KR101557531B1 - Method for preparing polycondensation resin - Google Patents

Abstract

It is an object of the present invention to provide a means capable of efficiently producing a high-quality polycondensation resin without interfering with fusion of low-order condensates or scaling in a pipe of a low-order condensate. According to the present invention, there is provided a method of producing a polycondensation resin comprising a step of solid-phase polymerizing a lower condensate, comprising the steps of: producing a lower condensate; A step of obtaining a compression-molded body, and a step of solid-phase-polymerizing the granular compression-molded body.

Description

METHOD FOR PREPARING POLYCONDENSATION RESIN [0002]

The present invention relates to a method for producing a polycondensation resin.

BACKGROUND ART Polycondensation resins such as polyamides, polycarbonates, and polyesters have been used in various fields such as optical applications, automotive applications, electric and electronic applications, and various containers. As a method for producing such a polycondensation resin, there can be used a method of producing a low-condensation product of a low-molecular-weight polycondensation resin, crystallizing and / or pulverizing the resultant, and then subjecting it to solid-phase polymerization under vacuum or in an inert gas atmosphere, A method for producing a polycondensation resin having a molecular weight is well known.

For example, JPH1-158033 A discloses a technique of making a low molecular weight crystalline aromatic polycarbonate (lower condensation product) high molecular weight by solid phase polymerization.

The polymerization method described in JPH1-158033 A has an advantage that a high molecular weight aromatic polycarbonate having good color and formability can be obtained. However, there has been a problem that fusion of low-order condensates, low-order condensates cause scaling in the pipe, or adhere to a large amount on the inner wall of the device.

Accordingly, it is an object of the present invention to provide a means capable of efficiently producing a high-quality polycondensation resin without any trouble such as fusion of low-order condensates and scaling in a pipe of a low-order condensate.

The present inventors have conducted studies to solve the above problems. As a result, it was found that prior to the solid-phase polymerization, the lower-order condensate was subjected to compression molding, and the obtained solid-phase-polymerized mixture of the lower-order condensate was solid-phase polymerized to solve the above problems, thereby completing the present invention.

That is, the present invention relates to a process for producing a polycondensation resin comprising a step of solid-phase polymerizing a lower condensate, which comprises the steps of producing a lower condensate, a step of obtaining a granular compression-molded product by compression- And a step of solid-phase-polymerizing the granular compression-molded body.

According to the production method of the present invention, it is possible to efficiently produce a high-quality polycondensation resin without interfering with fusing of low-order condensates or scaling in a pipe of a low-order condensate.

Hereinafter, the manufacturing method of the present invention will be described in detail for each step.

≪ Process for producing a low-condensation product &

In this step, a polycondensation reaction is carried out to produce a lower condensate of the polycondensation resin.

The polycondensation resin is not particularly limited, but from the viewpoint of productivity on an industrial scale, it is preferably a polyamide, a polycarbonate or a polyester, more preferably a polyamide. Hereinafter, the monomers and catalysts used in the synthesis of polyamides, polycarbonates and polyesters will be described.

«Polyamide»

The polyamide is obtained by a polycondensation reaction of a dicarboxylic acid and a diamine.

Specific examples of the dicarboxylic acid include, for example, terephthalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, , Aliphatic dicarboxylic acids such as 2-dimethylglutaric acid, 3,3-diethylsuccinic acid, suberic acid, azelaic acid, sebacic acid, undecane diacid and dodecane diacid; Alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; Isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylene dioxydiacetic acid, 1,3-phenylene dioxydiacetic acid, Aromatic dicarboxylic acids such as fumaric acid, 4,4'-oxydibenzoic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid and 4,4'- . These dicarboxylic acids may be used alone or in combination of two or more. If necessary, a small amount of polyvalent carboxylic acid components such as trimellitic acid, trimesic acid, and pyromellitic acid may be used in combination.

Specific examples of the diamine include, for example, ethylene diamine, propanediamine, 1,4-butanediamine, 1,6-hexanediamine (hexamethylenediamine), 1,7- 1,1-undecanediamine, 1,12-dodecanediamine, 2-methyl-1,1-octanediamine, Hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 2,4,6-tetramethyl-1,6-hexanediamine, Aliphatic alkylene diamines such as 2-methyl-1,8-octanediamine, 5-methyl-1,9-nonanediamine, meta-xylylenediamine, and para-xylylenediamine; Cyclohexanediamine, cyclohexanediamine, methylcyclohexanediamine, isophoronediamine, bis (4-aminocyclohexyl) methane, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, Amine, tricyclodecane dimethanamine, and other alicyclic diamines; aromatic diamines such as p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylsulfone and 4,4'-diaminodiphenyl ether. These diamines may be used alone or in combination of two or more.

