WO2014077545A1 - Production method for polycondensation resin - Google Patents

Abstract

The production method for a polycondensation resin of the present invention comprises the processes of: producing a low-order condensate by means of a polycondensation reaction; discharging the low-order condensate outside the system; and producing a polycondensation resin by subjecting the discharged low-order condensate to polymerisation. Here, the polycondensation reaction and the polymerisation are carried out in a batch type reaction vessel, and, in the process of discharging the low-order condensate outside the system, the low-order condensate is discharged outside the system while by-products produced in the polycondensation reaction or substances of the same kind as the raw materials of the polycondensation reaction are supplemented into the system. The production method makes it possible to produce a polycondensation resin of stable quality, in a batch type polymerisation method.

Description

Manufacturing method of polycondensation resin

The present invention relates to a method for producing a polycondensation resin. More specifically, the present invention relates to a process for producing a polycondensation resin capable of producing a polycondensation resin having stable quality.

Polycondensation resins such as polyamides, polycarbonates, polyesters, and the like each have excellent properties as engineer plastics, and thus are widely used in the automotive field, the electric and electronic fields, and the like. As a manufacturing method of polycondensation resin, although various techniques are disclosed, the continuous polymerization method, the batch polymerization method, etc. are widely known.

For example, as a continuous polymerization method, the first condensation product is continuously polymerized in Japanese Patent Application Laid-Open No. 06-287299 or the like, and it is continuously high-polymerization (polymerization) in a short time in a melter to efficiently and stable high molecular weight. A method of obtaining a polycondensation resin is disclosed. However, such a continuous polymerization method is capable of obtaining a polycondensation resin having a stable molecular weight only under specific manufacturing conditions, increasing the amount of investment due to the increased number of auxiliary equipment, and is not suitable for the production of multi-component resins because it is not easy to convert resin varieties. You may not.

In addition, as a batch polymerization method, a low-condensation polycondensation resin of low molecular weight polycondensation resin is produced in Japanese Patent Application Laid-Open No. 08-59824 and the like, and then crystallized and / or granulated, and then it is vacuumed or inert gas. A method for producing a high molecular weight polycondensation resin by solid phase polymerization in an atmosphere is disclosed. However, in such a conventional batch polymerization method, when discharging the polycondensate from each batch, there is a fear that the molecular weight of the polycondensate is irregularly distributed by the discharge time difference, and as a result, the quality of the polycondensation resin produced It may change.

An object of the present invention is to provide a method for producing a polycondensation resin that can produce a polycondensation resin of stable quality in a batch polymerization method.

The above and other objects of the present invention can be achieved by the present invention described below.

One aspect of the present invention relates to a method for producing a polycondensation resin. The manufacturing method comprises the steps of preparing a lower order condensate by a polycondensation reaction; Discharging the lower condensate out of the system; And a step of polymerizing the discharged lower order condensate to produce a polycondensation resin, wherein the polycondensation reaction and polymerization are performed in a batch reactor, and the step of discharging the lower order condensate out of the system, The lower condensate is discharged out of the system while replenishing the same kind of material as the by-product or the raw material of the polycondensation reaction in the system.

In an embodiment, the same kind of material as the by-product or raw material may be replenished into the system to maintain the chemical equilibrium of the formation reaction of the lower condensate at the beginning of the lower condensate discharge.

In an embodiment, the amount for replenishing the same kind of material as the by-product or raw material into the system so as to maintain a chemical equilibrium state of the reaction of formation of the lower condensate at the start of discharge is represented by Z (the same as the by-product or raw material). ± 5% of the supply per unit time of material of the kind):

[Equation 1]

In Equation 1, Z (unit: kg / hr) is a unit of a substance (vapor phase) of the same kind as a by-product or raw material introduced to maintain a chemical equilibrium state of the reaction of formation of the lower condensate at the start of lower condensate discharge. Supply per hour (steam feed rate), P _x (unit: kPa) is the pressure in the system, P _y (unit: kPa) is the temperature in the system (temperature of the reaction solution) T (unit: K, T [ K] = T '[° C.] + 273.15) means the saturated vapor pressure (theoretical value) per unit volume, V (unit: m ³ ) means the volume of the reaction solution, Y (unit: kg / m ³ ) Denotes the amount of saturated steam per unit volume (theoretical value) under the conditions of the temperature T and the saturated vapor pressure P _y , and L (unit: hr) means time for discharging all the lower condensates in the system.

In embodiments, the number average molecular weight of the lower condensate may be about 5 to about 50% of the number average molecular weight of the polycondensation resin.

In embodiments, the polycondensation resin may be polyamide, polycarbonate, or polyester.

In embodiments, the polycondensation resin may be formed by solid-phase polymerization of the lower condensate.

This invention has the effect of providing the manufacturing method of the polycondensation resin which can manufacture the polycondensation resin of stable quality in a batch polymerization method.

Hereinafter, the present invention will be described in detail.

Method for producing a polycondensation resin according to the present invention is a batch polymerization method wherein the polycondensation reaction and polymerization is carried out in a batch reactor, (A) a step of preparing a lower condensate by a polycondensation reaction, (B) And discharging the lower condensate out of the system, and (C) polymerizing the discharged lower condensate to produce a polycondensation resin. The present invention is carried out while the (B) the step of discharging the lower condensate out of the system is supplemented into the system (gas phase) material of the same kind as the by-products produced in the polycondensation reaction or the raw material (monomer) of the polycondensation reaction It is characterized by.

In an embodiment, the material of the same kind as the by-product or raw material may vary depending on the resin to be polymerized. For example, the same material as the by-product may be used when preparing polyamide, polycarbonate, and the like, and polyester In manufacturing, the same kind of material as the raw material can be used.

In addition, a substance of the same kind as the by-product or raw material may be replenished into the system to maintain the chemical equilibrium state of the reaction of formation of the lower condensate at the start of discharging the lower condensate.

(A) process for producing a lower order condensate

In this process, the polycondensation reaction of a monomer is performed and the low-order condensate of polycondensation resin is manufactured.

In embodiments, the polycondensation resin is not particularly limited, but may be polyamide, polycarbonate or polyester that can be produced on an industrial scale.

Hereinafter, the monomer, catalyst, etc. which are used for synthesis | combination of a polyamide, a polycarbonate, and polyester are demonstrated.

<Polyamide>

The polyamide is not particularly limited as can be obtained by polycondensation reaction of dicarboxylic acid with diamine and / or aminocarboxylic acid and (solid phase) polymerization (high polymerization).

Non-limiting examples of the dicarboxylic acid, malonic acid, dimethyl malonic acid, succinic acid, glutaric acid, adipic acid, 2-methyl adipic acid, trimethyl adipic acid, pimelic acid, 2,2-dimethylglu Aliphatic dicarboxylic acids such as taric acid, 3,3-diethyl succinic 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; Terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3-phenyl Rendioxydiacetic acid, diphenic acid, 4,4'-oxydibenzoic acid, diphenyl methane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, 4,4'- Aromatic dicarboxylic acids such as biphenyldicarboxylic acid; Etc. can be illustrated. These can be used individually or in mixture of 2 or more types. Moreover, if necessary, a small amount of polyhydric carboxylic acid components, such as trimellitic acid, trimesic acid, a pyromellitic acid, can also be used together.

Non-limiting examples of the diamine include 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-nonane Aliphatic diamines such as diamine, metaxylylenediamine and paraxylylenediamine; Cyclohexanediamine, methylcyclohexanediamine, isophoronediamine, bis (4-aminocyclohexyl) methane, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, norbornanedimethanamine, tricyclo Alicyclic diamines such as decandimethanamine; Aromatic diamines such as paraphenylenediamine, metaphenylenediamine, 4,4'-diaminodiphenylsulfone, and 4,4'-diaminodiphenyl ether; Etc. can be illustrated. These can be used individually or in mixture of 2 or more types.

As the aminocarboxylic acid, lactams such as laurolactam, aminocaproic acid, aminoundecanoic acid, and the like may be used, but are not limited thereto.

