JPH10204166A - Polyethylene naphthalate copolymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyethylene naphthalate copolymer excellent in moldability by reacting a dicarboxylic acid component contg. naphthalenedicarboxylic acid with a diol component contg. ethylene glycol and an alkylene oxide-dihydroxynaphthalene compd. adduct or an alkylene oxide-bisphenol compd. adduct. SOLUTION: A mixture comprising 50-99mol% ethylene glycol and 50-1mol% alkylene oxide-dihydroxynaphthalene compd. adduct represented by formula I (R1 is 1-10C alkylene; R2 is 1-12C alkyl, etc.; n is 1-5; and m is 0-2) or alkylene oxide-bisphenol compd. adduct represented by formula II (R1 and R2 are the same as in formula I) is used as the diol component. The diol component and a dicarboxylic acid component (e.g. 2,6-naphthalenedicarboxylic acid) are subjected to transesterification by heating in the presence of an Mg acetate catalyst and a heat stabilizer, then to melt polycondensation by adding a GeO2 to the reaction system, and finally to solid phase polymn., thus giving a copolymer having an intrinsic viscosity of 0.60-1.0dl/g.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyethylene naphthalate copolymer and a method for producing the same, and more particularly, to a polyethylene naphthalate copolymer having excellent moldability and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Polyethylene naphthalate resin has a glass transition point of 120 ° C., which is higher than polyethylene terephthalate resin, and has excellent chemical resistance and gas barrier properties. Have been. Above all, it is expected to be applied to fields that cannot be physically realized with polyethylene terephthalate resin, such as heat-resistant bottles and bottles used repeatedly.

A bottle is obtained by first molding a molded product usually called a preform by injection molding, heating the preform to an appropriate temperature, and then blowing a high-pressure gas (blow molding).

However, polyethylene naphthalate resin has poor uniform stretchability at the time of blow molding compared to polyethylene terephthalate resin due to the characteristics of the resin, and is required to be formed at a high stretch ratio in order to form a bottle having a uniform thickness. I needed to. Furthermore, it is necessary to increase the thickness of the preform in order to obtain a bottle having an appropriate thickness by high stretch ratio molding, and when the thickness is increased, the temperature distribution after heating becomes uneven, and the obtained bottle has There has been a problem that the appearance is inferior such as a decrease in transparency.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and has as its object to provide a polyethylene naphthalate copolymer having excellent moldability.

[0006]

SUMMARY OF THE INVENTION According to the present invention, the dicarboxylic acid component comprises (A) a structural unit mainly derived from naphthalenedicarboxylic acid, the diol component comprises (B) a structural unit derived from ethylene glycol in an amount of 50 to 99 mol%, and (C) a structural unit derived from an alkylene oxide adduct of a dihydroxynaphthalene represented by the following general formula [1] and / or (D) an alkylene oxide adduct of a biphenol represented by the following general formula [2]: A polyethylene naphthalate copolymer comprising 50 to 1 mol%.

[0007]

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(Wherein, R1 represents an alkylene group having 1 to 10 carbon atoms, R2 represents an alkyl group or alkenyl group having 1 to 12 carbon atoms, n is an integer of 1 to 5, and m is Is an integer from 0 to 2)

[0009]

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(Wherein, R 1 represents an alkylene group having 1 to 10 carbon atoms, R 2 represents an alkyl group or alkenyl group having 1 to 12 carbon atoms, n is an integer of 1 to 5, and m is Is an integer from 0 to 2)

[0011]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the polyethylene naphthalate copolymer of the present invention and a method for producing the same will be specifically described.

The polyethylene naphthalate copolymer of the present invention comprises, as a dicarboxylic acid component, a structural unit mainly derived from naphthalenedicarboxylic acid, and as a diol component, an alkylene oxide adduct of ethylene glycol and dihydroxynaphthalenes and / or a biphenol. And an alkylene oxide adduct of

As the dicarboxylic acid component (A) that can be used in the polyethylene naphthalate copolymer of the present invention, naphthalenedicarboxylic acid is used. As naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid,
Isomers such as 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid The body can be used.
Among these, 2,6-naphthalenedicarboxylic acid is preferred in terms of productivity and quality.

The naphthalenedicarboxylic acid used in the present invention may be a derivative such as an ester, an amide or an acid chloride.

