JP3136757B2 - Method for producing ester copolymer - Google Patents

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 having excellent thermal stability and mechanical properties, and a method for producing the same.

[0002]

2. Description of the Related Art A polyester-type block copolymer in which an aromatic polyester such as polybutylene terephthalate constitutes a hard segment, and a polytetramethylene glycol or polycaprolactone constitutes a soft segment has a tensile strength, a tear strength and a resistance to tearing. It is widely used in automotive parts, electric / electronic parts, and mechanical parts as a thermoplastic elastomer with excellent flex fatigue and heat resistance.

[0003]

However, these thermoplastic elastomers have insufficient 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 is reduced. The present invention has been made to solve these problems, and an object of the present invention is to provide an ester copolymer having low hardness and excellent heat resistance, mechanical properties, and workability.

[0004]

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

The aromatic dihydroxy compounds used in the method of the present invention include resorcinols such as resorcinol and 4-acetylresorcinol, and hydroquinones such as hydroquinone, chlorohydroquinone, bromohydroquinone, methylhydroquinone, phenylhydroquinone, methoxyhydroquinone and phenoxyhydroquinone. , 4,4'-dihydroxybiphenyl, 3,3
'-Diphenyl-4,4'-dihydroxybiphenyl,
4,4'-dihydroxybiphenyl ether, 4,
4'-dihydroxybiphenyl sulfide, 4,4
'-Dihydroxybiphenylsulfone, 3,3'-diphenyl-4,4'-dihydroxybiphenylsulfone, 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 And naphthalenes such as dihydroxynaphthalene. Preferably, hydroquinone,
4,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl ether and 4,4'-dihydroxybiphenyl sulfide.

The aromatic dicarboxylic acids include phthalic acids such as terephthalic acid and isophthalic acid, and 4,4'-
Biphenyl dicarboxylic 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, and 1,2-bis (4-carboxyphenoxy) ethane;
Dicarboxynaphthalenes such as -dicarboxynaphthalene and 2,6-dicarboxynaphthalene; and methyl or ethyl esters thereof 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 Methyl or ethyl ester of 6,6-dicarboxynaphthalene.

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

[0008] The method for producing the ester copolymer of the present invention comprises:
The aromatic oligoester comprising an aromatic dicarboxylic acid, an aromatic dihydroxy compound and an alkylene glycol is characterized by a melting reaction with an aliphatic diol. The copolymerization amount of the aromatic oligoester in the ester copolymer is as follows: 10 to 90 from heat resistance, mechanical strength and moldability
%, Preferably in the range of 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 an aromatic diacetoxy compound / aromatic dicarboxylic acid (monoester) is used in a molar ratio of 1/2 to 1/5. A method in which a melt reaction is performed at a reaction temperature of 240 to 300 ° C., an alkylene glycol is further added, and a transesterification reaction is performed at about 150 to 240 ° C.

The aliphatic diol used in the method of the present invention includes alkylene glycol, polyalkylene glycol, polysiloxane diol and the like, and polyalkylene glycol is preferable.

Examples of the polyalkylene glycol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, a copolymer of ethylene oxide and propylene oxide, a copolymer of ethylene oxide and tetrahydrofuran, and an ethylene oxide addition polymer of polypropylene glycol. Is mentioned. Among these, an ethylene oxide addition polymer of polytetramethylene glycol and polypropylene glycol is particularly excellent in mechanical strength and moldability. These may be used alone or as a mixture of two or more.

The optimum value of the number average molecular weight of the polyalkylene glycol used varies depending on its chemical structure, the kind of aromatic oligoester and the copolymerization ratio.
00, preferably 650-4000. When the number average molecular weight is less than 500, heat resistance and moldability are poor, and when the number average molecular weight exceeds 10,000, phase separation of the polymer occurs at the time of polymerization, and the reaction rate is undesirably reduced.

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

Examples of the conditions for producing the ester copolymer include a method in which an aromatic oligoester and a 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 tetramethoxytitanium, tetraethoxytitanium, tetran-propoxytitanium, tetraisopropoxytitanium and tetrabutoxytitanium, and di-n-titanium.
Butyltin dilaurate, di-n-butyltin oxide,
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. These catalysts are preferably used in an amount of 0.002 to 0.8% by weight based on the entire copolymer to be produced.

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

In order to improve the heat resistance, particularly the thermochromic property of the ester copolymer, a stabilizer may be added during or after the polymerization. Examples of the stabilizer include phosphoric acid, phosphorous acid, hypophosphorous acid derivatives, phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonate, dialkylpentaerythritol diphosphite, dialkylbisphenol A diphosphite, and other phosphorus compounds, hinders Sulfur-containing compounds such as dophenolic compounds, thioethers, dithionates, mercaptobenzimidazoles, thiocarbanilides, and thiodipropionates, and tin-based compounds such as tinmalate and dibutyltin monoxide are used. The amount of these stabilizers is 0.01 to 100 parts by weight of the ester copolymer.
Preferably it is 2 parts by weight.

In order to improve the moldability of the ester copolymer obtained in the present invention, a lubricant such as stearic acid salts such as calcium, barium and aluminum, stearic acid ester, silicone oil, waxes and ethylenebisstearylamide is added. be able to. These addition amounts are 0.05 to 100 parts by weight of the ester copolymer.
A range of 5 parts by weight is preferred.

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

[0020]

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

(1) ¹ H-NMR spectra were measured in pentafluorophenol at 100 ° C. and 400 times of integration using JNM-GX400 manufactured by JEOL.

(2) The ¹³ C-NMR spectrum was measured in pentafluorophenol at 100 ° C. and 18,000 times of integration using JNM-GX400 model manufactured by JEOL.

