JPH05287058A - Production of copolyester - Google Patents

Abstract

(57) [Summary] [Purpose] To provide an ester copolymer having low hardness, excellent heat resistance, mechanical properties, and processability. A method for producing an ester copolymer, characterized in that the melt reaction of an aromatic oligoester consisting of an aromatic dicarboxylic acid, an aromatic dihydroxy compound and an alkylene glycol and an aliphatic diol is carried out in the presence of an esterification catalyst. ..

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ester copolymer having properties as a thermoplastic elastomer and excellent in thermal stability and mechanical properties, and a method for producing the same.

[0002]

2. Description of the Related Art Polyester type block copolymers in which an aromatic polyester such as polybutylene terephthalate constitutes a hard segment and polytetramethylene glycol or polycaprolactone constitutes a soft segment have a tensile strength, a tear strength and a resistance to tearing. As a thermoplastic elastomer with excellent bending fatigue and heat resistance, it is widely used in automobile parts, electric / electronic parts, machine parts, etc.

[0003]

However, these thermoplastic elastomers do not have sufficient heat resistance and mechanical properties as electronic parts and mechanical parts, and have high hardness and lack rubber elasticity. Generally, when heat resistance is improved, workability decreases. The present invention has been made to solve these problems, and an object thereof is to provide an ester copolymer having low hardness and excellent heat resistance, mechanical properties, and processability.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found a novel method for producing an ester copolymer and completed the present invention. That is, the present invention is a method for producing an ester copolymer characterized by a melt reaction of an aromatic oligoester consisting of an aromatic dicarboxylic acid, an aromatic dihydroxy compound and an alkylene glycol and an aliphatic diol.

Examples of the aromatic dihydroxy compound used in the method of the present invention include resorcins such as resorcin and 4-acetylresorcin, hydroquinone, chlorohydroquinone, bromohydroquinone, methylhydroquinone, phenylhydroquinone, methoxyhydroquinone and phenoxyhydroquinone. , 4'-dihydroxybiphenyl, 3,3
′ -Diphenyl-4,4′-dihydroxybiphenyl,
4,4'-dihydroxybiphenyl ether, 4,
4'-dihydroxybiphenyl sulfide, 4,4
′ -Dihydroxybiphenyl sulfone, 3,3′-diphenyl-4,4′-dihydroxybiphenyl sulfone, 4,4′-dihydroxybenzophenone, 4,
Biphenols such as 4′-dihydroxybiphenylmethane, bisphenol A, 1,1-di (4-hydroxyphenyl) cyclohexane, 1,2-bis (4-hydroxyphenyl) ethane, 1,4-dihydroxynaphthalene, 2,6 -Naphthalenes such as dihydroxynaphthalene. Preferably, hydroquinone,
4,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl ether, and 4,4'-dihydroxybiphenyl sulfide.

As the aromatic dicarboxylic acid, phthalic acids such as terephthalic acid and isophthalic acid, 4,4'-
Biphenyldicarboxylic acids such as dicarboxybiphenyl, 4,4'-dicarboxybiphenyl ether, 4,4'-dicarboxybiphenyl sulfide, 4,4'-dicarboxybiphenyl sulfone, 3,3'-
Dicarboxyphenones such as dicarboxybenzophenone, 4,4′-dicarboxybenzophenone, 1,2-bis (4-carboxyphenoxy) ethane, 1,4
Examples thereof include dicarboxynaphthalenes such as dicarboxynaphthalene and 2,6-dicarboxynaphthalene, and their methyl or ethyl esters are preferably used. More preferably, terephthalic acid, 4,
4'-dicarboxybiphenyl, 4,4'-dicarboxybiphenyl ether, 4,4'-dicarboxybiphenyl sulfide, 4,4'-dicarboxybenzophenone, 1,2-bis (4-carboxyphenoxy) ethane, 2 , A methyl or ethyl ester of 6-dicarboxynaphthalene.

Further, as the alkylene glycol,
Examples thereof include ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol. Of these, ethylene glycol or butanediol is preferable from the viewpoint of polymerizability and mechanical strength.

The method for producing the ester copolymer of the present invention comprises:
The above-mentioned aromatic dicarboxylic acid, aromatic dihydroxy compound and aromatic oligoester consisting of alkylene glycol are characterized by melting reaction with an aliphatic diol. The copolymerization amount of the aromatic oligoester in the ester copolymer is 10 to 90 due to heat resistance, mechanical strength and moldability
% By weight, preferably 15 to 85% by weight.

