Claims
- 1. A process for producing a thermoset resin, which comprises reacting
- (A) an organic compound containing at least two groups selected from the class consisting of alcoholic hydroxyl groups, aromatic amino groups and aromatic aminomethyl groups, said organic compound being a monomer, an oligomer or a polymer, and
- (B) a poly(cyclic iminoether) represented by the following formula (I) ##STR30## wherein n is an integer of 2 to 4, R represents a hydrocarbon group having a valence of n which may be interrupted or substituted by an atom other than carbon or a group containing an atom other than carbon, Z represents a direct bond or a group of the formula ##STR31## R.sub.a, R.sub.b, R.sub.c, R.sub.d, R.sub.e and R.sub.f are identical or different, and each represents a hydrogen atom, methyl, ethyl, propyl, phenyl, tolyl or benzyl with the proviso that when n is 2, R may also represent a direct bond,
- with the proviso that when said organic compound (A) is a monomeric compound having at least two aromatic amino groups said poly(cyclic iminoether) is the compound represented by the formula (I) wherein Z represents the group of the formula ##STR32## in the presence of (C) a compound acting as an acid catalyst, at an elevated temperature.
- 2. The process of claim 1 wherein the organic compound (A) is monomeric aliphatic or alicyclic polyhydroxy compound having at least two alcoholic hydroxyl groups.
- 3. The process of claim 2 wherein the polyhydroxyl compound has a pKa of at least 9.0.
- 4. The process of claim 2 wherein the polyhydroxy compound is selected from the group consisting of ethylene glycol, propylene glycol, trimethylene glycol, butanediol, hexanediol, octanediol, decamethylenediol, diethylene glycol, triethylene glycol, glycerol, trimethylol propane, pentaerythritol, neopentyl glycol, cyclohexanedimethanol, dihydroxycyclohexane and trihydroxycyclohexane.
- 5. The process of claim 1 wherein the organic compound (A) is an oligomer or polymer having at least two aliphatic or alicyclic, alcoholic hydroxyl groups.
- 6. The process of claim 5 wherein the oligomer or polymer as the organic compound (A) is substantially linear and has a flow initiation temperature of not more than 300.degree. C.
- 7. The process of claim 1 wherein the oligomer or polymer as the organic compound (A) is selected from the group consisting of polyamides, polyethers, polysulfones, polyurethanes, polyesters, polyetherimides, polyetherketones, polysulfides, polyethylene, polystyrene and polybutadiene.
- 8. The process of claim 1 wherein the organic compound (A) is a monomeric aromatic polyamine having at least two aromatic amino groups.
- 9. The process of claim 8 wherein the aromatic amino groups of the aromatic polyamine are primary or secondary.
- 10. The process of claim 8 wherein the aromatic polyamine as the organic compound (A) is selected from the group consisting of 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylether, 3,4'-diaminodiphenylether, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, o-phenylenediamine, m-phenylenediamine, diaminonaphthalene, 4,4'-diaminodiphenylsulfide, 2,4-diaminotoluene, 2,6-diaminotoluene, 1,2-dianilinoethane, 4,4'-diaminobiphenyl and 2,2-bis[4-(4-aminophenoxy)phenyl]propane.
- 11. The process of claim 1 wherein the organic compound (A) is a monomeric aromatic polyamine having at least two aromatic aminomethyl groups.
- 12. The process of claim 11 wherein the aromatic aminomethyl groups of the aromatic polyamine are primary or secondary.
- 13. The process of claim 11 wherein the aromatic polyamine as the organic compound (A) is selected from the group consisting of p-xylylenediamine, m-xylylenediamine and a mixture of these.
- 14. The process of claim 1 wherein the organic compound (A) is a monomeric aromatic polyamine having an aromatic amino group and an aromatic aminomethyl group.
- 15. The process of claim 1 wherein the organic compound A is a polymer or oligomer having at least two groups selected from aromatic amino and aromatic aminomethyl groups as terminal groups.
- 16. The process of claim 15 wherein the polymer or oligomer as the organic compound (A) is substantially linear and has a melting point of not more than 300.degree. C.
- 17. The process of claim 15 wherein the polymer or oligomer as the organic compound (A) is selected from the group consisting of polyamides, polyethers, polysulfones, polyurethanes, polyesters, polyetherimides, polyetherketones, polyphenylenesulfides, polyethylene, polyazomethine and polyamideimides.
- 18. The process of claim 1 wherein the organic compound (A) has an alcoholic hydroxyl group and a group selected from aromatic amino and aromatic aminomethyl groups.
- 19. The process of claim 1 wherein the poly(cyclic iminoether) (B) is an oxazoline represented by the following formula (I-1) ##STR33## wherein R, R.sub.a, R.sub.b, R.sub.e, R.sub.f and n are as defined with regard to formula (I).
- 20. The process of claim 19 wherein n in formula (I-1) is 2.
- 21. The process of claim 19 wherein the n-valent hydrocarbon group for R in formula (I-1) is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 5 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms.
- 22. The process of claim 1 wherein the poly(cyclic iminoether) (B) is an oxazine represented by the following formula (I-2) ##STR34## wherein R, R.sub.a, R.sub.b, R.sub.c, R.sub.d, R.sub.e, R.sub.f and n are as defined with regard to (I).
- 23. The process of claim 22 wherein n in formula (I-2) is 2.
- 24. The process of claim 22 wherein the n-valent hydrocarbon group for R in formula (I-2) is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 5 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms.
- 25. The process of claim 1 wherein the poly(cyclic iminoether) (B) is a mixure of the oxazoline of formula (I-1) and the oxazine of formula (I-2).
