JP3218085B2 - Method for producing granules of polyester carbonate and its composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing polyester carbonate granules.
From the organic solvent solution of polyester carbonate, the bulk density is high, a method of producing a granular material of polyester carbonate that is easy to handle, more specifically, the particle size is large,
The present invention relates to a method for producing a granular material having excellent properties and containing substantially no fine powder. Further, the present invention provides a method for producing granules of a polyester carbonate composition, more specifically, a method for producing granules of a polyester carbonate composition comprising a polyester carbonate and at least one stabilizer, and more specifically, a pelletizing step. The present invention relates to a method for producing a granular material of a polyester carbonate composition which can be directly molded without passing through.

[0002]

2. Description of the Related Art As a method for producing a polyester carbonate from an organic solvent solution of a polyester carbonate, for example, a method of mixing an organic solvent solution of a polyester carbonate and a poor solvent such as acetone to precipitate the polyester carbonate (Japanese Patent Laid-Open No. 55-13942
No. 3), a method of obtaining a solid polyester carbonate by dropping an organic solvent solution of polyester carbonate in a large amount of methanol with stirring (JP-A-56-133).
No. 332) and further, a poor solvent for polyester carbonate such as methyl ethyl ketone and methyl isobutyl ketone [anti-solvent] and water are added to an organic solvent solution of polyester carbonate, and the mixture is heated to evaporate and distill off the organic solvent. (US Pat. No. 4,668,768) and the like are known. However, the polyester carbonate obtained by these methods contains fine powder and has a low bulk density,
There were difficulties in the scattering and fluidity during handling, such as scattering of fine powder during storage, bag collection, and molding, and bridging in the hopper of the extrusion molding machine during molding.

Further, an organic solvent solution of aromatic polyester carbonate is supplied to a kneader having a pulverizing mechanism for storing hot water maintained at a temperature higher than the boiling point of the organic solvent,
This is kneaded to remove the solvent and pulverize at the same time to produce polyester carbonate granules (JP-A-6060
JP-A-202127), a methylene chloride solution of an aromatic polyester carbonate is continuously supplied to a granulation tank, and heated while maintaining a suspension state in water to evaporate methylene chloride to obtain a granular aromatic polyester carbonate. At least a part of the water slurry containing the aromatic polyester carbonate granules extracted from the granulation tank and produced from the granulation tank is subjected to wet pulverization treatment and circulated to the granulation tank to produce aromatic polyester carbonate granules. Kaisho 5
8-206626), an organic solvent solution of an aromatic polyester carbonate is supplied into a container containing an aromatic polyester carbonate which is uniformly stirred,
A method for producing aromatic polyester carbonate granules, which is brought into contact with the granules and evaporates an organic solvent, is known (Japanese Patent Application Laid-Open No. 57-141427).

However, the methods disclosed in JP-A-60-202127 and JP-A-58-206626 require special devices and conditions such as a wet pulverizer and a kneader. According to the study of the present inventors, Japanese Patent Application Laid-Open No. 57-141427
In the method disclosed in Japanese Patent Application Laid-Open Publication No. H11-157, when using a general stirring tank, the obtained polyester carbonate becomes a rice cake-like product, and a granular material cannot be obtained, and it is essential to use a special device such as a kneader. There was found. These wet crushers, kneaders, kneaders and other devices are generally difficult to perform glass lining or Teflon coating, and the metal comes into contact with the organic solvent solution of polyester carbonate.
Inorganic substances such as nickel and iron, which may deteriorate the color tone of the polyester carbonate, may be mixed into the polyester carbonate, and a method for producing a granular material of the polyester carbonate by a simpler apparatus (such as a glass-lined stirring tank) is known. Was desired.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to remarkably excel in storage, bag collection, transportation, and handling during molding, substantially contains no fine powder, has a large particle size, and has a high bulk density. An object of the present invention is to provide a method for efficiently producing granules of polyester carbonate having excellent properties from a solution of polyester carbonate in an organic solvent without using a special apparatus. Another object of the present invention is to provide a method for producing a granular material of polyester carbonate that can be directly molded without performing a process such as pelletization, and more specifically, to mold a polyester carbonate having an excellent color tone. It is an object of the present invention to provide a method for producing polyester carbonate granules that can be produced.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to efficiently produce granules of polyester carbonate having good properties. A solvent and a polyester carbonate powder are added to form a suspension mixture, and while the organic solvent solution of the polyester carbonate is supplied to the suspension mixture, the organic solvent is distilled off. Not containing, uniform particle size, average particle size is about 1-4mm, bulk density 0.3-0.6g /
The present inventors have found that granules of polyester carbonate having a remarkably excellent handleability of about ml can be obtained and completed the present invention. That is, the present invention prepares a suspension mixture of water, a poor solvent for polyester carbonate and polyester carbonate powder, and supplies the suspension mixture with an organic solvent solution of polyester carbonate while stirring. A method for producing polyester carbonate granules for evaporating the solvent and forming granules, and
A suspension mixture of water, a poor solvent for polyester carbonate and polyester carbonate powder is prepared, and in the presence of a stabilizing agent, the suspension mixture is stirred and supplied with an organic solvent solution of polyester carbonate. The present invention relates to a method for producing granules of a polyester carbonate composition comprising a polyester carbonate for evaporating and removing an organic solvent to form granules and at least one stabilizer.

