JPH01259034A - Aromatic polyether and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject fluorescent polyether with a high glass transition temperature by reacting a specified aromatic dihalaide with phenolphthalin(derivative) in the presence of an alkaline metal compound in a neutral polar solvent. CONSTITUTION:A compound of formula I (Ar<1> is group of formula II, III or IV; X<1> and X<2> are halogen) is reacted with phenolphthalin(derivative) of formula V (R is 1-6C alkyl or 6-8C aryl; m is 0-3; n is 1-3) in the presence of an alkaline metal compound such as potassium carbonate in a neutral polar solvent such as dimethylformamide to provide the aimed polyether with a repeating unit of formula VI and >=0.1dl/g reduced viscosity of N-methylpyrrolidone solution with 0.2g/dl concentration at 30 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel aromatic polyether and a method for producing the same. More specifically, the present invention has a particularly high glass transition temperature, can emit intense light, and has excellent mechanical properties, heat resistance, solvent resistance, etc. The present invention relates to an aromatic polyether having a novel structure that is suitably used as a material for parts and a display material, etc., and a method for efficiently producing this polyether using readily available raw materials.

[Prior Art] In recent years, so-called engineering resins having various structures have been produced using rfF1 and are widely used in many fields. Among these engineering resins, many aromatic polyether resins exhibit excellent properties, such as polyether sulfone, polycyanoaryl ether, and polyether ether ketone. has not yet been fully satisfied, and there is a demand for the development of new polymers.

Aromatic polyether resins with various structures have been discovered so far. For example, aromatic polyether ether ketones include those consisting of repeating units represented by 2 (Japanese Patent Laid-Open No. 53
-97094), a copolymer having repeating units represented by the formula and those represented by the formula (JP-A No. 54-9
0296 Publication), and various structures have been proposed as polycyanoaryl ethers, such as those consisting of repeating units represented by the formula and those consisting of repeating units represented by the formula. (Japanese Unexamined Patent Publications No. 47-14270, No. 59-206433, No. 61-162523, No. 62-2232)
26, etc.), and as a polysulfone, one disclosed in Japanese Patent Application Laid-Open No. 49-86500 is well known.

However, these aromatic polyether resins
Although they have superior heat resistance compared to conventionally used general-purpose plastics, they do not have a sufficiently high glass transition temperature, and their rigidity tends to decrease at temperatures above this temperature. It has an unavoidable drawback.

[Problems to be Solved by the Invention] The present invention overcomes the drawbacks of such conventional aromatic polyether resins and improves the resin's inherent excellent v1 mechanical properties, heat resistance, and resistance. It is an object of the present invention to provide a novel aromatic polyether that maintains solvent properties and has a higher glass transition temperature than conventional polyethers, and a method for efficiently producing this polyether using readily available raw materials. It was done for a purpose.

[Means for Solving the Problems] As a result of extensive research into novel aromatic polyethers that have a higher glass transition temperature than conventional ones, the present inventors found that they have a specific structure and a specific Aromatic polyethers having a reduced viscosity greater than or equal to the above value are suitable for the purpose;
There is a substance that emits very bright light, and that this substance can be easily obtained by condensation polymerization of a specific monomer in the presence of a certain compound in a specific solvent, and that the above purpose can be achieved. The present invention was completed based on this finding.

That is, the present invention provides - Maximum <Ar' in the formula, R is an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 8 carbon atoms, m is an integer of 0 to 3, and n is an integer of 1 to 3. The reduced viscosity of a solution at a temperature of 30° C. of 0.2 g/Jl using N-methylpyrrolidone as a solvent is The present invention provides an aromatic polyether characterized by having a value of IJl/lt or more.

According to the present invention, this aromatic polyether is prepared in a neutral polar solvent in the presence of an alkali metal compound by -maximum % formula % () (in the formula, x1 and x2 are each a halogen atom, , they may be the same or different from each other, and Ar' has the same meaning as above) and - maximum (in the formula, R is alkyl having 1 to 6 carbon atoms group, carbon number 6-8
(m is an integer of 0 to 3, n is an integer of 1 to 3) with phenolphthalin or a derivative thereof.

The present invention will be explained in detail below.

The raw material monomers used in the present invention are a dihalogeno compound represented by the above-mentioned -maximum (II), and phenolphthalin and its derivatives represented by the above-mentioned -maximum ([11)].

