JP5492864B2 - Production method of polycondensation resin - Google Patents

Description

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

  Polycondensation resins such as polyamide, polycarbonate, and polyester are used in various fields such as optical applications, automotive fields, electrical and electronic applications, and various containers. As a method for producing such a polycondensation resin, a low-order condensate of polycondensation resin having a low molecular weight is prepared, crystallized and / or granulated, and then subjected to vacuum or inert gas flow. Are well known in the art for producing high molecular weight polycondensation resins by solid phase polymerization.

  For example, Patent Document 1 discloses a technique for increasing the molecular weight of a low molecular weight crystalline aromatic polycarbonate (low-order condensate) by solid phase polymerization.

Japanese Patent Laid-Open No. 1-158033

  The polymerization method described in Patent Document 1 has an advantage that a high-molecular-weight aromatic polycarbonate having good hue and moldability can be obtained. However, there has been a problem that the low-order condensates are fused with each other, the low-order condensates cause scaling in the piping, or a large amount adheres to the inner wall of the equipment.

  Therefore, the present invention provides means for efficiently producing a high-quality polycondensation resin without any trouble such as fusion of low-order condensates or scaling of the low-order condensates in the piping. With the goal.

  The present inventor has intensively studied to solve the above problems. As a result, the present inventors have found that the above-mentioned problems can be solved by subjecting the low-order condensate to compression molding before solid-phase polymerization, and subjecting the granular compression-molded product of the obtained low-order condensate to solid-phase polymerization. It came to complete.

  That is, the present invention is a method for producing a polycondensation resin including a step of solid-phase polymerization of a low-order condensate, the step of producing a low-order condensate, and compression molding the obtained low-order condensate. It is a manufacturing method of polycondensation resin including the process of obtaining a granular compression molding, and the process of solid-phase-polymerizing the said granular compression molding.

  According to the production method of the present invention, it is possible to efficiently produce a high-quality polycondensation resin without problems such as fusion between low-order condensates and scaling of the low-order condensate in the piping.

  Hereafter, the manufacturing method of this invention is demonstrated in detail for every process.

<Process for producing low-order condensate>
In this step, a polycondensation reaction is performed to produce a low-order condensate of polycondensation resin.

  Although it does not restrict | limit especially as said polycondensation resin, From a viewpoint of the productivity on an industrial scale, it is preferable that it is a polyamide, a polycarbonate, or polyester, and it is more preferable that it is a polyamide. Hereinafter, monomers and catalysts used for the synthesis of polyamide, polycarbonate, and polyester will be described.

≪Polyamide≫
Polyamide is obtained by a polycondensation reaction between 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, pimelic acid, and 2,2-dimethylglutaric acid. , 3,3-diethylsuccinic acid, suberic acid azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid and other aliphatic dicarboxylic acids; 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and other fats Cyclic dicarboxylic acid; isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3-phenylenedioxydi Acetic acid, diphenic acid, 4,4'-oxydibenzoic acid, diphenylmethane-4,4'-dicar Phosphate, diphenyl sulfone-4,4'-dicarboxylic acid, and aromatic dicarboxylic acids such as 4,4'-biphenyl dicarboxylic acid. These dicarboxylic acids can be used alone or in combination of two or more. If necessary, a small amount of a polyvalent carboxylic acid component such as trimellitic acid, trimesic acid, pyromellitic acid may be used in combination.

  Specific examples of the diamine include, for example, ethylenediamine, propanediamine, 1,4-butanediamine, 1,6-hexanediamine (hexamethylenediamine), 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 2 2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 2-methyl-1,8-octanediamine, 5-methyl-1,9-nonanediamine, Aliphatic alkylenediamines such as metaxylylenediamine and paraxylylenediamine; cyclohexanediamine Alicyclics such as methylcyclohexanediamine, isophoronediamine, bis (4-aminocyclohexyl) methane, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, norbornane dimethanamine, tricyclodecane dimethanamine Examples include diamines; aromatic diamines such as p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylsulfone, and 4,4′-diaminodiphenylether. These diamines can be used alone or in combination of two or more.

