JPH0713142B2 - Thermoplastic aromatic polyether pyridine and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a thermoplastic aromatic polyether pyridine and a method for producing the same.

This thermoplastic resin is called a thermoplastic aromatic polyether pyridine (hereinafter abbreviated as PEP), has two or more oxygen bonds to the pyridine ring and the pyridine ring in the repeating unit, and further, in the repeating unit. Is an alternating condensate composed of two different structures.

This PEP has a wide range of applications as a molding material, a film, an insulating material for wire coating, and the like, and it is expected that conductivity can be imparted by doping the nitrogen atom of the pyridine ring with a metal ion. Further, the PEP of the present invention is extremely useful as a functional polymer material such as the ability to trap and separate certain cations when processed with a hollow fiber or a thin film, and used as a polymer catalyst in a polymer reaction.

(Prior Art) Such a polyether resin having a pyridine ring in a repeating unit has hitherto not been known.

This polyether resin was newly found by the present inventors,
The manufacturing method has been completed.

Conventionally, general aromatic polyether resins have been produced by condensing aromatic bisphenols and aromatic dihalogen compounds. For example hydroquinone and 4,
Polyether ether ketone resin from 4'-difluorobenzophenone (JP-A-54-90296) and polyether sulfone resin from 4,4'-dihydroxydiphenyl sulfone and 4,4'-dichlorodiphenyl sulfone (JP-A-52-27)
500) are manufactured.

(Problems to be Solved by the Invention) However, in these known methods for producing an aromatic polyether resin, two raw materials such as 4,4′-difluorobenzophenone and 4,4′-dichlorodiphenyl sulfone are used as raw material compounds. It can be prepared for the first time by using an aromatic dihalogen compound in which the halogen atom is activated by an electron withdrawing group such as a carbonyl group or a sulfonyl group in the para position.

Further, in a linear condensate of para-substituted monomers such as the above-mentioned polyether resin, the resin becomes rigid and the fluidity at the time of molding is insufficient.

In order to improve the fluidity, a non-linear molecular structure is required, and a meta-type monomer is desired.

Further, in terms of the performance of heat resistant resins, resins having functions other than heat resistance are desired, such as molding processability, functional characteristics, etc., and electrical characteristics include insulation and conductivity. There is a demand for a resin that gives

(Means for Solving Problems) In response to such a technical level and social demands, the present invention and the like have a meta-system in which two halogen atoms are substituted in the meta position in one aromatic group. The aromatic dihalide compound, namely 2,6-dihalogenopyridine, was subjected to a condensation reaction with a dihydroxy compound, and it was surprising that a stable aromatic compound having a heterocycle with various useful functions with a high degree of condensation. It was found that a polyether resin was obtained (Japanese Patent Application No. 61-180180).

Further, among such 2,6-dihalogenopyridines, for example, 2,6-dichloropyridine was found to have a great difference in reactivity between the first and second chloro groups, and Of a bis (6-chloro-2-pyridyloxy) compound represented by the general formula (2) by reacting only the chloro group of the above with a dihydroxy compound (Japanese Patent Application No. 61-
165471).

The present inventors further differed from the aromatic polyether pyridine resin by the above-mentioned co-condensation by combining the bis (6-chloro-2-pyridyloxy) compound with another dihydroxy compound other than that used in the production thereof. It has been found that an alternating co-condensation resin having excellent performance can be produced.

That is, it is an alternating co-condensed aromatic polyether pyridine resin comprising a bis (6-chloro-2-pyridyloxy) compound and a dihydroxy compound other than that used therein, and a method for producing the same.

