JPS62164721A - Copolyester - Google Patents

Abstract

PURPOSE:To obtain a copolyester which is melt-moldable and excellent in heat distortion resistance, bending characteristic, and strength, comprising four specified kinds of structural units. CONSTITUTION:For example, an aromatic diol, a diphenyl ester of an aromatic hydroxycarboxylic acid and a diphenyl ester of an aromatic carboxylic acid are polycondensed by elimination of phenol to obtain a copolyester comprising 2.5-35mol% structural units of formula I (wherein X is F, Cl or Br and n is 2 or 4), 2.5-35mol% at least one structural unit selected from formula II-VII and 30-95mol% structural units of formula VIII and/or formula IX (at least one of the aromatic ring hydrogen atoms of the units of formulas II-IX may be substituted by a 1-4C alkyl or alkoxy or a halogen), having an intrinsic viscosity of 1.0-15, a bending modulus of 1X10<5>kg/cm<2>, a heat distortion temperature under a load of 18.62kg/cm<2>>=120 deg.C, a melt viscosity at 180-400 deg.C of 10<4>-10<2>P and a glass transition temperature >=120 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to copolymerized polyesters which are melt moldable and have excellent mechanical properties, in particular improved bending properties.

Among aromatic polyesters, resin groups that exhibit liquid crystallinity when melted have a high degree of orientation, and are known to exhibit excellent mechanical properties, especially tensile strength. The difference in mechanical properties in the direction perpendicular to this is so severe that the physical properties are greatly influenced by the flow state during melt processing, which poses a problem for industrialization.

In addition, industrialized materials also use a method of eliminating anisotropy by adding fillers, which is undesirable because it sacrifices the lightweight properties of the resin material and reduces specific strength.

For example, as shown in U.S. Pat.
- The tensile strength of the resin produced with hydroxybenzoic acid (60 mol%), 4゜4'-biphenol diacetate (I7.5 mol%) and terephthalic acid (I7.5 mol%) is 1900 kg/c 2 However, the bending strength is 123
0 kg/as", and the bending modulus is 8.4X10
'kg/am'.

Further, raw material monomers for aromatic polyesters are often crystalline, and therefore, melt polymerization conditions are naturally limited by the melting point of these monomers and the melting point of the resulting polymer. Furthermore, due to restrictions on the melting point and α of the polymer, there are also restrictions on the composition ratio of components that can be melt-polymerized.

Regarding the polymer containing component (I) of the present invention, please refer to Japanese Patent Publication No. 49-1795, Japanese Patent Publication No. 49-13235, Japanese Patent Publication No. 49-13235, Japanese Patent Publication No. 49-13235,
-13237, Japanese Patent Publication No. 49-13238, Japanese Patent Publication No. 59-
41331, JP-A-59-124926, JP-A-59-
124928, Japanese Patent Publication No. 59-223719.4e Leap Show 6
0-4529, JP-A-188420, JP-A-Sho 60
-188423, JP-A-60-192724, JP-A-6
0-192725 etc., insects, ingredients (l[[
) and (IV), for polymers containing
-77691, JP-A-59-157115, JP-A-55
-144024, JP 59-62630, U.S. Patent 4
, 473°682, etc.

Conventionally, the homopolymer of p-hydroxybenzoic acid was known as Econol E101J, but this resin had an extremely high melting point and could not be melt polymerized. Although workability was improved by adding acid, no significant progress was observed in mechanical strength, especially bending strength (Japanese Patent Laid-Open No. 1983-1999).
77691, JP-A-59-157115).

On the other hand, 1,2-bis(2-chloro7eth/xy)ethane-
It has recently been reported that polymers containing 4,4'-dicarboxylic acid are tough (Japanese Patent Application Laid-open No. 6O-4529).
Since the main chain contains the 71J7 attic component, the melting point is generally quite low, so its practical use is quite limited.

Additionally, a blend of PET and polyethylene-1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylate (Japanese Unexamined Patent Publication No. 59-207962) similarly has low thermal properties ( For example, 18.6' g f /
Cm 2 load heat distortion temperature), it is beyond the realm of improvement of PET.