  In this step, a phosphorus catalyst can be used from the viewpoints of increasing the polycondensation rate and preventing deterioration during the polycondensation reaction. For example, hypophosphite, phosphate, hypophosphorous acid, phosphoric acid, phosphate ester, polymetaphosphoric acids, polyphosphoric acids, phosphine oxides, phosphonium halogen compounds, etc. are preferred, hypophosphite, phosphate Hypophosphorous acid and phosphoric acid are particularly preferably used. Examples of hypophosphites include sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, magnesium hypophosphite, aluminum hypophosphite, vanadium hypophosphite, manganese hypophosphite, Preferred are zinc hypophosphite, lead hypophosphite, nickel hypophosphite, cobalt hypophosphite, ammonium hypophosphite, sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, secondary Magnesium phosphite is particularly preferred. Examples of phosphates include sodium phosphate, potassium phosphate, potassium dihydrogen phosphate, calcium phosphate, vanadium phosphate, magnesium phosphate, manganese phosphate, lead phosphate, nickel phosphate, cobalt phosphate, phosphoric acid. Ammonium and diammonium hydrogen phosphate are preferred. Examples of the phosphate ester include ethyl octadecyl phosphate. Examples of polymetaphosphoric acids include sodium trimetaphosphate, sodium pentametaphosphate, sodium hexametaphosphate, polymetaphosphoric acid, and the like. Examples of polyphosphoric acids include sodium tetrapolyphosphate. Examples of phosphine oxides include hexamethylphosphoramide.

  As addition amount of a phosphorus catalyst, 0.0001-5 mass parts is preferable with respect to 100 mass parts of preparation raw materials, and 0.001-1 mass part is more preferable. Further, the addition timing may be any time until the solid phase polymerization is completed, but it is preferable to be between the raw material charging time and the completion of polycondensation of the low-order condensate. Moreover, you may add many times. Furthermore, different phosphorus catalysts may be added in combination.

  Moreover, you may perform a polycondensation reaction in presence of terminal blocker at this process. When the end-capping agent is used, the molecular weight of the low-order condensate can be easily adjusted, and the melt stability of the low-order condensate is improved. The end capping agent is not particularly limited as long as it is a monofunctional compound having reactivity with the terminal amino group or terminal carboxyl group in the low-order condensate. For example, acid such as monocarboxylic acid, monoamine, phthalic anhydride, etc. Anhydrides, monoisocyanates, monoacid halides, monoesters, monoalcohols and the like can be mentioned. Among them, monocarboxylic acid or monoamine is preferably used as the end-capping agent from the viewpoint of reactivity and stability of the capping end, and in addition to the above-described properties, the monocarboxylic acid is easy to handle. More preferably used.

  The monocarboxylic acid preferably used as the end-capping agent is not particularly limited as long as it is a monocarboxylic acid having reactivity with an amino group. For example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, capryl Aliphatic monocarboxylic acids such as acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid and isobutyric acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; benzoic acid, toluic acid, α- Mention may be made of aromatic monocarboxylic acids such as naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, phenylacetic acid, or any mixture thereof. Among them, in terms of reactivity, stability of the sealing end, price, etc., acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, Benzoic acid is particularly preferred.

  The monoamine preferably used as the end-capping agent is not particularly limited as long as it is a monoamine having reactivity with a carboxyl group. For example, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, Aliphatic monoamines such as stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine; alicyclic monoamines such as cyclohexylamine, dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine, naphthylamine, or any of these Mention may be made of mixtures. Among them, butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline are particularly preferable from the viewpoints of reactivity, boiling point, stability of the sealing end, and price.

  The amount of the end-capping agent used in the production of the polyamide low-order condensate may vary depending on the reactivity of the end-capping agent used, the boiling point, the reactor, the reaction conditions, etc., but usually the molarity of the dicarboxylic acid or diamine. It is preferable to use it within a range of 0.1 to 15 mol% with respect to the number (Example 2 mol%).

≪Polycarbonate≫
There is no restriction | limiting in particular as a polycarbonate, The polycarbonate which has various structural units is mentioned. Usually, an aromatic polycarbonate produced by a reaction between a dihydric phenol and a carbonate precursor can be used.

  Examples of the dihydric phenol include 4,4′-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl). Propane (bisphenol A), 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-bis (4- Hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ketone, Examples include hydroquinone, resorcin, and catechol.

  In addition, examples of the dihydric phenol include hydroquinone and resorcinol. These dihydric phenols can be used alone or in combination of two or more.

  Among these dihydric phenols, bis (hydroxyphenyl) alkanes are preferable, and those using 2,2-bis (4-hydroxyphenyl) propane as the main raw material are particularly preferable.

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

  Further, this polycarbonate may have a branched structure in addition to the polymer chain having a linear molecular structure. As a branching agent for introducing such a branched structure, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3, 5-triisopropylbenzene, phloroglucin, trimellitic acid, isatin bis (o-cresol), etc. Further, as molecular weight regulators, phenol, pt-butylphenol, pt-octylphenol, p-cumyl Phenol and the like can be used.

