JPS62199620A - Aromatic copolyester formed article - Google Patents

Abstract

PURPOSE:To obtain the titled high polymerization degree formed article outstanding in heat and solvent resistances and mechanical strength, by using an aromatic copolyester of specified viscosity constituted by isophthalic acid, terephthalic acid and bisphenol S units. CONSTITUTION:The objective formed article can be obtained by using an aromatic copolyester constituted by structural units of formulae I, II and III, respectively, with the molar ratio of the units III/II of 1/9-6/4, having a logarithmic viscosity >=0.55 determined in the form of an orthochlorophenol solution of a concentration 0.5g/dl at 25 deg.C. Sad aromatic copolyester can be prepared, for example, by the following process: first, isophthaloyl dichloride and terephthaloyl dichloride are dissolved in a solvent prepared by distillation and purification, in the presence of 0.1-10wt% of isophthaloyl dichloride and/or terephthaloyl dichloride, of methylene dichloride. Following that, the resultant organic solvent solution and an aqueous NaOH solution of bisphenol S treated at 60-80 deg.C for 0.1-5hr are brought to interfacial polycondensation using as a catalyst a phosphonium salt.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to an aromatic copolyester molded article having excellent heat resistance, mechanical strength, and solvent resistance.

<Prior art> Terephthalic acid and isophthalic acid or their derivatives and 2
, 2-bis(4-hydroxyphenyl)propane (hereinafter abbreviated as bisphenol A) or a derivative thereof is known to be a polymer with excellent heat resistance and mechanical properties.

However, considering the heat resistance performance required of high-performance resins in recent years, this is not necessarily satisfactory. In particular, these high-performance resins are often used in the electrical and electronic fields, and are now required to have heat resistance in solder baths, for example.

In order to satisfy such demands in the practical field, the conventionally known aromatic polyesters as described above are clearly insufficient in terms of performance.

Generally speaking, the above-mentioned known polyesters have a drawback in that they have poor solvent resistance and cannot be used in fields where solvents are used.

In addition, other bisphenols as bisphenol components,
For example, a polymer copolymerized with bis(4-hydroxyphenyl) sulfone has been studied in JP-A-60-53532, but in this case, the logarithmic viscosity is as high as 0.59, but the heat resistance is still insufficient. Moreover, it was found that the solvent resistance was insufficient.

On the other hand, polyesters using only bis(4-hydroxyphenyl)sulfone (hereinafter abbreviated as bisphenol S) and terephthalic acid and isophthalic acid as dicarboxylic acids are reported in the Journal of Po1l/norSci.
ence 40.399 (1959).

However, this polyester
fPolymer 5science 40.399(1
As described in 959), since it has an electron-withdrawing sulfone group, the reactivity of phenolate ion, which is a reactive species during interfacial polycondensation, is low, so the logarithmic viscosity of the obtained polymer powder is It was as low as 0.54, and the films obtained therefrom were very brittle and did not have mechanical properties suitable for practical use.

Furthermore, recently, Journal of Poly
er 5ciance 21 3233 (1983), a system of bisphenol S, isophthalic acid and terephthalic acid (molar ratio 1/1) was investigated by a direct polycondensation method using an activating reagent such as allylsulfonyl chloride. Even in this case, the logarithmic viscosity of the polymer powder obtained was only as low as 0.34, and the film obtained from it was also very brittle and did not have sufficient mechanical properties for practical use. I didn't have it.

Further, JP-A-61-2730 discloses that a polymer powder with a high degree of polymerization can be obtained by carrying out an interfacial polycondensation reaction within a specific temperature range.

<Problems to be Solved by the Invention> However, the polymer obtained by the method described in JP-A No. 61-2730 has a wide molecular weight distribution even if the logarithmic viscosity of the powder is high; When the polymer is melt-molded, the degree of polymerization of the polymer decreases significantly due to the heat generated during melting. Therefore, the molded product obtained therefrom has a logarithmic viscosity of less than 0.55, making it impossible to obtain mechanical properties that can withstand practical use.

