WO1994013664A1 - Melamine derivatives for use in polymer compositions - Google Patents

Melamine derivatives for use in polymer compositions Download PDF

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Publication number
WO1994013664A1
WO1994013664A1 PCT/NL1993/000260 NL9300260W WO9413664A1 WO 1994013664 A1 WO1994013664 A1 WO 1994013664A1 NL 9300260 W NL9300260 W NL 9300260W WO 9413664 A1 WO9413664 A1 WO 9413664A1
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Prior art keywords
melamine
derivative
formula
amide
derivatives
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PCT/NL1993/000260
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French (fr)
Inventor
Veronika Maria Leonarda Jozefina Aarts
Renier Henricus Maria Kierkels
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Dsm N.V.
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Priority to AU57197/94A priority Critical patent/AU5719794A/en
Publication of WO1994013664A1 publication Critical patent/WO1994013664A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C08G73/0644—Poly(1,3,5)triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • C08G73/128—Unsaturated polyimide precursors the unsaturated precursors containing heterocyclic moieties in the main chain

Definitions

  • the invention relates to melamine derivatives suitable for use in thermosetting plastic compounds and as fire retardant components.
  • Melamine may be reacted with formaldehyde to produce resins for laminating and adhesive applications.
  • Melamine derivatives may also serve as an amino cross- linker in heat-cured paint systems, particularly in automotive applications.
  • Other uses have included the preparation of wet-strength resins for paper, water clarifying resins, ion-exchange resins, plastic molding compounds, and fire retardants in polymeric materials.
  • Melamine has flame-retarding properties and increases the scratch resistance of thermosetting molding compounds and is, therefore, a frequent component in polymer compositions.
  • melamine is poorly soluble in customary solvents.
  • the reactivity of the amino groups is relatively low, so that desired reactions between melamine and other chemicals proceed with difficulty.
  • R is H, C ⁇ -C ⁇ alkyl, or an aromatic residue
  • the invention relates to a melamine derivative according to formula (1)
  • R is hydrogen, Ci . —C 12 alkyl or aromatic residue.
  • the R subsituent can be an alkyl selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n- butyl, isobutyl, t-butyl, 3-methyl-2-butenyl, pentyl, 2,2- dimethyl propyl cyclohexyl, or dodecyl, or an aromatic residue such as, for instance, phenyl, benzyl or naphthyl When compared with melamine, these tetrahydrophthalic anhydride derivatives of melamine show improved miscibility in thermoplastics and rubbers.
  • tetrahydrophthalic anhydride should be understood to mean alkylated tetrahydrophthalic acid.
  • the alkyl group can be methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, t- butyl, 3-methyl-2-butenyl, pentyl, 2,2-dimethyl propyl, cyclohexyl, phenyl, benzyl, naphthyl or dodecyl.
  • Tetrahydrophthalic anhydride and a number of alkyl derivatives are commercially available.
  • Alkylated tetrahydrophthalic acid derivatives can be prepared by a Diels-Alders reaction of maleic anhydride to alkyl- substituted butadienes.
  • the melamine derivatives according to formula (1) can be prepared by reaction of melamine with tetrahydrophthalic anhydride in a suitable solvent.
  • a suitable solvent Dimethylsulphoxide (DMSO) and glacial acetic acid are especially preferred solvents.
  • the reaction temperature is generally between 50°C and 200°C, preferably between 80°C and 150°C.
  • R is hydrogen or C 1 -C 12 alkyl or a hydrocarbon aromatic residue as described hereinabove.
  • the compounds according to formula (2) can be prepared by epoxidizing the ethylenic unsaturation in the tetrahydrophthalic acid group by, for instance, the treatment of a derivative according to formula (1) with peracetic acid or hydrogen peroxide.
  • the epoxy compounds according to formula (2) are reactive with carboxylic acid groups, alkyl amines, and phenolic hydroxyl groups, and as a result can be used successfully as flame-retarding components in thermosetting epoxy and polyester compositions.
  • tetrahydrophthalic acid derivatives according to formula (1) are also suitable as raw material for cyclopentadienyl derivatives according to formula (3)
