JPH03223330A - Porous polycarbonate prepolymer, its production, and production of aromatic polycarbonate by using the same - Google Patents

Abstract

PURPOSE:To obtain the title prepolymer which can give a polycarbonate substantially free of impurities by selecting a porous crystalline aromatic polycarbonate prepolymer comprising repeating units of an aromatic carbonate, a terminal hydroxyl group and a terminal aryl carbonate group and having a specified compositional ratio of the terminal groups and specified physical properties. CONSTITUTION:A porous crystalline aromatic polycarbonate prepolymer comprising repeating units of an aromatic carbonate, a terminal hydroxyl group and a terminal aryl carbonate group, wherein the molar ratio of the hydroxyl groups to the aryl carbonate groups is (5:95) to (95:5), the number-average mol.wt. is 1000-15000, the specific surface area is 0.2m<2>/g or more and the degree of crystallinity is 5% or more (e.g. a prepolymer obtained by reacting bisphenol A with diphenyl carbonate and subjecting the product to necessary treatments) is selected.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention provides a (porous) crystalline aromatic polycarbon 7-tobre polymer porous body suitable for solid-state polymerization, a method for producing the same, and a solid state polymer using the porous body. This invention relates to a method for producing aromatic polycarbonate by phase polymerization.

(Prior art) In recent years, especially in the last 5 to 6 years, aromatic polycarbonate has
It is widely used in many fields as an engineering plastic with excellent heat resistance, impact resistance, and transparency.

Various studies have been conducted on the production method of aromatic polycarbonate, and among them, research has been conducted on the combination of aromatic dihydroxy compounds such as 2,2-bis(4-hydroxyphenyl)propane (hereinafter referred to as bisphenol A) and phosgene. Interfacial polycondensation methods (hereinafter sometimes simply referred to as "phosgene methods") have been industrialized. In this method, a mixed solvent of water or an alkaline aqueous solution and an organic solvent immiscible with water is usually used.

Industrially, a mixed solvent of caustic soda aqueous solution and methylene chloride is used. A tertiary amine or a quaternary ammonium compound is used as a polymerization catalyst, and by-product hydrogen chloride is removed as a base salt.

However, in this interfacial polycondensation method using phosgene, (1) toxic phosgene must be used, (2) the equipment is corroded by chlorine-containing compounds such as hydrogen chloride and sodium chloride, which are produced as by-products, and (3) ) It is difficult to separate impurities that adversely affect the physical properties of the polymer, such as sodium chloride, mixed into the resin. (4) Methylene chloride, which is commonly used as a reaction solvent, is a good solvent for polycarbonate and has a very high affinity. strong.

Therefore, methylene chloride inevitably remains in the produced polycarbonate. Industrially reducing the amount of methylene chloride remaining in the polycarbonate requires a great deal of expense, but it is still almost impossible to completely remove the methylene chloride remaining in the polycarbonate.

Methylene chloride remaining in the polymer decomposes due to heating during molding and generates hydrogen chloride, which not only causes corrosion of the molding machine but also causes a decline in the quality of the polymer. There is.

Furthermore, when attempting to produce ultra-high molecular weight polycarbonate (for example, number average molecular weight of 115,000 or more), the viscosity of the methylene chloride solution layer becomes extremely high, which not only makes stirring difficult but also causes the product to become sticky. This makes it very difficult to determine the proportion M between the polymer and methylene chloride. For this reason, it has been difficult to industrially produce ultra-high molecular weight polymers of good quality using the phosgene method.

Industrial implementation of the phosgene method still involves many problems.

On the other hand, a method for producing aromatic polycarbonate (4) from an aromatic dihydroxy compound and diaryl carbonate has been known for a long time. For example, a transesterification reaction of bisphenol A and diphenyl carbonate in a molten state is carried out in the presence of a catalyst A method for producing polycarbonate by eliminating phenol has been industrialized as the so-called transesterification method or otherwise known as the melting method.

However, this method produces high viscosity (
For example, 8,000 to 20,000 voices at 280°C)
The degree of polymerization of the desired aromatic polycarbonate cannot be increased unless phenol and finally diphenyl carbonate are distilled off from the melt of polycarbonate. and under high vacuum below 1mHg for a long time, e.g. 4 to 5 hours.
It is necessary to react over time.

Therefore, (1) special equipment suitable for high temperature and high vacuum conditions and powerful stirring equipment are required due to the high viscosity of the product, and (2) due to the high viscosity of the product, it is not commonly used in the plastics industry. The reactors and stirring type reactors used can only yield polymers with a weight average molecular weight of about 30,000; (3) since the reaction is carried out at high temperatures, branching and crosslinking are likely to occur due to side reactions, resulting in poor quality. (4) It is difficult to obtain a good polymer, and (4) coloration cannot be avoided due to long-term residence at high temperatures.
(See Mikio Matsugane et al., Plastic Materials Course [5], "Polycarbonate Resin," published by Nikkan Kogyo Shimbun, pp. 62-67, 1962).

Furthermore, it is known that polycarbonate obtained by the melting method has a wide molecular weight distribution and many branched structures, and therefore has inferior physical properties compared to polycarbonate produced by the phosgene method. It has been pointed out that it is somewhat inferior in strength, particularly has high brittle fracture, and has non-Newtonian flow behavior and poor formability (Mikio Matsugane, "Kobonshi", Vol. 27, No. 521).
1978].

By the way, the most common condensation polymers, such as poly5xamethylene adipamide (nylon 66) and polyethylene terephthalate (PET), are usually processed by melt polymerization to a molecular weight that has sufficient mechanical properties for plastics and fibers. Polymerization is carried out by heating the high molecular weight polymer produced in this way at a temperature that allows it to remain in the solid phase under reduced pressure or under a flow of dry nitrogen or the like at normal pressure. It is already known that it is possible to carry out polymerization and further increase the degree of polymerization.

In this case, it is thought that the terminal carboxyl group reacts with the nearby terminal amino group or terminal hydroxyl group in the solid polymer, and dehydration condensation progresses. Furthermore, in the case of polyethylene terephthalate, a part of the condensation reaction by removing ethylene glycol from the produced polymer also occurs.

In this way, the reason why nylon 6.6 and polyethylene terephthalate can be made to a high degree of polymerization through solid state polymerization is that these polymers are originally crystalline polymers with high melting points (265°C and 260'C), This is because the solid phase state can be maintained sufficiently at the temperature at which phase polymerization proceeds (for example, 230 to 250'C). More importantly, the compound to be desorbed must be a substance with a small molecular weight and a relatively low boiling point, such as water or ethylene glycol, so that it can easily move through the solid polymer and exit the system as a gas. This is because it can be removed.

On the other hand, a method has also been proposed for producing a high molecular weight aromatic polyester carbonate by melt polymerizing a high melting point aromatic polyester carbonate that has both an aromatic ester bond and a carbonate bond, and then further performing solid phase polymerization. This method uses a prepolymer obtained by reacting an aromatic dicarboxylic acid or an aromatic oxycarboxylic acid such as naphthalene dicarboxylic acid, parahydroxybenzoic acid, or terephthalic acid with a dihydroxy aromatic compound and a diaryl carbonate in a molten state. After crystallization, solid phase polymerization is performed.

Among these, when using parahydroxybenzoic acid, if the degree of polymerization increases to a certain degree by melt polymerization at 260 to 280 °C, this solid can no longer maintain a molten state and becomes solid. Since it is a highly crystalline prepolymer with a high melting point, there is no need for further crystallization (Japanese Patent Laid-Open No. 48
-22593 publication, JP-A-49-31796 publication,
U.S. Patent No. 4,107.143, Japanese Unexamined Patent Publication No. 1983-
(See Publication No. 98224).

However, these methods reduce the ester bond by 30%.
The above is a method that can be applied to the production of aromatic polyester carbonate which usually contains about 50% or more, but if the ester bond is less than 30%, the prepolymer will melt during solid phase polymerization, resulting in solid phase polymerization. It has also been reported that this was not possible (Japanese Patent Application Laid-Open No. 55-98224).

On the other hand, it is also known that the presence of such ester bonds has the effect of accelerating the carbonate bond formation reaction when producing aromatic polyester carbonates by the melt polycondensation method (Japanese Patent Publication No. 52-36797). (see publication).

According to Japanese Patent Publication No. 52-36797, when a high molecular weight aromatic polycarbonate containing ester bonds is produced by a melt polycondensation method, ester bonds are preformed in the molecular chain of an aromatic polycarbonate with a low degree of polymerization. It has been revealed that the melt polycondensation reaction is significantly accelerated by the introduction of the polycondensate. Naturally, it is presumed that the ester bond has such a polycondensation reaction promoting effect also in solid phase polymerization.

Therefore, polymers with 40 mol% of ester bonds obtained from naturally crystalline aromatic polyester carbonates with high melting points, such as parahydroxybenzoic acid, hydroquinone and diphenyl carbonate, and some crystallization operations, e.g. By heating to a temperature of
Aromatic polyester carbonates that can easily become crystalline polymers with high melting points, such as 2,6-naphthalene dicarboxylic acid, bisphenol A, and diphenyl carbonate, are used to solid-state polymerize a polymer containing 55 mol% of ester bonds to obtain a higher degree of polymerization. It is relatively easy to make this happen.

However, attempts to produce a high molecular weight aromatic polycarbonate containing no ester bonds by first producing a low molecular weight prepolymer using a melt polymerization method and then subjecting the prepolymer to solid phase polymerization have been unsuccessful.
There is no known example except for an attempt to obtain a highly crystalline special polycarbonate having a high melting point of 80 DEG C. or higher by face phase polymerization (Example 3 of JP-A No. 19591).

The method described in JP-A-52-1 (19591) involves the melt polymerization of diphenyl carbonate and an aromatic dihydroxy compound consisting of about 70% hydroquinone and about 30% bisphenol A at 280°C and a high temperature of 50.5 μHg. This is carried out under vacuum, and the solidified prepolymer having a melting point of over 280°C is subjected to solid phase polymerization at 280°C and 10.5 g of Hg for 4 hours.

However, for aromatic polycarbonate, which is a substantially amorphous polymer mainly composed of dihydroxydiarylalkane, such as bisphenol A, a relatively low molecular weight prebolymer is first produced, and then the prepolymer is subjected to solid state polymerization. Very few attempts have been made to produce high molecular weight polymers by attaching them.

For example, in the phosgene method using an acid binder, which is the most common method for producing aromatic polycarbonates, the compound that must be removed from the reaction system in order to proceed with the binding reaction is usually a non-containing compound such as sodium chloride. It is a solid in the solvent, and it is very difficult for it to move through the solid polymer and be extracted from the system. Therefore, it is essentially impossible to carry out this method on solid phase.

In addition, the most common aromatic polycarbonate, bisphenol A polycarbonate, has been replaced with bisphenol A polycarbonate.
Regarding the method of manufacturing by transesterification reaction between carbonate and diphenyl carbonate, melt polymerization method under high temperature and high vacuum has been considered. No consideration had been given to subjecting the compound to solid phase polymerization to increase the degree of polymerization.

This is because bisphenol A polycarbonate is an amorphous polymer with a glass transition temperature (Tg) of 149 to 150°C, so it was thought that solid phase polymerization would be impossible. In other words, in order to make solid phase polymerization possible for boat fishing, the polymer must undergo fusion, etc. at a temperature above the glass transition temperature (below the glass transition temperature, solid phase polymerization is impossible because molecular movement is impossible). However, in the case of amorphous polycarbonate, fusion may occur at temperatures above 150°C, and solid state polymerization will not substantially occur if left as is. This is because it was possible.

As described above, an attempt to produce an aromatic polycarbonate, which is a substantially amorphous polymer mainly composed of dihydroxodiarylalkane such as bisphenol A, by in-phase polymerization was previously filed by the present applicant. Method (Japanese Unexamined Patent Publication No. 63-223035, Unexamined Japanese Patent Application No. 64-17
No. 25, JP-A-64-4617, JP-A-64
-16826, JP-A-64-16827)
Except for this, nothing was done at all.

JP-A-63-223035 and JP-A-64-46
In Publication No. 17, bisalkyl carbonate of an aromatic dihydroxy compound, for example, bismethyl carbonate of bisphenol A represented by formula (I): Hs, is converted into bisphenol A by a self-condensation reaction in which dimethyl carbonate is eliminated under heating. It was shown that solid phase polymerization is possible in producing polycarbonate.

In this method, a prepolymer formula (■) in which both terminal groups have methyl carbonate groups is first prepared by prepolymerization, and then this prepolymer is treated with a solvent. Or
After heating and crystallizing, solid phase polymerization is performed.

Also, JP-A-64-1725, JP-A-64-16
In JP-A No. 826 and JP-A No. 64-16827, the terminal group is a methyl carbonate group, which can be obtained by, for example, the reaction of bismethyl carbonate of bisphenol A represented by formula (I) with diphenyl carbonate. A prepolymer consisting of phenyl carbonate groups, for example, a prepolymer represented by the following formula (■): (! is as described above) is prepared, subjected to solvent crystallization treatment or heating crystallization treatment, and then solid phase polymerization. It was shown that bisphenol A polycarbonate can be produced by this method.

In this method, unlike the reaction of the above-mentioned method, polycondensation proceeds by a reaction in which methyl phenyl carbonate is eliminated from the terminal groups methyl carbonate group and phenyl carbonate group. Compared to the polymerization method, it is possible to lower the polymerization temperature.

Therefore, one of the major features of solid phase polymerization is that thermal deterioration of the polymer during polymerization is suppressed and a polymer of good quality can be obtained, but in general, the polymerization rate is slow. This is a drawback. Even in the method for producing aromatic polycarbonate by the solid phase polymerization method involving the de-dimethyl carbonate reaction or the de-methyl phenyl carbonate reaction, the polymerization rate was still insufficient and a long polymerization time was required.

In these solid phase polymerization methods, it is possible to use a catalyst to shorten the polymerization time, but if this catalyst remains in the resulting polymer, it generally reduces the quality of the polymer (for example, during molding). There was a problem in that it was easy to cause silver streaks (such as silver streaks).

(Problems to be Solved by the Invention) The present invention overcomes various drawbacks of the conventional phosgene method and melting method, and provides a method for producing high-quality aromatic polycarbonate that does not contain chlorine compounds. Moreover, it was developed with the aim of providing a porous crystalline aromatic polycarbonate prepolymer suitable for solid-phase polymerization, which has a faster polymerization rate than conventional solid-phase polymerization methods and is easier to handle. Furthermore, the present invention also provides a method for producing this prepolymer and a method for producing aromatic polycarbonate by solid phase polymerization using this prepolymer.

(Means for Solving the Problems) The present inventors have proposed a method for producing an aromatic polycarbonate using as raw materials a dihydroxyaryl compound mainly composed of dihydroxydiarylalkane such as bisphenol A, and a diaryl carbonate such as diphenyl carbonate. We discovered that it was possible to achieve a high degree of polymerization by solid phase polymerization, which had never been attempted before, and filed a separate application (vFItl No. 63-240785, National No. 111
Patent tt [PCT/JP8810 (No. 1989, *a No. 63-327678).

These applications involve crystallizing a substantially amorphous prepolymer whose end groups are hydroxyl groups and aryl carbonate groups, and solid-state polymerizing this crystalline prepolymer to produce high-quality aromatic polycarbonate. In the present invention, it has been found that the degree of crystallinity of the crystalline prepolymer plays an important role in performing solid phase polymerization.

Based on these findings, the present inventors continued intensive research on the method for producing aromatic polycarbonate by solid phase polymerization. As a result, the specific surface area of the crystalline aromatic polycarbonate prepolymer We have discovered that it plays an important role in implementing the
Based on this knowledge, we have completed the present invention.

That is, the present invention: (A) ■ consists of a repeating unit of aromatic carbonate, a hydroxyl end group and an aryl carbonate end group, and the molar ratio of the hydroxyl group to the aryl carbonate group is 5:95 to 95:5; , number average molecular weight is 1,
000-15,000 and the specific surface area is 0.2+rf
/g or more and a crystallinity of 5% or more, a porous, crystalline aromatic polycarbonate prepolymer, and
(2) The porous, crystalline aromatic polycarbonate prepolymer described in (1) above is also characterized in that it is in the form of a granular molded body.

(B) ■ A method of producing a porous, crystalline aromatic polycarbonate prepolymer, comprising treating the amorphous aromatic polycarbonate prepolymer with a solvent under sufficient shear to crystallize and make the amorphous polycarbonate prepolymer porous. The aromatic polycarbonate prepolymer consists of a repeating unit of aromatic carbonate, a hydroxyl end group and an aryl carbonate end group, and the molar ratio of the hydroxyl group to the aryl carbonate group is 5:95.
~95:5, and the number average molecular weight is 1.000~15,
000, a method for producing a porous, crystalline aromatic polycarbohydrate prepolymer.

