JPH04146923A - Aromatic polyether based polymer and its production - Google Patents

Abstract

PURPOSE:To obtain the title polymer improved in heat resistance and excellent in mechanical strengths, solvent resistance, etc., by reacting a specified benzobisoxazole compound with a specified dihydric phenol in the presence of an alkali metal compound in an aprotic polar solvent. CONSTITUTION:A benzobisoxazole compound of formula I (wherein X is halogen) is reacted with a dihydric phenol of formula II [wherein Ar is a bivalent group such as a group of formula III, IV, V or VI (wherein R is a 1-13C bivalent group)] in the presence of an alkali metal compound in an aprotic polar solvent to obtain an aromatic polyether based polymer comprising repeating units of formula VII (wherein Ar is as defined above) and a reduced viscosity of 0.2dl/g or above as measured at 30 deg.C in a solution in a solvent comprising nitromethane containing 15wt.% AlCl3 in a concentration of 0.5g/dl. Thus it is possible to produce the title polymer which is an engineering resin having higher Tg and higher heat resistance than those of a conventional engineering resin such as polyether ketone or polyether sulfone and being excellent also in mechanical strengths and solvent resistance, etc., at good efficiency.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to aromatic polyether polymers and copolymers and methods for producing them. Aromatic polyether polymers and aromatic polyether copolymers that have excellent strength, solvent resistance, etc. and are useful as materials in the fields of electrical and electronic equipment, machinery, etc., and can be manufactured using simple processes. The present invention relates to an efficient manufacturing method.

[Prior Art] In recent years, plastics with various chemical structures have been developed as engineering resins, and are used in a wide range of fields, such as the automobile field, electric/electronic field, precision machinery field, OA equipment field, and optical communication equipment field. There is.

However, its performance has not yet been fully satisfied in all aspects, and furthermore, the required performance has become stricter, so the development of new materials is desired.

In order to fully meet these demands, engineering resins are required to have properties such as sufficient mechanical strength, heat resistance, and solvent resistance, but improving heat resistance is a particularly important issue. .

In fact, among the conventional thermoplastic engineering resins, polyether ether ketone (IC1) is a crystalline polymer that is said to have particularly excellent heat resistance.
On the other hand, polyethersulfone (PES) is known as a typical amorphous polymer, but the glass transition temperature (Tg), which is a measure of heat resistance, is different for each of these polymers. 145℃, 220
It is surprisingly low, around ℃, and cannot maintain sufficient rigidity at temperatures above their respective glass transition temperatures.

[Problems to be Solved by the Invention] The purpose of the present invention is to provide aromatic polyether polymers and novel engineering resins that have improved heat resistance, mechanical strength, solvent resistance, etc. An object of the present invention is to provide aromatic polyether copolymers and methods for efficiently producing these polymers.

[Means for Solving the Problems] The present inventors have conducted extensive research in order to develop a new engineering resin that has particularly excellent heat resistance.

As a result, we synthesized various new aromatic polyether polymers and copolymers consisting of specific repeating units, which have a benzobisoxazole structure and an aromatic ether structure in the polymer main chain, and improved their heat resistance, etc. When we investigated the characteristics,
If the benzobisoxazole structural units are present in a specific proportion or more and have a high molecular weight with a reduced viscosity [η/C] of a specific value or more, these novel polymers satisfy the above objectives and are practically advantageous. It was discovered that this material can be used as a highly heat-resistant engineering resin.

In addition, the present inventors conducted various studies on the production method of highly heat-resistant aromatic polyether polymers and copolymers having these novel structures. It has been found that a method of obtaining a predetermined aromatic polyether polymer or copolymer through condensation polymerization is a simple, efficient, and practically excellent method.

The present inventors have completed the present invention based on these findings.

That is, the present invention first relates to the following general formula [I] [However, Ar in the formula "I" is -@-@-1 (However, R is a divalent carbonized carbon having 1 to 13 carbon atoms. (It is a hydrogen group.)

] It has a repeating unit [I] represented by the following formula, and has a concentration of 0.5% using nitromethane containing 15% by weight of aluminum chloride as a solvent. The reduced viscosity [η, , /C] of a 5 g/di solution at 30°C is 0. The present invention provides an aromatic polyether polymer characterized in that it has a molecular weight of 2 dl/g or more.

Hereinafter, the aromatic polyether polymer of the present invention may be referred to as polyether polymer I.

