JPS62199614A - Production of aromatic polyester - Google Patents

Abstract

PURPOSE:To obtain the titled high-polymerization degree polyester outstanding in solvent and heat resistances and mechanical properties by interfacial polycondensation with a dicarboxylic acid dichloride, using each specific bisphenol and organic solvent. CONSTITUTION:First, (A) an organic solvent for the polycondensation is prepared by mixing 0.1-10pts.wt. of isophthaloyl dichloride and/or terephthaloyl dichloride with 100pts.wt. of a 1-10C halogenated hydrocarbon of a boiling point >=35 deg.C followed by distillation. Next, (b) isophthaloyl dichloride and/or terephthaloyl dichloride is dissolved in the resultant organic solvent to make an organic solvent solution of a concentration pref. 1-40wt%. This solution is then incorporated with (C) an aqueous alkali solution of bisphenol >=50mol% of which is bis(4-hydroxyphenyl)sulfone, with a concentration e.g. 1-30wt% followed by polycondensation at (T-15)-(T+15) deg.C (T being the boiling point of the component A), thus obtaining the objective polyester.

Description

Detailed Description of the Invention <Industrial Application Valve 95> The present invention relates to a method for producing an aromatic polyester having good solvent resistance and heat resistance, a high degree of polymerization, and excellent mechanical properties. More specifically, the present invention relates to a method for producing an aromatic polyester from an organic solvent solution of acid chloride and an alkaline aqueous solution of bisphenol by an interfacial polycondensation method.

<Prior Art> The production of aromatic polyesters composed of aromatic dicarboxylic acids and sphenols by interfacial polycondensation has been known for a long time. The manufacturing method is a method in which aromatic dicarboxylic acid dichloride dissolved in an organic solvent that is incompatible with water is reacted with bisphenol in an alkaline aqueous solution.
Various combinations are being considered.

Among them, a polymer consisting of isophthalic acid as an aromatic dicarboxylic acid component and 2,2-bis(4-hydroxyphenyl)propane (hereinafter abbreviated as bisphenol A) as a bisphenol component has crystallinity and is difficult to handle in organic solvents. It was difficult to achieve a high degree of polymerization due to the melting process, and only insufficient heat resistance, mechanical properties, etc. could be obtained.

For this reason, for example, the Journal of Polyme
r 5science, 40.399 (1959), by copolymerizing terephthalic acid as another dicarboxylic acid component, the resulting polymer is made substantially inferior, and the solubility is increased to achieve a high degree of polymerization. For example, as disclosed in JP-A No. 49-99395, interfacial polycondensation is carried out using a mixture of terephthalic acid dichloride and isophthalic acid dichloride and controlling the temperature at the initial stage of polymerization to 0 to 15°C. etc. have been proposed.

However, there is a problem in that such polymers cannot be used in applications where solvent resistance is strictly required.

On the other hand, polyesters made from bis(4-hydroxyphenyl)sulfone (hereinafter abbreviated as bisphenol S) are copolymerized with isophthalic acid dichloride and terephthalic acid dichloride as described above, for example, in Jour.
nal of Polymer 5science, 4
0.399 (1959).

<Problems to be solved by the invention> However, this polyester
of Polymer 5science, 40,3
99 (1959), the reactivity of phenolate ion, which is a reactive group during interfacial polymerization, is low due to the electron-withdrawing sulfone group, so it is difficult to use polymers with a high degree of polymerization. It is difficult to obtain, and polymers with a low degree of polymerization have poor heat resistance and solvent resistance, are extremely brittle, and cannot be put to practical use.

Therefore, as a result of intensive studies on polyesters containing bisphenol S as the main bisphenol component, we found that halogenated carbonaceous compounds having a carbon number of 1 to 10 and a boiling point T of 35°C or higher can be used as organic solvents for isophthalic acid dichloride and/or terephthalic acid dichloride. Using hydrogen, the first stage polycondensation was carried out at (T-15)℃~(T+15)''C (however 1,
T is the boiling point of the halogenated hydrocarbon, and ■≧35℃
) It has been found that a high degree of polymerization can be achieved by conducting the polymerization under the following temperature conditions.

However, even in this case, when the polymer obtained by polycondensation reaction was extruded and molded, the degree of polymerization decreased, and it was found that the heat resistance and mechanical properties of the molded product obtained were still insufficient. .

That is, the reality is that an aromatic polyester made of an aromatic dicarboxylic acid and bisphenol that satisfies all of solvent resistance, heat resistance, and mechanical properties, and a method for producing the same, have not yet been provided.

