Production of mixtures of diisocyanates and polyisocyanates from the diphenylmethane series with high contents of 4,4′-methylenediphenyl diisocyanate and 2,4′-methylenediphenyl diisocyanate
View Patent ↗A fraction of diisocyanates of the diphenylmethane series containing at least 95 wt. % binuclear methylenediphenyl diisocyanate is obtained by a) reacting aniline and formaldehyde in the presence of an acid catalyst to produce diamines and polyamines of the diphenylmethane series containing binuclear methylenediphenyl diamine, b) phosgenating the diamines and polyamines produced in a), optionally in the presence of a solvent, to produce a crude diisocyanate and polyisocyanate, and c) separating a fraction containing at least 95 wt. % binuclear methylenediphenyl diisocyanate with a 4,4′-MDI content of over 60 wt. %, a 2,4′-MDI content of 4 to 35 wt. % and a 2,2′-MDI content of 0.01 to 10 wt. %, relative to the mass of the fraction, and a maximum of 20 ppm phenyl isocyanate and optionally a maximum of 50 ppm solvent from the crude diisocyanate and polyisocyanate produced in b) in a single distillation step with optional upstream and/or downstream separation of low-boiling components.
1. A process for the production of a fraction of diisocyanates of the diphenylmethane series containing at least 95 wt. % binuclear methylenediphenyl diisocyanate comprising:
a) reacting aniline and formaldehyde in the presence of an acid catalyst to produce diamines and polyamines of the diphenylmethane series containing binuclear methylenediphenyl diamine,
b) phosgenating the diamines and polyamines of the diphenylmethane series containing binuclear methylenediphenyl diamine to produce a crude diisocyanate and polyisocyanate, and
c) separating from the crude diisocyanate and polyisocyanate a fraction containing at least 95 wt. % binuclear methylenediphenyl diisocyanate comprising greater than 60 wt. % 4,4′-MDI, from 4 to 35 wt. % 2,4′-MDI, from 0.01 to 10 wt. % 2,2′-MDI relative to the mass of the fraction, and no more than 20 ppm phenyl isocyanate in a single distillation step.
2. The process of claim 1 in which step b) is carried out in the presence of a solvent.
3. The process of claim 2 in which no greater than 50 ppm of solvent are present in the fraction separated in step c).
4. The process of claim 1 in which low-boiling material is removed before and/or after separating the fraction in step c).
5. The process of claim 1 in which a fraction containing at least 99 wt. % binuclear methylenediphenyl diisocyanate comprising greater than 76 wt. % 4,4′-MDI, from 5 to 22 wt. % 2,4′-MDI and from 0.2 to 3 wt. % 2,2′-MDI relative to the mass of the fraction, and a maximum of 10 ppm phenyl isocyanate is separated in step c).
6. The process of claim 2 in which no more than 20 ppm solvents are present in the fraction separated in step c).
7. A process for the production of a diphenymethane diisocyanate mixture comprising blending the fraction separated in step c) of claim 1 with a mixture containing an aromatic isocyanate.
8. The process of claim 7 in which the fraction separated in step c) of claim 1 is blended with a mixture containing a diisocyanate and/or polyisocyanate of the diphenylmethane series.
9. The process of claim 7 in which the fraction separated in step c) of claim 1 is blended with a mixture containing toluene diisocyanate.
10. The process of claim 7 in which the fraction separated in step c) of claim 1 is blended with a mixture containing naphthalene diisocyanate.
11. A process for the production of a polymer comprising:
(a) reacting the fraction separated in step c) of claim 1 and/or the blend produced according to any of claims 7 to 10 with
(b) a polyol.