In the production of polyamide, a phosphorus catalyst can be used for the purpose of improving the polycondensation rate and preventing deterioration during the polycondensation reaction. Examples of the phosphorus-based catalyst may include hypophosphite, phosphate, hypophosphorous acid, phosphoric acid, phosphate ester, polymetaphosphates, polyphosphates, phosphine oxides, phosphonium halide compounds, and mixtures thereof, but are not limited thereto. . For example, hypophosphite, phosphate, hypophosphorous acid, phosphoric acid, mixtures thereof, and the like can be used. As the hypophosphite, sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, magnesium hypophosphite, aluminum hypophosphite, vanadium hypophosphite, manganese hypophosphite, zinc hypophosphite, lead hypophosphite, nickel hypophosphite, cobalt hypophosphite, tea Ammonium phosphite etc. can be used, Specifically, sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, magnesium hypophosphite, etc. can be used. Examples of the phosphate salt include sodium phosphate, potassium phosphate, potassium dihydrogen phosphate, calcium phosphate, vanadium phosphate, magnesium phosphate, manganese phosphate, lead phosphate, nickel phosphate, cobalt phosphate, ammonium phosphate, and diammonium phosphate. Ethyl octadecyl phosphate etc. can be used as said phosphate ester. Examples of the polymetaphosphates include sodium trimethaphosphate, sodium pentametaphosphate, sodium hexametaphosphate, polymetaphosphate, and the like. As said polyphosphate, sodium tetrapolyphosphate etc. can be used. In addition, hexamethylphosphoamide may be used as the phosphine oxides. The phosphorus catalysts may be in the form of hydrates.

The addition amount of the phosphorus catalyst may be about 0.0001 to about 5 parts by weight, for example, about 0.001 to about 1 part by weight based on about 100 parts by weight of the monomer (injection raw material). The addition time of the phosphorus catalyst may be added at any time until the completion of the (solid phase) polymerization, but is preferably between the time of starting the raw material input and the completion of the polycondensation of the lower condensate. Moreover, you may add in several times and may mix and add 2 or more types of different phosphorus catalysts.

In addition, this process can perform the said polycondensation reaction in presence of terminal blocker. The use of the end-sealing agent makes it easier to control the molecular weight of the lower condensate and the finally produced polyamide, and can improve the melt stability of the lower condensate and the finally produced polyamide. The terminal blocker 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 the lower condensate. For example, acid anhydrides such as monocarboxylic acid, monoamine, phthalic anhydride, monoisocyanate, monoacid halide, monoesters, monoalcohols and the like can be exemplified, but is not limited thereto. The terminal blocker may be used alone or in combination of two or more thereof. Specifically, monocarboxylic acid or monoamine may be used in consideration of reactivity and sealing end stability, and more specifically, monocarboxylic acid having excellent handleability may be used.

The monocarboxylic acid 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, caprylic acid, lauric acid, tridecyl acid, micro Aliphatic monocarboxylic acids such as list acid, palmitic acid, stearic acid, pivaric acid and isobutyl acid; Alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; Aromatic monocarboxylic acids such as benzoic acid, toluic acid, α-naphthalene carboxylic acid, β-naphthalene carboxylic acid, methylnaphthalene carboxylic acid, and phenylacetic acid; Mixtures thereof and the like can be used. Specifically, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecyl acid, myristic acid, palmitic acid, stearic acid, benzoic acid, etc. Etc. can be used.

The monoamine is not particularly limited as long as it is a monoamine having reactivity with a carboxyl group. For example, aliphatic monoamines, such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine; Alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; Aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine; Mixtures thereof and the like can be used. Specifically, butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, aniline, etc. may be used in view of reactivity, boiling point, bag end stability and price.

In the preparation of the lower condensate, the amount of the end-sealing agent used may vary depending on the reactivity, boiling point, reaction apparatus, reaction conditions, etc. of the end-sealing agent used, but, for example, about 100 mole parts of dicarboxylic acid or diamine, 0.1 to about 15 mole parts.

In this step, the reaction can be accelerated by extracting by-products such as water produced by the polycondensation reaction out of the system. To this end, it is possible to use a method of removing the by-products together with an inert gas after crime prevention and / or introduction of an inert gas to carry out the reaction under reduced pressure.

<Polycarbonate>

There is no restriction | limiting in particular as said polycarbonate, The polycarbonate which has various structural units can be illustrated. Typically, the polycarbonate may be an aromatic polycarbonate prepared by the reaction of a dihydric phenol with a carbonate precursor.

Non-limiting examples of the dihydric phenol include 4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2- Bis (4-hydroxyphenyl) propane ("bisphenol A"), 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxy Phenyl) 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, hydroquinone, resorcinol, catechol, etc. can be illustrated. The said dihydric phenol can be used individually or in mixture of 2 or more types. For example, bis (hydroxyphenyl) alkanes can be used, and specifically, 2,2-bis (4-hydroxyphenyl) propane can be used as a main raw material.

Examples of the carbonate precursor include carbonyl halide, carbonyl ester, haloformate, and the like, but are not limited thereto. For example, diaryl carbonates such as phosgene, dihaloformate of dihydric phenol, diphenyl carbonate, dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and the like can be used. Reel carbonate can be used.

The polycarbonate may include a branched structure in addition to the linear structure of the molecular chain of the polymer chain. As a branching agent for introducing such a branching structure, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ', α "-tris (4-hydroxyphenyl) -1,3,5-tri Isopropylbenzene, fluoroglucin, trimellitic acid, isatinbis (o-cresol), etc. Moreover, as a molecular weight modifier, phenol, pt-butylphenol, pt-octylphenol, p-cumylphenol, etc. can be used. Can be used.

In this step (lower condensate production step), the polycondensation reaction can proceed at a sufficient rate without adding a catalyst, but a polymerization catalyst can be further used for the purpose of improving the reaction rate.

The polymerization catalyst is not particularly limited as long as it is a polycondensation catalyst used in this field, but alkali metal and alkaline earth metal hydroxides 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 tetramethylammonium hydride; Hydrogen 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; Aryl oxides 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; Boron compounds, such as boron oxide, boric acid, sodium borate, trimethyl borate, tributyl borate, and triphenyl borate; Silicon compounds such as silicon oxide, sodium silicate, tetraalkylsilicon, tetraarylsilicon and diphenylethylethoxysilicon; Germanium compounds such as germanium oxide, germanium tetrachloride, germanium ethoxide and germanium phenoxide; Tin compounds such as tin compounds bound with alkoxy groups or aryloxy groups such as tin oxide, dialkyl tin oxide, dialkyl tin carboxylate, tin acetate, and ethyl tin tributoxide, and organic tin compounds; Lead compounds such as lead oxide, lead acetate, lead carbonate, basic carbonate, lead and organic lead alkoxides or aryl oxides; Onium compounds such as quaternary ammonium salts, quaternary phosphonium salts and quaternary arsonium salts; Antimony compounds, such as antimony oxide (antimony trioxide etc.) and antimony acetate; Manganese compounds such as manganese acetate, manganese carbonate and manganese borate; Titanium compounds such as titanium oxide, titanium alkoxide or aryl oxide; Zirconium compounds such as zirconium acetate, zirconium oxide, zirconium alkoxide or aryl oxide, zirconium acetylacetone; Catalysts, such as these, can be illustrated. The said polymerization catalyst can be used individually or in mixture of 2 or more types.

When preparing the lower polycondensate of polycarbonate, the amount of the polymerization catalyst used may vary depending on the reactivity, boiling point, reaction apparatus, reaction conditions, etc. of the polymerization catalyst used, but about 1 part by weight of about 100 parts by weight of the monomer (injection raw material). X 10 ^-9 to about 1 part by weight, for example about 1 x 10 ^-7 to about 1 x 10 ^-3 parts by weight. The addition time of the polymerization catalyst may be added at any time until completion of the (solid phase) polymerization, but is preferably between the time of starting the raw material input and the completion of the polycondensation of the lower condensate. Moreover, you may add in several times and may mix and add 2 or more types of different polymerization catalysts.

This process can be accelerated by discharging the by-products such as aromatic monohydroxy compounds produced by the polycondensation reaction out of the system. To this end, a method of carrying out the reaction under reduced pressure and / or a method of removing the by-products together with the inert gas after introduction of the inert gas may be used.

<Polyester>

There is no restriction | limiting in particular as said polyester, The polyester obtained by making the acyl compound of the compound which has aliphatic diol or phenolic hydroxyl group, and aromatic dicarboxylic acid or aromatic dicarboxylic acid ester react can be illustrated.

The aliphatic diol may be, for example, one having an alkylene group having 2 to 10 carbon atoms, but is not limited thereto. Specifically, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,3-propanediol, 1,4-butanediol, 1,2-ethanediol, 1,5-pentanediol, 1,6- Hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexane dimethanol, trimethylolpropane, neopentylglycol, methylpentane Diols, mixtures thereof, and the like. In addition, the alkylene group of the aliphatic diol may be substituted with an alkyl group, a halogen atom, an ether group and the like not involved in the esterification reaction according to the present invention.