The aromatic polyether polymer of the present invention, that is, polyether polymer I, is a polymer consisting of the repeating unit [1];
It may be a homopolymer in which one type of repeating unit [I] is used alone as a repeating unit, or it may be a heteropolymer in which two or more types of repeating unit [I] are used as a repeating unit.

In addition, the polyether polymer I of the present invention has one or more repeating units [I] and one or more other repeating units within the range that does not impede the purpose of the present invention. It may also be a copolymer having repeating units. There are various types of such copolymers depending on the type of other repeating units and the composition ratio of repeating unit [I] and other repeating units.

Among them, copolymers consisting of the following specific repeating units (repeating units [I] and repeating units [■]) have particularly excellent heat resistance, and also have other properties as engineering resins such as mechanical strength and solvent resistance. It is particularly preferred because of its excellent properties.

That is, the present invention secondly provides a repeating unit [I] represented by the general formula [1] and the following general formula [■] ÷Ar'-0-Ar-0÷III] [wherein the formula [ II], Ar' is the formula [1]
Ar in formula [II] and Ar in formula [1] may be the same or different. ] [11
] and the repeating unit [1] and the repeating unit [II] relative to the total amount of the repeating unit [1] and the repeating unit [II]
I] content ratio is 0. 1 or more, and the concentration is 0.1 using nitromethane containing 15% by weight of aluminum chloride as a solvent. The reduced viscosity [η, , /C] of a 5 g/di solution at 30°C is 0. The present invention provides an aromatic polyether copolymer characterized by having a weight of 2d17g or more.

In addition, hereinafter, this repeating unit [I] and repeating unit [
The aromatic polyether copolymer of the present invention, which is composed of specific repeating units [11] and whose ratio of these repeating units is within the above specific range, may be referred to as polyether copolymer I-II. .

In the present invention, Ar in the repeating unit [I] and repeating unit [11] can be various divalent aromatic groups as described above. Among these, Ar is @
When R@, the R groups can be various divalent hydrocarbon groups having 1 to 13 carbon atoms.

As this hydrocarbon group, various types can be used, and usually a mono- or di-substituted methylene group substituted with an alkylene group, an alkyl group and/or an aryl group, 1.
A 1-cycloalkylidene group is preferred.

When R is an alkylene group, the alkylene group may be linear or branched, but it is usually a linear alkylene group, i.e. (CH2), -(however, m represents an integer of 1 to 13) is preferred. Among the linear alkylene groups, those having a carbon number of 1 to 1 are preferable.
~8 or so, specifically, for example, methylene group, 1.
2-ethylene group, trimethylene group, tetramethylene group,
Examples include hexamethylene group and octamethylene group.

When R is the mono- or di-substituted methylene group, examples of the substituted methylene group include a monoalkylmethylene group, a dialkylmethylene group, a monoarylmethylene group, a diarylmethylene group, and a 1.1-arylalkylmethylene group. I can do it.

Among these, preferred examples include (wherein, ph represents a phenyl group), and particularly preferred among them is CH.

Examples include C-.

CH3 When the above R is a 1,1-cycloalkylidene group, preferable examples include a 1,1-cyclohexylidene group, 1.
Examples include 1-cyclopentylidene group, and particularly preferred are 1゜1-cyclohexylidene group, i.e., \l. When the above Ar is a naphthylene group, this naphthylene group is
Although various types can be used, particularly preferred examples include 1,4-naphthylene group and 26-naphthylene group.

Ar' in the repeating unit [n] can be selected from the above-described divalent diphenylketone residue, diphenylsulfone residue, cyanophenylene group, and the like. Various types of cyanophenylene groups can be used, among which 2-cyano-1,3-phenylene group and 6-diatwo-1,3-
The phenylene group, that is, the polyether copolymer 1-II, contains various repeating units determined by the type of Ar [one or more types of II and one or more types of repeating units determined by the type of Ar and Ar' Various aromatic polyether copolymers can be made of one or more of the various repeating units [II] to be determined. There is no particular restriction on the arrangement type of the repeating units [II and repeating units [Ir] constituting the polymer, for example, random type, alternating type, block type, etc., or if necessary, a suitable branching agent may be introduced. Various types such as graft type, cross-linked type, and combinations of these types are possible. Among these, the random type is usually preferred because it can be produced by a simpler polymerization process.