In this step, a phosphorus-based catalyst can be used in view of an increase in the polycondensation rate and prevention of deterioration in the polycondensation reaction. For example, hypophosphite, phosphate, hypophosphorous acid, phosphoric acid, phosphoric acid ester, polymethic acid, polyphosphoric acid, phosphine oxide, and phosphonium halogen compound are preferable, and hypophosphite, phosphate, Can be particularly preferably used. Examples of the hypophosphite include sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, magnesium hypophosphite, aluminum hypophosphite, vanadium hypophosphite, manganese hypophosphite, zinc hypophosphite, lead thiophosphate, nickel hypophosphite, Cobalt phosphite and ammonium hypophosphite are preferable, and sodium hypophosphite, potassium hypophosphite, calcium hypophosphite and magnesium hypophosphite are more preferable. As the phosphate, for example, sodium phosphate, potassium phosphate, potassium dihydrogenphosphate, calcium phosphate, vanadium phosphate, magnesium phosphate, manganese phosphate, lead phosphate, nickel phosphate, cobalt phosphate, ammonium phosphate and ammonium dihydrogenphosphate are preferable Do. Examples of the phosphoric acid ester include ethyl octadecyl phosphate and the like. Examples of the polymetalic acid include sodium trimetaphosphate, sodium pentametaphosphate, sodium hexametaphosphate, and polymetaphosphoric acid. The polyphosphoric acid includes, for example, sodium tetrapolyphosphate. The phosphine oxides include, for example, hexamethylphosphoramide.

The addition amount of the phosphorus-containing catalyst is preferably from 0.0001 to 5 parts by mass, more preferably from 0.001 to 1 part by mass, per 100 parts by mass of the raw material for injection. The addition timing may be any time up to the completion of the solid phase polymerization, but it is preferably between the injection of the raw material and the completion of the polycondensation of the low condensation product. It may be added many times. Furthermore, other phosphorus catalysts may be added in combination.

In the present step, the polycondensation reaction may be carried out in the presence of a terminal sealing agent. When the end sealant is used, the molecular weight of the lower condensate is more easily controlled and the melt stability of the lower condensate is improved. The terminal sealing agent is not particularly limited as long as it is a monofunctional compound having reactivity with a terminal amino group or a terminal carboxyl group in a lower order condensate. For example, an acid anhydride such as a monocarboxylic acid, a monoamine or phthalic anhydride, a monoisocyanate , Mono-acid halides, mono-esters, mono-alcohols and the like. Of these, a monocarboxylic acid or a monoamine can be preferably used as a terminal sealing agent in view of the reactivity and the stability of the end sealant, and in addition to the above-mentioned characteristics, a monocarboxylic acid is more preferred Lt; / RTI >

The monocarboxylic acid preferably used as a terminal sealing agent is not particularly limited as long as it is a monocarboxylic acid having reactivity with an amino group and includes, for example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, Aliphatic monocarboxylic acids such as acetic acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid; Alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; Aromatic monocarboxylic acids such as benzoic acid, toluic acid,? -Naphthalenecarboxylic acid,? -Naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid, or any mixture thereof. Among them, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid and the like are preferable from the viewpoints of reactivity, stability of terminal sealing, Particularly preferred is an acid, benzoic acid.

The monoamine preferably used as the end sealant is not particularly limited as long as it is a monoamine having reactivity with a carboxyl group. Examples of the monoamine include methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decyl Aliphatic monoamines such as amine, stearylamine, dimethylamine, diethylamine, dipropylamine and dibutylamine; Alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; Aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine, or any mixture thereof. Among them, butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine and aniline are particularly preferable in view of reactivity, boiling point, stability of end sealing, and price.

The amount of the end sealant used when preparing the low-order condensate of polyamide may vary depending on the reactivity, boiling point, reaction apparatus, reaction conditions, etc. of the end sealant used, It is preferable to use it in the range of 15 mol%.

«Polycarbonate»

The polycarbonate is not particularly limited, and polycarbonate having various structural units may be mentioned. Usually, an aromatic polycarbonate produced by the reaction of a dihydric phenol and a carbonate precursor can be used.

Examples of the divalent phenol include 4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) Bis (3,5-dimethylphenyl) propane (bisphenol A), 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2- ) Propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) ether, bis 4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ketone, hydroquinone, resorcin, catechol and the like.

Other examples of the dihydric phenol include hydroquinone and resorcinol. These dihydric phenols may be used alone or in combination of two or more.

Of these divalent phenols, bis (hydroxyphenyl) alkanes are preferred, and 2,2-bis (4-hydroxyphenyl) propane as the main raw material is particularly preferred.

Examples of the carbonate precursor include a carbonyl halide, a carbonyl ester, a haloformate, and the like. Specific examples thereof include phosgene, dihaloformate of dihydric phenol, diphenyl carbonate, dimethyl carbonate, diethyl carbonate and the like.

In addition, the polycarbonate may have a branched structure in addition to the linear molecular structure of the polymer chain. Branching agents for introducing such branched structure include 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ', α "-tris (4-hydroxyphenyl) (O-cresol), and the like can be used. As the molecular weight regulator, phenol, pt-butyl phenol, pt-octyl phenol, p-cumyl phenol .

In the present step, the reaction is accelerated by extracting the aromatic monohydroxy compound and / or diaryl carbonate, which is produced as a by-product of the polycondensation reaction, out of the system. As a method therefor, a method of carrying out the reaction under reduced pressure, a method of introducing an inert gas to remove the condensed by-products accompanied by these gases, and a method of using them in combination are preferably used.

In this step, it is possible to proceed at a sufficient rate without adding a catalyst, but a polymerization catalyst can be used for the purpose of further increasing the reaction rate.