  In this step, the reaction is accelerated by extracting the aromatic monohydroxy compound and / or diaryl carbonate by-produced by the polycondensation reaction out of the system. As a method therefor, a method in which the reaction is performed under reduced pressure, a method in which an inert gas is introduced and the condensation by-product is removed by accompanying these gases, and a method in which these are used 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 a polymerization catalyst is not particularly limited as long as it is a polycondensation catalyst used in this field, but alkali metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and alkaline earths. Metal hydroxides; alkali metal salts, alkaline earth metal salts, quaternary ammonium salts of hydrides of boron and aluminum such as lithium aluminum hydride, sodium borohydride, tetramethylammonium borohydride; hydrogenation Alkali metal and alkaline earth metal hydrides such as lithium, sodium hydride and calcium hydride; Alkali metal and alkaline earth metal alkoxides such as lithium methoxide, sodium ethoxide and calcium methoxide; lithium phenoxide; Sodium phenoxide, Alkali metal and alkaline earth metal aryloxides such as gnesium phenoxide, LiO-Ar-OLi and NaO-Ar-ONa (Ar is an aryl group); alkali metals and alkaline earths such as lithium acetate, calcium acetate and sodium benzoate Metal organic acid salts; zinc compounds such as zinc oxide, zinc acetate and zinc phenoxide; boron compounds such as boron oxide, boric acid, sodium borate, trimethyl borate, tributyl borate, triphenyl borate; oxidation Silicon compounds such as silicon, sodium silicate, tetraalkyl silicon, tetraaryl silicon, diphenyl-ethyl-ethoxy silicon; germanium compounds such as germanium oxide, germanium tetrachloride, germanium ethoxide, germanium phenoxide Tin compounds such as tin compounds bonded to alkoxy groups or aryloxy groups such as tin oxide, dialkyltin oxide, dialkyltin carboxylate, tin acetate, ethyltin tributoxide, organotin compounds; lead oxide, lead acetate, carbonic acid Lead compounds such as lead, basic carbonates, lead and organic lead alkoxides or aryloxides; onium compounds such as quaternary ammonium salts, quaternary phosphonium salts, quaternary arsonium salts; antimony oxide, antimony acetate, etc. Antimony compounds of manganese; manganese compounds such as manganese acetate, manganese carbonate, manganese borate; titanium compounds such as titanium oxide, titanium alkoxide or aryloxide; zirconium acetate, zirconium oxide, zirconium alkoxide or aryl A catalyst such as a compound of zirconium such as rhoxide and zirconium acetylacetone can be mentioned. These polymerization catalysts can be used alone or in combination of two or more.

  When the low-order condensate of polycarbonate is in a molten state or a solution state, it can be obtained in a powdery or granular shape by treating with a crystallization solvent.

  There is no particular limitation on the method of treating with this crystallization solvent, but usually, a low-order condensate of polycarbonate is stirred in the crystallization solvent and crystallized in a slurry state, or the low-order condensate and the crystallization A method of crystallization while mixing and kneading a solvent with a mixer or a kneader is preferred. In the case of crystallization in a slurry state, a device having a high-speed stirring blade such as a Waring blender, a device equipped with a centrifugal pump with a cutter, or the like is used. In addition, when crystallization is performed using a mixer or a kneader, a device generally called a mixer or a kneader (powder industry manual, Nikkan Kogyo Shimbun Co., Ltd., pages 644 to 648, etc.) can be used. Examples include a corn blender, a ribbon blender, an excavator mixer, a pug mixer, a Henschel mixer, a Brabender, and a twin screw kneader.

  Examples of the crystallization solvent include esters such as ethyl acetate; ethers such as diethyl ether; ketones such as acetone and methyl ethyl ketone. Depending on the temperature conditions for crystallization, hydrocarbons such as hexane and octane; cyclic hydrocarbons such as cyclohexane and the like can also be used as the crystallization solvent. Among these, acetone is preferable because it can produce a low-order condensate of polycarbonate having a large specific surface area.

≪Polyester≫
There is no restriction | limiting in particular in the polyester which can be used for this invention, For example, the polyester obtained by making the acylated compound of the compound which has a phenolic hydroxyl group, and aromatic carboxylic acid react is mentioned.

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

  The compound having a phenolic hydroxyl group may have one phenolic hydroxyl group or two or more, but preferably has 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 preferably has one carboxyl group. As the compound having a phenolic hydroxyl group, aromatic diols and aromatic hydroxycarboxylic acids are particularly preferable.