  • R is hydrogen, C ⁇ -C ⁇ alkyl or an aromatic residue as described hereinabove, and n is 1, 2, or 3.
  • Such compounds can be prepared by a Diels-Alder reaction of the compounds according to formula (1) with cyclopentadiene in a suitable solvent.
  • Demethylsulfoxide and glacial acetetic acid are especially preferred solvents.
  • the reaction temperature is generally between 50°C and 200°C, preferably between 70°C and 160°C.
  • Derivatives according to formula (3) are very suitable as flame-retarding components and/or as adhesion promoting components in hydrocarbon resins for use as glues.
  • Melamine derivatives according to formula (1), (2), or (3) can be converted to the amide acid derivative or an amide ester derivative by hydrolysis or alcoholysis.
  • Hydrolysis takes place under basic conditions in an aqueous environment at a temperature between 10°C and 100°C, preferably between 15°C and 85°C.
  • the partly hydrolyzed compound is of interest since the free acid group can be used to form salts with, for example, alkali metals or tetraalkyl amines, to improve the water-solubility of the hydrolyzed compound.
  • the partly hydrolyzed compound can be esterified with an alcohol to yield an amide-ester compound.
  • the tetrahydrophthalic acid derivative can be converted to the corresponding amide ester.
  • the acid derivative can be allowed to react with an alcoholic alkali metal salt, such as sodium methanolate.
  • an alcoholic alkali metal salt such as sodium methanolate.
  • alcohols having 1-8 carbon atoms can be used for the esterification, methanol, butanol, and 2-ethyl hexanol are preferred.
  • An amide ester usually exhibits improved compatibility with polyesters, polyamides and the like.
  • Melamine derivatives according to formula (1), (2), or (3) and the amide-acid or amide-ester derivatives thereof can be alkoxylated with an aldehyde containing 1-8 carbon atoms such as formaldehyde, acetaldehyde and benzaldehyde.
  • the preferred aldehyde is formaldehyde, which results in a methylolated melamine derivative.
  • methylolation can be conducted by dissolving the melamine derivative in a formaldehyde-water mixture having a pH between 0 and 5 at a reaction temperature of, for instance, about 20 to about 50°C.
  • the alkoxylation generally takes place in an acid environment to limit undesirable hydrolysis of the imide bond.
  • the alkoxylated compound can be applied as a thermosetting resin and can also be applied in aminoplastics and phenoplastics.
  • the alkoxylated compounds can also be etherified with a C__-C ⁇ alcohol, such as methanol, butanol, or hexanol, at a pH of, for instance, between 0 and 6.
  • a C__-C ⁇ alcohol such as methanol, butanol, or hexanol
  • the resulting compounds can be used with excellent results as crosslinking compounds in heat-cured enamels such as those applied as coil coatings.
  • aldehyde equivalents can react with each melamine derivative.
  • the degree of alkoxylation can be between 1 and 4, although preferably it is between 2 and 4.
  • alkoxylation with five aldehyde equivalents is possible.
  • the degree of alkoxylation will be between 2 and 5, and is preferably between 2 and 4.
  • Example I Analogously to Example I, a reaction was carried out with melamine and 4-methyltetrahydrophthalic anhydride. The yield was 92% N-mono(4-methyl)tetra- hydrophthaloyl melamine.
  • Example I I I
  • Example II Analogously to Example I, a reaction was carried out with melamine 4-(3-methyl-2-butenyl)tetrahydrophthalic anhydride.
  • This anhydride derivative had been obtained by Diels-Alder addition of maleic anhydride to (3-methenyl-6- methyl)hepta-l,5 diene.
  • the melamine derivative yield was 84%.
  • Example IV In a round-bottom flask 1.8 grams of melamine derivative obtained in accordance with Example II was dissolved in 20 cl. of DMSO. To this mixture 540 mg. of sodium acetate was added and 2.5 grams of peracetic acid.
  • the epoxidized melamine derivative could be purified by recrystallization and washing.

Abstract

The invention relates to a melamine derivative, being an N-monotetratrahydrophthalyol melamine or a corresponding compound of a tetrahydrophthalic acid alkylated with 1-12 carbon atoms. The invention also relates to an epoxidized or cyclopentadiene-added derivative and a correponding amide-acid or amide-ester. If desired, these compounds can be condensed, alkoxylated and etherified. The compounds are used in polymer compositions.