The polyester carbonate used in the present invention may be any of aliphatic polyester carbonate, aromatic polyester carbonate, aliphatic polyester-aromatic polycarbonate and aromatic polyester-aliphatic polycarbonate, but is preferably aromatic polyester carbonate. Is used. Polyester carbonates are prepared by commonly known methods, for example, from dihydroxyaromatic compounds, phosgene or bischloroformates of dihydroxyaromatic compounds, and dibasic acid chlorides. The composition is not particularly limited, but the composition molar ratio of dihydroxy aromatic compound residue: dibasic acid residue: carbonate bond is 1: 0.33 to 0.75: 0.67 to
It is preferably about 0.25. There is no particular limitation on the average molecular weight of the polyester carbonate, but usually, the average molecular weight
Those having about 1000 to 50000 are preferably used. Examples of the dihydroxy aromatic compound used as a raw material of the aromatic polyester carbonate include a dihydroxy aromatic compound represented by the following formula.

HO-Ar ¹ -X-Ar ² -OH Here, Ar ¹ and Ar ² are each a divalent monocyclic aromatic group, and X is a group linking Ar ¹ and Ar ² . Ar ¹ and Ar ² are a phenylene group or a substituted phenylene group having a substituent, and examples of the substituent include a hydrocarbon group such as an alkyl group, a cycloalkyl group, an alkenyl group, and an aryl group, a nitro group, and an alkoxy group. Groups, halogen atoms and the like. Both Ar ¹ and Ar ² are p-phenylene, m-phenylene or o-phenylene, or one is p-phenylene and the other is m-phenylene or o-phenylene, or Is m
-Phenylene group, and the other is preferably an o-phenylene group, and particularly preferably, both Ar ¹ and Ar ² are p-phenylene groups. X is generally a single bond or a divalent hydrocarbon group, and includes a saturated hydrocarbon group, for example, an alkylidene group such as methylene, ethylene, 2,2-propylidene, cyclohexylidene, etc. Groups substituted with groups and the like are also included. Further, it may be a hydrocarbon group containing an aromatic group or other unsaturated hydrocarbon group, and further, a group containing atoms other than carbon and hydrogen,
For example -O -, - S -, - SO -, - SO 2 -, - CO
-Or the like.

Examples of dihydroxy aromatic compounds include:
Bis (4-hydroxyphenyl) methane, 1,1-bis (4 ′
-Hydroxyphenyl) ethane, 1,2-bis (4'-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl)
Diphenylmethane, bis (4-hydroxyphenyl) -1-
Naphthylmethane, 1,1-bis (4'-hydroxyphenyl)-
1-phenylethane, 2,2-bis (4'-hydroxyphenyl) propane ["bisphenol A"], 2- (4'-hydroxyphenyl) -2- (3'-hydroxyphenyl) propane, 2,2- Bis (4'-hydroxyphenyl) butane, 1,1-
Bis (4'-hydroxyphenyl) isobutane, 2,2-bis (4'-hydroxyphenyl) octane, 2,2-bis (3'-
Methyl-4'-hydroxyphenyl) propane, 2,2-bis (3'-ethyl-4'-hydroxyphenyl) propane,
2-bis (3'-n-propyl-4'-hydroxyphenyl)
Propane, 2,2-bis (3'-isopropyl-4'-hydroxyphenyl) propane, 2,2-bis (3'-sec-butyl-4'-hydroxyphenyl) propane, 2,2-bis (3 ' −
tert-butyl-4′-hydroxyphenyl) propane, 2,2-bis (3′-cyclohexyl-4′-hydroxyphenyl) propane, 2,2-bis (3′-allyl-4′-hydroxyphenyl) propane, 2,2-bis (3'-methoxy-4 '
-Hydroxyphenyl) propane, 2,2-bis (3 ', 5'-dimethyl-4'-hydroxyphenyl) propane, 2,2-bis (2', 3 ', 5', 6'-tetramethyl-4 '-Hydroxyphenyl) propane, 2,2-bis (3'-chloro-4'-hydroxyphenyl) propane, 2,2-bis (3', 5'-dichloro-4'-
Hydroxyphenyl) propane, 2,2-bis (3′-bromo-4′-hydroxyphenyl) propane, 2,2-bis (3 ′,
5'-dibromo-4'-hydroxyphenyl) propane, 2,2
-Bis (2 ', 6'-dibromo-3', 5'-dimethyl-4'-hydroxyphenyl) propane, bis (4-hydroxyphenyl) cyanomethane, 1-cyano-3,3-bis (4'-hydroxy Bis (hydroxyaryl) alkanes such as phenyl) butane and 2,2-bis (4′-hydroxyphenyl) hexafluoropropane;

