JP3753219B2 - Polyester polymerization catalyst, polyester produced using the same, and method for producing polyester - Google Patents

Description

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【表２】

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【発明の効果】
本発明によれば、アンチモン化合物以外の新規の重縮合触媒、およびこれを用いて製造されたポリエステルが提供される。本発明のポリエステルは、衣料用繊維、産業資材用繊維、各種フィルム、シート、ボトルやエンジニアリングプラスチックなどの各種成形物、および塗料や接着剤などへの応用が可能である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyester polymerization catalyst, a polyester produced using the same, and a method for producing the polyester. More specifically, the present invention relates to a novel polyester polymerization catalyst not using an antimony compound, a polyester produced using the same, and a polyester. It is related with the manufacturing method.
[0002]
[Prior art]
Polyester, especially polyethylene terephthalate (hereinafter abbreviated as PET), has excellent mechanical and chemical properties, and is used in many applications, such as textiles for clothing and industrial materials, packaging, and magnetic tape. It is applied to molded products such as various films and sheets, bottles and engineering plastics.
[0003]
Industrially, PET produces bis (2-hydroxyethyl) terephthalate by esterification or transesterification of terephthalic acid or dimethyl terephthalate with ethylene glycol, and polycondensates it using a catalyst at high temperature and under vacuum. Can be obtained. As a catalyst used at the time of polycondensation, antimony trioxide is widely used. Antimony trioxide is an inexpensive catalyst with excellent catalytic activity, but has a problem that darkening and foreign matter are generated in PET because metal antimony is precipitated during polycondensation. Recently, environmental problems related to antimony safety have been pointed out. Under such circumstances, polyesters containing no antimony are desired.
[0004]
Attempts have been made to use antimony trioxide as a polycondensation catalyst and to suppress the darkening and foreign matter of PET. For example, in Japanese Patent No. 2666502, the formation of black foreign matter in PET is suppressed by using a compound of antimony trioxide, bismuth and selenium as a polycondensation catalyst. Japanese Patent Application Laid-Open No. 9-291141 describes that the use of antimony trioxide containing sodium and iron oxides as a polycondensation catalyst suppresses the precipitation of metal antimony. However, these polycondensation catalysts cannot achieve the purpose of a polyester containing no antimony after all.
[0005]
Studies are also underway on polycondensation catalysts to replace antimony trioxide. In particular, tetraalkoxy titanate has already been proposed, but PET produced using this has a problem that it is highly colored and easily causes thermal decomposition.
[0006]
As an attempt to overcome such problems when tetraalkoxytitanate is used as a polycondensation catalyst, for example, JP-A-55-116722 proposes a method of using tetraalkoxytitanate simultaneously with a cobalt salt and a calcium salt. Has been. Japanese Patent Laid-Open No. 8-73581 proposes a method of using tetraalkoxy titanate as a polycondensation catalyst simultaneously with a cobalt compound and using a fluorescent brightening agent. However, in these proposals, coloring of PET when tetraalkoxy titanate is used as a polycondensation catalyst is reduced, but on the other hand, effective suppression of thermal decomposition of PET has not been achieved.
[0007]
As a polycondensation catalyst that replaces antimony trioxide and a polycondensation catalyst that overcomes the problems of using tetraalkoxy titanate, a germanium compound has been put into practical use, but this catalyst is very expensive. And the problem that the catalyst concentration in the reaction system changes and it becomes difficult to control the polymerization because it tends to distill out of the reaction system during the polymerization.
[0008]
Conventionally, even when a plurality of metal catalysts are combined, it has not been possible to have a catalytic activity higher than the sum of their catalytic activities.
[0009]
[Problems to be solved by the invention]
The present invention provides a novel polycondensation catalyst other than an antimony compound, and a polyester produced using the same.
[0010]
[Means for Solving the Problems]
As a result of intensive studies aimed at solving the above-mentioned problems, the authors of the present invention can have a catalytic activity higher than the sum of their catalytic activities by combining specific metal compounds. I found out. When the polycondensation catalyst of the present invention is used, a polyester excellent in quality without using an antimony compound can be obtained.