Description

MELAMINE DERIVATIVES FOR USE IN POLYMER COMPOSITIONS
Field of the Invention
The invention relates to melamine derivatives suitable for use in thermosetting plastic compounds and as fire retardant components.
Description of Related Art
Melamine may be reacted with formaldehyde to produce resins for laminating and adhesive applications. Melamine derivatives may also serve as an amino cross- linker in heat-cured paint systems, particularly in automotive applications. Other uses have included the preparation of wet-strength resins for paper, water clarifying resins, ion-exchange resins, plastic molding compounds, and fire retardants in polymeric materials. Melamine has flame-retarding properties and increases the scratch resistance of thermosetting molding compounds and is, therefore, a frequent component in polymer compositions. However, as a pure compound, melamine is poorly soluble in customary solvents. In addition, the reactivity of the amino groups is relatively low, so that desired reactions between melamine and other chemicals proceed with difficulty.
As a consequence, there is a need for melamine derivatives which, compared with melamine, exhibit improved solubility and provide different reactive groups. Derivatives of melamine (l,3,5-tri-amino-2,4,6- triazine) having the sought-after properties would be highly desirable chemicals. SUMMARY OF THE INVEN ION Novel derivatives of melamine exhibiting improved miscibility in themoplastic and rubber composition are depicted by formula (1):
Figure imgf000004_0001
wherein R is H, C^-C^ alkyl, or an aromatic residue,
DETAILED DESCRIPTION OF THE INVENTION
The invention relates to a melamine derivative according to formula (1)
Figure imgf000004_0002
wherein R is hydrogen, Ci.—C12 alkyl or aromatic residue. The R subsituent can be an alkyl selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n- butyl, isobutyl, t-butyl, 3-methyl-2-butenyl, pentyl, 2,2- dimethyl propyl cyclohexyl, or dodecyl, or an aromatic residue such as, for instance, phenyl, benzyl or naphthyl When compared with melamine, these tetrahydrophthalic anhydride derivatives of melamine show improved miscibility in thermoplastics and rubbers. Furthermore, these derivatives can be copolymerized, for instance, during curing of a rubber. As used in this specification, tetrahydrophthalic anhydride should be understood to mean alkylated tetrahydrophthalic acid. The alkyl group can be methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, t- butyl, 3-methyl-2-butenyl, pentyl, 2,2-dimethyl propyl, cyclohexyl, phenyl, benzyl, naphthyl or dodecyl.
Tetrahydrophthalic anhydride and a number of alkyl derivatives are commercially available. Alkylated tetrahydrophthalic acid derivatives can be prepared by a Diels-Alders reaction of maleic anhydride to alkyl- substituted butadienes.
The melamine derivatives according to formula (1) can be prepared by reaction of melamine with tetrahydrophthalic anhydride in a suitable solvent. Dimethylsulphoxide (DMSO) and glacial acetic acid are especially preferred solvents. The reaction temperature is generally between 50°C and 200°C, preferably between 80°C and 150°C.
Under these conditions, the reaction, in particular imide formation, proves to be unexpectedly rapid. Due to the rapidity and completeness of the above reaction, the intermediate product usually found in anhydride-amine reactions (an amide acid) is present in a much smaller than usual concentrations. The tetrahydrophthalic anhydride derivatives of melamine are also highly suitable as raw material for an epoxidized melamine derivative according to formula (2)
Figure imgf000005_0001
wherein R is hydrogen or C1-C12 alkyl or a hydrocarbon aromatic residue as described hereinabove. - A -
The compounds according to formula (2) can be prepared by epoxidizing the ethylenic unsaturation in the tetrahydrophthalic acid group by, for instance, the treatment of a derivative according to formula (1) with peracetic acid or hydrogen peroxide.
The epoxy compounds according to formula (2) are reactive with carboxylic acid groups, alkyl amines, and phenolic hydroxyl groups, and as a result can be used successfully as flame-retarding components in thermosetting epoxy and polyester compositions.
The tetrahydrophthalic acid derivatives according to formula (1) are also suitable as raw material for cyclopentadienyl derivatives according to formula (3)
Figure imgf000006_0001
where R is hydrogen, C^-C^ alkyl or an aromatic residue as described hereinabove, and n is 1, 2, or 3.