1,1-bis (4'-hydroxyphenyl) cyclopentane, 1,1-bis (4'-hydroxyphenyl) cyclohexane, 1,1-bis (4'-hydroxyphenyl) cycloheptane, 2,2 Bis (hydroxyaryl) cycloalkanes such as -bis (4'-hydroxyphenyl) adamantane, 4,4'-dihydroxydiphenyl ether, 4,4'-
Bis (hydroxyaryl) ethers such as dihydroxy-3,3'-dimethyldiphenyl ether and ethylene glycol bis (4-hydroxyphenyl) ether, 4,4'-
Bis (hydroxyaryl) sulfides such as dihydroxydiphenyl sulfide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'- Bis (hydroxyaryl) sulfoxides such as dimethyldiphenylsulfoxide; bis (hydroxyaryl) sulfones such as 4,4′-dihydroxydiphenylsulfone and 4,4′-dihydroxy-3,3′-dimethyldiphenylsulfone; bis (4 -Hydroxyphenyl) ketone, bis (4
Bis (hydroxyaryl) ketones such as -hydroxy-3-methylphenyl) ketone;

Further, 6,6'-dihydroxy-3,3,3 ', 3'-
Tetramethylspiro (bis) indane ["spirobiindanebisphenol"], trans-2,3-bis (4'-hydroxyphenyl) -2-butene, 9,9-bis (4'-hydroxyphenyl) fluorene, 3 , 3-Bis (4'-hydroxyphenyl) -2-butanone, 1,6-bis (4'-hydroxyphenyl) -1,6-hexanedione, 1,1-dichloro-2,2-bis (4 ' -Hydroxyphenyl) ethylene, 1,1-dibromo
-2,2-bis (4'-hydroxyphenyl) ethylene, 1,1-
Dichloro-2,2-bis (5'-phenoxy-4'-hydroxyphenyl) ethylene, α, α, α ', α'-tetramethyl-α, α'-bis (4-hydroxyphenyl) -p-xylene , Α, α, α ', α'-tetramethyl-α, α'
-Bis (4-hydroxyphenyl) -m-xylene, 4,4 '
-Dihydroxydiphenyl and the like. In addition to the above-mentioned dihydroxy aromatic compounds, hydroquinone, resorcin and the like are also used. These may be used alone or in combination of two or more. In the present invention, the dihydroxy aromatic compound particularly preferably used is bisphenol A.

Examples of dibasic acid chlorides include oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, derived from linear paraffinic hydrocarbons. Azelaic acid, saturated aliphatic dibasic acids such as sebacic acid and halogen-substituted aliphatic dibasic acids, further thioglycolic acid, aliphatic dibasic acids and maleic acid containing a heteroatom in the fatty chain such as dithioglycolic acid, Unsaturated aliphatic dibasic acids such as fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, homophthalic acid, o-phenylenediacetic acid, m-phenylenediacetic acid,
Chloride such as unsubstituted or aliphatic-substituted aromatic dicarboxylic acid such as p-phenylenediacetic acid, polycyclic aromatic dicarboxylic acid such as diphenic acid and 1,4-naphthalene dicarboxylic acid, and the like. These may be used alone or in combination of two or more. In the present invention, dibasic acid chlorides particularly preferably used are chlorides of aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid.

The organic solvent solution of polyester carbonate (hereinafter abbreviated as polyester carbonate solution) which is the object of the present invention may be prepared by dissolving polyester carbonate in an organic solvent, or may be prepared by an interfacial polymerization method or the like. An organic solvent solution of the produced polyester carbonate or a solution obtained by appropriately concentrating the solution may be used, or a solution prepared by another method may be used. The organic solvent used in the present invention can be arbitrarily used as long as it can dissolve the polyester carbonate.For example, chlorinated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and 1,2-dichloroethylene can be used. Or a mixture thereof is preferred. In the present invention, it is particularly preferable to use dichloromethane, which has a low boiling point and dissolves polyester carbonate well. The concentration of the polyester carbonate in the polyester carbonate solution can take any concentration up to the saturation concentration. However, since a substance having an excessively high concentration has a high viscosity and is difficult to handle, usually the concentration is preferably about 5 to 35% by weight.