In addition, this polyether copolymer I-II also contains, in addition to the repeating unit [II] and repeating unit [II],
If necessary, furthermore, to the extent that it does not impede the purpose of the present invention,
Other repeating units can also be included.

One of the important points in the polyether copolymer I-II is that the content ratio or molar ratio of the repeating unit [II] to the total amount of the repeating unit [II] and the repeating unit [II] is 0. 1 or more, preferably 0. It must be 5 or more. If the content ratio of this repeating unit [1] is less than 0.1, sufficient improvement in heat resistance cannot be achieved.

One of the important points in the present invention is that the polymer of the present invention (polyether polymer I or polyether copolymer r-n) is used at a concentration of 0. The reduced viscosity [η, , /C] of a solution of .5 g/di at 30°C is 0. 2dl
/g or more.

This reduced viscosity is 0. If it is less than 2 dl/g, the molecular weight of the polymer is insufficient, and high heat resistance may not be exhibited, and properties such as sufficient mechanical strength and solvent resistance may not be obtained, and the purpose of the present invention may not be achieved sufficiently. can only be achieved. Further, there is no particular restriction on the upper limit of the reduced viscosity, but if the reduced viscosity is too thick, molding may become difficult. The preferred range of this reduced viscosity [η, , /C] is:
Under the above measurement conditions, 0. 3-1. It is 2 dl/g.

The polyether copolymer of the present invention has, for example, a crystal melting point of about 330 to 400°C, has crystallinity, has a sufficiently high molecular weight, and exhibits sufficient heat resistance.
It is a polymer with excellent properties such as excellent solvent resistance, mechanical strength, and moldability, and is used in various electrical and single-child equipment fields such as the automobile field, precision machinery field, zero equipment field, and optical communication equipment field. It can be suitably used as a new material in a wide range of fields such as various mechanical fields.

There are no particular limitations on the in-shell production method for the aromatic polyether polymer (polyether polymer I) and aromatic polyether copolymer (polyether copolymer 1-II) of the present invention. It can be produced by any method using any reaction raw material, but usually
By each of the following methods, it is possible to manufacture efficiently with simple steps.

That is, the present invention provides a preferred method for producing an aromatic polyether polymer (polyether polymer ①) using the following general formula [■] [where X in the formula [I[r] is a halogen atom]. indicates
may be the same or different. ] A benzobisoxazole compound represented by the following general formula [■COHO-Ar-OH[IV ] [However, Ar in formula [IV] is Ar in the above formula [7]
expresses the same meaning as ] A method for producing an aromatic polyether polymer, which is characterized by reacting dihydric phenols represented by the following in a neutral polar solvent in the presence of an alkali metal compound (hereinafter, this production method will be referred to as the production method) In addition, as a preferred method for producing the aromatic polyether copolymer (polyether copolymer 1-n) of the present invention, the general formula [1 [r ] A benzobisoxazole compound represented by the above general formula [IV] and a dihydric phenol represented by the general formula [IV] and the following general formula [V] X-Ar' -X
[Vco[However, X in formula [V] represents a halogen atom, X may be the same or different, and X in formula [V] [I11]
A part or all of them may be the same or different. Also, the expression “■A in
r' is the same as Ar' in the above formula [11].

] A method for producing an aromatic polyether copolymer characterized by reacting a dihalogen compound represented by the following in the presence of an alkali metal compound in a neutral polar solvent (hereinafter, this production method will be referred to as production method ).

The manufacturing method (1) and the manufacturing method (H) will be explained in detail below.

X in the general formula [11] represents a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, fluorine atoms and chlorine atoms are preferred. Note that X in the benzobisoxazole compound represented by the general formula [1[1] may be the same type of halogen atom or may be different.

There are various types of benzobisoxazole compounds depending on the type and combination of X, and any of them can be used, but particularly preferred are compounds in which both X and F are, for example, 2, Mention may be made of 2-bis(4-fluorophenyl)benzobisoxazole and a compound in which both X and C], ie 2,2-bis(4-chlorophenyl)benzobisoxazole.

In addition, the various benzobisoxazole compounds mentioned above are 1
The species may be used alone or two or more species may be used in combination.

Ar in the dihydric phenols represented by the general formula [■]
becomes the repeating unit [1] and Ar in the repeating unit [1] through polymerization. Therefore, the general formula [1”
Ar in [V] represents the same meaning as Ar in the general formula IT] and general formula [■], specific examples thereof, preferred examples,
Particularly preferable examples are as described above, so detailed explanation thereof will be omitted.

