JPH04154834A - Aromatic copolyester and its production - Google Patents

Abstract

PURPOSE:To obtain the subject copolyester having a high glass transition temperature, excellent heat resistance and moldability and a high elasticity by reacting three kinds of specific dicarboxylic acids and an aromatic dicarboxylic acid with diols. CONSTITUTION:(A) 5-100mol% of carboxylic acids comprising 1,7-naphthalene dicarboxylic acid, 1,6-naphthalene dicarboxylic acid and 1,3naphthalene dicarboxylic acid or their reactive derivatives and (B) 95-0mol% of a compound of formula I [X is OH, halogen, etc.; Ar is phenylene whose bonding chains are elongated in the coaxial direction or in the parallel direction or a group of formula II (Y1 is single bond, lower alkylene, 0, etc.)] are polycondensed with (C) a compound of formula III (R is 2-8C aliphatic alkylene, phenylene, etc.,) to provide the objective copolyester, composed of 5-100mol% of three repeating units of formulas IV, V and VI, 0-95mol% of repeating units of formula VII and repeating units of formula VIII.

Description

Detailed Description of the Invention [Technical Field] The present invention relates to a novel linear aromatic copolyester, and more specifically, it has a high glass transition temperature, excellent heat resistance, high elastic modulus, and has excellent moldability and mechanical properties. The present invention relates to a linear aromatic copolyester with excellent mechanical strength and a method for producing the same.

[Prior Art] Many linear aromatic copolyesters have been known, for example, using bisphenols, hydroquinone, resorcinol, etc. as the diol component, and terephthalic acid, isophthalic acid, 2,6-naphthalenedicarbone as the dicarboxylic acid component. A method using an acid or the like, a method using P-hydroxybenzoic acid, etc. have been proposed. 1 British Patent No. 1,413,012 describes naphthalene-2°6
A polyester using -dicarboxylic acid is disclosed, and the diol component is tris(2-hydroxyethyl)isocyanurate-1.

Also, ERDOl,, UND K01+lE・IER
DGAS-PIETR(]CI+[iMTli.

=3- 15jAHRG, /JUNI 1962/NR, 6th 4th
1.6-, 1.7-, 2.3-, 2 on pages 38-441
．． Polyesters obtained from 6- or 2,7-naphthalene dicarboxylic acid and glycerin, trimethylolpropane or hexane 1-diol are disclosed.

Swiss Patent Section 634,681, page 1, happens to contain 1
, 7-naphthalene dicarboxylic acid and bisphenol A, but this is merely an example, and there is no description at all of what properties the polyester of this repeating unit has.

However, an aromatic copolyester obtained by polycondensing a diol with a mixture of 1,7-naphthalene dicarboxylic acid, 1,6-naphthalene cafflebonic acid and 1,3-naphthalene dicarboxylic acid as a carboxylic acid component has not yet been concretely proposed.

〔composition〕

The present inventors have discovered that diols and 1,7-naphthalene dicarboxylic acid, 1,6-naphthalene dicarboxylic acid, 1,3-naphthalene dicarboxylic acid, and/or bond chains extend coaxially. A linear aromatic copolyester was synthesized by polycondensation with an aromatic dicarboxylic acid, and its physical properties were found to have a high glass transition temperature and a heat resistance of 43SI+-, as well as high strength and high elasticity. The present inventors have discovered that they have various excellent properties, such as being soluble in various solvents and having excellent moldability, and have completed the present invention.

That is, the first aspect of the present invention is a 3-type mixed dicarboxylic acid repeating unit represented by the formula 5 to 1
0 to 95 mol% of dicarboxylic acid repeating units expressed as 00 mol% and formula %
and a diol-based repeating unit represented by the formula %().

(In the formula, Ar is a group selected from the group consisting of a phenylene group, a naphthylene group, and a group represented by the formula, in which bond chains extend coaxially or in parallel axes, and R in the formula has 2 to 2 carbon atoms. Y□
and Y2 are each independently selected from the group consisting of a single bond, a lower alkylidene group, an oxygen atom, a sulfur atom, a carbonyl group, and a sulfonyl group. ).