(C) ■ In a method for producing agglomerated powder of porous, crystalline aromatic polycarbonate prepolymer.

It is characterized in that sufficient pressure or heat is applied to the particles of the porous, crystalline aromatic polycarbonate prepolymer powder described in (1) above, and (2) the porous, crystalline aromatic polycarbonate prepolymer powder having the form of a powder or agglomerated powder Aromatic polycarbonate prepolymer is heated in a heating zone at a temperature above the glass transition temperature of the prepolymer and at which the prepolymer remains in a solid state, and polycondensation byproducts are removed from the heating zone before solid state polymerization. wherein the prepolymer having the form of powder or agglomerated powder is the prepolymer described above,
Moreover, the molecular weight and crystallinity of the obtained polycarbonate are increased by 35% or more from 6,000 to 200,000, respectively, by solid phase polymerization. The crystallinity is greater than the molecular weight and crystallinity of
5% or more, number average molecular weight 6,000-200.00
This is a method for producing a powder or agglomerated powder of a porous, crystalline aromatic polycarbonate with a
In the method for producing a powder or agglomerated powder of a porous, crystalline aromatic polycarbonate prepolymer described, the powder or agglomerated powder of a prepolymer is heated, and 0.1 g of the prepolymer is added thereto. ~1ONl(N,T
, P)/hr of inert gas is passed through, and the inert gas containing polycondensation by-products is discharged from the heating zone. In the method for producing powder or agglomerated powder of group polycarbonate prepolymers, removing polycondensation byproducts from the discharged inert gas or diluting the discharged inert gas with fresh inert gas. As a result, the content of polycondensation byproducts in the obtained inert gas was 5 mm as a partial pressure in the inert gas.
The method is characterized in that the inert gas whose temperature is below Hg is supplied to the heating zone as an inert gas.

(D) ■ A powder or agglomerated powder of porous, crystalline aromatic polycarbonate produced by the method described in any one of (1) to (2) above.

(E) ■ Granular molding of a porous, crystalline aromatic polycarbonate prepolymer, which consists of granulating the porous, crystalline aromatic polycarbonate prepolymer described in (1) above, which has the form of a powder or agglomerated powder. It is the method of manufacturing the body.

(F) ■ A porous, crystalline aromatic polycarbonate prepolymer having the form of a granular molded body is heated in a heating zone above the glass transition temperature of the prepolymer and at a temperature at which the prepolymer remains in a solid state. A method of performing solid phase polymerization while removing the condensation 11 product from the heating zone, wherein the prepolymer having the form of a granular molded body is the prepolymer according to claim (1),
Here, the molecular weight and crystallinity of the prepolymer are increased to 6,000 to 200,000 and 35% or more by solid phase polymerization, respectively, so the molecular weight and crystallinity of the obtained polycarbonate are A method for producing a porous, crystalline aromatic polycarbonate granular molded body having a crystallinity of 35% or more and a number average molecular weight of 6,000 to 200,000, which is larger than each of the molecular weight and crystallinity of , (2) In the method for producing a granular molded body described in [Phase] above, the granular molded body of the prepolymer is heated, and 0.1 to 5 ONf (N, T, P)/h is added per 1 g of the prepolymer.
It is also characterized in that the inert gas of r is circulated and the inert gas containing polycondensation by-products is discharged from the heating zone, and @ In the method for producing a granular molded body described in the above [phase], The polycondensation byproducts in the inert gas obtained by removing the polycondensation byproducts from the discharged inert gas or diluting the discharged inert gas with new inert gas. Content is 5 as partial pressure in inert gas
Another feature is that the inert gas of less than ml (g) is supplied to the heating zone as an inert gas.

(G) ■ A porous, crystalline aromatic polycarbonate granular molded body produced by the method described in any one of the above [phase] to @. - (H)o consisting of a repeating unit of aromatic carbonate, a hydroxyl end group and/or an aryl carbonate end group, and a number average molecular weight of 6,000 to 200,000,
Bulk density is 0.1-1. 1g/cm3, crystallinity is 3
It is a porous, crystalline aromatic polycarbonate molded body having a compressive breaking strength of 5% or more and a compressive breaking strength of 10 kg weight/c1M or more.

(J) ■ Heating a porous, crystalline aromatic polycarbonate powder, agglomerated powder, or granular molded body to bring the temperature to a temperature higher than the glass transition temperature of the polycarbonate and lower than the crystal melting point of the polycarbonate. A method for producing a molded body, which comprises holding the porous, crystalline aromatic polymer powder, agglomerated powder, or granular molding, and melting and adhering the surface of the powder, agglomerated powder, or granular molded body. The body consists of a repeating unit of aromatic carbonate, a hydroxyl end group and/or an aryl carbonate end group, and the number average molecular weight is 6,000 to 200.00.
0, specific surface area is 0°1nf/g or more and crystallinity is 35
% or more, a method for producing a porous, crystalline aromatic polycarbonate molded article having a bulk density of 0.1 to 1.1 gw/cm2 and a compressive breaking strength of 10 kgw/d or more and (1) In the method for producing a molded body according to (1) above, the porous, crystalline aromatic polycarbonate powder, agglomerated powder, or granular molded body is molded at a temperature below the glass transition temperature of the polycarbonate. It also has some distinctive features.

(K)＠ ■ An aromatic dihydroxy compound and an aromatic carbonate compound are reacted, and the number average molecular weight is 1,00.
0 to 15,000, and a prepolymerization step in which the amorphous prepolymer is reacted at a temperature and time sufficient to produce an amorphous prepolymer whose end groups are hydroxyl groups and aryl carbonate groups; The average porous, crystalline aromatic polycarbonate prepolymer powder produced by the shear force is The particle size should be 250 μm or less, and the specific surface area should be 0. 2
a crystallization and porosity process that is sufficient to make the po/g or higher; ■ a porous, crystalline prepolymer powder, or a porous, crystalline prepolymer agglomerate powder made from the prepolymer powder; A process of heating a body or a granular molded body at a temperature equal to or higher than the glass transition temperature of the prepolymer and at a temperature at which the prepolymer maintains a solid state in order to proceed with a solid-state polymerization reaction. The molecular weight and crystallinity of the prepolymer are 6,000 to 200,00, respectively.
Porous, crystalline aromatic polycarbonate subjected to a solid state polymerization step, in which the molecular weight and crystallinity of the resulting polycarbonate are increased by more than 0 and 35%, and thus the molecular weight and crystallinity of the resulting polycarbonate are greater than that of its prepolymer. [Phase] In the method for producing a porous, crystalline aromatic polycarbonate described in (1) above, the prepolymerization step (2) comprises combining an aromatic dihydroxy compound and phosgene in the presence of a molecular weight regulator. It is also characterized in that a prepolymer having a number average molecular weight of 1,000 to 15,000 is prepared by the reaction, and [Phase] The method for producing a porous, crystalline aromatic polycarbonate described in (1) above. In the prepolymerization step (2), an aromatic polycarbonate oligomer whose terminal groups mainly consist of aryl carbonate groups and a number average molecular weight of about 350 to 950 and an aromatic dihydroxy compound are heated at a sufficient temperature and for a sufficient period of time. It is also characterized in that it consists of reacting to prepare an amorphous prepolymer with a number average molecular weight of 1,000 to 15,000 having terminal hydroxyl groups and terminal aryl carbonate groups.

Hereinafter, embodiments of the present invention will be described.

FIG. 12 shows the mutual relationships among various aromatic polycarbonates according to the present invention.

In one preferred embodiment of the present invention, an amorphous aromatic polycarbonate prepolymer is first produced by prepolymerization in which an aromatic dihydroxy compound and an aromatic carbonate compound are reacted under heating, and then the amorphous prepolymer is The polymer is crystallized and made porous using a crystallization solvent,
A crystalline aromatic polycarbonate porous body is obtained by preparing a crystalline aromatic polycarbonate prepolymer porous body and subjecting it to solid phase polymerization.

The crystalline aromatic polycarbonate prepolymer porous body for solid-phase polymerization of the present invention usually consists of the following repeating units: 1 +0COAr-)-... (IV), the terminal group of which is directly bonded to the aromatic group Hydroxyl group (
-OH) and an aryl carbonate group: (-0COAr3) . . . -(V).

Here, Ar represents a divalent aromatic group, and Ar' represents a monovalent aromatic group.

The abundance ratio of terminal groups in the prepolymer varies depending on the number average molecular weight of the prepolymer, etc., but OH/-OC
The molar ratio of OA r ' is usually in the range of 5/95 to 9515. Within this range, in the sense that the solid phase polymerization rate can be further increased, 10/90 to 90/I
The range of O is preferable, and the even more preferable range is 20/
It is 80 to 80/20.

Further, the preferred range of the terminal group composition will be explained below, taking as an example the case where the prepolymer has a number average molecular weight of 4000.

In order to produce ultra-high molecular weight polycarbonate with a large number average molecular weight, for example 15,000 or more, in a short time, the molar ratio of 10H/-0COAr' is 40/60 to 60/
The range of 40 is preferable because the polymerization rate is fast.

With the conventional phosgene method and melt method (ester exchange method), the solution viscosity and melt viscosity rapidly increase, making it difficult or virtually impossible to produce the desired ultra-high molecular weight polycarbonate. By using the prepolymer of the present invention having the above average molecular weight and end group ratio, it is possible to produce the ultra-high molecular weight polycarbonate since there is no influence on purity.

In addition, it is preferable that the aromatic polycarbonate for general injection molding and extrusion molding (number average molecular weight s, ooo~13.000) has fewer terminal hydroxyl groups, and in order to manufacture this, it is necessary to reduce the number of terminal groups of the prepolymer. i.e., the molar ratio of 0 H/-OCOA r' is 5/95 to 4
9151, particularly preferably in the range of 20/80 to 40/60.

On the other hand, in order to produce aromatic polycarbonate with many terminal hydroxyl groups that are rich in chemical reactivity, OH/-O
It is desirable that the molar ratio of COA r' is in the range of 51/49 to 9515, particularly preferably 60/40 to 80/20.

The terminal groups of the crystalline aromatic polycarbonate porous material obtained by solid-phase polymerization of the prepolymers having various terminal group compositions usually contain both hydroxyl groups and aryl carbonate groups; It is also possible to produce products consisting only of groups, or those consisting only of aryl carbonate groups.

Furthermore, as will be described later, when a group other than a hydroxyl group and an aryl carbonate group includes, for example, an ethyl carbonate group, the hydroxyl group in the above ratio is replaced by the sum of the hydroxyl group and the ethyl carbonate group.

Aromatic 5Ar preferably has the formula (Vl)-Ar, for example
'-Y-Ar'' -- (VD (wherein, Ar' and Ar'' each independently represent a divalent carbocyclic or heterocyclic aromatic group each having 5 to 30 carbon atoms, Y represents a divalent alkane group having 1 to 30 carbon atoms, and is a divalent aromatic group represented by the following formula.

In the divalent aromatic group Ar', Ar'', one or more hydrogen atoms may be substituted with other substituents that do not adversely affect the reaction, such as a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a substituent having 1 to 10 carbon atoms. It may be substituted with 10 alkoxy groups, phenyl groups, phenoxy groups, vinyl groups, cyano groups, ester groups, amide groups, nitro groups, etc.

Preferred specific examples of the heterocyclic aromatic group used in the present invention include aromatic groups having one or more ring-forming nitrogen atoms, oxygen atoms, or sulfur atoms.

The divalent aromatic group represents, for example, a group such as substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted biphenylene, substituted or unsubstituted pyringine, and the substituents here are as described above. It is as follows.

A divalent alkane group is, for example, a formula: , a cycloalkyl group having 5 to 10 ring carbon atoms,
Carbocyclic aromatic group having 5 to 10 ring carbon atoms, 6 to 10 carbon atoms
10 carbocyclic aralkyl groups, and k represents an integer of 3 to 11).

Such divalent aromatic groups include, for example, the formula: group, a cycloalkyl group having 5 to 10 ring carbon atoms, or a phenyl group, where m and n are integers of 1 to 4, and when m is 2 to 4, each R5 may be the same or different. or when n is 2 to 4, each R6
may be the same or different, respectively.

Furthermore, the divalent aromatic group Ar has the formula (■): -Ar'
−Z−Ar” −−・−(■) (in the formula, Ar'
, Ar'' is as described above, Z is a bond, or -o--c
o--5- 3O, ---3O--COO--CON(R1)-, provided that R1 represents a divalent group such as the one described above. good.

Such divalent aromatic groups include, for example, CH3 CH.

(In the formula, R', R'm and n are as described above.)

In the prepolymer of the present invention, Ar is 2 as described above.
It may be composed of a single type of valent aromatic group, or it may be composed of two or more types.

Particularly preferred are residues of bisphenol A and substituted bisphenol A, formula (■): CH.

This is a case where the group represented by 1 contains 85 to 100 mol% of the total Ar.

Note that the prepolymer of the present invention has approximately 0
,01 to 3 mol% may contain a trivalent aromatic group.

In addition, Ar3 in the formula (V) represents a small number of carbocyclic or heterocyclic aromatic groups, but in this Ar3,
One or more hydrogen atoms are other substituents that do not adversely affect the reaction, such as a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a phenyl group,
It may be substituted with a phenoxy group, a vinyl group, a cyano group, an ester group, an amide group, a nitro group, or the like.

Representative examples of the monovalent aromatic group Ar' include phenyl group,
Examples include naphthyl group, biphenyl group, and pyridyl group. These may be substituted with one or more of the above-mentioned substituents.

Preferred examples of Ar” include, for example, CH.

Examples include.

The crystalline aromatic polycarbonate prepolymer porous body for solid phase polymerization of the present invention has a number average molecular weight of 1000 to 15,0
It is 00. Those having a number average molecular weight of less than 1°000 are undesirable because the solid phase polymerization time becomes long, and fusion tends to occur during the same phase polymerization, which is undesirable. on the other hand,
Even if it is larger than 15,000, no particular advantage is given to solid phase polymerization. A more preferable number average molecular weight range is 1.500 to 10,000. An even more preferable range is 2,000 to s, ooo.

The crystalline aromatic polycarbonate prepolymer porous body for solid phase polymerization of the present invention has a specific surface area of 0.2 rtT/g or more. This specific surface area plays an important role when producing a crystalline aromatic polycarbonate porous body from the above prepolymer by solid phase polymerization. Specific surface area is 0. In a prepolymer porous material with less than 2rrf/g,
This is because the solid phase polymerization rate becomes slow, making it disadvantageous to industrially produce aromatic polycarbonate.The larger the specific surface area of the crystalline aromatic polycarbonate prepolymer porous body of the present invention, the more This is advantageous because the polymerization rate becomes faster.

In this sense, the specific surface area of the prepolymer porous body needs to be 0.2 rrr/g or more, preferably 0.5 ryf/g or more, and more preferably 0.8 rrf/g or more. .

Note that this specific surface area value was measured using krypton gas by the BET method.

The large specific surface area of 0.2 nf/g or more that the crystalline aromatic polycarbonate prepolymer porous body of the present invention has is achieved by making the prepolymer porous. This can be seen, for example, in the scanning electron micrographs shown in Figures 1.2.4.5.6.7 and 8.

The aromatic polycarbonate prepolymer porous body for solid-state polymerization of the present invention is crystalline. There are no particular restrictions on this degree of crystallinity, but the value measured by X-ray diffraction is usually 5.
A range of 55% is preferred. If the degree of crystallinity is lower than 5%, fusion will easily occur and it will be difficult to carry out solid phase polymerization, and if it is too high than 55%, the solid phase polymerization rate will be slow.

From the point of view of ease of solid phase polymerization, crystallinity is 10 to 45.
% prepolymer is more preferred, and even more preferred is a prepolymer with a crystallinity of 15-40%.

The porous crystallinity of a crystallized prepolymer in the present invention is defined as the following using the powder XvA diffractograms (for example, Fig. 1O and Fig. 11) of a completely amorphous prepolymer and a crystallized prepolymer. means a value obtained by such a method.

Generally, when X-rays are projected onto a crystalline polymer, the scattering xvA
I! However, this appears as the sum of crystal scattering caused by the crystalline portion and amorphous scattering caused by the amorphous portion.