There are various types of dihydric phenols represented by the general formula [■], depending on the type of Ar, and any of them can be used. (4-hydroxyphenyl)ether, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl)ketone, bis(4-hydroxyphenyl)methane, 2.2-bis(4-hydroxyphenyl)propane [i.e. , bisphenol A], 1゜1-
Bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)-1,1-
Diphenylmethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, phenolphthalein, 1,4
-dihydroxybenzene [i.e.)Xhydroquinone], 4.4' dihydroxybiphenyl [i.e.
4'-biphenol], 1,4-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, and the like. The various dihydric phenols mentioned above may be used alone or in combination of two or more.

In the production method H, Ar' in the dihalogen compound represented by the general formula [V] becomes Ar' in the repeating unit [II] through polymerization. Therefore, Ar' in the general formula [V] is Ar' in the general formula [Ir]
' has the same meaning as ', and its specific examples, preferred examples, and especially preferred examples are as described above, so detailed explanation thereof will be omitted.

There are various types of dihalogen compounds represented by the general formula [V], depending on the type of Ar', the type of X, and combinations thereof, and any of them can be used, but these compounds are particularly preferably used. For example, bis(4-fluorophenyl)ketone, bis(4-chlorophenyl)
Ketone, bis(4-fluorophenyl)sulfone, bis(4-chlorophenyl)sulfone, 2,6-cyfluoropenzonitrile, 2,6-cyclopenzonitrile, 3
Examples include 6-bis(4-fluorobenzoyl)dibenzofuran. The various dihalogen compounds mentioned above may be used alone or in combination of two or more.

In the production method I, at least one or more of the benzobisoxazole compounds and one or more of the benzobisoxazole compounds
The dihydric phenols of at least one type are reacted in a neutral polar solvent in the presence of an alkali metal compound, and the resulting product is composed of a predetermined repeating unit and satisfies the predetermined reduced viscosity range [η, , /C]. An aromatic polyether polymer (polyether polymer I) of the present invention is produced.

There is no particular restriction on the ratio of the benzobisoxazole compound and the dihydric phenol used in the reaction in this production method I, but the ratio of the dihydric phenol used is the benzobisoxazole compound 1 used.
It is appropriate to select the amount per mole, usually about 0.98 to 1.02 moles, preferably about 1.00 to 101 moles. The reason why such a molar ratio is set to 1 or a ratio close to it is that in this polymerization reaction, the repeating unit [I] is constituted by an equimolar reaction of the benzobisoxazole compound and the dihydric phenol. .

Therefore, when it is intended to produce a copolymer having other repeating units in addition to the repeating unit [1], the proportion of each monomer used should be determined by considering the stoichiometric ratio of the copolymerization reaction in each case. may be selected appropriately.

In the production method (2), at least one or more of the benzobisoxazole compounds, one or more of the dihalogen compounds, and one or more of the dihydric phenols are combined with an alkali metal. The compound is reacted in a neutral polar solvent in the presence of the compound, and consists of the repeating unit [I] and repeating unit [11] in the predetermined ratio, and satisfies the range of the predetermined reduced viscosity [η, , /C]. aromatic polyether copolymer (polyether copolymer I)
■) Manufacture.

In this production method H, the ratio of the benzobisoxazole compound, the dihalogen compound, and the dihydric phenol to be subjected to the reaction is determined by the ratio of the repeating unit [I] and the repeating unit [■] in the obtained polymer as specified above. There is no particular restriction as long as the ratio is within the range of 0.95 to 1 mol of the total JiL of the benzobisoxazole compound and dihalogen compound used. ,02
The amount of the benzobisoxazole compound is selected to be approximately 1.00 to 1.01 mol, preferably in the range of approximately 1.00 to 1.01 mol, and the proportion of the benzobisoxazole compound to be used is usually 0.00 to 1.00 mol per 1 mol of the total amount of the benzobisoxazole compound and the dihalogen compound. 1 mole or more,
Preferably 0. It is appropriate that the amount is 3 moles or more.

Here, if the ratio of the benzobisoxazole compound used per 1 mol of the total amount of the benzobisoxazole compound and the dihalogen compound is less than 0.1 mol, the ratio of the repeating unit [I] in the obtained polymer will be the same as above. If the ratio is smaller than a predetermined value, a desired polymer with sufficiently improved heat resistance may not be obtained.

