JPS5857434A - Manufacture of polyester copolymer - Google Patents

Abstract

PURPOSE:To obtain a polyester copolymer having a low melting point and a proper crystallinity by the copolymerization of a dicarboxylic acid or its ester- forming derivative, a low-molecular weight diol, and a high-molecular weight diol. CONSTITUTION:A dicarboxylic acid or its ester-forming derivative (A) composed of terephthalic acid or a mixture of 50mol% or more terephthalic acid and one or more aromatic and aliphatic dicarboxylic acids other than terephthalic acid, a low-molecular weight diol (B) composed of a mixture of 1-50mol% 2-methyl- 1,3-propanediol and 99-50mol% 1,6-hexanediol, and one or more high-molecular weight diol (C) of polyalkylene ether glycols and polycaprolactone glycols (in such as amount that the proportion of the high-molecular weight diol component in the copolymer is 0-60wt%) are subjected to copolymerization.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing a polyester copolymer, and relates to a method for producing a novel polyester copolymer. More specifically, the present invention relates to a method for producing a polyester copolymer having a lower melting point and an appropriate degree of crystallinity than conventional polyester copolymers.

Conventionally, linear polyester copolymers have been used in a wide range of applications such as films, molded products, and fibers, but in general,
Polyester copolymers of this type that have a moderate degree of crystallinity have a high molecular weight and a high melting point, and are used in certain applications such as hot melt adhesives, binders for laminates, and plastic blend agents. Alternatively, it is not necessarily suitable for uses such as polyester elastic bodies. That is, these uses often require a polyester copolymer having a relatively low melting point and an appropriate degree of crystallinity.

In general, it is possible to change the melting point and degree of crystallinity of a small Liesdel copolymer by combining various two components consisting of a dicarboxylic acid component and a glycol component. However, in many cases, a decrease in the melting point also brings about an extreme decrease in the degree of crystallinity, and in some cases, it becomes difficult to balance the melting point and the degree of crystallinity.

However, as a result of intensive research, the present inventors found that +,6-hexanediol and 2-methyl-1,5
- By using m-compounds of noropanediol, it is possible to easily control the balance between melting point and crystallinity, and it is possible to create a polyester copolymer with a fairly low melting point and moderate crystallinity. They have discovered that this can be achieved and have arrived at the present invention.

That is, the present invention provides (A) terephthalic acid, or a mixture of 50 mol% or more of terephthalic acid and one or more dicarboxylic acids selected from aromatic dicarboxylic acids and aliphatic dicarboxylic acids other than terephthalic acid. dicarboxylic acid or ester thereof (B) 1 to 50 moles of 2-methyl-1,5-
A low molecular weight diol consisting of a mixture of noropanediol and 99-750 mol% F) 1.6-, xanediol, and (C) 1 or 2 diol selected from polyalkylene ether glycol and polycabrolactone glycol. A method for producing a holy ester copolymer, which is characterized by copolymerizing a high molecular weight diol with a high molecular weight diol of 100% or more (provided that the proportion of the high molecular weight diol component in the copolymer is Ω-6o*jii%). This is related to.

As the dicarboxylic acid component used in the present invention, terephthalic acid or its ester-forming derivative is suitable in order to maintain the thermal and mechanical strength of the obtained copolymer within a preferable range, but depending on the use, terephthalic acid or an ester-forming derivative thereof is suitable. ≦+11t or 2 selected from terephthalic acid, aromatic dicarboxylic acids other than terephthalic acid, and aliphatic dicarboxylic acids
A mixture with a dicarboxylic acid or more can also be used.

Examples of the aromatic dicarboxylic acids include isophthalic acid, 7-talum, 2,6-naphthalene dicarboxylic acid, and diphenyl dicarboxylic acid.
pl〆-dicarboxylic acid, his(p-carboxyphenyl)methane, anthracenedicarboxylic acid, ethylene bis-
Examples include p-benzoic acid, +14-te)ramethylenebis-p-benzoic acid, and the like. Examples of the aliphatic dicarboxylic acids include adipic acid, speric acid, yleic acid, sebacic acid, and dodecanedioic acid. can also be mentioned. In addition, polyvalent carboxylic acid such as trimellitic acid and pyromellitic acid with small wrinkles
They can also be mixed depending on the application.