Such polymerization catalysts are not particularly limited as long as they are polycondensation catalysts used in this field, but include hydroxides of alkali metals and alkaline earth metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide; Alkali metal salts, alkaline earth metal salts and quaternary ammonium salts of hydrides of boron or aluminum such as lithium aluminum hydride, sodium borohydride, and tetramethyl ammonium borohydride; Hydrogenated compounds of alkali metals and alkaline earth metals such as lithium hydride, sodium hydride and calcium hydride; Alkoxides of alkali metals and alkaline earth metals such as lithium methoxide, sodium ethoxide and calcium methoxide; Aryloxides of alkali metals and alkaline earth metals such as lithium phenoxide, sodium phenoxide, magnesium phenoxide, LiO-Ar-OLi and NaO-Ar-ONa (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 compounds such as zinc oxide, zinc acetate and zinc phenoxide; Compounds of boron such as boron oxide, boric acid, sodium borate, trimethyl borate, tributyl borate, triphenyl borate and the like; Silicon compounds such as silicon oxide, sodium silicate, tetraalkyl silicon, tetraaryl silicon and diphenyl ethyl ethoxy silicon; Germanium compounds such as germanium oxide, germanium tetrachloride, germanium ethoxide, and germanium phenoxide; Tin compounds such as tin compounds and organotin compounds bonded with alkoxy groups or aryloxy groups such as tin oxide, dialkyltin oxide, dialkyltin carboxylate, tin acetate and ethyl tin tributoxide; Lead compounds such as lead oxide, lead acetate, lead carbonate, basic carbonates, alkoxides or aryloxides of lead and organic lead; Onium compounds such as quaternary ammonium salts, quaternary phosphonium salts and quaternary arsenonium salts; Antimony compounds such as antimony oxide and antimony acetate; Manganese compounds such as manganese acetate, manganese carbonate, and manganese borate; Compounds of titanium such as titanium oxide, alkoxide of titanium or aryl oxide; And zirconium compounds such as zirconium acetate, zirconium oxide, alkoxide or aryloxide of zirconium, and zirconium acetylacetone. These polymerization catalysts may be used alone or in combination of two or more.

When the lower condensate of the polycarbonate is in a molten state or in a solution state, it can be obtained in the form of powder, granule or the like by treating with a crystallization solvent.

There is no particular limitation on the method of treating with the crystallization solvent, but a method of crystallizing a low-order condensate of a polycarbonate in the crystallization solvent to crystallize it into a slurry state, or a method of crystallizing a low- A method of crystallization while mixing and kneading is preferable. When the slurry is crystallized in a slurry state, a device having a high-speed stirring blade such as a waring blender or a device provided with a swirl pump with a cutter can be used. In the case of crystallization using a mixer or a kneader, a device commonly referred to as a mixer or a kneader (powder industry manual, Japan Daily Newspaper, equipment described on pages 644 to 648, etc.) may be used. , A ribbon blender, a shovel mixer, a pug mixer, a Henschel mixer, a blender, and a twin-screw kneader.

Examples of the crystallization solvent include, for example, esters such as ethyl acetate; Ethers such as diethylether; And ketones such as acetone and methyl ethyl ketone. Also, depending on the crystallization temperature conditions, hydrocarbons such as hexane and octane; Cyclic hydrocarbons such as cyclohexane and the like can also be used as the crystallization solvent. Of these, acetone is preferable because a low-order condensate of polycarbonate having a large specific surface area can be produced.

«Polyester»

The polyester usable in the present invention is not particularly limited and includes, for example, a polyester obtained by reacting an acyl compound of a compound having a phenolic hydroxyl group with an aromatic carboxylic acid.

The acyl group used in the present invention may be an acyl group obtained by acylating an aromatic diol and / or a phenolic hydroxyl group of an aromatic hydroxycarboxylic acid with a fatty acid anhydride, and the aromatic carboxylic acid may be an aromatic dicarboxylic acid and / or an aromatic hydroxycarboxylic acid do.

The compound having a phenolic hydroxyl group may have one phenolic hydroxyl group or two or more phenolic hydroxyl groups, but it is preferable to have one or two phenolic hydroxyl groups from the viewpoint of reactivity. When the compound having a phenolic hydroxyl group has only one phenolic hydroxyl group, it is preferable that the compound having one phenolic hydroxyl group also has one carboxyl group. As the compound having a phenolic hydroxyl group, an aromatic diol and an aromatic hydroxycarboxylic acid are particularly preferable.

The aromatic diols include, for example, 4,4'-dihydroxybiphenyl (4,4'-biphenol), hydroquinone, resorcin, methylhydroquinone, chlorohydroquinone, acetoxyhydroquinone, Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2, 7-dihydroxynaphthalene, 1, (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2- (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane, Bis- (4-hydroxy-3,5-dimethylphenyl) methane, bis- (4-hydroxy-3,5-dichlorophenyl) methane, bis- Phenyl) methane, bis- (4-hydroxy-3-methylphenyl) methane, Bis (4-hydroxyphenyl) ethane (4,4'-dihydroxydiphenyl) methane, bis- (4-hydroxyphenyl) Bis (4- hydroxyphenyl) ketone, bis- (4-hydroxy-3,5-dimethylphenyl) ketone, bis- , Bis- (4-hydroxyphenyl) sulfide, and bis- (4-hydroxyphenyl) sulfone. These may be used alone or in combination of two or more.

Of these, 4,4'-dihydroxybiphenyl, hydroquinone, resorcin, 2,6-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane or bis- Phenyl) sulfone is preferably used because it is readily available.

