JPH10204165A - Polyethylene naphthalate copolymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyethylene naphthalate copolymer having excellent moldability and to provide a process for producing the same. SOLUTION: This copolymer comprises a dicarboxylic acid component based on structural units derived from naphthalenedicarboxylic acid and a diol component comprising 50-99mol% structural units derived from ethylene glycol and 50-1mol% structural units derived from a bisphenol alkylene oxide adduct represented by the formula (R1 is a 1-4C alkyl; R2 is a 1-10C alkylene and/or -S- or SO2 ; R3 is a 1-12C alkyl or an alkenyl; n is an integer of 1-5; and m is an integer of 0-2).

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 that of polyethylene terephthalate resin, and has excellent chemical resistance and gas barrier properties. Therefore, it is expected to be used as a resin for various packaging materials. 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 prior art, and is intended to provide a polyethylene naphthalate having excellent moldability by copolymerizing an alkylene oxide adduct of a bisphenol with polyethylene naphthalate. It is intended to provide a phthalate copolymer.

[0006]

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

[0007]

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Wherein R 1 represents an alkyl group having 1 to 4 carbon atoms, and R 2 represents an alkylene group having 1 to 10 carbon atoms and / or
S- and -S02- groups, and R3 represents an alkyl group or alkenyl group having 1 to 12 carbon atoms. Further, n is an integer of 1 to 5, and m is 0 to 2
Is an integer. )

[0009]

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

The polyethylene naphthalate copolymer of the present invention comprises a structural unit mainly derived from naphthalenedicarboxylic acid as a dicarboxylic acid component, and a structural unit derived from ethylene glycol and an alkylene oxide adduct of bisphenols as a diol component. Consists of units.

As the dicarboxylic acid component (A) used in the polyethylene naphthalate copolymer of the present invention, naphthalenedicarboxylic acid is mainly used. As naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-
Use isomers such as naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid be able to. 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 in the range of 0 to 20 mol%, preferably 1 to 15 mol%, based on 100 mol% of the entire dicarboxylic acid component.

The diol component unit of the polyethylene naphthalate copolymer of the present invention comprises a unit (B) derived from ethylene glycol and a unit (C) derived from an alkylene oxide adduct (C) of a bisphenol. Consists of The alkylene oxide adduct of bisphenols (C) that can be used in the present application is a compound represented by the following general formula [1].

[0016]

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(Wherein, R 1 represents an alkyl group having 1 to 4 carbon atoms, and R 2 represents an alkylene group having 1 to 10 carbon atoms, and / or
S- and -S02- groups, and R3 represents an alkyl group or alkenyl group having 1 to 12 carbon atoms. Further, n is an integer of 1 to 5, and m is 0 to 2
Is an integer. )

Specific examples of the alkylene oxide adduct of bisphenols (C) used in the present invention include the following formulas [2] to [22].

[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

[Formula 13]

[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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Of these, the compound of the above formula [2] is preferred.

In the polyethylene naphthalate copolymer of the present invention, (B) a structural unit derived from ethylene glycol as a diol component and (C) an alkylene oxide adduct of a bisphenol represented by the above general formula [1] The proportion of the derived structural unit is usually 50 to 99 mol%, preferably 80 to 97 mol%, for the component (B), and 50 to 1 mol%, preferably 20 for the component (C).
To 3 mol%. If the amount of the component (C) is less than the above range, the effect of improving the moldability by the component (C), which is a feature of the present invention, is difficult to be obtained. And the gas barrier properties are reduced.

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

In the polyethylene naphthalate copolymer of the present invention, besides ethylene glycol and an alkylene oxide adduct of bisphenol as a diol component unit, other diol components may be used as long as the properties of the copolymer are not impaired. Good.

As other diol components, 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.

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 phosphorus compound may be added with a stabilizer. 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 hollow containers such as bottles, films, sheets, fibers and the like.

The hollow container can be formed by, for example, stretch blow-molding a preform made of the 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 stretching 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.

[0057]

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.

[0058]

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

Measurement method [Thickness distribution] Thickness distribution was measured by measuring the thickness at four points in the circumferential direction at the center of the body of the bottle, and if the variation was distributed within 30 μm, it was determined to be good and 30 μm. The ones exceeding the above were regarded as defective. [Transparency] Transparency was measured by cutting the bottle body and using 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 03, and the average value was evaluated.

[0060]

Example 1 140 parts by weight of ethylene glycol, 16 parts by weight of ethylene oxide adduct of bisphenol A, 244 parts by weight of 2,6-dimethylnaphthalate, manganese acetate tetrahydrate
0.25 parts by weight was charged into the reactor, and 2
The reaction was carried out with stirring at 40 ° C. for 3 hours. 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 to react 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. Ethylene glycol and bisphenol
As a result of NMR analysis, the copolymerization ratio of the ethylene oxide adduct of A was 95 mol% and 5 mol%, respectively.

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.

[0065]

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 changed as described in Table 1. Table shows the results. It is shown in FIG.

[0066]

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

[0067]

Comparative Example 2 Except for changing the stretching ratio of the preform,
A bottle was molded according to Comparative Example 1. Table 1 shows the results.

[0068]

【table 1】

[0069]

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[0070]

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[0071]

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[0072]

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Claims (2)

[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) General formula [1] of
A polyethylene naphthalate copolymer comprising 50 to 1 mol% of structural units derived from an alkylene oxide adduct of a bisphenol represented by the formula: [Formula 1] (Wherein, R 1 represents an alkyl group having 1 to 4 carbon atoms, R 2 represents an alkylene group having 1 to 10 carbon atoms, and / or a —S—, —S 02 — group, and R 3 represents an alkyl group having 1 to 12 carbon atoms. And n is an integer of 1 to 5, and m is an integer of 0 to 2.) 2. The polyethylene naphthalate copolymer according to claim 1, wherein the bisphenol is a compound represented by the following formula [2]. [0001]