JP2005290317A - Rigid-type heterocyclic polymer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition excellent in both tensile strength and compressive strength. <P>SOLUTION: This rigid-type heterocyclic polymer composition comprises 100 pts.wt. rigid-type heterocyclic polymer having a repeating unit expressed by formula(A) and/or formula(B)(wherein X represents either of O, S and NH; Ar<SP>1</SP>represents a 4-20C quadrivalent aromatic group; and Y represents either N or CH) and having reduced viscosity measured by methane sulfonic acid solution of 0.5 g/100 ml at 25°C of 0.05-200 dl/g and 1-150 pts.wt. at least a metal selected from the group consisting of an alkali metal, an alkaline earth metal and a derivative thereof. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a rigid heterocyclic polymer composition and a method for producing the same.

Azole polymers are expected as polymers with excellent heat resistance and chemical resistance. There are extensive examples of introduction of polybenzobisoxazole compounds (Patent Document 1), but studies on molded articles such as composites and fibers Has not been made.
International Publication No. 85/04178 Pamphlet

  An object of the present invention is to provide a composition in which a rigid benzobisazole intermolecular ionic bond is introduced, and which is excellent in both tensile strength and compressive strength, and a molded article therefrom.

The present invention provides the following formulas (A) and / or (B)
(A)
(B)
(X represents any of O, S, and NH, Ar ¹ represents a tetravalent aromatic group having 4 to 20 carbon atoms, and Y represents either N or CH.)
100 parts by weight of a rigid heterocyclic polymer having a reduced viscosity of 0.05 to 200 dl / g measured at 25 ° C. in a methanesulfonic acid solution having a repeating unit represented by formula (0.5 g / 100 ml) and alkali A rigid heterocyclic polymer composition comprising at least one metal selected from the group consisting of metals, alkaline earth metals, and transition metals, and 1 to 150 parts by weight of a derivative thereof.

  The polymer constituting the composition of the present invention is a polymer obtained by introducing a pyridine ring and / or a pyrazine ring into the skeleton of a rigid heterocyclic polymer. By using a composition to which at least one selected metal and derivatives thereof are added, molded articles such as fibers and films having excellent mechanical properties, particularly compression properties, can be obtained.

<Rigid heterocyclic polymer composition>
The rigid heterocyclic polymer composition of the present invention has the following formulas (A) and / or (B):
(A)
(B)
(X represents any of O, S, and NH, Ar ¹ represents a tetravalent aromatic group having 4 to 20 carbon atoms, and Y represents either N or CH)
100 parts by weight of a rigid heterocyclic polymer having a reduced viscosity of 0.05 to 100 dl / g measured at 25 ° C. with a methanesulfonic acid solution having a concentration of 0.5 g / 100 ml having a repeating unit represented by the formula: A rigid heterocyclic polymer composition comprising 1 to 150 parts by weight of at least one metal selected from the group consisting of metals, alkaline earth metals, and transition metals, and derivatives thereof.

  A preferred ratio of the alkali metal, alkaline earth metal, transition metal, and derivative thereof to 100 parts by weight of the rigid heterocyclic polymer is 0.0001 to 100 parts by weight, more preferably 0.001 to 30 parts by weight.

In the above formulas (A) and (B), Ar ¹ is a tetravalent aromatic group having 4 to 20 carbon atoms, and may contain 1 to 2 nitrogen atoms.

In the above formulas (A) and (B), the aromatic group of Ar ¹ and the pyridine ring or pyrazine ring each independently have one or more of its hydrogen atoms independently halogen groups such as fluorine, chlorine and bromine, C1-C6 alkyl groups such as methyl, ethyl, propyl, and hexyl groups; C5-C10 cycloalkyl groups such as cyclopentyl and cyclohexyl groups; C6-C10 aromatics such as phenyl groups It may be substituted with a group.

Among the repeating units represented by the above formula (A), the following (A-1) is preferable.
(A-1)
(X represents any of O, S, and NH, and Y, Z ¹ , and Z ² each independently represent either N or CH.)
The repeating unit represented by these is mentioned.

Among the repeating units represented by the above formula (B), the following (B-1) is preferable.
(B-1)
(X represents any of O, S, and NH, and Y, Z ¹ , and Z ² each independently represent either N or CH.)
The repeating unit represented by these is mentioned.

In the above formulas (A-1) and (B-1), X represents any one of O, S and NH, and is preferably selected from any one of S and O. In the above formulas (A) and (B), Y, Z ¹ and Z ² are each independently selected from N and CH.

The reduced viscosity of the rigid heterocyclic polymer of the present invention has a value measured in a methanesulfonic acid solution having a concentration of 0.5 g / 100 ml at 25 ° C. in the range of 0.05 to 200 dl / g.
The preferred range of the reduced viscosity of the rigid heterocyclic polymer of the present invention is 1.0 or more and 100 or less, more preferably 10 or more and 80 or less.