On the other hand, the resin shown in JP-A-59-41331 is a wholly aromatic polyester, and the most preferred one is 1,2-bis(2-chloro7e/xy)ethane-4,4
A polymer composed of '-nocarboxylic acid and 4,4'-diacetoxybiphenol has a high melting point and is extremely difficult to melt polymerize.

Further, JP-A-60-188423 only discloses optical anisotropy and moldability, but does not disclose mechanical properties at all.

Also, JP-A-60-188420, JP-A-60-192
724, JP-A No. 60-192725, etc., disclose optical anisotropy and elastic modulus of fibers, but they lack descriptions regarding the heat resistance of resins, and do not provide information on bending properties such as flexural strength and flexural modulus of resins, as well as tensile strength. There is no mention of strength, and the shortcomings of conventional resins have not been sufficiently improved.

Therefore, the inventors of the present invention have improved the above-mentioned drawbacks of conventional polyesters, and have developed polyesters that can be melt-processed into melt-polymerized composites, have heat deformation resistance and melting points that are not too low, and have high strength and high modulus of elasticity. As a result of intensive studies on copolyesters that can give molded articles, the present invention was arrived at. That is, the present invention provides a melt-processable copolymer which overcomes the drawbacks of conventional polyesters and is composed of the following structural units (I), (II), (III) and/or (rV) as main constituents. It provides polyester.

[However, X is F%CI or Br, and n is 2 or 41.For the structural unit (If), it is sufficient that at least one of the above six types is t*, and Unit (I
At least one of the hydrogen atoms on the aromatic ring of I), (III) and (I%F) is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen May be substituted with an atom.

The polyester of the present invention also has units (I) of from 2°5 to
Contains 35 mol%, preferably 5 to 30 mol%, more preferably 10 to 25 mol%, and contains 2.5 to 3 units (If).
Contains 5 mol%, preferably 5 to 30 mol%, more preferably 10 to 25 mol%, unit (nr), unit (■)
or 30 to 95 mol%, preferably 40 to 90 mol%, more preferably 50 mol% of the unit ([[) plus unit (IV)
It is necessary that the content be 80 mol%. If the total of units (I) and units [■] exceeds 70 mol% of the polyester, the melting point will be high and melt polymerization will be extremely difficult.

Regarding the 1st position (III) and the unit (IV), it is sufficient that at least one of them exists, but it is more preferable that they coexist.

Although the melting point of tree manure and moldability are not necessarily in parallel, the copolyester of the present invention can be melt-molded at 400°C or lower, preferably at 400°C or lower, and more preferably at 30°C or lower. has a melt viscosity of 10 at temperatures below 320°C.
The polymerization temperature of the copolyester of the present invention is 360°C or lower, preferably 340°C.
or less, more preferably 320°C or less.

Further, when the resin of the present invention is polymerized at a temperature exceeding 360° C., the polymer becomes colored and decomposition such as elimination of the halogen atom of the unit (I) occurs, which is not preferable.

In addition, when a substituent exists in the structural unit of the resin of the present invention,
The melting point of the resin is generally wide and unclear, but the plus transition temperature, which is an index of heat resistance, is equivalent to that of an unsubstituted resin, and exhibits high mechanical properties.

