JP4779412B2 - Method for producing copolyester - Google Patents

Description

  The present invention relates to a method for producing a copolyester having improved productivity.

  Polyesters represented by polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN) and the like are excellent in mechanical properties and chemical properties. In addition, highly functional copolyesters obtained by selecting a wide variety of acids / alcohols according to demands, for example, fibers for clothing and industrial materials, packaging, and magnetic tapes, depending on their properties. It is used in a wide range of fields such as optical films and sheets, hollow molded bottles, casings for electrical and electronic components, paints, adhesives, ink binders, and other engineering plastic molded products.

  In general, a polyester is produced by an esterification reaction or a transesterification reaction between a dicarboxylic acid and / or an ester-forming derivative thereof and a diol and / or an ester-forming derivative thereof, and this is produced using a catalyst at high temperature under vacuum. Manufactured by liquid phase polycondensation.

  Conventionally, antimony, germanium, and titanium compounds have been widely used as polyester polycondensation catalysts used during such polycondensation of polyester.

  Antimony trioxide is an inexpensive catalyst with excellent catalytic activity. However, if it is used in an amount of such a main component, that is, a practical polymerization rate, metal antimony is used during polycondensation. As a result of precipitation, darkening and foreign matter are generated in the polyester.

  Germanium compounds have already been put to practical use as catalysts that can obtain polyesters that have excellent catalytic activity other than antimony compounds and that do not have the above problems, but this catalyst is very expensive. In addition, there is a problem that it is difficult to control the polymerization because the concentration of the catalyst in the reaction system changes due to the fact that it is easy to distill from the reaction system to the outside during the polymerization. is there.

  Polyesters produced using a titanium compound typified by tetraalkoxy titanate are susceptible to thermal degradation during melt molding, and the polyesters are remarkably colored.

  With the above circumstances, it is a polycondensation catalyst that uses metal components other than antimony, germanium, and titanium as the main metal components of the catalyst, and has excellent catalytic activity, excellent color and thermal stability, and transparency of molded products. There is a need for polycondensation catalysts that provide excellent polyesters.

As a novel polycondensation catalyst that meets the above requirements, a catalyst system comprising an aluminum compound and a phosphorus compound has been disclosed and attracted attention (for example, see Patent Documents 1 to 4).
JP 2001-131276 A JP 2001-163963 A JP 2001-163964 A JP 2002-220446 A

Moreover, regarding the method for producing polyester using the polycondensation catalyst system, preferred addition times of the polycondensation catalyst system are disclosed (for example, see Patent Documents 5 to 7).
JP 2002-322250 A JP 2002-322255 A JP 2002-327052 A

  The polyester obtained by the polycondensation catalyst system has good color tone, transparency and thermal stability, and meets the above requirements. However, the polycondensation rate has not yet reached a sufficiently satisfactory level, and its improvement has been strongly desired. As one of the methods for increasing the polycondensation rate, in Patent Document 6, terephthalic acid is added to an oligomer obtained by esterification, and esterification is performed again at a high temperature, whereby specific viscosity conditions, acid value conditions, hydroxyl value conditions, A production method is described in which an oligomer that satisfies molecular weight conditions and esterification conditions is obtained, and the product is polycondensed. However, in the production method described in Patent Document 6, after addition of terephthalic acid to the oligomer obtained by the esterification reaction of dicarboxylic acid and diol, the solubility of terephthalic acid is poor, and thus esterification is performed at high temperature for a long time. However, the copolymer polyester has a problem that it is difficult to control the composition of the glycol component and the hydroxyl terminal group of the oligomer by esterification at a high temperature for a long time.

  The present invention is a polycondensation catalyst in which metal components other than antimony, germanium and titanium are used as the main metal component of the catalyst, maintaining color tone and thermal stability, having a high polycondensation rate, and achieving both quality and productivity. A method for producing a polymerized polyester is provided.

The inventor of the present invention has arrived at the present invention as a result of intensive studies to solve the above-mentioned problems. That is, the present invention relates to a method for producing a copolyester resin in which polycondensation is performed using a polymerization catalyst containing at least one selected from aluminum and a compound thereof and at least one selected from a phosphorus compound. Is added to an oligomer satisfying the following formula 1 obtained by the esterification reaction, and an amorphous polycarboxylic acid having a melting point of 400 ° C. or less is obtained to obtain an oligomer satisfying the following formula 2; The present invention relates to a method for producing a copolyester resin characterized by condensation.
(Formula 1) Reduced viscosity ≦ 0.4 dl / g
(Formula 2) 55 mol% ≦ hydroxyl end group ratio ≦ 75 mol%

  Since the method for producing a copolyester of the present invention can advance the esterification reaction at a low temperature and in a short time compared to the prior art, it is easy to control the terminal group composition of the product after the esterification reaction, and the glycol composition changes. Is also small. Further, the present inventors have found that a polycondensation rate is high, a high-quality copolyester resin is obtained as a whole, and the productivity is dramatically increased.

Hereinafter, the present invention will be described in detail.
The copolyester referred to in the present invention refers to a polyester composed of two or more kinds of polycarboxylic acids and / or ester-forming derivatives thereof and polyols and / or ester-forming derivatives thereof. In general, dicarboxylic acids and / or ester-forming derivatives thereof and diols and / or ester-forming derivatives thereof are used.

  Dicarboxylic acids include succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, 1,3 -For cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, dimer acid, etc. Saturated aliphatic dicarboxylic acids exemplified, or ester-forming derivatives thereof, unsaturated aliphatic dicarboxylic acids exemplified by fumaric acid, maleic acid, itaconic acid, etc., or ester-forming derivatives thereof, orthophthalic acid, isophthalic acid, terephthalic acid acid, -(Alkali metal) sulfoisophthalic acid, diphenic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid Acid, 4,4'-biphenyldicarboxylic acid, 4,4'-biphenylsulfone dicarboxylic acid, 4,4'-biphenyl ether dicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid, pamoin Examples thereof include aromatic dicarboxylic acids exemplified by acids, anthracene dicarboxylic acids and the like, and ester-forming derivatives thereof.

  Of these dicarboxylic acids, terephthalic acid, isophthalic acid, adipic acid, sebacic acid, and azelaic acid are preferable in terms of physical properties of the polyester, and other dicarboxylic acids are used as constituents as necessary.

  In addition to these dicarboxylic acids, a polyvalent carboxylic acid may be used in combination if the amount is small. Examples of the polyvalent carboxylic acid include ethanetricarboxylic acid, propanetricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3,4,3 ′, 4′-biphenyltetracarboxylic acid, and these Examples thereof include ester-forming derivatives.

  As glycols, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,4 -Butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, 1,10-decamethylene glycol, 1,12-dodecanediol, polyethylene glycol, polytrimethyl Aliphatic glycols exemplified by tylene glycol and polytetramethylene glycol, hydroquinone, 4,4′-dihydroxybisphenol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-bis (β-hydroxyethoxyphenyl) ) Sulfone, bis (p-hydroxyphenyl) ether, bis (p-hydroxyphenyl) sulfone, bis (p-hydroxyphenyl) methane, 1,2-bis (p-hydroxyphenyl) ethane, bisphenol A, bisphenol C, 2 , 5-naphthalenediol, aromatic glycols exemplified by ethylene glycol added to these glycols, and the like.