As the dihalogeno compound represented by the maximum (■) above, 4,4°-dihalogenodiphenyl sulfone represented by 434°-dihalogenobenzophenone represented by the maximum % formula % (2) is used. xl and X2 in (If-1), (■-2) and (IT-3) are each a halogen atom, and these may be the same or different, and As such, fluorine atoms and chlorine atoms are preferred.

The dihalogenobenzonitrile represented by formula (II-1) is, for example, 2,6-difluorobenzonitrile, 2,6-dichlorobenzonitrile, 2-fluoro-6-chlorobenzonitrile, 2,4- Examples include dichlorobenzonitrile, 2,4-difluorobenzonitrile, and among these, 2,6-difluorobenzonitrile and 2,6-dichlorobenzonitrile are preferred.

Examples of the 4,4'-dihalogenobenzophenone represented by the general formula (n-2>) include 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, and 4-chloro-4'-fluorobenzophenone. Among these, 4,4'-difluorobenzophenone and 4,4'-dichlorobenzophenone are preferred.

In addition, -4,4°- expressed by the above-mentioned formula (II-3)
Examples of dihalogenodiphenylsulfone include 4,
Examples include 4°-difluorodiphenylsulfone, 4,4′-dichlorodiphenylsulfone, 4-chloro-4°-fluorodiphenylsulfone, among which 4,4′-difluorodiphenylsulfone and 4,4′-difluorodiphenylsulfone are used.
゛-Dichlorodiphenyl sulfone is preferred.

One type of these dihalogeno compounds may be used, or two or more types may be used in combination.

Furthermore, examples of phenolphthalin and its derivatives represented by the above formula (Tff) include phenolphthalin represented by and phenolphthalin derivatives such as OOH CH 0OH CH, CH, CH3CH3 CHCH, Among these, phenolphthalin is preferred, and these may be used alone or in combination of two or more.

In the present invention, in addition to these phenolphthalin and derivatives thereof, dihydric phenols represented by the following formula can be used as comonomers, if desired. Examples of Ar'' in the general formula (■) include the following.

One type of these dihydric phenols may be used, or 21 types of dihydric phenols may be used.
You may use 1 or more in combination.

The alkali metal compound used in the present invention is not particularly limited as long as it can convert the phenolphthalin, derivatives thereof, and dihydric phenols used as desired into alkali metal salts, but Generally, alkali metal carbonates and alkali metal bicarbonates are preferably used. As an alkali metal carbonate,
Examples include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, and cesium carbonate. Among these, sodium carbonate and potassium carbonate are preferred, and potassium carbonate is particularly preferred.

Examples of alkali metal bicarbonates include lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, and cesium hydrogen carbonate. Among these, sodium hydrogen carbonate and calylum hydrogen carbonate are listed. Preferred, particularly potassium hydrogen carbonate.

The alkali metal carbonates and alkali metal bicarbonates are usually preferably used as anhydrides, but if desired, they can also be used as hydrates, concentrated aqueous solutions, and other water-containing forms. The water added to the system and the water produced by the reaction cause a reaction (condensation reaction).
It is desirable to appropriately remove it from the reaction system during or prior to the reaction.

The alkali metal compound may be used as an IFI, or two or more types may be used in combination, and part or all of the alkali metal compound may be used as an alkali metal salt of the hydroxyl group of phenolphthalin or its derivatives and as desired. It may also be used in the form of alkali metal salts of dihydric phenols used in

The neutral polar solvent used in the present invention includes known ones, such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide,
Sulfolane, dimethylimidazolidinone, diphenylsulfone, etc. can be suitably used, but among these, N-methylpyrrolidone and sulfolane are preferred;
Particularly suitable is N-methylpyrrolidone. These neutral polar solvents may be used alone or in combination of two or more, and may also be used in combination with other inert solvents,
In particular, it can also be used as a mixed solvent with aromatic solvents such as benzene, toluene, and xylene that can azeotropically remove water from the reaction system.

Regarding the usage ratio of the raw material monomer in the present invention, the above-mentioned formula (II
) is usually 0.
It is used at a ratio of 98 to 1.02, preferably 1,00 to 1.01. If this molar ratio deviates from the above range, the conversion rate of one of the components may decrease, which is not preferable.

In the present invention, the alkali metal compound has a total amount of alkali metal atoms of phenolphthalin or its derivatives and dihydric phenols used as desired, 17
The proportions used are 1.00 to 3.00 gram atoms, preferably 1.50 to 1.80 gram atoms per 2 moles.