As the dicarboxylic acid component of the polyethylene naphthalate copolymer of the present invention, other dicarboxylic acids may be used as long as the properties of polyethylene naphthalate are not impaired. Other dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, diphenyldicarboxylic acid, aromatic dicarboxylic acids such as diphenoxyethanedicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, etc. Alicyclic dicarboxylic acids such as aliphatic dicarboxylic acids and cyclohexanedicarboxylic acids can be used. Further, these ester derivatives can also be used.

The proportion of other dicarboxylic acids used is 0.5 to 20 mol%, preferably 1 to 15 mol%, based on 100 mol% of the whole dicarboxylic acid component.

In the polyethylene naphthalate copolymer of the present invention, the diol component is a structural unit (B) derived from ethylene glycol, an alkylene oxide adduct of dihydroxynaphthalenes (C) and / or an alkylene oxide adduct of biphenols. (D).

The alkylene oxide adduct (C) of dihydroxynaphthalenes which can be used in the present invention is a compound represented by the following general formula [1].

[0019]

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(Wherein, R 1 represents an alkylene group having 1 to 10 carbon atoms, R 2 represents an alkyl group or alkenyl group having 1 to 12 carbon atoms, n is an integer of 1 to 5, and m is Is an integer from 0 to 2)

In the polyethylene naphthalate copolymer of the present invention, an alkylene oxide adduct (D) of a biphenol which can also be used as a diol component
Is a compound represented by the following general formula [2].

[0022]

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(Wherein, R 1 represents an alkylene group having 1 to 10 carbon atoms, R 2 represents an alkyl group or alkenyl group having 1 to 12 carbon atoms, n is an integer of 1 to 5, and m is Is an integer from 0 to 2)

Specific examples of the alkylene oxide adduct (C) of dihydroxynaphthalenes that can be used in the present invention include the following formulas [3] to [6].

[0025]

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[0026]

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[0027]

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[0028]

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Specific examples of the alkylene oxide adduct (D) of biphenols that can be used in the present invention include the following formulas [7] to [9].

[0030]

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[0031]

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[0032]

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Among these compounds, the compounds of the above formula [3] or [7] are preferred.

The polyethylene naphthalate copolymer of the present invention comprises a unit (B) derived from ethylene glycol as a diol component unit, an alkylene oxide adduct of dihydroxynaphthalenes (C) and / or an alkylene oxide adduct of biphenols. Component (D), and the proportion of these components is usually 50 to 99 mol%, preferably 80%
To 97 mol%, and the component unit (C) and / or the component unit (D) are 50 to 1 mol%, preferably 2 to 100 mol%.
It is in the range of 0 to 3 mol%. If the amount of the component (C) and / or (D) is too small, the effect of improving the formability by the component (C) and / or (D), which is a feature of the present invention, is difficult to obtain. If the amount of the component (D) is more than the above range, the crystallinity of the copolymer decreases, and the gas barrier property decreases.

In the polyethylene naphthalate copolymer of the present invention, the component unit (B) and the component units (C) and / or (D) are randomly bonded.

In the polyethylene naphthalate copolymer of the present invention, other components other than the component (B), the component (C) and the component (D) may be used as long as the properties of the copolymer are not impaired as the diol component unit. A diol component may be used.

As the other diol component, specifically,
Diethylene glycol, triethylene glycol, polyethylene glycol, trimethylene glycol, butanediol, cyclohexanediol, polytetramethylene glycol, cyclohexanedimethanol, 1,3-bis
Examples thereof include (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, and bis (4-β-hydroxyethoxyphenyl) sulfone. Further, these ester derivatives can also be used.

Further, the polyethylene naphthalate copolymer of the present invention may contain other compounds, for example, benzoyl benzoic acid, diphenyl sulfone monocarboxylic acid, stearic acid, methoxy polyethylene glycol, phenoxy polyethylene glycol. Or a multifunctional compound such as trimesic acid, trimethylolethane, trimethylolpropane, and pentaerythritol.

These other compounds include dicarboxylic acid 100
0.01 to 20 mol%, preferably 0.05 to 10 mol, based on mol%
% Can be used as needed.

