Patent US3593073A successfully refreshed from Google Patents.
Patent US4540769A successfully refreshed from Google Patents.
US4540769A
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Preparation of N-glycidyl compounds
Assignee: Huntsman Advanced Materials Americas LLC
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Filing: 1984-09-25
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Granted: 1985-09-10
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Expires: 2004-09-25
Abstract
Abstract Aromatic N-glycidylamines are prepared by treatment of an amine having at least one, and preferably two or more aromatic amino hydrogen atoms, with epichlorohydrin in the presence, as catalyst, of a di- or higher-valent metal salt of nitric or perchloric acid, or of a carboxylic or sulphonic acid substituted by fluorine, chlorine or bromine on the carbon atom alpha to the carboxylic or sulphonic acid group, and dehydrochlorinating the product. The presence of the metal salt gives a product having a higher glycidyl content and a lower viscosity than does the same reaction in the absence of such a salt. Suitable aromatic amines include aniline, phenylene diamines, phenylene diamines substituted on the aromatic ring and bis(4-aminophenyl)methane. The metal salt may be of, for example, magnesium, calcium, zinc, manganese, nickel, iron, lanthanum, vanadium, ytterbium or uranium.
Inventors
- 👤 Bryan Dobinson
- 👤 Michael R. Thoseby
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-24 13:22
CPC Classifications
C; C07; C07D; C07D303/00; C07D303/02; C07D303/48; C07D303/36
Claims Analysis
Total Claims: 21
Claim 1
Independent Claim
84 words
A process for the preparation of aromatic N-glycidylamines which comprises (i) heating an amine having at least one aromatic amino hydrogen atom with at least 0.7 equivalent, per amino hydrogen equivalent of the amine, of epichlorohydrin, in the presence of a di- or higher-valent metal salt of (a) nitric or perchloric acid, or (b) a carboxylic or sulfonic acid substituted by fluorine, chlorine or bromine on a carbon atom alpha to the carboxylic or sulfonic acid group, and (ii) dehydrochlorinating the product from (i).
Claim 2
Dependent Claim
84 words
A process for the preparation of aromatic N-glycidylamines which comprises (i) heating an amine having at least one aromatic amino hydrogen atom with at least 0.7 equivalent, per amino hydrogen equivalent of the amine, of epichlorohydrin, in the presence of a di- or higher-valent metal salt of (a) nitric or perchloric acid, or (b) a carboxylic or sulfonic acid substituted by fluorine, chlorine or bromine on a carbon atom alpha to the carboxylic or sulfonic acid group, and (ii) dehydrochlorinating the product from (i).
Claim 3
Dependent Claim
18 words
A process according to claim 1, in which the amine has at least two aromatic amino hydrogen atoms.
Claim 4
Dependent Claim
23 words
A process according to claim 1, in which 0.8 to 1.5 equivalents of epichlorohydrin, per amino hydrogen equivalent of the amine, are used.
Claim 5
Dependent Claim
52 words
A process according to claim 1, in which the salt used as catalyst is a nitrate or perchlorate of a metal of group IIA, IIB, IIIB, VIIB or VIII of the Periodic Table, or a fluorine-, chlorine- or bromine-substituted carboxylate or sulfonate of a metal of group IIA or a transition metal.
Claim 6
Dependent Claim
53 words
A process according to claim 4, in which the salt used is a nitrate or perchlorate of magnesium, calcium, zinc, manganese, nickel, lanthanum, vanadium (as vanadyl), ytterbium, or uranium (as uranyl) or a fluorine-, chlorine- or bromine-substituted carboxylate or sulphonate of iron, zinc, cadmium, lanthanum, magnesium, vanadium (as vanadyl), manganese cobalt or nickel.
Claim 7
Dependent Claim
30 words
A process according to claim 5, in which the salt is magnesium perchlorate, calcium perchlorate, zinc perchlorate, nickel perchlorate, magnesium nitrate, manganese nitrate, lanthanum nitrate, ytterbium nitrate, or uranyl nitrate.