- 26. The process of claim 1 wherein the compound (C) acting as an acid catalyst is selected from the group consisting of (1) protonic acids having a pKa of not more than 2.5, (2) esters of protonic acids having a pKa of not more than 1.0, (3) salts of protonic acids having a pKa of not more than 2.5, (4) Lewis acids and complexes thereof, (5) alkyl halides, and (6) iodine
- 27. A process for producing a thermoset resin, which comprises reacting
- (A) an organic compound containing at least two groups selected from the class consisting of alcoholic hydroxyl groups, aromatic amino groups and aromatic aminomethyl groups, and
- (B) a poly(cyclic iminoether) represented by the following formula (I) ##STR35## wherein n is an integer of 2 to 4, R represents a hydrocarbon group having a valence of n which may be interrupted or substituted by an atom other than carbon or a group containing an atom other than carbon, Z represents a direct bond or a group of the formula ##STR36## R.sub.a, R.sub.b, R.sub.c, R.sub.d, R.sub.e and R.sub.f are identical or different, and each represents a hydrogen atom, methyl, ethyl, propyl, phenyl, tolyl or benzyl with the proviso that when n is 2, R may also represent a direct bond,
- in the presence of
- (C) a compound acting as an acid catalyst, at an elevated temperature, said compound acting as an acid catalyst being a halogenophenol represented by the following formula (III) ##STR37## wherein X.sub.1 and X.sub.2 are identical or different, and each represents a halogen atom, m is 0, 1 or 2, Y is --SO.sub.2 R.sub.1, --COR.sub.2, --CN or --NO.sub.2, R.sub.1 represents an alkyl group having 1 to 20 carbon atoms which may be substituted, an aryl group having 6 to 12 carbon atoms or --NR.sub.3 R.sub.4, R.sub.2 represents an alkyl group having 1 to 20 carbon atoms which may be substituted, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, --OR.sub.5 or --NR.sub.6 R.sub.7, and R.sub.3, R.sub.4, R.sub.5, R.sub.6 and R.sub.7 are identical or different and each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
- 28. The process of claim 27 wherein the halogenophenol of formula (III) has a 4-hydroxy-3,5-dichlorophenyl or 4-hydroxy-3,5-dibromophenyl skeleton.
- 29. A process for producing a thermoset resin, which comprises reacting
- (A) an organic compound containing at least two groups selected from the class consisting of alcoholic hydroxyl groups, aromatic amino groups and aromatic aminomethyl groups, and
- (B) a poly(cyclic iminoether) represented by the following formula (I) ##STR38## wherein n is an integer of 2 to 4, R represents a hydrocarbon group having a valence of n which may be interrupted or substituted by an atom other than carbon or a group containing an atom other than carbon, Z represents a direct bond or
- a group of the formula ##STR39## R.sub.a, R.sub.b, R.sub.c, R.sub.d, R.sub.e and R.sub.f are identical or different, and each represents a hydrogen atom, methyl, ethyl, propyl, phenyl, tolyl or benzyl with the proviso that when n is 2, R may also represent a direct bond,
- in the presence of
- (C) a compound acting as an acid catalyst, at an elevated temperature, said compound acting as an acid catalyst being a halogenophthalic acid represented by the following formula (IV) ##STR40## wherein X.sub.3 and X.sub.4 are identical or different and each represents a halogen atom, l is a number of 0, 1, 2 or 3, and R.sub.8 represents an alkyl group having 1 to 20 arbon atoms which may be substituted, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, --OR.sub.5 or --NR.sub.6 R.sub.7, and R.sub.5, R.sub.6 and R.sub.7 are identical or different and each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms,
- and/or a halogenophthalic anhydride represented by the following formula (V) ##STR41## wherein X.sub.3, X.sub.4 and l are as defined above.
- 30. The process of claim 29 wherein the halogenophthalic acid of formula (IV) is a tetrachlorophthalic acid or a tetrabromophthalic acid, and the halogenophthalic anhydride of formula (V) is a tetrachlorophthalic anhydride or a tetrabromophthalic anhydride.
- 31. The process of claim 1 wherein the organic compound (A) is used in such a proportion that the total equivalent number of the alcoholic hydroxyl groups, aromatic amino groups and aromatic aminomethyl groups of the organic comppound (A) is 0.1 to 1.2 per equivalent of the cyclic imionoether groups of the poly(cyclic iminoether).
- 32. The process of claim 31 wherein said total equivalent number of the organic compound (A) is 0.2 to 1.0.
- 33. The process of claim 1 wherein the compound (C) is used in an amount of 0.01 to 20 mole % based on the poly(cyclic iminoether) (B).
- 34. The process of claim 1 wherein the reaction is carried out at a temperature between 60.degree. and 340.degree. C.
- 35. A process for producing a thermoset resin, which comprises reacting
- (A') an organic compound containing at least two phenolic hydroxyl groups, or at least one phenolic hydroxyl group and at least one group selected from alcoholic hydroxyl groups, aromatic amino groups and aromatic aminomethyl groups, the phenolic hydroxyl groups being partly or wholly the 1-hydroxy group of a 1-hydroxydihalophenyl group free from an electron attracting atom or group other than halogen atoms, and
- (B) the poly(cyclic iminoether) represented by formula (I),
- in the presence of
- (C) a compound acting as an acid catalyst, at an elevated temperature.
- 36. The process of claim 35 wherein the organic compound (A') is represented by the following formula (II) ##STR42## wherein X.sub.5 and X.sub.6 are identical or different and each represents chlorine or bromine, and p and q are identical or different and each is 1 or 2.
- 37. A thermocurable composition for production of thermoset resins, said composition comprising
- (A) an organic compound containing at least two groups selected from the class consisting of alcoholic hydroxyl groups, aromatic amino groups and aromatic aminomethyl groups, said organic compound being a monomer, an oligomer or a polymer,
- (B) a poly(cyclic iminoether) represented by the following formula (I) ##STR43## wherein n is an integer of 2 to 4, R represents a hydrocarbon group having a valence of n which may be interrupted or substituted by an atom other than carbon or a group containing an atom other than carbon, Z represents a direct bond or a group of the formula ##STR44## R.sub.a, R.sub.b, R.sub.c, R.sub.d, R.sub.e and R.sub.f are identical or different, and each represents a hydrogen atom, methyl, ethyl, propyl, phenyl, tolyl or benzyl with the proviso that when n is 2, R may also represent a direct bond, and
- (C) a compound acting as an acid catalyst,
- with the proviso that when said organic compound (A) is a monomeric compound having at least two aromatic amino groups said poly(cyclic iminoether) is the compound represented by the formula (I) wherein Z represents the group of the formula ##STR45##
- 38. A thermocurable composition for production of thermoset resins, said composition comprises
- (A) an organic compound containing at least two groups selected from the class consisting of alcoholic hydroxyl groups, aromatic amino groups and aromatic aminomethyl groups,
- (B) a poly(cyclic iminoether) represented by the following formula (I) ##STR46## wherein n is an integer of 2 to 4, R represents a hydrocarbon group having a valence of n which may be interrupted or substituted by an atom other than carbon or a group containing an atom other than carbon, Z represents a direct bond or a group of the formula ##STR47## R.sub.a, R.sub.b, R.sub.c, R.sub.d, R.sub.e and R.sub.f are identical or different, and each represents a hydrogen atom, methyl, ethyl, propyl, phenyl, tolyl or benzyl with the proviso that when n is 2, R may also represent a direct bond, and
- (C) a compound acting as an acid catalyst, said compound acting as an acid catalyst being selected from the group consisting of a halogenophenol represented by the following formula (III) ##STR48## wherein X.sup.1, and X.sup.2 are identical or different, and each represents a halogen atom, m is 0, 1 or 2, Y is --SO.sub.2 R.sub.1, --COR.sub.2, --CN or --NO.sub.2, R.sub.1 represents an alkyl group having 1 to 20 carbon atoms which may be substituted, an aryl group having 6 to 12 carbon atoms or --NR.sub.3 R.sub.4, R.sub.2 represents an alkyl group having 1 to 20 carbon atoms which may be substituted, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, --OR or --NR.sub.6 R.sub.7, and R.sub.3, R.sub.4, R.sub.5, R.sub.6 and R.sub.7 are identical or different and each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, a halogenophthalic acid represented by the following formula (IV) ##STR49## wherein X.sub.3 and X.sub.4 are identical or different and each represents a halogen atom, l is a number of 0, 1, 2 or 3, and R.sub.8 represents an alkyl group having 1 to 20 arbon atoms which may be substituted, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, --OR.sub.5 or --NR.sub.6 R.sub.7, and R.sub.5, R.sub.6 and R.sub.7 are identical or different and each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and a halogenophthalic anhydride represented by the following formula (V) ##STR50## wherein X.sub.3, X.sub.4 and l are as defined above.
