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    isocyanate

    Copyright:

    © All Rights Reserved
    Download as PDF or read online from Scribd
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    3 views12 pages

    Us 5298651

    Uploaded by

    mghaffarzadeh
    isocyanate

    Copyright:

    © All Rights Reserved
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    of 12
    United States Patent McGhee et al, {54] PROCESS FOR PREPARING ISOCYANATES USING PHOSPHAZINE CATALYSTS {75] Inventors: William D, MeGhee, St. Louis; Thomas E. Waldman, Chesterfield, both of Mo. Monsanto Company, St. Louis, Mo. 961,238 Oct, 15, 1992 [73] Assignee: [21] Appl. No. [22], Filea: [51] Int. cus [32] US.G. 560/345; 560/24; 560/115; 560/157; 560/336; 564/12; 564/13, [58] Field of Search ... 560/336, 345, 24, 157, 560/115; 564/12, 13 [56] References Cited U.S. PATENT DOCUMENTS 3,481,967 12/1969 Ottmann et al. 44083,875 4/1978 Schmidbaus eta 4,130,576 12/1978 Hedaya et al. ‘COTC 263/04 - 560/342 564/12 “"s607345 4,178,309 12/1979 Luetzow et al. 300/32 4192815 3/1980 Sheludyakov et al ‘0/345 4297,501 10/1981 Becker et al 360/24 4341898 7/1982 Milligan et al. 560/24 4388238 6/1983 ‘360/24 x, 4567294 1/1986 S6X/555 4582923 4/1986 Stammann et al oon $60/24 5}063,282 11/1991 Ruckes et al. Sara x 5,105,001 4/1992 Goins etal... 564/13 X 5,189,205 2/1993 McGhee etal. - 560/345 OTHER PUBLICATIONS Belforte et al., Chem. Ber, 121, 1891-97, (1988) {ANAS A A "USOOS2986514, (11) Patent Number: 5,298,651 (45) Date of Patent: Mar. 29, 1994 Hori et al, Chemistry Express, vol. 1, No. 4, pp. 224-227, (1986). Schwesinger et al, Agew. Chem. Int. Ed. Engl, 26, #1, (1987), pp. 1167-1169. Primary Examiner—Iosé G. Dees ‘Assistant Examiner—Vera C. Clarke “Attorney, Agent, or Firm—Kenneth D. Goetz; Paul L. Passley; James C. Bolding i ‘ABSTRACT ‘A process for preparing isocyanates comprising (a) ‘contacting carbon dioxide and a primary amine in the presence of an aprotic organic solvent and a phospha- zene compound or a mixture of a phosphazene com- pound and an organic, nitrogenous base selected from the group consisting of guanidine compounds, amidine compounds, tertiary amines, pyridine and ‘mixtures thereof to produce the corresponding ammonium car- ‘bamate salt, and (b) reacting the ammonium carbamate salt with an electrophilic or oxophilic dehydrating agent to produce the corresponding isocyanate. A sec- cond embodiment comprises recovering the ammonium carbamate salt of step (8) prior to reacting the ammo- nium carbamate salt with an electrophilic or oxophilic déchydrating agent in the presence of an aprotic orgenic solvent and a phosphazene compound or a mixture of a phosphazene compound and an organic, nitrogenous base selected from the group consisting of guanidine compounds, amidine compounds, tertiary amines, pyri- dine and mixtures thereof. 24 Claims, No Drawings 5,298,651 1 PROCESS FOR PREPARING ISOCYANATES USING PHOSPHAZINE CATALYSTS BACKGROUND OF THEINVENTION 5 ‘The invention relates to a process for preparing iso- ‘cyanates. In one aspect, the invention relates to a new and useful process for preparing isocyanates from pri- ‘mary amines, carbon dioxide and an electrophilic or ‘oxophilic dehydrating agent. Tsocyanates, especially diisocyanates, are important ‘commodity chemicals for use in applications such as Preparation of urethane foam, urethane elastomers, ‘coatings, insecticides, herbicides, and the like. ‘Commercially, the phosgenation of primary amines is 1 by far the most widely used method for producing iso- ‘eyanates. The use of phosgene, however, has several disadvantages. The phosgenation route is long, energy intensive and requires handling highly corrosive materi- als, eg. hydrogen chloride, chlorine, sulfuric acid and 20 nitric acid, and highly toxic reagents and intermediates, eg. phosgene and chlorine. Furthermore, the phosgena- tion route requires use of process equipment which can withstand high temperatures and highly corrosive con- 4itions resulting in increased capital costs. ‘One non-phosgene method for the preparation of isocyanates involves reaction of primary amines and CO2 with a cobalt or manganese compound to produce metal carbamate complexes followed by reaction with an acyl halide in the presence of a solvent asi disclosed 30 by A. Belforte et al, “Incorporation and Deoxygen- ation of Carbon Dioxide: A Metal-assisted Facile Con- version of Carbon Dioxide and Primary Amines To Isocyanates”, Chem. Ber. 121, 1891-1897 (1988). How- ever, the process described therein requires long reac- 38 tion times and gives unsatisfactory yield of isocyanate for a commercially viable process. Another non-phosgene route to isocyanates is found in US. Pat. No. 4,192,815 (Sheludyakov et al.) which ‘loses