As a method for synthesizing an aromatic oligoester, for example, acetylation of an aromatic dihydroxy compound is carried out, and a molar ratio of aromatic diacetoxy compound / aromatic dicarboxylic acid (monoester) = 1/2 to 1/5. A method in which a melt reaction is performed at a reaction temperature of 240 to 300 ° C., alkylene glycol is further added, and a transesterification reaction is performed at about 150 to 240 ° C.

Examples of the aliphatic diol used in the method of the present invention include alkylene glycol, polyalkylene glycol, polysiloxane diol and the like, with polyalkylene glycol being preferred.

As the polyalkylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, a copolymer of ethylene oxide and propylene oxide, a copolymer of ethylene oxide and tetrahydrofuran, an ethylene oxide addition polymer of polypropylene glycol, etc. Is mentioned. Among these, ethylene oxide addition polymers of polytetramethylene glycol and polypropylene glycol are particularly excellent in terms of mechanical strength and moldability. You may use these individually or in mixture of 2 or more.

The number average molecular weight of the polyalkylene glycol to be used varies depending on its chemical structure, kind of aromatic oligoester and copolymerization ratio, but the optimum value varies from 500 to 100.
00, preferably 650 to 4000. When the number average molecular weight is less than 500, the heat resistance and molding processability are poor, and when the number average molecular weight exceeds 10,000, phase separation of the polymer occurs during polymerization and the reaction rate decreases, which is not preferable.

The copolymerization amount of polyalkylene glycol is 90 to 1 from the viewpoint of heat resistance, mechanical strength and moldability.
It must be in the range of 0% by weight, preferably 85 to 15% by weight. When it exceeds 90% by weight, moldability is poor, and when it is less than 10% by weight, flexibility and rubber elasticity may be insufficient.

The conditions for producing the ester copolymer include, for example, a method in which an aromatic oligoester and polyalkylene glycol are melt-reacted at about 150 to 300 ° C. under a reduced pressure of 5 mmHg or less in the presence of an esterification catalyst.

Examples of the esterification catalyst used in the present invention include titanium compounds such as tetramethoxy titanium, tetraethoxy titanium, tetra n-propoxy titanium, tetraisopropoxy titanium and tetrabutoxy titanium, and di-n-.
Butyltin dilaurate, di-n-butyltin oxide,
Examples thereof include tin compounds such as di-n-butyltin diacetate, acetates such as magnesium, calcium and zinc, and antimony chloride. Among them, a good catalyst is a titanium compound. It is preferable to use these catalysts in an amount of 0.002 to 0.8% by weight based on the total copolymer produced.

The number average molecular weight of the ester copolymer obtained in the present invention is 5,000 to 500,000, preferably 10
000 to 100,000. Number average molecular weight is 5000
If it is less than 5, mechanical properties will be inferior, and if it exceeds 500,000, there will be a problem in workability.

A stabilizer may be added during or after the polymerization in order to improve the heat resistance of the ester copolymer, particularly the thermochromic property. Examples of the stabilizer include phosphorus compounds such as phosphoric acid, phosphorous acid, hypophosphorous acid derivatives, phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonate, dialkylpentaerythritol diphosphite, and dialkylbisphenol A diphosphite, hinders. Dephenol compounds, thioether compounds, dithioate compounds, mercaptobenzimidazole compounds, thiocarbanilide compounds, sulfur-containing compounds such as thiodipropionic acid esters, and tin compounds such as tin malate and dibutyltin monoxide are used. The amount of these stabilizers added is 0.01 to 100 parts by weight of the ester copolymer.
It is preferably 2 parts by weight.

In order to improve the moldability of the ester copolymer obtained in the present invention, stearates such as calcium, barium and aluminum, stearates, silicone oil, waxes and lubricants such as ethylenebisstearylamide are added. be able to. The addition amount of these is 0.05 to 100 parts by weight of the ester copolymer.
A range of 5 parts by weight is preferred.

Further, with respect to the ester copolymer obtained in the present invention, known dyes, pigments, inorganic reinforcing agents, plasticizers, hindered amine light stabilizers, ultraviolet absorbers, foaming agents, epoxy compounds and isocyanate compounds are known. Additives can be added.

