such as methyl acetate and ethyl acetate: acetone, ketones such as methyl ethyl ketone: aromatic hydrocarbons such as benzene, toluene and xylene. These solvents may be used alone or in combination of two or more.

The amount of the solvent used for the solvent treatment of the amorphous prepolymer varies depending on the type of the amorphous prepolymer or the solvent, the required crystallinity, the treatment temperature, etc. 0.05-100 by weight
Double, preferably 0.1 to 50 times. On the other hand, the heating crystallization method is to crystallize the amorphous prepolymer by heating at a temperature above the glass transition temperature of the intended aromatic polyester carbonate and below the temperature at which the amorphous prepolymer begins to melt, It is a method to let. This method can be carried out extremely easily industrially because the amorphous prepolymer can be crystallized simply by holding it under heating.

As described above, the temperature Tc (° C.) for carrying out this heat crystallization is not less than the glass transition temperature of the target aromatic polyester carbonate and less than the melting temperature Tm (° C.) of the amorphous prepolymer. The temperature is not particularly limited as long as it is within the range, but since the crystallization rate of the amorphous prepolymer is low at a low temperature, a particularly preferable heating crystallization temperature T
c (° C.) is selected in the range represented by the formula Tm-50 ≦ Tc <Tm.

The heat crystallization of the amorphous prepolymer may be carried out while keeping a certain temperature in the above range constant, or may be carried out while changing the temperature continuously or discontinuously, Moreover, it is also possible to carry out by a method combining these. As a method of carrying out while changing the temperature, as the temperature of the solution of the amorphous prepolymer generally rises as the heating crystallization progresses, heating while raising the temperature at the same rate as this rising rate. A method of crystallizing is particularly preferable.

As described above, in the method of heating and crystallization while changing the temperature, the crystallization rate of the amorphous prepolymer is faster and the melting temperature thereof is higher than that in the heating and crystallization method under a constant temperature. be able to. The heating crystallization time varies depending on the chemical composition of the amorphous prepolymer, the presence or absence of a catalyst, the crystallization temperature, the crystallization method, etc., but is usually 1 to 200.
It is a range of time.

As described above, the amorphous prepolymer is crystallized by the crystallization step. The degree of crystallization depends on the chemical composition and the degree of polymerization of the amorphous prepolymer, the presence or absence of a catalyst, and the crystallization conditions. The crystallinity is usually in the range of 3 to 95%, though it varies depending on the case. It is of course possible to increase the molecular weight by the following solid phase polymerization step using the crystallized prepolymer having the crystallinity in such a range. In that case, the crystallinity is selected in the range of 5 to 90%, preferably 10 to 80%. This crystallinity is 5%
In the case of a crystallized prepolymer of less than, its melting temperature does not become so high, so that solid-phase polymerization cannot be performed by fusion during solid-phase polymerization, or at a relatively low temperature at which the prepolymer is not fused. It is necessary to carry out solid state polymerization for an extremely long time, which is disadvantageous for industrial implementation.
If it exceeds 90%, the solid-phase polymerization rate will be slow, and therefore it will take a long time to carry out solid-phase polymerization, which is disadvantageous for industrial implementation.

The crystallized prepolymer thus obtained can be easily converted into a high-molecular-weight aromatic polyester carbonate by subjecting the crystallized prepolymer to a solid-phase polyphase while maintaining the solid-phase state at a temperature lower than its melting temperature. You can In the solid-phase polymerization step, the reaction is promoted by extracting the aromatic monohydroxy compound and / or the diaryl carbonate, which are by-produced by the reaction, out of the system. For that purpose, nitrogen, argon, helium, an inert gas such as carbon dioxide, a method of introducing a lower hydrocarbon gas, etc., and a method of removing the diaryl carbonate and the aromatic monohydroxy compound by accompanying these gases, A method of performing the reaction under reduced pressure, a method of using these in combination, and the like are preferably used. Further, when introducing the gas for entrainment, it is preferable to heat these gases to a temperature near the reaction temperature.