The method for producing the polyethylene naphthalate copolymer according to the present invention will be described. In the present invention, the polyethylene naphthalate copolymer can be produced according to a conventionally known polyester production method. For example, a naphthalenedicarboxylic acid is directly esterified with an alkylene oxide adduct of ethylene glycol and bisphenols, or, when a dialkyl ester is used as a naphthalenedicarboxylic acid component, transesterification with an alkylene oxide adduct of ethylene glycol and bisphenols is performed. The polyethylene naphthalate copolymer can be produced by reacting and then performing a melt polycondensation reaction to remove excess diol components by heating under reduced pressure.

As the catalyst, known catalysts can be used. Specific examples of the transesterification catalyst include compounds such as magnesium, manganese, titanium, zinc, calcium, and cobalt. Compounds such as antimony, germanium, and titanium can be used. The addition amounts of the transesterification catalyst and the polycondensation catalyst may be arbitrary as long as the reactivity and heat resistance of the polyester are not impaired.

In the polycondensation step, a stabilizer may be added to the phosphorus compound. As the phosphorus compound, specifically, phosphates such as trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, trioctyl phosphate, triphenyl phosphate, triphenyl phosphite, trisdodecyl phosphite, trisnonyl Phosphites such as phenyl phosphite, methyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, dibutyl phosphate, monobutyl phosphate, phosphate esters such as dioctyl phosphate and phosphoric acid, and phosphorus compounds such as polyphosphoric acid. Can be.

In the polycondensation reaction, the polycondensation catalyst reacts with the dicarboxylic acid in an amount of 0.000 as metal atoms in the polycondensation catalyst.
Desirably it is present in an amount of 5 to 0.2 mol%, preferably 0.001 to 0.1 mol%. It is desirable that the intrinsic viscosity [η] of the polyester obtained by the above method is 0.40 to 1.0 dl / g, preferably 0.50 to 0.90 dl / g. The polyester obtained in this polycondensation step is usually melt-extruded and formed into granules (chips).

In the present invention, the polyester obtained in this polycondensation step may be further subjected to solid phase polycondensation. For example, the chip-like polyester obtained above, at a temperature of 160 ° C to less than the melting point, preferably at a temperature of 170 to 220 ° C for 8 to 40 hours,
Preferably, solid phase polymerization can be carried out for 15 to 30 hours. The intrinsic viscosity of the polyester after the solid-phase polycondensation is desirably 0.60 to 1.00 dl / g, preferably 0.75 to 0.95 dl / g.

The production process of the polyester including the esterification step and the polycondensation step as described above can be carried out by either a batch system or a semi-continuous system.

The polyethylene naphthalate of the present invention is used after being formed into a hollow container with a bottle, a film, a sheet and a fiber.

The hollow container can be formed by, for example, stretch blow molding a preform comprising the above-mentioned polyethylene naphthalate copolymer. As a stretch blow molding method, the above preform is stretched in the longitudinal direction at a temperature within the range of the stretching temperature in the composition, for example, at a temperature not lower than the crystallization temperature and not higher than the crystallization temperature, followed by further blow molding. Method of stretching in the horizontal axis direction (biaxial stretching blow method)
Etc. can be given.

For example, in order to produce the polyester container of the present invention by a biaxial stretch blow molding method, one end of a parison having a bottomed parison molded by an ordinary injection molding machine or a parison molded by an extrusion molding machine is used. The parison obtained by the bottoming is blown at 90 to 150 ° C., which is the stretching temperature of the polyester resin composition, and moves in the longitudinal direction in a longitudinal direction by blowing a rod and a pressurized gas in a molding die.
~ 3.5 times, preferably 2-3 times and 2-6 times in the horizontal direction,
A preferred example is a method of stretching 3 to 5 times. The blow mold temperature is usually room temperature, preferably 30 to 180 ° C, more preferably 100 to 150 ° C.

As a molding method by injection molding, either a two-stage system using a cold parison or a one-stage system using a hot parison may be used.

[0050]

According to the polyethylene naphthalate copolymer of the present invention and the method for producing the same, it is possible to provide a resin having excellent heat resistance and moldability.

[0051]

EXAMPLES Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

Measuring method [Thickness distribution] Thickness distribution is measured by measuring the thickness of four points in the circumferential direction of the bottle body, and when the difference in variation is distributed within 30 μm, it is determined as good and exceeds 30 μm. Something was bad. [Transparency] Transparency cuts the center of the bottle body,
Use a haze meter NDH-20D manufactured by Nippon Denshoku Co., Ltd.
The haze of the test piece was measured three times by a method according to MD 1003, and the average value was evaluated.

