JP3690622B2 - Granular polyarylate - Google Patents

Description

【００４１】
【表２】

【００４２】
【発明の効果】
本発明の粒状ポリアリレートは、活性末端を含むこと無く、蒿密度が高く、粒子径分布が狭く微粉も少ないのでハンドリングがよく、各種成形材料やアロイ等の原料、フィルム原料、バインダー樹脂の原料として使用することができる。また、本発明の方法によれば、粒子径分布の狭いポリアリレート粒子が連続的にかつ容易に得られるので工業的に極めて有利である。
【図面の簡単な説明】
【図１】図１は本発明を実施する装置の一例を示す概略図である。
【符号の説明】
１：造粒槽
２：撹拌機
３：導入管
４：補給水導入管
５：留出管
６：導出管
７：スラリーポンプ
８：湿式粉砕機
９：抜き出し管
10：循環スラリー導入管[0001]
BACKGROUND OF THE INVENTION
The present invention relates to granular polyarylate and a method for producing granular polyarylate from a polyarylate-containing solution.
[0002]
[Prior art]
Conventionally, various methods have been proposed for producing granular polyarylate from a polymer solution after interfacial polymerization. For example, the polyarylate solution after interfacial polymerization is added to a poor solvent that does not dissolve the polyarylate and is compatible with the solvent of the polymer under strong stirring, and a solvent precipitation method in which the polyarylate is precipitated. Solvent is distilled off by heating in an extruder or under reduced pressure, a kneader method for producing polyarylate powder, spray drying of spraying a solution of polyarylate to distill off the solvent, and spray drying producing fine powder. Law.
[0003]
In the production of the polyarylate powder by the solvent precipitation method, the poor solvent must be used about 20 times the volume of the methylene chloride solution, which is very expensive and requires strictly explosion-proof equipment. It was. Furthermore, the powder obtained by this method has a problem that the bulk density is low and handling is very bad. In the production of polyarylate powder by the kneader method, polyarylate is solidified in the form of block-like lumps, so that methylene chloride tends to remain inside, and this method requires a relatively high temperature. Therefore, there was a problem that the polyarylate was colored in some cases. Moreover, since the lump produced | generated has a large particle diameter, the process of grind | pulverizing a particle was further required.
[0004]
In the production of the polyarylate powder by the spray drying method, it is necessary to adjust the viscosity of the methylene chloride solution. For example, when a highly viscous solution is used, the polyarylate becomes a fiber and is difficult to obtain as a powder. . Moreover, even if it diluted to low viscosity and the powdery polyarylate was obtained, the particle diameter was set to 100 micrometers or less, and the handling was very bad.
[0005]
As a method for obtaining a powdered polyarylate that can solve these problems, JP-A-1-158042 gradually added an aqueous solution containing a dispersant to a polymer organic solvent solution. A method of producing a granular polymer having a uniform particle size of 100 microns or less by forming a W / O emulsion and then phase-inverting to an O / W emulsion and then distilling off the solvent is disclosed. According to this method, polymer particles having a uniform particle diameter can be obtained, but it is easy to form a W / O / W type multi-phase emulsion by going through the phase inversion process, and the emulsion is solidified as it is inside. There was a problem that polymer particles including an aqueous solution of the dispersant were formed, and the dispersant remaining inside became an impurity, which deteriorated the thermal stability and color tone of the polymer. Further, even if the dispersant does not remain inside, it is difficult to completely remove the surface dispersant.
[0006]
Japanese Patent Laid-Open No. 4-202220 discloses that polyarylate is polymerized at a high concentration so as to be precipitated as a gel or solid during the polymerization, and at this time, a dispersion stabilizer is added in advance to form particles. A method for producing a polyarylate powder is disclosed. According to this method, even if a polyarylate powder is obtained, the active acid chloride terminal is not deactivated by gelation during polymerization, and the unreacted monomer remains inside the polymer. There was a problem of deteriorating thermal stability.
[0007]
[Problems to be solved by the invention]
In view of such a situation, an object of the present invention is to provide a granular polyarylate that does not contain an active terminal, does not contain impurities such as a dispersant, has no fine powder, and is easy to handle, and such a granular poly An object of the present invention is to provide a method for producing granular polyarylate from which arylate can be easily obtained.
[0008]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have found that granular polyarylate having a specific particle size and particle size distribution has few fine powders and is excellent in powder flowability and handling. In addition, this granular polyarylate was added to a polyarylate-water system slurry having a specific slurry concentration maintained at a specific temperature, and thereafter, The present inventors obtained the knowledge that the slurry can be circulated while distilling off the solvent and wet grinding is performed in the circulation line, and the present invention has been achieved.