There is no particular restriction on the shape of the crystallized prepolymer in the case of carrying out this solid-phase polymerization reaction, but large lumps are not preferable because the reaction rate is slow and the handling is troublesome. A shape such as a shape, a bead shape, a granule shape, or a powder shape is preferable. Further, a crushed solid prepolymer after crystallization into an appropriate size is also preferably used. The crystallized prepolymer crystallized by solvent treatment is usually obtained in the form of porous granules or powder, and such a porous crystallized prepolymer is a by-product of aroma during solid phase polymerization. It is particularly preferable since the group monohydroxy compound and the diaryl carbonate can be easily extracted.

Reaction temperature T when carrying out the solid-state polymerization reaction
Regarding p (° C) and reaction time, the type (chemical structure, molecular weight, etc.) and shape of the crystallization prepolymer, the presence or absence and type and amount of the catalyst in the crystallization prepolymer, and the type of catalyst added as necessary The amount of the fragrance, the degree of crystallization of the crystallized prepolymer, the difference in the melting temperature Tm '(° C), the required degree of polymerization of the target aromatic polyester carbonate, or other reaction conditions, etc. A temperature above the glass transition temperature of the group polyester carbonate and within a range where the crystallized prepolymer during solid phase polymerization does not melt and remains in a solid state, preferably in the range represented by the formula Tm'-50≤Tp <Tm ' The solid phase polymerization reaction is carried out by heating at the temperature of 1 minute to 100 hours, preferably 0.1 to 50 hours.

Such a temperature range is, for example, about 150 to 35 in the case of producing a polyester carbonate having a bisphenol A skeleton and a terephthalic acid skeleton.
0 degreeC is preferable and about 180-300 degreeC is especially preferable.
In the solid-state polymerization step, effective stirring is not performed in order to heat the polymer during polymerization as uniformly as possible or to favorably extract the aromatic monohydroxy compound or diaryl carbonate produced as a by-product. This is the preferred method. As this stirring method, for example, a method using mechanical stirring such as a method using a stirring blade or a method using a reactor in which the reactor itself rotates, or a method of flowing with heated gas is preferably used.

When the crystallization of the amorphous prepolymer is carried out by heating crystallization, the system is depressurized or accompanied by a mere heating operation for reaching a predetermined crystallinity. It is also possible to extract the aromatic monohydroxy compound or diaryl carbonate from the system by introducing a heating gas for solid phase polymerization. The solid-state polymerization reaction in the present invention can proceed at a sufficient rate without adding a catalyst, which is the most preferred embodiment, but a catalyst can be used for the purpose of further increasing the reaction rate. If a catalyst is used in the prepolymerization step, the catalyst usually remains in the prepolymer to be produced, so it is not necessary to add a new catalyst, but the catalyst is removed for some reason, or the activity decreases. In some cases, a suitable catalyst can be added at that time. In this case, it is also a preferable method to add the catalyst component in a liquid or vapor phase state to the crystallized prepolymer. Examples of such a catalyst component include those described above that can be used in the prepolymerization step.

Thus, the degree of polymerization of the crystallized prepolymer can be increased by carrying out the solid phase polymerization step. Generally, Mn of aromatic copolycarbonate which is industrially useful is about 3000 to 150,000 (Mw is 60).
00 to 500,000), preferably 4000
~ 20,000 (Mw is about 10,000 to 50,000), more preferably about 6000 to 15,000 (Mw
Is about 15,000 to 40,000), but an aromatic copolycarbonate having such a degree of polymerization can be easily obtained by the solid phase polymerization method of the crystallization prepolymer of the present invention.

The shape of the aromatic polyester carbonate produced by such solid phase polymerization may depend on the shape of the crystallized prepolymer used, but it is usually
They are so-called powders such as beads, granules and powders.
Since the crystallinity of the aromatic polyester carbonate obtained by solid-state polymerization of the crystallized prepolymer is usually higher than that of the original prepolymer, in the method of the present invention, a crystalline aromatic carbonate is usually used. A polyester carbonate powder will be obtained.