As an acyl compound of the compound which has the said phenolic hydroxyl group, the acyl compound which acylated the phenolic hydroxyl group of aromatic diol and / or aromatic hydroxycarboxylic acid with fatty acid anhydride can be used. The compound having a phenolic hydroxyl group may have one or more phenolic hydroxyl groups, but from the viewpoint of reactivity, it is preferable to have one or two phenolic hydroxyl groups. Moreover, when the compound which has the said phenolic hydroxyl group has only one phenolic hydroxyl group, it is preferable that it contains one carboxyl group. As a compound which has the said phenolic hydroxyl group, aromatic diol and aromatic hydroxycarboxylic acid are especially preferable. Examples of the aromatic diol include 4,4'-dihydroxybiphenyl ("4,4'-biphenol"), hydroquinone, resorcinol, 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) propane, 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'-dihydroxydiphenyl ether), bis- (4-hydroxyphenyl) ketone, bis- (4-hydroxy-3,5-dimethylphenyl) ketone, bis- ( 4-hydroxy-3,5-dichlorophenyl) ketone, bis- (4-hydroxyphenyl) sulfide, bis- (4-hydroxyphenyl) sulfone, mixtures thereof and the like can be exemplified, but is not limited thereto. . Among them, 4,4'-dihydroxybiphenyl, hydroquinone, resorcinol, 2,6-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane and bis- (4-hydroxy Phenyl) sulfone etc. are easy to obtain and are widely used.

Acylates are obtained by acylating the compound having a phenolic hydroxyl group as described above. Acetylate can be illustrated as an acylate, but it is not limited to this. Here, the acylation may be to react the compound having an phenolic hydroxyl group and the acylating agent. As said acylating agent, an acyl anhydride or a halide is typical. The acyl group in the said acylating agent is aliphatic carboxylic acid, such as alkanoic acid (acetic acid, propionic acid, butyric acid, pivalic acid, etc.), higher alkanoic acid, such as palmitic acid, aromatic carboxylic acid, such as benzoic acid, and aryl fatty acids, such as phenylacetic acid. Can be derived from. As said acylating agent, fatty acid anhydride is especially preferable. As said fatty acid anhydride, acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, pivalic anhydride, 2 ethylhexanoic anhydride, monochloroacetic anhydride, dichloroacetic anhydride, trichloroacetic anhydride, monobromide anhydride Mother acetic acid, dibromoacetic anhydride, tribromoacetic anhydride, monofluoroacetic anhydride, difluoroacetic anhydride, trifluoroacetic anhydride, glutaric anhydride, maleic anhydride, succinic anhydride, β-bromo anhydride Propionic acid, mixtures thereof and the like can be exemplified. From the viewpoint of price and handleability, acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride and the like can be used, preferably acetic anhydride can be used.

In the acylation reaction of the compound having a phenolic hydroxyl group, the amount of the fatty acid anhydride may be about 1.0 to about 1.2 equivalents based on the phenolic hydroxyl group. When the amount of the fatty acid anhydride used is less than about 1.0 equivalent with respect to the phenolic hydroxyl group, there is a fear that the equilibrium during the acylation reaction is shifted toward the fatty acid anhydride, and thus unreacted aromatic diol or aromatic dicar when polymerization with polyester Acid may sublimate and the reaction system may be closed. Moreover, when the usage-amount of the said fatty acid anhydride exceeds about 1.2 equivalent with respect to the said phenolic hydroxyl group, there exists a possibility that a polyester may color.

The acylation reaction may be performed at about 130 to about 180 ° C., for example, at about 140 to about 160 ° C. for about 15 minutes to about 20 hours, for example, about 30 minutes to about 5 hours.

In the present invention, the aromatic dicarboxylic acid or aromatic dicarboxylic acid ester which reacts with the acyl compound of the compound having an aliphatic diol or phenolic hydroxyl group may be referred to collectively as aromatic dicarboxylic acids.

Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, methyl terephthalic acid and methyl Isophthalic acid, diphenylether-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, diphenylketone-4,4'-dicarboxylic acid, 2,2'- Diphenyl propane-4,4'- dicarboxylic acid, mixtures thereof, etc. can be illustrated. Among them, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid and the like are easily available and widely used.

Moreover, as said aromatic dicarboxylic acid ester, ester, such as methyl, ethyl, propyl, phenyl, of the said aromatic dicarboxylic acid can be illustrated. These can be used individually or in mixture of 2 or more types.

The reaction of the acylate of the compound having an aliphatic diol or phenolic hydroxyl group with aromatic dicarboxylic acids can proceed at a sufficient rate without adding a catalyst, but a polymerization catalyst can be further used for the purpose of improving the reaction rate. . As the polymerization catalyst, a polycondensation catalyst used in this field can be used without limitation. For example, the polymerization catalyst used for polycarbonate manufacture (polycondensation reaction) mentioned above can be used.

In preparing the lower condensate of polyester, the amount of the polymerization catalyst used may vary depending on the reactivity, boiling point, reaction apparatus, reaction conditions, etc. of the polymerization catalyst to be used. 5 parts by weight, for example about 0.0005 to about 1 part by weight. The addition time of the polymerization catalyst may be added at any time until completion of the (solid phase) polymerization, but is preferably between the time of starting the raw material input and the completion of the polycondensation of the lower condensate. Moreover, you may add in several times and may mix and add 2 or more types of different polymerization catalysts.

In this step (lower condensate production step), in order to produce polyester from aliphatic diols and aromatic dicarboxylic acids, first, esterification reaction of aliphatic diols and aromatic dicarboxylic acids is performed at about 160 ° C. or more and less than about 250 ° C. After the polymerization, the polycondensation reaction may be performed at about 250 ° C to about 350 ° C. In addition, in order to manufacture polyester from the acyl compound and aromatic dicarboxylic acid of the compound which has a phenolic hydroxyl group, after acylating and aromatic dicarboxylic acid of the compound which has a phenolic hydroxyl group is subjected to esterification reaction or transesterification reaction, , Polycondensation reaction can be carried out.

This process can be accelerated by discharging the by-products generated by the polycondensation reaction and the like out of the system. To this end, a method of carrying out the reaction under reduced pressure and / or a method of removing the by-products together with the inert gas after introduction of the inert gas may be used.

In an embodiment, the by-product of the polyester polycondensation reaction (esterification reaction) of the aliphatic diol and the aromatic dicarboxylic acids is water or alcohol formed from the hydroxyl group of the aromatic dicarboxylic acid or the alkoxy group of the aromatic dicarboxylic acid ester. Etc., such water or alcohol may be discharged out of the system to shift the equilibrium so that the production of polyester is advantageous.

In addition, the by-products of the polycondensation reaction (esterification reaction or transesterification reaction) of the acyl compound and aromatic dicarboxylic acid of the compound which has a phenolic hydroxyl group are monocarboxylic acid, a monocarboxylic acid ester, etc. Acids, monocarboxylic acid esters, and the like can be discharged out of the system in order to shift the equilibrium so that the production of the product (polyester) is favored. If necessary, a part of the outflowing monocarboxylic acid or the like is refluxed to the reactor, so that the raw material (aromatic dicarboxylic acids or the like) evaporated or sublimed together with the monocarboxylic acid or the like may be returned to the reactor together with the reflux. In addition, during the esterification or transesterification reaction of the acylates of the compounds having phenolic hydroxyl groups with aromatic dicarboxylic acids, acylating agents such as unreacted fatty acid anhydrides contained in the acylates are also evaporated during the reaction. It is preferable to discharge (distillate) out.

In the low-condensation product manufacturing process of this invention, low-condensation products, such as a polyamide, a polycarbonate, and polyester, inject | pour each monomer etc. into the pressure polymerization tank used normally, for example, stirring in a solventless solvent or a solvent. Synthesized by carrying out the polycondensation reaction under conditions.

The solvent may be water or alcohols such as methanol and ethanol. In the initial stage of the reaction, an excess of raw materials such as aliphatic diols and by-products may be used as the solvent.

The polycondensation reaction can be carried out by raising the temperature and increasing the pressure, usually under stirring conditions. At this time, the reaction temperature (polymerization temperature) can be adjusted after the raw material input, the reaction pressure (polymerization pressure) can be adjusted in accordance with the progress of the polymerization.

In this process, the reaction temperature, the reaction pressure and the reaction time can be appropriately set depending on the resin to be produced, and are not particularly limited. For example, the reaction temperature may be about 170 to about 400 ° C., the reaction pressure may be about 0.5 to about 3 kPa MPa, and the reaction time may be about 0.5 to about 10 hours. Moreover, it is preferable to perform the said polycondensation reaction under stirring from a viewpoint of prevention of adhesion of a lower order condensate to a reaction container, uniform progress of a polycondensation reaction, formation of the primary polycondensate powder with a particle size, etc.