A poor solvent for polyester carbonate (hereinafter abbreviated as a poor solvent) is a solvent having an ability to precipitate a polyester carbonate without removing an organic solvent when a sufficient amount is added to a polyester carbonate solution [anti- solvent), which is different from non-solvents which do not affect the solubility of the polyester carbonate even when added in a large amount (U.S. Pat.
8,768). Specific examples of the poor solvent include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and butyl acetate, and n-
Hexane, aliphatic hydrocarbons such as n-heptane, methylcyclohexane, alicyclic hydrocarbons such as cyclohexane,
Examples include alcohols such as methanol and isopropanol, and nitromethane, acetonitrile, ethylene carbonate, tetrahydrofuran, dioxane, and mixtures thereof. A feature of the present invention is to obtain granules of a substantially spherical polycarbonate having a uniform particle size, a high bulk density, and preferable poor solvents include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and acetic acid. Esters such as ethyl and butyl acetate.

Another feature of the present invention is that these poor solvents are mixed not with the polyester carbonate solution but with a suspension of water and polyester carbonate powder. It is known that a poor solvent is added to a polyester carbonate solution in advance and then supplied to warm water or the like to produce a solid polyester carbonate (Japanese Patent Application Laid-Open No. 58-1983).
-206626). But with this method,
Due to various factors such as the outside air temperature, the polyester carbonate solution may be supplied to hot water or the like, or the polyester carbonate in the polyester carbonate solution may be precipitated during the feeding, which may cause inconvenience in operation. . Further, in the initial stage of supplying the polyester carbonate solution, since almost no poor solvent is present in an aqueous medium such as hot water, a lump of polyester carbonate is generated in the initial stage, and the polyester which is sequentially supplied is formed. The poor solvent in the carbonate solution is accumulated in the aqueous medium due to the difference in boiling point from the organic solvent, and when the amount of the poor solvent reaches a predetermined amount, the polyester carbonate in the organic solvent remaining in the aqueous medium is removed. Precipitation and crushing of the initially formed lumps occur. That is, the method in which the poor solvent is added to the polyester carbonate solution cannot completely suppress the production of the fine powdered polyester carbonate.

In the method of the present invention, since the poor solvent is added to the aqueous medium in advance, the above-mentioned phenomenon does not occur, and a granular polyester carbonate substantially free of fine powder is obtained. In addition, adding the poor solvent to the aqueous medium in advance has an effect of uniformly dispersing the polyester carbonate powder, which is one of the components of the present invention described later, in water. The polyester carbonate powder serves as a core for producing the polyester carbonate granules, but if it is not uniformly dispersed in an aqueous medium, the effect is extremely low. Since polyester carbonate has almost no compatibility with water, simply adding polyester carbonate powder in water will cause agglomeration or spread only on the water surface, unless strong stirring is performed in this state , It is not possible to maintain an even distribution. However, by adding a predetermined amount of a poor solvent to water, the polyester carbonate powder can be evenly dispersed even with a very slight stirring, and that state can be maintained. The amount of the poor solvent used is preferably 0.05 to 1.5 times, more preferably 0.1 to 1.5 times by volume the amount of water used.
One time is preferred. If the amount of the poor solvent is less than 0.05 times, the uniformity of the particle size becomes poor, and a lump may be formed.If the amount of the poor solvent exceeds 1.5 times, the granularity of the produced polyester carbonate is reduced. It is not preferable because the body has a low bulk density and is close to a fine powder.

The amount of water used may be 0.5 times or more by volume ratio with respect to the amount of the polyester carbonate solution to be used, but is preferably 0.5 to 3 times by volume ratio. If the amount of water used is less than 0.5 times, it is not preferable because stirring of the slurry may be difficult due to the formation of polyester carbonate lumps. As long as the relationship between the amount of water and the poor solvent is within the above-mentioned range, the amount of water relative to the polyester carbonate solution is not inconvenient from the viewpoint of the properties of the produced polyester carbonate granules even when used in a large amount. However, the use of a large amount of water requires a large apparatus, and the use amount of a poor solvent increases.
In addition, since the thermal efficiency also deteriorates, it is not a good idea from an industrial point of view.

The polyester carbonate powder dispersed in a mixed solution of water and a poor solvent is a nucleus for producing polyester carbonate granules. There are no particular restrictions on the particle size and particle size distribution, but polyester carbonate powder having an average particle size of 0.1 to 1 mm is preferred. Some of the polyester carbonate granules produced by the method of the present invention may be pulverized and suspended. The amount of the polyester carbonate powder to be dispersed may be 0.5% by weight or more, preferably 0.5 to 50% by weight, particularly preferably 3 to 50% by weight, based on the amount of the polyester carbonate in the polyester carbonate solution. 30% by weight. If the amount of the polyester carbonate powder to be dispersed is less than 0.5% by weight, a lump of polyester carbonate is formed, and it is difficult to obtain polyester carbonate granules having uniform properties. In addition, the fact that the amount of the polyester carbonate powder to be dispersed is large is not particularly inconvenient in terms of the properties of the produced polyester carbonate granules, but is disadvantageous in terms of productivity.