Aromatic hydroxycarboxylic acids include, for example, parahydroxybenzoic acid, metahydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, 2-hydroxy-3-naphthoic acid, 1- 4-naphthoic acid, 4-hydroxy-4'-carboxydiphenyl ether, 2,6-dichloro-parahydroxybenzoic acid, 2-chloro-parahydroxybenzoic acid, 2,6- Parahydroxybenzoic acid, and 4-hydroxy-4'-biphenylcarboxylic acid. These may be used alone or in combination of two or more.

Among them, parahydroxybenzoic acid and 2-hydroxy-6-naphthoic acid are preferably used since they are easily available.

Acylation of the compound having a phenolic hydroxyl group as described above gives an acylate. The acyl group includes, but is not limited to, acetylates.

Acylation can be obtained by reacting an acylating agent with a compound having a phenolic hydroxyl group. As acylating agents, acyl anhydrides or halides are representative. The acyl group in the acylating agent may be derived from aliphatic carboxylic acids such as alkanoic acids (acetic acid, propionic acid, butyric acid, pivalic acid, etc.), higher alkanoic acids such as palmitic acid, aromatic carboxylic acids such as benzoic acid, have.

As the acylating agent, a fatty acid anhydride is particularly preferable. Examples of the fatty acid anhydride include acetic anhydride, anhydrous propionic acid, anhydrous butyric acid, anhydrous isobutyric acid, anhydride valeric acid, anhydrous pivalic acid, anhydrous 2-ethylhexanoic acid, Monochloroacetic acid, anhydrous dichloroacetic acid, anhydrous trichloroacetic acid, anhydrous monobromoacetic acid, anhydrous dibromoacetic acid, anhydrous tribromoacetic acid, anhydrous monofluoroacetic acid, anhydrous difluoroacetic acid, anhydrous triflu or o acetic acid, Tartaric acid, maleic anhydride, succinic anhydride and anhydrous? -Bromopropionic acid. These may be used in combination of two or more kinds. Acetic anhydride, propionic anhydride, butyric anhydride, and isobutyric anhydride are preferably used from the viewpoint of cost and handling property, and acetic anhydride is more preferably used.

The amount of the fatty acid anhydride to be used for the phenolic hydroxyl group in the aromatic diol and / or the aromatic hydroxycarboxylic acid is preferably 1.0 to 1.2 times equivalent. When the amount of the fatty acid anhydride to be used is less than 1.0 times the equivalent amount of the phenolic hydroxyl group, the equilibrium in the acylation reaction shifts to the fatty acid anhydride, and when the polyester is polymerized, the unreacted aromatic diol or aromatic dicarboxylic acid So that the reaction system tends to be closed. On the other hand, when the amount is more than 1.2 times the equivalent amount, the resulting liquid crystalline polyester tends to be markedly colored.

The acylation is preferably carried out at 130 to 180 ° C for 15 minutes to 20 hours, more preferably at 140 to 160 ° C for 30 minutes to 5 hours.

In the present invention, the reagent which reacts with the aforementioned acylate is an aromatic carboxylic acid. The aromatic carboxylic acid may be one having one carboxyl group or two or more carboxyl groups, but it is preferable to have one or two carboxyl groups from the viewpoint of obtaining good reactivity. When the aromatic carboxylic acid has only one carboxyl group, it is preferable that the aromatic carboxylic acid has another hydroxyl group. As the aromatic carboxylic acid, an aromatic dicarboxylic acid or an aromatic hydroxycarboxylic acid is particularly preferable.

Examples of the aromatic dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, methylterephthalic acid, 4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, diphenylketone-4,4'-dicarboxylic acid, 2,2'-diphenylpropane- Carboxylic acid. These may be used alone or in combination of two or more.

Of these, terephthalic acid, isophthalic acid or 2,6-naphthalenedicarboxylic acid is preferably used because it is easily available as an aromatic dicarboxylic acid. In the present embodiment, it is preferable that at least 5 mol% or more of the aromatic hydroxycarboxylic acid is contained in the total amount of the acylate and aromatic carboxylic acid of the compound having a phenolic hydroxyl group from the viewpoint of balancing both the heat resistance and the impact resistance well desirable.

In this step, an acylate of a compound having a phenolic hydroxyl group is subjected to an ester exchange reaction with an aromatic carboxylic acid.

When the acylated acylated fatty acid anhydride is reacted with an aromatic carboxylic acid in an ester exchange reaction, the equilibrium is shifted so as to favor the production of the product, so that the by-product fatty acid and the unreacted fatty acid anhydride are evaporated during the reaction and distilled out . In this case, a part of the fatty acid to be discharged may be refluxed and returned to the reactor so that the evaporated or sublimed raw material accompanying with the fatty acid may be condensed or reversed to return to the reactor. In this way, it is possible, for example, to return the precipitated carboxylic acid to the reactor together with the fatty acid.

The above-described polyesters may be used alone or in combination of two or more.

The lower-order condensate is synthesized by introducing the monomer or the like into, for example, a commonly used pressure polymerization vessel and performing polycondensation reaction in an aqueous solvent under stirring conditions.

An aqueous solvent is a water-based solvent. Examples of the solvent that can be used in addition to water include methanol, ethanol, and the like.

