JP2010121065A - Polyester and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerization catalyst for manufacturing a polyester being excellent in melting catalytic activity and solid phase polymerization activity, reducing a generation amount of a sublimation substance, enhancing crystallinity and having less content of a terminal end COOH concentration at a terminal end of the polyester chain. <P>SOLUTION: The polyester contains the polyester polymerization catalyst represented by formula (I) or (II). Alternatively, in the manufacturing method for the polyester, polymerization is performed using the compound represented by formula (I) or (II). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to polyester. More specifically, the present invention relates to a polyester containing a polymerization catalyst for producing a polyester having a high polymerization activity, generating a small amount of sublimation when the polyester is melted, and having a low content of terminal COOH groups, and a method for producing the same.

  Among polyesters, polyethylene terephthalate (hereinafter sometimes referred to as PET), polytrimethylene terephthalate (hereinafter sometimes referred to as PTT), polybutylene terephthalate (hereinafter sometimes referred to as PBT), and polyethylene. Naphthalate (hereinafter sometimes referred to as PEN), polytrimethylene naphthalate (hereinafter sometimes referred to as PTN), and polybutylene naphthalate (hereinafter sometimes referred to as PBN) have mechanical properties. It has excellent chemical properties and has many applications, such as textiles for clothing and industrial materials, various films and sheets for packaging and magnetic tape, and moldings such as bottles and engineering plastics. Has been made.

  These polyesters are generally produced by producing an oligomer having a degree of polymerization of 1 to 5 by esterification or transesterification, and polycondensing this using a polymerization catalyst for producing polyester under high temperature and vacuum. As a catalyst used in the polycondensation of these polyesters, antimony trioxide is widely used. Antimony trioxide is an inexpensive catalyst having excellent catalytic activity, but in the molding process represented by melt spinning and film formation of polyester obtained using this catalyst, a spinneret, There is a problem that foreign matter sublimated from the polyester accumulates on molding processing equipment such as dies and molds, which causes deterioration of the spinning condition, film filming condition, mold contamination, and other problems. Under such circumstances, polyesters having a reduced content of antimony element and polyesters having a reduced amount of sublimation are desired. However, if the amount of antimony trioxide used in the polyester production process is reduced, there will be problems in terms of productivity, such as a prolonged polycondensation reaction.

  Moreover, in the case of polyester used for industrial applications, in order to reduce hydrolyzability, it is required to reduce the content of terminal COOH groups present at the polyester terminal. In general, in the case of polyester used under processing conditions under wet heat, the higher the terminal COOH group content, the lower the degree of polymerization and intrinsic viscosity of the polyester over time, and as a result, the mechanical strength of the polyester molded product is impaired. End up. Therefore, there has been a demand for the production of a polyester having a low terminal COOH group content.

  On the other hand, among the above polyesters, PEN resin has mechanical properties such as strength, elongation, Young's modulus or elastic recovery rate, physical properties such as heat resistance or dimensional stability, or chemical properties such as chemical resistance or water resistance. It is well known that it has great industrial value because it is excellent and inexpensive. For example, it is widely used in fibers, resin molded products, films and the like.

  Since PEN has a rigid molecular chain when compared with PET, it has a drawback of low crystallinity. If the crystallinity of this PEN can be increased, various physical properties can be improved (higher strength, higher Young's modulus, higher toughness, higher heat and elastic modulus, improved dimensional stability, improved heat resistance, improved yarn production, reduced delamination It is expected that gas barrier properties can be improved. However, PEN having high crystallinity that meets this expectation has not been developed yet.

  As one of attempts to improve crystallinity, there is an example in which crystallinity is increased by copolymerization (for example, see Patent Documents 1 to 5). However, since the rigidity is lost when the copolymerization is performed, there is a drawback that the original physical properties (for example, strength, modulus, heat resistance) of the polyester are lowered.

Japanese Patent Laid-Open No. 08-048758 JP 08-048759 A Japanese Patent Laid-Open No. 08-048760 Japanese Patent Laid-Open No. 08-059806 Japanese Patent Laid-Open No. 08-157583

  It is an object of the present invention to contain a polymerization catalyst for producing a polyester having excellent catalytic activity during melt polymerization / catalytic activity during solid-phase polymerization. It is expected to provide a polyester with a low terminal COOH group content and a process for producing a polyester having such properties.

  As a result of intensive studies in order to achieve the object of the present invention, the present inventors have found a polyester containing a polymerization catalyst for polyester production in which an antimony compound and a specific phosphonic acid compound are reacted in advance. It has been found that the polyester of the present invention is expected to improve the crystallinity, can reduce the amount of sublimation during melting, and can provide a polyester having a low content of terminal COOH groups.