The raw material compounds that provide units (I) to the copolymerized polyester include 1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylic acid, 1,2-bis(2-pro,mophenoxy)ethane -4,4'-dicarboxylic acid, 1
．． 2-bis(2-fluorophenoxy)ethane-414
'-dicarboxylic acid, 1,4-bis(2-chlorophenoxy)butane-4,4'-dicarboxylic acid, 1,4-biλ(
2-promophenoxy)butane-4,4'-dicarboxylic acid, 1,4-bis(2-fluorophenoxy)butane-
Preferred examples include 4゜4'-dicarboxylic acids, esters thereof such as methyl and phenyl, and acid chlorides; however, as contaminants naturally expected from the synthesis process of these compounds, the following compounds are included in the WIN process of the present invention. It may be contained in a small amount so as not to impair the properties of the material. That is, 1(
2-chlorophenoxy)-2(2',6'-dichlorophenoxy)ethane-4,4'-dicarboxylic acid, 1(2-
chloro7eth/xy)-2(2't3',6'-)dichlorophenoxy)ethane/4,4'-dicarboxylic acid, 1.
2-bis(2,6-dichlorophenoxy)ethane-4,
4'-dicarboxylic acid, 1(2,6-dichloro7e/xy)-2(2', 3', 6'-)lichloroeF7e/
xy)ethane-4,4'-dicarboxylic acid, 1(phenoxy)-2(2'-chlorophenoxy)ethane-4,4'
-dicarboxylic acid, 1(2-bromophenoxy)-2(2
',6'-dibromophenoxy)ethane-4,4'-dicarboxylic acid, 1(2-bromophenoxy)-2<2'.

3',6'-tribromophenoxy)ethane-4
, 4'-dicarboxylic acid, 1,2-bis(2,6-dibromo7eth/xy)ethane-4,4'-dicarboxylic acid, 1(
2,6-nopuamo7technical/kin)-2(2',3',6'
-) Su70mophenoxy)ethane-4,4'-nocarboxylic acid, 1(phenoxy)-2(2'-bromophenoxy)ethane-4,4'-dicarboxylic acid, 1(2-fluorophenoxy)-2(2 ',6'-difluorophenoxy)ethane-4,4'-dicarboxylic acid, 1 (2-fluorophenoxy)-2(2',3',6'-)difluorophenoxy)ethane-4,4'-dicarboxylic acid acid, 1,
2-bis(2,6-difluorophenoxy)ethane-4
, 4'-dicarboxylic acid, 1(2,6-difluorophenoxy)-2(2'.

3',6'-)lifluorophenoxy)ethane-4,4
'-dicarboxylic acid, 1(phenoxy)-2(2'-fluorophenoxy)ethane-4,4'-dicarboxylic acid, 1
(2-chloro7e/xy)-4(2',6'-dichlorophenoxy)butane-4,4'-dicarboxylic acid, 1(2
-chlorophenoxy)-4(2',3',6'-)dichlorophenoxy)butane-4,4'-dicarboxylic acid, 1
g4-bis(2,6-dichloro7eth/oxy)butane-4
,4'-7carboxylic acid, 1(2,6-dichloro7eth/oxy)-4(2',3',6'-)dichlorophenoxy)
Butane-4゜4'-dicarboxylic acid, 1(phenoxy)-
4(2'-chloro7e7xy)butane-4,4'-7carboxylic acid, 1(2-bromophenoxy)-4(2', (
i'-dibromophenoxy)butane-4,4'-dicarboxylic acid, 1(2-bromophenoxy)-4(2',3'
, 6'-)dibromo7eth/xy)butane-4,4'-dicarboxylic acid, 1,4-bis(2,6-dibromophenoxy)butane-4,4'-dicarboxylic acid, 1(2,6- dibromophenoxy)-4(2',3',6'-)dibromophenoxy)butane-4,4'-dicarboxylic acid, 1(
7eth/xy)-4(2'-bromophenoxy)butane-
4,4'-dicarboxylic acid, 1(2-fluorophenoxy)-4(2',6'-difluorophenoxy)butane-4,4'-dicarboxylic acid, 1(2-fluoro7e/xy)-4( 2',3',6'-)su7fluorophenoxy)butane-4,4'-dicarboxylic acid, 1,4-bis(2
, 6-difluorophenoxy)butane-4,41-dicarboxylic acid, 1(2,6-difluorophenoxy)-4(
2', 3', 6'-)difluorophenoxy)
Butane-4,4'-dicarboxylic acid%-1 (phenoxy)
-4(2'-fluorophenoxy)butane-4゜4'-
These include dicarboxylic acids, their esters such as methyl and phenyl, and acid chlorides.