  Of these glycols, ethylene glycol, neopentyl glycol, 1,3-propylene glycol, 1,4-butylene glycol, and 1,4-cyclohexanedimethanol are preferred.

  In addition to these glycols, polyhydric alcohols may be used in combination in small amounts. Examples of the polyhydric alcohol include trimethylolmethane, trimethylolethane, trimethylolpropane, pentaerythritol, glycerol, hexanetriol, and the like.

  Moreover, you may use together hydroxycarboxylic acid. Examples of the hydroxycarboxylic acid include lactic acid, citric acid, malic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, 4-hydroxycyclohexanecarboxylic acid, or These ester-forming derivatives are exemplified.

  Moreover, combined use of cyclic ester is also permitted. Examples of the cyclic ester include ε-caprolactone, β-propiolactone, β-methyl-β-propiolactone, δ-valerolactone, glycolide, and lactide.

  Examples of ester-forming derivatives of polyvalent carboxylic acids or hydroxycarboxylic acids include alkyl esters and hydroxylalkyl esters of these compounds.

  Examples of ester-forming derivatives of diols include esters of diols with lower aliphatic carboxylic acids such as acetic acid.

  In the method for producing a copolyester of the present invention, first, the ratio of hydroxyl terminal groups of the oligomer obtained by the esterification reaction of dicarboxylic acid and diol ((hydroxyl terminal group / total terminal groups) × 100) is 55 to 75. % Oligomers must be produced. The hydroxyl terminal group is determined by calculating the acid value (AVo) and hydroxyl value (OHVo) of the oligomer by titration and calculating {OHVo / (OHVo + AVo)} × 100.

  In the production with a conventional catalyst or without catalyst, the oligomer obtained by esterification of a polycarboxylic acid and a polyol has a high proportion of hydroxyl end groups. When this is applied to a copolymerized polyester resin that undergoes polycondensation using a polymerization catalyst containing at least one selected from aluminum and its compounds and at least one selected from phenolic compounds as in the present invention, polycondensation The speed will be low. In the present invention, a polycarboxylic acid is further added to an oligomer having a reduced viscosity of 0.4 dl / g or less obtained by esterification of a polycarboxylic acid and a polyol, and then the esterification step is allowed to proceed. An oligomer having a terminal group ratio of 55 to 75% can be obtained. The lower limit of the reduced viscosity of the oligomer is not particularly limited, but is preferably 0.01 dl / g or more. Even if the proportion of hydroxyl end groups is less than 55% or more than 75 mol%, the time for the polycondensation reaction may be remarkably increased.

  At that time, if a polycarboxylic acid having a high melting point is added, the esterification process requires a high temperature for a long time, so that it is difficult to control the composition of the glycol component and the hydroxyl end groups of the oligomer.

  Therefore, in the present invention, as the polycarboxylic acid to be added to the oligomer obtained by esterification, non-crystalline or polycarboxylic acid having a melting point of 400 ° C. or lower is added to suppress the esterification temperature and the esterification time. This makes it easy to control the composition of the glycol component and the hydroxyl end groups of the oligomer.

  As the above-mentioned non-crystalline or polycarboxylic acid having a melting point of 400 ° C. or lower, isophthalic acid, adipic acid, sebacic acid and azelaic acid are preferable.

  Next, the polycondensation catalyst used in the present invention will be described. The polymerization catalyst includes at least one selected from aluminum and its compounds and at least one selected from phosphorus compounds. As the aluminum or aluminum compound, known aluminum compounds can be used without limitation in addition to metal aluminum.

Specific examples of aluminum compounds include aluminum formate, aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, aluminum benzoate, aluminum trichloroacetate, aluminum lactate, aluminum citrate, Carboxylates such as aluminum tartrate and aluminum salicylate, inorganic acid salts such as aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, aluminum nitrate, aluminum sulfate, aluminum carbonate, aluminum phosphate and aluminum phosphonate, aluminum methoxide, aluminum Etoxide, aluminum n-propoxide, aluminum iso-propoxide, aluminum n-butoxa Id, aluminum alkoxide such as aluminum t-butoxide, aluminum acetylacetonate, aluminum acetyl acetate, aluminum ethyl acetoacetate, aluminum ethyl acetoacetate And their partial hydrolysates, reaction products comprising aluminum alkoxides and aluminum chelate compounds and hydroxycarboxylic acids, aluminum oxide, ultrafine aluminum oxide, aluminum silicate, aluminum and titanium, silicon, zirconium, alkali metals and alkaline earths Examples thereof include complex oxides with metals. Of these, carboxylates, inorganic acid salts and chelate compounds are preferred, and among these, aluminum acetate, aluminum lactate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetylacetonate are particularly preferred.

Among these aluminum compounds, aluminum acetate, aluminum chloride, aluminum hydroxide, and aluminum hydroxide chloride having a high aluminum content are preferable, and aluminum acetate, aluminum chloride, and aluminum hydroxide chloride are more preferable from the viewpoint of solubility. Furthermore, the use of aluminum acetate is particularly preferred from the viewpoint of not corroding the device.

Here, aluminum hydroxide chloride is a general term for what is generally called polyaluminum chloride or basic aluminum chloride, and those used for water supply can be used. These are represented by, for example, the general structural formula [Al ₂ (OH) _n C _l6-n ] _m (where 1 ≦ n ≦ 5). Among these, those having a low chlorine content are preferable from the viewpoint of not corroding the device.

  The above-mentioned aluminum acetate is a general term for those having a structure of an aluminum salt of acetic acid represented by basic aluminum acetate, aluminum triacetate, aluminum acetate solution, etc. Among these, from the viewpoint of solubility and solution stability The use of basic aluminum acetate is preferred. Of the basic aluminum acetates, aluminum monoacetate, aluminum diacetate, or those stabilized with boric acid are preferred. When using the one stabilized with boric acid, it is preferable to use one stabilized with boric acid in an amount of equimolar or less with respect to basic aluminum acetate, and in particular, 1/2 to 1/3 molar amount. The use of basic aluminum acetate stabilized with boric acid is preferred. Examples of basic aluminum acetate stabilizers include urea and thiourea in addition to boric acid.

  The aluminum or aluminum compound may be added in the form of powder, but is preferably added in the form of a slurry or solution. In particular, it is preferable to add it in the form of a solution from the viewpoint of catalytic activity and the quality of the obtained polyester. That is, it is preferable to use those solubilized in a solvent such as water or glycol, particularly those solubilized in water and / or ethylene glycol.

The method for dissolving the aluminum compound is exemplified below.
(1) Preparation example of aqueous solution of basic aluminum acetate Water is added to basic aluminum acetate and stirred at 50 ° C. or lower for 3 hours or longer. The stirring time is more preferably 6 hours or longer. Thereafter, stirring is performed at 60 ° C. or more for several hours or more. The temperature in this case is preferably in the range of 60 to 100 ° C. The stirring time is preferably 1 hour or longer. The concentration of the aqueous solution is preferably 10 g / l to 30 g / l, particularly preferably 15 g / l to 20 g / l.