In addition, the reason why the total amount of the benzobisoxazole compound and dihalogen compound used and the amount of dihydric phenols used are set to equimolar amounts or a ratio close to that as described above is that the total amount of the benzobisoxazole compound and dihalogen compound is 1 This is because the repeating unit [I] and the repeating unit [■] are constituted by 1 mole of the dihydric phenol. Therefore, repeating unit [1] and repeating unit [
If you intend to produce a copolymer having other repeating units in addition to [II], the ratio of each monomer to be used should be appropriately selected taking into account the stoichiometric ratio of the copolymerization reaction in each case. good.

In the production method I and the production method H, the alkali metal compound to be used may be any compound that can convert the dihydric phenol into an alkali metal salt, and is not particularly limited, but is preferably an alkali metal compound. They are metal carbonates and alkali metal hydrogen carbonates.

Examples of the alkali metal carbonates include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, and cesium carbonate.

Among these, preferred are sodium carbonate and potassium carbonate.

Examples of the alkali metal hydrogen carbonate include lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, and cesium hydrogen carbonate.

Among these, preferred are sodium hydrogen carbonate and potassium hydrogen carbonate.

In the method of the present invention, among the various alkali metal compounds mentioned above, sodium carbonate and potassium carbonate can be particularly preferably used.

Examples of the neutral polar solvent include N,N-dimethylformamide, N,N-diethylformamide, and N,N-dimethylformamide.
-dimethylacetamide, N,N-diethylacetamide, N,N-dipropylacetamide, N,N-dimethylbenzoic acid amide, N-methyl-2-pyrrolidone, N-
Ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-isobutyl-2-pyrrolidone, N-n-propyl-2-pyrrolidone, N-n-butyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-methyl-3-methyl-2-pyrrolidone, N-ethyl-3-methyl-2-pyrrolidone, N-methyl-3,4,5-)dimethyl-2-pyrrolidone, N-methyl-2-piperidone,
N-ethyl-2-piperidone, N-isopropyl-2-piperidone, N-methyl-6-methyl-2-piperidone,
N-methyl-3-ethylpiperidone, dimethylsulfoxide, difersulfont, 1-methyl-1oxosulfolane, 1-ethyl-1-oxosulfolane, 1-phenyl-1-oxosulfolane, N, N'-dimethylimidazolidi Examples include non-diphenyl sulfone.

The proportion of the alkali metal compound used is usually 1.01 to 2.50 equivalents, preferably 1.02 to 1.20 equivalents, per hydroxyl group of the dihydric phenol.

There is no particular restriction on the amount of the neutral polar solvent to be used, but in the case of the production method I, per 1100 parts by weight of the benzobisoxazole compound, the dihydric phenols, and the alkali metal compound used, on the other hand. In the case of production method H, the ratio is usually in the range of 2OO to 2,000 parts by weight per 100 parts by weight of the total amount of the benzobisoxazole compound, the dihalogen compound, the dihydric phenol, and the alkali metal compound. It is appropriate to select

In the above-mentioned production method I and production method 2, there are no restrictions on the order and method of adding each component to the reactor when carrying out the respective polymerization reactions in j1, but usually, for example, A method of simultaneously adding each of the predetermined raw materials and the alkali metal compound to the polar melting edge and causing a reaction is preferably employed.

The reaction temperature is usually 150 to 380°C, preferably 1
A suitable temperature range is 80 to 340°C. If the reaction temperature is less than 150°C, the reaction rate is too slow to be practical, while if it exceeds 380°C, side reactions may occur.

Incidentally, the reaction temperature may be kept constant, or may be changed in various modes such as continuously or stepwise. For example, a method in which the reaction temperature is gradually raised from a low temperature such as room temperature and then maintained at an appropriate temperature within the above temperature range is preferably employed.

The reaction time for this series of reactions is usually 0. It is about 1 to 10 hours, preferably about 1 to 5 hours.

In order to carry out the polymerization reaction effectively, it is preferable to remove water present in the reaction system from the reaction system at an appropriate point after starting this series of reaction operations. A suitable method for removing this water is, for example, a method in which a small amount of an appropriate azeotropic solvent such as toluene is added to the reaction system, and the water is azeotropically removed with the azeotropic solvent at an appropriate temperature. be done.

The reaction pressure is not particularly limited and may be normal pressure, increased pressure, the autogenous pressure of the reaction system, or reduced pressure, but usually normal pressure or the autogenous pressure of the reaction system can be suitably used.