  Examples of the aromatic diol include 4,4′-dihydroxybiphenyl (4,4′-biphenol), hydroquinone, resorcin, methylhydroquinone, chlorohydroquinone, acetoxyhydroquinone, nitrohydroquinone, 1,4-dihydroxynaphthalene, 1,5 -Dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4- Hydroxy-3-chlorophenyl) pro Bis- (4-hydroxyphenyl) methane, bis- (4-hydroxy-3,5-dimethylphenyl) methane, bis- (4-hydroxy-3,5-dichlorophenyl) methane, bis- (4-hydroxy-) 3,5-dibromophenyl) methane, bis- (4-hydroxy-3-methylphenyl) methane, bis- (4-hydroxy-3-chlorophenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis -(4-hydroxyphenyl) ether (4,4'-dihydroxydiphenylether), bis- (4-hydroxyphenyl) ketone, bis- (4-hydroxy-3,5-dimethylphenyl) ketone, bis- (4-hydroxy) -3,5-dichlorophenyl) ketone, bis- (4-hydroxyphenyl) sulfide, bi - (4-hydroxyphenyl) sulfone. These may be used alone or in combination of two or more.

  Among these, 4,4′-dihydroxybiphenyl, hydroquinone, resorcin, 2,6-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane, or bis- (4-hydroxyphenyl) sulfone is It is preferably used because it is easily available.

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

  Among these, parahydroxybenzoic acid and 2-hydroxy-6-naphthoic acid are easily used because they are easily available.

  When the compound having a phenolic hydroxyl group described above is acylated, an acylated product is obtained. Examples of the acylated product include, but are not limited to, an acetylated product.

  The acylation can be obtained by reacting a compound having a phenolic hydroxyl group with an acylating agent. Representative acylating agents are acyl anhydrides or halides. The acyl group in the acylating agent includes 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, phenylacetic acid, etc. Of aryl fatty acids.

  The acylating agent is particularly preferably a fatty acid anhydride, and examples of the fatty acid anhydride include acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, pivalic anhydride, 2-ethylhexanoic anhydride, monochloro anhydride Acetic acid, dichloroacetic anhydride, trichloroacetic anhydride, monobromoacetic anhydride, dibromoacetic anhydride, tribromoacetic anhydride, monofluoroacetic anhydride, difluoroacetic anhydride, trifluoroacetic anhydride, glutaric anhydride, maleic anhydride, succinic anhydride, β -Bromopropionic acid. You may use these in mixture of 2 or more types. From the viewpoint of price and handleability, acetic anhydride, propionic anhydride, butyric anhydride, and isobutyric anhydride are preferably used, and acetic anhydride is more preferably used.

  The amount of the fatty acid anhydride used relative to the phenolic hydroxyl group in the aromatic diol and / or aromatic hydroxycarboxylic acid is preferably 1.0 to 1.2 times equivalent. When the amount of the fatty acid anhydride used is less than 1.0 equivalent to the phenolic hydroxyl group, the equilibrium during the acylation reaction is shifted to the fatty acid anhydride side, and the unreacted fragrance is produced during the polymerization to polyester. Group diols or aromatic dicarboxylic acids tend to sublimate and the reaction system tends to clog. On the other hand, when it exceeds 1.2 times equivalent, coloring of the obtained liquid crystalline polyester tends to be remarkable.

  The acylation is preferably carried out by reacting 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 to be reacted with the acylated product described above is an aromatic carboxylic acid. The aromatic carboxylic acid may have one or two or more carboxyl groups, but preferably has one or two carboxyl groups from the viewpoint of obtaining good reactivity. When the aromatic carboxylic acid has only one carboxyl group, it preferably has one more 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 terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, methylterephthalic acid, methylisophthalic acid, and diphenyl ether. -Ter-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, diphenyl ketone-4,4'-dicarboxylic acid, 2,2'-diphenylpropane-4,4'-dicarboxylic acid It is done. These may be used alone or in combination of two or more.

  Among these, terephthalic acid, isophthalic acid, or 2,6-naphthalenedicarboxylic acid is preferably used as the aromatic dicarboxylic acid because it is easily available. In the present embodiment, from the viewpoint of achieving both heat resistance and impact resistance in a well-balanced manner, at least 5 mol% of the aromatic hydroxycarboxylic acid in the total amount of the acylated product of the compound having a phenolic hydroxyl group and the aromatic carboxylic acid is used. It is preferable to contain an acid.

  In this step, an acylated product of a compound having a phenolic hydroxyl group and an aromatic carboxylic acid are subjected to a transesterification reaction.

  In transesterification of acylated products and aromatic carboxylic acids acylated with fatty acid anhydrides, the by-product fatty acids and unreacted fatty acid anhydrides are used in order to shift the equilibrium so that product formation is advantageous. Is preferably evaporated during the reaction and distilled out of the system. In this case, a part of the distilled fatty acid is refluxed and returned to the reactor, so that the raw materials and the like evaporated or sublimated with the fatty acid can be condensed or reverse sublimated and returned to the reactor. In this way, for example, the precipitated carboxylic acid can be returned to the reactor together with the fatty acid.

  In addition, you may use the polyester of said structure individually or in combination of 2 or more types.