The second aspect of the present invention is (3) three types of dicarboxylic acids consisting of 7-naphthalene dicarboxylic acid or its dihalide, 1,6-naphthalene dicarboxylic acid or its dihalide, and 1,3-naphthalene dicarboxylic acid or its dihalide 5-]00 The present invention relates to a method for producing an aromatic copolyester, which comprises reacting 95 to 0 mol % of aromatic dicarboxylic acids represented by the formula % and the diols represented by the formula %.

(In the formula, Ar and R are the same as above. X is a hydroxyl group, a halogen atom, or a methoxy group).

The above condensation reaction can be carried out by the per se known melt transesterification method (for example, see Japanese Patent Publication No. 50-31918), but when polycondensing with an aromatic diol, it is generally better to carry out the interfacial polycondensation method. This method is suitable because a polymer with little coloring and a high degree of polymerization can be obtained.

There is no particular restriction on the mixing ratio of the dicarboxylic acids of the formulas (1), (II), and (III), but usually (I) 5 to 90,
Preferably 10 to 45 mol wt%, (II) 5 to 90,
Preferably 10-45 mol wt%, (Ill)5-90
, preferably from 10 to 45 mol wt%.

In the diol component, in addition to the bisphenols described below, examples of aliphatic diol components include ethylene glycol, propylene glycol, butanediol,
Bentanediol, hexanediol, heptanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-ethyl-2-methyl-1,3-propanediol, triethylene glycol, 2,2,4
．． Examples include diols such as 4-tetramethylcyclobutanediol.

The lower alkylene group and the lower alkylidene group that may be represented by Y2 include a linear or branched return element 1.
~1, preferably i-4 alkylene groups and alkylidene groups are included, such as methylene, ethylene,
Examples include ethylidene, trimethylene, propylene, isopropylidene, butylene, hexamethylene and the like.

The following are examples of 11 bisphenols.

Bis(4-hydroxyphenyl)methane, 1.1bis(
4-hydroxyphenyl)ethane, 1. z-bis(4-
hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)n-butane, 1゜I-bis(4-hyroxyphenyl)n-butane , 2.2-bis(4-hydroxyphenyl)pentane, 3.3-bis(4-hydroxyphenyl)pentane, 2.2-bis(4-hydroxyphenyl)hexane, 1.1-bis(4-hydroxyphenyl) ) cyclohexane, bis(4-hydroxyphenyl)cyclohexylmethane, 2,4'-dihydroxydiphenylmethane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(4-hydroxyphenyl) )
Hebutane, bis(4-hydroxyphenyl)-4'-methylphenylmethane, ■, 4-bis(4-hydroxycumyl)benzene, ■, 3-bis(4-hydroxycumyl)benzene, 2,2- Bis(4-hydroxyphenyl)
Hexafluoropropane, 9,9-bis(4-hydroxyphenyl)fluorene, 4,4'-dihydroxy diphenyl ether, 4,4'-dihydroxy diphenyl sulfide, 4,4'-dihydroxy diphenyl sulfone, 2,4 '-dihydroxydiphenyl sulfone, 4,4'-dihydroxy diphenyl ketone, 2
, 2'-dihydroxydiphenyl, etc.

These aliphatic diols and bisphenols can be used alone, or two or more types can be used in combination.

The production of the aromatic copolyester of the present invention by the above-mentioned melt transesterification method includes (a) converting the diols mentioned above into diesters, mixing the diesters with dicarboxylic acids,
Either by melting and reacting in the presence of a transesterification catalyst, or by (b
) The above bisphenols can be mixed with a dicarboxylic acid dialkyl ester or a dicarboxylic acid diaryl ester, and the mixture is melted and reacted in the presence of a transesterification catalyst.

Examples of diesters of diols that can be used here include 1, for example, diacetate-1 and propione-1 of diols;
Examples include benzoate.