There is no particular restriction on the reaction atmosphere, but it is usually best to carry out the reaction in a so-called inert atmosphere. For example, a method in which the reaction is carried out while blowing an inert gas such as nitrogen or argon into the reaction system is preferably adopted. Ru.

After the reaction is completed, the desired polymer is separated from the neutral polar solvent solution containing the desired polymer according to a known method.
By purification, the desired polymer, i.e., polyether polymer I or polyether copolymer I-II
can be obtained.

As described above, the aromatic polyether polymer of the present invention (polyether polymer I
) and the aromatic polyether copolymer of the present invention (polyether copolymers I-II) can be efficiently produced by simple steps using production method H.

[Examples] The present invention will be explained in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

Example 1 2,2'-bis(4-fluorophenyl)-
Benzobisoxazole 10°45g (0.03 mol)
, 4.4'-thiodiphenol 6.55g (0,0
3 mol), 4.98 g (0,036 mol) of potassium carbonate, and 80 ml of N-methylpyrrolidone were added, and the temperature was raised to 190° C. over 40 minutes while blowing argon gas.

After the temperature was raised, a small amount of toluene was added and the generated water was removed by azeotropy. The reaction was carried out at 190°C for 2 hours and 30 minutes.

After the reaction was completed, the product was pulverized and washed with water and methanol in that order to obtain 14.3 g of light green powder. Yield is 90
%Met.

This copolymer has a glass transition temperature of 186°C and a melting point of 432°C as measured by Seiko Electronics' DSC, and a thermal decomposition onset temperature (Tel) of 464°C as measured by Seiko Electronics' TGA (5% in air). It was a crystalline polymer with a weight loss). In addition, aluminum chloride 15 of this polymer
0.5 g of polymer in nitromethane solution containing wt%
/dl concentration, reduced viscosity measured at 30"C is 0.26d
It was l/g.

Furthermore, it was confirmed from the infrared absorption spectrum and elemental analysis results shown in FIG. 1 that this polymer was an aromatic polyether polymer consisting of the following repeating units.

Example 2 In the same reaction vessel as in Example 1, 10.45 g of 2,2'-bis(4-fluorophenyl)-benzobisoxazole was added.
(0.03 mol), phenolphthalein 9.55 g
(0,03 mol), potassium carbonate 4.98 g (0,
036 mol) and N-methylpyrrolidone 80n+1 were charged. 1 over 40 minutes while blowing argon gas.
The temperature was raised to 90°C and maintained at this temperature for an additional 80 minutes to complete the reaction.

After the reaction was completed, the polymer was treated in the same manner as in Example 1 to obtain 17.9 g (yield: $95%) of a light brown polymer.

The glass transition point (Tg) of the 20 copolymer is 337°C, and the thermal decomposition onset temperature (Td: air content 5% weight loss) is 4
The temperature was 59°C.

The reduced viscosity of this polymer measured under the same conditions as Example 1 was 1.3 dl/g.

Furthermore, it was confirmed from the infrared absorption spectrum and elemental analysis results shown in FIG. 2 that this polymer was an aromatic polyether polymer consisting of the following edge-turning units.

Example 3 A 2,2′-bis(4-
Fluorophenyl)-benzobisoxacyl 10.45
g (0.03 mol), 4.4'biphenol 5.59
g (0.03 mol), potassium carbonate 4.38 g (0
, 032 mol) and 60.1 g of diphenylsulfone were charged. The temperature was raised from room temperature to 170'C and held at this temperature for 30 minutes.

Thereafter, the temperature was raised to 250'C over 20 minutes and maintained at this temperature for an additional 20 minutes. The temperature was further increased to 340'C over 30 minutes and maintained at this temperature for 45 minutes to complete the reaction.

After the reaction was completed, the contents were poured into a stainless steel vat and cooled. When cooled, the contents solidified, so they were pulverized using a Warning blender, washed four times with acetone and four times with water to remove the solvent nphenylsulfone and inorganic salts, and dried to a pale green color. 13.2 g of polymer (yield 88%) was obtained.

The melting point (Tm) of this polymer was 500°C, and the thermal decomposition temperature (Td: 5% weight loss in air) was 568°C.

It was confirmed that the glass transition temperature (Tg) was either impossible to measure because the crystallization rate was too high, or was at least 250°C or higher.