That is, the reality is that an aromatic polyester molded product that can satisfy all of the mechanical properties such as heat resistance, solvent resistance, and impact properties has not yet been provided.

Therefore, the problem of the present invention is to create a polyester using bisphenol S, terephthalic acid, and isophthalic acid, which has traditionally been difficult to achieve a high degree of polymerization, by satisfying both mechanical properties such as heat resistance and impact properties. The objective is to obtain a molded article having a sufficient degree of polymerization.

<Means for Solving the Problems> That is, the present invention is an aromatic copolyester molded article consisting of the following structural units (I), (II> and (III), and having a logarithmic viscosity of 0.55 or more.

-0-C)-302-C)-0--...(I>
(However, the molar ratio of In/II is in the range of 1/9 to 6/4, and the logarithmic viscosity in the present invention is 25°C at a concentration of 0°59/dJ using orthochlorophenol as a solvent. ) The aromatic copolyester of the present invention having the following structural units has isophthalic acid and terephthalic acid units as the dicarboxylic acid component, and bis(4-hydroxyphenyl)sulfone (bisphenol S) units as the diol component. It is what it is.

However, in the formula, isophthalic acid (II>) and terephthalic acid (I
The copolymerization ratio of II) is (III)/(II) is 1/9 to 6
/4.

In addition, as the dicarboxylic acid component, in addition to isophthalic acid and terephthalic acid units, to the extent that the effects of the present invention are not impaired,
As long as the copolymerizable dicarboxylic acid unit is 10 mol % or less, it may be contained.

The copolymerizable dicarboxylic acid unit is made from the corresponding dicarboxylic acid dichloride. Examples of the copolymerizable dicarboxylic acid dichloride include 4,4-diphenyldicarboxylic acid dichloride, 2,6-naphthalene dicarboxylic acid dichloride, and 1,2-bisphenoxyethane-4,4'-
Aromatic dicarboxylic acid dichlorides such as dicarboxylic acid dichloride and 1,2-bis(2-chlorophenoxy)ethane-4,4-dicarboxylic acid dichloride, aliphatic dicarboxylic acid dichlorides such as adipic acid dichloride and sebacic acid dichloride, and 4, Examples include alicyclic dicarboxylic acid dichloride such as 4-cyclohexanedicarboxylic acid dichloride.

In addition to the bisphenol S unit, the diol component may contain other copolymerizable bisphenol units as long as they do not impair the effects of the present invention.

Preferred specific examples of other copolymerizable bisphenols include 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, and 2,2-bis(4-hydroxyphenyl)propane. 4-hydroxy-3,5
-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-dimethylphenyl)propane, -hydroxy-3-methoxyphenyl)propane, 2,2-bis(4-hydroxy-3
,5-dimethoxyphenyl)propane, bis(4-hydroxy-3-methylphenyl)sulfone, bis(4-hydroxy-3,5-dimethylphenyl)sulfone, bis(4-hydroxy-3-chlorophenyl)sulfone, bis (4-hydroxy-3,5-dichlorophenyl)sulfone, bis(4-hydroxy-3-methoxyphenyl)
Sulfone, bis(4-hydroxy-3,5-dimethoxyphenyl) sulfone, bis(4-hydroxyphenyl)
Sulfoxide, 4.4”-dihydroxybiphenyl, 3
, 3'-dimethyl-4,4'-dihydroxybiphenyl, 3.3=, 5.5''-tetramethyl-4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)
Ketone, bis(4-hydroxy-3-methylphenyl)
ketone, bis(4-hydroxy-3,5-dimethylphenyl)ketone, etc., but the most preferred among these is 2,2-bis(4-hydroxyphenyl).
I use propane.

In the aromatic polyester of the present invention, it is necessary that the obtained molded product has a logarithmic viscosity of 0.55 or more,
More preferably 0.60 or more.

Further, for moldability reasons, the logarithmic viscosity is preferably 1.2 or less, particularly preferably 1.0 or less.