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

  The aqueous solvent is a solvent mainly composed of water. Examples of the solvent used other than water include methanol and ethanol.

  The synthesis of the low-order condensate in this step is usually carried out by raising the temperature and increasing the pressure under stirring conditions. The polymerization temperature is controlled after the raw materials are charged. The polymerization pressure is controlled in accordance with the progress of the polymerization.

  The reaction temperature and reaction time in this step are appropriately set depending on 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 this step, the polycondensation reaction may be performed batchwise or continuously. In addition, in order to produce a low-order condensate, such as prevention of adhesion of low-order condensate to the reaction vessel, uniform progression of the polycondensation reaction, and production of low-order condensate powder particles having a uniform particle size. The polycondensation reaction is preferably performed with stirring.

  Next, the low-order condensate produced above is taken out from the reaction vessel.

  If the low-order condensate is a crystalline powder, the low-order condensate is removed from the reaction vessel by taking out the low-order condensate from the reaction vessel, preferably in an inert gas atmosphere at a pressure below atmospheric pressure. Do.

  The inert gas atmosphere preferably has an oxygen concentration of 1% by volume or less from the viewpoint of preventing oxidative degradation of the low-order condensate.

  When the low-order condensate is a crystalline powder, the discharge rate of the low-order condensate from the reaction vessel is the scale of the reaction vessel, the amount of contents in the reaction vessel, the temperature, the size of the take-out port, and the take-out nozzle. It can be appropriately adjusted according to the length of the part.

<Step of compression molding low-order condensate to obtain a granular compression molded product>
In this step, the low-order condensate produced above is compression molded to obtain a granular compression molded product.

  The “granular compression molded product” represents a product obtained by compression molding the low-order condensate into a granular product. The shape of the granular compression-molded body may be unified to a certain shape, or may not be unified. The shape is not particularly limited, and specific examples include pellets, spheres, columns, disks, polygonal columns, cubes, rectangular parallelepipeds, cylinders, and lenses.

  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, and still more preferably 1.5 to 10 mm. If it is this range, the below-mentioned process trouble can be solved and solid phase polymerization can be performed efficiently. In addition, this particle diameter shall measure the short diameter and long diameter of a granular compression molding with a caliper, and shall employ the average value.

  Specific examples of process troubles caused by fine powder include clogging, wear, segregation, adhesion / aggregation, dust scattering, and flushing. Clogging that is likely to occur due to process troubles due to fine powder is supplied, discharged, stored and transported, wear is transported and pulverized, segregation is stored, adhesion and agglomeration is transported, supplied and discharged, dust collected and pulverized, dust scattering is collected During dusting, flushing occurs during supply and discharge. In particular, when a fine powder is involved, in the production process by solid phase polymerization, the fine powder is moved by an inert gas, and the residence time of the fine powder becomes long, which adversely affects the hue and composition of the polycondensation resin. In addition, if the amount of fine powder is large, the fine powder plays a role like an adhesive during solid-phase polymerization, adhesion between low-order condensates, and adhesion between a reaction vessel for solid-phase polymerization and the low-order condensate. May happen. The granular compression molded product obtained by this process can solve the above-mentioned process troubles.

  The obtained low-order condensate may be pulverized or subdivided into a size that can easily form a granular compression-molded product, that is, a particle diameter of 0.01 to 5 mm or less before compression molding. Specific examples of the method of pulverization include a method of pulverization using a commonly used pulverizer such as a hammer crusher. As a method of subdividing, for example, crystallization is performed by performing a shearing treatment in a molten state. An example is a method in which the sheet is once formed into a sheet at the same time in the process, and then the sheet is cut vertically and horizontally by the same technique as pelletizing.

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

  The compression pressure when performing compression molding is not particularly limited, but is preferably 10 to 800 MPa. Within this range, a large amount of fine powder is hardly accompanied during transportation, supply / discharge, and the granular compression molded body does not melt due to frictional heat between the compression molding machine and the granular compression molded body during compression molding. Can be molded well. 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 as it is after taking out the low-order condensate from the reaction vessel or after drying the low-order condensate taken out from the reaction vessel, or the low-order condensate taken out from the reaction vessel. May be carried out after storage.

<Step of solid-phase polymerization of granular compression molded product>
In this step, the polycondensation resin is produced by increasing the degree of polymerization by solid phase polymerization using the granular compression molded product of the low-order condensate obtained above. When the degree of polymerization is increased by solid phase polymerization, a polycondensation resin with less heat deterioration can be obtained.

  The polymerization method and conditions for solid-phase polymerization of the low-order condensate are not particularly limited, and a method capable of increasing the degree of polymerization while maintaining a solid state without causing fusion, aggregation, or deterioration of the low-order condensate and Any condition may be used.