- 39. A thermocurable composition for production of thermoset resins, said composition comprises
- (A') an organic compound containing at least two phenolic hydroxyl groups, or at least one phenolic hydroxyl group and at least one group selected from alcoholic hydroxyl groups, aromatic amino groups and aromatic aminomethyl groups, the phenolic hydroxyl groups being partly or wholly the 1-hydroxy group of a 1-hydroxydihalophenyl group free from an electron attracting atom or group other than halogen atoms,
- (B) the poly(cyclic iminoether) represented by formula (I), and
- (C) a compound acting as an acid catalyst.
- 40. A thermoset resin obtained by the process of any one of claims 1, 27, 29 and 35.
- 41. A composite thermoset resin material produced by performing the thermal reaction of any one of claims 1, 27, 29 and 35 in the presence of fillers, reinforcing fibers or a thermoplastic resin.
Priority Claims (9)
| Number |
Date |
Country |
Kind |
| 61-308515 |
Dec 1986 |
JPX |
|
| 62-12488 |
Jan 1987 |
JPX |
|
| 62-71861 |
Mar 1987 |
JPX |
|
| 62-115920 |
May 1987 |
JPX |
|
| 62-185544 |
Jul 1987 |
JPX |
|
| 62-192556 |
Aug 1987 |
JPX |
|
| 62-252453 |
Oct 1987 |
JPX |
|
| 62-253767 |
Oct 1987 |
JPX |
|
| 62-265343 |
Oct 1987 |
JPX |
|
Oxazolines of formula (I-1)
This is a continuation-in-part application of U.S. patent application Ser. No. 137,950 filed on Dec. 28, 1987, and now abandoned.
This invention relates to a process for producing a thermoset resin. More specifically, it relates to a process for producing a thermoset resin having excellent thermal stability, chemical resistance and mechanical properties at a high rate of curing with excellent moldability.
With the recent technological advance, there has been a demand for resins having excellent thermal stability, mechanical properties and moldability. Particular attention has been paid to reactive-molding resins obtained by using reactive monomers or oligomers which permit molding and polymerization at the same time using materials having a relatively low viscosity. Polyurethane resins, polyurea resins, nylon resins, epoxy resins and unsaturated polyester resins, for example, are known as such reactive-molding resins and some of them have gained commercial acceptance.
These resins, however, have some shortcomings despite their utility, and do not have entirely satisfactory properties and moldability. For example, the polyurethane resins have low thermal stability, and the unsaturated polyester resins require much time for reaction and molding.
The following prior art has previously been known on the reaction of cyclic iminoethers.
Angew. Chem. Internat. Edit., vol. 5, No. 10, pages 875-888 (1966) discloses a process for producing an N-(2-arylaminoethyl)amide represented by the following formula (C) ##STR1## wherein R is ethyl or phenyl, and R.sup.1 and R.sup.2 are hydrogen or methyl,
Japanese Patent Publication No. 57330/1986 discloses a process for producing an unsaturated polyester modified with an oxazoline, which comprises reacting an oxazoline derivative represented by the following formula ##STR4## wherein R represents an aliphatic, alicyclic or aromatic hydrocarbon radical having a valence of n, R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are identical or different and each represents hydrogen or a lower alkyl group, and n is an integer of 1 to 4,
Japanese Laid-Open Patent Publication No. 22,366/1981 discloses a carboxyl-containing polymer having a softening point of at least 40.degree. C. obtained by saponifying a copolymer of a vinyl ester of a saturated monocarboxylic acid and a vinyl monomer, and a powder paint composition comprising a compound having at least two oxazoline rings in the molecule.
U.S. Pat. No. 4,430,491 discloses a thermosetting polymeric composition prepared by effecting the step-growth polymerization reaction in the melt phase of a first reactant consisting of an oligomer containing a plurality of aromatic hydroxyl groups and a second reactant consisting of a compound having at least 2 oxazoline groups.
Japanese Laid-Open Patent Publication No. 68330/1984 discloses a process for producing an amide polymer which comprises reacting a linear polymer having an amide linkage with a compound having at least two 2-oxazolin-2-yl groups in the molecule under heat to add the 2-oxazolin-2-yl groups to the amide linkage.
U.S. Pat. No. 4,474,942 discloses a moldable crosslinked polyesteramide having the repeating unit structure of the formula
U.S. Pat. No. 4,579,937 discloses a process for producing a crosslinked polyesteramide which comprises reacting a bis(2-oxazoline) compound with a dicarboxylic acid in a molar ratio of the dicarboxylic acid to the bis(2-oxazolin) compound of not more than about 1 at an elevated temperature in the presence of an oxazoline ring-opening polymerization catalyst.
Japanese Laid-Open Patent Publication No. 137927/1985 discloses a process for producing a thermoset resin which comprises reacting a polycarboxylic acid having an ester linkage in the molecule obtained by reacting a polyhydric alcohol with an excess of a polycarboxylic acid, with a bis(2-oxazoline) compound.
