Process for the continuous preparation of (cyclo)aliphatic diisocyanates
View Patent ↗The invention relates to a multi-stage process for the continuous, phosgene-free preparation of (cyclo)aliphatic diisocyanates that comprises the conversion of (cyclo)aliphatic diamines into the corresponding (cyclo)alkylene biscarbamates and the thermal cleaving of the latter into the (cyclo)alkylene diisocyanates and alcohol. The urea used in accordance with the invention and also the urea employed for the preparation of urea equivalents (e.g. alkyl carbonates, alkyl carbamates) as a possible precursor for the synthesis of the (cyclo)aliphatic biscarbamates is unconditioned.
1. A process for continuously preparing (cyclo)aliphatic diisocyanates without removing by-products generated from impurities present in conditioned urea; consisting essentially of:
(1) reacting at least one (cyclo)aliphatic diamine with unconditioned urea, an unconditioned urea equivalent, or a combination thereof, and at least one alcohol to give (cyclo)aliphatic biscarbamates; and
(2) subsequently thermally cleaving the (cyclo)aliphatic biscarbamates to (cyclo)aliphatic diisocyanates,
wherein unconditioned urea and an unconditioned urea equivalent mean urea and an urea equivalent which have not been surface treated with inorganic substances, have not been surface treated by formaldehyde or a formaldehyde-containing component, and have not been melt treated by the addition of formaldehyde or a formaldehyde-containing component to a urea melt;
wherein the process yield utilizing unconditioned urea, unconditioned urea equivalent, or a combination thereof calculated based on (cyclo)aliphatic diamine used is a minimum of 4.8% greater than the process yield utilizing conditioned urea, a conditioned urea equivalent, or a combination thereof.
2. A multistage process for continuously preparing (cyclo)aliphatic diisocyanates without removing by-products generated from impurities present in conditioned urea; consisting essentially of:
(1) reacting at least one (cyclo)aliphatic diamine with unconditioned urea, an unconditioned urea equivalent, or a combination thereof, and at least one alcohol to give (cyclo)aliphatic biscarbamates; and
(2) subsequently thermally cleaving the (cyclo)aliphatic biscarbamates to (cyclo)aliphatic diisocyanates,
wherein the (cyclo)aliphatic biscarbamates are formed by one-stage, two-stage or multistage processes and wherein unconditioned urea and an unconditioned urea equivalent mean urea and an urea equivalent which have not been surface treated with inorganic substances, have not been surface treated by formaldehyde or a formaldehyde-containing component, and have not been melt treated by the addition of formaldehyde or a formaldehyde-containing component to a urea melt;
wherein the process yield utilizing unconditioned urea, unconditioned urea equivalent, or a combination thereof calculated based on (cyclo)aliphatic diamine used is a minimum of 4.8% greater than the process yield utilizing conditioned urea, a conditioned urea equivalent, or a combination thereof.
3. The process according to claim 1 , wherein
the (cyclo)aliphatic diisocyanate product has a purity greater than 99.5% by weight.
4. The process according to claim 3 , wherein
the unconditioned urea does not contain talc, bentonites, kieselguhr, diatoms, kaolin or other silicatic substances.
5. The process according to claim 1 ,
wherein the at least one alcohol is selected from the group consisting of methanol, ethanol, 1-propanol, 1-butanol, 2-butanol, 1-hexanol, and cyclohexanol.
6. The process according to claim 1 for preparing isophorone diisocyanate.
7. The process according to claim 1 , wherein
the maximum formaldehyde concentration of the urea present is 0.001 to 0.01% by weight.
8. The process according to claim 2 , wherein
the (cyclo)aliphatic diisocyanate product has a purity greater than 99.5% by weight.
9. The process according to claim 8 , wherein
the unconditioned urea does not contain talc, bentonites, kieselguhr, diatoms, kaolin or other silicatic substances.
10. The process according to claim 2 , wherein
the at least one alcohol is selected from the group consisting of methanol, ethanol, 1-propanol, 1-butanol, 2-butanol, 1-hexanol, and cyclohexanol.
11. The process according to claim 2 for preparing isophorone diisocyanate.
12. The process according to claim 2 , wherein
the maximum formaldehyde concentration of the urea present is 0.001 to 0.01% by weight.
13. The process according to claim 3 ,
wherein the process yield utilizing unconditioned urea, unconditioned urea equivalent, or a combination thereof calculated based on (cyclo)aliphatic diamine used is 4.8 to 7.4% greater than the process yield utilizing conditioned urea, a conditioned urea equivalent, or a combination thereof; and
wherein the purity of the (cyclo)aliphatic diisocyanate product prepared utilizing unconditioned urea, unconditioned urea equivalent, or a combination thereof is improved by no more than 1.5% over the (cyclo)aliphatic diisocyanate product prepared utilizing conditioned urea, a conditioned urea equivalent, or a combination thereof.
14. The process according to claim 8 ,
wherein the process yield utilizing unconditioned urea, unconditioned urea equivalent, or a combination thereof calculated based on (cyclo)aliphatic diamine used is 4.8 to 7.4% greater than the process yield utilizing conditioned urea, a conditioned urea equivalent, or a combination thereof; and
wherein the purity of the (cyclo)aliphatic diisocyanate product prepared utilizing unconditioned urea, unconditioned urea equivalent, or a combination thereof is improved by no more than 1.5% over the (cyclo)aliphatic diisocyanate product prepared utilizing conditioned urea, a conditioned urea equivalent, or a combination thereof.