[0011]
That is, the present invention provides a polyester polymerization catalyst comprising an aluminum compound of any one of aluminum acetate, aluminum chloride and aluminum hydroxide and one or more metal compounds selected from the group consisting of lithium, magnesium and manganese as a solution to the above problem. , Polyesters produced using the same and methods for producing the polyesters are provided.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides a novel polycondensation catalyst other than an antimony compound, and a polyester produced using the same. The polycondensation catalyst of the present invention is a polyester polymerization catalyst comprising an aluminum compound of any one of aluminum acetate, aluminum chloride and aluminum hydroxide and one or more metal compounds selected from the group consisting of lithium, magnesium and manganese .
[0013]
Examples of the metal compound of the present invention include lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, indium, thallium, germanium, tin, lead, bismuth, scandium, yttrium, zirconium, hafnium, vanadium, Examples thereof include one or more metal compounds selected from the group consisting of metal compounds such as chromium, manganese, iron, cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, tellurium, and silver.
[0014]
Among these metal compounds, one selected from the group consisting of metal compounds of lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, thallium, lead, manganese, iron, cobalt, nickel, copper, and zinc The above metal compounds are preferred.
[0015]
Further, one or more metal compounds selected from the group consisting of lithium, magnesium, thallium, lead, manganese, iron, nickel, copper, and zinc metal compounds are particularly preferable.
[0016]
These metal compounds are not particularly limited. For example, saturated aliphatic carboxylates such as formic acid, acetic acid, propionic acid, butyric acid and succinic acid of these metals, and unsaturated aliphatic carboxylic acids such as acrylic acid and methacrylic acid. Salts, aromatic carboxylic salts 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 sulfate, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid and bromic acid, 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, t-butoxy, etc. , Chelate compounds such as acetylacetonate, oxides, hydroxides, metal and the like, these saturated aliphatic carboxylic acid salts of are preferred, and acetic acid salts are particularly preferred.
[0017]
The amount of these metal compounds used is preferably 1 × 10 ^{−6 to} 0.1 mol, more preferably relative to the number of moles of all constituent units of the carboxylic acid component such as dicarboxylic acid or polycarboxylic acid of the polyester obtained. 5 × 10 ^{−6 to} 0.05 mol.
[0018]
Although it does not specifically limit as an aluminum compound of this invention, For example, aluminum formate, aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, aluminum benzoate, aluminum trichloroacetate, aluminum lactate , Carboxylates such as aluminum citrate, aluminum salicylate, inorganic acid salts such as aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, aluminum carbonate, aluminum phosphate, aluminum phosphonate, aluminum methoxide, aluminum ethoxide, aluminum Aluminum such as n-propoxide, aluminum iso-propoxide, aluminum n-butoxide, aluminum t-butoxide Aluminum alkoxide, aluminum acetylacetonate, aluminum acetylacetate, aluminum ethylacetoacetate, aluminum ethyl acetoacetate diiso-propoxide, organoaluminum compounds such as trimethylaluminum, triethylaluminum and partial hydrolysates , Aluminum oxide, metal aluminum and the like. Of these, carboxylates and inorganic acid salts are preferred, and among these, aluminum acetate, aluminum chloride, and aluminum hydroxide are particularly preferred.
[0019]
The amount of the aluminum compound used is preferably 5 × 10 ^{−7 to} 0.01 mol, more preferably 1 × with respect to the number of moles of all constituent units of the carboxylic acid component such as dicarboxylic acid and polyvalent carboxylic acid of the obtained polyester. 10 ^{−6 to} 0.005 mol.
[0020]
The polyester according to the present invention can be produced by a conventionally known method. For example, either a method of polycondensation after esterification of terephthalic acid and ethylene glycol, or a method of polycondensation after transesterification of an alkyl ester of terephthalic acid such as dimethyl terephthalate with ethylene glycol It can also be done by the method. The polymerization apparatus may be a batch type or a continuous type.
[0021]