U.S. Pat. No. 4,558,114 discloses a process for preparing a tough, high-softening polymer comprising polymerizing a bicyclic amide acetal of the formula ##STR5## wherein R, R' and R'" independently represent hydrogen or an alkyl group having from 1 to 18 carbon atoms, R'" also represents an alkyl ether, an aryl ether or an alkaryl ether group having from 1 to 18 carbon atoms and R" represents an alkyl group having from 1 to 18 carbon atoms or an alkaryl group having from 7 to 20 carbon atoms,
U.S. Pat. No. 4,613,662 discloses a process which comprises copolymerizing an oxazoline with a bis- or poly-phenolic compound in the presence of a catalyst which conforms to the formula M(X).sub.n where M represents an alkali or alkaline earth metal moiety, X represents BF.sub.3, BF.sub.4, BPH.sub.4 or ClO.sub.4, and n reperesents 1 or 2 at a temperature in the range of from about 100.degree. to 200.degree. C.
U.S. Pat. No. 4,640,969 discloses a process consisting essentially of interpolymerizing an oxazoline, a polyol and a polyisocyanate at a temperature in the range of from about 20.degree. C. to about 100.degree. C. at a pressure in the range of from atmospheric up to about 50 atmospheres wherein the oxazoline is one conforming to the formula ##STR7## wherein n represents 2 or 3, m represents 1 or 2, and when m is 1, R represents an alkyl group containing from 1 to 20 carbon atoms and an alkaryl group containing from 7 to 20 carbon atoms; when m is 2, R represents an alkylene group containing from 1 to 19 carbon atoms and R' and R" independently represent hydrogen, an alkyl group having from 1 to 10 carbon atoms or an aryl group containing from 6 to 12 carbon atoms.
Japanese Laid-Open Patent Publication No. 89,727/1987 discloses a process for producing a thermoset resin, which comprises heating a mixture composed of a bisoxazoline represented by the following formula ##STR8## wherein R represents an alkylene having 1 to 20 carbon atoms, an arylene having 6 to 12 carbon atoms or an alkarylene having 7 to 20 carbon atoms,
Among the above processes, those in which oxazolines having at least two oxazoline rings in the molecule are used involve reacting the oxazolines with carboxylic acids, phenols or amides having high reactivity with the oxazolines, or else involve using other highly reactive compounds such as isocyanates together.
It is an object of this invention to provide a process for producing a thermoset resin which comprises using a poly(cyclic iminoether) as one reactant.
Another object of this invention is to provide a process for producing a thermoset resin, which comprises very rapidly reacting a poly(cyclic iminoether) with a compound having relatively low reactivity such as an aliphatic polyhydroxy compound in the presence of a catalyst.
Still another object of this invention is to provide a process for producing a thermoset resin by reaction molding such as two-package mixing type reaction molding by performing the above reaction in the absence of a solvent.
Yet another object of this invention is to provide a process for producing a thermoset resin having excellent thermal stability, chemical resistance and mechanical properties.
A further object of this invention is to provide a thermocurable composition which serves as a starting composition in the practice of the process of this invention.
A still further object of this invention is to provide a composite thermoset resin material comprising the thermoset resin produced by the process of this invention and reinforced fibers.
Other objects and advantages of this invention will become apparent from the following description.
According to this invention, the above objects and advantages of this invention are achieved firstly by a process for producing a thermoset resin, which comprises reacting
When Z in formula (I) represents a direct bond, the poly(cyclic iminoether) of formula (I) shows oxazolines of the following formula (I-1) ##STR12## wherein R.sub.1, R.sub.a, R.sub.b, R.sub.e, R.sub.f and n are as defined with regard to formula (I), and when Z in formula is ##STR13## the compound of formula (I) shows oxazines represented by the following formula (I-2) ##STR14## wherein R, R.sub.a, R.sub.b, R.sub.c, R.sub.d, R.sub.e and R.sub.f and n are as defined above.
The hydrocarbon group may be aliphatic, alicyclic or aromatic, and is preferably 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.
When n is 2, examples of the hydrocarbon group preferably include alkylene groups having 1 to 10 carbon atoms such as methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, hexamethylene, neopentylene and decamethylene; divalent alicyclic groups having 5 to 10 carbon atoms such as cyclohexylene and ##STR15## and divalent aromatic hydrocarbon groups containing 6 to 12 carbon atoms such as p-phenylene, m-phenylene, naphthylene and biphenylene. Likewise, when n is 3, examples of the hydrocarbon group preferably include ##STR16##
When n is 4, examples of the hydrocarbon group preferably include the following. ##STR17##
The hydrocarbon group may be interrupted by an atom other than carbon, such as oxygen atom, a sulfur atom, or --NR.sub.g. R.sub.g is a hydrogen atom or a monovalent hydrocarbon group such as an alkyl group.
The above hydrocarbon group may be substituted by a group containing an atom other than carbon.
Examples of such a substituent group include chloro, bromo, nitro, methoxy, cyano, amide and acetamide.
In formula (I) given above R.sub.a, R.sub.b, R.sub.c, R.sub.d, R.sub.e and R.sub.f are identical or different, and each represents a hydrogen atom, methyl, ethyl, propyl, phenyl, tolyl or benzyl. Of these, hydrogen and methyl are preferred. Especially preferably, all of them are hydrogen atoms, or one of them is methyl and all others are hydrogen atoms.
Examples of the poly(cyclic iminoether) of formula (I) are given below.
Of these, 2,2'-bis(2-oxazoline), 2,2'-tetramethylenebis(2-oxazoline, 2,2'-m-phenylenebis(2-oxazoline), and 2,2'-p-phenylenebis(2-oxazoline) are preferred.
Of these, 2,2'-bis(5,6-dihydro-4H-1,3-oxazine), 2,2'-tetramethylenebis(5,6-dihydro-4H-1,3-oxazine), 2,2'-m-phenylenebis(5,6-dihydro-4H-1,3-oxazine) and 7-phenylenebis(5,6-dihydro-4H-1,3-oxazine) are preferred.
These poly(cyclic iminoethers) may be used singly or in combination with each other. When two or more of them are used in combination, a combination of the oxazoline and the oxazine, a combination of oxazolines, or a combination of oxazines may be conveniently used.
In the process of this invention, the poly(cyclic iminoether) may, as required, be used together with not more than 30 mole %, preferably not more than 25 mole %, more preferably not more than 20 mole %, based on the poly(cyclic iminoether), of a mono(cyclic iminoether).
Examples of preferred mono(cyclic iminoethers) are monoxazoline compounds represented by the following formula (I-1)' ##STR18## H wherein R.sup.1 represents a monovalent hydrocarbon group, and R.sub.a, R.sub.b, R.sub.e and R.sub.f are as defined with regard to formula (I), and
Use of the mono(cyclic iminoether) together makes it possible to control the reaction and adjust the crosslinking density advantageously.
In formulae (I-1)' and (I-2)', R' is a monovalent hydrocarbon group which may be aliphatic, alicyclic or aromatic. Preferred hydrocarbon groups include aliphatic groups having 1 to 10 carbon atoms, alicyclic groups having 5 to 10 carbon atoms and aromatic groups having 6 to 12 carbon atoms.
Examples of the mono(cyclic iminoether) include monoxazolines such as 2-ethyl-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-oxazoline and -phenyl-5-methyl-2-oxazoline, and oxazines such as 2-methyl-5,6-dihydro-4H-1,3-oxazine, 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-phenyl-5-methyl-5,6-dihydro-4H-1,3-oxazine and 2-phenyl-6-methyl-5,6-dihydro-4H-1,3-oxazine.
Among 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 organic compound (A), the other reactant used in this invention, contains at least two groups selected from alcoholic hydroxyl groups, aromatic amino groups and aromaic aminomethyl groups.
The organic compound (A) may be a low-molecular-weight compound or a high-molecular-weight compound; in other words, it may be a monomer, an oligomer or a polymer. Examples of the organic compound (A) include monomeric polyhydroxy compounds having at least two aliphatic or alicyclic alcoholic hydroxyl groups, oligomers or polymers having at least two aliphatic or alicyclic alcoholic hydroxyl groups, monomeric aromatic polyamines having at least two aromatic amino groups, monomeric aromatic polyamines having at least two aromatic aminomethyl groups, monomeric aromatic polyamines having an aromatic amino group and an aromatic aminomethyl group, polymers or oligomers having at least two groups selected from aromatic amino groups and aromatic aminomethyl groups as terminal groups, and compounds containing an alcoholic hydroxyl group and a group selected from aromatic amino groups and aromatic aminomethyl groups.
The monomeric polyhydroxy compounds having at least two aliphatic or alicyclic alcoholic hydroxyl groups preferably have a pKa value of at least 9.0 and contain 2 to 4 alcoholic hydroxyl groups in the molecule. Examples include ethylene glycol, propylene glycol, trimethylene glycol, butanediol, hexanediol, octanediol, decamethylene diol, diethylene glycol, triethylene glycol, glycerol, trimethylolpropane, pentaerythritol, neopentyl glycol, cyclohexanedimethanol, dihydroxycyclohexane and trihydroxycyclohexane.
The aliphatic or alicyclic oligomers or polymers having at least two alcoholic hydroxyl groups are preferably substantially linear and have a flow initiation temperature of not more than 300.degree. C., especially not more than 280.degree. C. It is to be understood in this invention that oligomers or polymers at least 50 mole %, preferably at least 60 mole %, more prefarably at least 70 mole %, above all at least 80 mole %, on an average, of the entire terminal groups are alcoholic hydroxyl groups have at least two alcoholic hydroxyl groups.
The aliphatic alcoholic hydroxyl groups are, for example, hydroxyl groups substituted on alkyl groups. The alicyclic alcoholic hydroxyl groups are, for example, hydroxyl groups substituted on saturated cyclic hydrocarbon groups such as cyclohexyl and cyclopentyl.
Examples of such oligomers or polymers are polyamides, polyethers, polysulfones, polyuretanes, polyesters, polyetherimides, polyetherketones, polysulfides, polyethylene, polystyrene and polybutadiene.
The polymers or oligomers having alcoholic hydroxyl groups as terminal groups can be produced by methods known per se.
The flow initiation temperature is the temperature at which a sample polymer can be melt-extruded under a pressure of 100 kg/cm.sup.2 using a flow tester equipped with a nozzle, 0.5 mm in diameter and 1 mm in length. These polymers or oligomers may have an inherent viscosity of about 0.05 to 0.7.
The monomeric aromatic polyamines having at least two aromatic amino groups are preferably those in which the amino groups are primary and/or secondary. Preferably, the aromatic polyamines have 2 to 4, preferably 2, aromatic amino groups in the molecule. Examples include 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylether, 3,4'-diaminodiphenylether, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, o-phenylenediamine, m-phenylenediamine, diaminonaphthalene, 4,4'-diaminodiphenylene sulfide, 2,4-diaminotoluene, 2,6-diaminotoluene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,2-dianilinoethane and 4,4'-diaminodiphenyl.
The monomeric aromatic polyamines having at least two aromatic aminomethyl groups are preferably those in which the amino groups in the aminomethyl groups are primary and/or secondary Examples of suitable aromatic polyamines are p-xylylenediamine, m-xylylenediamine and a mixture thereof.
The monomeric aromatic polyamines having an aromatic amino group and an aromatic aminomethyl group are preferably those in which the aromatic amino group and the amino moiety of the aromatic aminomethyl group are both primary and/or secondary. Examples include p-aminomethylaniline and aminomethylaniline.
The polymers or oligomers having at least two groups selected from aromatic amino groups and aromatic aminomethyl groups are preferably substantially linear and have a melting point of not more than 300.degree. C., especially not more than 280.degree. C. It is to be understood in this invention that oligomers or polymers in which at least 50 mole %, preferably at least 60 mole %, more preferably at least 70 mole %, above all at least 80 mole %, on an average, of the entire terminal groups are aromatic amino groups and/or aromatic aminomethyl groups have at least two such amino groups and/or aminomethyl groups.
Examples of such oligomers or polymers include polyamides, polyethers, polysulfone, polyurethanes, polyesters, polyetherimides, polyetherketones, polyphenylene sulfides, polyethylene, polyazomethine and polyamideimides.
These oligomers or polymers can be produced by blocking the terminal groups of a normally available thermoplastic resin such as a polyamide with aromatic amino groups and/or aromatic aminomethyl groups by methods known per se. For example, terminal groups, such as carboxyl groups or amide-forming functional groups thereof such as ester or acid halide groups in an oligomer or polymer may be converted into aromatic amino groups and/or aromatic methylamino groups by reacting the oligomer or polymer with a diamino compound having aromatic amino groups and/or aromatic methylamino groups. Isocyanate terminal groups in an oligomer or a polymer may be converted to aromatic amino groups and/or aromatic methylamino groups by likewise reacting them with a diamino compound, or hydrolyzing them.