  Furthermore, the rigid heterocyclic polymer of the present invention can be variously modified by adding various secondary additives as necessary. Examples of secondary additives include stabilizers, antioxidants, UV absorbers, pigments, colorants, various fillers, electrostatic agents, mold release agents, plasticizers, fragrances, antibacterial and antifungal agents, nucleation And other similar agents such as agents, lubricants, flame retardants, foaming agents, fillers and the like.

(Regarding the method for producing the wholly aromatic condensation polymer of the present invention)
The wholly aromatic condensation polymers (A) and (B) as described above can be industrially produced with good productivity according to the present invention by the following method.
That is, the following formulas (C) and (D)

(C)
(D)
(In the above formulas (C) and (D), X represents any of O, S and NH, Ar ¹ represents a tetravalent aromatic group having 4 to 20 carbon atoms, and (C) and (D) May be hydrochloride.)
At least one selected from the group consisting of an aromatic amine derivative represented by the formula:

(E)
(R ¹ and R ¹ ′ each independently represent hydrogen or an aromatic group having 6 to 20 carbon atoms.)
The method of making it react with at least 1 sort (s) of the aromatic dicarboxylic acid derivative represented by these is mentioned.

Ar ¹ in the above formulas (C) and (D) is the same as Ar ¹ described for the composition of the wholly aromatic azole, and R ¹ and R ¹ ′ in the general formula (E) are each independently hydrogen. Alternatively, it represents a monovalent aromatic group having 4 to 20 carbon atoms, and specific examples of the aromatic group include phenylene group, naphthalene group, biphenylene group, isopropylidene diphenyl group, diphenyl ether group, diphenyl sulfide group, diphenyl sulfone group, diphenyl ketone. Group. One or more hydrogen atoms of these aromatic groups are each independently a halogen group such as fluorine, chlorine or bromine; an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group or a hexyl group; It may be substituted with a C5-C10 cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; an alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group.

In the pyridine ring or pyrazine ring in the above formula (E), one or more of the hydrogen atoms are independently halogen groups such as fluorine, chlorine, bromine, methyl group, ethyl group, propyl group, hexyl group, etc. An alkyl group having 1 to 6 carbon atoms; a cycloalkyl group having 5 to 10 carbon atoms such as a cyclopentyl group and a cyclohexyl group; and an aromatic group having 6 to 10 carbon atoms such as a phenyl group.
The aromatic amine derivative represented by the above formula (C) is

(Z ¹ and Z ² each independently represent N or CH.)
Or its dihydrochloride, and / or

(Z ¹ and Z ² each independently represent N or CH.)
Or its dihydrochloride is preferable.
Moreover, the aromatic amine derivative represented by (D) is

(Z ¹ and Z ² each independently represent N or CH.)
Or its dihydrochloride, and / or

(Z ¹ and Z ² each independently represent N or CH.)
Or its dihydrochloride is preferable.

The number of moles of each monomer (reaction component) is the above formula (1)
The following mathematical formula (1)
0.8 ≦ (c + d) /e≦1.2 (1)
(Wherein c is an aromatic amine derivative represented by the above formula (C), d is an aromatic amine derivative represented by the above formula (D), and e is an aromatic dicarboxylic acid represented by the above formula (E). (The number of moles charged for each acid derivative.)
When (c + d) / e is preferably smaller than 0.8 or larger than 1.2, it may be difficult to obtain a polymer having a sufficient degree of polymerization. The lower limit of (c + d) / e is suitably 0.9 or more, more preferably 0.93 or more, and even more preferably 0.95 or more. Moreover, as an upper limit of (c + d) / e, 1.1 or less is suitable, More preferably, it is 1.07 or less, More preferably, it is 1.05 or less. Therefore, it can be said that the optimum range of (c + d) / e in the present invention is 0.95 ≦ (c + d) /e≦1.05.

  (C) and (D) may be used alone or in combination, and the molar ratio of (C) :( D) can be appropriately selected at an arbitrary ratio of 0: 100 to 100: 0.

  For the reaction, either a reaction performed in a solvent or a solvent-free heating and melting reaction can be employed. For example, it is preferable to carry out a heating reaction in a reaction solvent described later with stirring. The reaction temperature is preferably 50 ° C to 500 ° C, more preferably 100 ° C to 350 ° C. This is because if the temperature is lower than 50 ° C., the reaction does not proceed, and if the temperature is higher than 500 ° C., side reactions such as decomposition tend to occur. Although the reaction time depends on temperature conditions, it is usually 1 hour to several tens of hours. The reaction can be carried out from under pressure to under reduced pressure.

