JPH01266129A - Production of polyester - Google Patents

Abstract

PURPOSE:To obtain a polyester having a low content of minute foreign matter, a high softening point and low coloration, by performing a specified polyester production process in the presence of a specified Mg, Mn or Zn compound, a specified octane derivative and a specified P compound. CONSTITUTION:The production of a polyester by forming a polyester prepolymer by directly reacting a dicarboxylic acid component based on terephthalic acid with a glycol component based on ethylene glycol and polycondensing this polyester prepolymer in the presence of a polycondensation catalyst, is performed in the presence of a glycol-soluble magnesium compound, a glycol- soluble manganese compound or a glycol-soluble zinc compound, a 1,4- diazabicyclo(2.2.2)octane and a phosphorus compound. This process is also applicable to a polyester containing at most 20% monomer components in addition to polyethylene terephthalate.

Description

Detailed Description of the Invention "Industrial Application Field" The present invention is directed to a method for producing polyester, in particular, it has good electrostatic immersion properties in a cooling drum during bath melt film forming, and is free from minute foreign matter when formed into a film. The present invention relates to a method for producing polyester using a direct polymerization method, which has a high softening point, a high softening point, and little coloring.

``Prior Art'' Polyethylene terephthalate has excellent mechanical strength and chemical stability, and is widely used in film applications such as photographs, magnetic tapes, packaging, and capacitors in addition to fibers.

The manufacturing method for polyethylene terephthalate is to use dimethyl terephthalate and DMT as ethylene glycol ti.
method, and the direct weight method using terephthalic acid and ethylene glycol as raw materials are well known.

Polyester films have traditionally been manufactured using the MT method, but in recent years, manufacturers have been switching to the direct loading method in order to reduce manufacturing costs.

Polyester films are usually obtained by melt extrusion using an extruder, followed by l-axis or lambda-axis stretching.

The adhesion between the cooling drum and the sheet polyester during melt extrusion is extremely important in determining the flatness of the film surface, and to improve this, the adhesion between the extruder mouthpiece and the cooling drum is An X-pole is provided to apply a high voltage to the unsolidified polyester, thereby creating an electric charge on the unsolidified polyester and increasing its closeness with the cooling drum (hereinafter).

This is known as electrostatic adhesion. (for example.

(Tokuko Sho 37-g/Hiroko) However, when trying to speed up the film forming speed and increase film productivity, the amount of charge deposited on the unsolidified sheet decreased.
As a result, the adhesion with the cooling drum deteriorates and the surface becomes tatami-like.
Pinhole-like unevenness appears. A film obtained by stretching such a sheet has poor surface flatness and cannot be used particularly for photography.

This phenomenon is different from polyester produced by the DMT method, which uses a large amount of a gold compound as a catalyst for the transesterification reaction.
This phenomenon is most noticeable in IK heavy duty polyester, which does not use a metal catalyst in the esterification reaction.

Attempts have also been made to add an alkali metal compound or an alkaline earth metal compound to the polyester manufacturing process and to perform charge deposition immersion to improve static annotation adhesion. (For example, see JP-A No. 61-702A.) However, adding a large amount of such metals to polyester may cause the generation of fine aggregated foreign matter, the by-product of ether bonds that lower the softening point of the polymer, Polyesters obtained by this method tend to become completely discolored, making it difficult to use them as raw materials for polyester films having a quality that can be practically used for photography.

As a means of solving this problem, a technique of adding an alkali metal and/or alkaline earth metal compound and a phosphorus compound in addition to a compound of metals such as magnesium and manganese (for example, the 15-114322
In addition to compounds of metals such as magnesium and manganese, tertiary amines and hydroxylated ammonium compounds, specifically triethylamine, tributylamine, dimethylaniline, and pyridine. , quinoline, tetraethylammonium hydroxide, tetraethylammonium hydroxide, triethylbenzylammonium hydroxide, etc., and phosphorus compounds, specifically trimethyl phosphate, mono- or diethyl ester of phosphoric acid, phosphoric acid, triethyl phosphite, diethyl Technology of adding phosphite, phosphorous acid, etc. (for example, JP-A-65-//j≠
, 2) have also been disclosed.

These require particularly high levels of 1M color and minimal foreign matter. Its quality as a raw material for photographic film for printing plates and microfilm was not completely satisfactory.

1-8S, the problem that Uremei is trying to solve” The Ministry of the Invention and others have conducted an intensive study on the above-mentioned interrogation points, and found that although it contains a relatively large amount of metal compounds, there are still small foreign particles. It has a high softening point, low chromaticity per layer, and has a low chromaticity of m@layer.
It was possible to provide a method for producing polyester, which has excellent L@depositability and is particularly suitable as a raw material for photographic films for printing plates and microfilms.