  That is, the present invention is a polyester characterized by containing a polymerization catalyst for producing a polyester represented by the following general formula (I) or (II), and the problems of the above invention can be solved by the polyester of the present invention. .

［上記式中、Ｒ_１は炭素数１〜１２個からなる炭化水素残基を表し、Ｒ_２は水素原子または炭素数１〜１２個からなる炭化水素残基を表す。ｌ、ｍ、ｎはそれぞれ１以上の整数であり、Ｘ^ａ−は、ａ価の陰イオンを表す。］

[In the above formula, R ₁ represents a hydrocarbon residue having 1 to 12 carbon atoms, and R ₂ represents a hydrogen atom or a hydrocarbon residue having 1 to 12 carbon atoms. l, m, and n are each an integer of 1 or more, and X ^a− represents an a-valent anion. ]

  Thus, according to the present invention, a polyester containing a specific polyester production polymerization catalyst is excellent in solid-phase polymerization, and the amount of generated sublimates such as oligomers when processing polyester such as melt molding is reduced, resulting in high crystallinity. Therefore, it is possible to provide a polyester having a low content of terminal COOH groups.

The present invention will be described in detail below.
The polyester of the present invention is a polyester whose main repeating unit contains any one of ethylene terephthalate, trimethylene terephthalate, butylene terephthalate, ethylene naphthalate, trimethylene naphthalate, and butylene naphthalate. That is, polyester obtained by using terephthalic acid or naphthalene dicarboxylic acid or lower alkyl ester or lower aryl ester thereof as the dicarboxylic acid component, and ethylene glycol, 1,3-propanediol or 1,4-butanediol as the diol component Is shown. Among these, 2,6-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid are preferably used as naphthalenedicarboxylic acid. A main repeating unit represents that 70 mol% or more is comprised from said repeating unit among all the repeating units which comprise polyester. For example, when the main repeating unit is a polyester of ethylene terephthalate, it means that 70 mol% or more is composed of ethylene terephthalate with respect to all repeating units. The ratio of the main repeating unit is more preferably 80 mol% or more of all repeating units constituting the polyester, and most preferably 90 mol% or more of all repeating units constituting the polyester.

  The polyester of the present invention can be copolymerized with other copolymerization components in a range of less than 30 mol% of all dicarboxylic acid components constituting the polyester. Examples of copolymerizable dicarboxylic acid components include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid and other aliphatic dicarboxylic acids; isophthalic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, diphenylsulfonedicarboxylic acid Examples thereof include aromatic dicarboxylic acids such as acids and diphenyl ether dicarboxylic acids; alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid, decalin dicarboxylic acid and tetralin dicarboxylic acid; oxy acids such as glycolic acid and p-oxybenzoic acid.

  The polyester can be copolymerized with other diol components other than those described above within a range of less than 30 mol% of the total glycol components. Examples of copolymerizable diol components include 1,2-propanediol, hexamethylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, cyclohexane dimethanol, and 2,2-bis (4-β-hydroxyethoxyphenyl) propane. Diols can be mentioned.

  When the copolymerization amount of the above dicarboxylic acid component and / or glycol component exceeds 30 mol%, the physical properties inherent to the polyester, such as strength, modulus, Young's modulus, and dimensional stability, may be inferior. Therefore, the copolymerization amount is preferably 20 mol% or less, more preferably 10 mol% or less, based on the polyester.

  Further, the polyester of the present invention has a branched component, for example, an acid having a trifunctional or tetrafunctional or higher functional group capable of forming an ester such as tricarbaric acid, trimesic acid, trimellitic acid, or glycerin, trimethylolpropane, pentaerythritol. Alcohols having a functional group capable of forming an ester such as trifunctional or tetrafunctional or higher may be copolymerized. In that case, they are 1.0 mol% or less of the total dicarboxylic acid component which comprises polyester, Preferably it is 0.5 mol% or less, More preferably, it is 0.3 mol% or less. Furthermore, you may use the polyester obtained using the catalyst for polyester manufacture of this invention combining these copolymerization components 2 or more types.

(Esterification reaction)
Such polyester of this invention can be manufactured in accordance with the conventionally well-known manufacturing method of polyester. That is, after the ester exchange reaction between the dialkyl ester of dicarboxylic acid and the alkylene diol, which is the glycol component, as the acid component, the product of this reaction is heated under reduced pressure to remove the excess diol component and polycondensation Can be manufactured. Alternatively, by esterifying with a dicarboxylic acid and a diol component, the reaction product can also be produced by a conventionally known direct polymerization method such as a method of heating under reduced pressure.