  However, in order to prevent oxidative degradation of the low-order condensate and the resulting polycondensation resin, it is preferable to perform solid-state polymerization in an inert gas atmosphere such as helium gas, argon gas, nitrogen gas, carbon dioxide gas or under reduced pressure. .

  The temperature of the solid phase polymerization is not particularly limited, but the maximum reaction temperature is preferably 170 to 350 ° C. The maximum reaction temperature does not have to be at the end of the solid phase polymerization, and may be reached at any time until the end of the solid phase polymerization.

  There is no particular limitation on the solid-phase polymerization apparatus used in this step, and any known apparatus can be used. Specific examples of the solid phase polymerization apparatus include, for example, a uniaxial disk, a kneader, a biaxial paddle type, a vertical tower type apparatus, a vertical tower type apparatus, a rotary drum type, or a double cone type solid state polymerization apparatus. And drying equipment. From the viewpoint of apparatus cost and structure, it is preferable to use a simple vertical tower apparatus or vertical tower apparatus. When using powder, it has problems such as adhesion to the vessel wall and clogging of piping, so it was difficult to apply to continuous production under reduced pressure. In the present invention, it can be used as an apparatus for solid-phase polymerization in the case of performing in a continuous process. The use of such a vertical tower apparatus or vertical tower apparatus is also preferable from the viewpoint of industrial productivity or quality from the viewpoint of reducing residual monomers and oligomers.

  The reaction time of solid phase polymerization is not particularly limited, but usually 1 to 20 hours is preferably employed. During the solid state polymerization reaction, the low-order condensate may be stirred mechanically or by a gas stream.

  In the present invention, various fiber materials such as glass fibers and carbon fibers, inorganic powders, if necessary, in a step of producing a low-order condensate, a step of solid-phase polymerization, or an arbitrary step after solid-phase polymerization. Additives such as fillers, organic powder fillers, colorants, UV absorbers, light stabilizers, antioxidants, antistatic agents, flame retardants, crystallization accelerators, plasticizers, lubricants, and other polymers May be.

  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, chemical resistance, etc., making use of these properties, the polycondensation resin alone or necessary. Accordingly, various molding methods and spinning methods conventionally used for polycondensation resins in the form of compositions with various additives and other polymers described above, such as injection molding, blow molding, extrusion molding, and compression. It can be formed into various molded articles, fibers, and the like by molding methods such as molding, stretching, vacuum molding, and melt spinning. The resulting molded products and fibers can be used effectively in various applications such as engineering plastics, industrial materials such as electronic / electric parts, automobile parts, office machine parts, industrial materials, and household goods. it can.

  The present invention will be described in further detail using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples. In addition, logarithmic viscosity and melting | fusing point were measured with the following method.

<Measurement of logarithmic viscosity IV (dL / g)>
Polyamide was measured with a Ubbelohde viscometer at 25 ° C. using concentrated sulfuric acid as a solvent, polycarbonate at 20 ° C. with dichloromethane as a solvent, and polyester at 60 ° C. with pentafluorophenol as a solvent.

<Measurement of melting point Tm (° C.)>
Using a DSC manufactured by Seiko Instruments Inc., measurement was performed at a flow rate of 10 ml / min under a nitrogen flow at a heating rate of 10 ° C./min, and the endothermic peak temperature due to melting was measured as the melting point.

(Example 1: Production example of polyamide)
As raw materials, 83.8 g (0.504 mol) of terephthalic acid, 88.2 g (0.512 mol) of 1,10-decanediamine, 0.75 g of acetic acid as end-capping agent (0.012 mol, based on dicarboxylic acid) 2 mol%), 0.172 g of sodium hypophosphite monohydrate (0.1 parts by mass with respect to the charged raw material) and 115 g of water (40% by mass with respect to the charged raw material) as catalysts. Then, an autoclave reaction vessel having an internal volume of 1 liter equipped with a pressure regulating valve, an endoscopic window, and a bottom discharge valve was charged with nitrogen. While stirring, the temperature was raised to 180 ° C. over 0.5 hours and held for 0.5 hours, and it was confirmed that the contents became a homogeneous solution. Thereafter, the internal temperature was raised to 245 ° C. and maintained over 1 hour. After the internal pressure reached 3.0 MPa, the reaction was continued for 2 hours while distilling off water so as to maintain the same pressure.

  After the predetermined reaction time has elapsed, the low-order condensate produced while maintaining the temperature of the reaction vessel and the amount of water in the reaction system (32% by mass) from the bottom discharge valve at room temperature (25 ° C.) And discharged into a cyclone vessel at atmospheric pressure conditions. The discharge valve nozzle diameter at this time was 3 mm, and it took about 10 seconds for discharge. The oxygen concentration in the discharged container was 0.1% by volume, and a white, powdery low-order condensate was obtained.