[0053]

Example 1 140 parts by weight of ethylene glycol, formula (10)
16 parts by weight of an ethylene oxide adduct of 4,4'-dihydroxybiphenyl shown in 2,4,6-dimethylnaphthalate 244
Parts by weight and 0.25 parts by weight of manganese acetate tetrahydrate were charged into a reactor, and reacted at 240 ° C. for 3 hours with stirring at normal pressure under a nitrogen atmosphere. Then, the mixture was reacted at a heating temperature of 260 ° C. for 3 hours. Methanol produced by this reaction was constantly distilled out of the system.

Next, 0.24 parts by weight of a mixture solution of germanium dioxide and ethylene glycol in a weight ratio of 1:10 was added to the reaction system, and the mixture was stirred for 20 minutes, and 0.08 parts by weight of phosphoric acid was added, followed by a reaction for 1 hour. . Thereafter, the temperature was raised to 280 ° C. over 1 hour, the pressure in the system was reduced to 1 torr, and the reaction was further performed for 4 hours, and excess ethylene glycol was distilled out of the system. After completion of the reaction, the reaction product was melt-extruded into a strand outside the reactor, immersed in water, cooled, and then cut into chips by a strand cutter.

The intrinsic viscosity IV measured at 25 ° C. in a phenol / tetrachloroethane mixed solution (weight ratio = 1/1) of the polyester copolymer obtained by the liquid phase polymerization described above is 0.3.
It was 57 dl / g. The copolymerization ratio of the ethylene oxide adduct of ethylene glycol and 4,4′-dihydroxybiphenyl was analyzed by NMR, and as a result, 95 mol% and 5 mol, respectively.
Mol%.

The obtained polyester copolymer was molded with a molding machine.
(M-100A manufactured by Meiki Seisakusho Co., Ltd.) to obtain a bottle forming polyform. The molding temperature at this time was 280 to 300 ° C.

Next, the preform obtained as described above
The bottle was molded using a CORPOPLAST LB-01 molding machine to obtain a biaxially stretched bottle. At this time, the stretching temperature was 140 to 150 ° C, and the mold temperature was 100 ° C. The stretching ratio is 2.0 times in the longitudinal direction,
The width was 5.0 times. Table 1 shows the results.

[0058]

Examples 2 to 5 The type of diol component in Example 1
A polyethylene naphthalate copolymer was produced according to Example 1 except that the addition amount was described in Table 1. Table 1 shows the results.

[0059]

Comparative Example 1 A bottle was formed according to Example 1, except that 132 parts by weight of ethylene glycol and 246 parts by weight of 2,6-dimethylnaphthalate were used as raw materials. Table 1 shows the results
Shown in

[0060]

【table 1】

[0061]

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[0062]

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Claims (3)

[Claims] 1. The dicarboxylic acid component comprises (A) a structural unit mainly derived from naphthalenedicarboxylic acid, the diol component comprises (B) 50 to 99 mol% of a structural unit derived from ethylene glycol, and (C) 50 to 1 mol of a structural unit derived from an alkylene oxide adduct of a dihydroxynaphthalene represented by the general formula [1] and / or (D) an alkylene oxide adduct of a biphenol represented by the following general formula [2] % Of polyethylene naphthalate copolymer. [Formula 1] (Wherein, R1 represents an alkylene group having 1 to 10 carbon atoms, R2 represents an alkyl group or alkenyl group having 1 to 12 carbon atoms, n is an integer of 1 to 5, and m is 0 to 2 Which is an integer) (Wherein, R1 represents an alkylene group having 1 to 10 carbon atoms, R2 represents an alkyl group or alkenyl group having 1 to 12 carbon atoms, n is an integer of 1 to 5, and m is 0 to 2 Is an integer of 2. The polyethylene naphthalate copolymer according to claim 1, wherein the (C) alkylene oxide adduct of dihydroxynaphthalene is a compound represented by the following formula [3]. Embedded image 3. The polyethylene naphthalate copolymer according to claim 1, wherein (D) the alkylene oxide adduct of biphenyls is a compound represented by the following formula [7]. Embedded image [0001]