  The reaction usually proceeds even without a catalyst, but a transesterification catalyst may be used if necessary. Examples of transesterification catalysts used in the present invention include antimony compounds such as antimony trioxide, stannous acetate, tin chloride, tin octylate, tin compounds such as dibutyltin oxide and dibutyltin diacetate, and alkaline earth metal salts such as calcium acetate. And phosphorous acid such as alkali metal salts such as sodium carbonate and potassium carbonate, diphenyl phosphite and triphenyl phosphite. A preferable addition amount of the catalyst is about 0.0001 to 0.1 mol per 1 mol of the dicarboxylic acid component.

  In the reaction, a solvent can be used as necessary. Preferred solvents include 1-methyl-2-pyrrolidone, 1-cyclohexyl-2-pyrrolidone, dimethylacetamide, dimethyl sulfoxide, diphenyl ether, diphenyl sulfone, dichloromethane, chloroform, tetrahydrofuran, o-cresol, m-cresol, p-cresol, Although phosphoric acid, polyphosphoric acid, etc. can be mentioned, it is not limited to this.

  In order to prevent decomposition and coloring of the rigid heterocyclic polymer, the reaction is desirably performed in a dry inert gas atmosphere.

  The reduced viscosity of the rigid heterocyclic polymer thus produced has a value measured in a methanesulfonic acid solution having a concentration of 0.5 g / 100 ml at 25 ° C. in the range of 0.05 to 200 dl / g. It is. The preferred range of the reduced viscosity of the rigid heterocyclic polymer of the present invention is 1.0 or more and 100 or less, more preferably 10 or more and 80 or less.

(Metals and their derivatives)
As the at least one metal selected from the group consisting of alkali metals, alkaline earth metals, and transition metals used in the present invention, and derivatives thereof, metal salts that form complexes with organic nitrogen compounds can be preferably used. Specifically, alkali metals, alkaline earth metals, 4th period, 5th period, 6th period transition metal halides, hydroxides, hydrides, carbon monoxide, carbonates, acetates, Nitrate, nitrite, sulfite, cyanate, thiocyanate, stearate, borohydride, benzoate, hydrogen phosphate, bisphenol, phenol salt etc. and hydrates thereof Specific examples include lithium chloride, cupric chloride, and cobalt chloride, but are not limited thereto. Moreover, you may use these together.

  The metal used in the present invention and its derivative are preferably used in an amount of 0.1 to 10 mol per mol of the polymer unit. If the amount is less than 0.01 mol, the desired physical properties are not expected to be expressed. If the amount is more than 10 mol, the moldability is lowered and the physical properties of the molded product may be lowered.

(Method of kneading polymer and metal and derivatives thereof)
The polymer, metal, and derivatives thereof obtained by the above means can be kneaded by any conventionally known method, and a conventionally known kneading apparatus such as a single screw ruder, two screw ruder, or homogenizer can be used. . It is also preferable to perform polymerization by adding the above-mentioned metal and its derivative to a polymerization solvent in advance before the reaction of the polymer.

  Further, it is also preferable to use a metal such as a metal salt dissolved in a washing bath in a wet or dry jet spinning process.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited at all by these. In addition, each measured value in the following examples is a value obtained by the following method.
(1) Reduced viscosity: a value measured at 25 ° C. with a methanesulfonic acid solution having a concentration of 0.5 g / 100 ml.
(2) Mechanical properties: Nodule strength and tensile strength were determined using a Tensilon universal testing machine 1225A manufactured by Orientec Corporation. Knot strength / tensile strength: A value obtained by dividing the knot strength by the tensile strength was used as an index of fiber isotropicity.

<Reference Example 1> (Synthesis of monomer)
7 parts by weight of 4,6-diamino-1,3-benzenediol dihydrochloride was dissolved in 33 parts by weight of water deaerated with nitrogen. 5.347 parts by weight of pyridinedicarboxylic acid was dissolved in 64 parts by weight of 1M aqueous sodium hydroxide solution and degassed with nitrogen. An aqueous solution of 4,6-diamino-1,3-benzenediol dihydrochloride is dropped into an aqueous solution of disodium pyridinedicarboxylic acid over 10 minutes, and 4,6-diamino-1,3-benzenediol / pyridinedicarboxylate is added. Of white precipitate formed. At this time, the reaction temperature was maintained at 90 ° C. The obtained salt was filtered, dispersed and mixed in 3000 parts by weight of water deaerated with nitrogen, and filtered again. This dispersion mixing and filtration operation was repeated three times.

<Reference Example 2>
To 13.1 parts by weight of the pyridinedicarboxylate of 4,6-diamino-1,3-benzenediol obtained in Reference Example 1, 43.3 parts by weight of polyphosphoric acid, 15.0 parts by weight of phosphorus pentoxide, and chloride 0.1 part by weight of tin was added and stirred and mixed at 80 ° C. for 1 hour. Thereafter, the temperature was raised to 150 ° C. over 2 hours and stirred at 150 ° C. for 6 hours. Thereafter, the temperature was raised to 200 ° C. over 1 hour, and the reaction was carried out at 200 ° C. for 1 hour. The polymer obtained had a reduced viscosity of 36 dl / g.