Examples of starting compounds providing unit (II) are hydroquinone, 4,4'-oxydiphenol, 4,4'-thio:)phenol, 4,4'-sulfonyldiphenol,
At least one selected from bis7el/-el A, 2,6-hydroxyna7talene, and some of the hydrogen atoms on the aromatic ring of these diols have 1 to 4 carbon atoms. Alkyl group, alkoxy group, halogen atom (F,
Examples of hydroquinone substituted with CI, Br, I) include methylhydroquinone, 2
．． 5-dimethylhydroquinone, 2.6-dimethylhydroquinone, ethylhydroquinone, methoxyhydroquinone, 2.5-dimethoxyhydroquinone, chlorohydroquinone, 2.5-dichlorohydroquinone, 2,
6-dichlorohydroquinone, bromohydroquinone,
Examples include 2.5-dibromohydroquinone, 2.6-dibromohydroquinone, fluoro-a-hydro-a-quinone, and iodohydroquinone.

4. Examples of substituted products of 4'-oxydiphenol include:
3-Chloro-4,4'-oxyl 7-ol, 2-chloro-4,4'-oxyl 7-ol, 3,3'-dichloro-4,4'-oxydiphenol, 2. 2'-dichloro-4,4'-oxynophenol, 3,5-dichlorooxy-4,4'-nophenol, 2,3-dichloro-
4,4'-oxydiphenol, 3.3', 5-)lichloro4,4'-oxynophenol, 3.3'.

5.5'-tetrachloro-4,4'-oxydiphenol, 2.2',6.6'-tetrachloro-4,4'-oxynophenol, 3-bromo4,4'-oxydiphenol , 2-bromo-4,4'-oxydiphenol, 3,3'-dibromo-4,4'-oxynophenol, 2,2'-dibromo-4,4'-oxydiphenol, 3,5-dibromo -4,4'-oxydiphenol,
3.3', 5.5'tetrabromo-4,4'-oxynophenol, 3-methyl-4f4'-oxynophenol, 2-methyl-4,4'-oxynophenol, 3゜3'-tumethyl -4,4'-oxydiphenol, 2゜2'-trimethyl-4,4'-oxydiphenol, 3-
Examples include methoxy-4,4'-oxydiphenol, 2-methoxy-4,4'-oxynophenol, and 3,3-dimethoxy-4,4'-oxydiphenol.

4.4.4'-thiodiphenol, 4.4'-sulfonyldiphenol, and bisphenol A substituted products.
Substituents similar to those of 4'-oxynophenol can be mentioned.

Examples of substituted products of 2,6-cyhydroxyna-7talene include 1-chloro-2,6-cyhydroxyna-7talene, 3-chloro-2,6-cyhydroxyna-7talene, and 4-chloro-
2,6-cyhydroxyna7talene, 1,3-dichloro-
2,6-nohydroxyna 7talene, 1,5-dichloro-
2,6-cyhydroxyna 7-talene, 1.3゜5.7-tetrachloro-2,6-nohydro-a-xinaphthalene, 1-bromo 2,6-cyhydroxyna 7-talene, 3-bromo 2,6-cyhydroxyna 7-talene, 4-bromo-2,6
-cyhydroxyna7talene, 1,5-dibromo-2,6
-cyhydroxyna7talene, tomethyl-2,6-cyhydroxyna7talene, 3-methyl-2,6-nohydroxyna7talene, 4-methyl-2゜6-cyhydroxyna7talene, 1,5-trimethyl-2゜6 -cyhydroxyna7talene, 1-methoxy-2,6-cyhydroxyna7talene, 3-methoxy-2,6-cyhydroxyna7talene, 4
-methoxy-2,6-cyhydroxyna7talene, 1,5
-dimethoxy-2,6-cyhydroxyna7talene and the like. Regarding the compound of unit (II), in addition to these, lower acyl esters of these may be mentioned,
In that case, an example of a raw material compound that provides one unit (III) is 4-
Hydroxybenzoic acid, 3-chloro-4-hydroxybenzoic acid, 2-chloro-4-hydroxybenzoic acid, 3.5-
Dichloro-4-hydroxybenzoic acid, 3-bromo 4-
Hydroxybenzoic acid, 2-bromo-4-hydroxybenzoic acid, 3,5-dibromo-4-hydroxybenzoic acid,
3-Methyl-4-hydroxy rest 11! ! , 2-methyl-4-hydroxybenzoic acid, 3.5-methyl-4-hydroxybenzoic acid, 3-methoxy-4-hydroxybenzoic acid, 2-methoxy-4-hydroxybenzoic acid (Iling, 3.
5-dimethoxy-4-hydroxybenzoic acid, 3-722-4-hydroxybenzoic acid [2-722-4-hydroxybenzoic acid, etc., and lower acyl esters or lower alkyl esters thereof, As the ester, acetic ester is preferred, and as the lower furkyl ester, methyl ester is preferred.