[0009]
That is, the gist of the present invention is that the average particle size is 1000 to 8000 μm, and the particle size distribution is the following Rosin-Ramler distribution formula (1).
R = 100exp (−bx ⁿ ) (1)
[In the formula, R is the cumulative residual weight fraction (%), x is the particle diameter (μm), b (1 / μm) and n (−) are constants. ]
Is applied, the index n in the formula (1) is 3 or more, which is a granular polyarylate.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
Next, the present invention will be described in detail.
In the present invention, polyarylate is an amorphous aromatic polyester substantially composed of a dihydric phenol component and an aromatic dicarboxylic acid component.
Preferred as the dihydric phenol component constituting the polyarylate are resorcinol, hydroquinone, 4,4′-biphenol, 2,2′-biphenol, bis (4-hydroxyphenyl) methane, bis (2-hydroxyphenyl) methane, Bis (4-hydroxylphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxy) Phenyl) diphenylmethane, 4,4 ′-(m-phenylenediisopropylidene) bisphenol, 4,4 ′-(p-phenylenediisopropylidene) bisphenol, 4,4 ′-(p-phenylenediisopropylidene) bis (2 , 6-xylenol), (3,5-dimethyl-4-hydroxyphenyl) methane, bis (3-methyl-4-hydroxyphenyl) methane, bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (3,5-dimethyl) -4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (3,5-dimethyl-4- Hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 4,4 '-(1-methylpentylidene) Sphenol, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) Propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane,
[0012]
2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 1,1,1,3,3,3-hexafluoro -2,2-bis (4-hydroxyphenyl) propane, 4,4'-dihydroxylbiphenyl, 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxybiphenyl, 4,4'-dihydroxy Benzophenone, 1,4-di (4-hydroxyphenyl) -p-menthane, 1,4-di (3-methyl-4-hydroxyphenyl) -p-menthane, 1,4-di (3,5-dimethyl- And terpene diphenols such as 4-hydroxyphenyl) -p-menthane.
[0013]
In addition, the dihydric phenol may be selected from ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, dodecanediol, neopentylglycol, cyclohexanediol, and 1,4- A dihydric alcohol such as dihydroxymethylcyclohexane may be substituted.
[0014]
Furthermore, examples of the aromatic dicarboxylic acid component constituting the polyarylate include terephthalic acid, isophthalic acid, orthophthalic acid, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl. Group, phthalic acid derivatives substituted with 1 or 2 alkyl groups such as t-butyl group, naphthalenedicarboxylic acid derivatives such as 1,5-naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid, 4,4′- Examples include dicarboxybiphenyl, diphenic acid, 4,4′-dicarboxydiphenyl ether, bis (p-carboxyphenyl) alkane, 4,4′-dicarboxydiphenyl sulfone, and one or more of these are mixed. May be used. Among these, terephthalic acid and isophthalic acid are preferable, and a mixture of terephthalic acid and isophthalic acid is particularly preferable.
[0015]
Further, in the polyarylate, in addition to the above-mentioned aromatic dicarboxylic acid, other aliphatic dicarboxylic acids may be substituted as long as the properties are not substantially impaired. Examples of such dicarboxylic acids include dicarboxymethylcyclohexane, cyclohexanedicarboxylic acid, adipic acid, sebacic acid, glutaric acid, dodecanedioic acid and the like.
[0016]
The terminal of polyarylate is phenol, o, m, p-cresol, dimethylphenol, o, m, p-ethylphenol, o, m, pn-propylphenol, o, m, p-isopropyl. Monohydric phenols such as phenol, o, m, p-n-butylphenol, o, m, p-isobutylphenol, o, m, p-sec-butylphenol, o, m, p-tert-butylphenol, methanol, ethanol, Monohydric alcohols such as n-propanol, isopropanol, butanol, pentanol, hexanol, dodecyl alcohol, stearyl alcohol, benzyl alcohol, phenethyl alcohol, acetic acid, propionic acid, octanoic acid, cyclohexanecarboxylic acid, benzoic acid, toluic acid , Phenylacetic acid, p-te t- butyl benzoic acid, it may be blocked with a monovalent carboxylic acid such as p- methoxyphenyl acetate.
[0017]
Furthermore, the polyarylate preferably has a polystyrene-equivalent number average molecular weight of 5,000 or more, more preferably 10,000 to 300,000 as measured by gel permeation chromatography. When the molecular weight is less than 5,000, the mechanical properties as a polymer are lowered, and when it exceeds 300,000, the workability at the time of melting tends to be lowered.