In addition, as the dialkyl ester of dicarboxylic acid, dimethyl ester is particularly suitable, and as the sialyl ester, diphenyl ester, bis-2-naphthyl ester, bis-1-naphthyl ester, bis-4-chlorophenyl ester, bis- 1-Toluyl ester, bis-
4-toluyl ester, bis-4-phenylphenyl ester, bis-4-octylphenyl ester, bis-
Examples include 2,6-dimethylphenyl ester, and diphenyl ester is particularly preferred.

The above transesterification method is carried out at a temperature at which both monomer components melt, generally at least 180°C, preferably at least 250°C, and at a temperature within a range at which the monomer components do not decompose thermally.
More preferably, it can be carried out at a temperature within the range of 280 to 310°C and under any pressure, preferably under reduced pressure.

Further, as the transesterification catalyst that can be used in the above reaction, titanium compounds such as titanium tetrabutoxide, titanium tetrabutoxide, and titanyl oxalate are suitable, but antimony trioxide, zinc acetate, manganese acetate, etc. are also suitable. Available for use. These are the catalyst amount,
For example, it is convenient to use it in an amount of about 0.005 to 1.0 mol%, particularly 0.05 to 0.5 mol%, based on the total amount of acid components.

On the other hand, according to the interfacial polycondensation method, the aromatic copolyester of the present invention is not miscible with a solution (aqueous phase) in which at least one bisphenol is dissolved in an aqueous medium and a dicarboxylic acid dihalide is not miscible with the aqueous medium. It can be produced by contacting a solution (organic phase) dissolved in an organic solvent in the presence of a phase transfer catalyst to cause a polycondensation reaction.

The aqueous medium used to dissolve bisphenols is usually water. The concentration of bisphenols in the aqueous medium is not strictly limited, but is generally 0.1 to 10 mo1. /Q, preferably 0.2
A range of ˜5 mol/Q is convenient.

Further, it is preferable that this aqueous phase contains a neutralizing agent for capturing and neutralizing hydrogen halide produced as a by-product in the polycondensation reaction. Examples of such a neutralizing agent include sodium hydroxide, Examples include hydroxides, carbonates, and hydrogen carbonates of alkali metals or alkaline earth metals such as potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, and sodium hydrogen carbonate. Storium oxide is preferred.

These neutralizing agents are usually 0.5 to 2M, preferably 0.5 to 2M.
It can be present in the aqueous phase at a concentration of about 9-1.1M.

On the other hand, the dicarboxylic acid dihalide in the organic phase may be any of chloride, bromide, and fluoride, but chloride is generally preferred, and the organic solvents that can be used to dissolve these acid halide components include: For example, dichloromethane, chloroform, 1.
Includes halogenated aliphatic hydrocarbons such as 2-dichloroethane and sym-tetrachloroethane, and aromatic hydrocarbons such as benzene, toluene, anisole, chlorobenzene, acetophenone, benzonitrile, and nitrobenzene, with toluene and nitrobenzene being particularly preferred. It is.

There is no particular restriction on the concentration of the naphthalene dicarboxylic acid halide in these solvents, but generally, the m degree of the dicarboxylic acid dihalide is 0.05 to -1 mol/Q,
In particular, it is appropriate to set it within the range of 0.1-0.5 mol/(l).

Furthermore, as a phase transfer catalyst, for example, tetrabutylammonium chloride (8AC), benzyltriethylammonium chloride, penzyltriphenylphosphonium bromide (CTBPB), 18-crown-6
, dibenzo-18-crown-6, dicyclohexyl-
18-crown-6 and the like can be used, and among them, benzyltriethylammonium chloride can be used advantageously. These catalysts can generally be used in a range of 0 to 4 mol%, preferably 1 to 3 mol%, based on the amount of acid chloride component.

The aqueous phase and organic phase are usually brought into contact with each other under stirring. The reaction can generally be carried out at a temperature from room temperature to about 100°C, preferably room temperature, under normal pressure for about 5 to about 120 minutes.

In addition, the mixing ratio of the aqueous phase and the organic phase is usually adjusted so that the amount of bisphenols in the aqueous phase is 1 to 1.5 mol per 1 mol of the total amount of acid halide components in the organic phase.)
is appropriate.