(B) process to discharge the lower condensate out of the system

Next, in the present step, the produced lower condensate is discharged from the reaction vessel (in the system).

The present invention is characterized by a process for extracting the lower condensate out of the system. Specifically, the process produces the same type of (gas phase) material as the by-products produced in the polycondensation reaction or the raw material (monomer) of the polycondensation reaction, for example, the generation of the lower condensate at the start of discharge of the lower condensate. In order to maintain the chemical equilibrium of the reaction, the lower condensate is discharged out of the system while replenishing into the system. With this feature, it is possible to suppress fluctuations in the molecular weight of the lower order condensate caused by the time difference of discharge when the lower order condensate is extracted out of the system, and as a result, a polycondensation resin of stable quality can be obtained.

That is, in the present invention, when the lower condensate produced by the polycondensation reaction is discharged from the reactor (in the system), the space of the lower condensate discharged increases, so that the reaction solution (liquid state) and the gas phase in the system are increased. It was found that the change in the equilibrium of the solution-phase maintained was found, and as a result, the chemical equilibrium of the formation reaction of the lower condensate is different from the state at the start of discharging the lower condensate.

In the present invention, the "products of the same kind as the by-products produced in the polycondensation reaction or the raw material (monomer) of the polycondensation reaction", which are supplemented into the system, are used for the kind of the polycondensation resin to be manufactured, that is, the raw material (monomer) to be used. For example, in the production of polyamide, the by-product is water, in the production of polycarbonate, the by-product is an aromatic monohydroxy compound and the like, in the production of polyester prepared from aliphatic diols and aromatic dicarboxylic acids The by-products are water, alcohols, and the like, and in the production of polyesters prepared from acylates and aromatic dicarboxylic acids of compounds having phenolic hydroxyl groups, the by-products are monocarboxylic acids such as fatty acids, monocarboxylic acid esters and the like.

Further, in the present invention, the process of replenishing the same kind of material as the by-product or raw material into the system so as to maintain the chemical equilibrium state of the reaction of formation of the lower condensate at the start of discharging the lower condensate, specifically, the lower condensate It means the introduction of the same kind of material as the by-product or raw material into the system so that the vapor pressure of the by-product in the system can be maintained at the start of discharge. Here, the same kind as the by-product or raw material introduced to maintain the vapor pressure of the by-product or raw material in the system at the start of the lower condensate discharge (maintain the chemical equilibrium state of the reaction of formation of the lower condensate at the start of the lower condensate discharge) The supply amount (steam supply rate) per unit time of the substance (vapor phase) can be obtained by, for example, the following formula (1).

[Equation 1]

In Equation 1, Z (unit: kg / hr) is a unit of a substance (vapor phase) of the same kind as a by-product or raw material introduced to maintain a chemical equilibrium state of the reaction of formation of the lower condensate at the start of lower condensate discharge. Supply per hour (steam feed rate),

P _x (unit: kPa) means the pressure in the system,

P _y (unit: kPa) means the saturated vapor pressure (theoretical value) per unit volume at the temperature in the system (temperature of the reaction solution) T (unit: K, T [K] = T '[° C.] + 273.15),

V (unit: m ³ ) means the capacity of the reaction solution,

Y (unit: kg / m ³ ) means the amount of saturated steam (theoretical value) per unit volume under the conditions of the temperature T and saturated vapor pressure P _y ,

L (unit: hr) means time to discharge all lower condensate in a system.

Here, P _y and Y can be obtained as follows.

When the by-product or raw material is water, the saturated vapor pressure (theoretical value) Py can calculate the saturated water vapor pressure (P _y = P _ws ) from a Wagner equation represented by Equation 2 below, and the by-product or raw material is an organic compound. In the case of, the saturated vapor pressure (P _y = 0.01 P _aw ) can be calculated from the Antoine equation represented by the following equation (3). Below, as an organic compound, the anthoin constant of ethylene glycol was described as an example of an aromatic monohydroxy compound (by-product in polycarbonate manufacture), and an example of phenol and aliphatic diol (raw material in polyester manufacture). Such an antoin constant, for example, with reference to a chemical manual, NIST WebBook, etc., a known value of the compound can be applied.

[Equation 2]

In Equation 2, P _ws (unit: kPa) means Wagner's exact water vapor pressure,

P _c is the critical pressure 22120 kPa,

A is -7.76451, B is 1.45838, C is -2.7758, D is -1.23303,

x is 1- (T / T _c ), where T _c is 647.3 K as the critical temperature and T (unit: K) is the temperature of the reaction solution).

[Equation 3]

In Formula 3, P _aw (unit: bar) means a saturated vapor pressure,

T (unit: K) is the temperature of the reaction solution,

A, B and C are the antho constants, for phenol, A is 4.24688, B is 1509.677, C is -98.949, and for ethylene glycol, A is 4.97012, B is 1914.951, C is -84.996.

The saturated vapor amount (theoretical value) Y per unit volume can be calculated by the ideal gas state equation by the ideal gas state equation using the saturated vapor pressure Py at a predetermined temperature T of the by-product or raw material obtained by the above formula ( At this time, the volume is calculated as 1 m ³ ).

[Equation 4]

In Formula 4, Y (unit: kg / m ³ ) means the amount of saturated steam per unit volume (theoretical value) under the conditions of temperature T and saturated vapor pressure P _y ,

P _y (unit: kPa) means the saturated vapor pressure (theoretical value) per unit volume at temperature T (unit: K),

T (unit: K) is the temperature of the reaction solution,

Mw (unit: g / mol) is the weight average molecular weight of the by-product or raw material,

R is a gas constant, 8.3145.

In the formula _{1, [Y × (P x} / P y)] , the saturated amount of steam in the reaction system per unit suitable X: (unit kg / m ^3). That is, by calculating the saturated vapor pressure (theoretical value) P _y , the saturated vapor amount Y per unit volume at the saturated vapor pressure P _y , and the pressure P _x in the reaction system based on Boyle's law, the saturated vapor amount X per unit volume in the reaction system is X. = Y × (P _x / P _y ) [kg / m ³ ]. As such, the amount of steam X may represent the amount of steam in the system at the start of discharging the lower condensate out of the system.

In the present invention, when the lower condensate is discharged out of the system, the by-products of the gas phase are supplemented to maintain the vapor amount (X) in the system, thereby maintaining a chemical equilibrium state. Regarding the space volume increase V (unit: m ³ ) generated by the discharge of the reaction solution, the amount (unit: kg) of steam (unit: kg) added to maintain the steam amount X is equal to Y × ( P _x / P _y ) × V. In addition, the steam supply amount Z per unit time for adding the steam amount for a predetermined time L can be represented by the above formula (1).

In this invention, each numerical unit of said Formulas 1-4 can be used suitably matching a pressure, a volume, etc., and each unit of Formulas 1-4 is referred to as a reference.

In an embodiment, the amount of a substance of the same kind as a by-product or raw material supplemented into the system at the time of the lower condensate discharge, so as to maintain the chemical equilibrium of the lower condensate formation reaction at the beginning of the lower condensate discharge, It can be in the numerical range of ± 5%, for example ± 3%, specifically ± 1% of the steam feed rate (steam feed rate) Z per unit time calculated by. Within this range, it is possible to maintain the chemical equilibrium state of the lower order condensate formation reaction at the start of discharge.

The present invention discharges the lower condensate while introducing the same kind of by-product or raw material into the system at the steam supply rate as described above, without changing the chemical equilibrium state of the polycondensation reaction from the start of the discharge to the end of the discharge. In addition, the lower condensate can be discharged. Thereby, the molecular weight of the lower order condensate obtained after discharge | emission does not change with time difference at the time of discharge | release. That is, the present invention can obtain a low-order condensate having a narrow molecular weight distribution by the above procedure, and by using this as a raw material for obtaining a high-molecular weight polycondensate, a polycondensation resin of stable quality having a narrow molecular weight distribution can be obtained.

In the embodiment, the vapor of a substance of the same kind as the by-product or raw material supplied into the system can obtain the effect of the present invention even if supplied into the reaction solution, but in order to obtain a more excellent effect, it is preferably introduced into the gas phase part.

In the discharge step of the lower condensate, in order to maintain the chemical equilibrium of the production reaction of the lower condensate of the polycondensation reaction, it is preferable to maintain the temperature, the pressure and the like as the conditions at the time of the reaction.

In an embodiment, the lower condensate discharged from the reaction vessel can be recovered to the vessel at atmospheric pressure under an inert gas atmosphere. The inert gas atmosphere may prevent oxidative deterioration of the lower condensate, and the oxygen concentration may be 1% by volume or less.