The polyester carbonate solution may be supplied to a suspension mixture of water, a poor solvent and polyester carbonate powder by, for example, a supply means such as dropping, but any other method may be used. May be.
Also, the rate of supplying the polyester carbonate solution may be as fast as possible, but the amount of the organic solvent in the supplied polyester carbonate solution depends on the amount of the organic solvent evaporated and distilled during the supply of the polyester carbonate solution. Is preferably about 1 to 10 times by volume, and more preferably about 1 to 5 times by volume.
Usually, it is preferable to supply the entire amount of the polyester carbonate solution to be supplied in about 0.1 to 3 hours, depending on the method of evaporating and removing the organic solvent described below, the heating temperature, and the like. Obviously, feeding for a long time is not preferable in terms of productivity.

The method of evaporating and evaporating the organic solvent may be, in addition to evaporating and evaporating by ordinary heating, a method of evaporating and evaporating the organic solvent by heating while flowing an inert gas such as nitrogen, or a method of evaporating under reduced pressure. A method of distilling off is used. Normally, a suspension mixture of water, a poor solvent and polyester carbonate powder is kept heated while a polyester carbonate solution is supplied and the organic solvent is evaporated off. The heating temperature may be lower than the boiling point of the organic solvent of the polyester carbonate.However, if the heating temperature is significantly low, the evaporation rate of the organic solvent becomes slow, and a large amount of the organic solvent remains in the suspension mixture. Undesirably, particles or aggregates are formed, and it becomes difficult to obtain polyester carbonate granules of uniform quality. On the other hand, if the heating temperature is too high, it is not preferable because the poor solvent and water in the suspension mixture are evaporated off. Therefore, in the method of the present invention, the heating temperature of the suspension mixture is preferably set to a temperature not lower than the boiling point of the organic solvent of the polyester carbonate, from the boiling point of the organic solvent to the boiling point of the poor solvent for the polyester carbonate, and It is more preferable that the temperature be in the range below the boiling point of water.

By supplying the polyester carbonate solution to the suspension mixture of the water, the poor solvent and the polyester carbonate powder maintained in the above-mentioned temperature range while stirring, the organic solvent is distilled off by evaporation. The granules can be directly obtained without substantially undergoing the rice cake state and without being crushed by stirring. Therefore, it is not necessary to use a special stirring device, a stirring blade, a kneader, a pulverizer, and the like.In general, the dispersion state of the polyester carbonate powder in the suspension mixture is maintained, and the evaporation of the organic solvent is constantly performed. Agitation that can be performed efficiently (for example, about 100 to 300 rpm)
Thus, it is possible to easily and quantitatively produce polyester carbonate granules having uniform properties. The particles of the polyester carbonate produced by the method of the present invention can be filtered as it is after distilling off the organic solvent, or the particles of the polyester carbonate produced by the present invention can be obtained by evaporating the organic solvent. Does not change its properties due to stirring or heating.If the boiling point of the poor solvent is low, evaporate the organic solvent and then evaporate the poor solvent by elevating the heating temperature to the boiling point of the poor solvent. It may be distilled off and then filtered. The filtered granules are dried and manufactured by a usual method such as drying under reduced pressure and fluidized drying.

A method for producing granules of a polyester carbonate composition containing a stabilizer from a polyester carbonate solution in the presence of a stabilizer is also within the scope of the present invention. It is known that polyester carbonate causes considerable deterioration in hue and molecular weight due to heat history during pelletization and molding, and therefore, during pelletization, phosphorus-based processing stabilizers, antioxidants, etc. It is known to add stabilizing agents. Granules of the polyester carbonate composition obtained by the production method of the present invention can be directly formed and processed without going through a pelletizing step. This means that, unlike the conventional method, it is not necessary to take steps of molding and processing after the polyester carbonate obtained from the polyester carbonate solution is once pelletized, so that the number of times of receiving the heat history is small and the molecular weight is reduced. Instead, it is possible to provide a polyester carbonate molded article having a good color tone. The method for producing the polyester carbonate granules according to the present invention comprises:
Since the process is carried out at a relatively low temperature, the obtained granules are not deteriorated at all by heat, but when the obtained granules are directly formed into a molded article such as a film or a sheet, the granules are It is preferable to add a stabilizer during the production of.

The stabilizer may be present in the suspension mixture of the poor solvent for water, the polyester carbonate and the polyester carbonate powder during the production, or may be present in the polyester carbonate solution. good. In addition, the same or different stabilizers may be present in the suspension mixture and the polyester carbonate solution, respectively.In the production of the polyester carbonate granules, apart from the supply of the polyester carbonate solution,
The stabilizer may be supplied in liquid, solid, solution or suspension. Further, after the preparation according to the present invention, a granulated polyester carbonate containing a part of the filtered organic solvent or poor solvent is mixed with a stabilizer, and dried in a state where the stabilizer is present on the surface of the granulated body. A method is also acceptable. As a method for producing a granular material of a polyester carbonate composition containing a stabilizer, for example, a granular material is produced by using a polyester carbonate solution prepared by adding a stabilizer to a polyester carbonate solution obtained by interfacial polymerization. And a method of producing granules while supplying a polyester carbonate solution to a suspension mixture of a poor solvent for water, polyester carbonate, a polyester carbonate powder, and a stabilizer.