[0020]

EXAMPLES Next, the present invention will be explained in detail with reference to examples, but the present invention is not limited to these. Also,
The measuring instruments and methods used for the analysis and physical property evaluation of the ester copolymer obtained in the present invention are as follows.

(1) The ¹ H-NMR spectrum was measured by using JNM-GX400 type manufactured by JEOL in pentafluorophenol under the conditions of 100 ° C. and 400 times of integration.

(2) The ¹³ C-NMR spectrum was measured by using JNM-GX400 type manufactured by JEOL Ltd. in pentafluorophenol under the conditions of 100 ° C. and the number of integration of 18,000 times.

(3) The infrared absorption spectrum is from Hitachi
It was measured by the KBr tablet method using Model 270-30.

(4) Dynamic viscoelastic behavior is based on rheology
Using a DVE-V4 FT Rheospectr, it was measured at a frequency of 11 Hz and in the range of 30 to 200 ° C.

(5) The glass transition temperature was measured at a temperature rising rate of 10 ° C./minute using a DSC200 manufactured by Seiko Denshi Kogyo.

(6) The thermal decomposition temperature was measured using TG-DTA200 manufactured by Seiko Denshi Kogyo at a heating rate of 20 ° C./min.

(7) The molecular weight of the polymer is C
P-8000 was used, and gel permeation chromatography of a column system in which polystyrene gel GMH6 and GRCH were connected to the column was used, and the flow rate was 1.0 ml / min, the eluent was tetrahydrofuran, and the column temperature was 28 ° C.

(8) The hardness was measured with a micro rubber hardness meter manufactured by Kobunshi Keiki Co., Ltd. using a press sheet having a thickness of 2 mm.

(9) Mechanical properties (breaking strength, breaking elongation)
Was measured by a Shimadzu-made Autograph DCS-1000 using a press sheet having a thickness of 1 mm.

Reference Example (Synthesis of Aromatic Oligoester [b]) A stirrer chip was placed in a 500 ml eggplant-shaped flask equipped with a cooling tube, and 186.22 g (1 mol) of 4,4′-dihydroxybiphenyl [BP] was added. Acetic anhydride 255.
23 g (2.5 mol) was charged. After stirring and reacting at 100 ° C. for 3 hours, it was precipitated in ice water and recrystallized from ethanol to give 258.9 g of diacetoxybiphenyl [BPDA] (yield 96
%) Was obtained.

In a 500 ml four-neck separable flask equipped with a nitrogen introduction tube, a temperature sensor, a magnetic stirring blade, and a distillation tube, 40.54 g (0.15 mol) of BPDA and 54.03 g of monomethyl terephthalate [MMT] ( 0.3
Mole). After sufficiently substituting with nitrogen, the temperature was raised from room temperature to 240 ° C. in 1 hour under a nitrogen stream, and the reaction was performed at 240 ° C. for 3 hours, 280 ° C. for 2 hours, and further under reduced pressure for 30 minutes. After crushing, washing with acetone to give a melting point of 278
94.8 g (yield 81)
%) Was obtained.

Further, 51.05 g of oligoester [a] was placed in a 500 ml four-neck separable flask equipped with a nitrogen introduction tube, a temperature sensor, a magnetic stirring blade, and a distillation tube.
(0.1 mol), ethylene glycol [EG] 124.
04 g (2 mol) and 0.3 g of calcium acetate were charged. After sufficiently substituting with nitrogen, the mixture was reacted at 200 ° C. for 6 hours under a nitrogen stream. After precipitation in distilled water and washing, the melting point is 12
Aromatic oligoester [b] at 9 ° C 56.42 g
(Yield 99%) was obtained.

^{1 of the} obtained aromatic oligoester [b]
1 H-NMR is shown in FIG. 1, ¹³ C-NMR is shown in FIG. 2, and an infrared absorption spectrum is shown in FIG. As a result, it was found that the structure of the obtained oligoester is represented by the following formula.