  The obtained polyamide low-order condensate had an IV of 0.16 dL / g and a Tm of 310 ° C.

  Next, a pressure of 300 MPa was applied to this powdery low-order condensate using a tablet molding machine to produce a 4 mm diameter granular compression-molded product of the low-order condensate. 40 g of this granular compression-molded product was charged into a 500 ml rotary evaporator made of glass and subjected to solid phase polymerization for 3 hours under a vacuum of 30 rpm, 250 ° C. and 0.13 kPa.

  The obtained polyamide had an IV of 0.85 dL / g. Moreover, almost no adhesion of powder was observed on the reactor wall surface, and there was no stickiness due to resin fusion. Furthermore, no powder adhered to the vacuum vent line.

(Comparative Example 1)
A polyamide was obtained in the same manner as in Example 1 except that the powdery low-order condensate was directly solid-phase polymerized without producing a granular compression molded product.

  The obtained polyamide had an IV of 0.75. Moreover, there was almost no adhesion of powder to the reactor wall surface, and there was no stickiness due to resin fusion, but adhesion of the powder to the vacuum vent line was confirmed.

(Example 2: Polyamide production example)
Example 1 except that 100 g of a granular compression molded product was charged into a glass cylinder having a diameter of 5 cm and a length of 25 cm, left to stand, and solid-phase polymerized at 250 ° C. under a vacuum of 0.13 kPa for 3 hours. Similarly, a polyamide was obtained.

  The obtained polyamide had an IV of 0.80 dL / g. In addition, no powder adhered to the reactor wall surface, and there was no stickiness due to resin fusion. Furthermore, no powder adhered to the vacuum vent line.

(Comparative Example 2)
A polyamide was obtained in the same manner as in Example 2 except that the granular compression-molded body was not produced and the powder was directly solid-phase polymerized.

  The obtained polyamide IV was 0.65 dL / g. Further, a slight amount of powder adhered to the reactor wall surface and there was no stickiness due to resin fusion, but the adhesion of the powder to the vacuum vent line was confirmed.

(Example 3: Production example of polyamide)
As raw materials, 83.8 g (0.504 mol) of terephthalic acid, 88.2 g (0.512 mol) of 1,10-decanediamine, 0.75 g of acetic acid as end-capping agent (0.012 mol, based on dicarboxylic acid) 2 mol%), 0.172 g of sodium hypophosphite monohydrate (0.1 parts by mass with respect to the charged raw material) and 115 g of water (40% by mass with respect to the charged raw material) as catalysts. Then, an autoclave reaction vessel having an internal volume of 1 liter equipped with a pressure regulating valve, an endoscopic window, and a bottom discharge valve was charged with nitrogen. While stirring, the temperature was raised to 180 ° C. over 0.5 hours and held for 0.5 hours, and it was confirmed that the contents became a homogeneous solution. Thereafter, the internal temperature was raised to 220 ° C. over 1 hour and held. After the internal pressure reached 2.2 MPa, the reaction was continued for 2 hours while distilling off water so as to maintain the same pressure.

  After the predetermined reaction time has elapsed, the low-order condensate produced while maintaining the temperature of the reaction vessel and the amount of water in the reaction system (32% by mass) from the bottom discharge valve at room temperature (25 ° C.) The product was discharged into a cyclone container under atmospheric pressure conditions. The discharge valve nozzle diameter at this time was 3 mm, and it took about 10 seconds for discharge. The oxygen concentration in the discharged container was 0.1% by volume, and a white, powdery low-order condensate was obtained.

  The obtained polyamide low-order condensate had an IV of 0.06 dL / g and a Tm of 310 ° C.

  Next, a pressure of 300 MPa was applied to this powdery low-order condensate using a tablet molding machine to produce a 4 mm diameter granular compression-molded product of the low-order condensate.

  100 g of this granular compression-molded product was placed in 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 ° C. under a vacuum of 0.13 kPa for 3 hours.

  The obtained polyamide had an IV of 0.78 dL / g. In addition, no powder adhered to the reactor wall surface, and there was no stickiness due to resin fusion. Furthermore, no powder adhered to the vacuum vent line.

(Comparative Example 3)
A polyamide was obtained in the same manner as in Example 3 except that the granular compression-molded body was not produced and the powder was directly solid-phase polymerized.

  The obtained polyamide IV was 0.61 dL / g. In addition, adhesion of powder was observed on the reactor wall surface, and there was stickiness due to resin fusion. Furthermore, the adhesion of 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 water in a stirring tank of a polymerization reactor having a stirring tank, a condenser, and a decompression device 0.056 mg of potassium oxide was charged, 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 distilling out the reaction by-product phenol from the stirring tank. After cooling to room temperature (25 ° C.), the low-order condensate of polycarbonate was taken out from the stirring vessel. The mixture was pulverized, stirred in an acetone solvent, crystallized, filtered, and dried under reduced pressure at 100 ° C. to obtain a powdery low-order condensate of polycarbonate.