(About transesterification reaction catalyst)
The transesterification catalyst used in the case of a method utilizing a transesterification reaction when producing polyester is not particularly limited, but manganese, magnesium, titanium, zinc, aluminum, cerium, calcium, barium, cobalt, A compound containing lithium, sodium, potassium, cesium, or lead can be used. Examples of such compounds include manganese, magnesium, titanium, zinc, aluminum, calcium, cobalt, sodium, lithium, lead oxide, acetate, carboxylate, hydride, alcoholate, halide, carbonate, sulfuric acid. And phosphate. Of these, compounds of manganese, magnesium, calcium, cerium, zinc, titanium, sodium, and lithium are preferred from the viewpoints of melt stability of polyester, hue, small amount of insoluble foreign matter with respect to polyester, and spinning stability. Zinc compounds are preferred. Moreover, these compounds may use 2 or more types together. In addition, when the polymerization catalyst for producing a polyester contained in the polyester of the present invention is used for producing a polyester, the above-mentioned transesterification catalyst is represented by the following formula (IV) so that an appropriate intrinsic viscosity range can be reached within a reasonable polymerization time. ) Is preferably selected within a range that satisfies the above.
5 <M <100 (IV)
[In the above formula, M represents the ratio of the transesterification catalyst to the total acid component constituting the polyester, and the unit is mmol%. ]

(Polymerization catalyst for polyester production: antimony compound)
The polymerization catalyst for producing a polyester contained in the polyester of the present invention is a reaction product of an antimony compound and a phosphonic acid compound. The antimony compound here is a compound composed of trivalent antimony. Examples of such antimony compounds include antimony oxides, acetates, fatty acid salts, hydroxides, alkoxides, glycosides, carbonates, halides, sulfates, and phosphates. Preferably, antimony trioxide, antimony acetate, antimony chloride, tris (2-hydroxyethoxy) antimony, and antimony glycolate can be used.

(Polymerization catalyst for polyester production: phosphonic acid compound)
The phosphorus compound to be reacted with antimony in the polymerization catalyst for polyester production contained in the polyester of the present invention can be represented by the following general formula (V) or (VI).

［上記式中、Ｒ_１は炭素数１〜１２個からなる炭化水素残基を表し、Ｒ_２は水素原子または炭素数１〜１２個からなる炭化水素残基を表す。Ｒ_３、Ｒ_４は炭素数１〜１２個からなる炭化水素残基を表し、式中の官能基Ｒ_３およびＲ_４は同一でも異なっていても良い。］

[In the above formula, R ₁ represents a hydrocarbon residue having 1 to 12 carbon atoms, and R ₂ represents a hydrogen atom or a hydrocarbon residue having 1 to 12 carbon atoms. R ₃ and R ₄ represent a hydrocarbon residue having 1 to 12 carbon atoms, and the functional groups R ₃ and R ₄ in the formula may be the same or different. ]

In the chemical structural formula represented by the general formula (V) or (VI), R ₁ , R ₃ , and R ₄ are preferably a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, sec- A butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a phenyl group, a naphthyl group, and a benzyl group. These R ₁ , R ₃ and R ₄ may be the same organic group or different organic groups. More preferably, R ₁ is a phenyl group, and R ₃ and R ₄ are a methyl group, an ethyl group, or a phenyl group. Similarly, R ₂ can employ the same organic group as R ₁ except that a hydrogen atom can be employed.

  Examples of the phosphonic acid compound represented by the general formula (V) include phenylphosphonic acid, methyl phenylphosphonate, (2-hydroxyethyl) phenylphosphonate, benzylphosphonic acid, methyl benzylphosphonate, ethyl benzylphosphonate, 1- Naphthylphosphonic acid, 1-naphthylphosphonic acid methyl, 1-naphthylphosphonic acid ethyl, 2-naphthylphosphonic acid, 2-naphthylphosphonic acid methyl, 2-naphthylphosphonic acid ethyl, 4-hydroxybenzylphosphonic acid, 4- Examples include methyl hydroxybenzylphosphonate, ethyl 4-hydroxybenzylphosphonate, 4-biphenylphosphonic acid, methyl 4-biphenylphosphonate, and ethyl 4-biphenylphosphonate.