The synthesis of the lower condensate of the present step is usually carried out by elevating the temperature and increasing the pressure under stirring conditions. The polymerization temperature is controlled after the injection of the raw material. The polymerization pressure is controlled in accordance with the progress of the polymerization.

The reaction temperature and the reaction time in this step are appropriately set according to the resin to be produced and are not particularly limited. However, usually, the reaction temperature is preferably 170 to 400 ° C, and the reaction time is preferably 0.5 to 10 hours.

In the present step, the polycondensation reaction may be carried out in a batch manner or in a continuous manner. In addition, from the viewpoints of preventing the adhesion of the lower condensate to the reaction vessel and uniform progress of the polycondensation reaction, production of the low-condensation product granulated product having a particle diameter, and the like, a polycondensation reaction for producing a lower condensation product is carried out with stirring .

Next, the low-order condensate produced as described above is taken out of the reaction vessel.

When the lower condensate is a crystalline component, extraction of the lower condensate from the reaction vessel is carried out by taking out the lower condensate from the reaction vessel, preferably under an inert gas atmosphere, at a pressure not higher than atmospheric pressure.

From the viewpoint of preventing oxidation deterioration of the lower condensate, the inert gas atmosphere preferably has an oxygen concentration of 1% by volume or less.

The discharge speed of the low-order condensate from the reaction vessel when the low-order condensate is a crystalline powder can be appropriately controlled in accordance with the scale of the reaction vessel, the amount of the contents in the reaction vessel, the temperature, the size of the outlet, .

≪ Step of obtaining a granular compression-molded product by compression-molding low-order condensate &

In this step, the low-order condensate produced as described above is compression-molded to obtain a granular compression-molded body.

The term "granular compression-molded body" means that the low-order condensate is compression-molded into a granular body. The shapes of the granular compression-molded bodies may be uniform in a uniform shape or may not be uniform. There is no particular limitation on the shape, and concrete examples include a pellet shape, a spherical shape, a columnar shape, a disk shape, a polygonal shape, a cube shape, a rectangular parallelepiped shape, a cylindrical shape and a lens shape.

The particle diameter of the granular compression molded product obtained in this step is preferably 0.5 to 30 mm, more preferably 1.0 to 15 mm, still more preferably 1.5 to 10 mm. Within this range, the following process troubles can be solved, and solid-state polymerization can be efficiently performed. The particle diameter is measured by measuring the short diameter (short diameter) and the long diameter of the granular compression-molded body with a vernier caliper and adopting the average value.

Specifically, the process trouble caused by the fine powder is closure, abrasion, segregation, adhesion / aggregation, dust scattering, flushing, and the like. Clogging which is likely to occur due to process trouble caused by fine powder is not sufficient for supplying, discharging, storing, transporting, abrasion for transportation, grinding, segregation for storage, attachment and cohesion for transportation, supply / discharge, Flushing occurs at the time of supply and discharge. In addition, particularly when a fine powder is accompanied, a fine powder is blown off by an inert gas in a production process by solid phase polymerization, so that the residence time of the fine powder is prolonged and adversely affects the hue and composition of the polycondensation resin. Further, if the amount of the fine powder is large, the fine powder may act as an adhesive during the solid phase polymerization, and adhesion of the lower condensates to each other and adhesion of the reaction vessel for solid phase polymerization to the lower condensation product may occur. The granular compression-molded body obtained by this step can solve the above-mentioned process trouble.

The obtained low-order condensate may be pulverized or subdivided into granules having a particle size of 0.01 to 5 mm or less such that granular compression-molded bodies can be easily formed before compression molding. As a specific method for carrying out the pulverization, for example, there can be mentioned a method of pulverizing using a pulverizer such as a hammer crusher which is generally used. As the method of pulverizing the pulverizer, for example, there are a method of performing a shearing process in a molten state, A method of cutting the sheet longitudinally and transversely by a similar method of forming the sheet into a sheet shape at the same time and then pelletizing the sheet.

The method for obtaining the granular compression-molded product in this step is not particularly limited as long as the desired properties are maintained by compression-molding the low-order condensate and the polymer is not destroyed in the subsequent solid-phase polymerization step. Specifically, a method used in a general granulation process is preferably used, and extrusion granulation, compression granulation, and the like are more preferable. Examples of the extrusion assembly method include a screw type, a roll type cylindrical die type, and a roll type disk type. Examples of the compression assembly method include a compression roll method, a briquetting method, and a pressing method. More specifically, it is preferable to perform compression molding using a compression molding machine selected from at least one of the group consisting of a tablet molding machine, a compression roll machine, and a briquetting machine. More specific examples of the apparatus used in the present process include, for example, gear pelletizer GCS, briquetting machine & compacting machine MS (manufactured by Hosokawa Bee PEX Co., Ltd.), and the like.

The compression pressure at the time of compression molding is not particularly limited, but is preferably 10 to 800 MPa. In this range, there is almost no possibility that a fine powder is accompanied by a large amount during transportation, supply and discharge, and the granular compression-molded body is not melted by the heat of friction between the compression molding machine and the granular compression- have. The compression pressure is more preferably 50 to 500 MPa.

The temperature at the time of compression molding is not particularly limited.

The compression molding may be carried out after the low-order condensate is taken out from the reaction vessel as it is or after the low-order condensate taken out from the reaction vessel is dried or after the low-order condensate taken out from the reaction vessel is once stored .