<Reference Example 3>
To 13.1 parts by weight of the pyridinedicarboxylate of 4,6-diamino-1,3-benzenediol obtained in Reference Example 1, 43.3 parts by weight of polyphosphoric acid, 15.0 parts by weight of phosphorus pentoxide, and chloride The same operation as in Reference Example 2 was performed except that 1.82 parts by weight of lithium chloride was used for 0.1 parts by weight of tin. The polymer obtained had a reduced viscosity of 40 dl / g.

[Example 1]
The polymer dope obtained in Reference Example 2 was extruded into a coagulation bath of ion-exchanged water at 2.0 / min while maintaining a dope temperature of 180 ° C. using a cap having a hole diameter of 0.5 mm and one hole. The distance between the cap surface and the coagulation bath was 20 cm. The extruded fiber was wound up in a water washing bath made of a 10 wt% aqueous solution of lithium chloride at 100 m / min and washed in an aqueous solution for 3 hours to obtain a filament.

[Example 2]
The same operation as in Example 1 was performed except that 10 wt% cupric chloride was used in the water washing bath.

[Example 3]
The same operation as in Example 1 was performed except that the polymer dope obtained in Reference Example 3 was used and wound at 200 m / min.

[Comparative Example 1]
The same operation as in Example 1 was performed except that the polymer dope obtained in Reference Example 2 was used and wound up in a washing bath of ion-exchanged water at 50 m / min.

Claims (9)

The following formula (A) and / or (B)
(A)
(B)
(X represents any of O, S, and NH, Ar ¹ represents a tetravalent aromatic group having 4 to 20 carbon atoms, and Y represents either N or CH.)
100 parts by weight of a rigid heterocyclic polymer having a reduced viscosity of 0.05 to 200 dl / g measured at 25 ° C. in a methanesulfonic acid solution having a repeating unit represented by formula (0.5 g / 100 ml) and alkali A rigid heterocyclic polymer composition comprising 1 to 150 parts by weight of at least one metal selected from the group consisting of metals, alkaline earth metals, and transition metals, and derivatives thereof. The repeating unit represented by the above formula (A) is represented by the following formula (A-1)
(A-1)
(X represents any of O, S, and NH, and Y, Z ¹ , and Z ² each independently represent either N or CH.)
The rigid heterocyclic polymer composition according to claim 1. The repeating unit represented by the above formula (B) is represented by the following formula (B-1)
(B-1)
(X represents any of O, S, and NH, and Y, Z ¹ , and Z ² each independently represent either N or CH.)
The rigid heterocyclic polymer composition according to claim 1. Following formula (C), (D)
(C)
(D)
(X represents any of O, S and NH, Ar ¹ represents a tetravalent aromatic group having 4 to 20 carbon atoms, and (C) and (D) may be hydrochlorides.)
At least one selected from the group consisting of an aromatic amine derivative represented by the formula:
(E)
(R ¹ and R ¹ ′ each independently represent hydrogen or an aromatic group having 6 to 20 carbon atoms, and Y represents either N or CH.)
At least one aromatic dicarboxylic acid derivative represented by:
Following formula (1)
0.8 ≦ (c + d) /e≦1.2 (1)
(Wherein c is an aromatic amine derivative represented by the above formula (C), d is an aromatic amine derivative represented by the above formula (D), and e is an aromatic dicarboxylic acid represented by the above formula (E). (The number of moles charged for each acid derivative.)
To produce a rigid heterocyclic polymer, and at least one selected from the group consisting of alkali metals, alkaline earth metals, and transition metals with respect to 100 parts by weight of the obtained rigid heterocyclic polymer. The method for producing a rigid heterocyclic polymer composition according to claim 1, wherein 1 to 150 parts by weight of a seed metal and a derivative thereof are added. The aromatic amine derivative represented by the above formula (C) is
(Z ¹ and Z ² each independently represent N or CH.)
Or its dihydrochloride, and / or
(Z ¹ and Z ² each independently represent N or CH.)
The method for producing a rigid heterocyclic polymer composition according to claim 4, which is a dihydrochloride thereof. The aromatic amine derivative represented by (D) is
(Z ¹ and Z ² each independently represent N or CH.)
Or its dihydrochloride, and / or
(Z ¹ and Z ² each independently represent N or CH.)
The method for producing a rigid heterocyclic polymer composition according to claim 4, which is a dihydrochloride thereof.   A molded product obtained from the rigid heterocyclic polymer composition according to claim 1.   The molded body according to claim 7, wherein the molded body is a fiber.   The molded body according to claim 7, wherein the molded body is a film.