(2) Preparation Example of Ethylene Glycol Solution of Basic Aluminum Acetate Ethylene glycol is added to the above aqueous solution. The amount of ethylene glycol added is preferably 0.5 to 5 times the volume ratio of the aqueous solution. More preferably, the amount is 1 to 3 times. The solution is stirred at room temperature for several hours to obtain a uniform water / ethylene glycol mixed solution. Thereafter, the solution is heated and water is distilled off to obtain an ethylene glycol solution. The temperature is preferably 80 ° C. or higher, and preferably 200 ° C. or lower. More preferably, the water is distilled off by stirring at 90 to 150 ° C. for several hours. The system may be depressurized during distillation. By reducing the pressure, ethylene glycol can be rapidly distilled off at a lower temperature. In other words, the distillation can be performed at 80 ° C. or lower under reduced pressure, and the heat history applied to the system can be further reduced.

(3) Preparation example of aluminum glycol solution of aluminum lactate An aqueous solution of aluminum lactate is prepared. The preparation may be performed at room temperature or under heating, but is preferably performed at room temperature. The concentration of the aqueous solution is preferably 20 g / l to 100 g / l, particularly preferably 50 to 80 g / l. Ethylene glycol is added to the aqueous solution. The amount of ethylene glycol added is preferably 1 to 5 times the volume ratio of the aqueous solution. More preferably, the amount is 2-3 times. After stirring the solution at room temperature to obtain a uniform water / ethylene glycol mixed solution, the solution is heated and water is distilled off to obtain an ethylene glycol solution. The temperature is preferably 80 ° C. or higher, and preferably 120 ° C. or lower. More preferably, the water is distilled off by stirring at 90 to 110 ° C. for several hours.

  In the present invention, the amount of aluminum or aluminum compound used is preferably 0.001 to 0.5 mol%, more preferably 0.005 to 0, based on the number of moles of all structural units of the carboxylic acid component of the polyester obtained. .1 mol%. If the amount used is less than 0.001 mol%, the catalytic activity may not be sufficiently exhibited. If the amount used is 0.5 mol% or more, the thermal stability or thermal oxidation stability is lowered, resulting from aluminum. Occurrence of foreign matters or increased coloring may be a problem. Thus, even if the addition amount of the aluminum component is small, the polycondensation catalyst of the present invention has a great feature in that it exhibits sufficient catalytic activity. As a result, the thermal stability and thermal oxidation stability are excellent, and foreign matters and coloring caused by aluminum are reduced.

  The phosphorus compound constituting the polycondensation catalyst in the present invention is not particularly limited, but phosphoric acid and phosphoric acid esters such as trimethyl phosphoric acid, triethyl phosphoric acid, phenyl phosphoric acid and triphenyl phosphoric acid, phosphorous acid and trimethyl. Phosphite, triethyl phosphite, triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4′-biphenylene diphosphite And the like.

  More preferable phosphorus compounds in the present invention are at least one phosphorus compound selected from the group consisting of phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds, and phosphine compounds. It is. By using these phosphorus compounds, an effect of improving the catalytic activity is seen, and an effect of improving physical properties such as thermal stability of the polyester is seen. Among these, use of a phosphonic acid compound is preferable because of its great effect of improving physical properties and improving catalytic activity. Among the above-described phosphorus compounds, the use of a compound having an aromatic ring structure is preferable because the physical property improving effect and the catalytic activity improving effect are great.

  The phosphonic acid-based compound, phosphinic acid-based compound, phosphine oxide-based compound, phosphonous acid-based compound, phosphinic acid-based compound, and phosphine-based compound referred to in the present invention are represented by the following formulas (Formula 1) to (Formula 6), respectively. It refers to a compound having the structure represented.

  Examples of the phosphonic acid compound in the present invention include dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl benzylphosphonate, diethyl benzylphosphonate, and the like. Examples of the phosphinic acid compound in the present invention include diphenylphosphinic acid, methyl diphenylphosphinate, phenyl diphenylphosphinate, phenylphosphinic acid, methyl phenylphosphinate, phenylphenylphosphinate and the like. Examples of the phosphine oxide compound in the present invention include diphenylphosphine oxide, methyldiphenylphosphine oxide, and triphenylphosphine oxide.

  Among the phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds, and phosphine compounds, the phosphorus compounds of the present invention are represented by the following formulas (Chemical Formula 7) to (Chemical Formula 12). Are preferred.

  Among the above-described phosphorus compounds, the use of a compound having an aromatic ring structure is preferable because the physical property improving effect and the catalytic activity improving effect are great.

  In the present invention, as the phosphorus compound, the compounds represented by the following general formulas (Chemical Formula 13) to (Chemical Formula 15) are preferably used because the physical property improving effect and the catalytic activity improving effect are particularly large.

Wherein R ¹ , R ⁴ , R ⁵ and R ⁶ are each independently hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group or an amino group. Represents a hydrocarbon group having 1 to 50 carbon atoms including R ² and R ³ each independently represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. However, the hydrocarbon group may contain an alicyclic structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl.)

In the present invention, the phosphorus compound is particularly preferably a compound in which R ¹ , R ⁴ , R ⁵ and R ⁶ are groups having an aromatic ring structure in the above formulas (Chemical Formula 13) to (Chemical Formula 15).

  Examples of the phosphorus compound in the present invention include dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl benzylphosphonate, diethyl benzylphosphonate, diphenylphosphinic acid, diphenylphosphinic acid. Examples include methyl, phenyl diphenylphosphinate, phenylphosphinic acid, methyl phenylphosphinate, phenyl phenylphosphinate, diphenylphosphine oxide, methyldiphenylphosphine oxide, and triphenylphosphine oxide. Of these, dimethyl phenylphosphonate and diethyl benzylphosphonate are particularly preferred.

  Among the phosphorus compounds described above, a phosphorus metal salt compound is particularly preferable as the phosphorus compound in the present invention. The phosphorus metal salt compound is not particularly limited as long as it is a metal salt of a phosphorus compound. However, when a metal salt of a phosphonic acid compound is used, the physical properties improving effect and catalytic activity improving effect of the polyester, which are the problems of the present invention, are improved. Largely preferred. Examples of the metal salt of the phosphorus compound include a monometal salt, a dimetal salt, and a trimetal salt.

  Further, among the above-described phosphorus compounds, when the metal portion of the metal salt is selected from Li, Na, K, Be, Mg, Sr, Ba, Mn, Ni, Cu, and Zn, the catalytic activity is improved. Is preferable. Of these, Li, Na, and Mg are particularly preferable.

  In the present invention, as the phosphorus metal salt compound, at least one selected from compounds represented by the following general formula (Chemical Formula 16) is preferably used because of its large effect of improving physical properties and improvement of catalytic activity.

  (In the formula (Chem. 16), R1 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group, and a hydrocarbon group having 1 to 50 carbon atoms. R2 represents hydrogen. Represents a hydrocarbon group having 1 to 50 carbon atoms, including a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group, and R3 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, an alkoxyl group or a carbonyl group. 1 represents an integer of 1 or more, m represents 0 or an integer of 1 or more, 1 + m is 4 or less, and M represents a (l + m) -valent metal cation. N represents an integer equal to or greater than 1. The hydrocarbon group may include an alicyclic structure such as cyclohexyl, a branched structure, or an aromatic ring structure such as phenyl or naphthyl.

Examples of R ¹ include phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl, and the like. Examples of R ² include hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, long-chain aliphatic group, phenyl group, naphthyl group, Examples thereof include a substituted phenyl group, a naphthyl group, and a group represented by —CH ₂ CH ₂ OH. Examples of R ₃ O— include hydroxide ions, alcoholate ions, acetate ions, and acetylacetone ions.