≪ Process of solid-phase polymerizing the granular compression-molded article &

In this step, a high-polymerization degree by solid-state polymerization is carried out by using the granular compression-molded body of the low-order condensate obtained above to produce a polycondensation resin. When the polymerization degree is made higher by solid phase polymerization, a polycondensation resin with less thermal deterioration can be obtained.

The polymerization method and conditions for the solid phase polymerization of the lower condensate are not particularly limited, and any method or condition capable of achieving high polymerization while maintaining the solid state without causing fusion, aggregation, deterioration, or the like of the low- .

However, in order to prevent oxidation deterioration of the lower condensate and the resulting polycondensation resin, it is preferable to carry out solid phase polymerization in an inert gas atmosphere such as helium gas, argon gas, nitrogen gas or carbon dioxide gas or under reduced pressure.

The temperature for the solid phase polymerization is not particularly limited, but the maximum reaction temperature is preferably 170 to 350 占 폚. The maximum reaction temperature is not necessarily the end of the solid-state polymerization and may be reached at any point in time until the end of the solid-state polymerization.

The solid phase polymerization apparatus used in the present step is not particularly limited, and any known apparatus can be used. Specific examples of the solid phase polymerization apparatus include solid phase polymerization apparatuses such as a single-shaft disc, a kneader, a two-axis paddle type, a vertical type column type apparatus, a vertical type column type apparatus, a rotary drum type, And the like. From the viewpoint of the cost of the apparatus and the structure, it is preferable to use a simple vertical type of column type apparatus or a vertical type of column type apparatus. In the present invention, when a powder is used, it is difficult to apply it to continuous production under reduced pressure because it has problems such as adhesion to a wall of a device and clogging of piping. In the present invention, It is possible to use it as a device for solid phase polymerization. The use of such a vertical type of column type apparatus or a vertical type of column type apparatus is also preferable from the viewpoint of industrial productivity or quality such as reduction of residual monomers and oligomers.

The reaction time of the solid phase polymerization is not particularly limited, but is usually preferably 1 hour to 20 hours. During the solid phase polymerization reaction, the lower condensation product may be mechanically stirred or stirred by a gas stream.

In the present invention, various fiber materials such as glass fiber and carbon fiber, an inorganic powder-type filler, an organic powder-type filler Additives such as colorants, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, flame retardants, crystallization accelerators, plasticizers and lubricants, and other polymers may be added.

The polycondensation resin obtained by the production method of the present invention is excellent in performance such as heat resistance, mechanical performance, low water absorption property and chemical resistance, and can be produced by using the polycondensation resin alone or, if necessary, Various molding methods and spinning methods conventionally used for the polycondensation resin in the form of a composition with other polymers may be used such as molding methods such as injection molding, blow molding, extrusion molding, compression molding, drawing, vacuum molding, And can be molded into various molded products, fibers, and the like. Molded products and fibers obtained therefrom can be effectively used for various uses such as industrial plastics such as engineering plastics, electronic and electric parts, automobile parts, and office parts, industrial materials, and home appliances.

[ Example ]

The present invention will be described in more detail with reference to the following examples and comparative examples. However, the technical scope of the present invention is not limited to the following embodiments. The logarithmic viscosity and melting point were measured by the following methods.

≪ Measurement of logarithmic viscosity IV (dl / g)

The polyamide was prepared by using concentrated sulfuric acid as a solvent at 25 ° C, dichloromethane as a solvent at 20 ° C for polycarbonate, and pentafluorophenol as a solvent at 60 ° C, Respectively.

≪ Measurement of melting point Tm (占 폚)

Measurement was made at a temperature raising rate of 10 占 폚 / min under a nitrogen atmosphere at a flow rate of 10 ml / min using DSC manufactured by Seiko Instruments Inc., and the endothermic peak temperature due to melting was measured as a melting point.

(Example 1: Production Example of Polyamide)

(0.5124 mol) of terephthalic acid, 88.2 g (0.512 mol) of 1,10-decanedamine, 0.75 g (0.012 mol, 2 mol% with respect to dicarboxylic acid) of acetic acid as a terminal sealing agent, and sodium hypophosphite (0.1 part by mass with respect to the feedstock) and 115 g of water (40 percent by mass with respect to the feedstock) were placed in a flask equipped with a reflux condenser, a pressure regulating valve, an internal window, And the mixture was poured into an autoclave reactor having an internal volume of 1 liter to carry out nitrogen substitution. The temperature was raised to 180 캜 over 0.5 hours while stirring, and maintained for 0.5 hours to confirm that the content became a homogeneous solution. Thereafter, the internal temperature was raised to 245 DEG C over 1 hour, and the temperature was maintained. After the internal pressure reached 3.0 MPa, the reaction was continued for 2 hours while distilling off water to maintain the same pressure.

After the lapse of a predetermined reaction time, the low-condensation product produced while maintaining the temperature of the reaction vessel and the water content (32 mass%) in the reaction system was discharged from the bottom discharge valve in a cyclone vessel . At this time, the diameter of the discharge valve was 3 mm, and the discharge required about 10 seconds. The oxygen concentration of the discharged vessel was 0.1 vol%, and a white, powdery lower condensation product was obtained.

The IV of the obtained low-order condensate of polyamide was 0.16 dl / g, and Tm was 310 ° C.