In embodiments, the rate of discharge from the reaction vessel of the lower condensate may be appropriately adjusted according to the size of the reaction vessel, the amount of contents in the reaction vessel, the temperature, the size of the outlet, the length of the discharge nozzle, and the like. The logarithmic viscosity (IV) of the lower condensate may be about 0.05 to about 1.50 dL / g, for example about 0.08 to about 1.00 dL / g, specifically about 0.10 to about 0.80 dL / g. In the present invention, when discharging the lower condensate, the variation in the molecular weight of the polycondensate according to the time difference of discharging is suppressed, and therefore there is no variation due to the lapse of the discharging time even for the logarithmic viscosity (IV) of the lower condensate. For example, when the discharged lower order condensate is sampled every predetermined time, the algebraic viscosity variation of each sample is very small. That is, the logarithmic viscosity averages of the samples sampled every predetermined time are also in the above-mentioned ranges, and their standard deviations may be about 0.05 or less, for example, less than about 0.04, and the coefficient of variation may be about 2.5 or less, for example, about 2.0 or less. have. The sampling every predetermined time is not particularly limited, but may be, for example, sampling performed every about 10 minutes. In addition, the logarithmic viscosity IV can be obtained by the method of the Example mentioned later.

In embodiments, the number average molecular weight of the lower condensate is about 5 to about 50%, for example about 7 to about 50%, specifically about 8 to about 50%, of the number average molecular weight of the finally obtained polycondensation resin Can be. For example, the number average molecular weight of the lower condensate may be about 500 to about 25,000 g / mol, for example about 700 to about 20,000 g / mol, specifically about 800 to about 18,000 g / mol. In the present specification, the number average molecular weight of the condensate is polymethyl methacrylate (pMMA) as the standard material in the case of polyamide and polyester, and polystyrene is used in the case of polycarbonate, Means the value measured by gel permeation chromatography (GPC).

In the case of polyamide, the lower order condensate discharged from the reaction vessel by the above-described method, since its temperature drops to about 100 ° C. or less instantaneously by the latent heat of evaporation of water at the time of discharge, hardly causes thermal deterioration and deterioration by oxygen. Do not. The low-order condensate may be subjected to high polymerization in the state as it is to obtain a polycondensation resin. However, the low-condensation product is preferably subjected to high polymerization by solid-phase polymerization to obtain a polycondensation resin.

Since the lower condensate discharged evaporates most of the moisture entrained by the sensible heat of the lower condensate, the lower condensate can be cooled and dried simultaneously. In addition, when the discharge treatment is performed in an inert gas atmosphere such as nitrogen, the efficiency of drying and cooling can be improved, and when a cyclone-type solid-gas separation device is installed as the discharge container of the lower condensate, Out-of-system scattering can be suppressed, discharge treatment can be performed under high gas flux, and drying and cooling efficiency can be improved.

The low-order condensate obtained in this way has a high logarithmic viscosity as described above and a low residual amount of the unreacted product, and thus does not cause fusion or agglomeration between the low-order condensate particles at the time of high polymerization by solid phase polymerization described later. Solid phase polymerization can be carried out at a high temperature, and deterioration due to side reactions can be small.

If necessary, the low-density condensate may be subjected to a high polymerization degree, which will be described later, after performing a treatment to increase the specific gravity of the volume, a compacting process to uniform the particle diameter, and a granulation treatment.

In a specific example, a lower order condensate, such as a polycarbonate, can be obtained in the form of powder form, a granule form, etc. by processing with a crystallization solvent, when melted or in solution state. The method of treating with the crystallization solvent is not particularly limited, but in general, the lower condensate of polycarbonate is stirred in the crystallization solvent to crystallize in a slurry state, or the lower condensate and the crystallization solvent are used in a mixer or kneader. Crystallization by mixing or kneading. When crystallizing in a slurry state, a device having a high speed stirring blade such as a waring blender, a device having a swirl pump with a cutter, or the like can be used. In addition, when crystallizing using a mixer or a kneader, a device (generally referred to as a mixer or kneader) (such as a powder industry manual, a daily industrial newspaper, pages 644 to 648, etc.) can be used, for example, a cone blender, Ribbon blenders, shovel mixers, pug mixers, Henschel mixers, brabenders, twin screw kneaders and the like can be used.

Examples of the crystallization solvent include esters such as ethyl acetate; Ethers such as diethyl ether; Ketones such as acetone and methyl ethyl ketone; Etc. can be illustrated. Moreover, according to the temperature conditions of crystallization, Hydrocarbons, such as hexane and an octane; Cyclic hydrocarbons such as cyclohexane; Etc. can also be used as a crystallization solvent. Among these, acetone is preferable because it can manufacture the low order condensate of polycarbonate with a large specific surface area.

(C) polymerizing the discharged low order condensate to produce a polycondensation resin

In this step, the polycondensation resin is produced by polymerizing the low-order condensate discharged from the reaction vessel (in the system). It is preferable that the polycondensation resin of this invention is obtained by carrying out high polymerization degree by solid-phase-polymerizing the said lower order condensate.

In a specific example, the solid phase polymerization can be carried out continuously using the lower order condensate obtained from the reaction vessel, and can be carried out after drying the lower order condensate taken out of the reaction vessel. Further, the lower order condensate taken out of the reaction vessel may be stored once, and the lower order condensate removed from the reaction vessel may be carried out after the compacting or granulation treatment. When high polymerization degree is carried out by solid state polymerization, polycondensation resin with less thermal degradation can be obtained.

The polymerization method and conditions for solid-phase polymerization of the lower condensate are not particularly limited, and any method and conditions can be used to perform high polymerization while maintaining a solid state without causing fusion, aggregation, or deterioration of the lower condensate. . Preferably, in order to prevent oxidative deterioration of the lower order condensate and the resulting polycondensation resin, solid phase polymerization may be performed 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 may be, for example, about 170 to about 350 ° C. In addition, the time to reach the highest reaction temperature may be at any point from the solid phase polymerization start to the end.

There is no particular limitation on the solid phase polymerization apparatus used in the present process, and any known apparatus can be used. As a specific example of a solid-state polymerization apparatus, a uniaxial disk type | mold, a kneader, a biaxial paddle type | mold, a vertical column type apparatus, a vertical column type apparatus, a rotary drum type or a double cone type solid state polymerization apparatus, a dryer, etc. can be illustrated.

The reaction time of the solid phase polymerization is not particularly limited, but may be, for example, about 1 to about 20 hours. During the solid phase polymerization reaction, the lower order condensate may be mechanically stirred or agitated by gas flow.

In the present invention, various fiber materials such as glass fibers and carbon fibers, inorganic powder fillers, organic powder fillers, colorants, and ultraviolet rays, if necessary, in a step of preparing a lower condensate, a solid phase polymerization step, or any step after the solid phase polymerization. Additives such as absorbents, light stabilizers, antioxidants, antistatic agents, flame retardants, crystallization accelerators, plasticizers, lubricants, and other polymers may be added.

The polycondensation resin produced according to the production method of the present invention is excellent and stable in physical properties such as heat resistance, mechanical performance, low water absorption, chemical resistance and the like. Accordingly, the polycondensation resin may be used alone or as necessary in the form of a composition with the aforementioned various additives or other polymers, and various molding methods and spinning methods conventionally used for polycondensation resins, for example, injection molding, blow molding, It can shape | mold with various molded articles, a fiber, etc. by the shaping | molding methods, such as extrusion molding, compression molding, extending | stretching, vacuum forming, melt spinning, etc. Molded articles, such as fibers obtained by the molding method, are useful for various uses, such as industrial plastics, industrial materials, household goods, such as electronic and electrical parts, automobile parts, and office equipment parts, as well as applications as engineering plastics.

Hereinafter, the present invention will be described in more detail with reference to examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.

Property evaluation method

The evaluation of logarithmic viscosity (IV), molecular weight, melting point, crystallization temperature and color were carried out by the following method.

(1) Algebraic viscosity (IV)

The sample solution was prepared by dissolving the sample in a solvent at a concentration of 0.5 g / dL. Polyamide used 96% concentrated sulfuric acid as solvent, polycarbonate used dichloromethane, and polyester used o-chlorophenol. The number of drops of the solvent and the sample solution were measured using a Uberode viscometer at a temperature of 25 ° C. and calculated by Equation 5 below.

[Equation 5]

η _inh (algebra viscosity) = In (η _rel ) / c

In Equation 5, η _rel is t1 / t0 (where t1 is the number of falling seconds of the sample and t0 is the number of falling seconds of the blank), and c is the solution concentration (g / dL).