In addition, in producing the aromatic copolyester of the present invention,
Examples of carboxylic acid components include 1,7-naphthalene dicarboxylic acid, 1,6-naphthalene dicarboxylic acid, ■, 3-
Isomers of naphthalene dicarboxylic acids other than naphthalene dicarboxylic acid; dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenylsulfone dicarboxylic acid, diphenoxyethane dicarboxylic acid, adipic acid, and sebacic acid;
and/or p-oxybenzoic acid, m-oxybenzoic acid,
3-chloro-4-oxybenzoic acid, 3-methoxy-4-
A small amount of oxyacid such as benzoic acid, 2,6-oxynaphthoic acid, 1°4-oxynaphthoic acid, etc., to the extent that it does not substantially impair the physical properties of the aromatic copolyester of the present invention,
For example, it may be blended in an amount of 15 mol% or less.

The aromatic copolyester of the present invention produced by the method described above has a high glass transition temperature and excellent heat resistance, is soluble in various organic solvents, has excellent moldability, and has high strength. It has a high elastic modulus and can be used in a wide range of applications such as molded products, films, fibers, paints, adhesives, etc. in the electrical field, automobile field, machinery field, and medical miscellaneous goods field.

When used for such applications, the aromatic copolyester of the present invention may be supplemented with reinforcing agents such as glass fibers, carbon fibers, and asbestos; fillers, nucleating agents, flame retardants, pigments, antioxidants, and heat stabilizers. Additives such as additives, ultraviolet absorbers, anti-coloring agents, plasticizers, lubricants, and mold release agents can be added, or they can be kneaded with other thermoplastic resins.

〔Example〕

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

The physical properties were measured according to the following method.

Viscous 1□L follow-up: 0.1g of polymer is mixed with phenol/tetrachloroethane (
50/50) 0.5g/J dissolved in 20ml)
, take the other 10ml in an Ostwald viscometer and measure 30ml.
Place it in a constant temperature bath at ℃ and measure the falling time (1).

Next, measure in the same manner using only the measurement solvent (to). From these values, the intrinsic viscosity '+1jnh is determined using the following formula.

rt 1nh= I n (t/t o) 70.5
Note) As a guideline for to, measure with a viscometer for about 120 seconds.

Measurement was performed using a differential scanning calorimeter (Model DSC-20) manufactured by Etoseiko Electronics Co., Ltd. Approximately 10 cm of the obtained polymer was accurately weighed in an aluminum pan, and heated from 50°C to 40°C in a nitrogen gas stream.
The temperature was raised to 0°C at a rate of 10°C/mj, n, and the peak at the first inflection point was taken as Tg.

"Retsubunme I" Differential thermothermogravimetric simultaneous measuring device (T
g/ DTA-20 type). Precisely weigh about 10 cm in a platinum pan and heat at 10°C/min in a nitrogen gas stream.
The temperature was raised to 10% TGT weight loss point, which was taken as the thermal decomposition temperature.

Tensile strength, elongation, tension bullet ■Beast: ASTMD using Toyo Baldwin RT1445rl;m-
-822-83. Film length: 120n
+m, width 10100n, and both ends 10+n+n are held down with paper and glued to prevent the test piece from slipping from the grip. Measure the thickness at 5 points with a thickness gauge and use the average as the thickness. Hold the test piece between the grips and adjust the distance between the grips to 100cm. A load-elongation curve was recorded at a load of 10 kg and a tensile speed of 50 nn/min, and the tensile strength and elongation were calculated using the F formula.

Tensile strength (kg f/mrn') = maximum load kg
f/cross-sectional area m elongation (%) = elongation at break/100n force
Cut the 100 film lengthwise to 270 nm, @ ] Onn, press both ends ] On with paper and adhere to create a test piece.
, Measure the thickness at 5 points using a thickness gauge and take the average as the thickness. Hold the specimen between the grips and set the distance between the grips to 250m.
Adjust to m. A load-elongation curve was recorded at a load of 10 kg and a tensile speed of 25 nwn/mjn, and the tensile modulus of elasticity was calculated from the following formula.