The weights of the crystalline part and the amorphous part are respectively Mc, M, and the Xia scattering intensity proportional to them is rc,
r, toshi, h! , and can be separated, the crystallinity X, (%) is; N+. . C is the crystal scattering intensity per unit mass of a perfect crystal, which is also 11°. a represents the amorphous scattering intensity per unit mass of completely amorphous material, which is given by:

However, in the present invention, it is assumed that all crystallized prepolymer porous bodies have a value of 1, and the crystallinity Xc (%) is determined using the following formula.

■The total diffraction intensity curve obtained using an X-ray diffraction needle includes the so-called background based on scattering by air, scattering due to thermal movement of atoms, Compton scattering, etc., and the crystal scattering intensity and amorphous scattering intensity. Since it is expressed as a sum, it is necessary to separate each component in order to determine the degree of crystallinity from this.

The specific method used in the present invention is, for example, in Figure 1O and Figure 1.
The following method was used using Figure 1.

In the powder X-ray diffraction diffraction of the crystallized prepolymer porous material (FIG. 11), a straight line PQ (bess line) is drawn connecting the point (P) at 2θ-10° and the point (Q) at 2θ-35°. The points on the diffraction intensity curve and the baseline at 2θ-15°, where the crystal scattering intensity is considered to be zero, are (R) and (S), respectively.
shall be.

In the same way, a completely amorphous prepolymer (prepolymer melted at 280-300°C to form a sheet about 1 inch thick) was rapidly cooled from that temperature to 0"C to become completely amorphous. In the powder X-ray diffraction diagram (Fig. 1O) of
get.

1, = diffraction intensity at point (M), B, - diffraction intensity at point (N), diffraction intensity at I2-point (R), diffraction intensity at B2- (S), Y - diffraction intensity Assuming that the area surrounded by the curve KML and the straight line KL, Z = the area surrounded by the diffraction intensity curve PRQ and the straight line PQ, the crystallinity xe (%) as used in the present invention is given by the following equation.

Z 1. -B The shape of the crystalline aromatic polycarbonate prepolymer porous body of the present invention is usually powder or granule.

When carrying out solid phase polymerization using a powdered or granular crystalline prepolymer porous material, it is preferable to have a small amount of fine powder because it is easier to handle. During polymerization, fusion of prepolymers and polymers to each other and fusion of prepolymers and polymers to the reaction vessel for solid phase polymerization tends to occur, which is undesirable.In this sense, the proportion of fine powder of 50 μm or less is Prepolymers up to 10% by weight are suitable for solid state polymerization.

One of the preferred methods for producing the crystalline aromatic polycarbonate prepolymer porous material of the present invention is to prepolymerize a material having a number average molecular weight of 1,000 to 15.000 and having a terminal group consisting of a hydroxyl group and an aryl carbonate group. A non-crystalline aromatic polycarbonate prepolymer is produced, and this is stirred in a crystallization solvent under high shearing force so that the average particle size becomes 250μ or less, thereby crystallizing it and making it porous. This is the way to do it.

In this case, the solid amorphous prepolymer introduced into the crystallization solvent may be either solid or molten. In this method, crystallization and porosity occur from the solid surface of the prepolymer, so the solid prepolymer is mechanically pulverized in a crystallization solvent by applying high shear force, and its average particle size is It is effective to perform the crystallization treatment so that the specific surface area becomes 250μ or less in producing the porous body of the present invention having a specific surface area of 0.2ryf/g or more.

Here, the average particle size is the average particle size of the prepolymer in the crystallization solvent, and is measured using a microscope as described below. As a method for mechanically pulverizing the prepolymer in a crystallization solvent by applying a high shear force, a device with high-speed rotating blades such as a Waring blender, or a canter
There are methods such as using a centrifugal pump. In order to shorten the time required in the crystallization process, the amorphous prepolymer introduced into the crystallization solvent may be in the form of fibers, strands, films, or in the form of fibers, strands, films, etc., whether in the solid or molten state. By such a method, which is preferably in the form of small particles, a powdery or granular crystalline aromatic polycarbonate prepolymer porous body having a predetermined degree of crystallinity and a predetermined surface area can be obtained. For the purpose of reducing the amount, it is also a preferable method to agglomerate these powders to form secondary particles.

In the case of the crystallization and pulverization methods described above using solvents, it is necessary to remove the solvents in order to obtain the powder or granules. This removal method usually includes centrifugation, pressurization, or vacuum filtration, and since these methods are carried out under conditions where pressure is applied between the powders, agglomeration of fine powders and formation of secondary particles occur at the same time. This is a good thing.

The secondary particles thus obtained do not become pulverized even after the solvent is completely distilled off and can exist stably. Although the reason for this is not clear, it is probably because the low molecular weight polycarbonate oligomer present in the prepolymer porous body plays a role of adhesion between the fine particles. In this sense, when using the prepolymer porous body containing a small amount of the oligomer, it is preferable to add a low molecular weight polycarbonate oligomer and then perform the crystallization/porosity treatment.

Another method of agglomerating fine powder to form secondary particles takes advantage of the fact that fine powder easily fuses together. It can also be carried out by heating to an appropriate temperature that will cause the product to dry.

The average particle size of the aggregates (secondary particles) obtained in this way is 2
mm or less.

Note that the time required to crystallize the amorphous aromatic polycarbonate prepolymer using a crystallization solvent varies depending on the type, molecular weight, and shape of the prepolymer, the type of solvent used, the processing temperature, etc. , usually a few seconds ~
Crystallization takes place over a period of several hours.

In addition, the treatment temperature is usually selected in the range of -1O to 200℃, but even within the above range, the higher the crystallization treatment temperature, the faster the crystallization rate, and the crystalline aromatic polycarbonate with a larger specific surface area. This is preferable because a prepolymer porous body can be easily obtained.

Preferred solvents that can be used for crystallizing such amorphous prepolymers include, for example, chloromethane, methylene chloride, chloroform, carbon tetrachloride, chloroethane, dichloroethane (various! aliphatic halogenated hydrocarbons such as trichloroethylene and tetrachloroethane (various positional isomers); aromatic halogenated hydrocarbons such as chlorobenzene and dichlorobenzene; ethers such as tetrahydrofuran and dioxane; acetic acid Examples include esters such as methyl and ethyl acetate; ketones such as acetone and methyl ethyl ketone; and aromatic hydrocarbons such as benzene, toluene and xylene. These solvents are 1
Of these, acetone is a particularly preferred amorphous aromatic polycarbonate preboomer because it can produce a crystalline aromatic polycarbonate preboomer with a large specific surface. The amount of solvent used to crystallize the polycarbonate prepolymer varies depending on the type of the prepolymer and solvent, the required degree of crystallinity, the required specific surface area, the processing temperature, etc., but it usually depends on the weight of the prepolymer. It is in the range of 0.1 to 100 times, preferably 0.3 to 50 times.

Next, the granular molded crystalline aromatic polycarbonate prepolymer for solid phase polymerization of the present invention will be explained.

The prepolymer granular molded product has a number average molecular weight of 1,0
00 to 15.000, the terminal group consists of a hydroxyl group and an aryl carbonate group, and the specific surface area is 0.2n
It refers to a granular molded product made of a porous, crystalline aromatic polycarbonate prepolymer (porous body) with i/g or more, more preferably 0.5rrf/g or more, and has a compressive breaking strength of 5 kg weight/c4 or more. . Among them, the number average molecular weight, terminal group, and specific surface area are as above, and the crystallinity is 5 to 5.
It is made of a crystalline aromatic polycarbonate prepolymer porous body with a compressive fracture strength of 5K (according to X-ray diffraction method).
Particularly preferred is the prepolymer granular molded product having a weight of at least g weight/d.

Such prepolymer granular molded bodies are used during solid phase polymerization,
In addition to having excellent features such as easy handling before and after solid phase polymerization, no prepolymer scattering during surface phase polymerization, and no fusion during solid phase heavy metal polymerization,
With such a granular molded body, it is possible to dramatically improve the solid state polymerization rate.

There is no particular restriction on the shape of the prepolymer granular molded product of the present invention, and it is usually molded into a pellet shape, a spherical shape, a cylinder shape, a disk shape, a polygonal column shape, a cube shape, a rectangular parallelepiped shape, a cylindrical shape, a lens shape, etc. .

Further, the average particle diameter of the prepolymer granular molded product of the present invention is usually 0.5 mm to 30 mm, preferably 0.8 mm to 1
0 mm, particularly preferably 1 mm to 5 mm. 0.5
If it is smaller than mm, the fine powder tends to scatter or be easily fused when solid-phase heavy metal is formed. Moreover, if it is larger than 30 mm, it is not preferable in terms of handling.

The particle diameter of the granular compact is defined by the volume average diameter described in "Granulation Handbook J, edited by Japan Powder Industry Association, published in 1975, No. 19 to 20H.

In other words, the short axis diameter (when a particle is stabilized on a plane and the projected image of the particle on the plane is sandwiched between two parallel lines, the width of the particle where the distance between the parallel lines is the minimum is the W1 long axis) diameter (the distance between two parallel lines perpendicular to the parallel line of the short axis diameter when the projected image of the particle on the plane is sandwiched), and the height of the particle is h, then the volume average diameter is is defined by the following formula: Volume average diameter −3Lwh/(Lw+wh+hL) Any method may be used to produce such a prepolymer granular molded product, but This can be easily carried out by granulating and molding the aromatic polycarbonate tobreborimer porous body using a conventional powder granulation method such as a transfer method, a vibration method, a compression molding method, or an extrusion method.

Among these granulation methods, extrusion granulation method or compression granulation method is particularly preferred. This is because the extrusion granulation method or the compression granulation method can easily produce the granular molded article of the present invention having a compression breaking strength of 5 kg weight/cm 2 or more. The granulation temperature is below the melting point of the porous prepolymer, usually 100°
C or lower.

Such granulation can be carried out by a dry granulation method using the porous prepolymer in a dry state, or by a wet granulation method carried out in a wet state containing an appropriate liquid medium; When using a solvent when crystallizing an amorphous prepolymer in vP to produce a crystallized prepolymer porous body, the method of granulation is preferable. This is preferable because wet granulation can be carried out in a state in which a portion of the oxidizing solvent remains.

The polymer granular molded product obtained in this way has a weight of 5k
It has a compressive breaking strength of g weight/c+j or more.

This is because if the compressive breaking strength is lower than 5 kg weight/d, powdering may occur before and during solid phase polymerization, making handling difficult. The higher the compressive breaking strength, the more preferable it is, but 5 kg weight/cm2 is sufficient.

The compressive breaking strength of such a prepolymer granular molded product is measured using a Honya type hardness tester, and is the value of the load when a compressive load is applied to the granular molded product and the granular molded product breaks. It represents.

In addition, the method of installing the molded body during strength measurement is such that the strength of the molded body is measured to be the highest, and the average value of 8 measured values excluding the maximum and minimum values among the 10 measurements taken is taken. is the compressive fracture strength of the granular compact.

Next, the method for producing crystalline aromatic polycarbonate by solid phase polymerization of the present invention will be explained.

That is, according to the method of the present invention, the number average molecular weight is 1,
000 to 15,000, the terminal group consists of a hydroxyl group and an aryl carbonate group, and the specific surface area is o, 2
A method for producing a crystalline aromatic polycarbonate is provided by subjecting a porous crystalline aromatic polycarbonate prepolymer (porous body) of rd/g or more to solid phase polymerization under heating.

In the method of the present invention, it is more preferable to solid-phase polymerize a crystalline aromatic polycarbonate prepolymer porous body having a specific surface area of 0.2rd/g or more; It is preferable to solid-phase polymerize a crystalline aromatic polycarbonate prepolymer porous body in the range of .

Furthermore, as a preferred embodiment of the solid phase polymerization of the present invention,
A method for producing an aromatic polycarbonate includes solid phase polymerization of a granular molded body made of the above-mentioned crystalline aromatic polycarbonate prepolymer porous body and having a compressive breaking strength of 5 kg weight/d or more.

The aromatic polycarbonate obtained by this solid phase polymerization has a number average molecular weight higher than that of the prepolymer, and has a number average molecular weight in the range of 6000 to 200,000.
The crystallinity is in the range of 35 to 70%, the terminal group consists of a hydroxyl group or a carbonate group, or both, and the compressive breaking strength is 10 kg weight/cm2
This is the crystalline aromatic polycarbonate granular molded article described above.

It was completely unexpected that the compressive fracture strength of this crystalline aromatic polycarbonate granular molded product was 10 kg weight/cm2, which is higher than that of the prepolymer granular molded product as a raw material.

In the solid phase polymerization of the present invention, the condensation byproducts such as phenols and diaryl carbonate proceed while being removed from the prepolymer, so it was expected that the compressive fracture strength of the molded product would decrease, but surprisingly, It has become clear that the compressive fracture strength of the granular molded product after solid phase polymerization is stronger than that of the granular molded product of the prepolymer before polymerization. Based on this fact, it has become possible to obtain a crystalline polycarbonate granular molded product having a sufficiently high compressive fracture strength even within the compressive fracture strength range of the prepolymer granular molded product of the present invention.

The shape and particle size of the crystalline aromatic polycarbonate granular molded product obtained by solid-phase polymerization maintain almost the same shape and particle size as the crystalline aromatic polycarbonate prepolymer granular molded product that is the raw material.

That is, various shapes such as pellet, spherical, cylindrical, disk, polygonal column, cube, rectangular parallelepiped, cylinder, and lens are possible, and the particle size is usually 0.5 mm to 3 mm.
The range is 0 mm.

The solid phase polymerization of the present invention is carried out by heating a porous crystalline aromatic polycarbonate prepolymer body or a granular molded body made of the porous body, and the reaction temperature Tp when carrying out the solid phase polymerization reaction is ("C) and reaction time, the type (chemical structure, molecular weight, etc.) and shape of the crystalline prepolymer porous material, the presence or absence, type, and amount of catalyst in the crystalline prepolymer porous material, and additions as necessary. The type and amount of the catalyst to be used, the degree of crystallization of the porous crystalline prepolymer material, the difference in the melting temperature Tm ("C) of the crystals, the difference in the specific surface area of the porous crystalline prepolymer material, the desired crystalline aroma Although it varies depending on the required degree of polymerization of the group polycarbonate and other reaction conditions, solid phase polymerization can be carried out at a temperature higher than the glass transition temperature of the porous crystalline prepolymer and without melting the porous crystalline prepolymer during solid phase polymerization. It is necessary that the temperature is within the range that can be maintained.

Since the melting point of the crystalline prepolymer porous body increases as the polymerization progresses, one preferred method is to raise the polymerization temperature as the polymerization progresses.

Preferably, heating at a temperature in the range represented by the formula: % formula % (wherein Tp and Tm are as described above) for about 1 minute to 100 hours, preferably about 0.1 to 50 hours. A solid phase polymerization reaction is carried out. For example, when manufacturing bisphenol A polycarbonate, the temperature range is preferably about 150 to 260°C, particularly about 180 to 230°C.
0°C is preferred.

In the solid phase polymerization step, the reaction is promoted by extracting the aromatic monohydroxy compound and/or diaryl carbonate produced as by-products from the polycondensation reaction out of the system. Preferred methods for this purpose include a method of conducting the reaction under reduced pressure, a method of introducing an inert gas and removing the polycondensation by-products along with these gases, and a method of using these in combination.

The inert gas referred to here refers not only to so-called inert gases such as nitrogen, argon, helium, and carbon dioxide, but also to gases inert to solid phase polymerization such as lower hydrocarbon gases and acetone. Further, when introducing an inert gas for entrainment, it is preferable to heat these gases to around the reaction temperature.

As a preferred embodiment of the solid phase polymerization of the present invention, there is a method in which the above-mentioned gas is introduced and carried out under gas flow.
At this time, the gas flow rate per weight of the crystalline aromatic polycarbonate prepolymer porous body is important.

That is, when performing solid phase polymerization of the crystalline aromatic polycarbonate prepolymer porous body of the present invention, 0.1 to 1 ONff/hr, preferably 0.2 to INl/hr, per 1 g of the prepolymer porous body, It is preferable to circulate an inert gas of.

If the flow rate of the inert gas is less than 0.1 Nf/hr, the rate of in-phase polymerization becomes slow, which is not preferable.

Furthermore, if the flow rate of inert gas is greater than ON l/hr, there is an advantage that the solid phase polymerization rate becomes faster; This is not preferable since it causes problems such as being scattered during solid phase polymerization and adhering to the walls of the polymerization vessel, or being easily discharged outside the polymerization vessel.

On the other hand, in the case of solid phase polymerization of the granular molded product of the crystalline aromatic polycarbonate prebolimer porous body of the present invention, 0.1 to 5 ON7 per 1 g of the granular molded product! /hr, preferably 0°2-3ONj2/hr.