Examples of compounds providing the unit HV) are 6-hydroxy-2-7toic acid, 5-chloro-6-hydroxy-
2-7toic acid, 7-chloro-6-hydroxy-2-7toic acid, 1-chloro-6-hydroxy-2-7toic acid, 3-chloro-6-hydroxy-2-7toic acid, 5
．． 7-fuchloro-6-hydroxy-2-su7toic acid, 1
．． 5-cyclo-6-hydroxy-2-7toic acid, 1
,5.7-)lichloro-6-hydroxy-2-7toic acid, 5-promo6-hydroxy-2-7toic acid, 7
-promo 6-hydroxy-2-7toic acid, 1-promo 6-hydroxy-2-7toic acid, 3-promo 6
-Hyproxy-2-su7toic acid, 5,7-dipromo6
-Hydroxy-2-su7toic acid, 1,5-dibromo-6
-Hydroxy-2-7toic acid ζ1,5゜7-dripromo61 Hydroxy-2-7toic acid, 5-methyl-6
-Hydroxy-2-7toic acid, 7-methyl-6-hydroxy-2-7toic acid, 5-7todic acid.

Examples include cy-6-hydroxy-2-su-7toic acid, 7-medoxy-6-hydroxy-2-su-7toic acid, and lower acyl esters or lower alkyl esters thereof, and acetic acid ester is preferable as the lower 7-acyl ester. As the lower alkyl ester, methyl ester is preferred.

The copolymerized polyester of the present invention can be obtained by any method using the above-mentioned raw material compounds.For example, from an aromatic diol and a 7-enyl ester of an aromatic oxycarboxylic acid or a diphenyl ester of an aromatic dicarboxylic acid. or by reacting a mixture of an aromatic oxycarboxylic acid and an aromatic dicarboxylic acid with a required amount of diphenyl carbonate to convert each carboxylic acid into a 7-enyl ester, and then adding an aromatic nol, Although there are methods for performing phenol-removal polycondensation, it is preferably obtained by reacting an aromatic dicarboxylic acid with a 7-syloxy aromatic carboxylic acid and an aromatic diol acylate, and then performing monocarboxylation-a polycondensation.

The copolymerized polyester of the present invention is most preferably obtained by a two-step reaction as follows.

In the first stage reaction, 240-320℃ and 250-320℃
In the second stage reaction, the resin obtained in the first stage reaction is heated to 20°C and subjected to a deacylation reaction under an inert gas atmosphere, at a temperature of 290 to 320°C and in a vacuum of about 1 torr or less. Heating at a lower temperature yields an even higher degree of polymerization of the resin.

A catalyst can also be used to reach the desired intrinsic viscosity in a short time. Typical catalysts used here include dialkyltin oxides such as dibutyltin oxide, sialyl oxides, titanium dioxide, titanium alkoxysilicates, titanium alkoxides, potassium acetate, sulfurium acetate, calcium acetate, etc. Examples include alkali and alkaline earth metal salts of carboxylic acids, antimony trioxide, etc., and sodium acetate and potassium acetate are most preferred. The amount of these catalysts added is from o,oooi to 1% by weight, preferably from 0.01 to 0.2% by weight, based on the total monomer weight.