Subsequently, the powdery low-order condensate was subjected to a pressure of 300 MPa using a tablet molding machine to produce a granular compact of 4 mm in diameter in the low-order condensate. 40 g of the granulated and compression molded product was poured into a 500 ml rotary evaporator made of glass and subjected to solid state polymerization at a revolution speed of 30 rpm and a vacuum of 0.13 kPa at 250 캜 for 3 hours.

The IV of the obtained polyamide was 0.85 dl / g. On the wall surface of the reactor, adhesion of the powder was hardly observed, and there was no stickiness due to fusion of the resin. Also, adhesion of the powder to the vacuum vent line was not confirmed.

(Comparative Example 1)

A polyamide was obtained in the same manner as in Example 1 except that the granulated product in the form of powder was solid-phase-polymerized directly without preparing a granular compression-molded product.

The IV of the obtained polyamide was 0.75 dl / g. Further, on the wall surface of the reactor, adhesion of the powder was hardly observed, adhesion of the powder to the vacuum vent line was confirmed although there was no stickiness due to fusion of the resin.

(Example 2: Production example of polyamide)

A polyamide was obtained in the same manner as in Example 1 except that 100 g of the granulated and compression molded product was poured into a glass cylinder having a diameter of 5 cm and a length of 25 cm and allowed to stand and polymerized at 250 캜 for 3 hours under a vacuum of 0.13 3 for 3 hours. .

The IV of the obtained polyamide was 0.80 dl / g. Further, no adhesion of the powder was observed on the wall surface of the reactor, and there was no stickiness due to fusion of the resin. Further, adhesion of the powder to the vacuum vent line was not confirmed.

(Comparative Example 2)

A polyamide was obtained in the same manner as in Example 2 except that the granular phase was directly subjected to solid phase polymerization without preparing a granular compression molded product.

The IV of the obtained polyamide was 0.65 dl / g. In addition, adhesion of the powder was slightly observed on the wall surface of the reactor, and adhesion of the powder to the vacuum vent line was confirmed, although there was no stickiness due to fusion of the resin.

(Example 3: Production example of polyamide)

(0.5124 mol) of terephthalic acid, 88.2 g (0.512 mol) of 1,10-decanedamine, 0.75 g (0.012 mol, 2 mol% with respect to dicarboxylic acid) of acetic acid as a terminal sealing agent, and sodium hypophosphite 0.125 g of hydrate (0.1 part by mass based on the feedstock) and 115 g of water (40% by mass based on the feedstock) were charged into a 1 liter autoclave equipped with a distributor, pressure regulating valve, Clave reaction tank, and nitrogen substitution was carried out. The temperature was raised to 180 캜 over 0.5 hours while stirring, and maintained for 0.5 hours to confirm that the content became a homogeneous solution. Thereafter, the internal temperature was elevated to 220 DEG C over 1 hour and maintained. After the internal pressure reached 2.2 MPa, the reaction was continued for 2 hours while distilling off water to maintain the same pressure.

After the lapse of a predetermined reaction time, the lower condensate produced while maintaining the temperature of the reaction vessel and the water content (32 mass%) in the reaction system was discharged from the bottom discharge valve in a cyclone vessel . At this time, the diameter of the discharge valve was 3 mm, and the discharge required about 10 seconds. The oxygen concentration of the discharged vessel was 0.1 vol%, and a white, powdery lower condensation product was obtained.

The IV of the obtained low-order condensate of polyamide was 0.06 dl / g, and Tm was 310 ° C.

Subsequently, the powdery low-order condensate was subjected to a pressure of 300 MPa using a tablet molding machine to produce a granular compression-molded body having a diameter of 4 mm of the low-order condensate.

100 g of the granulated and compression molded product was poured into a glass cylinder having a diameter of 5 cm and a length of 25 cm, allowed to stand, and subjected to solid state polymerization at 250 DEG C under a vacuum of 0.13 kPa for 3 hours.

The IV of the obtained polyamide was 0.78 dl / g. Further, no adhesion of the powder was observed on the wall surface of the reactor, and there was no stickiness due to fusion of the resin. Further, adhesion of the powder to the vacuum vent line was not confirmed.

(Comparative Example 3)

A polyamide was obtained in the same manner as in Example 3 except that the granular phase was subjected to solid phase polymerization directly without producing a granular compression molded product.

The IV of the obtained polyamide was 0.61 dl / g. Further, adhesion of the powder was observed on the wall surface of the reactor, and there was a sticky period due to fusion of the resin. Furthermore, adhesion of the powder to the vacuum vent line was also confirmed.

(Example 4: Production example of polycarbonate)

228 g (1 mol) of 2,2-bis (4-hydroxyphenyl) propane, 223 g (1.04 mol) of diphenyl carbonate and 223 g (1.04 mol) of potassium hydroxide were added to a stirring vessel of a polymerization reactor equipped with a stirrer, a condenser, And the reaction was carried out at a temperature of 240 ° C and a reaction pressure of 1.3 kPa (10 torr) for 2 hours while allowing phenol as a reaction by-product to flow out from the stirring tank. After cooling to room temperature (25 캜), the lower condensate of the polycarbonate was taken out of the stirring tank. The mixture was pulverized, stirred in an acetone solvent, crystallized, filtered, and further dried under reduced pressure at 100 ° C to obtain a low-condensation product of a polycarbonate in powder form.

The IV of the resulting polycarbonate lower condensate was 0.16 dl / g, and Tm was 226 deg.