[0034]

[Chemical 2] Example 1 In a 500 ml four-neck separable flask equipped with a nitrogen introduction tube, a temperature sensor, a magnetic stirring blade, and a distillation tube, 11.42 g (0.02 mol) of oligoester [b] and polytetramethylene glycol ( PTMG; 29.06 g (0.01 mol) of number average molecular weight (Mn) = 2900 and 0.01 g of Irganox 1010 (phenolic stabilizer, manufactured by Ciba Geigy) were charged. After sufficiently substituting with nitrogen, 0.04 g of tetrabutoxytitanium (catalyst) was added. Under a nitrogen stream, the temperature is raised from room temperature to 200 ° C. in 30 minutes, reacted for 1 hour, heated to 250 ° C., and 1 mm.
The reaction was performed under a reduced pressure of Hg or less for 2 hours while allowing EG to flow out. Ester copolymer 31.6 showing good rubber elasticity
g (81% yield) was obtained. Of this ester copolymer
¹ H-NMR is shown in FIG. As a result, it was found that the structure of the obtained ester copolymer was represented by the following formula.

[0035]

[Chemical 3] (Where l is about 40 on average and p: q = 17: 83). The dynamic viscoelastic behavior of this ester copolymer is shown in FIG.
Table 1 shows the physical properties.

Example 2 In a 500 ml four-neck separable flask equipped with a nitrogen inlet tube, a temperature sensor, a magnetic stirring blade, and a distillation tube, 17.12 g (0.03 mol) of oligoester [b] and P were added.
29.13 g (0.01 mol) of TMG (Mn = 2900) and 0.01 g of Irganox 1010 were charged. After sufficiently substituting with nitrogen, 0.02 g of tetrabutoxytitanium (catalyst) was added. Under a nitrogen stream, the temperature is raised from room temperature to 200 ° C. in 30 minutes and reacted for 1 hour.
The temperature was raised to 0 ° C., and the reaction was performed under a reduced pressure of 1 mmHg or less for 2 hours while allowing EG to flow out. 36.0 g of an ester copolymer having good rubber elasticity and having the same structure as in Example 1.
(Yield 80%) was obtained. Table 1 shows the physical properties of this ester copolymer.

Example 3 In a 500 ml four-neck separable flask equipped with a nitrogen introducing tube, a temperature sensor, a magnetic stirring blade, and a distilling tube, 34.33 g (0.06 mol) of oligoester [b], P was added.
29.04 g (0.01 mol) of TMG (Mn = 2900) and 0.01 g of Irganox 1010 were charged. After sufficiently substituting with nitrogen, 0.05 g of di-n-butyltin dilaurate (catalyst) was added. Under a nitrogen stream, the temperature was raised from room temperature to 200 ° C. in 30 minutes, the reaction was performed for 1 hour, the temperature was raised to 250 ° C., and the reaction was performed under a reduced pressure of 1 mmHg or less for 2 hours while allowing EG to flow out. Ester copolymer 4 showing good rubber elasticity and having a structure similar to that of Example 1.
6.4 g (77% yield) was obtained. Table 1 shows the physical properties of this ester copolymer.

[0038]

[Table 1]

[0039]

According to the method of the present invention, an ester copolymer having a property as a thermoplastic elastomer and having an aromatic oligoester chain as a hard segment can be obtained.
This polymer has low hardness and excellent heat resistance, mechanical properties and processability.

[Brief description of drawings]

FIG. 1 is a diagram showing a ¹ H-NMR spectrum of an oligoester [b].

FIG. 2 is a diagram showing a ¹³ C-NMR spectrum of oligoester [b].

FIG. 3 is a diagram showing an infrared absorption spectrum of oligoester [b].

FIG. 4 is a diagram showing a ¹ H-NMR spectrum of an ester copolymer.

FIG. 5 is a diagram showing a dynamic viscoelastic behavior of an ester copolymer.

Claims (2)

[Claims] 1. An ester copolymer, characterized in that the melt reaction of an aromatic oligoester consisting of an aromatic dicarboxylic acid, an aromatic dihydroxy compound and an alkylene glycol with an aliphatic diol is carried out in the presence of an esterification catalyst. Production method. 2. An aromatic oligoester 1 represented by the following formula:
0 to 90% by weight and (In the formula, m and n are each 0 or 1, and R ₁ and R ₂ are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, and 1 carbon atom.
To alkoxy groups, C6 to C10 aryl groups, C7 to C12 alkylaryl groups or halogen groups, X
Is _{O, S, CH 2, C} 2 H 4, C (CH 3) 2, shows a CO or SO _2, Y is a polyalkylene glycol of the alkyl group shows a) a number average molecular weight 500 to 10,000 having 2 to 6 carbon atoms A number average molecular weight of 5, characterized in that the melting reaction with 90 to 10% by weight is carried out in the presence of an esterification catalyst.
Of 000 to 500000 ester copolymers.