Intrinsic viscosity of the copolymerized polyester of the present invention (0.1% by weight
), ηrel=relative viscosity] ranges from 1.0 to 15, preferably from 3.0 to 6, measured by capillary viscometer at 60°C in pentafluorophenol at a concentration of 0.1% by weight. It is in the range of .0. As the content of units (I) and (It) increases, the value of intrinsic viscosity decreases, but if it is less than 1.0, sufficient physical properties are not exhibited.*The content of units (III) and (IV) As the viscosity increases, the intrinsic viscosity increases, but when it exceeds 15, melt polymerization becomes extremely difficult.

The copolyester of the present invention is very tough and
X 10 'kI? It exhibits a bending modulus of elasticity of at least / am2 or close to it, and its heat resistance under a load of 18.6 kg/cm2 also exhibits a value of at least 120°C or close to it.

In general, improving bending properties requires a larger amount of reinforcing agent than improving tensile properties, which increases the weight of the molded product and reduces specific strength, which is not preferable. In the case of , the bending strength is high, and the elastic modulus is excellent, for example, equivalent to or higher than that of conventional ennonearing plastics such as polycarbonate, polyamide, polyphenylene sulfide, etc., with approximately 40% glass fiber added. It has physical properties. Furthermore, heat resistance can generally be improved by adding fillers. Long-term heat resistance is mostly controlled by the glass transition temperature of the resin, but the resin of the present invention exhibits a glass transition temperature of 120°C or higher or a value close to it.
Among the existing resins with improved bending properties, it has extremely high (I)
It is an excellent one with great value.

Furthermore, in terms of molding processing, there is a temperature range in the temperature range of 180 to 400°C where the melt viscosity is 104 to 10" voids, so extrusion molding, injection molding, compression molding,
Ordinary melt processing such as blow molding can be performed, and a molded product corresponding to a conventional glass miscellaneous filled product can be obtained using only resin.

In addition, fibers, films, three-dimensional molded products, containers, hoses,
They can be formed into pipes and the like, and can be processed into structures using them.

In addition, during molding, the aromatic copolyester of the present invention is mixed with reinforcing agents such as glass fibers, carbon fibers, asbestos, organic fibers, ceramic fibers, short metal fibers, fillers such as calcium carbonate and mica, nucleating agents, pigments, and dyes. Various desired properties can be imparted to the molded article by adding additives such as , antioxidants, stabilizers, plasticizers, lubricants, mold release agents, flame retardants, and other thermoplastic resins.

Next, the present invention will be explained in more detail with reference to Examples.

In addition, the characteristic evaluation in Examples was performed in the following manner.

Melting point and Las transition point: Differential scanning calorimeter (DSC) [
5SC1560, 5SC1 manufactured by Seiko Electronics Industry Co., Ltd.
560S] at a heating rate of 20° C./LIin.

Intrinsic viscosity: 0 in pentafluorophenol (60℃)
．． Measurements were made at a concentration of 1% by weight.

Tensile strength of molded product: ASTM D638, Type ■ Bending strength of molded product: ASTM D790 Flexural modulus of molded product: ASTM D790 Heat distortion temperature (I
8.6kg/cab2 load): ASTM D648 Impact strength of molded product (with notch): ASTM D
Example 1 A 51-sized Mitsuro flask was equipped with a stirrer, a distillate cooler, and a nitrogen gas inlet, and 668.2 g of 1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylic acid was added.
r (I, 8 mol), methyl hydroquinone noacetate 374.8 gr (I, 8 mol), 6-7 setoxy 2-
7toic acid 1B 6.5gr (0.18mol), p-
827.1g (4.59 mol) of acetoxybenzoic acid was charged, and after purging with nitrogen three times, the temperature was heated at 250°C under a nitrogen stream.
Polymerization was carried out for 2 hours at 280°C, 290°C, and 300°C.
Polymerization was carried out stepwise at 1 hour each at 310°C and 310°C. Next, using a water pump, 600 torr, 20
After polymerizing stepwise at 0 torr, 1100 torr, and 40 torr for 20 minutes each, switch to a vacuum pump, and
Polymerization was carried out at 320° C. for about 1 hour under torr to obtain a light brown glossy polymer.