  Among the compounds represented by the general formula (Chemical Formula 16), it is preferable to use at least one selected from the compounds represented by the following General Formula (Chemical Formula 17).

(In the formula (Chemical Formula 17), R ¹ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group, and a hydrocarbon group having 1 to 50 carbon atoms. Hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group, or a hydrocarbon group having 1 to 50 carbon atoms including carbonyl, l is an integer of 1 or more, m is 0 or an integer of 1 or more, l + m is 4 or less, M represents a (l + m) -valent metal cation, and the hydrocarbon group may contain an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl.

Examples of R ¹ include phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl, and the like. Examples of R ₃ O— include hydroxide ions, alcoholate ions, acetate ions, and acetylacetone ions.

  Among the above-described phosphorus compounds, the use of a compound having an aromatic ring structure is preferable because the physical property improving effect and the catalytic activity improving effect are great.

  Among the above formulas (Chemical Formula 17), when M is selected from Li, Na, K, Be, Mg, Sr, Ba, Mn, Ni, Cu, and Zn, the effect of improving the catalytic activity is large and preferable. Of these, Li, Na, and Mg are particularly preferable.

  In the present invention, as the metal salt compound of phosphorus, lithium [ethyl (1-naphthyl) methylphosphonate], sodium [ethyl (1-naphthyl) methylphosphonate], magnesium bis [ethyl (1-naphthyl) methylphosphonate], potassium [ (2-naphthyl) methylphosphonate ethyl], magnesium bis [(2-naphthyl) methylphosphonate ethyl], lithium [benzylphosphonate ethyl], sodium [benzylphosphonate ethyl], magnesium bis [benzylphosphonate ethyl], beryllium bis [Ethyl benzylphosphonate], strontium bis [ethyl benzylphosphonate], manganese bis [ethyl benzylphosphonate], sodium benzylphosphonate, magnesium bis [benzylphosphonic acid], sodium [(9- Nthryl) methylphosphonate], magnesium bis [(9-anthryl) methylphosphonate], sodium [ethyl 4-hydroxybenzylphosphonate], magnesium bis [4-hydroxybenzylphosphonate], sodium [4-chlorobenzylphosphone] Acid phenyl], magnesium bis [4-chlorobenzylphosphonate ethyl], sodium [methyl 4-aminobenzylphosphonate], magnesium bis [4-aminobenzylphosphonate methyl], sodium phenylphosphonate, magnesium bis [phenylphosphonic acid] Ethyl], zinc bis [ethyl phenylphosphonate] and the like. Among these, lithium [ethyl (1-naphthyl) methylphosphonate], sodium [ethyl (1-naphthyl) methylphosphonate], magnesium bis [ethyl (1-naphthyl) methylphosphonate], lithium [ethyl benzylphosphonate], Sodium [ethyl benzylphosphonate], magnesium bis [ethyl benzylphosphonate], sodium benzylphosphonate, magnesium bis [benzylphosphonic acid] are particularly preferred.

Among the phosphorus compounds described above, in the present invention, a phosphorus compound having at least one P—OH bond is particularly preferable as the phosphorus compound. By containing these phosphorus compounds, the effect of improving the physical properties of the polyester is particularly enhanced, and when the polyester is polymerized, the use of these phosphorus compounds together with the aluminum compound greatly improves the catalytic activity. .
The phosphorus compound having at least one P—OH bond is not particularly limited as long as it is a phosphorus compound having at least one P—OH in the molecule. Among these phosphorus compounds, the use of a phosphonic acid compound having at least one P—OH bond is preferred because of its great effect of improving the physical properties and improving the catalytic activity of the polyester.

  Among the above-described phosphorus compounds, the use of a compound having an aromatic ring structure is preferable because the physical property improving effect and the catalytic activity improving effect are great.

  In the present invention, as the phosphorus compound having at least one P—OH bond, it is preferable to use at least one selected from the compounds represented by the following general formula (Chemical Formula 18) because the physical property improving effect and the catalytic activity improving effect are large. .

(In the formula (Chemical Formula 18), R ¹ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group, and a hydrocarbon group having 1 to 50 carbon atoms. R ² represents , Hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group, n represents an integer of 1 or more, and the hydrocarbon group is an alicyclic structure such as cyclohexyl. And may contain an aromatic ring structure such as a branched structure or phenyl or naphthyl.)

Examples of R ¹ include phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl, and the like. Examples of R ² include hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, long-chain aliphatic group, phenyl group, naphthyl group, Examples thereof include a substituted phenyl group, a naphthyl group, and a group represented by —CH ₂ CH ₂ OH.

  Among the above-described phosphorus compounds, the use of a compound having an aromatic ring structure is preferable because the physical property improving effect and the catalytic activity improving effect are great.

  In the present invention, phosphorus compounds having at least one P-OH bond include ethyl (1-naphthyl) methylphosphonate, (1-naphthyl) methylphosphonic acid, ethyl (2-naphthyl) methylphosphonate, ethyl benzylphosphonate, benzylphosphone. Acid, ethyl (9-anthryl) methylphosphonate, ethyl 4-hydroxybenzylphosphonate, ethyl 2-methylbenzylphosphonate, phenyl 4-chlorobenzylphosphonate, methyl 4-aminobenzylphosphonate, ethyl 4-methoxybenzylphosphonate Etc. Of these, ethyl (1-naphthyl) methylphosphonate and ethyl benzylphosphonate are particularly preferred.

  As a preferable phosphorus compound in this invention, the phosphorus compound represented by Chemical formula (Formula 19) is mentioned.

(In the formula (Chemical Formula 19), R ¹ represents a hydrocarbon group having ¹ to 49 carbon atoms, or a hydrocarbon group having ¹ to 49 carbon atoms including a hydroxyl group, a halogen group, an alkoxyl group, or an amino group, and R ² , R ³ each independently represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group, which has an alicyclic structure, a branched structure or an aromatic ring structure. May be included.)

More preferably, at least one of R ¹ , R ² and R ^{3 in} the chemical formula (Chemical Formula 19) is a compound containing an aromatic ring structure.

  Specific examples of these phosphorus compounds are shown below.

  Moreover, since the phosphorus compound in this invention has a large molecular weight, since it is hard to be distilled off at the time of superposition | polymerization, an effect is large and preferable.

  The phosphorus compound in the present invention is preferably a phosphorus compound having a phenol moiety in the same molecule. In addition to enhancing the physical properties of polyester by containing a phosphorus compound having a phenol moiety in the same molecule, the effect of increasing catalytic activity by using a phosphorus compound having a phenol moiety in the same molecule during polyester polymerization Is larger, and therefore the polyester productivity is excellent.

  The phosphorus compound having a phenol moiety in the same molecule is not particularly limited as long as it is a phosphorus compound having a phenol structure, but a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound having a phenol moiety in the same molecule. When one or more compounds selected from the group consisting of a compound, a phosphonous acid compound, a phosphinic acid compound, and a phosphine compound are used, the effect of improving the physical properties of the polyester and the effect of improving the catalytic activity are greatly preferred. Among these, when a phosphonic acid compound having one or two or more phenol moieties in the same molecule is used, the effect of improving the physical properties of the polyester and the effect of improving the catalytic activity are particularly large and preferable.

  As a phosphorus compound which has the phenol part in the same molecule in this invention, the compound represented by the following general formula (Formula 26)-(Formula 28) is preferable.