The catalyst of the present invention has catalytic activity not only for polycondensation but also for esterification and transesterification. The transesterification reaction between an alkyl ester of a dicarboxylic acid such as dimethyl terephthalate and a glycol such as ethylene glycol is usually carried out in the presence of a transesterification catalyst such as zinc. The catalyst of the present invention is used in place of these catalysts. You can also. The catalyst of the present invention has catalytic activity not only in melt polymerization but also in solid phase polymerization or solution polymerization.
[0022]
The addition time of the polycondensation catalyst of the present invention is preferably before the start of the polycondensation reaction, but it can also be added to the reaction system before the start of the esterification reaction or transesterification reaction and at any stage during the reaction.
[0023]
The method for adding the polycondensation catalyst of the present invention may be in the form of powder or neat, or in the form of a slurry or solution of a solvent such as ethylene glycol, and is not particularly limited. Moreover, what mixed the aluminum compound and the metal compound previously may be added, and these may be added separately.
[0024]
The polycondensation catalyst of the present invention may be used in the presence of another polycondensation catalyst such as an antimony compound or a titanium compound.
[0025]
The polyester referred to in the present invention is composed of one or more selected from polycarboxylic acids containing dicarboxylic acids and ester-forming derivatives thereof, and one or more selected from polyhydric alcohols containing glycol. Or consisting of a hydroxycarboxylic acid and an ester-forming derivative thereof, or consisting of a cyclic ester.
[0026]
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 -Cyclobutane dicarboxylic acid, 1,3-cyclopentane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 2,5-norbornane dicarboxylic 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, 5- (alkaline Limetal) sulfoisophthalic acid, diphenic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, 4,4'-biphenyl sulfone dicarboxylic acid, 4,4'-biphenyl ether dicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid, pamoic acid, anthracene dicarboxylic acid Aromatic dicarboxylic acids exemplified in the above, or ester-forming derivatives thereof. Among these dicarboxylic acids, terephthalic acid and isophthalic acid are preferable.
[0027]
As polyvalent carboxylic acids other than these dicarboxylic acids, ethanetricarboxylic acid, propanetricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3, 4, 3 ', 4'-biphenyltetracarboxylic acid, And ester-forming derivatives thereof.
[0028]
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, polytrimethyleneglycol Aliphatic glycol, hydroquinone, 4,4′-dihydroxybisphenol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-bis (β-hydroxyethoxyphenyl) sulfone, exemplified by alcohol and polytetramethylene glycol Bis (p-hydroxyphenyl) ether, bis (p-hydroxyphenyl) sulfone, bis (p-hydroxyphenyl) methane, 1,2-bis (p-hydroxyphenyl) ethane, bisphenol A, bisphenol C, 2,5- Examples include aromatic glycols exemplified by naphthalenediol, glycols obtained by adding ethylene oxide to these glycols, and among these glycols, ethylene glycol and 1,4-butylene glycol are preferable.
[0029]
Examples of polyhydric alcohols other than these glycols include trimethylolmethane, trimethylolethane, trimethylolpropane, pentaerythritol, glycerol, hexanetriol and the like.
[0030]
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, and these Examples thereof include ester-forming derivatives.
[0031]
Examples of the cyclic ester include ε-caprolactone, β-propiolactone, β-methyl-β-propiolactone, δ-valerolactone, glycolide, and lactide.
[0032]
Examples of ester-forming derivatives of polyvalent carboxylic acids or hydroxycarboxylic acids include these alkyl esters, acid chlorides, acid anhydrides, and the like.
[0033]
The polyester of the present invention is preferably a polyester whose main repeating unit is alkylene terephthalate. The polyester in which the main repeating unit is composed of alkylene terephthalate means that the main acid component is terephthalic acid or an ester-forming derivative thereof, and the main glycol component is alkylene glycol. The alkylene glycol referred to here may contain a substituent or an alicyclic structure in the molecular chain.
[0034]
