Claims
- 1. A process for the selective preparation of 4,4'-diaminodiphenylmethane or a derivative thereof, which comprises reacting aniline or a derivative thereof with formaldehyde or a compound capable of producing formaldehyde in situ;
- said reaction being catalyzed by a zeolite catalyst selected from those based on:
- (A) Si, Al, B
- (B) Si, Al, Ti
- (C) Si, Al
- (D) Si, Ti
- (E) Fe, Si, Ti
- and Y zeolites
- and being carried out in a liquid phase in the presence of an inert solvent, said derivatives of aniline being represented by the following formula: ##STR3## wherein R represents a --COOR.sup.1 or --COR.sup.1 group and R.sup.1 represents a substituted or unsubstituted alkyl group of a substituted or unsubstituted aryl group; said reaction being carried out until any N-(4-aminobenzyl)aniline, or corresponding derivative thereof, formed as an intermediate product has been completely isomerized into 4,4'-diaminodiphenylmethane, or the corresponding derivative thereof.
- 2. The process according to claim 1, wherein said zeolite is based on Si, Al and B and has, in its calcined and anhydrous state, the following general formula:
- (HAlO.sub.2).sub.p .multidot.(B.sub.2 O.sub.3).sub.q .multidot.SiO.sub.2( 1)
- wherein p has a value of from 0.034 to 0.0050 and q has a value of from 0.1 to 0.005, the H+ of the HAlO.sub.2 being exchangeable at least in part by cations, the zeolite having an X-ray diffraction spectrum, as determined on a powder sample, the significant of which are as given in the following Table A:
- TABLE A______________________________________ d I.sub.rel______________________________________ 11.12 + 0.10 vs 9.98 + 0.10 s 9.74 + 0.10 m 6.34 + 0.07 mw 5.97 + 0.07 mw 4.24 + 0.05 mw 3.84 + 0.04 s 3.81 + 0.04 s 3.73 + 0.04 s 3.71 + 0.04 s 3.63 + 0.04 m 3.04 + 0.02 mw 2.97 + 0.02 mw______________________________________
- and in IR spectrum having the following bands:
- ______________________________________ wn I.sub.rel______________________________________ 1220-1230 w 1080-1110 s 890-920 mw 795-805 mw 550-560 m 450-470 ms______________________________________
- wherein wn is the wave number in cm.sup.-1 and I.sub.rel are the relative strengths, with a s standing for strong, ms for medium strong, m for medium, mw for medium weak and w for weak.
- 3. The process according to claim 1, wherein said zeolite is based on Si, Al and Ti and has, in its calcined and anhydrous state, the following general formula (expressed in terms of the molar ratios of the oxides):
- (HAlO.sub.2).sub.p .multidot.(TiO.sub.2).sub.q SiO.sub.2 ( 2)
- wherein p has a value greater than zero and less than or equal to 0.050 and p has a value greater than zero and less than or equal to 0.025, H+ of the HAlO.sub.2 being at least in part exchangeable or exchanged with cations, the zeolite having an X-ray diffraction spectrum, as determined on a powder sample, the more significant lines of which are as given in the following Table B:
- TABLE B______________________________________ d I.sub.rel______________________________________ 11.14 + 0.10 vs 9.99 + 0.10 s 9.74 + 0.10 m 6.36 + 0.07 mw 5.99 + 0.07 mw 4.26 + 0.05 mw 3.86 + 0.04 s 3.82 + 0.04 s 3.75 + 0.04 s 3.72 + 0.04 s 3.65 + 0.04 m 3.05 + 0.02 mw 2.99 + 0.02 mw______________________________________
- and an IR spectrum having at least the following bands:
- ______________________________________ wn I.sub.rel______________________________________ 1220-1230 w 1080-1110 s 960-975 mw 795-805 mw 550-560 m 450-470 ms______________________________________
- wherein wn stands for the wave number in cm.sup.-1 and I.sub.rel are the relative strengths, with s standing for strong, ms for medium strong, m for medium, mw for medium weak and w for weak.
- 4. The process according to claim 1, wherein said zeolite is based on Si and Al.
- 5. The process according to claim 1, wherein said zeolite is based on Si and Ti and has, in its calcined and anhydrous state, the following general formula:
- (TiO.sub.2).sub.x (SiO.sub.2).sub.1-x ( 3)
- wherein x is from 0.005 to 0.04.