There is no particular restriction on the amount of the neutral polar solvent used, but 10 parts by weight of the monomers usually used
Selected in the range of ~1,000 parts.

Next, to show a preferred embodiment a of the polymerization in the present invention, first, a required amount of phenolphthalin or its derivative, a dihalogeno compound represented by the above-mentioned formula 1), and an alkali metal compound are added to a neutral polar solvent. Add and heat to usually 150-350°C, preferably 18,0-250°C
The polymerization reaction is carried out at a temperature in the range of 15
Below 0°C, the reaction rate is too slow to be practical;
If the temperature exceeds 0°C, the resulting polymer tends to become more discolored due to deterioration. Make sure to raise the temperature gently during polymerization.
It is desirable to keep the polymerization system at a uniform temperature in order to obtain a good polymer without gels or coloring.The reaction time also depends on the reaction temperature, the type of raw material monomer, and the amount of alkali metal compound used. It depends on the type and amount, etc.
Although it cannot be determined generally, it usually takes 0.5 to 10 hours.
Preferably it is about 2 to 5 hours.

Furthermore, the polymerization reaction is preferably carried out under an inert atmosphere, for example, an inert gas atmosphere such as nitrogen, argon, helium, etc., or an air flow, and there is no particular restriction on the reaction pressure, but the reaction is usually carried out at around normal pressure. be exposed.

In addition, it is desirable to remove water generated during polymerization outside the system. Examples of methods for this removal include methods such as gas replacement in the reactor, gas flow, and addition of a solvent that is azeotropic with water to the polymerization system. A method such as distilling off the liquid out of the system is used.

The polymerization reaction can also be stopped by adding a suitable terminal terminator, such as an active halogen compound, to the polymerization solution and maintaining the reaction at the same temperature as the normal polymerization temperature.
Moreover, this makes it possible to eliminate phenol terminals contained in the polymer and stabilize it.

In this reaction, if desired, the above-maximum (II)
The dihalogeno compounds represented by may be used in combination of two or more, or dihydric phenols represented by the -m formula (■) may be used together with phenolphthalin or its derivatives. A desired copolymer can be obtained by appropriately selecting the combination and type of dihydric phenols. When producing this copolymer,
The raw material monomers may be charged all at once, or may be divided into appropriate portions and added as appropriate during the reaction. By doing so, it is possible to obtain copolymers with arbitrary bonds, such as random copolymers and block copolymers. I can do it. When dihydric phenols and phenolphthalin or its derivatives are used together, their molar ratio is 1=99 to 99+1, preferably 10
:90 to 90:10.

Next, to show another preferred embodiment R of the polymerization in the present invention, first, an alkali gold a salt of the hydroxyl group of phenolphthalin or its derivatives is prepared, and this and the dihalogeno compound represented by -max (ff>) are combined. The desired aromatic polyether can be obtained by heating in a neutral polar solvent and condensing it under the same conditions as above while accompanied by a dehalogenated alkali metal. , Similarly to the above, the dihalogeno compound may be used in combination of 28I or more as desired, and together with the alkali metal salt of the hydroxyl group of phenolphthalin or its derivative, a dihydric phenol represented by the -m formula (IV) can be used. Alkali metal salts of the following types may also be used.

The aromatic polyether thus produced can be separated from other components such as solvents and alkali halides by known methods, and then subjected to purification operations such as washing to recover a polymer of desired purity. can.

The thus obtained novel polymer of the present invention has a structure having a repeating unit represented by the aromatic bolier (Ar', R, m, and n in the formula have the same meanings as above). be. This polymer may contain 1a selected from the above-mentioned maximum % formula %, or may be a copolymer containing a mixture of two or more.

If desired, a copolymer having a repeating unit represented by -maximum (1) as well as a repeating unit represented by -maximum (Ar' and Ar' in the formula have the same meanings as above), Ar' in the repeating unit represented by this - removal allowance (V) may contain one type of the above-mentioned residue, or may contain a mixture of two or more types, and Ar' It may contain one kind of residue of the above-mentioned dihydric phenols, or two
It may contain a mixture of 81 or more.

When the aromatic polyether of the present invention is a copolymer as described above, a random copolymer, a block copolymer, etc.
Any type of bonded wet copolymer may be used, and if it contains repeating units represented by (1) and (V) above, the content ratio thereof should be 1:9 in molar ratio.
9 to 99:1. Preferably 10:90 to 90:
It is desirable that it be in the range of 10.