"Means for Solving All Problems" The present invention involves the direct reaction of difunctional carbonic acid, mainly terephthalic acid, and glycol, mainly ethylene glycol gold, to completely produce a low polymerization polymer of polynisder. When producing polyester (ri) by polycondensing a polyester low polymer in the presence of a polycondensation catalyst, a glycol-soluble magnesium compound, a glycol E'TM manganese compound, or a glycol-soluble zinc compound, This is a method for producing polyester, characterized in that diazabiacro(2+ 2+ ') octane and a phosphorus compound coexist.

The present invention applies to materials other than polyethylene terephthalate.

Also applicable to polyester containing 20% or less of copolymer components.
It is T-noh. The copolymerization components include aromatic dicarboxylic acids such as isophthalic acid, aliphatic dicarboxylic acids such as isochlorohexanedicarphonic acid, and aliphatic dicarboxylic acids such as adipic acid and cepatic acid as dicarboxylic acid components.

Glycol components that can be copolymerized include diethylene glycol, triethylene glycol, butanediol, and cyclohexamethanediol.

Examples include xylylene glycol.

Next, an outline of the present invention will be explained using polyethylene terephthalate as an example.

Although the present invention is applicable to any of the batch method, live burial @ method, and continuous ε manufacturing method, the batch method will be explained.

Terephthalic acid and ethylene glycol are made into a slurry before being added to the esterification reactor or in the esterification reactor. The molar ratio of terephthalic acid and ethylene glycol is preferably from /:1.06 to /:2, j.

Cover the reactor, raise the temperature of the reactor, heat the slurry, and start the esterification reaction of toethylene glycol terephthalate. The reaction takes place while stirring the system, its temperature is 21
70 to λzao'c is preferred. The pressure of the reaction system is operated at normal pressure or zero pressure, and is preferably rK9/cm2G or less. The esterification reaction proceeds even without the use of a catalyst. The reaction proceeds while removing 1 titl of water produced in the esterification reaction from the distillation column attached to the reaction vessel. When the esterification reaction is completed, water distillation stops.

Before entering the polycondensation reaction step, foreign substances in the reaction solution can be removed by passing it through a filter. The polycondensation reaction is carried out under reduced pressure at 270 to 2 deO'C while removing ethylene glycol by-produced in the condensation reaction from the reaction system. In order to avoid bumping of the reaction solution, it is preferable to perform the initial pressure reduction gradually. What is the final degree of vacuum that is usually adopted?

/ to 0.0/dragon Hg. M condensation reaction catalyst.

It is preferable to add it before starting the polymerization reaction step.

Used in the present invention. For glycol-soluble magnesium compounds, manganese compounds, and zinc compounds.

Vinegar removes salts, oxalates, benzoates, other carbonic acid insects, halides, and water-drinkable substances.

Specifically, magnesium acetate, manganese acetate, zinc acetate, manganese oxalate, manganese oxalate, zinc oxalate, magnesium benzoate, manganese benzoate, zinc acetate, magnesium chloride, manganese chloride% Examples include zinc chloride, magnesium bromide, manganese bromide, zinc bromide, and magnesium hydroxide.

Phosphorous compounds include arsenic acid and phosphorus r1! , 2 and/or their esters can be used.

Specific examples of the phosphorus compound include phosphorous acid, phosphoric acid, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, phosphoric acid, and mono- or diethyl phosphorous acid.

Known antimony compounds are used as polycondensation reaction catalysts.

A germanium compound or a titanium compound can be used alone or in combination of two or more.

Specific examples of polycondensation reaction catalysts include antimony trioxide,
Examples include germanium dioxide and titanium alkoxide.

Magnesium compounds, manganese compounds and/or
or zinc compound and i, 4 cm shea rust cyclo(2,,
? ,,2) Octane and the phosphorus compound start monopolycondensation anti-L6 from the time when the esterification reaction between the difunctional carbonic acid mainly consisting of terephthalic acid and the glycol mainly consisting of ethylene glycol is completed. It is preferable to add it at the same time.

Moreover, the polycondensation reaction catalyst can be added at any point in time when the polycondensation reaction starts.

Glycol-soluble magnesium compound used in the present invention,
The amount of the manganese compound or zinc compound to be added is preferably 1 to 10 f atoms per ioθOKg of polyester as the total amount of these gold maple atoms.

The amount of the phosphorus compound used in the present invention is
The phosphorus atom per ookg is preferably 3 times the total amount of metal atoms from the glycol-soluble magnesium compound, manganese compound, and zinc compound from O6j.

l1μm diazabicyclo (2゜co, 2) used in the present invention
The amount of octane added is 0 per 10ooH of polyester.
．． 2 to g moles are preferred.