The reduced viscosity of this polymer measured under the same conditions as in Example 1 was 0. It was 21 dl/g.

Furthermore, it was confirmed from the infrared absorption spectrum and elemental analysis results shown in FIG. 3 that this polymer was an aromatic polyether polymer consisting of the following repeating units.

Example 4 2.2'-bis(4-fluorophenyl)benzobisoxazole 5.23 g (0,015 mol) 2.6-cyclobenzonitrile 2.606 g (0,015 mol)
, 5.59 g (0.03 mol) of 4,4'-biphenol, 436 g (0.032 mol) of potassium carbonate, and 80 ml of N-methylpyrrolidone were charged.

The following operations were performed in the same manner as in Example 1.

The yield of the obtained copolymer was 11. The yield was 90%.

The reduced viscosity of this polymer measured under the same conditions as in Example 1 was 0. It was 81 dl/g. In addition, the glass transition temperature (T'g), melting point (Tm), and thermal decomposition temperature (Td: 5% weight loss in air) of this polymer are each 19
The temperature was 6°C, 410°C and 552°C.

Furthermore, it was confirmed from the infrared absorption spectrum and elemental analysis that this polymer was an aromatic polyether copolymer consisting of the following repeating units.

Example 5 1.Internal volume 300 m equipped with luene-filled Dean Starck wrap, stirring device, and argon gas inlet pipe
1 reaction vessel, 7°32 g of 2,6-bis-(4-fluorophenyl)-benzobisoxazole (0,02
1 mol), 2.6-cyfluorobenzonitrile 1.25
g (0,009 mol), 4.4'-biphenol5.
59g (0.03 mol), potassium carbonate 4.98g
(0,036 mol) and N-methylpyrrolidone 150 m
1 was added, and the temperature was raised to 1900C over 40 minutes while blowing argon gas.

After raising the temperature, a small amount of toluene was added and the generated water was removed by azeotropy. The reaction was carried out at 190°C for 75 minutes.

After the reaction was completed, the product was pulverized and washed successively with water and methanol to obtain 11.6 g (yield: 89%) of a light-colored copolymer.

It was confirmed from the infrared absorption spectrum and elemental analysis results shown in FIG. 4 that this copolymer was an aromatic polyether copolymer consisting of the following repeating units.

The reduced viscosity of this copolymer is 0. 63d1.7g, the melting point was 465°C, and the thermal decomposition initiation temperature was 556°C.

Example 6 Into the same apparatus as in Example 1, 7.32 g of 2,6-bis-(4-fluorophenyl)-benzobisoxazole was added.
(0,021 mol), 3.71 g (0,00
9 mol), 4.4'-biphenol 5.59 g (0,
03 mol), 4.98 g (0,036 mol) of potassium carbonate, and 150 ml of N-methylpyrrolidone were added. After blowing in argon gas, the temperature was raised to 190℃, and then
It was held at this temperature for 50 minutes.

After the reaction was completed, it was treated in the same manner as in the previous example to obtain 13.7 g (yield: 88%) of light brown powder.

It was confirmed from the infrared absorption spectrum and elemental analysis results shown in FIG. 5 that this copolymer was an aromatic polyether copolymer consisting of the following repeating units.

The reduced viscosity of this copolymer is 0. The melting point was 453°C, and the thermal decomposition starting temperature was 548°C.

Example 7 Into the same apparatus as in Example 1, 7.32 g of 2,6-bis=(4-fluorophenyl)-benzobisoxazole was added.
(0,021 mol), 4.4'-difluorodiphenylsulfone 2,2Lg (0°009 mol), 4.4'-
Biphenol 5.59g (0.03 mol), potassium carbonate 4. 98 g (0,036 mol) and 120 ml of N-methylpyrrolidone were charged. The temperature was raised to 190° C. while blowing argon gas, and the temperature was maintained for an additional 80 minutes to complete the reaction.

After the reaction was completed, it was treated in the same manner as in the previous example to obtain 13.1 g (yield: 93%) of a pale colored powder.

This copolymer was confirmed from the infrared absorption spectrum and elemental analysis results shown in FIG. 6 to be an aromatic polyether copolymer consisting of the following repeating units.

The reduced viscosity of this copolymer is 0. It is 78 dl/g,
The melting point was 433°C, and the thermal decomposition onset temperature was 507°C.

