JPH04154836A - Aromatic copolyetser and its production - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

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

[Prior art]

Many linear aromatic polyesters have been known in the past, and for example, bisphenols, hydroquinone, resorcinol, etc. are used as the diol component, and terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, etc. are used as the dicarboxylic acid component. A method using p-hydroxybenzoic acid or a method using p-hydroxybenzoic acid has been proposed.

British Patent No. 1,413,012 describes naphthalene-2
A polyester using 6-dicarboxylic acid is disclosed, but the diol component is tris(2-hydroxyethyl)in cyanurate.

Also, ERDOL UND KOHLE-ERDGAS
-PETROCHEMIE.

15, JAFIRG, /JUNI 1962/NR, 6
1,6-11.7-2.3-1 on pages 438-441
Polyesters obtained from 2,6- or 2,7-naphthalene dicarboxylic acid and glycerin, trimethylolpropane or hexanetriol are disclosed.

The first page of Swiss Patent No. 634681 happens to have 1°7.
Although a repeating unit of -naphthalene dicarboxylic acid and bisphenol A is shown, this is merely an example, and there is no description at all about what properties the polyester of this repeating unit has.

However, aromatic polyesters obtained by polycondensing 1,3-naphthalene dicarboxylic acid with diols have not yet been specifically proposed.

〔composition〕

The present inventors have developed a linear aromatic polyester by polycondensing diols with 1,3-naphthalene dicarboxylic acid and/or an aromatic dicarboxylic acid whose bond chains extend coaxially or in parallel axes. When we synthesized and investigated its physical properties, we found that it has a high glass transition temperature, excellent heat resistance, high strength, high elastic modulus, is soluble in various solvents, and has excellent moldability. The present invention was completed based on the discovery that it has various excellent properties.

That is, the first aspect of the present invention includes 5 to 100 mol% of dicarboxylic acid repeating units represented by the formula and 95 to O mol% of dicarboxylic acid repeating units represented by the formula
and -0-R-0-...(m) The present invention relates to an aromatic polyester characterized by being substantially composed of a diol-based repeating unit represented by -0-R-0-...(m).

(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 the bond chains both extend in the coaxial direction or in the parallel axis direction, and in the formula, R
is an aliphatic alkylene group having 2 to 8 carbon atoms, a phenylene group,
Each of Yl and Y2 is independently selected from the group consisting of a naphthylene group and a group represented by , and Yl 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. This is the base that was created. ) The second aspect of the present invention is 1,3-naphthalene dicarboxylic acid, its diester or sybarite 5 to 100 mol %, aromatic dicarboxylic acids represented by the formula % formula % 95 to O mol %, and a diol represented by the formula % formula % The present invention relates to a method for producing an aromatic polyester, which is characterized by reacting the aromatic polyester with the following.

(In the formula, Ar and R are the same as above. Q is a hydroxyl group,
It is 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 better to carry out the interfacial polycondensation method. Generally, it is preferable because a polymer with little coloring and a high degree of polymerization can be obtained.

In the diol component, the aliphatic diol component includes ethylene glycol, propylene glycol, butanediol, bentanediol, hexanediol, heptanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-ethyl-2- Methyl-
1,3-propanediol, triethylene glycol,
Examples include diols such as 2,2,4,4-tetramethylcyclobutanediol. Further, in the aromatic diol component, the lower alkylene group and the lower alkylidene group that may be represented by Y2 include linear or branched alkylene groups having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, and alkylidene groups having 1 to 8, preferably 1 to 4 carbon atoms. Groups include, for example, methylene, ethylene, ethylidene, trimethylene, propylene, isopropylidene, butylene, hexamethylene, and the like.

Specific examples of bisphenols include the following.

Bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, ■, 2-bis(4
-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)n-butane, 1゜1-bis(4-hydroxyphenyl)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)-
〇- Phenylmethane, bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(4-hydroxyphenyl)hebutane, bis(4-hydroxyphenyl)-4'-
Methylphenylmethane, 1,4-bis(4-hydroxycumyl)benzene, 1,3-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'-dihydroxy diphenyl 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 aromatic polyester of the present invention can be produced by the above-described melt transesterification method by (a) converting the diols into diesters, mixing the diesters with dicarboxylic acids, and melting and reacting them in the presence of a transesterification catalyst; (b) The above diols 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 diacetates, propionates, and benzoates of diols.