Means for Solving Problems〉 Therefore, the present inventors conducted a thorough study on a method for producing a polyester in which 50 mol% or more of bisphenol is bisphenol S. As an organic solvent for acid dichloride and/or terephthalic acid dichloride, a boiling point T of 35 is purified by distillation in the presence of 0.1 to 10 parts by weight of isophthalic acid dichloride and/or terephthalic acid dichloride per 100 parts by weight of the organic solvent. ℃ or more carbon number 1-1
The polycondensation was carried out using 0 halogenated hydrocarbons (T-
15>"C: ~ (T+15)°C (wherein, T is the boiling point of the halogenated hydrocarbon, and T≧35°C), a polymer with an extremely high degree of polymerization can be obtained. This discovery led to the creation of the present invention.

That is, the present invention uses an interfacial polycondensation method from an organic solvent solution of isophthalic acid dichloride and/or terephthalic acid dichloride and an alkaline aqueous solution of bisphenols in which 50 mol% or more of the bisphenols is bis(4-hydroxyphenyl) sulfone. When producing an aromatic polyester, 0 parts of isophthalic acid dichloride and/or terephthalic acid dichloride is
．． The boiling point T when purified by distillation in the presence of 1 to 10 parts by weight is 35
℃ or higher, a halogenated hydrocarbon having 1 to 10 carbon atoms is used as an organic solvent, and the first polycondensation is carried out at (T-15>℃).
This is a method for producing an aromatic polyester, characterized in that the process is carried out at a temperature of ~(t+15)°C (where T is the boiling point of the halogenated hydrocarbon, and T≧35°C).

Note that the organic solvent in the production method of the present invention is organic solvent 1.
In the presence of 0.1 to 10 parts by weight of isophthalic acid dichloride and/or terephthalic acid dichloride based on 0.00 parts by weight, the distilled product is used, and the polycondensation reaction is carried out at (T-15) It is important to carry out the reaction at a temperature of +15>° C. in order to obtain a polyester with a high degree of polymerization.

Isophthalic acid dichloride and/or terephthalic acid dichloride used as a raw material in the present invention becomes the dicarboxylic acid component of the aromatic polyester of the present invention.

Isophthalic acid dichloride (I) and/or in the present invention
Alternatively, the molar ratio of terephthalic acid dichloride (II>) is (I)/(II>= 515 or higher, especially 7/3
J′! % or more is preferable.

Further, as the dicarboxylic acid component, other copolymerizable dicarboxylic acid dichlorides can be used together with isophthalic acid dichloride and/or terephthalic acid dichloride within a range that does not impair the effects of the present invention.

Examples of other copolymerizable dicarboxylic acid dichlorides include 4,4-diphenyldicarboxylic acid dichloride, 2,6-naphthalene dicarboxylic acid dichloride, and 1,2-dicarboxylic acid dichloride.
Aromatic dicarboxylic acid dichlorides such as -bis(phenoxy)ethane-4,4=-dicarboxylic acid dichloride and 1°2-bis(2-chlorophenoxy)ethane-4°4'-dicarboxylic acid dichloride, adipic acid dichloride and sebacin Examples include aliphatic dicarboxylic acid dichlorides such as acid dichloride and alicyclic dicarboxylic acid dichlorides such as 4,4-cyclohexanedicarboxylic acid dichloride.

Isophthalic acid dichloride and/or terephthalic acid dichloride are supplied to the polycondensation reaction system as an organic solvent solution.

In the present invention, the organic solvent solution of isophthalic acid dichloride and/or terephthalic acid dichloride is a halogenated hydrocarbon having 1 to 10 carbon atoms, and the boiling point (76
0mh> is 35°C or higher. Specifically, methylene chloride, chloroform, 1,2-dichloroethane,
1,1-dichloroethane, 1,1.2-1-dichloroethane, 1°1.1-trichloroethane, 1,1. L 2
-tetrachloroethane, 1. L 2,2-tetrachloroethane, 1,3-dichloropropane, 1.1-dichloropropane, 1,2-dichloropropane, 1.2.3-trichloropropane, 1,1.2-trichloropropane ,
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, methylene chloride, chloroform, 1,2-dichloroethane, etc. , 1,2,3-trichloropropane are preferably used, and methylene chloride is particularly preferably used.

The most important thing in the production method of the present invention is to purify the organic solvent by distillation in the presence of isophthalic acid dichloride and/or terephthalic acid dichloride.

Before using it as an organic solvent for isophthalic acid dichloride and/or terephthalic acid dichloride, it is distilled in the presence of isophthalic acid dichloride and/or terephthalic acid dichloride to remove impurities that may react with these. This is to remove it.

