EP0986536A1 - Procede de preparation d'isocyanates organiques - Google Patents

Procede de preparation d'isocyanates organiques

Info

Publication number
EP0986536A1
EP0986536A1 EP98925567A EP98925567A EP0986536A1 EP 0986536 A1 EP0986536 A1 EP 0986536A1 EP 98925567 A EP98925567 A EP 98925567A EP 98925567 A EP98925567 A EP 98925567A EP 0986536 A1 EP0986536 A1 EP 0986536A1
Authority
EP
European Patent Office
Prior art keywords
radicals
solvent
decomposition
polymeric
isocyanates
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98925567A
Other languages
German (de)
English (en)
Inventor
Joris Karel Peter Bosman
Herbert Russell Gillis, Jr.
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huntsman International LLC
Original Assignee
Huntsman International LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huntsman International LLC filed Critical Huntsman International LLC
Priority to EP98925567A priority Critical patent/EP0986536A1/fr
Publication of EP0986536A1 publication Critical patent/EP0986536A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C263/00—Preparation of derivatives of isocyanic acid
    • C07C263/06—Preparation of derivatives of isocyanic acid from or via ureas

Definitions

  • the present invention relates to a method for the preparation of polymeric isocyanates by thermal decomposition of polymeric ureas.
  • EP-A 583.637 discloses the decomposition of trisubstituted ureas at elevated temperature (90-400 °C) and in the presence of a solvent into a volatile monoisocyanate and a secondary amine of which the boiling point is higher than that of the isocyanate and higher than the reaction temperature. Only examples of the preparation of aliphatic monoisocyanates by this method are given.
  • US-A 3.936.484 describes the decomposition of trisubstituted ureas at elevated temperatures (above 230°C) and in the presence of an inert carrier to form isocyanates and amines. The isocyanate yield is from 60 to 88%.
  • FR-A 1.473.821 concerns the pyrolysis into isocyanates and amines of substituted ureas in the liquid phase (temperature less than 200°C) in the presence of a particular class of solvents. The reaction times however are long (6-35 hours) and the isocyanate yield only moderate (60-75%).
  • the invention thus concerns a method for the preparation of polymeric isocyanates by decomposing at moderate temperature polymeric ureas of the formula R 1 (NHCONR 2 R 3 ) x wherein x is at least 2, R 1 is an organic radical of valency x and R 2 and R 3 are monovalent organic radicals, into polymeric isocyanates of the formula R ⁇ NCO),, and secondary amines of the formula R 2 NHR 3 characterised in that at least one of the radicals R 2 and R 3 is bound to the nitrogen atom of the amine by a tertiary carbon atom.
  • Non-volatile organic isocyanates can be obtained in high yields via a fast reaction in the absence of a solvent or from concentrated solutions.
  • R 1 is a substituted or unsubstituted, saturated or unsaturated, aliphatic, cycloaliphatic or aromatic hydrocarbon radical optionally containing hetero-atoms.
  • the urea composition which is subjected to decomposition may be a mixture of polymeric urea compounds of different functionalities which, upon decomposition, result in a mixture of polymeric isocyanates. It will be understood that in such instances the value for x is an average of the functionalities of all species present in the urea mixture.
  • the term 'functionality' as used herein is defined as number averaged functionality.
  • the average value of x is generally between 2 and 15, preferably between 2 and 10 and more preferably from 2 to 3.
  • polymeric refers to a functionality of 2 or higher.
  • R 1 are tolylene, methylene diphenylene or polymethylene polyphenylene radicals or mixtures thereof.
  • R 2 and R 3 may be any monovalent organic radicals, provided one of said radicals contains a tertiary carbon atom by which it is attached to the nitrogen atom.
  • radicals R 2 and R 3 and the nitrogen atom of the amine may together also form a heterocyclic compound.
  • the radical containing a tertiary carbon atom is preferably a tertiary alkyl group having from 4 to 12 carbon atoms, more preferably a tertiary butyl or an at least 2,2-disubstituted piperidine group.
  • Secondary amines which may be formed upon decomposition include tertbutylmethylamine, tert.butyl ethylamine, tert.butylpropylamine, tert.butylisopropylamine.tert.butyl n-butylamine, tert.butyl sec.butylamine, tert.butyl isobutylamine, di(tert.butyl)amine, and higher linear, branched or cyclic alkyl tert.butylamines, tert. butyl phenylamine, 2,2-dimethylpiperidine, 2,2-diethylpiperidine, 2,2-methylethyl piperidine , 2,2,6-trimethylpiperidine,
  • Functional groups not interacting with secondary amines nor ureas under the applied reaction conditions such as a halogen, nitrile, olefine, ether, cumulene or nitro group may be present as well.
  • difunctional isocyanates which can be made according to the present method include diphenylmethane diisocyanates such as 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenyl methane diisocyanate and mixtures thereof, toluene diisocyanates such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and mixtures thereof, m-phenylene diisocyanate, 1 ,4-butylene diisocyanate, 1 ,6-hexylene diisocyanate, 1 ,5-naphthylene diisocyanate, 1 ,4-cyclohexylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1 ,4-xylylene diisocyanate and isophorone diisocyanate. Trifunctional and
  • any mixtures of di- and polyfunctional isocyanates may be obtained depending on the composition of the starting urea mixture.
  • the method of the present invention can advantageously be used for the preparation of diphenylmethane diisocyanates, toluene diisocyanates, polymethylene polyphenylene poiyisocyanates, or mixtures of any of these.
  • the reaction may be carried out in an inert solvent, i.e. any solvent not interacting with the ureas, isocyanates or secondary amines under the applied reaction conditions.