It is preferable that the process be carried out by passing an inert gas of. In the case of such a granular molded product, since there are no problems such as scattering during solid phase polymerization, the inert gas flow rate can be increased to 5 ONl/hr per 1 g of the granular molded product. It has been found that the solid phase polymerization rate can be dramatically improved as the flow rate of the inert gas increases, but even if the flow rate is greater than 5ONR/hr per gram of the granular compact, the contribution rate to the improvement of the polymerization rate is It gradually becomes smaller, so 5ONff
There is no need to increase it more than i/hr. From the point of view of improving the degree of polymerization, it is more preferable to use an inert gas flow rate of 0.2 to 3 ON liter/hr per 1 g of the granular compact.

When performing solid phase polymerization by introducing an inert gas, the inert gas after use can be discharged without being reused, but this increases the cost, so these inert gases are usually not recovered. and then provided for reuse.

In this case, the inert gas after use contains aromatic hydroxy compounds and the like which are polycondensation by-products during solid phase polymerization. Therefore, when recovering and reusing the inert gas used in solid phase polymerization, the condensation polymerization by-products, aromatic hydroquine compounds, etc. contained in the inert gas must be completely separated before reuse. It was considered necessary to provide it to However, even if condensation polymerization by-products, aromatic hydroquine compounds, etc. are present in the gas to be reused, the partial pressure must be reduced to 5 mmH.
It has been found that, unexpectedly, solid phase polymerization proceeds when the amount is less than 100 g.

On the other hand, when inert gas is reused in this way, the partial pressure of aromatic hydroxy compounds, etc. contained in the gas does not need to be lower than 0.001 mmHg; If it is lower than 0.001 mmHg, there is no particular problem in performing solid phase polymerization, but the cost of recovering and reusing the inert gas used in solid phase polymerization will be high, and if it is not carried out industrially. This is because it is not desirable for

When carrying out the solid phase polymerization of the present invention, the solid phase polymerization apparatus may be of any type, such as a batch type, a continuous type, or a combination of these. For example, a tumbler type , kiln type, paddle dryer type, screw conveyor type, vibrating type, fluidized bed type, fixed bed type, moving bed type, etc.

The solid phase polymerization reaction of the present invention can proceed at a sufficient rate without the addition of a catalyst, and this is the most preferred embodiment, but a catalyst can also be used for the purpose of further increasing the reaction rate. However, such catalysts usually remain intact in the final aromatic polycarbonate product, and these residual catalysts can affect polymer physical properties (e.g., color, heat resistance, hot water resistance, weather resistance, etc.). Since this often has an adverse effect, it is preferable to use as little catalyst as possible.

If a polymerization catalyst is used when producing the crystalline aromatic polycarbonate prepolymer porous body of the present invention, the catalyst usually remains in the prepolymer porous body obtained, so there is no need to add a new catalyst. However, since the catalyst may be removed or the activity may be reduced during the crystallization and porosity treatment, in that case, an appropriate catalyst may be added as necessary. That is, a catalyst component in a liquid or gaseous state can also be added to the crystalline prepolymer porous body.

Such a polymerization catalyst is the same as that used for prepolymer production, and is not particularly limited as long as it is a polycondensation catalyst used in this field, but lithium hydroxide, sodium hydroxide, potassium hydroxide, hydroxide, etc. Hydroxides of alkali metals and alkaline earth metals such as calcium; alkali metal salts and alkaline earth metal salts of boron and aluminum hydrides such as lithium aluminum hydroxide, sodium boron hydroxide, and tetramethylammonium boron hydroxide. , quaternary ammonium salts; alkoxides of alkali metals and alkaline earth metals such as lithium methoxide, sodium ethoxide, calcium methoxide; lithium phenoxide, sodium phenoxide, magnesium phenoxide, Li0-^r-OLi, Na0 -Ar-
Aryloxides of alkali metals and alkaline earth metals such as 0Na (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, and zinc Zinc compounds such as phenoxyto; boron compounds such as boron oxide, boric acid, sodium borate, trimethyl borate, tributyl borate, triphenyl borate; silicon oxide, sodium silicate, tetraalkyl silicon, tetraaryl silicon, diphenyl-ethyl-
Silicon compounds such as ethoxysilicon: germanium oxide, germanium tetrachloride, germanium ethoxide,
Compounds of germanium such as germanium phenoxide; tin compounds bonded with alkoxy or aryloxy groups such as tin oxide, dialkyl tin oxide, diaryl tin oxide, dialkyl tin carboxylate, tin acetate, ethyl tin triptoxide, and organic tin compounds Tin compounds such as lead oxide, lead acetate, lead carbonate, basic lead carbonate, lead and organic lead alkoxides or aryloxy groups; quaternary ammonium salts, quaternary phosphonium salts, quaternary Onium compounds such as grade arsonium salts; Antimony compounds such as antimony oxide and antimony acetate; Manganese compounds such as manganese acetate, manganese carbonate, and manganese borate; Compounds: Catalysts such as zirconium acetate, zirconium oxide, zirconium alkoxides or aryloxides, and zirconium compounds such as zirconium acetylacetone can be used.

When catalysts are used, the amount of these catalysts to be used for the crystalline aromatic polycarbonate prepolymer porous body is as follows:
In the case of a metal-containing catalyst, the amount is converted into the amount of the metal, and in the case of a metal-free catalyst, the amount of the element serving as a cation species in the catalyst is usually in the range of IPPm to 500 ppm.

In the solid phase polymerization of the present invention, it is easy to carry out substantially without adding such a catalyst, and the quality of the aromatic polycarbonate obtained in this way is extremely excellent. This is one of the major features of the method of the present invention.

In the present invention, "no catalyst" means that the amount of catalyst used is less than the minimum value of 1 ppm.

By subjecting the crystalline aromatic polycarbonate prepolymer porous material of the present invention to homopolymerization using the method described above, the specific surface area can be reduced to 0. lrd/g or more and a number average molecular weight higher than that of the prepolymer porous material, the range of which is from 6°000 to 200,000. can be obtained.

Further, by solid-phase polymerizing the crystalline aromatic polycarbonate prepolymer porous body of the present invention having a crystallinity of 5 to 55% by the method described above, a specific surface area of 0.1nf can be obtained.
/g or more, the degree of crystallinity is 35 to 70%, and the number average molecular weight is higher than that of the prepolymer porous body, and the range is 6,000 to 200,000.
0, a crystalline aromatic polycarbonate porous body can be easily obtained.

In addition, when the crystalline aromatic polycarbonate obtained by such a method is in the form of powder or granules with a small particle size, the crystalline aromatic polycarbonate is heated at a temperature lower than its crystal melting point. By compression molding or extrusion molding, the number average molecular weight can be reduced to 6. ooo~200,
000, the degree of crystallinity is 35 to 70%, the main terminal group consists of a hydroxyl group or an aryl carbonate group, or both, the compressive breaking strength is 10 kg weight/cd or more, and the specific surface area is is 0°In(7
A crystalline aromatic polycarbonate molded article having a weight of less than 100 g can be easily obtained.

Furthermore, the specific surface area obtained by the method of the present invention is 0.
．． If the crystalline aromatic polycarbonate porous material having a molecular weight of 1 rd/g or more is in the form of powder or granules, it can be molded in a similar manner to have a number average molecular weight of 6,000 to 6,000. 200,000, the crystallinity is 35 to 70%, the main terminal group consists of a hydroxyl group or an aryl carbonate group, or both, and the specific surface area is O,Inf/g or more,
A porous molded article of crystalline aromatic polycarbonate having a compressive breaking strength of 10 kg weight/C- or more can be easily obtained.

Furthermore, the crystalline aromatic polycarbonate porous body obtained by the method of the present invention is heated to a temperature above its glass transition temperature to its crystal melting point to partially melt the crystalline aromatic polycarbonate porous body. The bulk density can be reduced to 0. 1-1.0g/c
A porous molded body of crystalline aromatic polycarbonate, which is j, can be easily obtained.

The specific surface area of the present invention is O.1rrf/g or more, the crystallinity is 35 to 70%, and the number average molecular weight is 6,000 to 200.
．． Crystalline aromatic polycarbonate porous materials in the range of Even without pre-drying, almost no hydrolysis of the powder occurs during molding.

Therefore, it can be said that such a powder is an aromatic polycarbonate particularly suitable for molding methods using powder such as rotation molding and sinter molding.

The crystalline aromatic polycarbonate porous body, crystalline aromatic polycarbonate granular molded body, crystalline aromatic polycarbonate molded body, and crystalline aromatic polycarbonate porous molded body obtained by solid-state polymerization of the present invention are all It is a highly crystalline polymer with a high crystalline melting point and a sharp melting point peak.
It is clearly distinguished from the aromatic polycarbonate produced by the melting method (ester exchange method).

In addition, since the aromatic polycarbonate porous bodies and various molded bodies of the present invention are produced by solid-phase polymerization of crystalline prepolymers, rearrangement of molecular chains occurs during solid-phase heavy metallization, resulting in unprecedentedly high crystallinity. It seems to be.

In the case of polycarbonate using bisphenol A,
The melting point peak measured by differential scanning calorimeter (DSC) is 23
0 to 300°C, and the half width of the melting point peak is 3 to 8°C.

DSC measurement is performed under an inert gas atmosphere at lO″C/min.
The experiment was carried out under the conditions of a temperature increase rate of 5 to 10 mg and a sample amount of 5 to 10 mg.

These highly crystalline aromatic polycarbonates If have better chemical resistance and solvent resistance than ordinary amorphous polycarbonates. Due to these characteristics, these crystalline aromatic polycarbonates are used for sintered bodies, filter gas or liquid adsorbents, wall materials, heat insulating materials, and the like. The shape thereof can be various shapes such as a sheet, a disk, a cylinder, a sphere, a rectangular parallelepiped, and a cube.

The method for producing the amorphous aromatic polycarbonate prepolymer, which is the starting material of the present invention, is not particularly limited.

Examples of such manufacturing methods include the following methods.

■ A method using transesterification between an aromatic dihydroxy compound and diaryl carbonate.

■ Aromatic dihydroxy compound and diaryl carbonate are reacted in a molar ratio (range of 1:1.2 to 1:2), and the terminal group is mainly composed of aryl carbonate group and the number average molecular weight is about 350 to 950. A method in which an aromatic polycarbonate oligomer is produced in advance and the oligomer is transesterified with an aromatic dihydroxy compound.

■ By reacting an aromatic dihydroxy compound and a diaryl carbonate at a molar ratio (in the range of 1,2:1 to 2:1), an aromatic product whose terminal groups are mainly composed of hydroxyl groups and whose number average molecular weight is about 350 to 950 is produced. A method in which a group polycarbonate oligomer is produced in advance and the oligomer is transesterified with diaryl carbonate.

■ A method using an interfacial polycondensation method between an aromatic dihydroxy compound and phosgene in the presence of a molecular regulator.

(2) In the interfacial polycondensation method, the aromatic dihydroxy compound is obtained by reacting an excess amount of phosgene and an aromatic monodihydroxy compound (molecular weight regulator), and the terminal group mainly consists of an aryl carbonate group.
A method in which an aromatic polycarbonate oligomer having a number average molecular weight of about 350 to 950 is prepared in advance, and the oligomer is transesterified with an aromatic dihydroxy compound.

When amorphous aromatic polycarbonate prepolymers are produced by the methods of (1), (2), and (3) above, it is easy to make these amorphous prepolymers substantially free of chlorine compounds. The crystalline aromatic polycarbonate prepolymer porous body and the crystalline aromatic polycarbonate obtained from such an amorphous prepolymer are substantially free of chlorine compounds.

In addition, even if phosgene or the like is used as in the methods ① and ① above, when the amorphous aromatic polycarbonate prepolymer or aromatic polycarbonate oligomer used in the present invention has a relatively low molecular weight, Since it is easy to separate and remove chlorine compounds, these prepolymers and oligomers can be highly purified and substantially free of chlorine compounds. Therefore, even if these methods are used, the crystalline aromatic polycarbonate prepolymer porous body and the crystalline aromatic polycarbonate can be made substantially free of chlorine compounds.

The aromatic dihydroxy compound used as a raw material for the amorphous aromatic polycarbonate prepolymer has the formula (IX): HO-Ar-OH... (IX) (wherein, Ar is as described above). The diaryl compound is represented by the formula (X)
: Ar' 0COAr--(X) (wherein, Ar
3 is as described above. ).

Typical examples of diaryl carbonates include (R in the formula) and R@ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and 1 to 10 carbon atoms.
Alkoxy group having 5 to 10 ring carbon atoms, cycloalkyl! or represents a phenyl group, p and 9 are integers of 1 to 5, and when p is 2 or more, each R'l may be different, and when q is 2 or more, each R'l
may be different. ) Substituted or unsubstituted diphenyl carbonates can be mentioned.

Among these diphenyl carbonates, symmetrical diaryl carbonates such as diphenyl carbonate and lower alkyl-substituted diphenyl carbonates such as ditolyl carbonate and di-t-butylphenyl carbonate are preferred, but diaryl carbonates with the simplest structure are particularly preferred. Certain diphenyl carbonates are preferred.

These diaryl carbonates may be used alone or in combination of two or more types, but if two or more types are used, the reaction system becomes complicated and there is no advantage, so symmetrical diaryl carbonate 1 It is better to use seeds.

In addition, as a molecular weight regulator used in the interfacial polycondensation method, an aromatic monohydroquine compound represented by the general formula (XI): Arco-H--(XI) (Ar' is as described above) can be mentioned.

Preferred aromatic monohydroxo compounds include, for example, phenol, o, m, p-cresol, 2,6-xylenol, pt-butylphenol, p-octylphenol (various octyl groups), etc. Among them, phenol and pt-butylphenol are particularly preferred.

In addition, along with these aromatic monohydroxy compounds,
Other molecular weight regulators, such as monohydric alcohols such as methanol, ethanol, 11 dimethyl chloroformate, ethyl chloroformate, isopropyl chloroformate,
Haloformates such as cyclohexyl chloroformate; Monovalent thiols such as methyl mercaptan and ethyl mercaptan; Monovalent halothioformates such as dimethyl lyrorothioformate and ethyl lyrorothioformate:
It is also effective to use monocarboxylic acids and derivatives thereof such as acetic acid, propionic acid, benzoic acid, sodium acetate, acetic anhydride, acetyl chloride, and propionyl chloride.

Furthermore, in order to accelerate the prepolymerization, it is also effective to add 5 mol % or less of a basic acid or a reactive derivative thereof to the aromatic dihydroxy compound and cause the reaction to occur.

The dibasic acid or its reactive derivative may be aliphatic, aromatic, or alicyclic; specific examples include:
Terephthalic acid, isophthalic acid, phthalic acid, naphthalene
1,5-dicarboxylic acid, diphenyl-2,2°-dicarboxylic acid, cis-1°2-cyclohexanedicarboxylic acid,
Examples include dibasic acids such as oxalic acid, succinic acid, sepatic acid, adipic acid, maleic acid, and fumaric acid, and alkali metal salts, alkaline earth metal salts, amine salts, and acid halides of these dibasic acids. can.

Next, preferred embodiments for producing aromatic polycarbonate by the method of the present invention will be described, including the following methods (A), (B), and (C).

(A) In producing a crystalline aromatic polycarbonate from an aromatic dihydroxy compound and a diaryl carbonate, (a) the aromatic dihydroxy compound and the aromatic carbon 7
- by reacting the compound under heating, the number average molecule ill,
000 to 15,000, and a prepolymerization step of preparing an amorphous aromatic polycarbonate prepolymer having terminal groups of hydroxyl groups and aryl carbonate groups, [1) crystallizing the amorphous aromatic polycarbonate prepolymer, A crystallization step of preparing a crystalline aromatic polycarbonate prepolymer porous body having a specific surface area of 0.2rd/g or more, and (C) i. In order to further increase the degree of polymerization by heating to a temperature higher than the glass transition temperature of the crystalline prepolymer porous body and in which the crystalline prepolymer porous body or the granular molded body of the porous body can maintain a solid phase state. A method for producing a crystalline aromatic polycarbonate, the method comprising sequentially carrying out the steps of solid phase polymerization.

In this method, the amorphous prepolymer obtained in the prepolymerization step as step (a) is crystallized and made porous in the crystallization step (b), and then solid-phase polymerized in the step (C). In the prepolymerization step, the mixture of the aromatic dihydroxy compound and diaryl carbonate is heated to remove the aromatic monohydroxy compound, which is a compound in which a hydroxyl group is bonded to an aryl group based on diaryl carbonate, while Prepare an amorphous prepolymer.