More specifically, the general formula (1) (In the formula, X or Y is and Which are different from each other, n is a degree of polymerization and is an integer of 10 or more), and a thermoplastic aromatic polyether pyridine represented by the general formula (2) (In the formula, X is the same as in the case of the general formula (1)) and a bis (6-chloro-2-pyridyloxy) compound represented by the general formula (3) HO-Y-OH (3) , X is the same as in the case of the general formula (1)), and a dihydroxy compound represented by the general formula (1) is present in a substantially equimolar amount, and under these substantially anhydrous conditions, an alkali metal carbonate and / or bicarbonate. Alternatively, it is a method for producing a thermoplastic aromatic polyether pyridine represented by the above formula (1), which comprises polycondensing in the presence of a hydroxide.

The degree of polymerization (n) of this polyether pyridine is an integer of 10 or more, preferably 50 to 3000.

This polyether pyridine is stable to heat and various atmospheres because most of it consists of ether bonds.

Further, the general aromatic polyether resins described above take a linear bond from the structure of the raw material compound, whereas in the PEP of the present invention, the ether groups facing each other in the pyridine ring are in the meta position, so It is also featured that it can have an arbitrary folded structure by combining with the diphenols.

Further, it is possible to change various properties by combining diphenols. That is, the glass transition temperature (Tg), crystallinity, flexibility, toughness, adhesiveness, etc. can be arbitrarily changed. For example, when a meta-dihydroxy compound is combined with a bis (6-chloro-2-pyridyloxy) compound composed of a para-dihydroxy compound, the glass transition temperature and the toughness are lower than those of the para-alone resin, but the flexibility is low. And adhesiveness are improved.

The selection of such a structure is important in that various performances can be adjusted appropriately for various applications.

Thus, the PEP of the present invention is a novel alternating unit co-condensation resin having a nitrogen atom in the aromatic nucleus, and is characterized by having various highly functional performances.

The bis (6-chloro-2-pyridyloxy) compound represented by the general formula (2) as a raw material is obtained by condensing 2,6-dichloropyridine and diphenols. Obtained (Japanese Patent Application No. 61-16547)
1). These are 2,2-bis [4- (6-chloro-2-pyridyloxy) phenyl] propane, 4,4-bis (6-chloro-2-pyridyloxy) diphenyl sulfide, 1,
4-bis (6-chloro-2-pyridyloxy) benzene, 1,3-bis (6-chloro-2-pyridyloxy) benzene, 1,6-bis (6-chloro-2-pyridyloxy) naphthalene, 1 , 5-bis (6-chloro-2-pyridyloxy) naphthalene, 2,6-bis (6-chloro-2-
Pyridyloxy) naphthalene, 2,7-bis (6-chloro-2-pyridyloxy) naphthalene, 1,7-bis (6-
Chloro-2-pyridyloxy) naphthalene, 4,4'-bis (6-chloro-2-pyridyloxy) benzophenone, 4,4'-bis (6-chloro-2-pyridyloxy)
Diphenylmethane, 4,4'-bis (6-chloro-2-pyridyloxy) diphenylsulfone, 4,4'-bis (6
-Chloro-2-pyridyloxy) diphenyl sulfoxide, 4,4'-bis (6-chloro-2-pyridyloxy)
Diphenyl ether and 4,4'-bis (6-chloro-
2-pyridyloxy) diphenyl and the like.

The dihydroxy compound represented by the general formula (3) as the other raw material is hydroquinone, resorcin, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-thiodiphenol, 4,4 '. -Dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxybenzophenone, 2,2-bis (4-hydroxyphenyl) propane, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,5-
Examples thereof include dihydroxynaphthalene, 2,6-dihydroxynaphthalene and 1,7-dihydroxynaphthalene.

The bis (6-chloro-2-pyridyloxy) compound and the dihydroxy compound must be reacted in substantially equimolar amounts, but the substantially equimolar amount means that the bis (6-chloro-2 -Pyridyloxy) compound or dihydroxy compound is used in an excess amount in the range of about 10 mol%. This serves to suppress the reaction and to control the molecular weight of the polycondensate by slightly overusing one of the reaction components.