(In the formulas (Chemical Formula 26) to (Chemical Formula 28), R ¹ is a carbon having 1 to 50 carbon atoms including a phenol part, a substituent such as a hydroxyl group, a halogen group, an alkoxyl group, or an amino group, and a phenol part. Represents a hydrocarbon group having a number of 1 to 50. R ⁴ , R ⁵ and R ⁶ each independently represents a substituent such as hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group or an amino group. Represents a hydrocarbon group having 1 to 50 carbon atoms, and R ² and R ³ are each independently hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, or an alkoxyl group. Represents a hydrocarbon group, provided that the hydrocarbon group may contain a branched structure, an alicyclic structure such as cyclohexyl, or an aromatic ring structure such as phenyl or naphthyl, and the ends of R ² and R ⁴ are bonded to each other. Moyo Yes.)

  Examples of the phosphorus compound having a phenol moiety in the same molecule in the present invention include p-hydroxyphenylphosphonic acid, dimethyl p-hydroxyphenylphosphonate, diethyl p-hydroxyphenylphosphonate, diphenyl p-hydroxyphenylphosphonate, bis. (P-hydroxyphenyl) phosphinic acid, methyl bis (p-hydroxyphenyl) phosphinate, phenyl bis (p-hydroxyphenyl) phosphinate, p-hydroxyphenylphenylphosphinic acid, methyl p-hydroxyphenylphenylphosphinate, p- Phenyl hydroxyphenylphenylphosphinate, p-hydroxyphenylphosphinic acid, methyl p-hydroxyphenylphosphinate, phenyl p-hydroxyphenylphosphinate, bis (p-hydro Shifeniru) phosphine oxide, tris (p- hydroxyphenyl) phosphine oxide, bis (p- hydroxyphenyl) methyl phosphine oxide, and the following formula (Formula 29), and the like compounds represented by to (Formula 32). Among these, a compound represented by the following formula (Chemical Formula 31) and dimethyl p-hydroxyphenylphosphonate are particularly preferable.

As a compound represented by the above formula (Chemical Formula 31), SANKO-220 (manufactured by Sanko Co., Ltd.) can be used.

  Among the phosphorus compounds having a phenol moiety in the same molecule in the present invention, at least one selected from a specific phosphorus metal salt compound represented by the following general formula (Formula 33) is particularly preferable.

(In Formula (Chemical Formula 33), R ¹ and R ² each independently represent hydrogen and a hydrocarbon group having 1 to 30 carbon atoms. R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or R ⁴ represents a hydrocarbon group having 1 to 50 carbon atoms including an alkoxyl group, R ⁴ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, an alkoxyl group, or a carbonyl group including carbonyl. Examples of R ⁴ O— include hydroxide ion, alcoholate ion, acetate ion, acetylacetone ion, etc. l is an integer of 1 or more, m is 0 or an integer of 1 or more, and l + m is 4 or less. M represents a (l + m) -valent metal cation, n represents an integer of 1 or more, and the hydrocarbon group includes an alicyclic structure such as cyclohexyl, a branched structure, and an aromatic ring structure such as phenyl or naphthyl. Moyo .)

  Among these, at least one selected from compounds represented by the following general formula (Formula 34) is preferable.

(In formula (Chemical Formula 34), Mn + represents an n-valent metal cation. N represents 1, 2, 3 or 4.)

  Among the above formulas (Chemical Formula 33) or (Chemical Formula 34), when M is selected from Li, Na, K, Be, Mg, Sr, Ba, Mn, Ni, Cu, Zn, the catalytic activity is improved. The effect is large and preferable. Of these, Li, Na, and Mg are particularly preferable.

  Specific metal salt compounds of phosphorus in the present invention include lithium [3,5-di-tert-butyl-4-hydroxybenzylphosphonate], sodium [3,5-di-tert-butyl-4-hydroxybenzyl] Ethyl phosphonate], sodium [3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid], potassium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], magnesium bis [3 , 5-di-tert-butyl-4-hydroxybenzylphosphonic acid ethyl], magnesium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid], beryllium bis [3,5-di-tert- Methyl butyl-4-hydroxybenzylphosphonate], strontium bis [3,5-di tert-butyl-4-hydroxybenzylphosphonate ethyl], barium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate phenyl], manganese bis [3,5-di-tert-butyl-4- Ethyl hydroxybenzylphosphonate], nickel bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate], copper bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate] Zinc bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate] and the like. Among these, lithium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], sodium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], magnesium bis [ Ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate] is particularly preferred.

  Among the phosphorus compounds having a phenol moiety in the same molecule in the present invention, at least one selected from specific phosphorus compounds having at least one P—OH bond represented by the following general formula (Formula 35) is particularly preferable.

(In formula (Chemical Formula 35), R ¹ and R ² each independently represent hydrogen and a hydrocarbon group having 1 to 30 carbon atoms. R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or A hydrocarbon group having 1 to 50 carbon atoms including an alkoxyl group is represented, and n represents an integer of 1 or more.
The hydrocarbon group may contain an alicyclic structure such as cyclohexyl, a branched structure, or an aromatic ring structure such as phenyl or naphthyl. )

  Among these, at least one selected from compounds represented by the following general formula (Formula 36) is preferable.

(In formula (Chemical Formula 36), R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. The hydrocarbon group is a fatty acid such as cyclohexyl. (It may contain a ring structure, a branched structure, or an aromatic ring structure such as phenyl or naphthyl.)

Examples of R ³ include hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, long-chain aliphatic group, phenyl group, naphthyl group, Examples thereof include a substituted phenyl group, a naphthyl group, and a group represented by —CH ₂ CH ₂ OH.

  Specific phosphorus compounds having at least one P-OH bond in the present invention include ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-hydroxy Methyl benzylphosphonate, isopropyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, phenyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl Examples include octadecyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, and the like. Of these, ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and methyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate are particularly preferred.

  Among the phosphorus compounds having a phenol moiety in the same molecule in the present invention, at least one phosphorus compound selected from specific phosphorus compounds represented by the following general formula (Formula 37) is preferable.

(In the above formula (Chemical Formula 37), R ¹ and R ² each independently represent hydrogen and a hydrocarbon group having 1 to 30 carbon atoms. R ³ and R ⁴ are each independently hydrogen and carbon atoms having 1 to 50 carbon atoms. Represents a hydrocarbon group having 1 to 50 carbon atoms including a hydrogen group, a hydroxyl group or an alkoxyl group, n represents an integer of 1 or more, and the hydrocarbon group is an alicyclic structure such as cyclohexyl, a branched structure, or an aromatic such as phenyl or naphthyl. It may contain a ring structure.)

  Among the above general formulas (Chemical Formula 37), it is preferable to use at least one selected from the compounds represented by the following General Formula (Chemical Formula 38) because the effect of improving the physical properties of the polyester and the effect of improving the catalytic activity are high.

(In the above formula (Chemical Formula 38), R ³ and R ⁴ each independently represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. The group may contain an alicyclic structure such as cyclohexyl, a branched structure, or an aromatic ring structure such as phenyl or naphthyl.)

Examples of R ³ and R ⁴ include short chain aliphatic groups such as hydrogen, methyl and butyl groups, long chain aliphatic groups such as octadecyl, phenyl groups, naphthyl groups, substituted phenyl groups and naphthyl groups. An aromatic group such as a group, a group represented by —CH ₂ CH ₂ OH, and the like.