If the logarithmic viscosity of the polymer is less than 0.55, it is not preferable because mechanical properties such as heat resistance and strength are poor. Further, from this point of view, it is preferable that the glass transition temperature is 235°C or higher, particularly 240'C or higher.

In addition, the glass transition temperature is determined by PerkinElmer's DSC-
This is a value measured using a sample I[type] at a heating rate of 20° C./min for sample '+omg.

The aromatic polyester of the present invention cannot be obtained simply by interfacial polycondensation of an organic solvent solution of isophthalic acid dichloride and terephthalic acid dichloride and an alkaline aqueous solution of bisphenol S, and the aromatic polyester of the present invention cannot be obtained by simply interfacial polycondensation of an organic solvent solution of isophthalic acid dichloride and terephthalic acid dichloride and an alkaline aqueous solution of bisphenol S. It can be obtained by adding .

(1) The organic solvent of the organic solvent solution of isophthalic acid dichloride and terephthalic acid dichloride has a boiling point of 35
A halogenated hydrocarbon having a temperature of 1 to 10 carbon atoms and having a temperature of 1 to 10 °C or higher is purified by distillation in the presence of 0.1 to 10% by weight of isophthalic acid dichloride and/or terephthalic acid dichloride.

(2) Before applying the alkaline aqueous solution of bisphenol S to the polycondensation reaction, prepare a
It is used after being pretreated at a temperature range of 0.1 to 5 hours.

(3) A phosphonium salt represented by the following general formula is used as a catalyst during polycondensation.

1 R4 (In the formula, R1 to R4 represent a group selected from Cn Czn+ 1 , C6H5 to XG, t Cj , Br, and I.) (4) Polycondensation (T-15>'C to
>'C (where T is the boiling point of the halogenated hydrocarbon, and T≧35°C).

(5) Finally, the obtained polymer powder is 10 to 50 (
Treat with acetone or methyl ethyl ketone.

The organic solvent used in the operation (1) has a boiling point (760
mHQ) is a halogenated hydrocarbon having 1 to 10 carbon atoms and having a temperature of 35°C or higher. Specifically, methylene chloride, chloroform, 1,2-dichloroethane, 1,1-dichloroethane, 1,1.2-trichloroethane, 1,1.1-trichloroethane, 1゜1.1.2-tetrachlor Ethane, 1,3-dichloropropane, 1,1-dichloropropane, 1° 2-dichloropropane, 1,2,3-trichloropropane, 1.1.2-tripropane, 1° 1.1-trichloropropane, trichlorethylene, tetrachlorethylene, 1,2.3-trichloropropene, di(2-chloroethoxy)methane, di(2-chloroethyl)ether, chlorobenzene, O-dichlorobenzene, m -dichlorobenzene, p-dichlorobenzene, dibromomethane, bromoform, 1,1-dibromoethane, 1,2-dibromoethane, dibromoethylene, bromobenzene, etc., methylene chloride, chloroform, 1,2-dichloroethane, , 2,3-trichloropropane can be preferably used.

The most preferred among these is methylene chloride.

In the operation (1), the most important thing is to use an organic solvent purified by distillation of the above organic solvent in the presence of 0.1 to 10% by weight of isophthalic acid dichloride and/or terephthalic acid dichloride, This is done by subjecting isophthalic acid dichloride and terephthalic acid dichloride to interfacial polycondensation as an organic solvent solution.

The concentration of the organic solvent solution of isophthalic acid dichloride and terephthalic acid dichloride of the present invention varies depending on the reaction conditions, the type of organic solvent, etc., but is usually 1 to 40% by weight, preferably 2 to 30% by weight, more preferably 3% by weight. A range of 15% by weight is used.

As the alkali for the alkaline aqueous solution of bisphenol S in operation (2), sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. are preferable, and sodium hydroxide is particularly preferably used.

The most important thing in operation (2) is that before subjecting the alkaline aqueous solution of bisphenol S to interfacial polycondensation,
0.1 in the temperature range of ~80°C, preferably 60-80°C
Pre-treatment for ~5 hours.