[0062]

EXAMPLES The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. The molecular weight is the value of the number average molecular weight (Mn) and the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC). Also,
Both the prepolymerization reaction device and the solid-phase polymerization reaction device were designed so that deoxidation and drying were taken into consideration and oxygen and water during the reaction were mixed as little as possible.

The ratio of the terminal groups (aryl carbonate group + aryl ester group) to hydroxyl group in the oligomer, the amorphous prepolymer and the aromatic polyester carbonate was measured by high performance liquid chromatography and measured according to A.M. The method of Horbach et al. [Phenolic-
According to the OH group quantification method, a prepolymer or a polymer is dissolved in acetic acid-acidified methylene chloride, TiCl ₄ is added, and the resulting red complex is colorimetrically quantified with light having a wavelength of 546 nm. Chem. 88
P. 215 (1965)].

The crystallinity is determined by the wide-angle X-ray diffraction method from the area of the amorphous part and the crystal part of the diffraction chart by the following formula: area of crystal part × 100 / (area of amorphous part + area of crystal part) It was The ratio of the ester bond and the carbonate bond in the obtained aromatic polyester carbonate is determined from the intensity ratio of the ester absorption (1720 cm ^-1 ) and the carbonate absorption (1750 cm ^-1 ) in the infrared absorption spectrum according to JP-A-55-98224. I asked.

[0065]

Example 1 2,2-bis (4-hydroxyphenyl)
A colorless and transparent oligomer with Mn = 1700 was synthesized from propane (hereinafter referred to as bisphenol A) and diphenyl carbonate according to the method described in JP-A-1-158033. The ratio of the terminal groups of this oligomer is 9 when the terminal hydroxyl group (referred to as —OH group) is 9
The content was 7.2 mol% and the terminal phenyl carbonate group was 2.8 mol%.

17.0 g of this oligomer (Mn ¹ = 17)
00, β = 0.019, γ = 0.001) and 2.9 g (α = 0.009) of terephthalic acid diphenyl ester were placed in a 50 ml three-necked flask equipped with a stirrer, gas inlet, and gas suction port. After repeating degassing under reduced pressure and introduction of dry nitrogen gas several times, the mixture was placed in an oil bath and heated to 280 ° C., while reacting with dry nitrogen gas of 20 Nl / Hr for 1 hour, then the reaction system was changed to 30 The pressure was reduced over a period of time, and the reaction was finally performed at 2 to 5 mmHg for another 30 minutes to distill phenol and diphenyl carbonate.

As a result, 18.9 g of a colorless and transparent amorphous prepolymer having Mn of 3520 was obtained. The proportion of terminal groups of this amorphous prepolymer is 28 mol% of -OH groups, [-
O-CO-O-Ph group + -CO-O-Ph (representing terminal ester group)] was 72 mol%. Then, 10 g of this amorphous prepolymer was crushed to obtain 20 ml of acetone.
By immersing in, 9.9 g of a crystallized prepolymer having a crystallinity of 22% was obtained.

5 g of this crystallized prepolymer was added to an inner diameter of 15
5Nl / Hr in a mm gas flow reactor
Solid phase polymerization was performed by flowing heated nitrogen gas at a flow rate of 210 ° C. for 2 hours and 230 ° C. for 3 hours. As a result, M
A white aromatic polyester carbonate having n = 12400, Mw = 28420 and a crystallinity of 30% was obtained. The ratio of the ester bond to the carbonate bond was 25 mol%: 75 mol%, and the terminal (-O-CO-O-Ph group + -CO-
O-Ph group) is 86 mol%, terminal -OH group is 14 mol%
Met.

[0069]

Example 2 Mn was prepared from bisphenol A and diphenyl carbonate according to JP-A No. 1-158033.
= 740 colorless and transparent oligomers were synthesized. The ratio of the terminal groups of this oligomer was 99.9 mol% for terminal --OH groups and 0.1 mol% for terminal / phenyl carbonate groups.