(2) molecular weight

Molecular weight (number average molecular weight (Mn) and weight average molecular weight (Mw), unit: g / mol) by dissolving 10 mg of a resin sample in 10 g of solvent using Shodex GPC-101 manufactured by Showa Denko Co., Ltd. ) Was used for the measurement. In measuring the molecular weight of polyamide and polyester, two columns of HFIP-806M were used, the solvent was hexafluoroisopropanol (HFIP), and polymethylmethacrylate (pMMA) was used as a standard sample. In measuring the molecular weight of the polycarbonate, the column used three LF-804, the solvent was tetrahydrofuran (THF), and polystyrene was used as a standard sample. The measurement conditions of GPC were column temperature 40 degreeC, and solvent flow volume 1.0 ml / min. The data processing software calculated | required number average molecular weight (Mn) and weight average molecular weight (Mw) using SIC-480II which is the same company product as the above.

(3) melting point, crystallization temperature

Using a DSC manufactured by Seiko Instruments, Inc., the sample in an amorphous state was heated at 30 ° C. to 350 ° C. at a temperature increase rate of 10 ° C./min under a nitrogen atmosphere at a flow rate of 10 ml / min, and then held for 5 minutes. Then, it measured to 200 degreeC by the temperature-fall rate of 10 degree-C / min, and measured the endothermic peak temperature by melting at the time of temperature rising as the melting point and the exothermic peak temperature by crystallization at the time of temperature-fall as crystallization temperature, respectively.

(4) color (YI)

The YI value was measured using the NW-11 compact colorimeter made by Nippon Denshoku Kogyo Co., Ltd.

(5) saturated steam pressure

When the by-product or raw material is water, the saturated vapor pressure (P _y , P _y = P _ws ) was calculated from the Wagner equation represented by Equation 2 below, and in the case of an organic compound (phenol, ethylene glycol), an antholite represented by Equation 3 below Saturated vapor pressures (P _y , P _y = 0.01 P _aw ) were calculated from the Antoine equation.

[Equation 2]

In Formula 2, P _ws (unit: kPa) means Wagner's exact water vapor pressure, P _c is the critical pressure 22120 kPa, A is -7.76451, B is 1.45838, C is -2.7758, D is -1.23303 , x is 1- (T / T _c ), where T _c is 647.3 K as the critical temperature and T (unit: K) is the temperature of the reaction solution).

[Equation 3]

In Formula 3, P _aw (unit: bar) means saturated vapor pressure, T (unit: K) is the temperature of the reaction solution, A, B and C is an antho constant, in the case of phenol, A is 4.24688 , B is 1509.677, C is -98.949, and for ethylene glycol, A is 4.97012, B is 1914.951, and C is -84.996.

Example

Example 1: Preparation of Polyamide

As raw materials, 44.84 kg (0.270 kmol = 65 mol%) of terephthalic acid, 21.24 kg (0.145 kmol = 35 mol%) of adipic acid, 48.93 kg (0.421 kmol = 100 mol%) of 1,6-hexamethylenediamine, terminal sealant 1.52 kg of benzoic acid (0.012 kmol = 3 mol parts relative to 100 mol parts of dicarboxylic acid), 115 g of sodium hypophosphite monohydrate (0.1 part by weight based on 100 parts by weight of the input raw material) and 77.8 kg of water (the input raw material 100) 40 parts by weight) was injected into a 500L autoclave reactor equipped with a partial condenser, a pressure regulating valve, an end window, a liquid level gauge, and a bottom discharge valve, and subjected to nitrogen substitution. Next, the contents were stirred, the temperature was raised to 130 ° C. over 1 hour, and the contents were confirmed to be a homogeneous solution. Next, the internal temperature was raised to 250 ° C. over 3 hours and maintained. After the internal pressure reached 3.8 MPa, the reaction was continued for 2 hours while distilling off water to maintain the same temperature and pressure. Thereafter, while maintaining the reaction temperature at 250 ° C, the pressure was lowered to 3.4 MPa for 30 minutes, and at the time point at which 51 kg of water was distilled off (25% by weight of the reaction liquid), the reaction was terminated, and the discharge operation was started. It was.

It was confirmed by a liquid level meter that the reaction liquid volume at the start of discharge was 128 liters. The opening of the bottom discharge valve and the discharge control valve was adjusted to discharge the reaction solution for 1.1 hours. While the reaction liquid is discharged, in order to maintain the chemical equilibrium of the reaction liquid state (chemical equilibrium of the formation reaction of the lower condensate), an amount of water vapor that can maintain a constant amount of water, which is a by-product of the reaction and a solvent, is added to the gas phase. Supplied. The supply rate Z of steam calculates the saturated steam pressure P _y (P _ws ) (250 ° C., 4.0 MPa) at the temperature in the autoclave according to the Wagner equation (Formula 2), and based on the following formulas 1 and 4, Saturated water vapor volume Y (16.5 kg / m ³ under the same conditions) and saturated water vapor volume Y × (P _x / P _y ) [kg / m ³ ] in the reaction system are calculated, taking into account the volume (V) and the discharge time (L). Thereby, the amount of water vapor introduced (water vapor introduction rate) per unit time was 1.6 kg / hour:

[Equation 1]

In Equation 1, Z (unit: kg / hr) is a unit of a substance (vapor phase) of the same kind as a by-product or raw material introduced to maintain a chemical equilibrium state of the reaction of formation of the lower condensate at the start of lower condensate discharge. Supply per hour (steam feed rate), P _x (unit: kPa) is the pressure in the system, P _y (unit: kPa) is the temperature in the system (temperature of the reaction solution) T (unit: K, T [ K] = T '[° C.] + 273.15) means the saturated vapor pressure (theoretical value) per unit volume, V (unit: m ³ ) means the volume of the reaction solution, Y (unit: kg / m ³ ) Denotes the amount of saturated steam per unit volume (theoretical value) under the conditions of the temperature T and the saturated vapor pressure P _y , and L (unit: hr) means time for discharging all the lower condensates in the system.

[Equation 4]

In Equation 4, Y (unit: kg / m ³ ) means the amount of saturated steam per unit volume (theoretical value) under the conditions of temperature T and saturated vapor pressure P _y , P _y (unit: kPa) is the temperature T (unit: K) means the saturated vapor pressure (theoretical value) per unit volume, T (unit: K) is the temperature of the reaction solution, Mw (unit: g / mol) is the weight average molecular weight of the by-product or raw material, R is the gas As a constant, it is 8.3145.

Here, the water vapor was supplied into the autoclave using a metering pump, passed through a preheater, and supplied by saturated water vaporization. During the discharge operation, the temperature of the reactor was maintained at 250 ° C., and the pressure regulating valve was maintained at 3.4 MPa in the fully closed state. The resulting lower condensate was discharged from the bottom discharge valve to the vessel at room temperature (25 ° C.) and atmospheric pressure under a nitrogen atmosphere. The operation of discharging the lower condensate was able to discharge the whole amount stably. The low order condensate immediately after the discharge was a temperature of 83 ° C. and a water content of 1.8% by weight. Sampling was performed every 0.1 hours from the start of discharge, and the logarithmic viscosity (IV) was measured for each sample. As a result, the average value of IV of each sample was 0.13 dL / g, standard deviation 0.003, and a coefficient of variation of 2%. In other words, the variation in the ash was very small and the quality was stable. In addition, the discharged lower condensates solidified, and all of these lower condensates were pulverized and mixed, and the number average molecular weight (Mn) was 1,200 g / mol.

10 kg of the obtained lower-order condensate was injected into a conical tumbler with an internal volume of 50 L of oil jacket, and the pressure was reduced to 0.13 kPa after nitrogen replacement. The heating oil was circulated while maintaining the vacuum, and the internal temperature was raised to 245 ° C. over 2 hours, and then the solid phase polymerization reaction was continued at the same temperature for 5 hours. After the predetermined reaction time had elapsed, the mixture was cooled to room temperature (25 ° C) to obtain a highly polymerized polyamide.

The average value (n = 10) of IV of obtained polyamide (polycondensation resin) was 0.86 dL / g, the standard deviation 0.015, and the coefficient of variation 2%. The variation in the ash was very small and the quality was stable. Melting point by DSC measurement was 324 ° C, crystallization temperature was 294 ° C, YI was 2, Mn was 12,000 g / mol, and sufficiently high polymerized color, high heat-resistant polyamide was obtained.

Example 2: Preparation of Polyamide

45.00 kg (0.172 kmol) of polyamide 66 salt prepared in advance, 33.60 kg (0.202 kmol) of terephthalic acid, 35.10 kg (0.195 kmol as hexamethylenediamine) of 64.5% by weight of hexamethylenediamine, 12.5 kg of distilled water Injected into a 500L autoclave reactor equipped with a control valve, an end window, a liquid level gauge, and a bottom discharge valve, nitrogen replacement was performed. It heated up to 130 degreeC for 1 hour, stirring, and confirmed that the content became a homogeneous solution. Thereafter, the internal temperature was maintained at 255 ° C. for 3.5 hours. It hold | maintained for 30 minutes after that, reaction was complete | finished by reaction temperature 260 degreeC and internal pressure 4.0 MPa, and discharge operation | movement was started.