The amount of isophthalic acid dichloride and/or terephthalic acid dichloride used in this distillation purification needs to be 0.1 to 10 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the halogenated hydrocarbon. Parts by weight. Considering the amount of impurities in the organic solvent, 0.1 part by weight or more is necessary, and it is not economical to add more than necessary, so the limit is 10 parts by weight.

Further, the concentration of the organic solvent solution of isophthalic acid dichloride and/or terephthalic acid dichloride of the present invention varies depending on the reaction conditions, the type of organic solvent, the type of polyester produced, etc., but is usually 1 to 40% by weight, preferably 2 to 40% by weight. 3
A range of 0% by weight, more preferably 3-15% by weight is used.

Furthermore, the bisphenols used as the other raw material in the present invention need to contain at least 50 mol% or more of bisphenol S, preferably 90 mol% or more, particularly 96.5 mol% or more. .

If the content of bisphenol S is less than 50 mol%, it is not preferable because the chemical resistance becomes poor, the heat resistance becomes insufficient, and the glass transition point becomes low.

Preferred specific examples of bisphenols other than bisphenol S include 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3
-methylphenyl)propane, 2,2-bis(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-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-monodihydroxyphenyl, 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.

The amount of bisphenols used in the present invention relative to the dicarboxylic acid component is not particularly limited, but preferably 0.7 to 1.5 mol per mol of the dicarboxylic acid component;
More preferably, it is 0.9 to 1.2 mol.

Such bisphenols are supplied to the polycondensation reaction system as an alkaline aqueous solution. Preferred examples of the alkali include sodium hydroxide, potassium hydroxide, and lithium hydroxide, with sodium hydroxide being particularly preferred.

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 organic solvent solution of isophthalic acid dichloride and/or terephthalic acid dichloride thus prepared and the alkaline aqueous solution of bisphenols are polycondensed by an interfacial polycondensation method.

In the present invention, the polycondensation reaction is carried out from (T-15)°C to (T
It is important to carry out the process at a temperature of +15>'C.

Here, T is the boiling point at 760axHIJ 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 T is 35°C or higher.

The reaction temperature is preferably (T-10>'C to (T+5)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.

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

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 that solution is finished, the The temperature may be raised to (T+15>'C, or the temperature may be allowed to cool to (T-15>'C).

In any case, the most preferable method is to carry out the entire polymerization step while maintaining 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.

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.

In addition, examples of catalysts for promoting the polymerization reaction include triethylbenzylammonium chloride, cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, cetyltrimethylammonium iodide, cetyltrimethylammonium hydroxaside, cetyltriethylammonium chloride, and cetyltriethylammonium bromide. , cetyltri-n-butylammonium bromide, cetyltri-n-butylammonium chloride, dodecyltrimethylammonium bromide, dodecyltrimethylammonium chloride, dodecyltrimethylammonium iodide,
dodecyltrimethylammonium hydroxaside,
n-decyltrimethylammonium bromide, n-decyltrimethylammonium chloride, n-decyltrimethylammonium iodide, n-decyltriethylammonium chloride, octyltrimethylammonium bromide, octyltrimethylammonium chloride, octyltrin-butylammonium bromide, cetyltrimethylphosphonium chloride ,
Cetyltrimethylphosphonium bromide, cetyltriphenylphosphonium chloride, cetyltriphenylphosphonium bromide, cetyltrin-butylphosphonium bromide, dodecyltrimethylphosphonium bromide, dodecyltrimethylphosphonium chloride, dodecyltriphenylphosphonium bromide, dodecyltriphenylphosphonium chloride, n-decyltrimethyl Phosphonium bromide, n-decyltrimethylphosphonium chloride, octyltrimethylphosphonium bromide, octyltriethylphosphonium chloride, 2-methyl-5-laurylbenzylammonium chloride, triphenylmethylphosphonium iodide, tetrabutylammonium bromide, 2
-Methyl-5-lauryl-1゜3-xylylenebistrimethylammonium chloride, stearylisoquinolium chloride, N-laurylpyridinium chloride, benzyltritertiarybutylammonium chloride, n-amyltriphenylphosphonium bromide,
Quaternary ammonium salts, quaternary phosphonium salts such as octyltriphenylphosphonium bromide, dioctyldiphenylphosphonium chloride, trioctylphenylphosphonium iodide, etc. or tertiary amines such as trimethylamine, triethylamine, benzyldimethylamine are used. .

<Example> This will be explained in more detail with reference to the following examples.