In addition, as the dialkyl ester of dicarboxylic acid, dimethyl ester is particularly suitable, and as the diaryl ester, diphenyl ester, bis-2-naphthyl ester, bis-1-naphthyl ester, bis-4-chlorophenyl ester, bis-1 -Toluyl ester, bis-
Examples include 4-1helyl ester, bis-4-phenylphenyl ester, bis-4-octylphenyl ester, and bis-2,6-dimethylphenyl ester, with diphenyl ester being 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 at which the monomer components do not decompose thermally, more preferably at a temperature in the range of 280 to 310°C. It can be carried out at temperatures within 100 mL 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 natrab 1-oxide, titanium tetraethoxide, and titanyl oxalate are suitable, but in addition, antimony trioxide, zinc acetate, Manganese acetate and the like can also be used. These are advantageously used in catalytic amounts, for example in amounts of the order of 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 polyester of the present invention is prepared by combining a solution (aqueous phase) in which at least one kind of bisphenols is dissolved in an aqueous medium, and an organic solvent in which dicarboxylic acid dihalide is immiscible with the above aqueous medium. It can be produced by bringing into contact a solution (organic phase) dissolved in , in the presence of a phase transfer catalyst, and causing 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 10rnol/Q, preferably 0.2
−5 mo], /Q is convenient.

In addition, 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 neutralizing agents include sodium hydroxide and hydroxide. Examples include hydroxides, carbonates, and hydrogen carbonates of alkali metals or alkaline earth metals such as potassium oxide, calcium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, and sodium hydrogen carbonate, among which sodium hydroxide is suitable.

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.

The concentration of the above-mentioned phthalene dicarboxylic acid halide in these solvents is not particularly limited, but generally the dicarboxylic acid dihalide concentration is in the range of 0.05 to 1 mol/a, particularly 0.1 to 0.5 mol/Q. It is appropriate to make it within the range.

Furthermore, as a phase transfer catalyst, for example, tetrabutylammonium chloride (TBAC), penzyltriethylammonium 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.

Also, the mixing ratio of the aqueous phase and organic phase is normal.

It is appropriate to adjust the amount of bisphenols in the aqueous phase to 1 to 1.5 mol per 1 mol of the total amount of acid halide components in the organic phase.

In addition, in the production of the aromatic polyester of the present invention, as a carboxylic component, for example, an isomer of naphthalene dicarboxylic acid of 1,3-naphthalene dicarboxylic acid, terephthalic acid, isophthalic acid, diphenylsulfone dicarboxylic acid , dicarboxylic acids such as diphenoxyethanedicarboxylic acid, adipic acid, and sebacic acid, and/or p-oxybenzoic acid, m-oxybenzoic acid, 3-chloro-4-oxybenzoic acid, and 3-methoxy-4-benzoic acid. ,
An oxyacid such as 2,6-oxynaphthoic acid or 1,4-oxynaphthoic acid is used in a small amount such as 15 mol% or less that does not substantially impair the physical properties of the aromatic polyester of the present invention to be produced. May be blended.

The aromatic polyester 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 purposes, the aromatic polyester of the present invention may contain reinforcing agents such as glass fiber, carbon fiber, and asbestos; fillers, nucleating agents, flame retarding agents, pigments, antioxidants, and heat stabilizers. , UV absorbers, color inhibitors, plasticizers,
Additives such as 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.

Note that the physical properties were measured according to the following method.

Placement - 1 discharge: 0.1 g of polymer was mixed with phenol/tetrachloroethane (
50150) Dissolve in 20ml 0.5g/di),
Take 10ml of it into an Ostwald viscometer and heat it at 30°C.
Place it in a constant temperature bath and measure the falling time (1).

Next, a similar measurement is performed using only the measurement solvent (to). From these values, the intrinsic viscosity ηinh is determined using the following formula.

ηjnh=I n (t/t o)/0.5 Note) As a rough guide for to, measure with a viscometer for about 120 seconds.

Glass T: Measured using a differential scanning calorimeter (Model DSC-20) manufactured by Seiko Electronic Industries. 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/min, and the peak at the first inflection point was taken as Tg.

Thermal decomposition temperature: Seiko Electronics Industries Co., Ltd. differential thermogravimetric simultaneous measuring device (Tg
/DTA-2 (type I). Approximately 10 cm of the mixture was accurately weighed in a platinum pan, and heated at a rate of 10° C./min in a nitrogen gas stream to determine the 10% wt loss point as the thermal decomposition temperature.