It was confirmed by a liquid level meter that the reaction liquid amount at the start of discharge was 88.8L. The opening degree of the bottom discharge valve and the discharge control valve was adjusted to discharge this for 0.9 hours. While the reaction solution is discharged, the vapor is supplied to the gas phase in an amount sufficient to maintain a constant amount of water, which is a byproduct of the reaction and a solvent, so as to maintain the chemical equilibrium of the reaction liquid state (the chemical equilibrium of the production reaction of the lower condensate). It was. The feed rate Z of steam determines the saturated steam pressure P _y (P _ws ) (260 ° C., 4.7 MPa) at the temperature in the autoclave according to the Wagner equation, and is the same as in Example 1, wherein the equations 1 and 4 Based on this, the amount of saturated water vapor Y (19.1 kg / m ³ under the same conditions) and the amount of water vapor Y × (P _x / P _y ) [kg / m ³ ] in the reaction system are calculated, and the volume (V) and the discharge time (L) are calculated. ), The water vapor supply amount (water vapor supply rate) per unit time was 1.6 kg / hour. Here, the water vapor was supplied into the autoclave using a metering pump, passed through a preheater, and supplied by saturated water vaporization.

During the discharge operation, the temperature of the reactor was maintained at 260 ° C., the pressure regulating valve was kept in a fully closed state, and the steam pressure was maintained at 4.0 MPa. The resulting lower condensate was discharged from the bottom discharge valve to the vessel at room temperature (25 ° C.) and atmospheric pressure under a nitrogen atmosphere. The operation of discharging the lower condensate was able to discharge the whole amount stably. The low order condensate immediately after the discharge was a temperature of 85 ° C. and a water content of 2.3% by weight. Sampling was carried out every 0.1 hours from the start of discharge, and the logarithmic viscosity (IV) was measured for each sample. As a result, the average value of the samples IV was 0.16 dL / g, standard deviation 0.003, and coefficient of variation 2%. The variation in the ash was very small and the quality was stable. In addition, Mn of the obtained lower condensate was 1,500 g / mol.

10 kg of the resulting lower condensate was injected into a conical tumbler with an inner volume of 50 L of oil jacket, and the pressure was reduced to 0.13 kPa after nitrogen replacement. The heating oil was circulated while maintaining the vacuum, and the internal temperature was raised to 245 ° C. over 2 hours, and then the solid phase polymerization reaction was continued at the same temperature for 5 hours. After predetermined reaction time passed, it cooled to room temperature (25 degreeC), and the high polymerization degree polyamide was obtained.

The average value (n = 10) of IV of the obtained polyamide was 0.95 dL / g, the standard deviation 0.025, and the coefficient of variation 3%. The variation in the ash was so small that the quality was stable. Melting | fusing point by DSC measurement was 301 degreeC, the crystallization temperature was 268 degreeC, YI was 5, Mn was 14,500 g / mol, and the high heat resistant polyamide which was sufficiently high polymerization degree was obtained.

Comparative Example 1: Preparation of Polyamide

The low-order condensate was synthesized under the same conditions as in Example 1 except that water vapor was not supplied at the time of discharge operation. As a result, since the contents liquid solidified at the time of about 80% discharge, the discharge operation was stopped. Sampling was performed every 0.1 hours from the start of discharge, and the average value of IV of the obtained lower-order condensate was 0.15 dL / g, standard deviation 0.027, and coefficient of variation 18%. The variation in the batch was large. In addition, Mn of the obtained lower condensate was 1,500 g / mol.

As a result of performing solid-phase polymerization of the obtained lower-order condensate in the same manner as in Example 1, many deposits in the device derived from the low molecular weight material were observed after the completion of the reaction. The average value (n = 10) of IV of the obtained polyamide was 0.68 dL / g, the standard deviation 0.038, and the coefficient of variation 6%. Compared with the polyamide of the Example, IV was low and the variation in ash was also large. Melting | fusing point by DSC measurement was 315 degreeC, the crystallization temperature was 295 degreeC, YI was 8, and Mn was 9,800 g / mol.

Comparative Example 2: Preparation of Polyamide

Synthesis of the lower order condensate was carried out under the same conditions as in Example 2, except that water was supplied at a metering pump at 15 L / hour and the water vapor pressure was maintained at 4.0 MPa during the discharge operation. As a result, although the discharge operation was satisfactory, the average value of IV of the low-order condensate obtained by sampling every 0.1 hours from the start of discharge was 0.13 dL / g, standard deviation 0.025, and coefficient of variation 19%. In other words, the variation in the batch was large. In addition, Mn of the obtained lower condensate was 1,200 g / mol.

As a result of solid-phase polymerization of the obtained lower order condensate in the same manner as in Example 2, many deposits in the device derived from the low molecular weight substance were observed after the completion of the reaction. The IV average value (n = 10) of the obtained polyamide was 0.71 dL / g, the standard deviation 0.043, and the variation coefficient 6%. Compared with the Example, IV was low and the variation in ash was also large. Melting | fusing point by DSC measurement was 300 degreeC, crystallization temperature was 275 degreeC, YI was 9, and Mn was 10,300 g / mol.

Example 3: Synthesis of Polycarbonate

Into a polymerization reactor stirring vessel having an internal volume 2L autoclave stirring tank, a condenser, and a pressure reducing device, 456 g (2 mol) of 2,2-bis (4-hydroxyphenyl) propane, 446 g (2.08 mol) of diphenyl carbonate, And 0.112 mg of potassium hydroxide was added, and the polycondensation reaction was carried out at a temperature of 240 ° C. and a pressure of 1.3 kPa (10 torr) while leaving phenol as a reaction by-product out of the stirring tank for 2 hours. After completion | finish of reaction, pressure reduction was stopped and the temperature was maintained at 240 degreeC, 12.8 g of phenols were supplied in the system with the high temperature HPLC pump, and the pressure was 400 kPa which is the saturated vapor pressure of phenol. The reaction solution amount was 540 mL. The opening degree of the bottom discharge valve and the discharge control valve was adjusted to discharge this for 0.25 hours. In order to maintain the chemical equilibrium of the reaction liquid state (chemical equilibrium of the formation reaction of the lower condensate) while the reaction liquid was discharged, an amount of phenol was supplied to the gas phase to maintain a constant amount of phenol as a byproduct of the reaction. . The supply rate Z of phenol obtains the saturated phenol vapor pressure P _y (0.01 P _AW ) (240 ° C., 400 kPa) at the temperature in the autoclave from the above-mentioned antoin formula (Equation 3). on the basis of the first and fourth, saturated phenol steam quantity Y and (8.8 g / L = 8.8 kg / m 3 under the same conditions), saturation in the reaction system phenol steam quantity Y × calculating the _{(P x / P y) [} kg / m 3] The volume (V) and the discharge time (L) were considered to be 19.1 g / hour. The supply of phenol was carried out in a high temperature HPLC pump, in an autoclave, as saturated phenol vapor.

During the discharge operation, the temperature of the reactor was maintained at 240 ° C., the pressure regulating valve was kept in a fully closed state, and the phenol vapor pressure was maintained at 400 kPa. The resulting lower condensate was discharged from the bottom discharge valve to the vessel at room temperature (25 ° C.) and atmospheric pressure under a nitrogen atmosphere. The operation of discharging the lower condensate was able to discharge the whole amount stably. Samples taken after 0 minutes, 5 minutes, 10 minutes, and 15 minutes after discharge were measured, and the algebraic viscosity (IV) of each sample was measured. As a result, all were 0.14 dL / g. Very small, stable quality. The lower condensate of the polycarbonate collected in the container was ground, acetone was added, crystallized, and dried under reduced pressure at 100 ° C. to obtain a polymer powder. IV of the lower polycondensate (granule) of the obtained polycarbonate was 0.14 dL / g, Tm was 226 degreeC, and Mn was 2,900 g / mol.

100 g of the polycarbonate lower condensate was injected into a glass 500 mL rotary evaporator and subjected to solid phase polymerization under a rotation speed of 30 rpm, 220 ° C., and vacuum at 0.13 kPa for 2 hours. The average value (n = 5) of IV of the obtained polycarbonate was 0.45 dL / g, the standard deviation 0.006, and the coefficient of variation 1.4%. The variation in the ash was very small and the quality was stable. In addition, Mn of the obtained polycarbonate was 11,800 g / mol.