Claim 8
Dependent Claim
27 words
A process according to claim 5, in which the salt has an anion derived from a substituted carboxylic or sulphonic acid having at most 4 carbon atoms.
Claim 9
Dependent Claim
24 words
A process according to claim 7, in which the anion is derived from trifluoroacetic acid, trifluoromethanesulphonic acid, trichloroacetic acid, 2,2-dichloropropionic acid or tribromoacetic acid.
Claim 10
Dependent Claim
30 words
A process according to claim 8, in which the salt is magnesium trifluoroacetate, manganese trifluoroacetate, nickel trifluoroacetate, vanadyl trifluoroacetate, magnesium trifluoromethanesulphonate, cobalt trifluoromethanesulphonate, magnesium trichloroacetate, magnesium 2,2-dichloropropionate, or magnesium tribromoacetate.
Claim 11
Dependent Claim
29 words
A process according to claim 1, 4 or 5, in which the amount of the salt present is from 0.1 to 10 parts per 100 parts of the amine.
Claim 12
Dependent Claim
22 words
A process according to claim 1, in which the catalyst is incorporated into the reaction mixture dissolved in an inert organic solvent.
Claim 13
Dependent Claim
31 words
A process according to claim 11, in which the solvent is 2-methoxyethanol, isodecanol, ethylene glycol, diethylene glycol, N-methylpyrrolidone, gamma butyrolacetone, benzyl alcohol, dibutyl phthalate, butane-1,4-diol, ethyl methyl ketone, benzene or toluene.
Claim 14
Dependent Claim
17 words
A process according to claim 1, in which the amine has one or two primary amine groups.
Claim 15
Dependent Claim
84 words
A process according to claim 13, in which the amine is an aniline, an aminophenylindane or an amine of formula I or II: ##STR2## where R 1 , R 2 , R 3 , and R 4 are the same or different and represent alkyl groups of from 1 to 4 carbon atoms, or hydrogen atoms, and X represents a valency bond, an alkylene group of from 1 to 4 carbon atoms, an oxygen atom, a sulfur atom or a carbonyl or sulfonyl group.
Claim 16
Dependent Claim
29 words
A process according to claim 14, in which the amine is aniline, 1,3,3-trimethyl-1-(4-aminophenyl)-5-aminoindane, 1,3,3-trimethyl-1-(4-aminophenyl)-6-aminoindane, o-, m-, or p-phenylenediamine, 2,4-diethyl-6-methyl-1,3-phenylenediamine, bis(4-aminophenyl)methane, bis(4-aminophenyl)ketone, bis(4-aminophenyl)ether, bis(4-aminophenyl)sulfide, bis(3-aminophenyl) or bis(4-aminophenyl)sulfone, 4,4'-diamino-3-ethyldiphenylmethane or bis(4-amino-3-ethylphenyl)methane.
Claim 17
Dependent Claim
13 words
A process according to claim 1 which is effected in an inert solvent.
Claim 18
Dependent Claim
14 words
A process according to claim 1 which is effected at 50° to 100° C.
Claim 19
Dependent Claim
27 words
A process according to claim 1, in which dehydrochlorination is effected by addition of sodium or potassium hydroxide, optionally together with a quaternary ammonium halide as catalyst.
Claim 20
Dependent Claim
11 words
An aromatic N-glycidylamine prepared by a process according to claim 1.
Claim 21
Dependent Claim
18 words
A material obtained by curing an N-glycidyl group-containing epoxide resin prepared by a process according to claim 1.
References Cited (Backward Citations)
GB865314A
Cited
US2951825A
Cited
GB1386594A
Cited
US4026858A
Cited
US4101459A
Cited
US4115296A
Cited
US4130511A
Cited
GB2111977A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1988-09-09 | 1989-03-11 | 1989-09-10 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1992-09-09 | 1993-03-11 | 1993-09-10 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1996-09-09 | 1997-03-11 | 1997-09-10 | $7700.00 | Window Closed / Lapsed |