However, the reduced viscosity ηSp/C is 0.5 g/dj at 25°C using orthochlorophenol! It is measured using a solution and is calculated using the following formula.

(In the formula, 11 is the flow time of the polymer solution, t2 is the flow time of only the solvent, and C is the polymer solution concentration (g/d, Il)
It is. ) Below, viscosity refers to reduced viscosity.

Further, when the obtained polymer was formed into a film by melt pressing, the following method was used.

In other words, 5 to 10 g of polymer powder is put into a hydraulic warping machine (manufactured by Toho Press Co., Ltd.) heated to 350°C, and the cage pressure is 1 kg.
/cr/ was pressed for 1 minute under the following conditions, then roughly pressed for 1 minute under a gauge pressure of 50 KI/cr/l, and then cooled in a cooling press to form a film.

In addition, the glass transition temperature is determined by PerkinElmer's DSC
- Using type II, 10 cm of this film sample was heated at a heating rate of 2
This is a value measured at 0°C/min.

Example 1 13,000 parts by weight of methylene chloride, 200 parts by weight of isophthalic acid dichloride, and zeolite were placed in a 20ρ distillation apparatus equipped with a rectification column and a cold water condenser, and the water bath temperature was 5.
Distillation was carried out at 0°C, and the fraction having a top temperature of 40°C was collected. The amount to be collected was about 1000 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 dissolved, 30 parts by weight.
The temperature was adjusted to ℃. A stream of N2 was passed through the solution for 30 minutes,
10 parts by weight of triethylbenzylammonium chloride was added.

A solution of 406 parts by weight of isophthalic acid dichloride (5% by weight to methylene chloride) dissolved in 8000 parts by weight of methylene chloride purified by distillation by the above method was added over 10 minutes to the above reaction solution which was kept at 30°C and stirred. Stirring was continued for 30 minutes while maintaining the temperature at 30°C. Then acetone 20000
The polymer was poured into a portion by weight to precipitate and then separated, washed three times with 30,000 parts by weight of water, filtered and dried to obtain a white powdery polymer with a yield of 95%.

Next, this polymer was molded into a film using a press heated to 350°C, and the viscosity of the film was measured, and it was found to have a high degree of polymerization of 0.58.

In addition, the glass transition temperature of the film obtained above was
When measured at cm, it was found to have a high value of 230.20°C.

In addition, the polymer powder obtained by the polymerization reaction was
After pelletizing by an extruder with a screw of
The pellets were placed in a 5-ounce screw in-line injection molding machine set at 320 to 350°C, and the mold temperature was 1.
Izot impact test piece (174''
/2°'X5/2°゛), heat deformation temperature measurement test piece (1/2°'
8"'X1/2""Xll/2") was molded.

When the notched impact strength was measured using a 1q Izot test piece, it was a high value of 8 KEI·cm/cm.

Furthermore, when the heat distortion temperature (18.56 KW/cri) was measured, it was a high value of 202°C, indicating that the polymer had excellent impact resistance and heat resistance.

Furthermore, it was found that the polymer of the present invention was unchanged in 1-toluene, acetone, and ethyl acetate, and only swelled in chloroform, indicating that it had excellent solvent resistance.

Comparative Example 1 Except that unpurified methylene chloride was used as it was instead of using methylene chloride purified by distillation in Example 1,
A polycondensation reaction was carried out in exactly the same manner as in Example 1.

The polymer yield after drying was 93%.

Next, this polymer was molded using a press heated to 350°C, and the viscosity of the film was measured, and it was found to be 0.4
2, which was found to be a fairly low value.

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

Effects of the Present Invention> The aromatic polyester produced by the production method of the present invention has good solvent resistance and heat resistance, a high degree of polymerization, and excellent mechanical properties.

Claims (1)

[Claims] 50 of organic solvent solution of isophthalic acid dichloride and/or terephthalic acid dichloride and bisphenol
When producing an aromatic polyester by an interfacial polycondensation method from an alkaline aqueous solution of bisphenols whose mol% or more is bis(4-hydroxyphenyl)sulfone, isophthalic acid dichloride and/or A halogenated hydrocarbon having a carbon number of 1 to 10 and having a boiling point T of 35° C. or higher, purified by distillation in the presence of 0.1 to 10 parts by weight of terephthalic acid dichloride, is used as an organic solvent to carry out the polycondensation (T- 15)℃～(t+15)℃(
However, T is the boiling point of the halogenated hydrocarbon, and T≧3
The temperature is 5°C. ) A method for producing aromatic polyester, characterized in that it is carried out under temperature conditions of: