JP2680034B2 - Method for producing crosslinked resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to a method for producing a crosslinked resin, and more specifically, a crosslinked resin excellent in heat resistance, chemical resistance and mechanical properties is rapidly crosslinked. And a method of manufacturing with excellent moldability.

<Prior Art> In recent years, with the progress of technology, a resin having excellent heat resistance and mechanical properties and excellent moldability has been demanded. Among these resins, a reaction-molding type resin using a reactive monomer or oligomer, that is, a resin in which molding and polymerization are simultaneously performed by using a relatively low-viscosity raw material has attracted attention. As such resins, polyurethane resins, polyurea resins, nylon resins, epoxy resins, unsaturated polyester resins and the like are known, and some of them are commercialized.

However, each of these resins has advantages and disadvantages, for example, polyurethane resins have low heat resistance, and unsaturated polyester resins have drawbacks such as reaction, that is, molding takes time, and thus they do not always have sufficient performance and moldability. It cannot be said that

On the other hand, thermoplastic resins such as polyamide, polyester, polysulfone, polyether sulfone, polyether imide, polyarylate, polyphenylene sulfide, and polyether ketone are known as polymers that are melt-moldable and have excellent mechanical properties. Polymers have insufficient heat resistance as compared with thermosetting resins, and also have problems in chemical resistance and the like.

<Purpose of the Invention> The present inventors have conducted extensive studies to develop a novel resin having advantages of a thermoplastic resin, particularly moldability and thermosetting resin, particularly heat resistance, and chemical resistance. By heating and reacting a composition comprising a thermoplastic linear oligomer or linear polymer and a polyoxazoline derivative and / or polyoxazine derivative in the presence of a specific catalyst, the composition is tough and heat-resistant. The inventors have found that a crosslinked resin excellent in chemical resistance and the like can be formed quickly and easily, and have reached the present invention.

Therefore, an object of the present invention is to provide a method for producing a crosslinked resin having the above-mentioned characteristics.

<Structure of the Invention> The production method of the present invention has (A) at least one group selected from the group consisting of an aromatic amino group, an aromatic aminomethyl group and a hydroxyl group at the terminal, and is substantially linear. And a melting point of 300 ° C. or lower and an intrinsic viscosity of 0.05 to
A thermoplastic polymer and / or oligomer of 0.7, and (B) the following formula (I) The polycyclic imino ether represented by the formula (C) is represented by the following formula (II) A halogenophenol compound represented by the following formula (III) And a halogenophthalic acid compound represented by the following formula (IV) [Wherein the definitions of X ₃ , X ₄ and l are the same as above. ] It is a manufacturing method of the crosslinked resin characterized by making it heat-react in the presence of the compound which acts as a catalyst of at least 1 sort (s) selected from the group which consists of halogenophthalic anhydride represented by these.

 Hereinafter, the present invention will be described in detail.

Examples of the thermoplastic polymer and / or oligomer used as the component A in the present invention include aromatic polyester, polyamide, aromatic polycarbonate, polysulfone, polyether, polyethersulfone, polyetherimide, polyolefin, acrylic resin and the like. Yes, but of these, the glass transition point (Tg) is
It is preferably 50 ° C. or higher. This glass transition point (T
The higher the g) is, the higher the heat resistance of the crosslinked resin obtained is. Therefore, it is more preferable that the glass transition point (Tg) is 100 ° C. or higher.

In the method of the present invention, the thermoplastic polymer or oligomer used as the component A contains 50% of all end groups at the molecular ends.
% Or more, more preferably 60% or more, particularly preferably 70%
It is preferable to have a functional group capable of non-reacting with the polycyclic imino ether (B) represented by the formula (I) in the above proportions. Examples of such a functional group include an amino group, a carboxyl group and a hydroxyl group. The amino group is preferably an aromatic amino group or an aromatic aminomethyl group.

Aromatic amino terminal is aminophenyl Amino naphthyl It is particularly preferable that the terminal is aminophenyl terminal. Aromatic aminomethyl end is aminomethylphenyl Aminomethylnaphthyl Etc., and it is particularly preferable that the terminal is aminomethylphenyl.

As a method for blocking the ends of the thermoplastic oligomer or polymer with an aromatic amino group and / or an aromatic aminomethyl group, various conventionally known chemical reactions can be used.

For example, in the case of an oligomer or polymer having a carboxyl group or an amide-forming functional group thereof, such as an ester or an acid halogen, at a terminal thereof, by reacting with a diamino compound having an aromatic amino group and / or an aromatic aminomethyl group. Can be preferably achieved, and in the case of an oligomer or polymer having an isocyanate terminal, it can be preferably achieved by similarly reacting a diamino compound.

The carboxyl group may be an aliphatic, alicyclic or aromatic carboxylic acid, and the polymer or oligomer having a terminal carboxyl group can be produced by various conventionally known methods.

The hydroxyl group may be an aromatic hydroxyl group, an alicyclic hydroxyl group, or an aliphatic hydroxyl group. Hydroxyphenyl as the aromatic hydroxyl group Hydroxy naphthyl Examples include substituted hydroxyphenyl and substituted hydroxynaphthyl. The substituent used here is not particularly limited, and examples thereof include an alkyl group having 1 to 6 carbon atoms and 6 to 12 carbon atoms.
Aryl group, halogen, sulfonyl group And the like. Among them, a functional group that lowers the pKa value to a hydroxyl group, such as a halogen, a sulfonyl group, or a carbonyl group, for example, a 2,6-dichloro-hydroxyphenyl group. 2,6-dibromo-hydroxyphenyl group Hydroxyphenylsulfonyl group Hydroxyphenylcarbonyl group Are most preferred. Specific examples of the alicyclic hydroxyl group include hydroxycyclohexyl and hydroxycyclopentyl.

Specific examples of the aliphatic hydroxyl group include hydroxyalkyl, substituted hydroxyalkyl, hydroxymethylphenyl, hydroxymethylnaphthyl, substituted hydroxymethylphenyl, substituted hydroxymethylnaphthyl and the like. Here, the substituent is the same as in the case of the substituted hydroxyphenyl.

As a method for producing an oligomer or polymer having a terminal hydroxyl group, various conventionally known chemical reactions can be used. For example, in the case of producing an oligomer or polymer having polysulfone as the main chain and having a hydroxyphenyl group at the terminal, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) and dichlorodiphenylsulfone are used as the former It can be easily and preferably achieved by charging and polymerizing in a mole number larger than the latter.

In the present invention, the terminal group is preferably an aromatic amino group, an aromatic aminomethyl group, a carboxyl group or a hydroxyl group, and particularly preferably an aromatic amino group, an aromatic methylamino group or a hydroxyl group.

The degree of polymerization of the thermoplastic polymer or oligomer used in the present invention is preferably about 0.05 to 0.7 in terms of intrinsic viscosity. The melting point is preferably 300 ° C. or lower, and particularly preferably 280 ° C. or lower. Further, the thermoplastic polymer or oligomer used in the present invention is preferably linear.

In the present invention, a polycyclic imino ether is used as the B component in combination with the A component as described above.

The polycyclic iminoether represented by the above formula (I) used in the method of the present invention has the following formula (I1) when Z is a direct bond. Represents an oxazoline represented by the formula: When the following formula (I2 Oxazines represented by

In the above formula (I) (in the formulas (including I1 and (I2)), R is an n-valent hydrocarbon residue. This hydrocarbon residue is an atom other than a carbon atom or a group containing an atom other than a carbon atom. It may be interrupted or substituted, n is 2 to 4
Is an integer. Therefore, an n-valent hydrocarbon residue is 2
Is a trivalent, trivalent or tetravalent hydrocarbon residue. However, when n is 2, R can represent a direct bond.

The hydrocarbon residue may be, for example, aliphatic, alicyclic or aromatic. Preferably, it is an aliphatic group having 1 to 10 carbon atoms, an alicyclic group having 5 to 10 carbon atoms, or an aromatic group having 6 to 12 carbon atoms.

As the hydrocarbon residue, when n = 2, for example, an alkylene group having 1 to 10 carbon atoms such as methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, hexamethylene, neopentylene and decamethylene; cyclohexylene, A divalent alicyclic group having 5 to 10 carbon atoms such as: p-phenylene, m
-C6-C12 divalent aromatic hydrocarbon groups such as phenylene, naphthylene and biphenylene can be mentioned as preferable ones. Similarly, when n = 3, for example, Are preferred.

Further, when n = 4, for example, Are preferred.

The hydrocarbon residue as described above may be interrupted by an atom other than carbon atom such as oxygen atom, sulfur atom or -NRg-. Rg is a hydrogen atom or a monovalent hydrocarbon such as an alkyl group.

Further, the hydrocarbon residue as described above may be substituted with a group containing an atom other than carbon atom.

Examples of such a substituent include chloro, bromo,
Examples include nitro, methoxy, cyano, amide, acetamide and the like.

In the above formula (I), Ra, Rb, Rc, Rd, Re and Rf
Are the same or different and are a hydrogen atom, methyl, ethyl, propyl, phenyl, tolyl or benzyl. Among these, a hydrogen atom or methyl is preferable, and it is more preferable that all are hydrogen atoms or one is methyl and all the others are hydrogen atoms.

Examples of the polycyclic imino ether of the above formula (I) include the following compounds.

Examples of oxazolines of formula (I1; 2,2'-bis (2-
Oxazoline), 2,2'-ethylenebis (2-oxazoline), 2,2'-tetramethylenebis (2-oxazoline), 2,2'-hexamethylenebis (2-oxazoline), 2,2'-octa Methylenebis (2-oxazoline), 2,2'-1,4-cyclohexylenebis (2-oxazoline), 2,2'-bis (4-methyl-2-oxazoline), 2,2'-bis (5 -Methyl-2-oxazoline),
2,2'-m-phenylene bis (2-oxazoline), 2,
2'-p-phenylenebis (2-oxazoline), 2,2 '
-M-phenylenebis (4-methyl-2-oxazoline), 2,2'-m-phenylenebis (5-methyl-2-oxazoline), 2,2'-p-phenylenebis (4-methyl-2-) Oxazoline), 2,2'-p-phenylenebis (5
-Methyl-2-oxazoline), 1,3,5-tris (2-oxazolinyl-2) benzene and the like.

Of these, 2,2'-bis (2-oxazoline), 2,
2'-tetramethylenebis (2-oxazoline), 2,2 '
-M-phenlenebis (2-oxazoline), 2,2'-p
-Phenylenebis (2-oxazoline) is preferred.

Examples of oxazines of formula (I2; 2,2'-bis (5,6-
Dihydro-4H-1,3-oxazine), 2,2'-ethylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2'-tetramethylenebis (5,6-dihydro-4H -1,3-oxazine), 2,2'-hexamethylenebis (5,6-dihydro-4H
-1,3-oxazine), 2,2-octamethylenebis (5,6-
Dihydro-4H-1,3-oxazine), 2,2'-1,4-cyclohexylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2'-bis (4-methyl- 5,6-dihydro-4H-
1,3-Oxazine), 2,2'-bis (5-methyl-5,6-dihydro-4H-1,3-oxazine), 2,2'-bis (6-methyl-5,6-dihydro- 4H-1,3-oxazine), 2,2'-
m-Phenylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2'-p-phenylenebis (5,6-dihydro-4)
H-1,3-oxazine), 2,2'-m-phenylenebis (4
-Methyl-5,6-dihydro-4H-1,3-oxazine), 2,
2'-m-phenylene bis (5-methyl-5,6-dihydro-4H-1,3-oxazine), 2,2'-m-phenylene bis (6-methyl-5,6-dihydro-4H-1) , 3-Oxazine), 2,2'-p-phenylenebis (4-methyl-5,6-
Dihydro-4H-1,3-oxazine), 2,2'-p-phenylenebis (5-methyl-5,6-dihydro-4H-1,3-oxazine), 2,2'-p-phenylenebis ( 6-methyl-5,
6-dihydro-4H-1,3-oxazine) and the like.

Of these, 2,2'-bis (5,6-dihydro-4H-1,3
-Oxazine), 2,2'-tetramethylene bis (5,6-dihydro-4H-1,3-oxazine), 2,2'-m-phenylene bis (5,6-dihydro-4H-1,3- Oxazine), 7-p
-Phenylenebis (5,6-dihydro-4H-1,3-oxazine) is preferred.

In the present invention, the polycyclic imino ethers may be used alone or in combination of two or more. When two or more kinds are used in combination, oxazolines and oxazines or oxazolines and oxazines can be used.

In the method of the present invention, in addition to the polycyclic iminoether, if necessary, the monocyclic iminoether is used in an amount of 30 mol% or less, preferably 25 mol% or less, more preferably 20 mol% or less based on the polycyclic iminoether. be able to.

Examples of such monocyclic imino ethers include compounds represented by the following formula (I′1) And a monooxazoline compound represented by the following formula (I′2) The monooxazine compound represented by is preferably used. By using such a monocyclic imino ether, it becomes possible to advantageously carry out the control of the reaction and the adjustment of the crosslinking density.

In the above formulas (I′1 and (I′2), R ′ is a monovalent hydrocarbon residue. The hydrocarbon residue may be, for example, aliphatic, alicyclic or aromatic. .
Preferably, it is an aliphatic group having 1 to 10 carbon atoms, an alicyclic group having 5 to 10 carbon atoms, or an aromatic group having 6 to 12 carbon atoms.

Such monocyclic imino ethers include, for example, 2
-Methyl-2-oxazoline, 2-ethyl-2-oxazoline, 2-propenyl-2-oxazoline, 2-phenyl-2-oxazoline, 2-tolyl-2-oxazoline, 2,5-dimethyl-2-oxazoline, 2 , 4-Dimethyl-2-oxazoline, 2-phenyl-4-methyl-2-
Monooxazolines such as oxazoline, 2-phenyl-5-methyl-2-oxazoline; and 2-methyl-
5,6-Dihydro-4H-1,3-oxazoline, 2-ethyl-
5,6-dihydro-4H-1,3-oxazine, 2-propenyl-5,6-dihydro-4H-1,3-oxazine, 2-phenyl-5,6-dihydro-4H-1,3-oxazine, 2-tolyl-
5,6-dihydro-4H-1,3-oxazine, 2-phenyl-
4-methyl-5,6-dihydro-4H-1,3-oxazine, 2
Mention is made of monooxazines such as -phenyl-5-methyl-5,6-dihydro-4H-1,3-oxazine, 2-phenyl-6-methyl-5,6-dihydro-4H-1,3-oxazine You can

Of these, 2-phenyl-2-oxazoline, 2
-Tolyl-2-oxazoline, 2-phenyl-5,6-dihydro-4H-1,3-oxazine and 2-tolyl-5,6-dihydro-4H-1,3-oxazine are preferred.

The use ratio of the thermoplastic oligomer or polymer which is the A component of the present invention and the polycyclic imino ether which is the B component varies depending on these types, but the weight ratio of A component / B component is 90/10 to 30/70. Further, it is preferably about 80/20 to 40/60.

The crosslinked resin of the present invention is a composition in which the thermoplastic oligomer or polymer of the component A and the polycyclic iminoether of the component B are uniformly melt-mixed to obtain a composition having a flow starting temperature of 160 ° C or lower. Then, the composition thus prepared is heated and reacted in the presence of a compound which acts as a catalyst of the component C.

Examples of the compound (C) that acts as a catalyst include the following compound groups.

The following formula (II) A halogenophenol represented by the following formula (III) And a halogenophthalic acid represented by the following formula (IV) [Wherein the definitions of X ₃ , X ₄ and l are the same as above. ] The halogenophthalic anhydride represented by these.

The halogenophenol (i) represented by the above formula (II) is one of the suitable catalysts.

In the above formula (II), X ¹ and X ² are the same or different and each is a halogen atom. As the halogen atom, for example, chlorine atom and bromine atom are particularly preferable. m is 0,1
Or a number of two. m is preferably 1. Further, in that case (m = 1), with respect to the hydroxyl group in the formula (II)
It is particularly preferred that X ₂ is bonded at the ortho position.

Y is -SO ₂ R _1, -COR _2, -CN, or -NO _2.

The above formula (II) can be represented by the following formulas according to these definitions of Y.

[Here, the definitions of X ¹ , X ² and m are as described above. ] [Here, the definitions of X ¹ , X ² and m are as described above. ] In the above formula (II1, the alkyl having 1 to 20 carbon atoms of R ₁ may be linear or branched. Alkyl having 1 to 10 carbons is preferable. Methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-
Butyl, n-pentyl, n-hexyl, n-heptyl,
Examples thereof include n-octyl, n-nonyl, n-decyl and n-dodecyl. These alkyl groups may be substituted with a substituent such as a halogen, a hydroxyl group, a carboxyl group, a nitro group, a cyano group, an amino group, an alkoxy group, an alkoxycarbonyl group, an acyl group and an acyloxy group.

Examples of the aryl having 6 to 12 carbon atoms of R ₁ include phenyl, tolyl, naphthyl and the like. These aryl groups may be substituted with the same substituents as those exemplified above as the substituent of the alkyl group.

R ₁ represents a group —NR ₃ R ₄ R ₃ or R ₄ optionally substituted alkyl having 1 to 12 carbons and aryl having 6 to 12 carbons are the same as those described above for R _1. The thing can be illustrated. Further, the cycloalkyl having 5 to 10 carbon atoms of R ₃ or R ₄ includes, for example, cyclopentyl, cyclohexyl, And the like.

Examples of the compound of the above formula (II1 include bis (3,5
-Dichloro-4-hydroxyphenyl) sulfone, bis (3,5-dibromo-4-hydroxyphenyl) sulfone, 3,5-dichrome-4-hydroxybenzenesulfonic acid amide, 3,5-dibromo-4-hydroxybenzenesulfone Examples thereof include acid amide and 3,5-dibromo-4-hydroxybenzenesulfonic acid N-methylamide.

As the above formula (II2, R ₂ optionally substituted alkyl having 1 to 20 carbons, cycloalkyl having 5 to 10 carbons, and aryl having 6 to 12 carbons are represented by the above formula (II1). The same group as can be illustrated.
Also, as the group —NR ₆ R ₇ , the same groups as those described above for the group —NR ₃ R ₄ can be exemplified.

Examples of the group —OR ₅ of R ₂ and R ₅ include the same groups as those described above for the groups R ₃ and R ₄ .

As the compound of the above formula (II2, for example, bis (3,5
-Dichloro-4-hydroxyphenyl) ketone, bis (3,5-dibromo-4-hydroxyphenyl) ketone,
Methyl 3,5-dichloro-4-hydroxybenzoate, 3,5-
Methyl dibromo-4-hydroxybenzoate, methyl 3,5-dibromo-4-hydroxybenzoate, 3,5-dibromo-4-hydroxybenzoic acid amide, 3,5-dibromo-4
-Hydroxybenzoic acid N-ethylamide, 3,5-dibromo-4-hydroxybenzoic acid and the like can be mentioned.

Examples of the compound of the above formula (II3) include 3,5-dichloro-4-hydroxy-benzonitrile and 3,5-dibromo-4-hydroxybenzonitrile.

Examples of the compound of the above formula (II4) include 3,5-dichloro-4-hydroxynitrobenzene and 3,5-dibromo-4-hydroxynitrobenzene.

Among the halogenophenols represented by the above formula (II), those having a 4-hydroxy-3,5-dichlorophenyl skeleton or a 4-hydroxy-3,5-dibromophenyl skeleton are preferable, and particularly those represented by the above formula (II1) The compound, especially (3,5-dibromo-4-hydroxyphenyl) sulfone, is particularly preferred.

The halogenophthalic acids represented by the above formula (III) and / or the halogenophthalic anhydride represented by the above formula (IV) are also suitable catalysts.

In formula (III), X ₃ and X ₄ are the same halogen atoms as defined for X ₁ , eg chlorine or bromine. l is a number 0, 1, 2 or 3. Of these, l
Is preferably 1, 2 or 3, and particularly preferably 2 or 3. In the formula (III), R ₈ has the same definition as R _{2 in} the above formula (II), and therefore R ₈ can be the same groups as those exemplified for R ₂ .

In formula (IV), the definitions of X ₃ , X ₄ and l are the same as those in formula (III).

Examples of the compounds represented by the formulas (III) and (IV) include the following compounds.

(I) dicarboxylic acids and their anhydrides; eg 3,4,5,6
-Tetrabromo (or tetrachloro) phthalic acid, 3,4,
5,6-Tetrabrom (or tetrachlor) -phthalic anhydride, 3,4,5-Tribrom (or trichlor) -phthalic acid, 3,4,5-Tribrom (or trichlor) -phthalic anhydride, 3,4 , 6, -Tribromo (or trichloro) -phthalic acid, 3,4,6, -tribromo (or trichloro) -phthalic anhydride and the like.

(Ii) dicarboxylic acid monoester; for example, 3,4,5,6-tetrabromo (or tetrachloro) -phthalic acid monomethyl ester, 3,4,5,6-tetrabromo (or tetrachloro) -phthalic acid monoethyl castel, 3, 4,5,6-Tetrabromo (or tetrachloro) -phthalic acid monopropyl ester, 3,4,5,6-Tetrabromo (or tetrachloro) -phthalic acid monoisopropyl ester, 3,4,5,6
-Tetrabrom (or tetrachloro) -phthalic acid monobenzyl ester, 3,4,5,6-tetrabromo (or tetrachloro) -phthalic acid monophenyl ester and the like.

(Iii) dicarboxylic acid monoamide; for example, 3,4,5,6-tetrabromo (or tetrachloro) -phthalic acid monoamide, N-methyl-3,4,5,6-tetrabromo (or tetrachloro) -phthalic acid monoamide, N- Ethyl-3,4,5,
6-Tetrabromo (or tetrachloro) -phthalic acid monoamide, N-propyl-3,4,5,6-tetrabromo (or tetrachloro) -phthalic acid monoamide, N-phenyl-3,4,5,6-tetrabromo (or tetrachloro) ) −
Phthalic acid monoamide and the like.

(Iv) ketocarboxylic acids; for example 2-carboxy-3,4,5,
6-Tetrabrom (or tetrachloro) -phenylmethylketone, 2-carboxy-3,4,5,6-tetrabrom (or tetrachloro) -phenylethylketone and the like.

Of these, the above dicarboxylic acids and their anhydrides are preferable, tetrachlorophthalic acids, tetrabromophthalic acids and their anhydrides are more preferable, and among them, 3,4,
5,6-tetrabromo (or tetrachloro) phthalic acid,
3,4,5,6-Tetrabrom (or tetrachloro) phthalic anhydride is particularly preferred. In the method of the present invention, the catalyst (C) may be used alone or in combination of two or more.
The catalyst (C) is based on the polycyclic imino ether (B)
It is usually used in a proportion of 0.01 to 20 mol%, preferably 0.1 to 10 mol%.

In the present invention, the flow disclosure temperature is a temperature at which a polymer can be melt extruded under a pressure of 100 kg / cm ² using a flow tester equipped with a nozzle having a diameter of 0.5 mm and a length of 1 mm.
If the flow starting temperature of the composition exceeds 160 ° C, the melting stability after addition of a catalyst to the composition decreases, so the lower the better, the more preferable flow starting temperature is 150 ° C or lower, and the particularly preferable flow rate. The starting temperature is below 140 ° C.

As the heating reaction method, the composition composed of the component A and the component B and the catalyst are physically and uniformly mixed, or they are melt-mixed at a temperature not lower than the flow starting temperature of the composition and not higher than 160 ° C. to form a reaction composition. A preferable example is a method in which a reaction product is obtained, and then the reaction composition is filled in a mold having a desired shape and reacted by heating. In the method of obtaining this reaction composition, A
The thermoplastic oligomer or polymer of the component generally has a high flow starting temperature (160 ° C. or higher), but the composition is formed by plasticizing by uniformly mixing the component B polycyclic iminoether with the component. Since the starting temperature of the flow of the substance can be lowered, the oligomer or polymer of the component A and the polycyclic iminoether of the component B are melt-mixed at a temperature equal to or higher than the melting point of the component A.
A more preferable example is a method of mixing the catalyst at a temperature of ℃ or less.

The heating reaction temperature of this reactive composition is preferably 160 ° C. or higher, more preferably 170 ° C. or higher, and particularly preferably 180 ° C. or higher.

The reaction time may be any time as long as the target resin is sufficiently cured, and this time depends on the type of raw material used,
It varies depending on the use ratio, reaction temperature, etc., but is preferably
10 seconds / 60 minutes, more preferably 20 seconds to 30 minutes, particularly preferably 30 seconds to 15 minutes. The reaction can be performed under normal pressure to pressure.

Incidentally, the cross-linking resin of the present invention, if necessary, carbon fiber, reinforcing agents such as glass fibers, various fillers, fillers, pigments, colorants, oxidation stabilizers, ultraviolet absorbers, additives such as release agents May be appropriately mixed.

<Effect of the Invention> The crosslinked resin thus obtained is, for example, in the state where the crosslinked polymer of the polycyclic imino ether of the component B and the oligomer or polymer of the component A are molecularly entangled, and the crosslinked polymer and the component A are It has a higher heat distortion temperature than the oligomer or polymer of component A, and has excellent chemical resistance and mechanical properties.

<Examples> Hereinafter, the present invention will be described in detail with reference to examples, but the examples are for the purpose of description and the present invention is not limited thereto.

In the examples, "part" means "part by weight", and the heat distortion temperature is a value measured by DMA (Dynamic Thermomechanical Property Measuring Device) at a temperature rising rate of 10 ° C / min.

Example 1 318 parts of diphenylisophthalate and 104 parts of hexamethylenediamine were charged in a reactor equipped with a stirrer, and the mixture was placed in a nitrogen stream 2
The mixture was heated to 50 ° C., and the reaction was carried out for 30 minutes while distilling the phenol produced by the reaction out of the system.

Next, 40 parts of 4,4'-diaminodiphenyl ether was added and the reaction was further continued for 60 minutes. The obtained polymer had an intrinsic viscosity of 0.37 and a heat distortion temperature of 132 ° C. Next, 70 parts of the polymer chip and 30 parts of m-phenylenebis (2-oxazoline) were mixed and melt-extruded at 200 ° C. using a biaxial ruder. The flow starting temperature of the obtained composition was 124 ° C.

Then, 100 parts of the composition was uniformly mixed with 5 parts of bis (3,5-dibromo-4-hydroxyphenyl) sulfone, and the mixture was mixed at 180 ° C.
It was melted in and was extruded into a mold heated to 200 ° C. After 15 minutes, the mold was cooled to obtain a molded product. The obtained molded product is transparent and has a Tg of 189 ° C, a bending strength of 2300 kg / mm ² , and a bending elastic modulus of 36200 kg.
It did not melt when immersed in NMP at / cm ² .

Examples 2 to 4 and Comparative Example 1 318 parts of diphenylisophthalate and 109 parts of m-xylylenediamine were charged into a reactor equipped with a stirrer and a nitrogen stream was supplied 260
The mixture was heated to ℃ and the phenol produced by the reaction was distilled out of the system. After 60 minutes, 79 parts of 4,4'-diaminodiphenylmethane was added to the reaction product and the reaction was continued for another 60 minutes. The obtained polymer had an intrinsic viscosity of 0.24 and a heat distortion temperature of 183 ° C. Next, 100 parts of the polymer and the amount shown in Table 1 below were used.
2,2'-m-Phenylenebis (2-oxazoline) was melt-mixed at 260 ° C using a biaxial ruder. The flow initiation temperature of each of the obtained compositions was 150 ° C. or lower. Next, 100 parts of the composition was uniformly mixed with a predetermined amount of bis (3,5-dibromo-4-hydroxyphenyl) sulfone at 155 ° C, and then charged into a mold heated to 200 ° C and kept for 15 minutes. The physical properties of the obtained molded product are shown in Table 1.

As a comparative example, 2,2'-m-phenylenebis (2-
The physical properties are shown when oxazoline) is not added.

Examples 5 to 7 and Comparative Example 2 Polymers obtained by reacting 159 parts of diphenylisophthalate and 78 parts of m-xylylenediamine while distilling out phenol generated at 260 ° C. to the outside of the system as in Example 2. Had an intrinsic viscosity of 0.15 and a heat distortion temperature of 152 ° C.

Next, 100 parts of the polymer and the amount of 2,2 'shown in Table 2 below were used.
-M-Phenylenebis (5,6-dihydro-4H-1,3-oxazine) was melt mixed in a nitrogen stream at 260 ° C. The flow starting temperature of each of the obtained mixtures was 150 ° C. or lower. Next, 100 parts of the composition was uniformly mixed with a predetermined amount of halogenated phenol shown in the table below at 150 ° C., then charged into a mold heated to 200 ° C. and held for 15 minutes. The physical properties of the obtained molded product are shown in Table 2. For comparison, the physical properties of the polymer without addition of 2,2'-m-phenylenebis (5,6-dihydro-4H-1,3-oxazine) are shown.

Examples 8 to 10 and Comparative Example 3 2000 parts of dimethyl sulfoxide, 600 parts of triene, 2,2-bis (4-hydroxyphenyl) propane (in a three-necked flask equipped with a Dean-Stark tube, a stirrer, a thermometer and a nitrogen tube, 308 parts of bisphenol A), 431 parts of 4,4'-dichlorodiphenyl sulfone and 414 parts of anhydrous potassium carbonate were charged.

Heat the mixture to 150 ° C and hold at 145-155 ° C for 5 hours,
Water was continuously removed by azeotrope with toluene.

Next, 200 parts of 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane and 102 parts of potassium carbonate were added, and the mixture was further reacted at 145-155 ° C for 4 hours. After the obtained viscous solution was cooled, it was poured into a large amount of methanol stirred with a blender to precipitate the polymer. The precipitated polymer was thoroughly washed with water and methanol and then dried.

The obtained polymer (oligomer) has an intrinsic viscosity of 0.24 and Tg.
Was 190 ° C. Next, 100 parts of the polymer was mixed with a predetermined amount of the cyclic imino ether shown in Table 3 and melt-extruded at 250 ° C. The flow starting temperature of the obtained composition is
It was below 150 ° C. Then, 100 parts of the composition was uniformly mixed with the amount of bis (3,5-dibromo-4-hydroxyphenyl) sulfone shown in Table 3 and melted at 160 ° C.
It was pressed into a mold heated to ℃. After holding at that temperature for 10 minutes, it was cooled to obtain a molded product. All the obtained molded articles were transparent and had Tg shown in Table-3.

Example 11 500 parts of 4,4′-diphenylmethane diisocyanate and 159 parts of diethylene glycol were dissolved in 2000 parts of dioxane, the solution was heated under reflux, and the oligomer terminal was hydrolyzed with an aqueous hydrochloric acid solution to give an aromatic amino group at the terminal. Was synthesized. The oligomer had an intrinsic viscosity of 0.16 and a heat distortion temperature of 83 ° C.

140 parts of the oligomer (component A) and 60 parts of 2,2'-m-phenylenebis (2-oxazoline) were uniformly melt mixed at 150 ° C, and then bis (3,5-dibromo-4-hydroxyphenyl) Add 8 parts of sulfone and mix, 1 at 180 ℃
Hold for 0 minutes. The obtained resin is NMP at a heat distortion temperature of 192 ℃.
It did not change when immersed in.

Example 12 318 parts of diphenylisophthalate and 104 parts of hexamethylenediamine were charged in a reactor equipped with a stirrer, and the mixture was placed in a nitrogen stream 2
The reaction was carried out for 30 minutes while heating to 50 ° C and distilling out the phenol generated by the reaction to the outside of the system.

Next, 40 parts of 4,4'-diaminodiphenylmethane was added and the reaction was further continued for 60 minutes. The obtained polymer has an intrinsic viscosity
At 0.33, the heat distortion temperature was 130 ° C. Next, 70 parts of the polymer chip and m-phenylene bis (2-oxazoline)
30 parts were mixed and melt-extruded at 200 ° C. using a twin-screw ruder. The flow starting temperature of the obtained composition was 121 ° C.

Next, 100 parts of the composition was uniformly mixed with 3 parts of tetrabromophthalic acid, melted at 180 ° C., and extruded into a mold heated to 200 ° C. After 15 minutes, the mold was cooled to obtain a molded product. The obtained molded product was transparent and had a Tg of 182 ° C., a bending strength of 2280 kg / cm ² , and a bending elastic modulus of 35500 kg / cm ² , and did not dissolve even when immersed in NMP.

Examples 13 to 16 and Comparative Example 4 318 parts of diphenylisophthalate and 156 parts of m-xylylenediamine were placed in a reactor equipped with a stirrer, and the mixture was placed in a nitrogen stream 2
The phenol produced by the reaction was heated to 60 ° C. to distill it out of the system.

The polymer obtained has an intrinsic viscosity of 0.15 and a heat distortion temperature of 152 ° C.
Met.

Next, 100 parts of the polymer and 2,2 'in the amounts shown in Table 4 below.
-M-phenylene bis (2-oxazoline) and 260 ℃
It was melt-mixed in a nitrogen stream. The flow starting temperature of each of the obtained mixtures was 150 ° C. or lower.

Next, 100 parts of the composition was uniformly mixed with a predetermined amount of a halogenated phthalic acid derivative shown in the table below at 150 ° C, and then 200 ° C.
The mixture was charged into a mold heated to 1, and held for 5 minutes. The physical properties of the obtained molded product are shown in Table 4. 2,2'-m as Comparative Example 4
-The physical properties of the polymer without the addition of phenylene bis (2-oxazoline) are shown.

Examples 17 to 19 and Comparative Example 5 Dimethyl sulfoxide 2000 was placed in a three-necked flask equipped with a Dean-Stark tube, an agitator, a thermometer and a nitrogen tube.
Parts, toluene 400 parts, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) 107 parts, 4,4′-dichlorodiphenyl sulfone 150 parts, and anhydrous potassium carbonate 145 parts. The mixture is heated to 150 ° C, 145-155
The temperature was kept at 0 ° C. for 5 hours and the water was continuously removed by an azeotrope with toluene.

Then, the reaction product was cooled and then poured into a large amount of methanol while stirring with a blender to precipitate a polymer. The precipitated polymer was thoroughly washed with water and methanol and then dried.

The obtained polymer (oligomer) has an intrinsic viscosity of 0.17 and Tg.
Was 190 ° C. Next, 100 parts of the polymer was mixed with a predetermined amount of the cyclic imino ether shown in the table below, and melt-extruded at 250 ° C. The flow starting temperature of each of the obtained compositions was 15
It was below 0 ° C.

Next, 100 parts of the composition was uniformly mixed with the halogenated phthalic acid derivative shown in the table below, melted at 130 ° C., and held in a mold heated to the temperature shown in the table for a predetermined time, followed by cooling. A molded product was obtained.

 The physical properties of the obtained molded product are shown in Table-5.

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Claims (1)

(57) [Claims] 1. A) (A) having at least one group selected from the group consisting of an aromatic amino group, an aromatic aminomethyl group and a hydroxyl group at the end, being substantially linear and having a melting point of 300 ° C. A thermoplastic polymer and / or an oligomer having an intrinsic viscosity of 0.05 to 0.7, and (B) the following formula (I): The cyclic imino ether represented by the formula (C) is represented by the following formula (II) A halogenophenol compound represented by the following formula (III) And a halogenophthalic acid compound represented by the following formula (IV) [Here, the definitions of X ₃ , X ₄ and l are the same as above. ] The method for producing a crosslinked resin, which comprises reacting by heating in the presence of at least one compound selected from the group consisting of halogenophthalic anhydride represented by: and acting as a catalyst.