The number average molecular weight of the amorphous prepolymer produced in this prepolymerization step is selected within the range of 1,000 to 15,000. The number average molecular weight of the amorphous prepolymer can be appropriately controlled by various conditions such as temperature, time, pressure, and stirring. Usually, the degree of polymerization is 100°C to 320°C, preferably 16°C to 280°C, Polymerization time is 0. 5-2
This is the board circumference at 0 hours. The pressure is usually normal pressure or reduced pressure.

It is preferred that the prepolymerization reaction is carried out in the melt.

Of course, when carrying out this prepolymerization reaction, a solvent inert to the reaction, such as methylene chloride, chloroform,
．． Although 2-dichloroethane, tetrachloroethane, dichlorobenzene, tetrahydrofuran, diphenylmethane, diphenyl ether, etc. may be used, it is usually carried out without a solvent and in a molten state.

Diaryl carbonate in this prepolymerization reaction,
The usage ratio (feeding ratio) with the aromatic dihydroxy compound varies depending on the types of diaryl carbonate and aromatic dihydroxy compound used, reaction temperature, and other reaction conditions, but the diaryl carbonate is
Usually 0.6 per mole of aromatic dihydroxy compound
It is used in a proportion of 1.8 to 1.8 mol, preferably 0.7 to 1.6 mol, more preferably 0.8 to 1.5 mol.

The ends of the amorphous prepolymer obtained in this way are
Usually, a terminal aryl carbonate group such as, for example, Ar3-0CO-1 (Ar" is as defined above) and a terminal aryl carbonate group, such as, for example, 0-Ar- (Ar" is as defined above). It consists of a terminal hydroxyl group based on a dihydroxydiaryl compound.

Regarding the crystallization step (b) and solid phase polymerization step (C),
This is as detailed in the first half of the present invention.

(B) In producing a crystalline aromatic polycarbonate from an aromatic dihydroxy compound and phosgene, (a) the aromatic dihydroxy compound and phosgene are reacted in the presence of a molecular weight regulator, so that the number average molecular weight is 1.
,000 to 15,000, a prepolymerization step for preparing an aromatic polycarbonate prepolymer having a specific surface area of 0.000 to 15,000. a crystallization step of preparing a porous crystalline aromatic polycarbonate prepolymer body of 2rrf/g or more, and (C) converting the porous crystalline aromatic polycarbonate prepolymer body or the granular molded body of the porous body into the porous crystalline prepolymer body. A solid phase polymerization step for further increasing the degree of polymerization by heating to a temperature higher than the glass transition temperature of the porous crystalline prepolymer body and in a range where the porous crystalline prepolymer body or the granular molded body of the porous body can maintain a solid phase state. A method for producing crystalline aromatic polycarbonate in a sequential manner.

In this method, the prepolymerization step can normally be carried out using a known method in which an aromatic dihydroxy compound and phosgene are reacted in the presence of the above-mentioned molecular weight/w moderator, acid binder, and solvent.

As the nucleic acid binding agent, for example, a 5 to 10% by weight aqueous alkali solution or a tertiary amine such as pyridine is preferably used.

Further, as the solvent, methylene chloride, chloroform, carbon tetrachloride, tetrachloroethylene, chlorobenzene, xylene, etc. are usually used.

Phosgene can be introduced into the reaction system by blowing it as a gas into a mixture of an aromatic dihydroxy compound, an acid binder, a molecular weight regulator, and a solvent (ethylene chloride is particularly preferred), or by dissolving it in a solvent and dropping it into the mixture. It is advantageous to add

Furthermore, the molecular weight regulator can be added before, during, or after the phosgene reaction, but it is preferably added before or during the reaction.

The polymerization temperature is usually in the range of -30 to 100°C, and the polymerization time is usually in the range of 1 minute to 10 hours.

The number average molecular weight of the prebolimer produced in the prepolymerization step is 1,000 to 15,000, and is easily achieved by adjusting conditions such as the amount of molecular weight regulator, reaction temperature, and phosgene addition rate. .

The terminal end of the prepolymer after the reaction usually contains a chloroformate group (-Ar
OCOCl) and alkali metal phenolate groups (e.g. -A r ON a ) are present. After this chloroformate group is completely hydrolyzed into a phenolate group with an aqueous alkali solution, the phenolate group of the alkali metal can be converted into a terminal hydroxyl group by neutralizing the alkali metal phenolate group with an aqueous acid solution and washing with pure water.

Furthermore, if a monohydric alcohol such as ethanol or a chloroformate of a monohydric alcohol such as ethyl chloroformate is used as a molecular weight modifier in addition to an aromatic monohydroxy compound, the terminal groups of the prepolymer may be is mainly composed of carbonate groups and alkyl carbonate groups, but in addition to these groups, hydroxyl groups are also often present.

The prepolymer obtained by such a prepolymerization step is usually a solution in an organic solvent (methylene chloride is particularly preferred). There are no particular restrictions on the method of obtaining a solid prepolymer from this solution, but for example, after thoroughly washing and neutralizing the prepolymer solution obtained in the prepolymerization step, ■ concentrating it, drying it, and then pulverizing it. or 2) heating the prepolymer solution and blowing steam into it while stirring at high speed to distill off the solvent, etc. are preferably used.

In order to produce the crystalline polycarbonate prepolymer porous body of the present invention from the solid prepolymer obtained in this way, the prepolymer is introduced in a solid or molten state into a crystallization solvent. It is preferable to advance crystallization and porosity while applying high shear force and crushing so that the average particle size becomes 250 μm or less.

Examples of crystallization solvents used at this time include acetone,
Examples include methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, xylene, ethyl acetate, acetonitrile, and toluene. Particularly preferred is acetone.

Note that the solid phase polymerization step is as described in detail in the first half of the present invention, but as a terminal group, in addition to a phenyl carbonate group and a hydroxyl group, a polymer containing an alkyl carbonate group such as an ethyl carbonate group is used. In the case of polymers, the solid phase polymerization reaction involves, in addition to the above-mentioned reaction in which phenol and diphenyl carbonate are eliminated and polycondensation, a reaction in which phenylethyl carbonate is eliminated and polycondensation also occurs. It seems that there are.

(C) In producing a crystalline aromatic polycarbonate from an aromatic polycarbonate oligomer whose terminal groups mainly consist of aryl carbonate groups and a number average molecular weight of about 350 to 950 and an aromatic dihydroxy compound, (a) i aromatic A polycarbonate oligomer and an aromatic dihydroxy compound are reacted under heating to prepare an amorphous aromatic polycarbonate prepolymer with a number average molecular weight of 1.000 to 15,000 and terminal groups consisting of a hydroxyl group and an aryl carbonate group. (b) a crystallization step of crystallizing the amorphous aromatic polycarbonate prepolymer to prepare a crystalline aromatic polycarbonate prepolymer porous body having a specific surface area of 0.2 nf/g or more; C) The crystalline aromatic polycarbonate prepolymer porous body or the granular molded body of the porous body is heated to a temperature higher than the glass transition temperature of the crystalline prepolymer porous body, and the crystalline prepolymer porous body or the porous body is molded into granules. A method for producing a crystalline aromatic polycarbonate, which comprises sequentially performing a phase polymerization step in which the polycarbonate is heated to a temperature within a range where the polycarbonate can maintain a solid state, and the degree of polymerization is further increased.

In this method, aromatic polycarbonate oligomers whose terminal groups are mainly composed of aryl carbonate groups are used, and as described above, such oligomers can be easily obtained by transesterification or interfacial polycondensation.

Both the crystallization step and the solid phase polymerization step are as described above.

In carrying out the present invention, the type of reactor used in any of the steps of prepolymerization, crystallization, and solid phase polymerization may be any type, including batch type, continuous type, and a combination of these types. It may be a method.

The crystalline aromatic polycarbonate prepolymer porous body and the granular molded body of the porous body of the present invention are extremely excellent as prepolymers for solid phase polymerization, but of course they can be used for purposes other than solid phase polymerization, such as sintered bodies, etc. It can also be used as a raw material for filters, adsorbents, and powder coatings, or mixed with other resins.

In addition, the crystalline aromatic polycarbonate porous body or granular molded body that has reached a predetermined molecular weight through solid phase polymerization can be made colorless and transparent by cooling it first or introducing it into an extruder as it is without cooling and pelletizing it. Amorphous polycarbonate pellets can be obtained. The latter case, when introduced into the extruder without cooling, is advantageous because it requires less labor for the extruder and also increases the output rate of the extruder.

Furthermore, since the granular molded product has a sufficiently high bulk density, it can be directly subjected to injection molding or extrusion molding without being pelletized through an extruder. The melt extrusion granulation process requires energy and also causes a deterioration in the quality of the aromatic polycarbonate due to heating and melting, but the method of the present invention can omit this step, resulting in a major innovation in the process.

Furthermore, according to the method of the present invention, aromatic polycarbonates with molecular weight distributions ranging from small to large can be produced relatively freely. This is because, for example, if a prepolymer with a small molecular weight distribution is used, an aromatic polycarbonate with a small molecular weight distribution can be obtained, and if a prepolymer with a wide molecular weight distribution is used, an aromatic polycarbonate with a wide molecular weight distribution can be obtained. This is one of the major features of the present invention.

As a measure representing molecular weight distribution, the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) is usually used as the ratio M w / M
The value of n is used, and in the case of condensation polymers, when this value is 2, it is theoretically the smallest molecular weight distribution. From the viewpoint of physical properties such as fluidity during molding, strength, and elongation, it is generally better to have a smaller molecular weight distribution.In practice, the value of Mw/Mn is 2.5 or less, especially 2.
It is difficult to produce polymers of 4 or less. In existing methods, such as the transesterification method known as the so-called melt method, the viscosity becomes extremely high at the end of polymerization, which tends to cause the reaction to become non-uniform, making it impossible to reduce the molecular weight distribution and resulting in poor yields. The polycarbonate usually has Mw/Mn>2.6. In addition, even in the phosgene method currently practiced industrially, this value is 264 to 3.5, and is usually in the range of 2.5 to 3.2.

On the other hand, in the method of the present invention, Mw/Mn=2.2~
Aromatic polycarbonates of 2.5 are also easily obtained. This is thought to be due to the fact that relatively low molecular weight materials such as prepolymers can easily be obtained with a narrow molecular weight distribution and are subjected to solid phase polymerization.

Furthermore, the crystalline aromatic polycarbonates obtained by the process of the invention, for example the crystalline aromatic polycarbonates obtained from bisphenol A, the most important polycarbonate, are white and opaque as they are, but this can be increased to temperatures higher than their crystalline melting point. An amorphous aromatic polycarbonate with good transparency and no coloration can be obtained by heating to a high temperature or by conventional melt molding. It is also a major feature of the present invention that the aromatic polycarbonate obtained by the method of the present invention is free from coloration.

In the existing so-called melting method for producing bisphenol A polycarbonate from bisphenol A and diphenyl carbonate, it is necessary to react a highly viscous material for a long time under a high vacuum of I m Hg or less at a high temperature around 300 ° C. Due to thermal decomposition of polymers and trace amounts of oxygen,
However, in the method of the present invention, even in prepolymerization by transesterification, for example, 250"C
Hereinafter, since it can be carried out in a short time at a relatively low temperature, preferably 240'C or less, and the crystallization step and solid phase polymerization step can also be carried out at a relatively low temperature, for example, 230'C or less,
This is because polymer modification, which occurs in the melt transesterification method, hardly occurs.

The crystalline aromatic polycarbonate porous body obtained by the method of the present invention can be mixed with various inorganic fillers such as various heat stabilizers, antioxidants, mold release agents, flame retardants, glass fibers, etc. as needed, and used as engineering plastics. Can be used for various purposes. Furthermore, it is particularly important for industrial use because it can be mixed with other polymers to produce polymer alloys directly from powder with good mixability.

Furthermore, aromatic polycarbonates containing no chlorine atoms can also be obtained, and these aromatic polycarbonates are particularly important as materials for optical instruments and electronics. In addition, in the solid phase polymerization method, the number average molecular weight is 15, which is difficult or impossible to produce with the phosgene method or the conventional transesterification method (melt method).
,000 or more is possible. It is also possible to produce polycarbonates having reactive hydroxyl groups at the ends.

(Example) Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited in any way by these examples.

Note that ■ molecular weight is the number average molecular weight (hereinafter referred to as M
n) and weight average molecular weight (hereinafter abbreviated as Mw).

When Taflon A2500 manufactured by Idemitsu Petrochemical ■ was measured using this method, Mn = 10.700, M w -2B, 00
It was 0.

■ The proportion of terminal groups in the prepolymer and polycarbonate can be determined by high-performance liquid chromatography analysis or NM
Obtained by analysis using R.

(2) The specific surface area is determined by measuring the surface area of the sample using krypton gas using AcureSorb Model 2100-02 manufactured by Takafusa Seisakusho, and dividing it by the weight of the sample.

■ The average particle size of the prepolymer in the crystallization solvent is determined by taking out a portion of the slurry that has become homogeneous by stirring, diluting it with a solvent, dispersing it with ultrasound, and casting it onto a glass plate. It was further dried and measured using a microscope.

■ The particle size distribution of the dried particles was determined using a micro electromagnetic vibrating sieve model M-2 manufactured by Tsutsui Kagaku Kiki ■.
It is determined by sieving through 70 μ on, 850 μ on, 600 μ on, 250 μ on, 150 μ on, 75 μ on, 50 μ on, and 50 μ on, and measuring the weight of each.

(2) The degree of crystallinity is measured using the X-ray diffraction method as described above.

■ In Examples 18 to 24, the compressive fracture strength of the molded product was measured using a Honsya type hardness tester, and the compressive fracture strength of the molded product was determined by measuring two approximately parallel surfaces of the molded product (area I = 2 or more, and the spacing between the surfaces was approximately 1 ~2m)
Strength (kg weight/
aj), and in Examples 33 and 34, the strength (kg weight/d) at the time of breaking of the molded body was measured using an Instron type universal tester.

■ Also, the partial pressure of phenol in the phenol-saturated nitrogen used is "Kagaku Handran" published by Maruzen in 1980, n-128.
From the page, the following formula: (P: Phenol vapor pressure [Pus Hg), t: Temperature [℃]
) is determined from the phenol thin pressure.

In the following examples, a crystalline aromatic polycarbonate prepolymer porous body is referred to as a crystalline prepolymer porous body, an amorphous aromatic polycarbonate prepolymer is referred to as an amorphous prepolymer, and a crystalline aromatic polycarbonate porous body is referred to as a crystalline aromatic polycarbonate porous body. A porous crystalline polycarbonate body is referred to as a crystalline aromatic polycarbonate porous molded body, a crystalline aromatic polycarbonate porous molded body is referred to as a crystalline polycarbonate porous molded body, and a crystalline aromatic polycarbonate grain core molded body is referred to as a crystalline polycarbonate granular molded body.

Example 1 13.0 kg of bisphenol A and 13.4 kg of diphenyl carbonate were charged into a glass-lined 401 prepolymerization vessel equipped with a stirrer, a gas inlet, and a gas outlet.
After melting by raising the temperature to 180°C and degassing under reduced pressure,
The temperature is raised to 230°C over time. During the temperature rise, N was flowed to remove distilled phenol from the system. Thereafter, the N□ flow is stopped and the pressure is reduced stepwise to reach lmHg pressure after 2 hours. During this time, phenol and diphenyl carbonate produced as by-products are continuously removed from the system.

Furthermore, the reaction was carried out under reduced pressure conditions of 1 m Hg pressure for 2 hours to obtain an amorphous prepolymer [amorphous About 10 kg of prepolymer (1) was obtained.

10 kg of this amorphous prepolymer (1) in a molten state at about 240°C was passed through a die having 20 holes of 1 mm diameter.
It is extruded for 1 hour into a Waring blender type acetone tank filled with 15 kg of acetone at 40 to 50°C. Simultaneously with extrusion, the stirrer in the acetone tank is rotated at high speed at 1.00 rpm.

The molten strand is stretched by stirring, turned into a thin fiber, immersed in an acetone solution, and pulverized using strong shearing force. The average particle size of the crystalline prepolymer in acetone is 15
It was 0. Thereafter, acetone is distilled off by reducing the pressure while heating the acetone tank to obtain a crystalline prepolymer porous body. The crystalline prepolymer porous body is white and opaque.

When its surface was observed with a scanning electron microscope, it was found that there were many pores (Fig. 1, 3°060x).
Furthermore, when a relatively large lump (approximately 800μ) is divided with tweezers and its cross section is observed with a scanning electron microscope, it is found that there are many holes in the cross section as well (Fig. 2, 1,0
For comparison, when the amorphous prepolymer (1) was cooled from the molten state to room temperature and observed with a scanning electron microscope, it was found that the surface was smooth and there were no pores (Fig. 3, 4,400 times).

The specific surface area of this crystalline prepolymer porous material is 1°5%/
g, crystallinity is 28%. 10 kg of this crystalline prepolymer porous body was preheated to 146°C, and the lower part was
Solid state polymerization was carried out in a stainless steel cylindrical gas flow reactor (inner diameter 60 cm, height 1 m) having pores of ~50 μm and a sintered filter plate with a thickness of approximately 5 μm. At this time, preheated nitrogen gas is uniformly supplied from the bottom of the polymerization vessel through a sintered filter at a rate of 1 ONrrr/hr, and is discharged from the top of the polymerization vessel. The polymerization temperature was controlled by preheating the supply gas, and after increasing the temperature from 140℃ to 180℃ in 30 minutes, the polymerization temperature was increased from 180℃ to 220℃ by 10"C.
/hr, then held at 220°C for 5 hours to perform polymerization, Mn = 13,000, Mw = 31,200.
A crystalline polycarbonate porous body is obtained.

This crystalline polycarbonate porous body has a specific surface area of 0.
8nf/g, crystallinity is 45%, and the melting point peak determined by DSC is 271°C, and the half-width is 4°3°C. DS
A C chart is shown in FIG.

Adding 250 ppm of trisnonylphenyl phosphite as a heat stabilizer to this crystalline polycarbonate porous body,
When melt extrusion is performed at 280°C, a colorless and transparent amorphous polycarbonate is obtained.

When this is injection molded at 300°C, no silver streaks occur,
Color is measured using a colorimeter CR-200b (Minolta camera)
(manufactured by), L value: 91.1, b value: 3.5,
It is colorless and transparent.

Example 2 An amorphous prepolymer similar to that obtained in Example 1 −(
1) Melt extrude 10 kg at about 240°C, cool with water, and then form into pellets. The obtained amorphous pellet is pulverized using a pulverizer for plastics (manufactured by FRITSCH, West Germany) to obtain a powder having a particle size of 1 or less.

The acetone tank used in Example 1 was charged with 15 ml of acetone, kept at 40°C, and the above powder was gradually added to the tank while stirring for 1 hour to effect crystallization and porosity. Stirring is performed at 1.00 rpm as in Example 1. The particle size of the prepolymer in the obtained acetone was 180 μm.Next, in the same manner as in Example 1, the acetone was distilled off and dried.

1,020 times that of the obtained crystalline prepolymer porous body, 3
．． Scanning electron micrographs at 060x and 6,020x are shown in Figures 4 to 6, and it can be seen that it is a porous body with uniform pore diameters. The specific surface area of this crystalline prepolymer porous material is 1.2
nf/g, crystallinity is 26%.

When the obtained crystalline prepolymer porous body was subjected to solid phase polymerization in the same manner as in Example 1, Mn = 12.500, Mw = 29
,000 crystalline polycarbonate porous body is obtained.

When injection molding is carried out in the same manner as in Example 1, a molded piece with no colorless transparency or silver streaks as in Example 1 is obtained.

Example 3 10 kg of amorphous Brevolimer Beleft (approximately 2-diameter, approximately 3-length) produced in the same manner as in Example 2 was added to an acetone bath without pulverization for 1 hour. The crystallization operation is carried out with stirring, and the average particle size of the prepolymer in acetone obtained is 230 μ. The obtained crystalline prepolymer porous material has a larger particle size than that of Example 2 (some of which have the original pellet shape).

), and compared to Example 2, there is a tendency for the whiteness to be lower and to be slightly transparent.

Its specific surface area is 0.4rd/g and crystallinity is 23%.

Solid state polymerization of this crystalline prepolymer porous material was carried out at 220°C.
When carried out in the same manner as in Example 2 except that the holding time was 14 hours, Mn = 13.000, Mw = 31,40
0 crystalline polycarbonate porous body is obtained. Example] The polymerization time is longer than that of Example 2.

Comparative Example 1 10 kg of the pulverized amorphous prepolymer prepared in the same manner as in Example 2 is dissolved in 1002 methylene chloride, and then the methylene chloride is distilled off under reduced pressure at room temperature. Thereafter, it is maintained at 40° C. in a vacuum dryer and dried overnight. The resulting powder is crystallized, with a crystallinity of 25% and a specific surface area of 0.0.
F/g.

Solid phase polymerization of this crystalline prepolymer powder was carried out in the same manner as in Example 1, except that the holding time at 220°C was changed to 8 hours, 13 hours, and 24 hours.
100.13 hours Mn=8゜900.24 hours Mn
= 9,200 aromatic polycarbonate is obtained,
The increase in molecular weight has reached a plateau, and the target Mn = 12,50
Cannot reach 0.

Mn=12,500 corresponds to a high viscosity grade of aromatic polycarbonate resins currently on the market, and the inability to produce products with this molecular weight can be said to considerably impair industrial value.

Comparative Example 2 10 kg of the pulverized amorphous prepolymer prepared in the same manner as in Example 2 is placed in saturated tetrahydrofuran vapor at about 40° C. for 24 hours to crystallize it.

The specific surface area of the obtained crystalline prepolymer is 0.05rd
/g, crystallinity is 20%.

When the solid phase polymerization of this crystalline prepolymer was carried out in the same manner as in Example 1 except that the holding time at 220°C was 24 hours, the increase in molecular weight reached a plateau as in Comparative Example 1. The Mn of the resulting polycarbonate is 8,800.

Comparative Example 3 10 kg of bismethyl carbonate of bisphenol A was placed in the same prepolymerization vessel as in Example 1, and 301 liters of dry argon gas preheated to 280°C was added! Mn was stirred while being introduced at a flow rate of
Next, this prepolymer was crystallized with methylene chloride and dried in the same manner as in Comparative Example 1.

The solid phase polymerization of this prepolymer was carried out in the same manner as in Example 1 except that the holding time at 220°C was 24 hours and 50 hours. In 24 hours, Mn=6.500 and Mw=1
6,800, and in 50 hours Mn=7.100, Mw
= 18,000 is obtained, but the increase in molecular weight has reached a plateau.

Comparative Example 4 Prepolymerization was carried out in the same manner as Comparative Example 3, except that 3 g of dibutyltin oxide was used as a catalyst and the prepolymerization temperature was 250°C, and the prepolymerization time was 6 hours and Mn = 3,100.
, an amorphous prepolymer with Mw=6.400 is obtained. This amorphous prepolymer was crystallized with methylene chloride and dried in the same manner as in Comparative Example 1, and then in the same manner as in Example 1, except that the holding time at 220°C was changed to 24 hours and 40 hours. When solid phase polymerization is performed, Mn=8°50 in 24 hours.
Polycarbonate with Mn=10,300 is obtained in 0.40 hours.

However, Mn=8,500 and Mn=10.3
When polycarbonate No. 00 is injection molded at 300° C., silver generation is severe in both cases, and some surfaces become cloudy and opaque.

Example 4 A polymer was produced from bisphenol A and diphenyl carbonate in the same manner as in Example 1, except that the polymerization temperature was 235°C.The number average molecular weight was 3,900, and the molar ratio of the terminal hydroxyl group and the terminal phenyl carbonate group was 35/65
10 kg of amorphous polycarbonate prepolymer of about 2
The mixture was heated to 40°C to melt it, passed through a die with 20 holes of 1 inch diameter, and pressed into a Waring Prender type mixing tank containing 12 kg of acetone at 40-50°C in the form of a thin strand for 1 hour. At the same time as extrusion, mix the acetone and prepolymer mixture with a knife blade stirrer at 50 or
The slurry obtained by performing crystallization, porosity, and pulverization at the same time by stirring at a high speed of pm is milky white and contains a large amount of fine powder.

The average particle size of the prepolymer in acetone is 180μ.

When this slurry is allowed to stand still, the crystalline prepolymer porous material precipitates, and the upper part of the acetone solution becomes transparent. When a portion of this transparent solution was taken out and the acetone was dried, 390 microns of polycarbonate oligomer having a number average molecular weight of 710 was contained per 12 kg of acetone.

This acetone slurry of the porous crystalline prepolymer is heated while being stirred, the acetone is distilled off, and the slurry is finally dried.

When the dried crystalline prepolymer porous material was taken out and the particle size was measured, it was found that 50 μ pass was 2.8% and 50 μ on was 3.4%.
, 75μ on 12.6%, 150u on 11.7%, 2
50μ on 20.7%, 600μ on 26.8%, 85
0μ on 15.4%, 1070μ on 6.5%.

It is thought that the polycarbonate oligomer plays the role of an adhesive during drying and causes aggregation, resulting in secondary particles and an increase in particle size. Further, the specific surface area of this crystalline prepolymer porous body is 1.7 bo/g, and the crystallinity is 29%.

Using 9.5 kg of the obtained porous crystalline prepolymer, solid phase polymerization was carried out using a 70J2 stainless steel tumbler type solid phase polymerization vessel.The zero polymerization conditions were as follows: while introducing a small amount of nitrogen into the system , the pressure was reduced to 1-2 m Hg using a vacuum pump, and the temperature was increased from 180"C to 220°C.
When the temperature is raised at a rate of .degree. C./hr and then maintained at 220.degree. C. for 7 hours, a crystalline polycarbonate porous body with Mn=11,500 is obtained.

There is no adhesion of polycarbonate to the wall of the tumbler, and almost no adhesion to the back filter installed between the tumbler and the vacuum pump.

Crystalline polycarbonate porous material obtained by solid phase polymerization is
When melt extrusion granulation was performed at 80° C., a colorless and transparent amorphous aromatic polycarbonate pellet was obtained.

Light transmittance of flat plate injection molded at 300″C (ASTM
D1003) is 90.4%, haze (ASTM
D1003) is 0.3%.

Example 5 An acetone slurry of a porous crystalline prepolymer obtained in the same manner as in Example 4 was passed through a punch-type centrifuge,
Cough prepolymer is separated into porous material and acetone solution. 9 kg of the obtained crystalline prepolymer porous material and 650 g of a separately manufactured acetone solution of a polycarbonate oligomer with Mn = 850 (30% by weight of oligomer 4) were thoroughly mixed, and the acetone was distilled off while stirring, and finally Dry.

The peak density in the particle size distribution of the dried crystalline prepolymer porous material is 600 μ path, and the 50 μ path is 3.5%.
It is. The specific surface area of this crystalline prepolymer porous material is 1
．． 5r+ (7 g, crystallinity is 28%.

When solid phase polymerization of this crystalline prepolymer porous material was carried out in the same manner as in Example 4, a crystalline polycarbonate porous material with Mn = 10.800 (specific surface area: 0°8n (7 g, terminal hydroxyl group and terminal phenyl group) was obtained. The molar ratio of carbonate groups is 4/96) is obtained.

Adhesion of polycarbonate to the tumbler and clogging of the bank filter were not observed.

Example 6 A product with a number average molecular weight of 5,100 produced in the same manner as in Example 1 except for reacting for 3 hours under reduced pressure conditions of 1 mHg pressure.
In Example 4, an amorphous prepolymer with a molar ratio of terminal hydroxyl groups to terminal phenyl carbonate groups of 30/70 was prepared.
When processed in the same manner as above, the specific surface area becomes 1. 3n (7g, particle size distribution peak 850μ pass, 50μ bath 1.
A 3% crystalline prepolymer porous body is obtained.

Solid state polymerization of this crystalline prepolymer porous material was carried out at 220°C.
A crystalline polycarbonate with Mn = 10,200, crystallinity 4%, crystal melting point 262°C, and specific surface area 0°6rrf/g was produced in the same manner as in Example 4, except that the holding time was 6 hours. A porous body is obtained. No polycarbonate adhesion to the tumbler or clogging of the back filter was observed.

Example 7 Aqueous solution of 64.8 g of sodium hydroxide dissolved in 800 g of water, 137 g of bisphenol A, 400 g of methylene chloride
Mix d and 1.7 g of phenol to form an emulsion, and add 58.5 g of phosgene while stirring at 10 to 20°C.
g was gradually blown into the solution over 1 hour to react.

Thereafter, 0.12 g of triethylamine was added to this reaction solution, and the mixture was stirred for 1 hour. To the resulting prepolymer methylene chloride solution, an aqueous sodium hydroxide solution was added.
The remaining chloroformate groups are decomposed and converted to phenolate groups.

Then, neutralize with phosphoric acid and wash thoroughly with water.8 Next, methylene chloride in the methylene chloride solution of the prepolymer is distilled off,
Further, it was dried overnight in a vacuum dryer.

The obtained solid was pulverized in the same manner as in Example 2, then placed in a small Waring Blengu containing 300 g of acetone, crystallized and made porous under high speed stirring (1,00 Orpm), and then the acetone was distilled off. By doing so, a crystalline prepolymer porous body is obtained.

Next, this was subjected to solid phase polymerization to obtain a number average molecular weight of 9.500 and a specific surface area of 0. 5n (7 g of crystalline polycarbonate porous material is obtained.

In addition, the molecular weight of the crystalline prepolymer porous material is Mn=2,
300, Mw=4,600, crystallinity 28%, specific surface area 1.3n (7g), molar ratio of terminal hydroxyl group to terminal phenyl carbonate group 45/65.

In addition, chlorine analysis (potential titration method and atomic absorption method) of this prepolymer was performed, but no chlorine compounds could be detected.

In addition, solid phase polymerization is carried out using a rotary evaporator.
Pour the polymer preheated to 140"C into a flask, and
It is carried out by raising the temperature to 180 °C in 30 minutes under a reduced pressure of ~3 Hg, then increasing the temperature from 180 °C to 220 °C at a rate of 10 °C/hr, and holding at 220 °C for 4 hours.

Example 8 An aqueous solution of 62 g of sodium hydroxide dissolved in 800 g of water, 137 g of bisphenol A, and 40 g of methylene chloride (ld
and 1.7 g of phenol were mixed.

A milk layer is formed, and 55 g of phosgene is gradually blown into the milk layer while stirring at 10 to 20''C over 1 hour for reaction.

After that, 6 g of phosgene was blown into this reaction solution over 5 minutes, and then 0.13 g of triethylamine was added and 1.5 g of
Then, the same treatment as in Example 7 is carried out to obtain a crystalline prepolymer porous body.

The crystalline prepolymer porous body was subjected to solid phase polymerization in the same manner as in Example 7, so that the weight and molecular weight of the porous material was -25,
000 (Mw/Mn=2.3), specific surface area 0.5rd/
A porous crystalline polycarbonate body of H is obtained.

In addition, the molecular weight of the crystalline prepolymer porous material is Mn=3,
300, Mw=6.500, crystallinity 28%, specific surface area 1. Onf/g, the molar ratio of the terminal hydroxyl group to the terminal phenyl carbonate group is 40,760.

Example 9 13 kg of bisphenol A and 1-diphenyl carbonate
Prepolymerization was carried out in the same manner as in Example 1, except that 13 kg was used, to obtain about 12 kg of an amorphous prepolymer having Mn=3,200 and a molar ratio of terminal hydroxyl groups to terminal phenyl carbonate groups of 50,150.

10 kg of this amorphous prepolymer was molten at about 240"C and was poured into a hole 20 with a diameter of 11III from the bottom of the prepolymerization vessel.
15k from the top of the acetone bath through a die with 15k
The lower part of this acetone tank is connected by piping to the suction port of a centrifugal pump with a cutter (product name: Sandoku Cutter Pump SD-, manufactured by Sansho Tokushu Steel Co., Ltd.). Furthermore, the delivery port of the pump is connected to the side of the acetone tank by piping.

When this thin-wound pump with a cutter is operated, the contents in the acetone tank are circulated between the acetone tank and the pump. The solids passing through the pump are pulverized by a cutter rotating at high speed.

By extruding the amorphous prepolymer into acetone while operating the pump, an acetone slurry containing a porous crystalline prepolymer is obtained.

The average particle size of the crystalline prepolymer porous material in this acetone slurry was 190μ, and when acetone was distilled off from this acetone slurry in the same manner as in Example 1 and the prepolymer was dried, the specific surface area was 1.9rd. /g, crystallinity 3
A 1% crystalline prepolymer porous body is obtained. Part 3,
Scanning electron micrographs at 060x and 6.020x are shown in Figures 7-8.