  • isocyanates formed in the decomposition reaction can serve as a solvent for the reaction as well.
  • Suitable inert solvents which may be employed include, for example, aromatic hydrocarbons such as benzene, halogenated aromatic hydrocarbons such as monochlorobenzene, ortho-dichlorobenzene, trichlorobenzene or 1-chloronaphthalene, alkylated aromatic hydrocarbons like toluene, xylene, ethylbenzene, cumene or tetrahydronaphthalene, other functionalised aromatic hydrocarbons such as anisole, diphenylether, ethoxybenzene, benzonitrile, 2-fluoroanisole, 2,3-dimethylanisole or trifluorotoluene or mixtures thereof.
  • aromatic hydrocarbons such as benzene, halogenated aromatic hydrocarbons such as monochlorobenzene, ortho-dichlorobenzene, trichlorobenzene or 1-chloronaphthalene, alkylated aromatic hydrocarbons like toluene,
  • Preferred solvents comprise monochlorobenzene or ortho-dichlorobenzene.
  • any of the abovementioned solvents may also be used to generate the carrier gas.
  • the carrier gas serves to physically remove any secondary amine without forming a chemical bond with it.
  • Mixtures of at least one of the above solvents with a lower boiling inert solvent used to provide a carrier gas may also be used.
  • additional lower boiling inert solvents are alkanes such as n-pentane, n-hexane, n-heptane or higher or branched alkanes, cyclic alkanes like cyclopentane, cyclohexane or derivatives thereof, halogenated alkanes like chloroform, dichloromethane, carbontetrachloride, and alkanes with other functional groups like diethylether, acetonitrile, dioxane and the like.
  • the method may be carried out at atmospheric pressure, preferably under nitrogen.
  • the reaction preferably takes place under reduced pressure.
  • the pressure is preferably reduced to between 10 "4 and 50 mbar, and more preferably to between 0.1 and 10 mbar.
  • reaction time is dependent on the temperature and on the type and quantity of the urea compound, but will normally not exceed 5 hours. Reaction times of less than 3 hours are common, and reaction times of less than 1 hour have been achieved without any problem.
  • the reaction temperature largely depends on whether a solvent is present or not and on the type of urea compound used. Generally, it will be between 50 and 350°C.
  • temperatures will preferably be between the melting point of the starting urea compound and 350°C.
  • the temperature will preferably be between 50 and 200°C, and more preferably between 150 and 190°C.
  • the method may be conducted in any suitable apparatus which can be equipped, if required, with agitation means and heating and/or cooling means to keep the temperature within the desired range.
  • a distillation column is generally attached to said apparatus.
  • the method of the present invention may be conducted batchwise or as a semi-continuous or continuous process.
  • reactants may be varied to suit the particular apparatus and/or reactants employed.
  • the isocyanates and amines obtained by this method are generally of high purity and no additional treatment is required to further purify said products. Only the solvent, if present, needs to be removed.
  • reaction products formed may be subjected to known purification methods, such as filtration, extraction, crystallisation or distillation.
  • the released diphenylmethane diisocyanate containing 307% by weight NCO-groups was recovered.
  • a tarry residue of 2.6% by weight remained in the pyrolysis flask.
  • Example 1 was repeated, but 3.4 g of diphenylmethane bis(N-t-butylmethylurea) was used instead of 5 g, the pressure was reduced to 2.5 mbar instead of being reduced to 0.3 mbar and the diphenylmethane diisocyanate was not distilled. After 25 minutes at 225°C diphenylmethane diisocyanate containing 30.2% by weight NCO-groups remained in the pyrolysis flask.
  • Example 4 (comparative) Example 3 was repeated, but a 10% dispersion of diphenylmethane bis (diisopropylurea) in ODCB was used.
  • This comparative example shows that when a secondary amine not according to the invention is split off a significantly lower yield of isocyanates is obtained.
  • Example 3 was repeated, but a 10% dispersion of diphenylmethane bis (N-t-butylmethylurea) in cumene was used.
  • the dispersion was heated to about 155°C and the solvent/amine mixture was distilled off.
  • the volume was kept constant in the pyrolysis flask by addition of cumene.
  • Example 6 Example 3 was repeated, but using mixtures of monochlorobenzene(MCB)/ODCB or toluene/ODCB as a solvent. In both cases, after 90 minutes at about 155°C (reflux temperature of " the mixture) diphenylmethane diisocyanate containing 28% by weight NCO-groups was obtained.
  • Example 3 was repeated, but a 10% dispersion of polyphenylene polymethylene poly(N-t-butylmethylurea) in ODCB/methylenechloride was used. After 90 minutes at about 155°C (reflux temperature of the mixture) polyphenylene polymethylene polyisocyanate containing 24% by weight NCO-groups was obtained.
  • Example 3 was repeated, but a 1% dispersion of polyphenylene polymethylene poly(N-t-butylmethylurea) in ODCB/methylenechloride was used.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de préparation d'isocyanates polymériques par décomposition d'urées polymériques de la formule R?1(NHCONR2R3)¿x, dans laquelle x représente au moins 2, R1 représente un radical organique de valence x et R2 et R3 représentent des radicaux organiques monovalents, en isocyanates polymériques de la formule R1(NCO)x et en amines secondaires de la formule R2NHR3 caractérisée par le fait que les radicaux R2 et R3 sont liés à l'atome d'azote de l'amine par un atome de carbone tertiaire.
EP98925567A 1997-05-31 1998-05-11 Procede de preparation d'isocyanates organiques Withdrawn EP0986536A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP98925567A EP0986536A1 (fr) 1997-05-31 1998-05-11 Procede de preparation d'isocyanates organiques