In the present invention, 1 to 50 moles of 2-methyl-1,5-noropanediol and 99 to 50 moles of low molecular weight diol are used.
It is necessary to use a mixture with 0 mol≦1,6-hexanediol. 2-Methyl-1,5-propanediol has a 1-methyl group in its side chain and is an asymmetric diol in terms of its chemical structure, making the structure of polyester copolymers containing it as a copolymer component disordered. , is a very effective compound in lowering melting point and crystallinity. Moreover, 2
(Since the hydroxyl groups of Ll are all primary, they are highly reactive and easily react with compounds having carboxyl groups such as terephthalic acid to form ester bonds.

On the other hand, 1,6-hexanediol is a diol in which six methylene groups are bonded in a linear chain and has primary hydroxyl groups at both ends, and it easily reacts with compounds having carboxyl groups to form ester bonds. The polyester obtained by forming and reacting with a dicarboxylic acid exhibits high crystallinity.

According to the present invention, the melting point and crystallization of a first polyester copolymer obtained by combining the above 12 types of low molecular weight glycol components that exhibit contradictory tendencies as described above in terms of melting point, crystallization M, and degree of crystallization are obtained. 2-2 used in the present invention can be easily controlled within the desired range.
The proportion of methyl-1,5-propanediol in the low molecular weight glycol component is 1 to 50 molar, preferably 16 to 4 molar.
0 mol%, but as low as 1 mol%, the above-mentioned characteristics of ttV-2-methyl-1,6-propanediol could not be exhibited, and the melting point and crystallinity of the resulting copolymer were low. The melting point and crystallinity of the resulting polyester copolymer become too high, and the melting point and crystallinity of the resulting polyester copolymer drop extremely below 50 mol.
I don't like anything too much. Nine, the main F! In AK, as described above, a polymer 111 or two or more high molecular weight diols selected from polyalkylene ether glycol and polycabulactone glycol are used as polymerization reaction components, if necessary. These polymeric diols impart properties such as resistance, abrasion resistance, shock resistance, flexibility, or elastic recovery to the resulting copolymer, but these properties may be essential depending on the use of the copolymer. be.

The above-mentioned polyalkylene ether glycols include diethylene glycol, triethylene glycol, or polyeglobylene oxide) glycol having a higher degree of incorporation, poly(tetramethylene oxide) glycol, poly(hexamethylene oxide) glycol, and copolymers thereof. etc., or a mixture of these may be used. The number average molecular weight of these polyalkylene ether glycols is 100 to 5000°, preferably 100 to 5000°.
It's zoooo. Further, the above-mentioned polycarbonate glycol is obtained by ring-opening polymerization of lactone using an appropriate catalyst in the presence of a low molecular weight glycol such as ethylene glycol, and its number average molecular weight is 500 to 4000°, preferably 800 to 5000. be. The most preferable lactone is ε-caprolactone, and others include enanthratan, β-gropiolactone, dimethylgropiolactone, butyrolactone, r-valerolactone, r-caprolactone, r-cabrirolactone, chlorolactone, δ-valerolactone, δ-caprolactone, etc. can also be used, but two or more of these lactones can also be used in combination. In the reaction of the present invention, the proportion of the high molecular weight diol component used is such that the proportion in the obtained polymer is 0 to 60% by weight, preferably 0 to 40% by weight, and 60% by weight.
When ψ is more than p, the resulting copolymer becomes too soft, so ψ is not preferable.

For the polyester copolymerization t4-(1'>IIf of the present invention), conventionally known polyester manufacturing methods can be directly applied. That is, a method of directly polycondensing a dicarboxylic acid compound and a diol compound. or a method of reacting an ester-forming derivative such as a lower alkyl ester of dicarboxylic acid or a halogen derivative with a diol compound.

An example of the so-called transesterification method using lower alkaline esters of dicarboxylic acids is shown in which dimethyl terephthalate and an excess molar number, that is, a total of 1.1 to 2.0 times the molar amount of 1,6-hexane are used. Diol, 2
- A mixed diol consisting of methyl-1,5-propanediol and a polymer diol is subjected to an esterification exchange reaction under a nitrogen stream at a temperature of tSO to 24Q"C at atmospheric pressure using a conventional esterification catalyst, After distilling methanol and adding catalysts, color inhibitors, etc. as necessary, 5 @
Polycondensation is carried out at about 200-280'C under reduced pressure below rHj. A wide range of catalysts can be used as the catalyst, including tetramethoxytitanium, tetramethoxytitanium, tetramethoxytitanium,
Titanium compounds such as tetra-n-propoxytitanium, tetra-1so-propoxytitanium, tetrabutoxytitanium, di-n-butyl ditin, -dilaurate, di-n-butyl-
Examples include tin compounds such as tin-oquinide, diptyl-tin-di74et-), combinations of magnesium, acetates such as silak, zinc, and antimony oxide or the above-mentioned titanium compounds. These catalysts are preferably used in an amount of 0.002 to 0.8 weight based on the total copolymer produced.