  Examples of the phosphonic acid compound represented by the general formula (VI) include dimethyl phenylphosphonate, diethyl phenylphosphonate, bis (2-hydroxyethyl) phenylphosphonate, dimethyl benzylphosphonate, diethyl benzylphosphonate, 1-naphthylphosphone. Dimethyl acid, diethyl 1-naphthylphosphonate, dimethyl 2-naphthylphosphonate, diethyl 2-naphthylphosphonate, dimethyl 4-hydroxybenzylphosphonate, diethyl 4-hydroxybenzylphosphonate, dimethyl 4-methylbenzylphosphonate, Examples include diethyl 4-methylbenzylphosphonate, dimethyl 4-biphenylphosphonate, and diethyl 4-biphenylphosphonate.

Further, in the hydrocarbon groups of R _{1 to} R ₄ represented in the above formulas (V) and (VI), one or two or more hydrogen atoms may be substituted with another functional group. Examples of other substituents include substitution with a hydroxyl group, an ester group, an alkoxy group, or a halogen atom. Preferred examples of the hydrocarbon group substituted with such a substituent include the following functional groups and structural isomers thereof.

［上記式中、ｑは１〜１０までの整数を表し、Ｐｈは芳香環を表す。］

[In the above formula, q represents an integer of 1 to 10, and Ph represents an aromatic ring. ]

(Polymerization polymerization catalyst: structural formulas (I) and (II))
The polymerization catalyst for producing a polyester contained in the polyester of the present invention is a reaction product of an antimony compound and a phosphonic acid compound, and is preferably represented by the following general formula (I) or (II).

［上記式中、Ｒ_１は炭素数１〜１２個からなる炭化水素残基を表し、Ｒ_２は水素原子または炭素数１〜１２個からなる炭化水素残基を表す。ｌ、ｍ、ｎはそれぞれ１以上の整数であり、Ｘ^ａ−は、ａ価の陰イオンを表す。］

[In the above formula, R ₁ represents a hydrocarbon residue having 1 to 12 carbon atoms, and R ₂ represents a hydrogen atom or a hydrocarbon residue having 1 to 12 carbon atoms. l, m, and n are each an integer of 1 or more, and X ^a− represents an a-valent anion. ]

In the above formula (I), l, m, and n need to be selected so as to satisfy the following formula (VII), and in the above formula (II), l, m, and n must be selected so as to satisfy the following formula (VIII). . This is because the compounds represented by the general formulas (I) and (II) as a whole need to balance the charge of the cation species and the anion species.
l + n × a = m × 3 (VII)
l × 2 + n × a = m × 3 (VIII)

Further, a is a numerical value that can be arbitrarily taken as long as it is a valence that can be taken by ordinary organic and inorganic anionic species, but is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1. ~ 4. As for the functional group R ₁ in the above formulas (III) and (IV), the functional groups as mentioned in the item of the phosphonic acid compounds represented by the general formulas (I) and (II) can be preferably employed. . X ^a- may be any as long as there are no special circumstances such as the compound represented by the formulas (III) and (IV) hardly existing from organic functional groups and inorganic functional groups that are generally known. Can be adopted. Among these many functional groups, O ²⁻ , HO ⁻ , HCOO ⁻ , CH ₃ COO ⁻ , CH ₃ CH ₂ COO ⁻ , CH ₃ CH ₂ CH ₂ COO ⁻ , Ph (COO ⁻ ) _r [r ^{_{= 1~6], HO-CH 2}} CH 2 -O -, (O-CH 2 CH 2 -O) 2-, HO-CH 2 CH 2 CH 2 -O -, (O-CH 2 CH 2 CH 2 ^{_{-O) 2-, HO-CH 2}} CH 2 CH 2 CH 2 -O -, (O-CH 2 CH 2 CH 2 CH 2 -O) 2-, HO-CH 2 C (CH 3) 2 CH 2 - Preferable examples include O ⁻ , (O—CH ₂ C (CH ₃ ) ₂ CH ₂ —O) ²⁻ , HCO ₃ ⁻ , CO ²⁻ , F ⁻ , Cl ⁻ , Br ⁻ and I ⁻ .

(Ratio of antimony compound to phosphonic acid compound)
It is preferable that the polymerization catalyst for polyester production represented by the above chemical formula (I) or (II) satisfies the requirement represented by the following formula (III).
0.25 <1 / m <6.0 (III)
In the above formula (III), when the value of 1 / m is less than 0.25, the ratio of the phosphonic acid compound is too small, so that the effect of improving the polymerization rate intended by the present invention cannot be obtained, and the polyester obtained Thermal stability will also be low. On the other hand, when l / m exceeds 6.0, since the ratio of the phosphonic acid compound to the antimony atom is excessive, the catalyst deactivation effect of the antimony compound by the phosphone compound is remarkably exhibited, and the polymerization rate improvement aimed at by the present invention is improved. The effect cannot be obtained. The value range of 1 / m is preferably 0.35 to 4, more preferably 0.45 to 2.