Examples of stabilizers for polyester carbonates include processing stabilizers such as phosphorus-based processing stabilizers, antioxidants and the like, heat stabilizers, and light-resistant stabilizers such as ultraviolet absorbers. Specific examples thereof include tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, tristearyl phosphite, triphenyl phosphite, tricresyl phosphite, tris (nonylphenyl) phosphite, and tris ( 2,4-di-t-
Butylphenyl) phosphite, decyl-diphenyl phosphite, phenyl-di-2-ethylhexyl phosphite, phenyl-didecyl phosphite, tricyclohexyl phosphite, distearyl-pentaerythrityl-diphosphite, tris (mixed mono-, di- Phosphites such as -phenyl) phosphite, dinonylphenyl-bis (nonylphenyl) phosphite, octyl- [2,2′-di (4,6-di-t-butylphenyl) methylene] phosphite,

Triethylphosphine, triisopropylphosphine, tri-n-butylphosphine, tricyclohexylphosphine, allyldiphenylphosphine, triphenylphosphine, diphenylphosphine, tris
(2,4-dimethylphenyl) phosphine, tris (2,4,6-
Trimethylphenyl) phosphine, tris (o-tolyl)
Phosphine, tris (o-anisyl) phosphine, diphenylbutylphosphine, diphenyloctadecylphosphine, tris- (p-nonylphenyl) phosphine, tris (naphthyl) phosphine, diphenyl- (hydroxymethyl) phosphine, diphenyl-acetoxymethylphosphine, diphenyl- (Β-ethylcarboxyethyl) phosphine, diphenylbenzylphosphine, diphenyl- (p-hydroxyphenyl) phosphine, diphenyl-1,4-dihydroxyphenyl-2-phosphine,
Organic phosphines such as phenylnaphthylbenzylphosphine, triphenylphosphonite, dinonylphenylphosphonite, diisooctylphenylphosphonite, phenyl (2,4,6-trimethylphenyl) phenylphosphonite, [(3-ethyloxetanyl- 3) -Methyl]-
(2,4,6-trimethylphenyl) phenylphosphonite,
Organic phosphonites such as tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphonite,

2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-ethylphenol, 2,2′-methylenebis (6-t-butyl-p-cresol), 4,4′-methylenebis (6-t-butyl-o-cresol), 4,4′-methylenebis (6-t-butyl-m-cresol), tetrakis- [methylene-3- (3 ′, 5′- Di-tert-butyl-4'-hydroxyphenyl) propionate] methane, 4,4'-thiobis (6-tert-butyl-m-cresol), stearyl-
β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-
Di-tert-butyl-4-hydroxybenzyl) benzene, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,5-di-tert-butyl-4-
Phenolic antioxidants such as hydroxybenzylphosphonate-diethyl ester, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5
-Bis (α, α-dimethylbenzyl) phenyl] -2H
-Benzotriazole, 3 ', 3'-bis [2- (5'-octyl
-2'-hydroxyphenyl) benzotriazolyl] methane and the like. These polyester carbonate stabilizers may be used alone or in combination of two or more. The amount of the polyester carbonate stabilizer used is preferably the minimum amount that exhibits a stabilizing effect. Although there is a difference depending on each stabilizer, it is generally preferable to use about 0.1 ppm to 5000 ppm.

[0027]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the invention. Example 1 A mixed solution of 2 liters of distilled water and 0.9 liter of acetone was added with a particle size of 0.25 to 1
25 g of polyester carbonate powder (5 wt% with respect to the polyester carbonate in the supplied polyester carbonate solution) was dispersed and heated to 50 ° C. About 200r
Under stirring at pm, 2.5 kg of a dichloromethane solution of a polycarbonate containing 20% by weight of a polyester carbonate having an average molecular weight of 26,000 produced from bisphenol A, phosgene, and terephthalic acid chloride was supplied over 40 minutes.
The dichloromethane was evaporated off. The resulting polyester carbonate granules were separated by filtration and dried at 120 ° C. and 30 to 40 mmHg for 6 hours. Table 1 (Table 1) shows the particle size and bulk density of the obtained polyester carbonate granules. Substantially spherical particles of polyester carbonate having a uniform particle size were obtained.

Example 2 In Example 1, 25 g of the polyester carbonate powder was used.
Instead of using polyester carbonate powder
Granules of polyester carbonate were produced in the same manner as in Example 1 except that 150 g (30 wt% with respect to the polycarbonate in the supplied polyester carbonate solution) was used. Table 1 shows the particle diameter and bulk density of the obtained polyester carbonate granules. Substantially spherical particles of polyester carbonate having a uniform particle size were obtained.