The compounds having an alcoholic hydroxyl group and a group selected from aromatic amino groups and aromatic aminomethyl groups are preferably those in which the alcoholic hydroxyl group is aliphatic or alicyclic, and the aromatic amino group and the amino moiety of the aromatic amino methyl group are primary and/or secondary. Examples include p-beta-hydroxyethoxyaniline, m-betahydroxyethoxyaniline, p-hydroxymethylaniline, m-hydroxymethylaniline, p-beta-hydroxyethylaniline, p-beta-hydroxyethylaniline, p-aminomethylbenzylalcohol, and m-aminomethylbenzylalcohol.
In the present invention, the organic compounds (A) may be used singly or in combination with each other.
In the process of this invention, the organic compound (A) and the poly(cyclic iminoether) (B) may be used in such proportions that basically the total amount of the alcoholic hydroxyl groups, aromatic amino groups and aromatic aminomethyl groups in the organic compound (A) is preferably 0.1 to 1.2 equivalents, more preferably 0.2 to 1.0 equivalent, especially preferably 0.5 to 0.9 equivalent, per equivalent of the iminoether groups of the poly(cyclic iminoether) (B).
If the organic compound (A) is an oligomer or polymer, the above proportions correspond to a (A)/(B) weight ratio of from 90/10 to 37/70, preferably from 80/20 to 40/60.
The process of this invention is practiced by heating the organic compound (A) and the poly(cyclic iminoether) (b) in the presence of the compound (C) acting as an acid catalyst.
Examples of the compound (C) acting as an acid catalyst are given below.
(i) Protonic acids having a pKa of not more than 2.5
(ii) Esters of protonic acids having a pKa of not more than 1.0
(iii) Salts of protonic acids having a pKa of not more than 2.5
(iv) Lewis acids and complexes thereof
(v) Alkyl halides
(vi) Iodine
(vii) Halogenophenols represented by the following formula (III) ##STR20## wherein X.sup.1 and X.sup.2 are identical or different, and each represents a halogen atom, m is 0, 1 or 2, Y is --SO.sub.2 R.sub.1, --COR.sub.2, --CN or --NO.sub.2, R.sub.1 represents an alkyl group having 1 to 20 carbon atoms which may be substituted, an aryl group having 6 to 12 carbon atoms or --NR.sub.3 R.sub.4, R.sub.2 represents an alkyl group having 1 to 20 carbon atoms which may be substituted, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, --OR.sub.5 or --NR.sub.6 R.sub.7, and R.sub.3, R.sub.4, R.sub.5, R.sub.6 and R.sub.7 are identical or different and each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
(viii) Halogenophthalic acids represented by the following formula (IV) ##STR21## wherein X.sub.3 and X.sub.4 are identical or different, and each is selected from the groups defined for X.sub.1, l is a number of 0, 1, 2 or 3, and R.sub.8 is selected from the groups defined for R.sub.2, and/or
The protonic acids (i) having a pKa of not more than 2.5 in (i) are preferably organic sulfonic acids, phosphonic acids or inorganic acids Specific examples include organic sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid and p-toluenesulfonic acid, phosphonic acids such as phenylphosphonic acid, and inorganic acids such as sulfuric acid, phosphoric acid, phosphorous acid, phosphinic acid and perchloric acid.
The esters (ii) of protonic acids having a pKa of not more than 1.0 are preferably esters of organic sulfonic acids and esters of inorganic protonic acids. The alcohol components forming the esters are preferably aliphatic alcohols having 1 to 10 carbon atoms. Specific examples of the esters (ii) are sulfonic acid esters such as methyl benzenesulfonate, ethyl benzenesulfonate, methyl p-toluenesulfonate, ethyl trifluoromethanesulfonate and ethyl D-toluenesulfonate, and esters of inorganic protonic acids such as dimethyl sulfate
The salts (iii) of protonic acids having a pKa of not more than 2.5 are preferably salts of the protonic acids (i), for example salts with organic amine compounds such as hexmethylenediamine, piperazine, m-xylylenediamine, 4,4'-diaminodiophenylmethane, pyridine, and 2,2'-m-phenylenebis(2-oxazoline).
Examples of preferred Lewis acids and complexes thereof (iv) include such Lewis acids as titanium tetrachloride, tin tetrachloride, zinc chloride, aluminum chloride and boron trifluoride, and complexes of these Lewis acids with ethers or phenols, such as boron trifluoride etherate.
Preferred alkyl halides (v) are alkyl iodides and alkyl bromides. The alkyl group in the alkyl halide (v) preferably has 1 to 10 carbon atoms, and may be substituted by phenyl. Specific examples of the alkyl halide (v) are methyl iodide, ethyl iodide, propyl iodide, butyl iodide, benzyl iodide and benzyl bromide.
The iodine (vi) is elemental iodine.
The halogenophenol (vii) of formula (III) are one type of preferred catalysts.
In formula (III), X.sup.1 and X.sup.2 are identical or different, and each represents a halogen atom. Chlorine and bromine atoms are especially preferred as the halogen atom. m is a number of 0, 1 or 2, preferably 1. When m is 1, X.sup.2 is especially preferably bonded at the ortho-position to the hydroxyl group in formula (III).
Y is --SO.sub.2 R.sub.1, --COR.sub.2, --CN or --NO.sub.2. Formula (III) may be written as follows according to the definition of Y. ##STR23## wherein X.sup.1, X.sup.2 and m are as defined, R.sub.1 represents an alkyl group having 1 to 20 carbon atoms which may be substituted, an aryl group having 6 to 12 carbon atoms which may be substituted, or --NR.sub.3 R.sub.4 in which R.sub.3 and R.sub.4 are identical or different and each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms ##STR24## wherein X.sup.1, X.sup.2 and m are as defined above, and R.sub.2 represents an alkyl group having 1 to 20 carbon atoms which may be substituted, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, --OR.sub.5 or --NR.sub.6 R.sub.7 in which R.sub.5, R.sub.6 and R.sub.7 are identical or different and each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted, a cycloalkyl group having 5 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms. ##STR25## wherein X.sup.1, X.sup.2 and m are as defined above. ##STR26## wherein X.sup.1, X.sup.2 and m are as defined above.