- 6. The process according to claim 1, wherein said zeolite is based on Si, Ti and Fe and has, in its calcined and anhydrous state, the general formula:
- (HFeO.sub.2).sub.p .multidot.(TiO.sub.2).sub.q .multidot.SiO.sub.2( 4)
- wherein p has a value greater than zero and less than or equal to 0.050 and q has a value greater than zero and less than or equal to 0.025, with H+ of HFeO.sub.2 being at least in part exchangeable with cations, the zeolite having an X-ray diffraction spectrum, as determined on a powder sample, the more significant lines of which are as given in the following Table C:
- TABLE C______________________________________ d I.sub.rel______________________________________ 11.14 + 0.10 vs 9.99 + 0.10 s 9.74 + 0.10 m 6.36 + 0.07 mw 5.99 + 0.07 mw 4.26 + 0.05 mw 3.86 + 0.04 s 3.82 + 0.04 s 3.75 + 0.04 s 3.72 + 0.04 s 3.65 + 0.04 m 3.05 + 0.02 mw 2.99 + 0.02 mw______________________________________
- and an IR spectrum with at least the following bands:
- ______________________________________ wn I.sub.rel______________________________________ 1220-1230 w 1080-1110 s 960-975 mw 795-805 mw 550-560 m 450-470 ms______________________________________
- wherein wn is the wave number in cm.sup.-1 and I.sub.rel are the relative strengths, where s stands for strong, ms for medium strong, m for medium, mw for medium weak and w for weak.
- 7. The process according to claim 1, wherein said zeolite is selected from the zeolites SK 40, SK 41 and SK 500.
- 8. The process according to claim 1, wherein said zeolite is in the form of microspheres comprising an amorphous oligomeric silica binder and a zeolite selected from group (A), (B), (D), or (E), the molar ratio of oligomeric silica to zeolite being from 0.05 to 0.12, and the crystals of zeolite being caged by means of Si--O--Si bridges.
- 9. The process according to claim 8, wherein said microspheres have a diameter of from 5 to 1000 microns.
- 10. The process according to claim 8, wherein said microspheres comprising oligomeric silica and a zeolite selected from groups (A), (B), (D) or (E) have been prepared by dispersing zeolite crystals in an aqueous solution of silica and tetraalkylammonium hydroxide such that said zeolite contains from 7 to 12% by weight of tetraalkylammonium and from 23 to 28% by weight of water and drying the thus obtained suspension;
- said aqueous solution being prepared by the hydrolyzation in a liquid phase of a tetraalkylorthosilicate in an aqueous solution of tetraalkylammonium hydroxide at a temperature of from ambient temperature to 200.degree. C. for a period of from 0.2 to 10 hours.
- 11. The process according to claim 10, wherein said tetraalkylorthosilicate is tetraethylosilicate.
- 12. The process according to claim 10, wherein said hydrolysis takes place at a temperature of from 40 to 100.degree. C.
- 13. The process according to claim 10, wherein the alkyl group of said tetraalkylammonium contains from 1 to 5 carbon atoms.
- 14. The process according to claim 13, wherein said tetraalkylammonium is tetrapropylammonium.
- 15. The process according to claim 1, wherein said inert solvent is selected from alcohols, aromatic and aliphatic hydrocarbons, ethers, chloroaromatic and nitroaromatic compounds.
- 16. The process according to claim 1, wherein said reaction is carried out a temperature of from ambient temperature to 200.degree..
- 17. The process according to claim 16, wherein the temperature at which said reaction is carried out is from 70 to 150.degree. C.
- 18. The process according to claim 5, wherein x is from 0.01 to 0.025.
- 19. The process according to claim 4, wherein said zeolite is ZSM-5.
- 20. A process for producing 4,4'-diaminodiphenylmethane, or derivatives thereof, which comprises the steps of:
- (1) Condensing formaldehyde with an aniline compound in the presence of a zeolite catalyst so that 4,4'-diaminodiphenylmethane and N-(4-aminobenzyl)aniline, or corresponding derivatives thereof, comprise at least 70%, by weight, of the reaction product and
- (2) Converting the N-(4-aminobenzyl)aniline, or corresponding derivatives thereof, produced in step (1) into 4,4'-diaminodiphenylmethane, or the corresponding derivatives thereof, by isomerizing said condensation reaction product in the presence a zeolite; said aniline compound being represented by the following formula: ##STR4## wherein R represents H, a --COOR.sup.1 or a --COR.sup.1 group and wherein R.sup.1 represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group; wherein said zeolite catalyst used in steps (1) and (2) is selected from those based on:
- (A) Si, Al, B
- (B) Si, Al, Ti
- (C) Si, Al
- (D) Si, Ti
- (E) Fe, Si, Ti
- and Y zeolites.
Priority Claims (2)
Number |
Date |
Country |
Kind |
22071 A/86 |
Oct 1986 |
ITX |
|
22074 A/86 |
Oct 1986 |
ITX |
|
Parent Case Info
This application is a continuation of application Ser. No. 07/464,582 filed on Jan. 11, 1990, now abandoned, which is a continuation of Ser. No. 07/325,011 filed on Mar. 17, 1989, now abandoned, which is a continuation of Ser. No. 07/111,259 filed on Oct. 22, 1987, now abandoned.
US Referenced Citations (8)
Foreign Referenced Citations (3)
Number |
Date |
Country |
2623681 |
Jan 1977 |
DEX |
3202687 |
Aug 1983 |
DEX |
2066809 |
Jul 1981 |
GBX |
Continuations (3)
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Number |
Date |
Country |
Parent |
464582 |
Jan 1990 |
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Parent |
325011 |
Mar 1989 |
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Parent |
111259 |
Oct 1987 |
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