In the polycondensation method of the present invention, an alkali metal carbonate is used as a base, but a bicarbonate or hydroxide is used, but in the case of an alkali metal hydroxide, the amount of caustic soda or caustic potassium is strictly specified, It is necessary to use a stoichiometric amount, and it is generally difficult to increase the degree of condensation. This is considered to be caused by side reactions such as hydrolysis of dihalides if it is in an excessive amount (Polymer (Vol. 25), 1827-1836 (1984)). It is also necessary to completely remove water. For this reason, preferred bases of the present invention are alkali metal carbonates and bicarbonates. Examples of the alkali metal carbonate and bicarbonate include potassium carbonate, sodium carbonate, cesium carbonate, rubidium carbonate, potassium bicarbonate and sodium bicarbonate.
Industrially preferably used are potassium carbonate and sodium carbonate, and there is no problem in using two kinds of them in admixture or partially mixing other carbonates or bicarbonates.

The total amount of these alkali metal salts used is preferably at least 2 g atom of alkali metal per mol of the dihydroxy compound, that is, at least 1 atom of alkali metal for each hydroxyl group.
If it is less than this range, the degree of condensation is lowered. Also, a large excess of carbonate or bicarbonate should not be used to avoid adverse side reactions. Most preferably, the alkali metal has from 1 to 1.2 atoms per hydroxyl group.

Next, in the method of the present invention, the method as described in JP-B-53-7959, that is, the reaction can be carried out while stirring and kneading without a solvent, but industrially it is preferably carried out in a solvent. .

As this solvent, an aprotic polar solvent is preferable,
For example, 1,3-dimethyl-2-imidazolidinone, hexamethylphosphoramide, formamide, N-methylformamide, N, N-dimethylformamide, N, N-dimethylelmamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N, N, N ', N'-tetramethylurea, 2-pyrrolidone, N-methylpyrrolidone,
Examples thereof include dimethyl sulfoxide, dimethyl sulfone, sulfolane and the like. More preferably 1,3-dimethyl-2-
Imidazolidinone, N-methylpyrrolidone, dimethyl sulfone and sulfolane.

The amount of these solvents used is usually about 0.5 to 10 times the weight of the raw materials.

The reaction temperature is in the range of 90 to 300 ° C, preferably 120 to 250.
It is better to carry out the reaction while gradually raising the temperature in the range of ° C.

For the purpose of facilitating the reaction, macrocyclic polyethers such as crown ethers, nitrogen-containing macrocyclic polyethers such as cryptate, and nitrogen-containing chain polyethers such as tris (3,6-dioxaheptyl) amine. Ethers and polyethylene glycol dialkyl ethers may be used as phase transfer catalysts.

As a general embodiment of the polycondensation reaction using the above raw materials and reagents, a predetermined amount of a bis (6-chloro-2-pyridyloxy) compound, a dihydroxy compound, a base and a solvent are charged. Then, add a solvent such as benzene, toluene or chlorobenzene to remove water. The solvent for this dehydration is effective in constantly and rapidly removing water in the system or water generated by the reaction by azeotropic distillation to obtain a polycondensation solvent.

The reaction is carried out while stepwise raising the temperature while aerating an inert gas such as nitrogen, argon, helium or carbon dioxide, and distilling off the initial dehydrated solvent. Eventually 200-250 ℃
The reaction time for raising the temperature to a certain degree and ending the reaction is approximately in the range of 4 to 20 hours.

Post-treatment after reaction is a method of precipitating a general polymer,
That is, a method is adopted in which the reaction solution is discharged into methanol, water or the like to cause precipitation. In addition, some of the halogenated hydrocarbons are soluble in the solvent by diluting the reaction solution with the above solvent, adding water to extract the inorganic salt or reaction solvent, separating the solution, and precipitating with methanol or the like. It may be.