Such compounds can be prepared by a Diels-Alder reaction of the compounds according to formula (1) with cyclopentadiene in a suitable solvent. Demethylsulfoxide and glacial acetetic acid are especially preferred solvents. The reaction temperature is generally between 50°C and 200°C, preferably between 70°C and 160°C. Derivatives according to formula (3) are very suitable as flame-retarding components and/or as adhesion promoting components in hydrocarbon resins for use as glues.
Melamine derivatives according to formula (1), (2), or (3) can be converted to the amide acid derivative or an amide ester derivative by hydrolysis or alcoholysis. Hydrolysis takes place under basic conditions in an aqueous environment at a temperature between 10°C and 100°C, preferably between 15°C and 85°C. The partly hydrolyzed compound is of interest since the free acid group can be used to form salts with, for example, alkali metals or tetraalkyl amines, to improve the water-solubility of the hydrolyzed compound.
The partly hydrolyzed compound can be esterified with an alcohol to yield an amide-ester compound. Under basic conditions, the tetrahydrophthalic acid derivative can be converted to the corresponding amide ester. The acid derivative can be allowed to react with an alcoholic alkali metal salt, such as sodium methanolate. Although alcohols having 1-8 carbon atoms can be used for the esterification, methanol, butanol, and 2-ethyl hexanol are preferred.
An amide ester usually exhibits improved compatibility with polyesters, polyamides and the like.
Melamine derivatives according to formula (1), (2), or (3) and the amide-acid or amide-ester derivatives thereof can be alkoxylated with an aldehyde containing 1-8 carbon atoms such as formaldehyde, acetaldehyde and benzaldehyde. The preferred aldehyde is formaldehyde, which results in a methylolated melamine derivative. For example, methylolation can be conducted by dissolving the melamine derivative in a formaldehyde-water mixture having a pH between 0 and 5 at a reaction temperature of, for instance, about 20 to about 50°C. By preference, the alkoxylation generally takes place in an acid environment to limit undesirable hydrolysis of the imide bond. The alkoxylated compound can be applied as a thermosetting resin and can also be applied in aminoplastics and phenoplastics.
The alkoxylated compounds can also be etherified with a C__-Cβ alcohol, such as methanol, butanol, or hexanol, at a pH of, for instance, between 0 and 6.
The resulting compounds can be used with excellent results as crosslinking compounds in heat-cured enamels such as those applied as coil coatings.
For a derivative according to one of the formulas (1), (2), or (3), four aldehyde equivalents can react with each melamine derivative. As a general matter, it is not necessary to effect a complete reaction, e.q. , methylolation, and therefore the degree of alkoxylation can be between 1 and 4, although preferably it is between 2 and 4.
If an amide-acid or amide-ester derivative is used, alkoxylation with five aldehyde equivalents is possible. In general, the degree of alkoxylation will be between 2 and 5, and is preferably between 2 and 4.
EXAMPLES The invention will be further described with reference to the following representative examples.
Example I
In a 5 liter round-bottom flask 1 mole of melamine was dissolved in 1.2 liter of DMSO at 100°C.
Subsequently, 2 moles of tetrahydrophthalic anhydride in DMSO were added dropwise to the melamine solution, while the reaction mixture maintained at 100°C. After 90 minutes the mixture was cooled and then poured into ice water having excess ice, to form a precipitate. Sodium carbonate was used to set the pH at 8.8. The resulting precipitate was filtered off and washed with acetone. After drying at 100°C the yield proved to be 90% N-monotetrahydrophthaloyl melamine.
Example II
Analogously to Example I, a reaction was carried out with melamine and 4-methyltetrahydrophthalic anhydride. The yield was 92% N-mono(4-methyl)tetra- hydrophthaloyl melamine. Example I I I
Analogously to Example I, a reaction was carried out with melamine 4-(3-methyl-2-butenyl)tetrahydrophthalic anhydride. This anhydride derivative had been obtained by Diels-Alder addition of maleic anhydride to (3-methenyl-6- methyl)hepta-l,5 diene. The melamine derivative yield was 84%.
Example IV In a round-bottom flask 1.8 grams of melamine derivative obtained in accordance with Example II was dissolved in 20 cl. of DMSO. To this mixture 540 mg. of sodium acetate was added and 2.5 grams of peracetic acid.
After reacting 20 hours, a portion of the phthaloyl derivative was epoxidized. The epoxidized melamine derivative could be purified by recrystallization and washing.