(Method for producing a polymerization catalyst for polyester production)
As a manufacturing method of the polymerization catalyst for polyester production contained in the polyester of the present invention, it can be prepared by reacting an antimony compound and a phosphonic acid compound in an appropriate organic solvent. A suitable solvent used in the reaction is not particularly limited, but it is preferable that the antimony compound and the phosphonic acid compound have high solubility. A solvent having a low boiling point that is easy to remove in a reduced-pressure atmosphere during the polymerization reaction of the polyester is preferred. Such solvents include ethylene glycol, diethylene glycol, triethylene glycol, trimethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, dimethylformamide, diethylformamide, dimethylacetamide, Diethylacetamide, dimethyl sulfoxide, diethyl sulfoxide, methanol, ethanol, 1-propanol, 2-propanol, n-butanol, isobutanol, sec-butanol, t-butanol, n-pentanol, n-hexanol, diethyl ether, tetrahydrofuran, Examples include 1,4-dioxane, acetone, and methyl ethyl ketone.

  As a method of reacting an antimony compound and a phosphonic acid compound, an organic solvent, an antimony compound and a phosphonic acid compound are added to a reaction vessel having a stirring device, a solvent reflux device (cooler or condenser), and a heating device, and the mixture is heated and stirred. The method can be adopted. At this time, water, methanol, ethanol, ethylene glycol or the like is generated as a by-product depending on the compound used. In general, since the reaction of the polymerization catalyst for polyester production is a reversible reaction, it is preferable to proceed the reaction while removing these by-products from the reaction vessel as necessary.

  The polymerization catalyst for polyester production produced in such an operation in an organic solvent can be concentrated and diluted as necessary. As a concentration method, a general concentration method such as evaporation of an organic solvent or freeze drying can be employed. Moreover, the polymerization catalyst for polyester production can be purified to a powder form by concentration.

  When the polymerization catalyst for producing a polyester contained in the polyester in the present invention is used as a slurry dissolved in a solvent, the water content present in the solvent is preferably 0.1% by weight or less. When the water content exceeds 0.1% by weight, the polymerization catalyst for polyester production reacts with water, and antimony oxide is generated by the hydrolysis reaction. The water content is more preferably 0.05% by weight or less.

(Other polymerization catalysts that may be used in combination)
In addition to the polymerization catalyst for polyester production contained in the polyester of the present invention, another polymerization catalyst can be used in combination to carry out the polymerization reaction of the polyester. Although it does not specifically limit about the polymerization catalyst to be used, Antimony compounds other than the catalyst compound of this invention, a titanium compound, a germanium compound, an aluminum compound, a zirconium compound, and a tin compound can be used. Examples of such a compound include antimony, titanium, germanium, aluminum, zirconium, tin oxide, acetate, carboxylate, hydride, alcoholate, halide, carbonate, sulfate and the like. Moreover, these compounds may use 2 or more types together.

(About stabilizer)
If necessary, a stabilizer can be added to the polyester obtained using the polymerization catalyst for producing a polyester contained in the polyester of the present invention. As the stabilizer, a known phosphorus compound is preferably used. As the phosphorus compound, orthophosphoric acid, phosphorous acid, dimethyl phosphate, diethyl phosphate, trimethyl phosphate, triethyl phosphate, dimethyl phosphite, diethyl phosphite, trimethyl phosphite, triethyl phosphite, triethylphosphonoacetate are preferable. It can be illustrated.

(Total phosphorus compound amount)
The total amount of phosphorus compound contained in the total of the polymerization catalyst phosphonic acid and stabilizer phosphorus compound contained in the polyester of the present invention is 5 to 300 mmol with respect to the total dicarboxylic acid component constituting the polyester. % Is preferable. When the total phosphorus compound amount exceeds 300 mmol%, the polymerization activity of the present invention is remarkably lowered. On the other hand, if it is less than 5 mmol%, the thermal stability at the time of melting is poor, the thermal decomposition at the time of melt processing of the polyester is severe, and this causes a significant decrease in the degree of polymerization. The total phosphorus amount is preferably in the range of 10 to 200 mmol%, more preferably 15 to 100 mmol%.

(About degree of polymerization)
The intrinsic viscosity of the polyester of the present invention is preferably an intrinsic viscosity in the range of 0.10 to 2.00 dL / g, more preferably 0.30 to 1.50 dL / g, and still more preferably 0.40. It is the range of -1.30 dL / g. The intrinsic viscosity can be calculated from a value obtained by measuring a dilute solution obtained by dissolving the obtained polyester chip in a mixed solvent of phenol / tetrachloroethane = 6/4 (weight ratio) at 35 ° C. using an Ostwald viscometer. it can.