Comparative Example 3: Synthesis of Polycarbonate

After completion of the polycondensation reaction, the pressure reduction was stopped and the temperature was maintained at 240 ° C., except that phenol was used instead of phenol, and the pressure was set to 400 kPa even during discharge, in the same manner as in Example 3 above, polycarbonate Lower order condensates were obtained. The IV of the obtained lower condensate is 0.14 dL / g after 0 minutes of discharge, 0.15 dL / g after 5 minutes, 0.15 dL / g after 10 minutes, 0.16 dL / g after 15 minutes, and the IV rises toward the second half of the discharge. Showed a tendency. Mn was 3,100 g / mol.

The resulting lower condensate was subjected to solid phase polymerization in the same manner as in Example 3. The average value (n = 5) of IV of the obtained polycarbonate was 0.46 dL / g, the standard deviation 0.012, and the coefficient of variation 2.6%. The variation in the ash was about twice as large as in Example 3. In addition, Mn of the obtained polycarbonate was 12,100 g / mol.

Example 4: Synthesis of Polyester

830 g (5 mol) of terephthalic acid, 372 g (6 mol) of ethylene glycol, and 373 mg of antimony trioxide were added to a stirring tank of a polymerization reactor having an internal volume of 2 L of an autoclave stirring tank, a condenser, and a decompression device. The esterification reaction was performed for 5 hours at the temperature of 260 degreeC and the pressure of 100 kPa, flowing out the produced water. Next, the temperature was raised to 280 ° C, the pressure was gradually reduced to 5 torr, and the polycondensation reaction was carried out while flowing water, which was a reaction byproduct, out of the stirring bath for 2 hours.

After completion | finish of reaction, pressure reduction was stopped and the temperature was maintained at 280 degreeC, the ethylene glycol which is a reaction raw material was introduce | transduced into 10.8 g system with the high temperature HPLC pump, and the pressure was set to 750 kPa which is the saturated vapor pressure of ethylene glycol. The reaction liquid amount was 960 mL. The opening degree of the bottom discharge valve and the discharge control valve was adjusted to discharge it in one hour. While the reaction liquid is discharged, in order to maintain the chemical equilibrium of the reaction liquid state (chemical equilibrium of the formation reaction of the lower condensate), an amount of ethylene glycol is supplied to the gas phase to maintain a constant amount of ethylene glycol as a reaction raw material. It was. The feed rate Z of ethylene glycol determines the saturated ethylene glycol vapor pressure P _y (P _aw ) (750 kPa at 280 ° C) at the temperature in the autoclave from the _anthroid formula, and the formula (1) and Based on (6), the amount of saturated ethylene glycol vapor Y (10.1 g / L = 10.1 kg / m <3> in the same conditions) and the amount of saturated ethylene glycol vapor Y * (P _x / P _y ) [kg / m 3] in the reaction system are calculated. And, considering the volume (V) and the discharge time (L), it was 9.7 g / hour. The ethylene glycol was supplied into an autoclave by a high temperature HPLC pump and performed as saturated ethylene glycol vapor.

During the discharge operation, the temperature of the reaction vessel was maintained at 280 ° C, the pressure regulating valve was kept in a fully closed state, and the ethylene glycol vapor pressure was maintained at 750 kPa. The resulting lower condensate was extracted and cooled in water in a strand shape from the bottom discharge valve, and pelletized with a strand cutter to obtain a lower condensate of polyethylene terephthalate. The operation of discharging the lower condensate was stable, allowing the entire discharge. After 0 minutes of discharge, 10 minutes later, 20 minutes later, 30 minutes later, and 60 minutes later, samples were taken, and the logarithmic viscosity (IV) of those samples was measured. As a result, all were 0.52 dL / g. The variation in the ash was very small and the quality was stable. IV of the obtained polyethylene terephthalate lower condensate was 0.52 dL / g, and Mn was 14,800 g / mol.

100 g of the pellet was injected into a 500 mL glass rotary evaporator, crystallized at 170 ° C. for 2 hours under a nitrogen atmosphere, and then solidified for 12 hours under vacuum of 30 rpm, 220 ° C., and 0.13 kPa. The average value (n = 5) of IV of the obtained polyethylene terephthalate was 0.86 dL / g, the standard deviation 0.004, and the coefficient of variation 0.5%. The variation in the ash was very small and the quality was stable. Moreover, Mn of obtained polyester (polyethylene terephthalate) was 31,100 g / mol.

Comparative Example 4: Synthesis of Polyester

After completion of the polycondensation reaction, the pressure reduction was stopped and the temperature was maintained at 280 ° C., except that ethylene glycol was used instead of ethylene glycol, except that the pressure was maintained at 750 kPa even during discharge. The lower order condensate of polyethylene terephthalate was obtained. The obtained lower condensate IV is discharged at 0.53 dL / g after 0 minutes, 0.53 dL / g after 10 minutes, 0.54 dL / g after 20 minutes, 0.55 dL / g after 30 minutes, and 0.57 dL / g after 60 minutes. The IV tended to increase toward the end of. Mn was 15,800 g / mol.

The obtained lower order condensate was subjected to solid phase polymerization in the same manner as in Example 4. The average value (n = 5) of IV of the obtained polyethylene terephthalate was 0.90 dL / g, the standard deviation 0.016, and the coefficient of variation 1.8%. The variation in the ash was about four times larger than in the examples. Moreover, Mn of obtained polyester (polyethylene terephthalate) was 33,300 g / mol.

The conditions for producing the lower order condensates of Examples 1 and 2 and Comparative Examples 1 and 2 are shown in Table 1, and the evaluation results are shown in Table 2. In addition, the conditions of manufacturing the lower order condensate of Examples 3 and 4 and Comparative Examples 3 and 4 are shown in Table 3, and the evaluation results are shown in Table 4 below.

Table 1

TABLE 2

TABLE 3

Table 4

From Table 2 and Table 4, it can be seen that the polycondensation resin produced according to the production method of the present invention does not vary in molecular weight according to the time difference at the time of discharging the lower condensate, thereby obtaining stable quality. Moreover, it turns out that the polycondensation resin of stable quality is obtained by the (solid state) superposition | polymerization of the lower order condensate of stable quality.

Simple modifications or variations of the invention may be readily made by those skilled in the art, and all such modifications or changes may be considered to be included within the scope of the present invention.

Claims (6)

1. Preparing a lower order condensate by a polycondensation reaction;

   Discharging the lower condensate out of the system; And

   And polymerizing the discharged lower order condensate to produce a polycondensation resin,

   The polycondensation reaction and polymerization is to be carried out in a batch reactor,

   The step of discharging the lower condensate out of the system, wherein the lower condensate is discharged out of the system while replenishing a substance of the same kind as a by-product or a raw material of the polycondensation reaction into the system. Method for producing a synthetic resin.
2. The polycondensation resin according to claim 1, wherein a substance of the same kind as the by-product or raw material is supplemented into the system to maintain a chemical equilibrium state of the reaction of formation of the lower condensate at the start of discharging the lower condensate. Way.
3. The method of claim 1, wherein the amount for replenishing a substance of the same kind as the by-product or raw material into the system so as to maintain a chemical equilibrium state of the reaction of formation of the lower condensate at the start of discharging is represented by Z (by-product or raw material) Method for producing a polycondensation resin, characterized in that ± 5% of the supply amount per unit time of the same kind of material):

   [Equation 1]

   

   In Equation 1, Z (unit: kg / hr) is a unit of a substance (vapor phase) of the same kind as a by-product or raw material introduced to maintain a chemical equilibrium state of the reaction of formation of the lower condensate at the start of lower condensate discharge. Supply per hour (steam feed rate), P _x (unit: kPa) is the pressure in the system, P _y (unit: kPa) is the temperature in the system (temperature of the reaction solution) T (unit: K, T [ K] = T '[° C.] + 273.15) means the saturated vapor pressure (theoretical value) per unit volume, V (unit: m ³ ) means the volume of the reaction solution, Y (unit: kg / m ³ ) Denotes the amount of saturated steam per unit volume (theoretical value) under the conditions of the temperature T and the saturated vapor pressure P _y , and L (unit: hr) means time for discharging all the lower condensates in the system.
4. The method of claim 1, wherein the number average molecular weight of the lower condensate is about 5 to about 50% of the number average molecular weight of the polycondensation resin.
5. The method of claim 1, wherein the polycondensation resin is polyamide, polycarbonate, or polyester.
6. The method for producing a polycondensation resin according to claim 1, wherein the polycondensation resin is formed by solid-phase polymerization of the low-order condensate.