When this crystalline prepolymer porous material was solid-phase polymerized in the same manner as in Example 1 except that the final polymerization temperature was 230°C and the holding time at 230'C was 10 hours, Mn = 2
An ultra-high molecular weight polycarbonate porous body with Mw=6,000 and Mw=65,000 is obtained. Then another 240°
When the polymerization temperature is raised to C and the reaction is carried out at that temperature for 10 hours, an ultra-high molecular weight crystalline polycarbonate porous body with Mn=4o, ooo, Mw=100.000 is obtained.

Example 1O Instead of using 13.0 kg of bisphenol A and 13.4 kg of diphenyl carbonate, bisphenol A
Prepolymerization, crystallization, and solid phase polymerization are carried out in the same manner as in Example 1, except that 6.5 kg of bisphenol carbonate and 13.3 kg of bisphenol carbonate of bisphenol A are used.

The crystalline prepolymer porous body obtained by prepolymerization and crystallization has a molecular weight of Mn=2.500 and a specific surface area of 0.
8rrr/g, crystallinity is 31%, molar ratio of terminal hydroxyl group to terminal phenyl carbonate group is 4215
B, and the crystalline polycarbonate porous body obtained by face phase polymerization has Mn=13,000.

Example 11 Instead of using 13.0 kg of bisphenol A and 13.4 kg of diphenyl carbonate, bisphenol A
Prepolymerization and crystallization are performed in the same manner as in Example 1 using 13.0 kg and 12.1 kg of diphenyl carbonate.
The molecular weight of the obtained crystalline prepolymer porous body is Mn-4
, 300, specific surface area is 1.5rd/g, crystallinity is 30
%, the molar ratio of terminal hydroxyl groups to terminal phenyl carbonate groups is 65/35.

When this crystalline prepolymer porous material was subjected to solid phase polymerization in the same manner as in Example 1, Mn = 12.300 and the molar ratio of terminal hydroxyl groups to terminal phenyl carbonate groups was 98/
A crystalline aromatic polycarbonate porous body having substantially both terminals having hydroxyl groups is obtained.

Further, when this crystalline aromatic polycarbonate is heated in the presence of glycidyl polyether obtained from bisphenol A and epichlorohydrin and an amine curing agent (triethylenetetramine) and reacted, a cured product insoluble in a solvent is obtained.

Example 12 Aqueous solution of 64.8 g of sodium hydroxide dissolved in 800 g of water, 137 g of bisphenol A, 400 g of methylene chloride
Mix m and 1.7 g of phenol to form an emulsion, and add 58.5 g of phosgene to this while stirring at 10-20°C.
was gradually blown into the solution over a period of 1 hour to allow the reaction to occur.

Then, 0.8 ethyl chloroformate was added to this reaction solution.
After adding 6 g of phosgene dissolved in 40af of methylene chloride and blowing in 6 g of phosgene for 5 minutes, 0.15 g of triethylamine was added and stirred for 2 hours.Next, by carrying out the same treatment as in Example 7, A crystalline prepolymer porous body is obtained.

The crystallinity of the obtained crystalline prepolymer porous body is 25%.
, and Mn=3. ooo, Mw=6.300 and specific surface area is 1. 3rrf/g. The molar ratio of the terminal hydroxyl group, terminal ethyl carbonate group, and phenyl carbonate group is 26/23151.

Next, the crystalline prepolymer porous body obtained in this way was placed in a flask of a vacuum evaporator equipped with a heating furnace,
After preheating to 180°C, the temperature is raised from 180°C at a rate of 5°C/hr while rotating the flask, and the reaction is carried out under reduced pressure of 2 to 3 m Hg while adding dry nitrogen little by little. After reaching 220°C, the reaction was continued for an additional 4 hours, resulting in a weight average molecular weight of 24. OOO(Mw/Mn
= 2.2) of a crystalline polycarbonate porous body (specific surface area of 0°6 n(/g)).

Example 13 An aqueous solution of 58 g of sodium hydroxide dissolved in 800 g of water, 24 g of bisphenol Al, 400 d of methylene chloride, and 1.2 g of phenol were mixed to form an emulsion, and to this,
While stirring at 10-20"C, 53 g of phosgene is gradually blown in over 1 hour for reaction.

Thereafter, 6 g of phosgene was blown into the reaction solution over 5 minutes, and then 0.15 g of triethylamine was added, followed by stirring for 2 hours.

Next, a crystalline prepolymer porous body is obtained by performing the same treatment as in Example 7.

The solid state polymerization of the crystalline prepolymer porous body was carried out at 220°C.
The procedure was carried out in the same manner as in Example 7, except that the holding time was 5 hours.The number average molecular weight was 11,200, and the specific surface area was 0. A porous crystalline polycarbonate body of 3 bo/g is obtained.

The molecular weight of the crystalline prepolymer porous material is Mn-9,
100, crystallinity 21%, specific surface area 0°8rrf/g
, the molar ratio of terminal hydroxyl groups to terminal phenyl carbonate groups is 40/60.

Example 14 Bisphenol Al 48g, P-tert-butylphenol 1.4g, phenol 0.8g, methanol 0.
50g, 162g dry pyridine and 600g methylene chloride
m/! After charging into the flask, add 10 to 2
At 0°C, 65 g of phosgene is bubbled in over 90 minutes, followed by 400 m/! of methylene chloride! was added to the flask, and 50ml of methylene chloride solution containing 5g of phosgene was added to the flask.
After clearing and reacting for 90 minutes, this was mixed with 10 layers of salt #900mj! Add to and stir well.

Next, the methylene chloride layer containing the prepolymer is separated by 5 minutes, and the resulting prepolymer is treated with methylene chloride in the same manner as in Example 7 to obtain a crystalline Brevo one-dimensional porous body.

Next, solid phase polymerization was performed in the same manner as in Example 12 at 220°C.
At a retention time of 10 hours, the weight average molecular weight was 124.000 (
A crystalline polycarbonate porous body having Mw/Mn=2.5) is obtained.

In addition, Mn of the crystalline prepolymer porous body is 3°600,
Crystallinity is 23%, specific surface area is 1. 8n (7g)

The ratio of aryl carbonate end groups, methyl carbonate end groups and hydroxyl end groups is 4B/36/16.

Example 15 Aqueous solution of 69 g of sodium hydroxide dissolved in 850 g of distilled water, 146 g of biphenol A, 400 m of methylene chloride
and 1.7 g of phenol are mixed to form an emulsion, and 62 g of phosgene is gradually blown into the emulsion over 1 hour while stirring at 10 to 20 ''C. Thereafter, this reaction solution is added to a telescope. A solution of 1.3 g of phthaloyl chloride dissolved in 160 mj! of methylene chloride is added, then 6.4 g of phosgene is blown into the mixture, and 10 minutes after the end of the blowing, 0.16 g of triethylamine is added and stirred for 1 hour.

The reaction mixture is then separated to remove the methylene chloride phase containing the prepolymer. After washing thoroughly with IN hydrochloric acid, rinse thoroughly with water.

10 ppm of the obtained prepolymer in methylene chloride solution.
Example 1
It was treated in the same manner as in 2 to obtain a crystalline prepolymer porous body.

This is subjected to solid phase polymerization in the same manner as in Example I2 to obtain a crystalline polycarbonate porous body having a weight average molecular weight of 33.000 (Mw/Mn=2.4).

The crystalline prepolymer porous body has Mn of 3,200, Mw of 6,500, crystallinity of 25%, and specific surface area of 1. 0r
rf/g.

Example 16 Aqueous solution of 64.8 g of sodium hydroxide dissolved in 800 g of water, 137 g of bisphenol A, 400 g of methylene chloride
d and 1.7 g of phenol were mixed to form an emulsion, and to this was added 58.5 g of phosgene while stirring at 0 to 20°C.
g was gradually blown into the solution over a period of 1 hour for reaction.

Thereafter, 6 g of phosgene was blown into the reaction solution over 5 minutes, and then 0.15 g of triethylamine was added and stirred for 2 hours.

Next, a crystalline prepolymer porous body is obtained by performing the same treatment as in Example 7.

100 g of the crystalline prepolymer porous material is about 40 to 50
Inner diameter 50m with glass filter with μ pores
Pour into a glass gas flow type polymerization reactor, and feed 12ONj of nitrogen and gas from the bottom of this glass filter! /hr and solid phase polymerization at normal pressure 210°C for 3 hours, weight average molecular weight = 25,000 (Mw / Mrr =
2.3) Obtain a crystalline polycarbonate porous body with a specific surface area of 0.5 rrr/g.

In addition, the molecular weight of the crystalline prepolymer porous material is Mn=3,
300, Mw=6,500. Crystallinity is 28%, specific surface area is 1. 0 po/g, and the molar ratio of terminal hydroxyl groups to terminal phenyl carbonate groups is 40/60.

Example 17 Aqueous solution of 64.8 g of sodium hydroxide dissolved in 800 g of water, 137 g of bisphenol A, 400 g of methylene chloride
1d and 18 g of phenol are mixed to form an emulsion, and 58.5 g of phosgene is gradually blown into the emulsion while stirring at 10 to 20° C. over a period of 1 hour to react.

Thereafter, 6 g of phosgene was blown into this reaction solution over 5 minutes, and then 0.15 g of triethylamine was added and stirred for 2 hours. The methylene chloride phase is separated, neutralized with phosphoric acid, and then washed repeatedly with water. After distilling off the methylene chloride, it is vacuum dried to obtain an oligomer whose terminal groups are 98% phenyl carbonate groups and 2% hydroxyl groups.

The number average molecular weight of this oligomer is 800.

28.4g of bisphenol A per 100g of this oligomer
were mixed, subjected to melt polymerization at 230°C, and crystallized in the same manner as in Example 2. The molecular weight of the crystalline prepolymer porous body thus obtained is Mn=3,800.
The Pt surface area is 0.9rd/g.

Solid phase polymerization is performed in the same manner as in Example 12 to obtain a crystalline polycarbonate porous body having a weight average molecular weight of 28,300 (Mw/Mn=2.4).

Example 18 An acetone slurry of a porous crystalline prepolymer obtained in the same manner as in Example 1 was dried until the acetone content was 135 M%, and this wet powder was prepared using a compact extrusion II (manufactured by Fuji Paudal ■, EXKF-1). Approximately 40°C (type Berenotar)
A granular compact having a diameter of about 2 mm and a length of about 3 mm was produced. This granular molded body is dried at 120° C. for 2 hours.

The resulting granular molded product has a number average molecular weight of 4.000, a molar ratio of terminal hydroxyl groups to terminal phenyl carbonate groups of 33/67, a specific surface area of 2°2n(/g, a compressive breaking strength of 7 kg/cm2, and a crystalline structure. The degree of oxidation is 22%.

100 g of this granular compact was charged into a glass flow polymerization vessel with an inner diameter of 50 mm equipped with a glass filter having pores of about 40 to 50 μm, and N2 gas was supplied from the bottom of the glass filter at a rate of 15 ONl/hr to normal pressure. , 210
By carrying out solid phase polymerization at .degree. C. for 3 hours, a crystalline polycarbonate granular molded body having a number average molecular weight of 12,100 and a crystallinity of 45% is obtained. The shape of this granular molded body is
It is almost the same as the original granular compact, and no powdering is observed.

The compressive fracture strength of the crystalline polycarbonate granular molded body is 4
3Kg weight/cm3, and its equilibrium moisture content is 0.04
%, which is about an order of magnitude lower than that of commercially available amorphous polycarpo-primary toperents.

Example 19 13g of bisphenol A and 13g of diphenyl carbonate
An amorphous prepolymer containing no chlorine compound and having a number average molecular weight of 3,800 and a molar ratio of terminal hydroxyl groups to terminal phenyl carbonate groups of 50,150, produced by the same method as in Example 1 except that Kg was used. Using,
A crystalline polycarbonate prepolymer granular molded body was obtained in the same manner as in Example I8. However, the shape of the granular molded body is made to have a diameter of about 1 mm and a length of about 3 mm.

The resulting granular molded product has a number average molecular weight of 3.800, a molar ratio of terminal hydroxyl groups to terminal phenyl carbonate groups of 50,150, a specific surface area of 1°9 Bo/g, a compressive breaking strength of 11 kg/cm2, and a crystallinity of 25. %.

100 g of this granular compact is subjected to solid phase polymerization in the same manner as in Example 18. However, the polymerization is carried out at 210°C for 13 hours and then at 220°C for 3 hours.

The number average molecular weight of the crystalline polycarbonate granular molded product obtained is 17,100, and the crystallinity is 51%. The shape of this molded product was almost the same as the original granular molded product, and no powdering was observed. The compressive breaking strength of the molded body is 55 kg/cm2.

The equilibrium moisture content of this crystalline polycarbonate granular molded body is 0.04%.

Comparative Example 5 The crystalline prepolymer prepared in Comparative Example 1 was molded using a small extruder in the same manner as in Example 18 to form a molded product with a diameter of approximately 2 mm and a diameter of approximately 3 mm.
A long granular molded body is produced. The specific surface area of this granular compact is 0.04'n (/g).

When solid phase polymerization is carried out in the same manner as in Example 18, no powdering is observed, but the Mn of the resulting polycarbonate is 8,100.

Example 20 A crystalline preform was produced in the same manner as in Example 18, except that the wet powder was molded into a granular molded body with a diameter of approximately 10 mm and a height of approximately 5 mm using a compression molding machine at a pressure of 1 ton/d. A granular molded body of polymer is obtained.

The resulting granular molded product has a number average molecular weight of 3,9001, a molar ratio of terminal hydroxyl groups to terminal phenyl carbonate groups of 35/65, a specific surface area of 2.1 rrr/g, a compressive breaking strength of 26 kg/cIM, and a crystallinity of 22%. It is.

Using 100 g of this granular compact, the polymerization temperature was set to 220"C.
Solid phase polymerization was carried out under the same conditions as in Example 18, except that one polymerization time was 2 hours, to obtain a crystalline polycarbonate granular molded body having a number average molecular weight of 12.900 and a crystallinity of 40%.

The shape of this molded product was almost the same as the original granular molded product, and no powdering was observed. The compressive breaking strength of the molded body is 120 kg/cm2.

Examples 21 to 24 Using amorphous prepolymers produced from bisphenol A, diphenyl carbonate, and various dihydroxydiaryl compounds, granular molded bodies are prepared and solid-state polymerized in the same manner as in Example 18.

The results are summarized in Table 1.

In any case, the crystallinity of the crystalline prepolymer porous body is in the range of 20 to 38%, and no powdering is observed during solid phase polymerization, and the crystallinity obtained by solid phase polymerization is The crystallinity of the polycarbonate granular molded body is 40~
It is 58%.

Example 25 Example 1 except that 3.0 kg of bisphenol AI and 13.2 kg of diphenyl carbonate were used as raw materials.
was polymerized in the same manner as in Example 1, and then obtained by the same solvent crystallization method using acetone as in Example 1, with a number average molecular weight of 4.1.
00, molar ratio of terminal hydroxyl group to terminal phenyl carbonate group is 37/63, crystallinity 25%, specific surface area 1. Using a 1 bo/g crystalline prepolymer porous body,
Solid state polymerization is carried out in a glass gas flow reaction group with an internal diameter of 15 mm and equipped with a glass filter having pores of about 40 to 50 μm.

The polymerization conditions were as follows: 2.5N1 of nitrogen was added from the bottom of the glass filter to 2g of the charged crystalline prepolymer porous material.
/hr and carried out at 210'C under normal pressure. A crystalline polycarbonate porous body having a number average molecular weight of 10,800 is obtained in a polymerization time of 2 hours.

Examples 26 to 28 and Comparative Examples 6 to 7 A crystalline polycarbonate multibody was obtained in the same manner as in Example 25, except that the nitrogen flow rate, polymerization time, and temperature were changed as shown in Table 2.

The results It is shown in Table 2.

Example 29 After prepolymerizing in the molten state in the same manner as in Example 1 except that 13.0 kg of bisphenol A and 13.3 kg of diphenyl carbonate were used, crystallization and porosity were performed in acetone in the same manner as in Example 1. , and then dried to obtain a number average molecular weight of 4,100 and a molar ratio of terminal hydroxyl groups to terminal phenyl carbonate groups of 35/
65, crystallinity 25%, specific surface area 1. Using a crystalline prepolymer porous body of 0 i/g, solid phase polymerization is carried out in a glass gas flow type reaction group with an inner diameter of 15 mm.

The polymerization conditions were as follows: Nitrogen gas (phenol partial pressure 0°028 mmHg) saturated with phenol as an inert gas was flowed at 2.5 Nl/hr through 2 g of the charged crystalline prepolymer porous material, and Pressure from 180°C to 210°C
°C for 30 minutes and then kept at 210"C for 2 hours and 30 minutes, the number average molecular weight was 11.400.
A crystalline polycarbonate porous body is obtained.