[0018]
The granular polyarylate of the present invention has an average particle diameter in the range of 1000 to 8000 μm. If the average particle size is less than 1000 μm, the hopper may block the particles, and if it exceeds 8000 μm, it is difficult to air-powder the powder. In addition, the value directly measured with the microscope was employ | adopted for the average particle diameter said by this invention.
[0019]
Furthermore, the particle size distribution of the granular polyarylate of the present invention is such that n is 3 or more, preferably 5 or more, when the Rosen-Rammel distribution formula represented by the formula (1) is applied.
R = 100exp (−bx ⁿ ) (1)
[In the formula, R is the cumulative residual weight fraction (%), x is the particle diameter (μm), b (1 / μm) and n (−) are constants. ]
The distribution formula of Rosin-Rammler is described in Yoshitoshi Oyama, Chemical Engineering II (15th edition, pages 7-8, Iwanami Zensho). In general, n is an index representing the breadth of the particle size distribution.
[0020]
In the formula (1), when n is less than 3, the particle size distribution is wide, so that the powder fluidity is deteriorated or the proportion of fine powder is increased. Therefore, it is easy to cause clogging with a hopper during molding or extrusion. Become. Further, b is an index representing the size of the particle, but is not particularly limited in the present invention because it is represented by the average particle diameter as described above.
[0021]
Further, the granular polyarylate of the present invention preferably has a bulk density of 0.2 or more. 0.3 or more is more preferable. If the bulk density is less than 0.2, the handling tends to deteriorate, which is not preferable. The bulk density can be measured by a known method. In the present invention, the bulk density when not tapping is employed.
[0022]
Next, the manufacturing method of the granular polyarylate of this invention is demonstrated.
In the method for producing a granular polyarylate of the present invention, the polyarylate solution to be applied is not particularly limited, such as a solution obtained by dissolving a polyarylate obtained by solution polymerization, melt polymerization, interfacial polymerization or the like in a solvent. It is preferable to use the polyarylate solution after the liquid-liquid separation after the polymerization because the operation can be continuously performed.
Further, when producing a granular polyarylate, a polyarylate having a deactivated terminal and having no acid halide group or the like is used.
[0023]
Interfacial polymerization is carried out in the presence of a polymerization catalyst by mixing an aromatic dicarboxylic acid halide dissolved in a solvent for dissolving a polymer with an alkaline aqueous solution in which the divalent phenol compound and optionally the above-described end-blocking agent are dissolved. And the above-mentioned aromatic dicarboxylic acid halide is reacted at 2 to 50 ° C. with stirring for 0.5 to 5 hours.
As the solvent for dissolving the polymer, known solvents such as methylene chloride, chloroform and 1,2-dichloroethane can be used, but considering the evaporation of the solvent described later, those having a boiling point as low as possible are preferable.
[0024]
The amount of the solvent during the interfacial polymerization varies depending on the molecular weight of the polymer, but it is usually preferred that the polymer concentration be 5 to 25% by weight. If the polymer concentration exceeds 25% by weight, the polymer may be gelled and precipitated during polymerization. It is difficult to deactivate active ends such as acid halide groups in the gel polymer, and such a polymer adversely affects the color tone at the time of molding.
The amount of alkaline water is usually in the range of 1 to 3 times the volume of methylene chloride. Examples of the alkali used during the reaction include sodium hydroxide and potassium hydroxide.
[0025]
Further polymerization catalysts include trimethylamine, triethylamine, tri-n-butylamine, tri-n-propylamine, tri-isopropylamine, trihexylamine, tridecylamine, N, N-dimethylcyclohexylamine, pyridine, quinoline, dimethylaniline. Tertiary amines such as trimethylbenzylammonium halide, tetramethylbenzylammonium halide, triethylbenzylammonium halide, quaternary ammonium salt such as tri-n-butylbenzylammonium halide, tetra-n-butylammonium halide, etc., trimethyl Benzylphosphonium halide, tetramethylbenzylphosphonium halide, triethylbenzylphosphonium halide, tri-n-butylbenzylphosphonium halide , Quaternary phosphonium salts such as tetra-n-butylphosphonium halide, triphenylbenzylphosphonium halide, tetraphenylphosphonium halide, 18-crown-6, 18-benzocrown-6, 18-dibenzocrown-6, 15-crown -5 and the like, and quaternary ammonium salts are particularly preferable from the viewpoint of polymerization rate and price.
[0026]
Next, after completion of interfacial polymerization, an acid is added to stop and neutralize the reaction, and the aqueous phase containing salts and unreacted monomers and the solution phase in which polyarylate is dissolved are used by a known method such as a decanter or a centrifuge. To separate. As the acid used at this time, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid and the like are preferable.