The aromatic polyether has a reduced viscosity [η sp/c] of 0, I Je measured at a temperature of 30° C. of a solution with a concentration of 0 and 2 t/di using N-methylpyrrolidone as a solvent.
/, or more is required. This reduced viscosity is 0.
If it is less than IJ1/g, it will not sufficiently exhibit the desired properties as a polymer and is unsuitable.

The aromatic polyether of the present invention has characteristics such as not only excellent mechanical properties, heat resistance, and solvent resistance, but also a high glass transition temperature (Ty) and may emit fluorescence. However, it is suitably used as an engineering resin, as a material for parts in various fields, as a display material, etc.

[Example] Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited in any way by these examples.

(Example 1) 300 m equipped with a stirrer, argon gas blowing tube, thermocouple and Dean-Starck trap filled with toluene
Add 25% of phenolphthalin to a separable flask.
371 g (0.08 mol), 2.6-cyclobenzonitrile 13.76111 (0.08 mol), potassium carbonate 17.414y (0.126 mol), N-methylpyrrolidone 100xj! The temperature was raised from room temperature to 195°C over 45 minutes while blowing argon gas and stirring. At this point, about 3 ml of toluene was added to the reaction system, and the water produced by refluxing the toluene was heated for 90 minutes. removed by
・9 Next, toluene was removed, and heating and stirring was continued at this temperature for an additional 2 hours.

After cooling, the product was precipitated in water, pulverized in a Warning blender, and then washed three times with 11 parts of water and once with 11 parts of methanol to obtain a polymer powder of 32.6 y (yield: 9).
8%).

This polymer has a reduced viscosity of 0.6411/II (30℃
, N-methylpyrrolidone, 0.2 g/V1), glass transition temperature 229°C, thermal decomposition onset temperature 435°C (in air,
The infrared absorption spectrum of this polymer is shown in Figure 1.
The absorption based on the nitrile group at m-' is 1240cz-'
Absorption based on ether bonds was observed.

This polymer was confirmed to be an aromatic polyether having the repeating units shown below.

Furthermore, a press film was produced at 320°C, and a wavelength of 32
When irradiated with 0nm ultraviolet rays, strong green fluorescence (
The wavelength was 470-500 nm).

(Example 2) In Example 1, 4,4'-difluorobenzophenone 17.6 was used instead of 2,6-dichlorobenzonitrile.
Polymer 39.09<yield 98%) was obtained in the same manner as in Example 1 except that 39 (0.08 mol) was used.

This polymer has a reduced viscosity of 0.56J1/9 (30℃, N
-Methylpyrrolidone, 0.29/jj, glass transition temperature 214°C, and thermal decomposition onset temperature 421°C. Also,
When this polymer was analyzed by infrared absorption spectrum, it was found that 1
Absorption based on ether bond at 240cz-' is 1
Absorption based on carbonyl group was observed at 650 cm-'.

This polymer was confirmed to be an aromatic polyether having the repeating units shown below.

A press film was prepared from this polymer and irradiated with ultraviolet rays, but no fluorescence was observed.

(Example 3) In Example 1, 2,4°-difluorodiphenylsulfone was used instead of 2,6-cyclobenzonitrile.
41.2 g (yield: 97%) of a polymer was obtained in the same manner as in Example 1, except that 34 g (0.08 mol) was used.

This polymer has a reduced viscosity of 0.89J1# (30℃, N-
Methylpyrrolidone, 0.21? /J1), the glass transition temperature was 234°C, and the thermal decomposition start temperature was 435°C. Also,
Infrared absorption analysis of this polymer revealed that it was 1240 cr'
An absorption based on an ether bond was confirmed at 1230 ct-', and an absorption based on a sulfonyl group was confirmed at 1230 ct-'.

This polymer was confirmed to be an aromatic polyether having the repeating units shown below.

Furthermore, when a press film was prepared at 320° C. and irradiated with ultraviolet light, it emitted strong fluorescence.

(Example 4) 20.34 g of 4.4°-difluorodiphenylsulfone
(0.08 mol) phenolphthalin 12.685 g (
0.04 mol), phenolphthalein 12.606 g
(0,04 mol), potassium carbonate 17.414 g (0,
132 mol> and 100 t/N-methylpyrrolidone, the same operation as in Example 1 was carried out to obtain a copolymer of 41.6 mol.
y (yield 98%) was obtained.