"Example" The present invention will be specifically explained by examples.

In addition, in the example, the "division" indicating filter is "seniorbu".
shows.

[Example-7] Terephthalic acid (Ti'A) 100% was added to the esterification reactor.
Part, ethylene glycol (EU), part and f! 'Add 0.022 parts of antimony trioxide, which is a condensation catalyst,
While stirring the contents thoroughly to form a slurry, raise the temperature.
While removing by-product water from the distillation column, the reaction temperature was increased to 21°C.
7! It reached 0C.

After allowing the reaction to continue as it is for approximately ≠ hours and confirming that the by-product of water has completely stopped, the polyester low polymer, which is the reaction product, is transferred to a polycondensation skin LC and can, and a magnesium acetate μ water tank is added. , 0.03/part and 1'1≠-diazabicyclo(
2+ 2+ 2) 0°001 parts of octane and 0 parts of phosphoric acid
．． 022 parts were added. After leaving the system as it is for 70 minutes with stirring, the system was gradually depressurized and
A polycondensation reaction was carried out at 'c for about ≠ hours to obtain a polyester. The intrinsic viscosity (IV) of the obtained polyester was measured and found to be 1.20.46 (measured at λt 0CK in a solvent of phenol/tetrachloroethane (gravity ratio)). 1. Colorimeter N1 to see yellowness
)-10/D type (manufactured by Nippon Seishoku Kogyo Co., Ltd.) to measure b<ii.3. It was r. The softening point measured by a falling ball type softening point meter was 2600C. When this is applied to a bath melt extruder to form a film.

When a current voltage of rKV was applied between the extrusion die and the cooling drum, a sheet-like polyester with good adhesion to the cooling drum and excellent flatness was obtained. Furthermore, this sheet-like polyester was biaxially stretched to 100μ
Microscopic foreign matter was observed under an optical microscope as a film with a thickness of m.

Only a few were found that were longer than -04m.

This polyester film was sufficiently usable for printing original photographs and microfilms.

[Example-2] In place of the magnesium acetate in Example-1, OoO portion of manganese acetate (n) was used.

A film similar to that of Example 1 could be formed, and the quality for use as a photographic film was satisfactory.

Also, in the same way as in Example -/, characteristic values are added and the results are
Shown in the table.

[Example 3] Instead of phosphoric acid in Example 7, 50,073 parts of triphenyl phosphate was added. A film similar to that of Example 7 could be formed, and the quality for use as a photographic film was satisfactory.

In addition, as in Example 1, the characteristic values were also measured and the results were reported.
Shown in the table.

[Comparative example-7] - Actual example -/ and 1,44-diazabicyclo (λ.

2) The same operation was carried out except that octane was not completely added. The polycondensation reaction took about IA,j hours. The obtained polyester was soldered at 1 = 0.6 hiro. The b value of the pellet was 3.6, which was almost the same as Example-/, but the softening point was 2!70C, which was clearly lower than Example-7, and it lacked one strength for use in photographic film. It was inappropriate.

The effect was seen when the voltage applied to the bath melt extruder was jKV, and the flatness of the obtained film was excellent.

Characteristic 1 was measured in the same manner as in Example 7, and the results are shown in Table 1.

[Comparative example - λ]

The same operation as in Example 7 was performed except that magnesium acetate was not added. Berrett's b value is 3.2
The yellowish tinge was less compared to Example-7. A film was formed using this pellet under the same conditions as in Example 7, but the electrostatic dense layer was poor, resulting in a sheet with tatami-like unevenness, and the unevenness remained even after stretching. Only bad film was obtained, and it could not be used for photography.

Also, in the same manner as in Example 1, the characteristic values were measured and the results were reported.
Shown in the table.

[Comparative example-3] Example-/of, 1,≠diazabicyclo(ko, 2).

2) Tetraethylammonium hydroxide was added instead of octane. Although the film was formed under the same film forming conditions as in Example 1, there were many minute foreign particles and it was bad as an X-ray photographic film. It appeared and I couldn't use it.

In addition, in the same manner as in Example-/, all characteristic values were measured, and all results were
Shown in the table.

Claims (1)

[Claims] A low polymer of polyester is produced by directly reacting a difunctional carboxylic acid mainly composed of terephthalic acid with a glycol mainly composed of ethylene glycol, and the low polymer of polyester is polycondensed in the presence of a polycondensation catalyst. At least when producing polyester, a glycol-soluble magnesium compound, a glycol-soluble manganese compound, or a glycol-soluble zinc compound and 1,4-diazabicyclo(2,
2,2) A method for producing polyester characterized by coexisting octane and a phosphorus compound.