When the polymerization catalyst for producing a polyester contained in the polyester of the present invention is used for producing a polyester, a range satisfying the following formula (IX) so that the appropriate intrinsic viscosity range can be reached within a reasonable polymerization time. Are preferably selected.
5 <M <100 (IX)
[In the above formula, M represents the ratio of the polymerization catalyst for production of the polyester of the present invention to the total acid components constituting the polyester, and the unit is mmol%. ]

(About solid phase polymerization)
Since the polymerization catalyst for producing a polyester contained in the polyester of the present invention also has a solid phase polymerization activity, the polyester can be subjected to solid phase polymerization as required. That is, after producing a polyester chip having an intrinsic viscosity of 0.40 to 0.70 dL / g by a liquid phase polymerization reaction (melt polymerization reaction), the polyester chip is crystallized, and then subjected to a temperature of 220 to 260 ° C. and a vacuum. Stir under heat. By performing this operation, a solid-phase polymerized polyester having an intrinsic viscosity of 0.70 to 1.50 dL / g can be obtained. The solid phase polymerization can be carried out in substantially the same manner as normal solid phase polymerization.

(Other additives)
In order to increase the mechanical strength, dimensional stability, and heat resistance of the polyester prepared by the polymerization catalyst for producing a polyester contained in the polyester of the present invention, a filler can be added as a reinforcing agent. Examples of the filler include montmorillonite, bentonite, hectorite, plate iron oxide, plate calcium carbonate, plate boehmite or needle boehmite, and carbon nanotube.

  Various other additives such as heat stabilizers, antifoaming agents, color adjusters, flame retardants, antioxidants, ultraviolet absorbers, infrared absorbers, fluorescent whitening agents are optionally added to the polyester of the present invention. Additives such as plasticizers or impact resistance agents may be copolymerized or mixed.

  In order to suppress the production of diethylene glycol, a base component can be added to the polyester used in the present invention as necessary. Examples of the base component include organic acid alkyl metal salts such as sodium acetate, lithium acetate, potassium acetate, and cesium acetate, amine compounds such as triethylamine, and ammonium compounds such as tetraethylammonium hydroxide. be able to.

  The present invention will be further described in the following examples, but the scope of the present invention is not limited by these examples. Various characteristics were measured by the following methods.

(A) Intrinsic viscosity (IV)
A dilute solution obtained by dissolving a polyester chip in a mixed solvent of phenol / tetrachloroethane = 6/4 (weight ratio) was measured at 35 ° C. using an Ostwald viscometer.

(I) Diethylene glycol (DEG) content Polyester chips are decomposed using hydrazine hydrate (hydrated hydrazine), and the content of diethylene glycol in the decomposition product is determined by gas chromatography (manufactured by Hewlett-Packard (HP6850 type)). It measured using.

(C) Differential scanning calorimeter The differential scanning calorimeter was measured using a TA instruments Q20 type differential scanning calorimeter. The measurement conditions are as follows.
(1) Using a differential scanning calorimeter, the polyester sample was heated to 300 ° C. under a nitrogen stream and heated at 20 ° C./min, held for 2 minutes, and then measured under a temperature drop condition of 10 ° C./min. The exothermic peak that appeared was observed, and the energy was calculated from the peak area. (The temperature at the apex of the exothermic peak was expressed as Tcd, and the crystal exothermic energy obtained from the peak area was expressed as ΔHcd.)
(2) Using a differential scanning calorimeter, the polyester sample is heated to 300 ° C. under a temperature rising condition of 20 ° C./min, and held and melted at 300 ° C. for 2 minutes, and then rapidly cooled and solidified in liquid nitrogen. A quenched polyester sample was prepared. A differential scanning calorimeter was used for the rapidly cooled polyester sample, and an exothermic peak that appeared under a temperature increase condition of 10 ° C./min was observed under a nitrogen stream, and energy was calculated from the peak area. (The temperature at the top of the exothermic peak was expressed as Tc, and the energy obtained from the peak area was expressed as ΔHc.)