The concentration of the alkaline aqueous solution is usually 1 to 30% by weight, preferably 2 to 20% by weight, and more preferably 3 to 15% by weight.

The amount of bisphenol S used in the present invention relative to isophthalic acid dichloride is not particularly limited, but is preferably 0.7 to 1.5 per mole of dicarboxylic acid component.
mol, more preferably 0.9 to 1.2 mol.

Such bisphenols are supplied to the polycondensation reaction system as an alkaline aqueous solution.

The phosphonium salts used as catalysts in the operation (3) include cetyltrimethylphosphonium chloride, cetyltrimethylphosphonium bromide, cetyltriphenylphosphonium chloride, cetyltriphenylphosphonium bromide, cetyltrin-butylphosphonium bromide, dodecyltrimethylphosphonium bromide, and dodecyltrimethylphosphonium bromide. Chloride, dodecyltriphenylphosphonium bromide, dodecyltriphenylphosphonium chloride, n-decyltrimethylphosphonium bromide, n-decyltriphenylphosphonium chloride, octyltrimethylphosphonium bromide, octyltriethylphosphonium chloride, triphenylmethylphosphonium iodide, n-
These include amyltriphenylphosphonium bromide, octyltriphenylphosphonium bromide, dioctyldiphenylphosphonium chloride, and trioctylphenylphosphonium iodide.

In operation (4), the polycondensation reaction (T-15>'C~(
It is important to carry out the process under the temperature condition of T+15>'C. Here, T is the boiling point at 760 mtlj of a halogenated hydrocarbon having 1 to 10 carbon atoms used as an organic solvent for isophthalic acid dichloride and/or terephthalic acid dichloride, and has a boiling point of 35°C or higher.

The reaction temperature is preferably (T-10)'C to (T15)C.
, more preferably (T-5'')'C to T°C.

In the present invention, the order and method of supplying the organic solvent solution and the alkaline aqueous solution to the polycondensation reaction system are arbitrary. When both or one of the organic solvent solution and the alkaline aqueous solution is supplied to the polycondensation reaction system, the temperature from the start of mixing of both groove liquids to the end of mixing must be at least (T-15>'C or higher. If one of the two groove solutions is gradually supplied to the polycondensation reaction system while simultaneously allowing the polycondensation reaction to proceed gradually, after the supply of the solution is finished,
The temperature may be raised stepwise or continuously to (T+15>'C), or may be allowed to cool to (T-15)''C.

In any case, the most preferred method is to carry out the entire polymerization step while maintaining the temperature at (T-15)'C or higher.

In the present invention, the order and method of supplying the organic solvent solution and the alkaline aqueous solution to the polycondensation reaction system are arbitrary.

Further, the reaction time t is preferably 0.1≦t≦10 hours, and preferably 0.1≦t≦1 hour.

In the operation (5), 10-50% of the polymer powder obtained by interfacial polycondensation is used. (T'-20)'C-T using ffi acetone or methyl ethyl ketone.

'C (T' represents the boiling point of acetone or methyl ethyl ketone) for 0.5 to 10 hours.

Anionic activators such as sodium lauryl sulfate, octadecylbenzenesulfonate, cationic activators such as cetyltrimethylammonium chloride, coconut alkyltrimethylammonium chloride, and nonionic activators such as polyethylene oxide are used as dispersants during polycondensation. It's okay.

The aromatic polyester molded article of the present invention is obtained by subjecting the aromatic polyester obtained as described above to ordinary melt molding such as extrusion molding, injection molding, compression molding, blow molding, etc. It can be widely used as a variety of molded products such as three-dimensional molded products, containers, and hoses.

In addition, during molding, for the aromatic polyester of the present invention,
Reinforcing agents for glass fiber, carbon fiber, asbestos, etc., fillers, nucleating agents, pigments, antioxidants, stabilizers, plasticizers, lubricants,
Additives such as mold release agents and flame retardants and other polymers can be added to impart desired properties to the molded article.

<Example> The present invention will be described in detail below with reference to Examples.