Tensile: ASTMD- using RTM-25rtm manufactured by Toyo Baldwin Co., Ltd.
822-83. Film lengthwise 120cm,
The test piece is cut into a width of 100 mm, and both ends of the test piece are held down by 10+ nm with paper and adhered to prevent it 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 ]0Onn. The load is 10 kg and the pulling speed is 50 mm/min.
Record the elongation curve and calculate the tensile strength and elongation using the following formula.

Tensile strength (kg g; f 7mm) = maximum load kg
f/cross-sectional area mm elongation (%) = elongation at break/100 fields x 1
The 00 film was cut into 270 mm length @10nro, and both ends 101II11 were held down with paper and adhered to prepare a test piece. The thickness is measured at 5 points using a thickness gauge, and the average is taken as the thickness. Hold the test piece between the grips and set the distance between the grips to 250.
Adjust to TIrfl. Load] 25mm/mi in Okg
A load-elongation curve is recorded at a tensile speed of n, and the tensile modulus of elasticity is calculated from the following formula.

Tensile modulus (kgf/m%) = (slope of tangent to load-elongation curve kg f / wn
x 250m)/cross-sectional area mm Examples] 1.3-dimethylnaphthalate 36.6 g, ethylene glycol 19.2 g, manganese acetate 0.0366 g
A mixture consisting of 0.0264 g of antimony dioxide and 0.0264 g of antimony dioxide was heated at 165 to 240°C for about 3 hours to distill off methanol. Then trimethyl phosphate 0.025
2g was added, and the pressure was gradually reduced at 270℃ (0.5~0
．． The polymerization was continued for 90 minutes against 2 mmHg). Intrinsic viscosity ηinh and glass transition temperature T of the obtained polyester
g, thermal decomposition temperature Td are shown in Table-2.

Examples 2 to 4 20.4 mQ of a 1M aqueous sodium hydroxide solution is placed in a three-touch flask equipped with a mechanical stirrer, and the bisphenols shown in Table 1 and 0.06 g of benzyltriethylammonium chloride are added to dissolve the flask. To this solution, a solution prepared by dissolving 7 naphthalene dicarboxylic acid dichlorides shown in Table 1 in 20 mQ of nitrobenzene was added at once with stirring, and the mixture was stirred at room temperature for 100 minutes at a stirring speed of 800 rpm.

Thereafter, the polymerization solution is left to stand to separate the nitrobenzene solution containing the polymer, which is then washed with acetic acid water, further washed with ion-exchanged water, and then poured into acetone 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 added to 20 m Q
completely dissolved in tetrachloroethane, and this solution is cast using a glass rod onto a glass plate whose surface has been cleaned.

This glass plate was placed horizontally in a vacuum dryer and dried at room temperature for 12 hours, at 80°C for 12 hours, and at 150°C for 24 hours.
created a film. The intrinsic viscosity ηjnh, glass transition temperature Tg, and thermal decomposition temperature of the polymer are shown in Table 2, and the tensile strength, elongation, and tensile modulus are shown in Table 3.

Table-1 Table-2 Table-3

Claims (1)

[Claims] 1. 5 to 100 mol% of dicarboxylic acid repeating units represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. Yes▼・・・(II) Dicarboxylic acid repeating unit represented by 95-0 mol%
An aromatic polyester characterized by being substantially composed of a diol-based repeating unit represented by and -O-R-O- (III). (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 ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ , in the formula R
is an aliphatic alkylene group having 2 to 8 carbon atoms, a phenylene group,
Naphthylene group and the groups represented by formula ▲ Numerical formula, chemical formula, table, etc. ▼ where Y_1 and Y_2 are single bonds, lower alkylidene groups, oxygen atoms, sulfur atoms, carbonyl groups, Each group is independently selected from the group consisting of sulfonyl groups. ) 5 to 100 mol% of 2,1,3-naphthalene dicarboxylic acid, its diester or dihalide, 95 to 0 mol% of aromatic dicarboxylic acids represented by the formula QOC-Ar-COQ, and a diol represented by the formula HO-R-OH A method for producing aromatic polyester, which is characterized by reacting with (In the formula, Ar and R are the same as above. Q is a hydroxyl group,
It is a halogen atom or a methoxy group. )