  Specific phosphorus compounds in the present invention include diisopropyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, di-n-butyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, Examples include dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and diphenyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate. Of these, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and diphenyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate are particularly preferred.

  Among the phosphorus compounds having a phenol moiety in the same molecule in the present invention, a particularly desirable compound in the present invention is at least one phosphorus compound selected from compounds represented by chemical formulas (Chemical Formula 39) and (Chemical Formula 40).

  As the compound represented by the above chemical formula (Chemical Formula 39), Irganox 1222 (manufactured by Ciba Specialty Chemicals) is commercially available, and as the compound represented by the chemical formula (Chemical Formula 40), Irganox 1425 (Ciba Specialty Chemical) Chemicals) is commercially available and can be used.

  In the present invention, it is a preferred embodiment that the phosphorus compound is preheated in at least one solvent selected from the group consisting of water and alkylene glycol. The treatment improves the polycondensation catalyst activity by using the above-mentioned phosphorus compound in combination with the above-mentioned aluminum or aluminum compound, and decreases the foreign matter forming property due to the polycondensation catalyst.

  The solvent used when heat-treating the phosphorus compound in advance is not limited as long as it is at least one selected from the group consisting of water and alkylene glycol, but it is preferable to use a solvent that dissolves the phosphorus compound. As the alkylene glycol, it is preferable to use glycol which is a constituent component of the target polyester such as ethylene glycol. The heat treatment in the solvent is preferably performed after dissolving the phosphorus compound, but may not be completely dissolved. Further, it is not necessary that the compound retains the original structure after the heat treatment, and the solubility in the solvent may be improved by the modification by the heat treatment.

  Although the temperature of heat processing is not specifically limited, It is preferable that it is the range of 20-250 degreeC. More preferably, it is the range of 100-200 degreeC. The upper limit of the temperature is preferably around the boiling point of the solvent used. Although the heating time varies depending on conditions such as temperature, the heating temperature is preferably in the range of 1 minute to 50 hours, more preferably 30 minutes to 10 hours, and even more preferably 1 to 5 hours. Range. The pressure of the heat treatment system may be normal pressure, higher or lower, and is not particularly limited. The concentration of the solution is preferably 1 to 500 g / l as a phosphorus compound, more preferably 5 to 300 g / l, and still more preferably 10 to 100 g / l. The heat treatment is preferably performed in an atmosphere of an inert gas such as nitrogen. The storage temperature of the solution or slurry after heating is not particularly limited, but is preferably in the range of 0 ° C to 100 ° C, and more preferably in the range of 20 ° C to 60 ° C. It is preferable to store the solution in an atmosphere of an inert gas such as nitrogen.

  When the phosphorus compound is previously heat-treated in a solvent, aluminum or a compound thereof may coexist. Alternatively, the aluminum of the present invention or a compound thereof may be added in a powder form, a solution form, or a slurry form to a phosphorus compound that has been previously heat-treated in a solvent. Furthermore, you may heat-process the solution or slurry after addition. The solution or slurry obtained by these operations can be used as the polycondensation catalyst of the present invention.

  As the usage-amount of the phosphorus compound in this invention, 0.0001-0.5 mol% is preferable with respect to the number-of-moles of all the structural units of the carboxylic acid component of polyester obtained, 0.005-0.05 mol% More preferably it is.

  In the present invention, a polycondensation catalytic activity having high practicality can be expressed by using the above-mentioned aluminum or its compound in combination with a phosphorus compound, but it can be selected from a smaller amount of alkali metal, alkaline earth metal and compound thereof. It is a preferred embodiment that at least one of these is allowed to coexist as the second metal-containing component. The coexistence of such a second metal-containing component in the catalyst system is effective in improving productivity by obtaining a catalyst component having an increased reaction rate in addition to an effect of suppressing the formation of diethylene glycol, and thus a higher reaction rate. .

  A technique of adding an alkali metal compound or an alkaline earth metal compound to an aluminum compound to obtain a catalyst having sufficient catalytic activity is known. When such a known catalyst is used, a polyester having excellent thermal stability can be obtained. However, a known catalyst used in combination with an alkali metal compound or an alkaline earth metal compound is added in an amount to obtain practical catalytic activity. However, when an alkali metal compound is used, the hydrolysis resistance of the resulting polyester is reduced and the amount of foreign matter resulting from the alkali metal compound is increased. Moreover, when used for a film, the film properties and the like deteriorate. In addition, when an alkaline earth metal compound is used in combination, the thermal stability of the obtained polyester is lowered when it is attempted to obtain practical activity, coloring due to heating is large, the amount of foreign matter generated is increased, and water resistance is increased. Degradability also decreases.

When adding an alkali metal, an alkaline earth metal and a compound thereof, the amount M (mol%) used is 1 × 10 ⁻⁶ or more and 0.1 or more relative to the number of moles of all polycarboxylic acid units constituting the polyester. It is preferably less than mol%, more preferably 5 × 10 ^{−6 to} 0.05 mol%, still more preferably 1 × 10 ^{−5 to} 0.03 mol%, and particularly preferably 1 × 10 10. ^{-5 to} 0.01 mol%. Since the addition amount of alkali metal and alkaline earth metal is small, it is possible to increase the reaction rate without causing problems such as deterioration of thermal stability, generation of foreign substances, coloring, deterioration of hydrolysis resistance, etc. is there. When the amount M of the alkali metal, alkaline earth metal, or compound thereof is 0.1 mol% or more, the thermal stability decreases, the generation of foreign matter and coloring, and the hydrolysis resistance become problems in product processing. A case occurs. When M is less than 1 × 10 ⁻⁶ , the effect is not clear even when added.

  In the present invention, the alkali metal or alkaline earth metal constituting the second metal-containing component preferably used in addition to aluminum or a compound thereof includes Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr. , Ba is preferable, and among these, at least one selected from Li, Na, Mg or a compound thereof is more preferable. Examples of the alkali metal and alkaline earth metal compounds include saturated aliphatic carboxylates such as formic acid, acetic acid, propionic acid, butyric acid, and succinic acid, and unsaturated aliphatic carboxylates such as acrylic acid and methacrylic acid. , Aromatic carboxylates such as benzoic acid, halogen-containing carboxylates such as trichloroacetic acid, hydroxycarboxylates such as lactic acid, citric acid and salicylic acid, carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen carbonate, phosphorus Inorganic acid salts such as acid hydrogen, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid and bromic acid, and organic sulfonates such as 1-propanesulfonic acid, 1-pentanesulfonic acid and naphthalenesulfonic acid , Organic sulfates such as lauryl sulfate, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, tert-butyl Alkoxides such as alkoxy, chelate compounds and the like acetylacetonate, hydrides, oxides, and hydroxides and the like.