Example 1 13,000 parts by weight of methylene chloride, 200 parts by weight of isophthalic acid dichloride, and zeolite were placed in a distillation apparatus equipped with a rectification column and a cold water condenser at 20° C., and the water bath temperature was 5° under nitrogen.
Distillation was carried out at 0°C, and the fraction having a top temperature of 40°C was collected. The yield was about 10,000 parts by weight.

Next, 3500 parts by weight of bisphenol and 40 parts by weight of sodium lauryl sulfate were added to a reaction layer equipped with a temperature control jacket, a stirring device, and a cooler, and 1 part by weight of sodium hydroxide was added.
60 parts by weight, 12,000 parts by weight of water, and 10 parts by weight of n-amyltriphenylphosphonium bromide were added and dissolved, and then the temperature was adjusted to 80'C and stirring was continued for 1 hour (
It's pu. A stream of nitrogen was then passed through the solution after cooling to an internal temperature of 35°C.

A solution of 324.8 parts by weight of isophthalic acid dichloride and 81.2 parts by weight of terephthalic acid dichloride dissolved in 8000 parts by weight of methylene chloride purified by distillation by the above method was added to the above reaction solution which was kept at 35°C and stirred. The mixture was added over a period of 30 minutes, and stirring was continued for 30 minutes while maintaining the temperature at 35°C. Next, the polymer was poured into 2000 parts by weight of acetone to precipitate it, separated, washed three times with 30,000 parts by weight of water, and the filtered polymer was further treated in 2,000 parts by weight of acetone at 55°C for 2 hours. After that, hot filtration,
After drying, a white powdery polymer was obtained with a yield of 92%.

The logarithmic viscosity of the obtained polymer powder was 0.78.

Next, when this polymer was molded into a film using a press heated to 350°C, it was found that the polymerization degree was as high as 0.74.

Kaya 1 shows the molecular foot distribution of the powdered polymer and the molded film.

DW for LOG [old (logarithm of molecular weight)]
/DLOG [Old (integrated open/integrated LOG [Old, ie, open separated) is a molecular foot distribution curve.

This was determined by gel permeation chromatography (GPC-244) to orthochlorophenol/chloroform (4/6
) to the column TS using the solvent -GEL-C)1860
．． These are the results measured at 2%, using polystyrene for molecular weight calibration.

In addition, the glass transition temperature of the film determined by 1q above is D
When measured with SC-[, it was found to have a high value of 252.3°C.

In addition, 30 m of polymer powder obtained by polycondensation reaction was
Pelletization was performed using an extruder with a screw of φ.

Next, this pellet was subjected to a 5 oz screw in-line injection molding machine set at 320 to 360°C, and an Izot impact test piece (1/4°
'XI/2°'

When the notched impact strength was measured using the obtained Izot test piece, it was a high value of 22 kg·cm / cm.

In addition, when we measured the heat distortion temperature (18,56 KfJ/Cd), it was a high value of 215 °C, and the mechanical properties
The molded product was found to have excellent heat resistance.

The logarithmic viscosity of the obtained molded product was 0.59, which remained unchanged in toluene, acetone, and ethyl acetate solvents, and only swelled in chloroform solvent, indicating excellent solvent resistance. It was found that it has.

Comparative Example 1 Journal of Polymer 5cienc
The polycondensation reaction was carried out according to the method described in J.E. 40, 399 (1959).

That is, using the same apparatus as in Example 1, take 3500 parts by weight of bisphenol, 120 parts by weight of sodium lauryl sulfate, 160 parts by weight of sodium hydroxide, and 12000 parts by weight of water.
Parts by weight were added and dissolved, followed by stirring while maintaining the temperature at 10°C.

Next, 324.8 parts by weight of isophthalic acid dichloride and 81.2 parts by weight of terephthalic acid dichloride were added to 800 parts by weight of methylene chloride.
The solution dissolved in the 0-type hot section was added over 5 minutes to the above reaction solution, which was kept at 10'C and stirred, and then heated for 3 minutes while keeping it at 10'C.
Stirring was continued for 0 minutes. Next, the polymer was poured into 20,000 parts by weight of acetone to precipitate and then separated.
After washing three times with 0,000 parts by weight of water, the mixture was filtered and dried to obtain a white powder polymer with a yield of 95%.