In formula (III-1), the C.sub.1 -C.sub.20 alkyl group for R.sub.1 may be linear or branched, and preferably has 1 to 10 carbon atoms. Examples of the alkyl group are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl and n-dodecyl groups. These alkyl groups may be substituted by a substituent selected from, for example, halogens, a hydroxyl group, a carbonyl group, a nitro group, a cyano group, an amino group, alkoxy groups, alkoxycarbonyl groups, acyl groups and acyloxy groups.
Examples of the aryl group having 6 to 12 carbon atoms for R.sub.1 are phenyl, tolyl and naphthyl groups. These aryl groups may be substituted by the same substituents as exemplified above as substituents for the alkyl groups.
The optionally substituted C.sub.1 -C.sub.12 alkyl groups and C.sub.6 -C.sub.12 aryl groups for R.sub.3 or R.sub.4 in the group represented by R.sub.1 may be the same as those exemplified above with regard to R.sub.1. Examples of the C.sub.5 -C.sub.10 cycloalkyl groups for R.sub.3 or R.sub.4 are cyclopentyl, cyclohexyl and ##STR27##
Specific examples of the compounds of formula (III-1) include bis(3,5-dichloro-4-hydroxyphenyl)sulfone, bis(3,5-dibromo-4-hydroxyphenyl)sulfone, 3,5-dichloro-4-hydroxybenzenesulfonamide, 3,5-dibromo-4-hydroxybenzenesulfonamide, and 3,5-dibromo-4-hydroxybenzenesulfonic acid N-methylamide.
The optionally substituted C.sub.1 -C.sub.20 alkyl group, the C.sub.5 -C.sub.10 cycloalkyl group, and the C.sub.6 -C.sub.12 aryl group for R.sub.2 in formula (III-2) may be the same as those exemplified above with regard to formula (III-1) R.sub.6 and R.sub.7 in the group --NR.sub.6 R.sub.7 may be the same as those exemplified above with regard to R.sub.3 R.sub.4.
Examples of group R.sub.5 in the group --OR.sub.5 represented by R.sub.2 may be the same as those given above with regard to groups R.sub.3 and R.sub.4.
Specific examples of the compounds of formula (III-2) include bis(3,5-dichloro-4-hydroxyphenyl)ketone, bis(3,5-dibromo-4-hydroxyphenyl)ketone, methyl 3,5-dichloro-4-hydroxybenzoate, methyl 3,5-dibromo-4-hydroxybenzoate, methyl 3,5-dibromo-4-hydroxybenzoate, 3,5-dibromo-4-hydroxybenzamide, 3,5-dibromo-4-hydroxybenzoic acid N-ethylamide, and 3,5-dibromo-4-hydroxybenzoic acid.
Examples of the compounds of formula (III-3) include 3,5-dichloro-4-hydroxy-benzonitrile, and 3,5-dibromo-4-hydroxybenzonitrile.
Examples of the compounds of formula (III-4) include 3,5-dichloro-4-hydroxynitrobenzene, and 3,5-dibromo-4-hydroxynitrobenzene.
Of the halogenophenols of formula (III), those having a 4-hydroxy-3,5-dichlorophenyl or 4-hydroxy-3,5-dibromophenyl skeleton are preferred, and (3,5-dibromo-4-hydroxyphenyl)sulfone is particularly preferred.
The halogenophthalic acids of formula (IV) and/or the halogenophthalic acid anhydrides of formula (V) in (viii) above are also a preferred type of catalysts.
In formula (IV), X.sub.3 and R.sub.4 represent the same halogen atoms defined with regard to X.sub.1, such as chlorine and bromine atoms. l is a number of 0, 1, 2 or 3. Preferably, l is 1, 2 or 3, above all 2 or 3. R.sub.8 in formula (IV) is the same as R.sub.2 in formula (III).
In formula (V), X.sub.3, X.sub.4 and l are as defined for formula (IV).
Examples of the compounds of formula (IV) and (V) are given below.
(i) Dicarboxylic acids and their anhydrides
3,4,5,6-tetrabromo(or tetrachloro)phthalic acid, 3,4,5,6-tetrabromo(or tetrachloro)phthalic anhydride, 3,4,5-tribromo(or trichloro)phthalic acid, 3,4,5-tribromo(or trichloro)phthalic anhydride, 3,4,6-tribromo(or trichloro)phthalic acid, and 3,4,6-tribromo(or trichloro)phthalic anhydride.
(ii) Monoesters of dicarboxylic acids
monomethyl 3,4,5,6-tetrabromo(or tetrachloro)phthalate, monoethyl 3,4,5,6-tetrabromo(or tetrachloro)phthalate, monopropyl 3,4,5,6-tetrabromo(or tetrachloro)phthalate, monoisopropyl 3,4,5,6-tetrabromo( or tetrachloro)phthalate, monobenzyl 3,4,5,6-tetrabromo(or tetrachloro)phthalate, monobenzyl 3,4,5,6-tetrabromo(or tetrachloro)phthalate, and monophenyl 3,4,5,6-tetrabromo(or tetrachloro)phthalate.
(iii) Dicarboxylic acid monoamides
3,4,5,6-tetrabromo(or tetrachloro)phthalic monoamide, N-methyl-3,4,5,6-tetrabromo(or tetrachloro)phthalic monoamide, N-ethyl-3,4,5,6-tetrabromo(or tetrachloro)phthalic monoamide, N-propyl-3,4,5,6-tetrabromo(or tetrachloro)phthalic monoamide, N-decyl-3,4,5,6-tetrabromo(or tetrachloro)phthalic monoamide, and N-phenyl-3,4,5,6-tetrabromo(or tetrachloro)phthalic monoamide.
(iv) Ketocarboxylic acids
2-carboxy-3,4,5,6-tetrabromo(or tetrachloro)phenylmethyl ketone and 2-carboxy-3,4,5,6-tetrabromo(or tetrachloro)phenylethyl ketone.
Among these, the dicarboxylic acids and anhydrides thereof are preferred. Tetrachlorophthalic acids, tetrabromophthalic acids, and anhydrides of these are more preferred. Particularly preferred are 3,4,5,6-tetrabromo(or tetrachloro)phthalic acid and 3,4,5,6-tetrabromo(or tetrachloro)phthalic anhydride.
The above exemplified catalyst compounds may be used singly or in combination as the catalyst (C) in the process of this invention. The amount of the catalyst (C) is usually 0.01 to 20 mole %, preferably 0.1 to 10 mole %, based on the poly(cyclic iminoether) (B).