7.4 g of this oligomer (Mn ¹ = 74
0, β = 0.020, γ = 0) and 3.5 g (α = 0.011) of terephthalic acid diphenyl ester were used, and prepolymerization, crystallization and solid phase polymerization were carried out according to Example 1. As a result, a white aromatic polyester carbonate having Mn = 13320, Mw = 30800 and a crystallinity of 41% was obtained. The ratio of the ester bond and the carbonate bond was 54 mol%: 46 mol%, the terminal (—O—CO—O—Ph group + —CO—O—Ph group) was 89 mol%, and the terminal —OH group was 11 mol%. %Met.

[0071]

Comparative Example 1 Using 68.4 g of bisfunol A, 16.6 g of terephthalic acid and 94.2 g of diphenyl carbonate, prepolymerization was carried out according to the method described in JP-A No. 1-158033, and then according to Example 1. Crystallization and solid state polymerization were performed. As a result, the obtained polyester carbonate had only Mn = 5440.

[0072]

Comparative Example 2 Diphenyl terephthalate ester 31.8
g (0.1 mol), bisphenol A 68.3 g (0.
3 mol) and 47.1 g of diphenyl carbonate (0.2
2 mol) was used to carry out polymerization in the same manner as in Comparative Example 1. As a result, the obtained polyester carbonate had Mn = 509.
It was only 0.

[0073]

Examples 3 to 6 The same procedure as in Example 1 was carried out except that 85 mol% of bisphenol A and 15 mol% of the other dihydroxydiaryl compound were used instead of bisphenol A. The results are shown in Table 1.

[0074]

[Table 1]

[0075]

Example 7 Instead of crystallizing the amorphous prepolymer with acetone in Example 1, heat crystallization was performed.
5 g of the amorphous prepolymer was put into the above-mentioned solid-state polymerization apparatus, and 5
It was heated at 190 ° C. for 10 hours under a nitrogen stream of Nl / Hr. The crystallinity of the obtained crystallized prepolymer was 13%.

Then, solid phase polymerization was carried out in the same manner, and Mn = 10.
230 white crystalline aromatic polyester carbonates were obtained.

[0077]

Examples 8 to 11 In Example 1, prepolymerization, crystallization and solid phase polymerization were carried out using a diphenyl ester other than terephthalic acid. The results are shown in Table 2.

[0078]

[Table 2]

[0079]

INDUSTRIAL APPLICABILITY The present invention relates to the production of a high molecular weight aromatic polyester carbonate by a transesterification reaction method,
The molar ratio of the reactants can be adjusted easily and accurately, and as a result, a high molecular weight product can be easily obtained, and the terminal hydroxyl group can be adjusted to a much higher degree than (terminal aryl carbonate group + terminal aryl ester group). A small amount of aromatic polyester carbonate can be produced.

Claims (1)

[Claims] 1. (a) The following [Chemical formula 1] And the number average molecular weight (Mn) is 500 to 5,000.
And the proportion of the terminal hydroxyl groups in all the terminal groups is 60 to 100 mol%, and the following [Chemical Formula 2]: And a diaryl ester monomer of aryldicarboxylic acid represented by the formula (b) below [Formula 1] (Where Mn ¹ is the number average molecular weight of the oligomer, α is the number of moles of the aryl dicarboxylic acid diaryl ester, β is the number of moles of the terminal hydroxyl groups of the oligomer, and γ is the number of moles of the terminal aryl carbonate group of the oligomer. A prepolymerization step of producing an amorphous prepolymer having Mn in the range of 1000 to 10000 by mixing so as to satisfy the above requirement, and (c) crystallizing the amorphous prepolymer. A crystallization step of preparing a crystallized prepolymer having a degree of crystallinity in the range of 5 to 90%, and (d) a glass transition temperature of the aromatic polyester carbonate for producing the crystallized prepolymer or higher. And to increase the degree of polymerization by heating the crystallized prepolymer to a temperature in a range where the crystallized prepolymer can maintain a solid state. The method for producing an aromatic polyester carbonate is characterized in that