(D) Generated amount of sublimate The amount of sublimate generated from the polyester sample was measured using a sublimate amount measuring apparatus shown in FIG. The apparatus for measuring the amount of sublimation is as follows: 1: Heating medium for heating polyester, 2: Sublimation device made of metal, 3: Polyester sample, 4: Aluminum plate for weighing sublimation, 5: Aluminum plate fixing base, 6: Cooling water inlet side 7: Cooling water outlet side, 8: Vacuum suction outlet. The measurement method is shown below.
A polyester sample (3) weighed 40.0 grams and a preliminarily weighed aluminum plate for weighing sublimate (4) were placed in a metal sublimate apparatus (2), and then 20 ° C. cooling water was added (6) To (7) to control the temperature of the sublimate weighing aluminum plate to 20 ° C. The vacuum suction outlet (8) is connected to a vacuum pump, and is controlled so that the vacuum is kept constant so that the inside of the sublimation apparatus is always 13.33 kPa (100 mmHg). In this state, after assembling the sublimation amount measuring device, the polyester sample (3) is heated by passing through the heating medium (1) for heating the polyester controlled at 320 ° C., and the polyester is melted. At this time, the compound sublimated from the polyester is captured by the cooled sublimate weighing aluminum plate (4) while moving toward the vacuum suction (8) outlet. Sublimate weighing aluminum plate (4) is controlled at 20 ° C, polyester sample (3) is melted and the pressure inside the sublimation device is maintained at 13.33 kPa. Then, the amount of sublimate was measured by weighing the aluminum plate for weighing sublimate (4).

(E) Terminal COOH group content 40.00 grams of a polyester sample powdered using a pulverizer and 100 mL of benzyl alcohol were added to a flask, and the polyester sample was placed under a nitrogen stream at 215 ± 1 ° C for 4 minutes. Was dissolved in benzyl alcohol. After dissolution, the sample solution is cooled to room temperature, and then an appropriate amount of a 0.1% by weight phenol red benzyl alcohol solution is added, and titration is quickly performed with a N normal sodium hydroxide benzyl alcohol solution, causing discoloration. The amount of dripping up to was AmL. As a blank, 0.1% by mass of phenol red benzyl alcohol was added to 100 mL of benzyl alcohol, and titrated quickly with a benzyl alcohol solution of N normal sodium hydroxide. The amount of dripping until discoloration occurred was BmL. did. From these values, the terminal COOH group content in the polyester sample was calculated by the following formula.
COOH end group content ^{(eq / 10 6 g) =} (A-B) × 10 -3 × N × 10 6/40
The benzyl alcohol used here was obtained by distilling a reagent-grade product and storing it in a light-shielding bottle. As the N normal sodium hydroxide solution of benzyl alcohol, a solution obtained by titrating with a sulfuric acid solution having a known concentration in advance by a conventional method and obtaining the normality N accurately was used.

(F) Phosphorus, manganese, and antimony contents in polyester A polyester sample was heated and melted to prepare a circular disk, which was measured using a Rigaku fluorescent X-ray apparatus 3270, and quantified.

[Reference Example 1]
-Preparation of polymerization catalyst for polyester production Add 1000 parts by mass of ethylene glycol and 8.4 parts by mass of antimony trioxide to a reaction vessel with a reflux apparatus, heating apparatus, stirrer, and temperature sensor, and heat at 180 ° C for 1 hour. Antimony trioxide was completely dissolved. Thereafter, 9.1 parts by mass of phenylphosphonic acid manufactured by Nissan Chemical Co., Ltd. was added to the total amount of the ethylene glycol solution. Thereafter, the mixture was further reacted for 2 hours while flowing out the water generated during the reaction under reflux conditions to prepare a polymerization catalyst for polyester production. In the prepared catalyst, antimony atom: phenylphosphonic acid is calculated to be 1: 1 (molar ratio).

[Example 1]
-Manufacture of a polyester chip Manganese acetate tetrahydrate 0.030 mass part (30 with respect to dimethyl 2,6- naphthalene dicarboxylate) to the mixture of 100 mass parts of dimethyl 2, 6- naphthalene dicarboxylate and 50 mass parts of ethylene glycol. Millimole%) was charged into a reactor equipped with a stirrer, a rectifying column and a methanol distillation condenser, and methanol produced as a result of the reaction was distilled out of the reactor while gradually raising the temperature from 150 ° C to 245 ° C. The transesterification reaction was carried out. Thereafter, the polymerization catalyst for production of polyester prepared in Example 1 weighed so as to have an antimony atomic weight of 40 mmol% with respect to dimethyl 2,6-naphthalenedicarboxylate was added to the reactor to complete the transesterification reaction. Thereafter, the obtained transesterification reaction product was transferred to a polycondensation reaction vessel equipped with a stirrer, a nitrogen inlet, a vacuum port and a distillation apparatus, heated to 295 ° C., and subjected to a polycondensation reaction at a high vacuum of 30 Pa or less. And polyester was obtained. Further, it was made into a chip according to a conventional method. The results are shown in Tables 1 and 2.