The process of this invention is carried out by reacting the organic compound (A) and the poly(cyclic iminoether) (B) in the presence of the catalyst (C) at an elevated temperature with the proviso that when said organic compound (A) is a monomeric compound having at least two aromatic amino groups said poly(cyclic iminoether) (B) is the compound represented by the formula (I) wherein Z represents the group of the formula ##STR28##
The reaction is carried out after an mixture of the organic compound (A), the poly(cyclic iminoether) (B) and the catalyst (C) is prepared, or by suitably mixing these components (A), (B) and (C), for example by preparing a mixture of part of the organic compound (A) and the catalyst (C) and a mixture of the remainder of the organic compound (A) and the poly(cyclic iminoether) (B). Usually, mere mixing of these compounds does not initiate the reaction at a sufficient rate. The reaction is carried out, for example, by heat-melting the intimate mixture of the components (A), (B) and(C), filing the molten mixture in a mold of the desired shape, and reacting the mixture in the mold under heat (one-package method) or by mixing the two mixtures as prepared above by a mixing means such as a mixing head, directly putting the mixture into a mold of the desired shape heated in advance to the reaction temperature and thus performing the reaction (two-package method).
Generally, oligomers or polymers have a high flow initiation temperature or melting point. If the organic compound (A) is an oligomer or polymer, it is desirable to prepare a mixture of (A), (B) and (C) by first mixing the oligomer or polymer with the poly(cyclic iminoether), and mixing the resulting mixture with the catalyst (C) at a relatively low temperature because the plasticizing effect of the poly(cyclic ainminoether) (B) can lower the flow initiation temperature of the oligomer or polymer (A).
The optimum reaction temperature differs with the types and amounts of the starting materials and the catalyst, etc. Usually, the reaction is carried out at a temperaure of 60.degree. to 340.degree. C., preferably 80.degree. to 260.degree. C.
The reaction time may be one which is sufficient for curing the desired resin, and may vary depending upon the types and amounts of the starting materials, and the reaction temperature. It is preferably 10 seconds to 60 minutes, more preferably 20 seconds to 30 minutes, especially preferably about 30 seconds to 15 minutes.
The reaction may be carried out under atmospheric to elevated pressures. Preferably, the reaction is carried out in an atmosphere of an inert gas such as nitrogen or argon to avoid the inclusion of water in the atmosphere or to prevent oxidative degradation of the resin.
The process of this invention can give a thermosetting resin having excellent thermal stability, chemical resistance and mechanical properties at high rates of curing with excellent moldability.
Investigations of the present inventors have shown that when a specific compound having a phenolic hydroxyl group which differs from the organic compound (A) is used instead of the compound (A), the objects of this invention can equally be achieved by using a compound acting as an acid catalyst.
Accordingly, the present invention also provides a process for producing a thermoset resin, which comprises reacting
(A') an organic compound containing at least two phenolic hydroxyl groups, or at least one phenolic hydroxyl group and at least one group selected from alcoholic hydroxyl groups, aromatic amino groups and aromatic aminomethyl groups, the phenolic hydroxyl groups being partly or wholly the 1-hydroxy group of a 1-hydroxydihalophenyl group free from an electron attracting atom or group other than halogen atoms, and
(B) the poly(cyclic iminoether) represented by formula (I), in the presence of a compound acting as an acid catalyst, at an elevated temperature.
Suitable compounds having at least two phenolic hydroxyl groups (A') include, for example, compounds of the following formula (II) ##STR29## wherein X.sub.5 and X.sub.6 are identical or different and each represents a chlorine or bromine atom, and p and q are identical or different and each is 1 or 2.
As can be seen from formula (II), the compounds of formula (II) do not have an electron attracting atom or group at sites other than halogen atoms (X.sub.5, X.sub.6).
In formula (II), X.sub.5 and X.sub.6 are identical or different and each represents a chlorine or bromine atom, and p and q are identical or different and each represents 1 or 2.
Specific examples of the compounds of formula (II) are 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, and 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane.
The poly(cyclic iminoethr) (B) and the catalyst (C) in the other aspect of the process of this invention are the same as described hereinabove. The reaction may be carried out under the same conditions as in the first aspect of the invention already described hereinabove.
The other aspect of the process of this invention can equally give a thermoset resin having the excellent properties described hereinabove.
As required, reinforcing materials such as carbon fibers, aramid fibers, and glass fibers, various fillers such as titanium dioxide, calcium carbonate, alumina, talc, clay, diatomaceous earth, zinc flower, carbon black, barium sulfate, graphite, red iron oxide, re lead, glass powders, mica, silica and various metal powders, pigments, coloring agents, oxidation stabilizers, ultraviolet absorbers, mold releasing agents thermoplastic resins such as polyethylene, polypropylene, polystyrene, polysulfones, polyethersulfones, acrylic resins, polyetherimides, polycarbonates, polyethers and polyolefins and other additives may be properly incorporated in the reaction system in carrying out the process of this invention.
For example, by carrying out the process of this invention in the presence of reinforcing materials such as carbon fibers and glass fibers, a composite thermoset resin material containing the reinforming materials can be produced.
In addition to the reaction components (A) and (B), or (A') and (B), a polyisocyanate compound may be used as a third reaction component in the practice of the process of this invention. Aromatic, aliphatic or alicyclic compounds having at least 2 isocyanate groups and modified products thereof may be used as the polyisocyanate compound. Examples of the aromatic polyisocyanate compounds are 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, polymethylene polyphenylisocyanate, and xylylene diisocyanate. Examples of the alicyclic polyisocyanate compounds are isophorone diisocyanate and methylenebis(cyclohexyl isocyanate). Hexamethylene diisocyanate is an example of the aliphatic polyisocyanate. Examples of the modified products are dimers, trimers, prepolymer-type modification products, carbodiimide modified products and urea modified products of the above-exemplified polyisocyanate. These polyisocyanate compounds may be used in combination.
Among them, 4,4'-diphenylmethane diisocyanate and modified products thereof are especially preferably used as the polyisocyanate compound.
The amount of the polyisocyanate compound is 0.1 to 9 equivalents per equievalent of the iminoether groups of the compounds (B).
US Referenced Citations (5)
Foreign Referenced Citations (2)
| Number |
Date |
Country |
| 0266708 |
May 1988 |
EPX |
| 62-104838 |
May 1987 |
JPX |
Continuation in Parts (1)
|
Number |
Date |
Country |
| Parent |
137950 |
Dec 1987 |
|
Patent Grant
4931512