  Among these alkali metals, alkaline earth metals or their compounds, when using strongly alkaline substances such as hydroxides, these tend to be difficult to dissolve in diols such as ethylene glycol or organic solvents such as alcohols. However, it must be added to the polymerization system in an aqueous solution, which may cause a problem in the polymerization process. Furthermore, when a strongly alkaline material such as a hydroxide is used, the polyester is liable to undergo side reactions such as hydrolysis during the polymerization, and the polymerized polyester tends to be colored, and the hydrolysis resistance also decreases. Tend to. Accordingly, the alkali metal or their compounds or alkaline earth metals or their compounds suitable for the present invention are preferably saturated aliphatic carboxylates, unsaturated aliphatic carboxylates, aromatics of alkali metals or alkaline earth metals. Aromatic carboxylates, halogen-containing carboxylates, hydroxycarboxylates, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid, bromic acid Selected inorganic acid salts, organic sulfonates, organic sulfates, chelate compounds, and oxides. Among these, from the viewpoint of ease of handling, availability, and the like, it is preferable to use an alkali metal or alkaline earth metal saturated aliphatic carboxylate, particularly acetate.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not restrict | limited to these Examples. In addition, the evaluation method was implemented with the following method.

1. Measurement of reduced viscosity (ηsp / c) 0.10 g of a polyester resin was dissolved in 25 cm ³ of a mixed solvent of phenol / tetrachloroethane (60:40, weight ratio), and measured at 30 ° C. using an Ubbelohde viscosity tube.

2. Measurement of oligomer AVo (acid value) 0.2 g of oligomer was precisely weighed and dissolved in 20 ml of chloroform, and titrated with 0.1N KOH ethanol solution using phenolphthalein as an indicator, per 10 ⁶ g of resin Equivalent (unit: eq / 10 ⁶ g).

3. Measurement of oligomer OHVo (OH value) 0.5 g of oligomer was precisely weighed, 10 ml of acetylating agent (acetic anhydride pyridine solution 0.5 mol / L) was added, and immersed in a water bath at 95 ° C. or more for 90 minutes. Immediately after taking out from a water tank, 10 ml of pure water was added and it stood to cool to room temperature. It was titrated with 0.2N-NaOH-CH ₃ OH solution using phenolphthalein as an indicator. Do the same for the blank without the sample. In advance, 20 ml of N / 10-hydrochloric acid is titrated with 0.2N-NaOH-CH ₃ OH solution using phenolphthalein as an indicator, and the factor (F) of the solution is determined according to the following formula.
F = 0.1 × f × 20 / a
(F = factor of N / 10-hydrochloric acid, a = drop constant (ml))
OHVo (eq / ton) is calculated according to the following formula.
OHVo = {(B−A) × F × 1000 / W} + AVo
(A = titration constant (ml), B = blank titration constant (ml), F = factor of N / 5-NaOH—CH ₃ OH solution, W = weight of sample (g))

4. Calculation of OHV% (ratio of hydroxyl end groups) Calculated according to the following formula from OHVo and AVo obtained by the above method.
OHV% = {OHVo / (OHVo + AVo)} × 100

5. Composition of polyester resin Using a nuclear magnetic resonance analyzer (NMR) Gemini-200 manufactured by Varian in chloroform-d solvent, ¹ H-NMR analysis was performed and the integration ratio was determined.

<Preparation of polycondensation catalyst solution>
(Ethylene glycol solution of phosphorus compound)
After adding 2.0 liters of ethylene glycol to a flask equipped with a nitrogen introduction tube and a cooling tube at room temperature and normal pressure, while stirring at 200 rpm in a nitrogen atmosphere, Irganox 1222 (Ciba 39) represented by -200 g of Specialty Chemicals) was added. Further, 2.0 liters of ethylene glycol was added, the jacket temperature was changed to 196 ° C., the temperature was raised, and the mixture was stirred under reflux for 60 minutes from the time when the internal temperature reached 185 ° C. or higher. Thereafter, the heating was stopped, the solution was immediately removed from the heat source, and the solution was cooled to 120 ° C. or less within 30 minutes while maintaining the nitrogen atmosphere. The mole fraction of Irganox 1222 in the obtained solution was 40%, and the mole fraction of the compound whose structure changed from Irganox 1222 was 60%.

(Ethylene glycol solution of aluminum compound)
After adding 5.0 liters of pure water to a flask equipped with a condenser under normal temperature and pressure, 200 g of basic aluminum acetate (hydroxyaluminum diacetate) was added as a slurry with pure water while stirring at 200 rpm. . Further, pure water was added so as to be 10.0 liters as a whole, and the mixture was stirred at room temperature and normal pressure for 12 hours. Thereafter, the jacket temperature was changed to 100.5 ° C., the temperature was raised, and the mixture was stirred under reflux for 3 hours from the time when the internal temperature reached 95 ° C. or higher. Stirring was stopped and the mixture was allowed to cool to room temperature. At that time, when undissolved particles were observed, the solution was filtered through a glass filter (3G) to obtain an aqueous solution of an aluminum compound.
Subsequently, 2.0 liters of an aqueous solution of the above aluminum compound and 2.0 liters of ethylene glycol were charged into a flask equipped with a distillation apparatus at room temperature and normal pressure. After stirring at 200 rpm for 30 minutes, a uniform water / ethylene glycol mixed solution was prepared. Obtained. The jacket temperature was then changed to 110 ° C. and the temperature was raised, and water was distilled off from the solution. When the amount of distilled water reached 2.0 liters, the heating was stopped and the mixture was allowed to cool to room temperature to obtain an ethylene glycol solution of an aluminum compound.

<Example 1>
A reaction vessel equipped with a stirrer, a thermometer, and a distillation cooler was charged with 50 parts of terephthalic acid, 40 parts of isophthalic acid, 58 parts of adipic acid, 80 parts of ethylene glycol, and 73 parts of neopentyl glycol, and 230 ° C. over 4 hours. The first esterification reaction was carried out while gradually elevating the temperature until the distilled water was removed from the system. Thereafter, an oligomer having a reduced viscosity of 0.4 dl / g or less was cooled to 180 ° C. or less, 10 parts of isophthalic acid was charged, and the temperature was gradually raised to 190 ° C. over 30 minutes to carry out a second esterification reaction. The oligomer obtained by the second esterification was sampled, the AVo (acid value) and OHVo (OH value) of the oligomer were measured, and OHV% (ratio of hydroxyl end groups) was calculated. Subsequently, the polycondensation catalyst solution was prepared by using 0.04 mol% of phosphorus compound ethylene glycol solution and aluminum compound ethylene glycol mixed solution as phosphorus atoms and 0.03 mol as aluminum atoms with respect to the acid component in the polyester. After the addition so as to be mol%, the initial polymerization under reduced pressure was carried out to 10 mmHg over 1 hour, the temperature was raised to 270 ° C., and the latter polymerization was conducted at 1 mmHg or less to obtain a polyester resin.

<Example 2>
A reaction vessel equipped with a stirrer, thermometer, and distillation cooler was charged with 50 parts of terephthalic acid, 50 parts of isophthalic acid, 50 parts of adipic acid, 80 parts of ethylene glycol, and 73 parts of neopentyl glycol, and 230 ° C. over 4 hours. The first esterification reaction was carried out while gradually elevating the temperature until the distilled water was removed from the system. Thereafter, an oligomer having a reduced viscosity of 0.4 dl / g or less was cooled to 180 ° C. or less, 8 parts of adipic acid was added, and the temperature was gradually raised to 180 ° C. over 30 minutes to perform a second esterification reaction. Subsequently, the oligomer sampling and calculation of OHV%, the step of adding a polycondensation catalyst solution, and the polycondensation step were carried out in the same manner as in Example 1 to obtain a polyester resin.