Additionally, additives such as a coloring inhibitor, a polymerization accelerator, a whitening agent, a light-fastening agent, and a crystallization accelerator can be added to the reaction mixture as required.

The copolymer obtained by the method of the present invention is a molding material,
It can be used for applications in which polyester copolymers have traditionally been used, such as film materials and adhesive materials, but especially hot-melt adhesives, binders for laminates, plastic blends, and polyester elastomers. It can be used in applications requiring a low specific gravity melting point and appropriate degree of crystallinity, such as, to exhibit extremely excellent effects.

The following is an example of the production of a polyester elastomer according to the present invention, and an example of the application of the resulting i-lyester co-enriched material, in which it is used as a hot melt adhesive. The present invention is not limited.

In addition, parts in the examples mean parts by weight, and the measured values were obtained by the following self-measurement method.

1) The copolymer composition was determined by analyzing the nuclear magnetic resonance spectrum of the obtained copolymer. Diol constituent residues are indicated by their relative position relative to all diol residues, and polyalkylene ether glycol residues are indicated by their superposition relative to the copolymer.

2) The intrinsic viscosity is tetrachloroethane-phenol (5
part: 2 parts) in a mixed solvent at 25°C.

5) Melting point and heat of fusion were measured by differential scanning calorimetry 1lIFK, and Sn was used as a reference material for the heat of fusion.

4) Adhesive strength Japan Industrial Standards' Tensile Breaking Adhesive Strength Test Method for Adhesives (JIB K 6850) K was followed.

That is, the tensile shear adhesive strength of a test piece heat-pressed to a thickness of 100μ-K at 150°C between aluminum plates treated according to JXB K 684 B was measured using a Tensilon UTM-■SCO model universal testing machine manufactured by Toyo Baldwin. .

Example 1 9.9 parts of dimethyl phthalate, 2-methyl-1,
14.6 parts of 5-propanediol and 44.7 parts of 1,6-hexanediol were added to Y-labdoxytitanium catalyst a, O
7 parts together with a double helical ring type stirrer, and stirred at 180°C under normal pressure and nitrogen stream.
The mixture was then heated at 250° C. for 2.5 hours, and 89% of the theoretical amount of methanol produced was dripped out. 1. Next, 0.08 part of lysosil 7 osphite was added to the reaction mixture K), and the temperature was raised to 260°C, and the pressure in the system was reduced to 0.2 over 40 minutes.
The pressure was reduced to 111H&, and polymerization was carried out for 5.5 hours under the conditions ↑゛.

The intrinsic viscosity of the obtained polyester was 0.780 taA
ll, the melting point is +22-'C-1 heat of fusion is 5.0
7 c*L/11.

In addition, the copolymerized polyester was found to contain 2-methyl-1,5-protinediol 2 by nuclear magnetic resonance spectrum analysis.
It was found that it contained 9 mol % of diol residues and 1 mol % of 1,6-hexanedi-luminium.

Practical Examples 2-6 and Comparative Examples 1-2 Table-1! A batch was conducted under exactly the same batch conditions as in Example 1 using the charging amount shown in the IC. Table 1 shows the theoretical values of each polymer obtained.

Table 2 shows the measurement results of the tensile shear adhesive strength of the polyester copolymers obtained in Reference Examples and Comparative Examples.

Table-2 Note) In the case of the comparative example, the thermocompression bonding temperature was 170°C.

Applicant's agent Kaoru Furutani

Claims (1)

[Claims] t(mu)terephthalic acid, or a mixture of 50 moles or more of terephthalic acid and one or more dicarboxylic acids selected from aromatic dicarboxylic acids and aliphatic dicarboxylic acids other than terephthalic acid. (B) a mixture of 1 to 507 moles of 2-methyl-1,5-propanediol and 99 to 50 moles of 1,6-hexanediol; (0) one or two selected from polyalkylene ether glycol and polyalkylene ether glycol;
I
i) A method for producing a polyester copolymer, which comprises copolymerizing with.