Claims
C L A I M S
Melamine derivative according to formula 1
Figure imgf000010_0001
where R is hydrogen or C1-C12 alkyl. Melamine derivative according to formula 2
Figure imgf000010_0002
where R is hydrogen or C^-C^ alkyl. Melamine derivative according to formula 3
Figure imgf000010_0003
where R is hydrogen or C^-C^ alkyl and n is any one of the numbers 1, 2 or 3.
Amide-acid derivative of a compound according to any one of the formulas (1), (2) or (3).
Amide-ester derivative of a compound according to any one of the formulas (1), (2) or (3) and an alcohol with 1-8 carbon atoms.
6. Alkoxylated melamine derivative of a compound according to any one of claims 1-5, with an aldehyde with 1-8 carbon atoms.
7. Etherified alkoxylated melamine derivative of a compound according to claim 6 and an alcohol with 1-8 carbon atoms.
8. Polymer composition comprising a melamine derivative according to any one of claims 1-7.
9. Process for the preparation of a melamine derivative according to formula (1) by dissolving melamine in a suitable solvent and allowing the melamine to react at a suitable temperature with a tetrahydro phthalic anhydride and recovering the desired melamine derivative.
10. Derivatives, composition and process as substantially covered in the specification and the examples.
PCT/NL1993/000260 1992-12-15 1993-12-03 Melamine derivatives for use in polymer compositions WO1994013664A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU57197/94A AU5719794A (en) 1992-12-15 1993-12-03 Melamine derivatives for use in polymer compositions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BE9201096A BE1006449A3 (en) 1992-12-15 1992-12-15 Melamine DERIVATIVE.
BE9201096 1992-12-15

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997031914A1 (en) * 1996-03-01 1997-09-04 Cytec Technology Corp. Cyclic imido-1,3,5-triazine crosslinking agents
US5955471A (en) * 1998-01-13 1999-09-21 Sk Corporation Tetrahydroisoquinolinealkanol derivatives and pharmaceutical compositions containing same
EP1279673A1 (en) * 2001-07-26 2003-01-29 Agrolinz Melamin GmbH Imidotriazine derivatives
US6706856B2 (en) * 1999-11-02 2004-03-16 Dsm N.V. Crystalline melamine and its use in amino-formaldehyde resins

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3590042A (en) * 1968-09-05 1971-06-29 Universal Oil Prod Co N-s-triazyl imides of halo substituted polyhydropolycyclicdicarboxylic acids
US3763090A (en) * 1968-09-05 1973-10-02 Universal Oil Prod Co Flame retardant compositions of matter
EP0409334A2 (en) * 1989-07-20 1991-01-23 Stamicarbon B.V. Anisotropic polymers based on an S-triazine derivative

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3590042A (en) * 1968-09-05 1971-06-29 Universal Oil Prod Co N-s-triazyl imides of halo substituted polyhydropolycyclicdicarboxylic acids
US3763090A (en) * 1968-09-05 1973-10-02 Universal Oil Prod Co Flame retardant compositions of matter
EP0409334A2 (en) * 1989-07-20 1991-01-23 Stamicarbon B.V. Anisotropic polymers based on an S-triazine derivative

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997031914A1 (en) * 1996-03-01 1997-09-04 Cytec Technology Corp. Cyclic imido-1,3,5-triazine crosslinking agents
US5807929A (en) * 1996-03-01 1998-09-15 Cytec Technology Corp. Cyclic imido-1,3,5-triazine crosslinking agents
US6013797A (en) * 1996-03-01 2000-01-11 Cytec Technology Corp. Cyclic imido-1,3,5-triazine crosslinking agents
US5955471A (en) * 1998-01-13 1999-09-21 Sk Corporation Tetrahydroisoquinolinealkanol derivatives and pharmaceutical compositions containing same
US6706856B2 (en) * 1999-11-02 2004-03-16 Dsm N.V. Crystalline melamine and its use in amino-formaldehyde resins
EP1279673A1 (en) * 2001-07-26 2003-01-29 Agrolinz Melamin GmbH Imidotriazine derivatives

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AU5719794A (en) 1994-07-04

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