<Example 3>
A reaction vessel equipped with a stirrer, thermometer, and distillation cooler was charged with 86 parts of terephthalic acid, 30 parts of isophthalic acid, 47 parts of sebacic acid, 81 parts of ethylene glycol, and 73 parts of neopentyl glycol, and 230 ° C. over 4 hours. The first esterification reaction was carried out while gradually elevating the temperature until the distilled water was removed from the system. Thereafter, an oligomer having a reduced viscosity of 0.4 dl / g or less was cooled to 180 ° C. or less, 13 parts of sebacic acid was added, and the temperature was gradually raised to 160 ° C. over 30 minutes to perform a second esterification reaction. Subsequently, the oligomer sampling and calculation of OHV%, the step of adding a polycondensation catalyst solution, and the polycondensation step were carried out in the same manner as in Example 1 to obtain a polyester resin.

<Example 4>
A reactor equipped with a stirrer, thermometer, and distillation cooler was charged with 55 parts of terephthalic acid, 30 parts of isophthalic acid, 80 parts of azelaic acid, and 124 parts of ethylene glycol, and the temperature was gradually raised to 230 ° C over 4 hours. The first esterification reaction was performed while removing the distilled water out of the system. Thereafter, an oligomer having a reduced viscosity of 0.4 dl / g or less was cooled to 180 ° C. or less, charged with 12 parts of azelaic acid, gradually heated to 150 ° C. over 30 minutes, and subjected to a second esterification reaction. Subsequently, the oligomer sampling and calculation of OHV%, the step of adding a polycondensation catalyst solution, and the polycondensation step were carried out in the same manner as in Synthesis Example 1 to obtain a polyester resin.
The characteristic values of Examples 1 to 4 of the polyester resin are shown in Table 1.

<Comparative Example 1>
A reaction vessel equipped with a stirrer, thermometer, and distillation cooler was charged with 30 parts of terephthalic acid, 50 parts of isophthalic acid, 58 parts of adipic acid, 80 parts of ethylene glycol, and 73 parts of neopentyl glycol, and 230 ° C. over 4 hours. The first esterification reaction was carried out while gradually elevating the temperature until the distilled water was removed from the system. Thereafter, an oligomer having a reduced viscosity of 0.4 dl / g or less is cooled to 180 ° C. or less, charged with 20 parts of terephthalic acid having a melting point exceeding 400 ° C., gradually heated to 260 ° C. over 60 minutes, An esterification reaction was performed. Subsequently, the oligomer sampling and calculation of OHV%, the step of adding a polycondensation catalyst solution, and the polycondensation step were carried out in the same manner as in Example 1 to obtain a polyester resin.

<Comparative example 2>
A reaction vessel equipped with a stirrer, thermometer, and distillation cooler was charged with 65 parts of terephthalic acid, 30 parts of isophthalic acid, 60 parts of sebacic acid, 81 parts of ethylene glycol, and 73 parts of neopentyl glycol, and 230 ° C. over 4 hours. The first esterification reaction was carried out while gradually elevating the temperature until the distilled water was removed from the system. Thereafter, an oligomer having a reduced viscosity of 0.4 dl / g or less is cooled to 180 ° C. or less, 21 parts of terephthalic acid having a melting point exceeding 400 ° C. is charged, and the temperature is gradually raised to 260 ° C. over 60 minutes. An esterification reaction was performed. Subsequently, the oligomer sampling and calculation of OHV%, the step of adding a polycondensation catalyst solution, and the polycondensation step were carried out in the same manner as in Example 1 to obtain a polyester resin.

<Comparative Example 3>
A reaction vessel equipped with a stirrer, thermometer and distillation cooler was charged with 33 parts of terephthalic acid, 30 parts of isophthalic acid, 92 parts of azelaic acid, and 124 parts of ethylene glycol, and the temperature was gradually raised to 230 ° C. over 4 hours. The first esterification reaction was performed while removing the distilled water out of the system. Thereafter, the oligomer having a reduced viscosity of 0.4 dl / g or less is cooled to 180 ° C. or less, charged with 22 parts of terephthalic acid having a melting point exceeding 400 ° C., gradually heated to 260 ° C. over 60 minutes, An esterification reaction was performed. Subsequently, the oligomer sampling and calculation of OHV%, the step of adding a polycondensation catalyst solution, and the polycondensation step were carried out in the same manner as in Example 1 to obtain a polyester resin.

<Comparative example 4>
A reaction vessel equipped with a stirrer, thermometer, and distillation cooler was charged with 50 parts of terephthalic acid, 35 parts of isophthalic acid, 58 parts of adipic acid, 80 parts of ethylene glycol, and 73 parts of neopentyl glycol, and 230 ° C. over 4 hours. The first esterification reaction was carried out while gradually elevating the temperature until the distilled water was removed from the system. Thereafter, an oligomer having a reduced viscosity of 0.4 dl / g or less was cooled to 180 ° C. or less, 15 parts of isophthalic acid was added, and the temperature was gradually raised to 190 ° C. over 30 minutes to carry out a second esterification reaction. Subsequently, the oligomer sampling and calculation of OHV%, the step of adding a polycondensation catalyst solution, and the polycondensation step were carried out in the same manner as in Example 1 to obtain a polyester resin.

<Comparative Example 5>
A reaction vessel equipped with a stirrer, thermometer, and distillation cooler was charged with 50 parts of terephthalic acid, 50 parts of isophthalic acid, 58 parts of adipic acid, 80 parts of ethylene glycol, and 73 parts of neopentyl glycol, and 230 ° C. over 4 hours. The esterification reaction was carried out while gradually elevating the temperature until the water was distilled out of the system. Without adding the polycarboxylic acid, the oligomer sampling and calculation of OHV%, the step of adding the polycondensation catalyst solution, and the polycondensation step were carried out in the same manner as in Example 1 to obtain a polyester resin.
Table 2 shows the characteristic values of Comparative Synthesis Examples 1 to 5 of the polyester resin.

  The production methods of the polyesters of Examples 1 to 4 have a short esterification time, a high polycondensation rate, and high productivity. Moreover, the fluctuation | variation of the glycol composition of copolyester resin is not seen. On the other hand, Comparative Examples 1 to 4 outside the present invention have a long esterification time, a low polymerization rate, and poor productivity. Moreover, the glycol composition fluctuation | variation of copolymer polyester resin is large. In Comparative Example 5, the esterification time was short, but the polymerization rate was very slow.

  Since the method for producing a copolyester of the present invention can advance the esterification reaction at a low temperature and in a short time compared to the prior art, it is easy to control the terminal group composition of the product after the esterification reaction, and the glycol composition changes. Is also small. In addition, the polycondensation rate is high, and a high-quality copolyester resin is obtained as a whole, and the productivity is dramatically increased.

Claims (1)

Esterification reaction of polycarboxylic acid and polyol in a method for producing a copolyester resin by polycondensation using a polymerization catalyst containing at least one selected from aluminum and a compound thereof and at least one selected from a phosphorus compound A polycarboxylic acid having a melting point of 400 ° C. or less and at least one selected from the group consisting of isophthalic acid, adipic acid, sebacic acid and azelaic acid , After obtaining the oligomer which satisfy | fills following formula 2, the said oligomer is polycondensed, The manufacturing method of the copolyester resin characterized by the above-mentioned.
(Formula 1) Reduced viscosity ≦ 0.4 dl / g
(Formula 2) 55 mol% ≦ hydroxyl end group ratio ≦ 75 mol%