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

(4) The dynamic viscoelastic behavior was measured by Rheology.
Using a DVE-V4 FT Rheospectler, the measurement was performed at a frequency of 11 Hz and a range of 30 to 200 ° C.

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

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

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

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

(9) Mechanical properties (rupture strength, elongation at break)
Was measured using an autograph DCS-1000 manufactured by Shimadzu Corporation using a 1 mm-thick press sheet.

Reference Example (Synthesis of Aromatic Oligoester [b]) A stirrer chip was placed in a 500 ml eggplant 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) were charged. After stirring at 100 ° C. for 3 hours, the mixture was precipitated in ice water and recrystallized from ethanol to give 258.9 g of diacetoxybiphenyl [BPDA] (yield: 96).
%).

In a 500 ml four-neck separable flask equipped with a nitrogen inlet tube, a temperature sensor, a magnetic stirring blade, and a distilling tube, 40.54 g (0.15 mol) of BPDA and 54.03 g of monomethyl terephthalate [MMT] ( 0.3
Mol). After sufficiently purging with nitrogen, the temperature was raised from room temperature to 240 ° C. in 1 hour under a nitrogen stream, and the reaction was carried out at 240 ° C. for 3 hours, at 280 ° C. for 2 hours, and further under reduced pressure for 30 minutes. After the pulverization, the mixture is washed with acetone to give a melting point of 278.
94.8 g of oligoester [a] having a yield of 81 ° C. (yield 81
%).

Further, 51.05 g of oligoester [a] was placed in a 500 ml four-neck separable flask equipped with a nitrogen inlet tube, a temperature sensor, a magnetic stirring blade, and a distilling tube.
(0.1 mol), ethylene glycol [EG]
04 g (2 mol) and 0.3 g of calcium acetate were charged. After sufficiently purging 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 was 12
56.42 g of aromatic oligoester [b] having a temperature of 9 ° C
(99% yield).

^{1 of the} obtained aromatic oligoester [b]
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 was represented by the following formula.

[0034]

Embedded image Example 1 In a 500 ml four-neck separable flask equipped with a nitrogen inlet tube, a temperature sensor, a magnetic stirring blade, and a distilling tube, 11.42 g (0.02 mol) of oligoester [b], polytetramethylene glycol ( PTMG; 29.06 g (0.01 mol) of number average molecular weight (Mn) = 2900) and 0.01 g of Irganox 1010 (phenol-based stabilizer, manufactured by Ciba Geigy) were charged. After sufficiently purging with nitrogen, 0.04 g of tetrabutoxytitanium (catalyst) was added. Under a nitrogen stream, the temperature was raised from room temperature to 200 ° C. for 30 minutes, reacted for 1 hour, raised to 250 ° C., 1 mm
The reaction was carried out for 2 hours under a reduced pressure of Hg or less while allowing EG to flow. Ester copolymer 31.6 showing good rubber elasticity
g (yield 81%) was obtained. This ester copolymer
FIG. 4 shows the ¹ H-NMR. As a result, it was found that the structure of the obtained ester copolymer was represented by the following formula.

[0035]

Embedded image (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 distilling tube, 17.12 g (0.03 mol) of oligoester [b], P
29.13 g (0.01 mol) of TMG (Mn = 2900) and 0.01 g of Irganox 1010 were charged. After sufficient nitrogen replacement, 0.02 g of tetrabutoxytitanium (catalyst) was added. Under a nitrogen stream, the temperature was 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 carried out under a reduced pressure of 1 mmHg or less while flowing out EG for 2 hours. 36.0 g of an ester copolymer showing good rubber elasticity and having the same structure as in Example 1.
(80% yield). Table 1 shows the physical properties of this ester copolymer.

Example 3 In a 500 ml four-neck separable flask equipped with a nitrogen inlet tube, a temperature sensor, a magnetic stirring blade, and a distilling tube, 34.33 g (0.06 mol) of oligoester [b], P
29.04 g (0.01 mol) of TMG (Mn = 2900) and 0.01 g of Irganox 1010 were charged. After sufficient nitrogen replacement, 0.05 g of di-n-butyltin dilaurate (catalyst) was added. The temperature was raised from room temperature to 200 ° C. for 30 minutes in a nitrogen stream, and the reaction was carried out for 1 hour. The temperature was raised to 250 ° C., and the reaction was carried out while flowing out EG for 2 hours under reduced pressure of 1 mmHg or less. Ester copolymer 4 showing good rubber elasticity and having the same structure as in Example 1.
6.4 g (77% yield) were 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 properties as a thermoplastic elastomer and having an aromatic oligoester chain in a hard segment can be obtained.
This polymer has low hardness and excellent heat resistance, mechanical properties and workability.

[Brief description of the 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 view showing an infrared absorption spectrum of oligoester [b].

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

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

Claims (2)

(57) [Claims] An ester copolymer characterized in that the melting reaction of an aromatic oligoester comprising 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:
0-90% by weight (Wherein, m and n are each 0 or 1; R ₁ and R ₂ are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, 1 carbon atom;
An alkoxy group having 4 to 4, an aryl group having 6 to 10 carbon atoms, an alkylaryl group or a halogen group having 7 to 12 carbon atoms, X
Represents O, S, CH ₂ , C ₂ H ₄ , C (CH ₃ ) ₂ , CO or SO ₂ , and Y represents an alkyl group having 2 to 6 carbon atoms.) Polyalkylene glycol having a number average molecular weight of 500 to 10,000 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.
000 to 500,000 ester copolymer production method.