[Comparative Example 1]
-Manufacture of a polyester chip Manganese acetate tetrahydrate 0.030 mass part (30 with respect to dimethyl 2,6- naphthalene dicarboxylate) to the mixture of 100 mass parts of dimethyl 2, 6- naphthalene dicarboxylate and 50 mass parts of ethylene glycol. Millimoles), 0.0056 parts by mass of sodium acetate trihydrate was charged into a reactor equipped with a stirrer, a rectifying column and a methanol distillation condenser, and the temperature of the reaction was gradually increased from 150 ° C. to 245 ° C. The transesterification reaction was performed while distilling the resulting methanol out of the reactor. Thereafter, 0.026 parts by mass of phenylphosphonic acid (40 mmol% with respect to dimethyl 2,6-naphthalenedicarboxylate) was added to complete the transesterification reaction. Thereafter, 0.024 parts by mass of diantimony trioxide is added to the obtained transesterification reaction product, and the mixture is transferred to a polycondensation reaction vessel equipped with a stirrer, a nitrogen inlet, a vacuum port and a distillation apparatus, and the temperature is raised to 295 ° C. The polyester was obtained by performing a polycondensation reaction at a high vacuum of 30 Pa or less. Further, it was made into a chip according to a conventional method. The results are shown in Tables 1 and 2.

[Comparative Example 2]
-Manufacture of a polyester chip Manganese acetate tetrahydrate 0.030 mass part (30 with respect to dimethyl 2,6- naphthalene dicarboxylate) to the mixture of 100 mass parts of dimethyl 2, 6- naphthalene dicarboxylate and 50 mass parts of ethylene glycol. Millimoles), 0.0056 parts by mass of sodium acetate trihydrate was charged into a reactor equipped with a stirrer, a rectifying column and a methanol distillation condenser, and the temperature of the reaction was gradually increased from 150 ° C. to 245 ° C. The transesterification reaction was performed while distilling the resulting methanol out of the reactor. Thereafter, 0.023 parts by mass of trimethyl phosphate (40 mmol% based on dimethyl 2,6-naphthalenedicarboxylate) was added to complete the transesterification reaction. Thereafter, 0.024 parts by mass of diantimony trioxide is added to the obtained transesterification reaction product, and the mixture is transferred to a polycondensation reaction vessel equipped with a stirrer, a nitrogen inlet, a vacuum port and a distillation apparatus, and the temperature is raised to 295 ° C. The polyester was obtained by performing a polycondensation reaction at a high vacuum of 30 Pa or less. Further, it was made into a chip according to a conventional method. The results are shown in Tables 1 and 2.

  Thus, according to the present invention, the polyester containing a specific polymerization catalyst for polyester production is excellent in solid-phase polymerization, and the amount of generated sublimates such as oligomers when the polyester is processed such as melt molding is reduced, resulting in high crystals. Therefore, it is possible to provide a polyester having a low content of terminal COOH groups.

It is a measuring apparatus figure of the sublimate generation amount implemented by the Example of this invention and the comparative example.

Explanation of symbols

1: Heating medium for polyester heating 2: Metal sublimation device 3: Polyester sample 4: Aluminum plate for sublimation weighing 5: Aluminum plate fixing base 6: Cooling water inlet side 7: Cooling water outlet side 8: Vacuum suction outlet

Claims (4)

A polyester comprising a polymerization catalyst for producing a polyester represented by the following general formula (I) or (II).

[In the above formula, R ₁ represents a hydrocarbon residue having 1 to 12 carbon atoms, and R ₂ represents a hydrogen atom or a hydrocarbon residue having 1 to 12 carbon atoms. l, m, and n are each an integer of 1 or more, and X ^a− represents an a-valent anion. ] The polyester according to claim 1, which contains a transesterification catalyst and satisfies the following formulas (III) and (IV).
0.25 <1 / m <6.0 (III)
5.0 <M <100 (IV)
[M represents the content of the transesterification catalyst with respect to all the acid components constituting the polyester, and the unit is mmol%. ] X ^a- is ^{_{O 2-, CH 3 COO -,}} HO-CH 2 CH 2 O -, or _{(O-CH 2 CH 2 -O} ) according to claim 1 or 2, characterized in that a ^2-either The polyester described. A process for producing a polyester, characterized by polymerization using a compound represented by the following general formula (I) or (II).

[In the above formula, R ₁ represents a hydrocarbon residue having 1 to 12 carbon atoms, and R ₂ represents a hydrogen atom or a hydrocarbon residue having 1 to 12 carbon atoms. l, m, and n are each an integer of 1 or more, and X ^a− represents an a-valent anion. ]

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