Example 3 Granules of polyester carbonate were produced in the same manner as in Example 1, except that methyl ethyl ketone was used instead of acetone. Table 1 shows the particle diameter and bulk density of the obtained polyester carbonate granules. Substantially spherical particles of polyester carbonate having a uniform particle size were obtained.

Example 4 Granules of polyester carbonate were produced in the same manner as in Example 1 except that ethyl acetate was used instead of acetone. Table 1 shows the particle diameter and bulk density of the obtained polyester carbonate granules. Substantially spherical particles of polyester carbonate having a uniform particle size were obtained.

Comparative Example 1 For comparison, a poor solvent was added to a polyester carbonate solution to produce a polyester carbonate. That is, 25 g of a polyester carbonate powder having a particle size of 0.25 to 1 mm was dispersed in 2 liters of distilled water and heated to 50 ° C. Into this suspension was added 2.5 kg of a dichloromethane solution containing 20% by weight of a polyester carbonate having an average molecular weight of 26,000 and prepared from bisphenol A, phosgene and terephthalic acid chloride.
Dichloromethane was distilled off while supplying a polyester carbonate solution to which 0.9 l of acetone had been added over 40 minutes. The obtained polyester carbonate was a mixture of a lump and a fine powder, and had a poor uniform particle size.
In addition, there is a lump having a diameter of about 30 mm, which is extremely inappropriate for use in pelletizing or molding.

Comparative Example 2 Polyester carbonate was produced without adding the polyester carbonate powder. That is, 0.9 l of acetone was added to 2 l of distilled water and heated to 50 ° C. To this mixed solution was added 2.5 kg of a dichloromethane solution containing 20% by weight of a polyester carbonate having an average molecular weight of 26,000 and prepared from bisphenol A, phosgene, and terephthalic acid chloride.
The dichloromethane was evaporated off while feeding over 40 minutes. The obtained polyester carbonate contained a large amount of fine powder and had a poor uniformity in particle diameter, and was poor in handleability causing scattering of the fine powder and the like.

Comparative Example 3 According to the method of US Pat. No. 4,668,768, instead of supplying a polyester carbonate solution, a mixture of the polyester carbonate solution, water and a poor solvent was heated, and the organic solvent was distilled off. In this manner, granules of polyester carbonate were produced. That is, 2 liters of distilled water and 0.9 liters of acetone were added to 2.5 kg of a dichloromethane solution containing 20% by weight of a polyester carbonate having an average molecular weight of 26000 and prepared from bisphenol A, phosgene, and terephthalic acid chloride, and then heated to 50 ° C. The dichloromethane was evaporated from the liquid. During the distillation of dichloromethane, gelation of the polyester carbonate occurs,
In the process of crushing the gel, a large amount of the solvent in the gel was suddenly distilled out, which was dangerous in operation. Further, the obtained polyester carbonate contained a large amount of fine powder, and had a poor uniform particle size.

Comparative Example 4 In Example 1, 25 g of polyester carbonate powder
Instead of using polyester carbonate powder 1.5
A polyester carbonate granule was produced in the same manner as in Example 1 except that g (0.3% by weight based on the amount of the polyester carbonate in the supplied polyester carbonate solution) was used. The obtained polyester carbonate contained a lump and a fine powder, and was not used for molding.

Comparative Example 5 In Example 1, instead of using 0.9 l of acetone,
A polyester carbonate granule was produced in the same manner as in Example 1 except that 4 l of acetone was used. The obtained polyester carbonate had an extremely low bulk density.

Comparative Example 6 For comparison, polyester carbonate was produced without adding a poor solvent. That is, a particle size of 0.25 to 2 liters of distilled water
Disperse 25g of 1mm polyester carbonate powder
Heated to 50 ° C. To this suspension, 2.5 kg of a dichloromethane solution containing 20% by weight of a polyester carbonate having an average molecular weight of 26,000 produced from bisphenol A, phosgene, and terephthalic acid chloride was supplied over 40 minutes,
The dichloromethane was evaporated off. Although the obtained polyester carbonate did not contain fine powder, most of the polyester carbonate had a particle size of about 10 mm, the particle size was not uniform, and the shape of the granular material was various. These were unsuitable for pelletizing or forming.

Example 5 A granulated polyester carbonate composition was prepared in the same manner as in Example 1 except that 150 ppm of tris (nonylphenyl) phosphite was added to the polyester carbonate solution as a stabilizer in advance. Was manufactured.
Table 1 shows the particle size and bulk density of the obtained granules of the polyester carbonate composition. Substantially spherical granules of the polyester carbonate composition having a uniform particle size were obtained.