Example 30 and Comparative Example 8 50'C (X Example 30) and 63°C as inert gas
Solid state polymerization of the same crystalline prepolymer porous material as in Example 29 was carried out in the same manner as in Example 29, except that nitrogen gas saturated with phenol was used in (Example 8), and the results are shown in Table 3. .

Table 3: When the partial pressure of phenol in nitrogen gas was 2.3 mmHH, the number average molecular weight increased to 6.800, but when the partial pressure of phenol was 5.7 mmHg, the molecular weight hardly increased. I understand.

Example 31 As a crystalline prepolymer porous body, the number average molecule is 13.9
80, a granular molded body with a molar ratio of terminal hydroxyl groups and terminal phenyl carbonate groups of 36/64, a degree of crystallinity of 25%, and a specific surface area of 0.9 rrr/g (diameter of about 1 mm, length of about 0
．． 5-2. The number average molecular weight of the crystalline polycarbonate porous material obtained in 3 hours of solid-phase polymerization under the same conditions as in Example 29 using 0CII) is 10,500.

Example 32 A continuous gas flow reaction in a moving bed made of 5US304 with an inner diameter of 15C1 and an effective length of 1 m, equipped with an air pump and a gas cooling device, using a granular molded body of a crystalline prepolymer similar to that used in Example 31. Perform solid phase polymerization using a vessel.

The feeding rate of the granular compact from the top of the reactor was 1°2 kg/hr, the polymerization temperature was 210°C, and the nitrogen gas was 6Nrr.
r/hr to the lower part of the reactor, and the gas discharged from the reactor was cooled to 0 °C, then heated again to 21O °C,
Continuous operation for 20 hours is carried out by feeding the reactor. Between 7 hours and 20 hours after the start of operation, the number average molecular weight of the granular compacts discharged from the lower part of the reactor is 10.800 to 20 hours.
11,000, and nitrogen gas can be recovered and reused.

Note that the partial pressure of phenol at 0°C is 0.028 mmHg from the above formula.

Example 33 The crystalline polycarbonate porous body with Mn=13,000 obtained in Example 1 was heated at 30°C and under a pressure of 1°000 kg@
/cm2 to obtain a press sheet of 15 CI square and 3 mm thick. The apparent density of this press sheet is 1.0
3g/cm2, the specific surface area is 0.5rr(/g,
It remains porous even after molding. The crystalline melting point peak of this porous crystalline polycarbonate molded body is 271°C, and the degree of crystallinity is 45%. When the compressive breaking strength was measured using an Instron type universal tester, it was found to be 25k.
g weight/cd.

Example 34 The crystalline polycarbonate porous body with Mn=13,000 obtained in Example 1 was heated at 200°C and under a pressure of 500 kg/w.
Compression molding is performed using ci to produce a 15 cm square and 3 mm thick press sheet. The apparent density of this crystalline polycarbonate molded body (press sheet) is 1.05 g/cm2, and the specific surface area is 0.08r+(/g).The crystal melting point peak of this product is 273°C, and the crystallinity is is 46%.The compressive breaking strength was measured using an Instron type universal tester and was 150 kg weight/d.

(Effects of the invention) ■In the phosgene method, which is an existing industrial manufacturing method for aromatic polycarbonate, by-products containing electrolytes such as sodium chloride and chlorine are produced, and these impurities are inevitably included in the resin. ing.

In addition, chlorine-containing compounds such as methylene chloride, which are used in large quantities as solvents, also remain in the resin.

These impurities have a negative impact on resin properties, so the phosgene method involves complex and expensive cleaning and removal steps to reduce their content in the resin. It is impossible to completely remove it.

On the other hand, the aromatic polycarbonate obtained by the method of the present invention is substantially free of such impurities, so it is not only superior in quality, but also naturally has a surface side that separates them. The method of the present invention is industrially advantageous because it does not require any additional steps.

■Furthermore, the melt transesterification method requires an expensive, high-viscosity reactor capable of high temperature and high vacuum, and has the disadvantage that the polymer is susceptible to yellowing due to thermal deterioration at high temperatures. The method of the present invention does not require special equipment and the resulting aromatic polycarbonate is of excellent quality.

■Also, the crystalline aromatic polycarbonate prepolymer porous body and its granular molded body of the present invention have an extremely fast solid state polymerization rate and have a small proportion of fine powder, so they do not adhere to the polymerization vessel or fuse with each other. There is no problem of adhesion, and it is extremely effective in carrying out industrial solid phase polymerization methods.

(2) In addition, it is possible to produce ultra-high molecular weight polymers that are difficult or impossible to produce using the phosgene method or the conventional transesterification method (melt method), and is suitable for that purpose.

It is also possible to produce polycarbonates having reactive hydroxyl groups at both ends.

[Brief explanation of drawings]

FIG. 1 is a scanning electron micrograph of the surface of the crystalline prepolymer porous material of the present invention obtained in Example 1 (magnification: 3
060 times). FIG. 2 shows a scanning electron micrograph (magnification: 1,020 times) of a cross section of the crystalline prepolymer porous material of the present invention obtained in Example 1, which was cut with a bin set. Figure 3 is a scanning electron micrograph (magnification: 4.40) of the amorphous prepolymer (1) obtained by prepolymerization in Example 1.
0 times). FIG. 4 shows a scanning electron micrograph (magnification: 1,020 times) of the surface of the crystalline prepolymer porous body obtained in Example 2. FIG. 5 shows an enlarged scanning electron micrograph (magnification: 3,060 times) of a portion of FIG. 4. FIG. 6 shows an enlarged scanning electron micrograph (magnification: 6.020 times) of a portion of FIG. 5. FIG. 7 is a scanning electron micrograph (magnification: 3,06
0 times). Part 8 shows a scanning electron micrograph (magnification: 6.020 times) that is an enlarged portion of FIG. 7. FIG. 9 shows a DSC chart of the crystalline polycarbonate porous material of the present invention obtained in Example 1. FIG. 10 and FIG. 1L show examples of Xla diffraction patterns before and after crystallization of the prepolymer, respectively. FIG. 12 shows the interrelationship of various aromatic polycarbonates according to the present invention. 1.'' Figure 2 Figure 1 Figure 781 Figure 6 Figure 1 Figure 11 Prayer angle 2θ (°) Procedural amendment March 12, 1990

Claims (1)

[Scope of Claims] (1) consisting of a repeating unit of aromatic carbonate, a hydroxyl end group and an aryl carbonate end group, and the molar ratio of the hydroxyl group to the aryl carbonate group is 5:95 to 95:5; Number average molecular weight is 1,00
0 to 15,000 and a specific surface area of 0.2 m^2/g
The above, characterized in that the degree of crystallinity is 5% or more,
Porous, crystalline aromatic polycarbonate prepolymer. (2) The prepolymer according to claim (1), which is in the form of a granular molded body. (3) A method for producing a porous, crystalline aromatic polycarbonate prepolymer, comprising treating the amorphous aromatic polycarbonate prepolymer with a solvent under sufficient shear to crystallize and make it porous. wherein the amorphous aromatic polycarbonate prepolymer consists of a repeating unit of aromatic carbonate, a hydroxyl end group and an aryl carbonate end group, and the molar ratio of the hydroxyl group to the aryl carbonate group is 5:95.
~95:5, and the number average molecular weight is 1,000~15,
000. A method for producing a porous, crystalline aromatic polycarbonate prepolymer, characterized in that the prepolymer is (4) By applying sufficient pressure or heat to the particles of the porous, crystalline aromatic polycarbonate prepolymer powder according to claim (1), agglomerated powder of the porous, crystalline aromatic polycarbonate prepolymer is produced. How to manufacture. (5) A porous, crystalline aromatic polycarbonate prepolymer in the form of a powder or agglomerated powder is heated in a heating zone at a temperature above the glass transition temperature of the prepolymer and at which the prepolymer remains in a solid state. , a method of performing solid phase polymerization while removing polycondensation byproducts from a heating zone, wherein the prepolymer having the form of powder or aggregated powder is the prepolymer according to claim (1). ,
Moreover, here, the molecular weight and crystallinity of the prepolymer are increased from 6,000 to 200,000 and 35% by solid phase polymerization, respectively.
% or more, therefore, the molecular weight and crystallinity of the resulting polycarbonate are higher than the molecular weight and crystallinity of its prepolymer, respectively, with a crystallinity of 35% or more, Number average molecular weight is 6,000
200,000 porous, crystalline aromatic polycarbonate powder or agglomerated powder. (6) heating the powder or the agglomerated powder of prepolymer;
There, per 1 g of the prepolymer, 0.1 to 10 Nl (
N. T. The method according to claim (5), characterized in that an inert gas of P)/hr is passed through and the inert gas containing polycondensation by-products is discharged from the heating zone. (7) Polycondensation by-products in the inert gas obtained by removing polycondensation by-products from the discharged inert gas or diluting the discharged inert gas with new inert gas. Claim (6) characterized in that an inert gas whose product content is 5 mmHg or less as a partial pressure in the inert gas is supplied to the heating zone as an inert gas.
) method described. (8) Powder or agglomerated powder of porous, crystalline aromatic polycarbonate produced by the method according to any one of claims (5) to (7). (9) Granulating a porous, crystalline aromatic polycarbonate prepolymer having the form of a powder or agglomerated powder, wherein the prepolymer having the form of a powder or agglomerated powder is: A method for producing a porous, crystalline aromatic polycarbonate prepolymer granular molded article, characterized in that the prepolymer according to claim (1) is used. (10) Polycondensation is carried out by heating a porous, crystalline aromatic polycarbonate prepolymer in the form of a granular molded body in a heating zone above the glass transition temperature of the prepolymer and at a temperature at which the prepolymer remains in a solid state. A method of performing solid phase polymerization while removing by-products from a heating zone, wherein the prepolymer having the form of a granular molded body is the prepolymer according to claim (1), Since the molecular weight and crystallinity of the prepolymer are increased by 6,000 to 200,000 and more than 35% by polymerization, respectively, the molecular weight and crystallinity of the obtained polycarbonate are therefore higher than that of the prepolymer. The crystallinity is 35% or more and the number average molecular weight is 6,000 to 200, which is characterized by being larger than each of the molecular weight and crystallinity.
A method for producing 000 porous, crystalline aromatic polycarbonate granular molded bodies. (11) The granular molded body of the prepolymer is heated, and 0.1 to 50 Nl (N.T.
．． The method according to claim 10, characterized in that an inert gas of P)/hr is passed through and the inert gas containing polycondensation by-products is discharged from the heating zone. (12) Polycondensation by-products in the inert gas obtained by removing polycondensation by-products from the discharged inert gas or diluting the discharged inert gas with new inert gas. Claim (1) characterized in that an inert gas whose product content is 5 mmHg or less as a partial pressure in the inert gas is supplied to the heating zone as an inert gas.
11) The method described. (13) A porous, crystalline aromatic polycarbonate granular molded article produced by the method according to any one of claims (10) to (12). (14) Consisting of repeating units of aromatic carbonate, hydroxyl end groups and/or aryl carbonate end groups, number average molecular weight of 6,000 to 200,000, and bulk density of 0.1 to 1.1 g/cm^3 , crystallinity is 35
% or more, and a compressive breaking strength of 10 kg weight/cm^2 or more. (15) Heating a porous, crystalline aromatic polycarbonate powder, agglomerated powder, or granular molded body and maintaining the temperature at a temperature higher than the glass transition temperature of the polycarbonate and lower than the crystalline melting point of the polycarbonate. , a method for producing a molded body comprising melting and adhering the surface of the powder, agglomerated powder, or granular molded body, the porous, crystalline aromatic polymer powder, agglomerated powder, or granular molded body is composed of a repeating unit of aromatic carbonate, a hydroxyl end group and/or an aryl carbonate end group, and has a number average molecular weight of 6,000 to 200,00.
0, specific surface area is 0.1 m^2/g or more and crystallinity is 3
Porous, crystalline, characterized by having a bulk density of 0.1 to 1.1 g/cm^3, and a compressive breaking strength of 10 kg/cm^2 or more. A method for producing an aromatic polycarbonate molded article. (16) A method for producing a molded body comprising molding a porous, crystalline aromatic polycarbonate powder, agglomerated powder, or granular molded body at a temperature below the glass transition temperature of the polycarbonate, the porous, crystalline The aromatic polymer powder, agglomerated powder, or granular molded body consists of a repeating unit of aromatic carbonate, a hydroxyl end group and/or an aryl carbonate end group, and has a number average molecular weight of 6,000 to 200,00.
0, specific surface area is 0.1 m^2/g or more and crystallinity is 3
5% or more, a bulk density of 0.1 to 1.1 g/cm^3, and a compressive breaking strength of 10 kg/cm^2 or more, porous, crystalline. A method for producing a polycarbonate molded article. (17) In producing a porous, crystalline aromatic polycarbonate, [1] an aromatic dihydroxy compound and an aromatic carbonate compound are reacted, and the number average molecular weight is 1,000 to 15,
000 and a prepolymerization step in which the amorphous prepolymer is reacted at a temperature and time sufficient to produce an amorphous prepolymer whose end groups are hydroxyl groups and aryl carbonate groups. The average particle size of a porous, crystalline aromatic polycarbonate prepolymer powder produced by a shear force upon treatment with a solvent under sufficient shear force to crystallize to a degree of crystallinity and simultaneously render the prepolymer porous. The diameter is 250 μm or less, and the specific surface area is 0.
2m^2/g or more, [3] a porous, crystalline prepolymer powder, or made from the prepolymer powder; A step of heating a porous, crystalline prepolymer agglomerated powder or granular molded body to a temperature above the glass transition temperature of the prepolymer and at a temperature at which the prepolymer maintains a solid state in order to advance a solid state polymerization reaction. Here, the molecular weight and crystallinity of the prepolymer by solid phase polymerization are 6,000 to 200,000 and 35%, respectively.
a solid-state polymerization step, characterized in that the molecular weight and crystallinity of the polycarbonate obtained are higher than that of its prepolymer; , a method for producing crystalline aromatic polycarbonate. (18) In producing a porous, crystalline aromatic polycarbonate, [1] In the presence of a molecular weight regulator, an aromatic dihydroxy compound and phosgene are reacted to have a number average molecular weight of 1,000.
a prepolymerization step to prepare a prepolymer of 0 to 15,000, [2] under sufficient shear to crystallize the amorphous prepolymer to a degree of crystallinity of 5% or more and at the same time make the prepolymer porous; When treated with a solvent, the average particle size of the porous, crystalline aromatic polycarbonate prepolymer powder generated by the shearing force is set to 250 μm or less, and the specific surface area is set to 0.
2m^2/g or more, [3] a porous, crystalline prepolymer powder, or made from the prepolymer powder; A step of heating a porous, crystalline prepolymer agglomerated powder or granular molded body to a temperature above the glass transition temperature of the prepolymer and at a temperature at which the prepolymer maintains a solid state in order to advance a solid state polymerization reaction. Here, the molecular weight and crystallinity of the prepolymer by solid phase polymerization are 6,000 to 200,000 and 35%, respectively.
a solid-state polymerization step, characterized in that the molecular weight and crystallinity of the polycarbonate obtained are higher than that of its prepolymer; , a method for producing crystalline aromatic polycarbonate. (19) In producing a porous, crystalline aromatic polycarbonate, [1] an aromatic polycarbonate oligomer whose terminal group mainly consists of an aryl carbonate group and a number average molecular weight of about 350 to 950 and an aromatic dihydroxy compound; A prepolymerization step of reacting at sufficient temperature and time to prepare an amorphous prepolymer having a terminal hydroxyl group and a terminal aryl carbonate group and having a number average molecular weight of 1,000 to 15,000, [2] the amorphous A porous, crystalline aromatic polycarbonate produced when the prepolymer is treated with a solvent under sufficient shear to crystallize the prepolymer to a degree of crystallinity of 5% or more and at the same time to make the prepolymer porous. The average particle size of the prepolymer powder is 250 μm or less, and the specific surface area is 0.
2m^2/g or more, [3] a porous, crystalline prepolymer powder, or made from the prepolymer powder; A step of heating a porous, crystalline prepolymer agglomerated powder or granular molded body to a temperature above the glass transition temperature of the prepolymer and at a temperature at which the prepolymer maintains a solid state in order to advance a solid state polymerization reaction. Here, the molecular weight and crystallinity of the prepolymer by solid phase polymerization are 6,000 to 200,000 and 35%, respectively.
a solid-state polymerization step, characterized in that the molecular weight and crystallinity of the polycarbonate obtained are higher than that of its prepolymer; , a method for producing crystalline aromatic polycarbonate.