  The obtained polycarbonate low-order condensate had an IV of 0.16 dL / g and a Tm of 226 ° C.

  Next, a pressure of 300 MPa was applied to the powdery low-order condensate using a tablet molding machine to prepare a 4 mm diameter granular compression molded product of a polycarbonate low-order condensate.

  40 g of this granular compression-molded product was charged into a 500 ml rotary evaporator made of glass and subjected to solid phase polymerization for 3 hours under a vacuum of 30 rpm, 220 ° C. and 0.13 kPa.

  The obtained polycarbonate had an IV of 0.56 dL / g. Moreover, almost no adhesion of powder was observed on the reactor wall surface, and there was no stickiness due to resin fusion. Furthermore, no powder adhered to the vacuum vent line.

(Comparative Example 4)
A polycarbonate was obtained in the same manner as in Example 4 except that the granular compression-molded body was not produced and the powder was directly solid-phase polymerized.

  The obtained polycarbonate had an IV of 0.55 dL / g. In addition, adhesion of powder was observed on the reactor wall surface, and there was stickiness due to resin fusion. Furthermore, the adhesion of powder to the vacuum vent line was also confirmed.

(Example 5: Production example of polycarbonate)
Similar to Example 4 except that 100 g of the granular compression-molded body was charged in a glass cylinder having a diameter of 5 cm and a length of 25 cm, left to stand, and solid-phase polymerized under a vacuum of 220 ° C. and 0.13 kPa for 3 hours. Thus, a polycarbonate was obtained.

  The obtained polycarbonate had an IV of 0.53 dL / g. In addition, no powder adhered to the reactor wall surface, and there was no stickiness due to resin fusion. Furthermore, no powder adhered to the vacuum vent line.

(Comparative Example 5)
A polycarbonate was obtained in the same manner as in Example 5 except that the granular compression-molded body was not produced and the powder was directly solid-phase polymerized.

  The obtained polycarbonate had an IV of 0.48 dL / g. In addition, adhesion of powder was observed on the reactor wall surface, and there was stickiness due to resin fusion. Furthermore, the adhesion of powder to the vacuum vent line was also confirmed.

(Example 6: Production example of polyester)
In a stirring tank and a stirring tank of a polymerization reactor having a condenser, 207.0 g (1.5 mol) of parahydroxybenzoic acid, 19.9 g (0.11 mol) of biphenol, 43.3 g of 4,4′-dihydroxydiphenyl ether (0.21 mol), 53.4 g (0.32 mol) of terephthalic acid and 229.5 g (2.25 mol) of acetic anhydride were charged and kept at 140 ° C. for 5 hours with stirring. Next, while distilling off excess acetic anhydride and by-product acetic acid under a nitrogen stream, the contents were heated to 170 ° C., held at this temperature for 1 hour, and further heated to 350 ° C. over 4 hours. And reacted at this temperature for 30 minutes. After cooling to room temperature (25 ° C.), the low-order polyester condensate was taken out of the stirring vessel and powdered with a pulverizer.

  The obtained polyester low-order condensate had an IV of 1.10 dL / g and a Tm of 320 ° C.

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

  100 g of this granular compression-molded product was placed in 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 ° C. under a vacuum of 0.13 kPa for 3 hours.

  The obtained polyester had an IV of 3.02 dL / g. In addition, no powder adhered to the reactor wall surface, and there was no stickiness due to resin fusion. Furthermore, no powder adhered to the vacuum vent line.

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

  The obtained polyester had an IV of 2.73 dL / g. Further, no stickiness due to resin fusion was observed on the reactor wall surface, but adhesion of powder was observed, and adhesion of powder to the vacuum vent line was also confirmed.

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

Claims (3)

A process for producing a polycondensation resin comprising a step of solid-phase polymerization of a low-order condensate,
Producing a low-order condensate;
Compression molding the obtained low-order condensate at a compression pressure of 50 to 500 MPa to obtain a granular compression molded product having a particle size of 1.5 to 10 mm ;
Solid-phase polymerization of the granular compression molded body,
Only contains the a logarithmic viscosity IV of 0.53dL / g~3.02dL / g polycondensation resin after solid phase polymerization method for producing a polycondensation resin.   The manufacturing method according to claim 1, wherein the solid-phase polymerization is performed using a vertical tower apparatus or a vertical tower apparatus.   The manufacturing method of Claim 1 or 2 whose said polycondensation resin is polyamide.