Example 6 Example 1 was repeated except that 150 ppm of tris (nonylphenyl) phosphite was added as a stabilizer to a suspension mixture of water, acetone and polyester carbonate powder in advance. In the same manner as in the above, granules of the polyester carbonate composition were produced. Table 1 shows the particle size and bulk density of the obtained granules of the polyester carbonate composition. Substantially spherical granules of the polyester carbonate composition having a uniform particle size were obtained.

[0039]

[Table 1]

Use Example 1 The polyester carbonate granules obtained in Example 1 were dried, and were injected into an injection molding machine (PS-20E2ASE manufactured by Nissei Plastics Industries, Ltd.).
Using a mold, a test piece having a thickness of 2 mm and a size of 80 × 40 mm was formed at 280 ° C. The yellowness (YI value) was measured by a colorimeter (manufactured by Suga Test Instruments) by a transmission measurement method.
It was 3.

Use Example 2 In the same manner as in Use Example 1, except that the granules of the polyester carbonate composition obtained in Example 5 were used instead of using the granules of polyester carbonate obtained in Example 1, In the same manner as in Example 2, a test piece having a thickness of 2 mm and a size of 80 × 40 mm was formed. The yellowness (YI value) was measured by a colorimeter (manufactured by Suga Test Instruments) by a transmission measurement method, and as a result, the YI value was as good as 2.0.

Use Example 3 The procedure of Use Example 1 was repeated, except that the granules of the polyester carbonate composition obtained in Example 6 were used instead of the granules of the polyester carbonate obtained in Example 1. In the same manner as in Example 1, a test piece having a thickness of 2 mm and a size of 80 × 40 mm was formed. When the yellowness (YI value) was measured by a colorimeter (manufactured by Suga Test Instruments) by a transmission measurement method, the YI value was as good as 1.9.

Use Example 4 Tris (nonylphenyl) phosphite 15 was added to the polyester carbonate obtained in Comparative Example 2 as a stabilizer.
After adding and mixing 0 ppm, drying and sieving, the particle size is 0.25 to 1
mm, and pelletized with a 20 mmφ extruder (Toyo Seiki twin screw extruder, extrusion temperature 270 ° C.). Next, the pellet was injected into an injection molding machine (PS20E2 manufactured by Nissei Plastic Industrial Co., Ltd.)
(ASE type), a test piece having a thickness of 2 mm and a size of 80 × 40 mm was formed at 280 ° C. When the yellowness (YI value) was measured by a transmission measurement method using a color difference meter (manufactured by Suga Test Instruments), the YI value was 5.9.

[0044]

According to the present invention, polyester of excellent quality in storage, bag collection, transportation, and handling during molding, containing substantially no fine powder, having a high bulk density and a large particle size. Granules of carbonate and its composition can be efficiently produced without using special equipment. In addition, the granules of the polyester carbonate and the composition obtained by the present invention can be directly molded without performing a treatment such as pelletization, and the heat history of the molded product can be reduced. And a polyester carbonate molded article excellent in the above. Therefore, the production method of the present invention is extremely useful industrially.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Akihiro Yamaguchi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Examiner, Mitsui Toatsu Chemicals Co., Ltd. Satoshi Morikawa (56) References JP-A-60-202127 (JP, A) JP-A-55-139423 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08J 3/14

Claims (6)

(57) [Claims] 1. An organic solvent solution of a polyester carbonate is supplied to a suspension mixture of water, a poor solvent for the polyester carbonate, and a polyester carbonate powder while stirring, while the organic solvent is being distilled off by evaporation. A method for producing a granular material of polyester carbonate, characterized by forming 2. The method according to claim 1, wherein the poor solvent is in a volume ratio with respect to the amount of water.
2. The method of claim 1, wherein the amount of the polyester carbonate powder is 0.05 to 1.5 times, and the amount of the polyester carbonate powder is 0.5 to 50% by weight of the amount of the polyester carbonate in the organic solvent solution. 3. An organic solvent is supplied to a suspension mixture of water, a poor solvent for polyester carbonate, and polyester carbonate powder while supplying an organic solvent solution of polyester carbonate with stirring in the presence of a stabilizer. A process for producing granules of a polyester carbonate composition comprising a polyester carbonate and at least one stabilizer, wherein the granules are formed by evaporation and distillation. 4. The method according to claim 1, wherein the poor solvent is in a volume ratio to the amount of water.
4. The method for producing a particulate polyester carbonate composition according to claim 3, wherein the amount is 0.05 to 1.5 times, and the amount of the polyester carbonate powder is 0.5 to 50% by weight of the amount of the polyester carbonate in the organic solvent solution. 5. The process for producing a particulate polyester carbonate composition according to claim 3, wherein the stabilizer is present in the suspension mixture. 6. The method for producing a particulate polyester carbonate composition according to claim 3, wherein the stabilizer is present in a solution of the polyester carbonate in an organic solvent.