Further, the polymer solution phase is washed with water to remove residual salts and monomers, and subsequently used in the method for producing granular polyarylate of the present invention.
[0027]
Next, embodiments of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic view showing an example of an apparatus for carrying out the present invention. In FIG. 1, a polyarylate heated and circulated in a granulation tank 1 at a normal pressure or a reduced pressure at 40 to 100 ° C. The polyarylate solution obtained as described above is continuously or intermittently supplied into the aqueous slurry from the introduction pipe 3, stirred and mixed by the stirrer 2, and evaporated methylene chloride is distilled into the distillation pipe 5. While distilling off the solvent, the mixed polyarylate-water-based slurry is introduced from the outlet pipe 6 into the circulation line provided in the granulation tank 1. In the granulation tank 1, when the circulating polyarylate-water slurry and the polyarylate solution are stirred and mixed, they come into contact with each other, so the mixed polyarylate-water slurry introduced into the circulation line from the outlet pipe 6 is mixed. The coalesced particles passing through the wet pulverizer 8 are dispersed again. After wet pulverization with a wet pulverizer 8 in the circulation line, a part of the polyarylate-water slurry is extracted from the extraction tube 9 as product slurry, and the remainder is returned from the circulation slurry introduction tube 10 to the granulation tank 1. Circulate. A necessary amount of water is supplied into the granulation tank 1 from the makeup water introduction pipe 4, and the polyarylate-water slurry is circulated between the granulation tank 1 and the circulation line by the slurry pump 7.
[0028]
At this time, S = T / V × 100 defined by the following formula (2) (2)
[In the formula, S represents the slurry concentration (%), T represents the resin weight (kg) in the stirring tank, and V represents the amount of water (kg) in the stirring tank. ]
The polyarylate-water type slurry concentration S is set to 10 to 30%, preferably 15 to 25%. The slurry concentration is preferably kept as constant as possible. Usually, the slurry concentration is adjusted by adjusting the supply amount of the polyarylate solution and the supply amount of makeup water. If the slurry concentration is less than 10%, the resin tends to adhere to the granulation tank 1, and if it exceeds 30%, uniform stirring of the slurry becomes difficult.
[0029]
In the present invention, the granulating tank 1 is not particularly limited as long as the polyarylate solution can maintain a suspended state in water. As the shape of the stirring blade of the stirrer 2 used in the granulation tank 1, the slurry tends to rise as the solvent evaporates. Therefore, it is preferable to select a stirring type. For example, an inclined paddle type, an inclined turbine type, and a bull margin type can be appropriately selected from two to six blades. Although the stirring speed is not particularly required, it is usually in the range of 100 to 800 rpm although it depends on the shape of the stirring blade in order to uniformly disperse the slurry and prevent floating.
[0030]
The polyarylate concentration of the polyarylate solution that can be used in the present invention is preferably 5 to 25% by weight, and more preferably 10% to 25% by weight in consideration of the production rate.
The temperature of the granular polyarylate-water-based slurry for evaporating the solvent in the granulating tank 1 is 40 ° C. to 100 ° C., but usually 40 ° C. to 98 ° C., and the temperature, pressure and evaporation area, and polyarylate It is determined from the evaporation rate of the solvent determined by the boiling point of the solvent.
The pressure in the granulation tank 1 is normal pressure or reduced pressure. The pressure is also determined by the desired evaporation rate as described above.
The wet pulverizer 8 is not particularly limited as long as it can be continuously pulverized.
[0031]
According to the method as described above, a granular polyarylate having a small amount of fine powder and a particle size distribution can be produced. In this method, by supplying a polyarylate solution into the slurry and carrying out a dispersion treatment, it is considered that particles having a narrower particle size distribution than those obtained by simple wet pulverization treatment are generated because the dispersion and coalescence of primary particles are balanced. It is done.
[0032]
In the production method of the present invention, an additive such as an antioxidant such as a hindered phenol compound, a phosphorous acid compound, a hindered amine compound or a thioether compound, or a colorant is added to the polyarylate solution after polymerization. Thus, it is possible to obtain granular polyarylate particles containing various additives.
[0033]
【Example】
Next, the present invention will be described in detail with reference to examples and comparative examples. However, the present invention is not limited to these examples, and various modifications and applications are possible without departing from the spirit of the present invention. is there.