The logarithmic viscosity of the obtained polymer powder was 0.52, indicating a low degree of polymerization as in the above-mentioned known literature.

Next, when this polymer was molded into a film using a press heated to 350°C, the film obtained was very brittle, and the logarithmic viscosity of the film was 0.48, which is a considerably lower value than in Example 1. It turned out to be.

Furthermore, when the glass transition temperature was measured, it was found to be a low value of 218.degree. 4.degree.

When molded by injection molding in the same manner as in Example 1, the molded product obtained was so brittle that it was impossible to measure its physical properties.

Comparative Example 2 A polycondensation reaction was carried out by the method described in JP-A-61-2730.

That is, using the same apparatus as in Example 1, 3,500 parts by weight of bisphenol, 160 parts by weight of sodium lauryl sulfate, and 12,000 parts by weight of water were added and dissolved, followed by stirring while maintaining the temperature at 10'C.

Next, 324.8 parts by weight of isophthalic acid dichloride and 81.2 parts by weight of terephthalic acid dichloride were added to 800 parts by weight of methylene chloride.
0 parts by weight of the solution was added over 10 minutes to the above reaction solution which was kept at 35°C and stirred.
The beating continued for 0 minutes.

Then, it was poured into 20,000 parts by weight of acetone to precipitate the polymer, separated, washed three times with 30,000 parts by weight of water, filtered, and dried to obtain a white powder polymer with a yield of 93%. .

The logarithmic viscosity of the obtained polymer powder was 0.98, and a polymer with a considerably high degree of polymerization was obtained.

Figure 2 shows a molecular weight distribution diagram of the polymer powder and the film formed from the molded product. The measurement method was the same as in Example 1.

This polymer is shown in Example 1 of the present invention as shown in vz times.
Molecular weight distribution of polymer powder with 1q.

1ti), many have low molecular weight matrices.

Furthermore, when this polymer was molded into a film using a press heated to 350° C., it was found that the peak of the molecular weight distribution was at a lower molecular weight than in Example 1 (<sqw). The logarithmic viscosity of this film was 0.51.

In addition, the glass transition temperature of the obtained film was determined by DSC-■
When measured, it was found to have a value of 222.3°C.

In addition, 30 m of polymer powder obtained by polycondensation reaction was
Pelletization was performed using an extruder with a screw of φ.

Next, this pellet was subjected to a 5-ounce screw in-line injection molding machine set at 320 to 350°C, and an Izot impact test piece (1/4°'
X1/2°'X5/2"), heat deformation temperature measurement test piece (1
/8°'XI/2''X11/2'') was molded.

When the notched impact strength was measured using the obtained Izot test piece, it was found that the value was 2 Kg·cm / cm or less, which was an extremely low value compared to Example 1.

Furthermore, when the heat distortion temperature (18.56 Kg/cyt) was measured, it was found to be 194° C., and it was found that both mechanical properties and heat resistance were significantly inferior to Example 1.

The obtained molded article had a logarithmic viscosity of 0.37.

<Effects of the Invention> According to the present invention, an aromatic copolyester molded article having good solvent resistance and heat resistance, a high degree of polymerization, and excellent mechanical properties can be obtained.

[Brief explanation of drawings]

Figure 1 shows the molecular weight distribution curves of the polymer powder and film obtained in Example 1, and Figure 2 shows the molecular weight distribution curves of the polymer powder and film obtained in Comparative Example 2.゛

Claims (1)

[Claims] Consisting of the following structural units (I), (II) and (III),
An aromatic copolyester molded product having a logarithmic viscosity of 0.55 or more. ▲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) (However, , III/II is in the range of 1/9 to 6/4, and the logarithmic viscosity in the present invention is measured at 25°C at a concentration of 0.5 g/dl using orthochlorophenol as a solvent. )