preparation of isocyanates by reacting a pri- 40 mary amine with CO; and hexamethyidisilazane in the presence of an acidic catalyst, e.g. HSOs, followed by decomposition of the resulting silyl esters of carbamic acid in the presence of a dehydration agent. However, the process described therein requires long reaction ‘times and is not commercially practicable. ‘A non-phosgene process for preparing isocyanates which is economical, commercially viable, and can produce isocyanates with high yield under mild reac- tion conditions and short reaction times is highly desir~ 0 able. 10 2s 4s SUMMARY OF THE INVENTION Itis an object of the invention to provide a process for preparing isocyanates. It is a further object of the invention to provide an efficient and economic process for preparing isocyanates that is commercially viable. It is a still further object of the invention to provide a process for preparing isocyanates which are not easily synthesized via phosgene routes. According to the invention, a process for preparing isocyanates is provided which comprises (a) contacting ‘carbon dioxide and a primary amine in the presence of an aprotic organic solvent and a phosphazene com- pound or a mixture of a phosphazene compound and an 65 organic, nitrogenous base selected from the group con- sisting of guanidine compounds, amidine compounds, tertiary amines, pyridine and mixtures thereof under 55 2 conditions of time and temperature sufficient to pro- duce the corresponding ammonium carbamate salt, and (©) reacting the ammonium carbamate salt with an elec- trophilic or oxophilic dehydrating agent under reaction conditions of time and temperature sufficient to pro- duce the corresponding isocyanate. In one embodiment, the ammonium carbamate salt of step (a) is recovered prior to reacting the ammonium carbamate salt with an electrophilic or oxophilic dehydrating agent in the pres- ence of an aprotic organic solvent and phosphazene compound or a mixture of a phosphazene compound and an organic, nitrogenous base selected from the ‘group consisting of guanidine compounds, amidine compounds, tertiary amines, pyridine and mixtures thereof. DETAILED DESCRIPTION OF THE, INVENTION AA first embodiment of the invention relates to a pro- ccess for preparing isocyanates comprising (a) contact- ing CO and a primary amine in the presence of an aprotic organic solvent and a phosphazene compound ‘or a mixture of a phosphazene compound and an or- ‘ganic, nitrogenous base selected from the group consist- ing of guanidine compounds, amidine compounds, ter- tiary amines, pyridine and mixtures thereof under reac- tion conditions of time and temperature sufficient to produce the corresponding ammonium carbamate salt, and (b) reacting the ammonium carbamate salt with an electrophilic or oxophilic dehydrating agent under re- action conditions of time and temperature sufficient to produce the corresponding isocyanate. ‘A second embodiment of the invention relates 10 process for preparing isocyanates comprising (a) con- tacting CO2 and a primary amine in the presence of an aprotic organic solvent and a phosphazene compound for mixture of a phosphazene compound and an or- ‘ganic, nitrogenous base selected from the group consist- ing of guanidine compounds, amidine compounds, ter- tiary amines, pyridine and mixtures thereof under reac- tion conditions of time and temperature sufficient to produce the corresponding ammonium carbamate salt, (©) recovering the ammonium carbamate salt, and (c) reacting the ammonium carbamate salt with an electro- philic or oxophilic dehydrating agent in the presence of an aprotic organic solvent and an organic, nitrogenous base under reaction conditions of time and temperature ‘sufficient to produce the corresponding isocyanate. The isocyanates made according to this invention are readily recoverable and well suited for use in prepara- ion of urethane foams, elastomers and coatings, ins: cides, and herbicides. The isocyanates produced by the process of the in- vention can be represented by the formula: RaoN=c=0 ‘wherein Rp is selected from the group consisting of linear or branched alkyl, alkenyl, cycloalkyl, cycloalke- nyl, aryl, aralkyl, aralkensl, alkenaryl and alkary! radi- cals having | to about 22 carbon atoms, a radical repre- sented by the formal tRatt ita NERO N=c=o 5,298,651 3 4 1 radical represented by the formula: ‘The result of the reaction of the ammonium carba- ‘mate salt with the electrophilic or oxophilic dehydrat- -Re-N=c=-0 ‘ng agent may be represented by the equation (2). a radical represented by the formula: RNHCO}~ 4H Buse-+"Dehydratng “PGC OF CH= Cr OF HC OCH EN omy cH Cts ‘or isocyanates produced by the process ofthe invention Agen’

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