Example 8 Into the same apparatus as in Example 1, 5.23 g of 2,6-bis(4-fluorophenyl)-benzobisoxazole was added.
(0.015 mol), 3.81 g (0.015 mol) of 4,4'-difluorodiphenylsulfone, 5.59 g (0.03 mol) of 4,4'-biphenol, 4.98 g (0.036 mol) of potassium carbonate. mol) and 150 ml of N-methylpyrrolidone were added. The temperature was raised to 190° C. while blowing argon gas, and this temperature was maintained for an additional 210 minutes to complete the reaction.

After the reaction was completed, it was treated in the same manner as in the previous example to obtain 12.5 g (yield: 92%) of a pale colored powder.

It was confirmed from the infrared absorption spectrum and elemental analysis that this copolymer was an aromatic polyether copolymer consisting of the following repeating units.

The reduced viscosity of this copolymer is 1. 10 dl/g,
The glass transition point was 229°C, the melting point was 422°C, and the thermal decomposition onset temperature was 518°C.

[Effects of the Invention] According to the present invention, a high molecular weight aromatic polyether polymer and an aromatic polyether copolymer having a new structure having a specific repeating unit having a specific structure called a benzobisoxazole structure are produced. Compared to conventional engineering resins such as PEEK and PES, these polymers have a particularly high glass transition temperature (Tg), improved heat resistance, and sufficient mechanical strength.
Since it also satisfies other engineering resin properties such as solvent resistance, it can be advantageously used in a wide range of fields.

Moreover, according to the present invention, heat-resistant aromatic polyether polymers and aromatic polyether copolymers having the above-mentioned excellent properties can be efficiently produced in a simple process. Can you provide any method?

[Brief explanation of the drawing]

Figures 1 to 6 are sequential examples 1.2.3.5.6.7.
The infrared absorption spectrum of the aromatic polyether #polymer obtained in is shown.

Claims (1)

[Claims] 1. The following general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] [However, Ar in the formula [I], ▲There are mathematical formulas, chemical formulas, tables, etc.▼ , ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R is a divalent hydrocarbon group having 1 to 13 carbon atoms.) . Solution 2 having a repeating unit [I] represented by [I] and having a concentration of 0.5 g/dl using nitromethane as a solvent containing 15% by weight of aluminum chloride, represented by the following general formula [I] Repeating unit ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [I] [However, Ar in the formula [I] is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R is a divalent hydrocarbon group having 1 to 13 carbon atoms.) . 】［I］
and the following general formula [II] ■Ar'-O-Ar-O■ [II] [However, Ar' in formula [II] is: ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas, chemical formulas ,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ , Ar represents the same meaning as Ar in the formula [I] above, and the formula [ Ar in [II] and Ar in formula [I] may be the same or different. ], and the content ratio of the repeating unit [I] to the total amount of the repeating unit [I] and the repeating unit [II] is 0.1 or more in molar ratio. At the same time, the concentration is 0.5g/using nitromethane containing 15% by weight of aluminum chloride as a solvent.
Reduced viscosity [η_s_p/C
] is 0.2 dl/g or more. 3. The following general formula [III] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [III] [However, X in formula [III] represents a halogen atom, and
may be the same or different. ] A benzobisoxazole compound represented by the following general formula [IV] HO-Ar-OH[IV] [However, Ar in formula [IV] has ▲ mathematical formula, chemical formula, table, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc.▼. , ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R is a divalent hydrocarbon group having 1 to 13 carbon atoms.) ] The method for producing an aromatic polyether polymer according to claim 1, characterized in that the dihydric phenols represented by the following are reacted in a neutral polar solvent in the presence of an alkali metal compound. 4. The following general formula [III] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [III] [However, X in formula [III] represents a halogen atom, and
may be the same or different. ] Benzobisoxazole compound represented by the following general formula [IV] HO-Ar-OH[IV] [However, Ar in formula [VI] has ▲ mathematical formula, chemical formula, table, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R is a divalent hydrocarbon group having 1 to 13 carbon atoms.) . ] Dihydric phenols represented by the following general formula [V] , ▲Mathematical formula, chemical formula,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ where X represents a halogen atom, and X may be the same or different. Further, X in formula [V] may be partially or entirely the same as X in formula [III], or may be different. ] The method for producing an aromatic polyether copolymer according to claim 2, characterized in that the dihalogen compound represented by these is reacted in a neutral polar solvent in the presence of an alkali metal compound.