(Action and Effect) The PEP of the present invention is a novel thermoplastic aromatic polyether having a pyridine ring in the repeating unit, has excellent heat resistance and molding processability, can be manufactured at low cost, and has a nitrogen atom in the pyridine ring. It has the characteristic that new characteristics can be expected. Therefore, various applications are conceivable, and the provision of such a new and useful resin contributes to the industrial development and is of great significance.

(Examples) Hereinafter, the present invention will be described in more detail with reference to Examples.

The viscosity, the results of thermal analysis and the rheological properties of the polymers obtained in the following examples are shown in Table 2. The measuring method is as follows.

The logarithmic viscosity ηinh was calculated by the following formula.

ηinh = 1n (t / t ₀ ) / C where 1n is the natural logarithm, t is the solvent phenol / tetrachloroethane (weight ratio 6/4) 0.5g aromatic polyether pyridine dissolved in 100ml mixed solvent Of the mixed solvent alone at 35 ° C., t ₀ is the flowing time (second) at 35 ° C. of the mixed solvent alone, and C is the concentration (g / dl) of the solution to be measured.

In addition, the average molecular weight obtained from the calibration curve by GPC (▲
)) And the average degree of polymerization in the general formula (1) corresponding to the molecular weight thereof were determined. The results are shown in Table 2.

The glass transition temperature Tg and the melting point Tm are measured by the DSC method,
The 5% thermogravimetric reduction temperature Td ₅ is a value measured in air by DTA-TG.

The crystallinity was measured by the X-ray diffraction XRD method.

Flow characteristics are based on Shimadzu's advanced flow tester (CFT-5
00). Measuring conditions are: die length 10mm under predetermined temperature and load, die diameter 1mm, preheating time 5 minutes, measurement drop range 3
7 mm rather than mm.

Example 1 Purification into 100 ml flask equipped with stirrer and water separator
2,2-bis (4-hydroxyphenyl) propane 11.42g
(0.05 mol), 4,4'-bis (6-chloro-2-pyridyloxy) diphenyl 20.46 g (0.05 mol), anhydrous potassium carbonate 7.6 g (0.055 mol), 1,3-dimethyl-2-imidazolidinone 25 ml and 20 ml toluene were charged. The temperature was raised with stirring while passing nitrogen gas, and azeotropic dehydration was carried out for 1 hour under the reflux of toluene. Continuously, toluene was gradually removed to the outside of the system while maintaining the reflux state, and the temperature was raised.
Then, toluene was added dropwise at 170 to 180 ° C. from time to time, and the reaction was carried out for 3 hours while distilling and distilling off. After this, the temperature is further raised to 20
The reaction was completed at 0 ° C. for 3 hours and 220 ° C. for 3 hours. After cooling the viscous resin solution, the resin solution was added dropwise to 800 ml of vigorously stirred methanol in a high speed mixer.
After the dropping, stirring was continued for 10 minutes, and the produced white powder was filtered. This white powder is further added with 300 ml of 70% aqueous methanol solution.
After stirring, filtration, washing with water and drying, a polymer was obtained.

Examples 2 to 10 Polymers of various polyether pyridines were obtained by the method of Example 1 by changing the kinds of raw material bis (6-chloro-2-pyridyloxy) compound, dihydroxy compound, base and solvent as shown in Table 1. It was

Claims (2)

[Claims] 1. A general formula (1) (In the formula, X or Y is and Which are different from each other, n is a degree of polymerization and is an integer of 10 or more). 2. General formula (2) (Where X is and And a bis (6-chloro-2-pyridyloxy) compound represented by the general formula (3) HO-Y-OH (3) (wherein Y is and A dihydroxy compound represented by the formula (1) is present in a substantially equimolar amount, and these are polycondensed in the presence of an alkali metal carbonate and / or bicarbonate or hydroxide under substantially anhydrous conditions. General formula (1) characterized by (Wherein, X or Y is the same as and different from those in the general formulas (2) and (3), and n is a degree of polymerization and is an integer of 10 or more). Production method.