[0034]
Reference Example 1 (Preparation of polyarylate by interfacial polymerization)
In a reaction vessel equipped with a stirrer, 100 parts by weight of 2,2-bis (4-hydroxyphenyl) propane, 3.4 parts by weight of p-tert-butylphenol, 41.4 parts by weight of sodium hydroxide, trimethylbenzylammonium chloride 0 .6 parts by weight were charged and dissolved in 1350 parts by weight of water (aqueous phase). Separately, 93 parts by weight of a mixture of terephthalic acid chloride / isophthalic acid chloride = 1/1 was dissolved in 767 parts by weight of methylene chloride (organic phase). This organic phase was added to the previously prepared aqueous phase under strong stirring, and a polymerization reaction was carried out for 3 hours. Thereafter, 50 parts by weight of acetic acid was added to stop the reaction, the aqueous phase and the organic phase were separated, and washing with water was repeated until the organic phase became neutral to obtain a methylene chloride solution in which 17% by weight of polyarylate was dissolved. .
[0035]
Example 1
A granular polyarylate was produced using the apparatus shown in FIG.
First, 135 L of hot water at 50 ° C. was charged into the granulating tank 1 having an actual volume V = 250 L, and 22.95 kg of dried polyarylate particles were charged to prepare a slurry concentration S of 17%.
Next, the 17 wt% polyarylate methylene chloride solution obtained in Reference Example 1 was supplied from the introduction pipe 3 at a rate of 25.9 kg / hr, and hot water at 50 ° C. from the makeup water inlet 4 at a rate of 25.9 kg / hr. While supplying, the polyarylate-water slurry was introduced from the outlet pipe 6 into the circulation line, and circulated by the slurry pump 7 at Q = 100 L / min. Dispersion treatment was carried out with a wet pulverizer 8 (commercial name Gorator) in the circulation line. In the granulating tank 1, evaporated methylene chloride was extracted from the distillation pipe 5. At this time, the inside of the granulation tank 1 was maintained at 50 ° C. at normal pressure, and stirred at 200 rpm by a stirrer 2 having inclined paddle blades.
[0036]
With the start of the supply of the polyarylate methylene chloride solution, 30.3 kg / hr (0.43 L / min) of the polyarylate-water slurry (resin content 17% by weight) for the product is withdrawn from the withdrawal pipe 9, and the remainder is a circulating slurry introduction pipe 10 is introduced into the granulation tank 1 and circulated.
The extracted granular polyarylate-water slurry was filtered using a solid-liquid separator and dried to obtain granular polyarylate.
[0037]
Examples 2-4, Comparative Examples 1-3
In the same manner as in Example 1, the slurry concentration S was changed by changing the circulation flow rate Q, the initial amount of charged polyarylate particles, and the amount of water supplied, and granular polyarylate was produced. The conditions are shown in Table 1.
[0038]
Comparative Example 4
Using the polyarylate solution obtained in Reference Example 1, methylene chloride was distilled off using a continuous biaxial kneader manufactured by Satake Corporation. Instead of the polyarylate methylene chloride solution, the mass obtained was carried out in the same manner as in Example 1 except that it was supplied to the granulation tank at 4.4 kg / hr as in Example 1 as the resin component. Manufactured.
[0039]
Table 2 shows the results of Examples 1 to 4 and Comparative Examples 1 to 4.
The bulk density was measured without tapping, and the average particle size was measured using a microscope.
The cumulative residual weight fraction was measured by sieving using a JIS sieve, and n of the Rosin-Rammler equation was obtained from each measured value. Moreover, about the handling, the presence or absence of the fine powder was evaluated visually.
[0040]
[Table 1]

[0041]
[Table 2]

[0042]
【The invention's effect】
The granular polyarylate of the present invention does not contain an active terminal, has a high density, a small particle size distribution and a small amount of fine powder, so that it is easy to handle, as a raw material for various molding materials and alloys, a raw material for a film, and a raw material for a binder resin. Can be used. Moreover, according to the method of the present invention, polyarylate particles having a narrow particle size distribution can be obtained continuously and easily, which is extremely advantageous industrially.
[Brief description of the drawings]
FIG. 1 is a schematic diagram showing an example of an apparatus for carrying out the present invention.
[Explanation of symbols]
1: Granulating tank 2: Stirrer 3: Introducing pipe 4: Supplementary water introducing pipe 5: Distilling pipe 6: Outlet pipe 7: Slurry pump 8: Wet pulverizer 9: Extraction pipe
10: Circulating slurry introduction pipe

Claims (1)

The average particle size is 1000 to 8000 μm, and the particle size distribution is the following Rosin-Rammel distribution formula (1)
R = 100exp (−bx ⁿ ) (1)
[In the formula, R is the cumulative residual weight fraction (%), x is the particle size (μm), b (1 / μm) and n (−) are constants. ], The index n in Formula (1) is 3 or more, and the granular polyarylate characterized by the above-mentioned.

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