Tensile modulus of elasticity (kgf/min) = (slope of tangent to load-elongation curve k K f / n X
250 nin)/cross-sectional area mm Example 1 1.7-dimethylnaphthalate 1-12.2 g, 1,6-
Dimethylnaphthalate h12.2g, 1,3-dimethylnaphthalate I2.2g, manganese acetate 0.0366g
A mixture consisting of 0.0264 g of antimony trioxide and 0.0264 g of antimony trioxide was heated at 165 to 240°C for about 3 hours to distill off methanol.

After that, 0.0252 g of trimethyl phosphate
was added, and then the pressure was gradually reduced (0.5 to 0
Polymerization was continued for 90 minutes for 2 nynt (g). Table 2 shows the intrinsic viscosity η]n11, glass transition temperature Tg, and thermal decomposition temperature of the obtained polyester.

Examples 2 to 4 20.4 ml of a 1M aqueous sodium hydroxide solution was placed in a Nillo flask equipped with a mechanical stirrer.

The diols in the table below and benzyltriethyl = 20 = Add and dissolve 0.06 g of ammonium chloride.

Add 20% of the dicarboxylic acid dichloride shown in the table below to this solution.
A solution of m1 dissolved in benzene is added at once with stirring, and the mixture is stirred at room temperature for 100 minutes at a stirring speed of 800 rpm. Thereafter, the polymerization solution was separated by standing to separate 7 volumes of nitrobenzene IM containing the polymer, which was then washed with acetic acid water, further washed with ion-exchanged water, and then washed with acetic acid water.
to precipitate the polymer. The precipitated polymer was filtered, washed with water, and then dried under reduced pressure. 3 g of the obtained polymer was completely dissolved in 20 ml of Te1-lachloroethane, and this solution was cast using a glass plate onto a glass plate whose surface had been cleaned. This glass plate was placed horizontally in a vacuum dryer at room temperature for 12 hours, then at 80°C for 12 hours.
It was dried at ℃ for 24 hours to create a film. The intrinsic viscosity ηjnh, glass transition temperature Tg, and thermal decomposition temperature of the polymer are shown in Item-2 below, and the tensile strength, elongation, and tensile modulus are shown in Item-3 below.

Table-1 Table-2 Table-3 [Effects] The aromatic copolyester of the present invention has excellent mechanical properties,
Although it exhibits high heat resistance, it is soluble in various solvents and has excellent moldability.

Patent applicant: Showa Shell Sekiyu Co., Ltd.

Claims (1)

[Claims] 1. Formulas ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼・・・(III) Three types of mixed dicarboxylic acid repeating units 5 to 1
0 to 95 mol% of dicarboxylic acid repeating units represented by the formula ▼ Numerical formulas, chemical formulas, tables, etc. ▼ (IV)
and a diol-based repeating unit represented by the formula -O-R-O-(V). (In the formula, Ar is a group selected from the group consisting of a phenylene group, a naphthylene group, in which both bond chains extend in the coaxial direction or parallel axes direction, and a group represented by the formula ▲ Numerical formula, chemical formula, table, etc. ▼ , where R is a group selected from the group consisting of an aliphatic alkylene group having 2 to 8 carbon atoms, a phenylene group, a naphthylene group, and a group represented by the formula ▲ Numerical formula, chemical formula, table, etc. ▼ Y_
1 and Y_2 are single bonds, lower alkylidene groups, oxygen atoms,
These are groups each independently selected from the group consisting of a sulfur atom, a carbonyl group, and a sulfonyl group. ) Three types of dicarboxylic acids 5 to 100 consisting of 2,1,7-naphthalene dicarboxylic acid or its dihalide, 1,6-naphthalene dicarboxylic acid or its dihalide, and 1,3-naphthalene dicarboxylic acid or its dihalide
A method for producing an aromatic copolyester, which comprises reacting 95 to 0 mol % of aromatic dicarboxylic acids represented by the formula XOC-Ar-COX with a diol represented by the formula HO-R-OH. (In the formula, Ar and R are the same as above. X is a hydroxyl group, a halogen atom, or a methoxy group.)