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP97201626 1997-05-31
EP97201626 1997-05-31
PCT/EP1998/002734 WO1998054129A1 (fr) 1997-05-31 1998-05-11 Procede de preparation d'isocyanates organiques
EP98925567A EP0986536A1 (fr) 1997-05-31 1998-05-11 Procede de preparation d'isocyanates organiques

Publications (1)

Publication Number Publication Date
EP0986536A1 true EP0986536A1 (fr) 2000-03-22

Family

ID=8228383

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98925567A Withdrawn EP0986536A1 (fr) 1997-05-31 1998-05-11 Procede de preparation d'isocyanates organiques

Country Status (4)

Country Link
EP (1) EP0986536A1 (fr)
AU (1) AU7763498A (fr)
WO (1) WO1998054129A1 (fr)
ZA (1) ZA984489B (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1976825B1 (fr) * 2006-01-13 2011-06-08 Basf Se Procede de production d'isocyanates
US8871969B2 (en) 2011-05-30 2014-10-28 Basf Se Process for the production of polyisocyanates
JP2014524892A (ja) * 2011-05-30 2014-09-25 ビーエーエスエフ ソシエタス・ヨーロピア ポリイソシアネートの製造法
US8772527B2 (en) 2012-04-27 2014-07-08 Basf Se Process for isomerization of cis-2-pentenenitrile to 3-pentenenitriles
WO2014082910A1 (fr) * 2012-11-28 2014-06-05 Basf Se Procédé de production de polyisocyanates

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03173859A (ja) * 1989-04-06 1991-07-29 Arco Chem Technol Inc 芳香族アミンからの芳香族モノーおよびポリイソシアネートの製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9854129A1 *

Also Published As

Publication number Publication date
ZA984489B (en) 1998-11-30
WO1998054129A1 (fr) 1998-12-03
AU7763498A (en) 1998-12-30

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