Acid components include oxalic 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-cyclobutane Examples include dicarboxylic 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 or ester-forming derivatives thereof, unsaturated aliphatic dicarboxylic acids exemplified by fumaric acid, maleic acid, itaconic acid and the like, or ester-forming derivatives thereof, orthophthalic acid, isophthalic acid, 5- ( Alkali metal) sulfoisophthalate Acid, diphenic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4'- Examples include biphenyl dicarboxylic acid, 4,4′-biphenylsulfone dicarboxylic acid, 4,4′-biphenyl ether dicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p′-dicarboxylic acid, pamoic acid, anthracene dicarboxylic acid, etc. Aromatic dicarboxylic acids or their ester-forming derivatives, ethanetricarboxylic acid, propanetricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3, 4, 3 ', 4'-biphenyltetracarboxylic acid Polycarboxylic acids exemplified in the above and their ester-forming derivatives A body or the like can also be included as a copolymerization component. Further, hydroxycarboxylic acids exemplified by lactic acid, citric acid, malic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, 4-hydroxycyclohexanecarboxylic acid, etc. Alternatively, an ester-forming derivative thereof can be included. In addition, cyclic esters exemplified by ε-caprolactone, β-propiolactone, β-methyl-β-propiolactone, δ-valerolactone, glycolide, lactide and the like can also be included.
[0035]
The main glycol component alkylene glycol is 1,2-propylene glycol, 1,3-propylene 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, Examples include 3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, 1,10-decamethylene glycol, and 1,12 dodecanediol. Two or more of these may be used at the same time. In addition, aliphatic glycols such as diethylene glycol, triethylene glycol, polyethylene glycol, polytrimethylene glycol, and polytetramethylene glycol, hydroquinone, 4,4′-dihydroxybisphenol, and 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) ) Aromatic glycols such as ethane, bisphenol A, bisphenol C, 2,5-naphthalenediol, glycols in which ethylene oxide is added to these glycols, trimethylolmethane, trimethylo Ruetan may include trimethylolpropane, pentaerythritol, glycerol, a polyhydric alcohol such as exemplified such as hexanetriol.
[0036]
The polyester of the present invention is particularly preferably polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, poly (1,4-cyclohexanedimethylene terephthalate), polyethylene naphthalate, polybutylene naphthalate, and copolymers thereof. Polyethylene terephthalate is more preferable.
[0037]
In the polyester of the present invention, other optional polymers and stabilizers, antioxidants, antistatic agents, antifoaming agents, dyeing improvers, dyes, pigments, matting agents, fluorescent whitening agents, and other additions An agent may be contained.
[0038]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples from the first. In each example and comparative example, the intrinsic viscosity (IV) of the polyester was measured as follows. Measurement was performed at a temperature of 30 ° C. using a 6/4 mixed solvent (weight ratio) of phenol / 1,1,2,2-tetrachloroethane.
[0039]
Example 1
To 8900 parts by weight of bis (2-hydroxyethyl) terephthalate, a 5 g / l ethylene glycol solution of lithium acetate as a catalyst was added to 0.05 mol% as lithium with respect to the acid component in the polyester, and then aluminum chloride 0.014 mol% of 3 g / l ethylene glycol solution as aluminum with respect to the acid component in the polyester was added and stirred at 245 ° C. for 10 minutes at normal pressure. Subsequently, the temperature of the reaction system was gradually decreased to 1 mmHg or less while raising the temperature to 275 ° C. over 50 minutes, and a polycondensation reaction was further performed at the same temperature and pressure for 3 hours. Table 1 shows the physical property values of the obtained polymer.
[0040]
(Examples 2-5 and Comparative Examples 1-4)
A polyester was polymerized in exactly the same manner as in Example 1 except that the catalyst was changed. Tables 1 and 2 show physical property values of the obtained polymers.
[0041]
[Table 1]

[0042]
[Table 2]

[0043]
【The invention's effect】
According to the present invention, a novel polycondensation catalyst other than an antimony compound and a polyester produced using the same are provided. The polyester of the present invention can be applied to fibers for clothing, fibers for industrial materials, various films, sheets, various molded products such as bottles and engineering plastics, and paints and adhesives.

Claims (3)

A polyester polymerization catalyst comprising an aluminum compound of aluminum acetate, aluminum chloride or aluminum hydroxide and one or more metal compounds selected from the group consisting of lithium, magnesium and manganese . A polyester produced using the catalyst according to claim 1 . A method for producing a polyester, wherein the catalyst according to claim 1 is used.