The intrinsic viscosity of the polymer was 2.8, the glass transition temperature was 118°C, and the melting point was 182°C.

This polymer was used as Promat 165 manufactured by Jujuki Kogyo Co., Ltd.
/75, molded into dumbbell test pieces, bending test pieces, etc., and measured their mechanical and thermal properties. As a result, the following resin has relatively high heat resistance, high strength, and high modulus of elasticity. Met.

Tensile strength 2 * 490 kg/c x 2 Bending strength 2,470 kg/cm" Flexural modulus 1,7 x 10' kg/cm
"Fizot impact strength 45, Okg-Cm/C
m Heat deformation temperature 120.9°C Examples 2 to 4 Using the same polymerization apparatus and polymerization method as in Example 1, resins were obtained with the charging composition shown in Table I. The intrinsic viscosity of these resins,
The glass transition temperature and melting point were measured and the values shown in Table 3 were obtained.

In addition, the thermal and mechanical properties of these resins were measured in the same manner as in Example 1, and the results are shown in Table 2.The heat distortion temperature and glass transition temperature showed a relatively good agreement, indicating that these resins are relatively heat resistant. It turned out to be a resin with good properties. In addition, it was an excellent resin having high mechanical strength and high elastic modulus.

Example 5 A 300 ml Mitsuro 7 flask was equipped with a stirrer, a distillate cooler and a nitrogen gas inlet, and 37. 1g
r (0.1 mol), methoxyhydroquinone diacetate 22.4 gr (0.1 mol), 6-7 setoxy 2-
7) zfi157. Ogr (0,2475 mol)
, 9.5 gr (0,0525 mol) of p-7 setoxybenzoic acid were charged, and polymerization was carried out in the same manner as in Example 1 to obtain a glossy brown polymer. The intrinsic viscosity of the polymer is 3.
0, and the glass transition temperature was 128°C. Although the melting point was unclear, using a Shimadzu 70-Tester CFT-500, a load of 10 k was applied from the narrow mouth (0.5 mmφ x 1 mm L).
When extruded at a temperature increase rate of 3°C/akin and a temperature increase rate of 3°C/akin, it began to flow at 255°C.

Examples 6 to 10 The same monomers as in Example 5 were used except for the unit (2), and for the unit (2), equivalent moles of aromatic diols shown in Table (2) were used. The polymerization apparatus and polymerization method were the same as in Example 5. The intrinsic viscosity, glass transition temperature, and melting point of each resin are also shown in Table (3), and all of them showed sufficiently high glass transition temperatures, with Example 6.7 showing particularly high values.

Examples 11 to 18 Using the same polymerization apparatus and polymerization method as in Example 5, resins were obtained with the charging compositions shown in Table 1. The intrinsic viscosity of these resins,
The plus transition temperature and melting point are summarized in Table ■, and the glass transition temperature is at least 11°0°C or higher, and is approximately 120°C.
It was about ℃.

Claims (1)

[Claims] Consisting of the following structural units (I), (II), (III) and/or (IV) as main constituents, and the unit (I) includes ▲a mathematical formula, a chemical formula, a table, etc.▼ [However, X is F, Cl or Br, and n is 2 or 4], and the unit (II) is: ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc. At least one selected from ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and the unit (III
) is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and the unit (IV) is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and the aromatic units of units (II), (III), and (IV) are At least one hydrogen atom on the ring may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a halogen atom, and the ratio of each component is such that (I) is 2.5 to 35 mol%, (II) is 2.5 to 35 mol%, and (I
II), (IV) or the total of (III) and (IV) is 30 to 9
A melt-processable copolymerized polyester characterized in that the content thereof is 5 mol %.