The reduced viscosity of this copolymer is 1.18 J1/it (30
℃, N-methylpyrrolidone, 0.2y/, jl), the glass transition temperature is 255℃, and the thermal decomposition onset temperature is 445℃.
It was °C.

Further, the results of infrared absorption spectrum analysis of this copolymer were the same as in Example 3, and it was confirmed that it was an aromatic polyether consisting of the repeating units shown below.

Further, when a press film obtained by press-molding this polymer at 320° C. was not irradiated with ultraviolet rays with a wavelength of 320 nm, strong green fluorescence (470 nm) was emitted.

(Example 5) In the same flask as in Example 1, 11.128 g (0.08 mol) of 2,6-cyfluorobenzonitrile, 34.257 y (0.08 mol) of thymolphthalin, and 18.2431 F potassium carbonate ( 0,132 mol) and N-methylpyrrolidone 100R1 were added, and while stirring and blowing argon gas, the temperature was raised from room temperature to 195°C over 45 minutes. Approximately 3xl of toluene was then added to the reaction system, and toluene was added. The reaction was carried out for 60 minutes under reflux.

After the reaction was completed, the product was cooled, precipitated in water, pulverized in a blender manufactured by Warning, and washed three times with 11 parts of water and once with 11 parts of methanol to obtain 41.3 g of polymer powder (yield: 98%). %) was obtained.

The reduced viscosity of this polymer is 0.89H/II (30℃,
N-methylpyrrolidone, 0.2y/Vi'), had a glass transition temperature of 231°C, and a thermal decomposition onset temperature of 385°C.

As a result of infrared absorption spectrum analysis of this polymer, 225
The absorption based on the nitrile group at 0 cc' is also 1 240
Absorption based on ether bond was observed in cr', and it was confirmed that it was an aromatic polyether having the retardation unit shown below.

Furthermore, when a film obtained by press-molding this polymer at 310 DEG C. was irradiated with ultraviolet rays with a wavelength of 320 nm, it emitted strong blue fluorescence (450 to 460 nm).

(Example 6) 4.4′- instead of 2.6-cyfluorobenzonitrile
difluorodiphenylsulfone to 20.34y (0,0
The same operation as in Example 5 was carried out except that 8 mol) was used,
A polymer 50.4y (yield 98%) was obtained.

The original viscosity of the conopolymer is 0.25 Jl/y (30
°C, N-methylpyrrolidone, 0.2y/Jl),
Glass transition temperature is 242℃, thermal decomposition onset temperature is 390℃
Met.

The results of infrared absorption spectrum analysis of this polymer were the same as in Example 3, and it was confirmed that it was an aromatic polyether consisting of the repeating units shown below.

Furthermore, when a press film obtained by press-molding this polymer at 320° C. was irradiated with ultraviolet rays with a wavelength of 320 nm, it emitted strong blue fluorescence (450 to 460 nm).

[Effects of the Invention] The aromatic polyether of the present invention is a novel polymer having residues of phenolphtasone or its derivatives in the repeating unit, and has excellent tRW properties such as heat resistance and solvent resistance. , the glass transition temperature is high (e.g. 210-250
℃), some of which emit fluorescent light, and are used as engineering resins, such as in the electronic and electrical fields, mechanical fields,
It is suitably used as a material for various parts in the automobile field and as a display material.

Further, according to the method of the present invention, the aromatic polyether can be
The method of the present invention is a practically advantageous method because it can be efficiently produced by simple operations using industrially easily available raw materials.

[Brief explanation of the drawing]

FIG. 1 is an infrared absorption spectrum diagram of an example of the aromatic polyether of the present invention.

Claims (2)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Ar^1 in the formula is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ Mathematical formulas, chemical formulas, There are tables etc. ▼, R is an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 8 carbon atoms, m is an integer of 0 to 3, and n is an integer of 1 to 3). of a solution with a concentration of 0.2 g/dl using N-methylpyrrolidone as a solvent at 30°C.
An aromatic polyether having a reduced viscosity of 0.1 dl/g or more at a temperature of 0.1 dl/g or more. (2) In the presence of an alkali metal compound in a neutral polar solvent, the general formula There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, X^1 and X^2 are each halogen atoms,
They may be the same or different) and the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (R in the formula is an alkyl group having 1 to 6 carbon atoms) , carbon number 6-8
2. The aromatic polyether according to claim 1, characterized in that the aromatic polyether is reacted with phenolphthalin or a derivative thereof represented by: manufacturing method.