Subsequently, the powdery low-order condensate was subjected to a pressure of 300 MPa using a tablet molding machine to produce a granular compact of a polycarbonate lower-order condensate having a diameter of 4 mm.

40 g of the granulated and compression molded product was poured into a 500 ml rotary evaporator made of glass and subjected to solid phase polymerization under a vacuum of 0.13 kPa at 220 캜 and 30 rpm for 3 hours.

The IV of the obtained polycarbonate was 0.56 dl / g. Further, on the wall surface of the reactor, the adhesion of the powder was scarcely observed, and there was no stickiness due to fusion of the resin. Further, adhesion of the powder to the vacuum vent line was not confirmed.

(Comparative Example 4)

A polycarbonate was obtained in the same manner as in Example 4 except that the granular phase was subjected to solid phase polymerization directly without producing a granular compression molded product.

The IV of the obtained polycarbonate was 0.55 dl / g. In addition, adhesion of the powder was observed on the wall surface of the reactor, and stickiness was caused by fusion of the resin. Also, adhesion of the powder to the vacuum vent line was confirmed.

(Example 5: Production example of polycarbonate)

Polycarbonate was obtained in the same manner as in Example 4 except that 100 g of the granulated and compression molded product was poured into a glass cylinder having a diameter of 5 cm and a length of 25 cm and allowed to stand and subjected to solid phase polymerization at 220 캜 for 3 hours under a vacuum of 0.13 3 Respectively.

The IV of the obtained polycarbonate was 0.53 dl / g. No adhesion of the powder was observed on the wall surface of the reactor, and there was no stickiness due to fusion of the resin. Also, adhesion of the powder to the vacuum vent line was not confirmed.

(Comparative Example 5)

A polycarbonate was obtained in the same manner as in Example 5 except that the granular phase was solid-phase polymerized directly without producing a granular compression-molded body.

The IV of the obtained polycarbonate was 0.48 dl / g. In addition, adhesion of the powder was observed on the wall surface of the reactor, and stickiness was caused by fusion of the resin. Also, adhesion of the powder to the vacuum vent line was confirmed.

(Example 6: Production Example of Polyester)

207.0 g (1.5 mol) of parahydroxybenzoic acid, 19.9 g (0.11 mol) of biphenol and 43.3 g (0.21 mol) of 4,4'-dihydroxy diphenyl ether were placed in a stirring vessel of a polymerization reactor equipped with a stirrer and a condenser. ), 53.4 g (0.32 mol) of terephthalic acid and 229.5 g (2.25 mol) of acetic anhydride were introduced and kept at 140 DEG C for 5 hours under stirring. Then, while the excess acetic anhydride and by-product acetic acid were removed by distillation under a nitrogen stream, the contents were heated to 170 DEG C, kept at this temperature for 1 hour, heated to 350 DEG C over 4 hours, Min. After cooling to room temperature (25 캜), the lower condensate of the polyester was taken out from the stirring tank and made into a powder by a pulverizer.

The IV of the resulting low-order condensate of polyester was 1.10 dl / g, and Tm was 320 deg.

Subsequently, a low-order condensate of the polyester in the form of a powder was subjected to a pressure of 300 MPa using a tablet molding machine to produce a granular compact of 4 mm in diameter of a low-order condensate of polyester.

100 g of the granular compression-molded body was poured into a glass cylinder having a diameter of 5 cm and a length of 25 cm, allowed to stand, and subjected to solid phase polymerization at 280 캜 under a vacuum of 0.13 kPa for 3 hours.

The IV of the obtained polyester was 3.02 dl / g. No adhesion of the powder was observed on the wall surface of the reactor, and there was no stickiness due to fusion of the resin. Also, adhesion of the powder to the vacuum vent line was not confirmed.

(Comparative Example 6)

A polyester was obtained in the same manner as in Example 6 except that the granular compression-molded product was not directly produced and the powder was solid-phase-polymerized.

The IV of the obtained polyester was 2.73 dl / g. In addition, the wall surface of the reactor did not show stickiness due to fusion of the resin, but the attachment of the powder was observed, and the adhesion of the powder to the vacuum vent line was also confirmed.

The results of the above Examples and Comparative Examples are summarized in Table 1 below.

[Table 1]

Claims (7)

A process for producing a polycondensation resin comprising a step of subjecting a lower condensate to solid phase polymerization,
A step of producing a lower condensate;
Compression-molding the obtained low-order condensate at a compression pressure of 10 to 800 MPa to obtain a granular compression-molded body having a particle diameter of 1.5 to 10 mm; And
And solid-phase polymerizing the granular compression-molded body,
And the logarithmic viscosity (IV) of the polycondensation resin after solid phase polymerization is 0.53 to 3.02 dl / g.
The method for producing a polycondensation resin according to claim 1, wherein the step of solid-state polymerization is carried out in a vertical type apparatus or a vertical type apparatus.
The method for producing a polycondensation resin according to claim 1, wherein the polycondensation resin is a polyamide.
The method for producing a polycondensation resin according to claim 1, wherein the polycondensation resin is polycarbonate.
The method for producing a polycondensation resin according to claim 1, wherein the polycondensation resin is a polyester.
delete The method for producing a polycondensation resin according to claim 1, wherein the maximum reaction temperature of the solid state polymerization is 170 to 350 占 폚.