WO1998054129A1 - Method for the preparation of organic isocyanates - Google Patents
Method for the preparation of organic isocyanates Download PDFInfo
- Publication number
- WO1998054129A1 WO1998054129A1 PCT/EP1998/002734 EP9802734W WO9854129A1 WO 1998054129 A1 WO1998054129 A1 WO 1998054129A1 EP 9802734 W EP9802734 W EP 9802734W WO 9854129 A1 WO9854129 A1 WO 9854129A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- radicals
- solvent
- decomposition
- polymeric
- isocyanates
- Prior art date
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.
- 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
- 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,
- any of the abovementioned solvents may also be used to generate the carrier gas.
- 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.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP98925567A EP0986536A1 (en) | 1997-05-31 | 1998-05-11 | Method for the preparation of organic isocyanates |
AU77634/98A AU7763498A (en) | 1997-05-31 | 1998-05-11 | Method for the preparation of organic isocyanates |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP97201626 | 1997-05-31 | ||
EP97201626.5 | 1997-05-31 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998054129A1 true WO1998054129A1 (en) | 1998-12-03 |
Family
ID=8228383
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1998/002734 WO1998054129A1 (en) | 1997-05-31 | 1998-05-11 | Method for the preparation of organic isocyanates |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0986536A1 (en) |
AU (1) | AU7763498A (en) |
WO (1) | WO1998054129A1 (en) |
ZA (1) | ZA984489B (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007082818A1 (en) * | 2006-01-13 | 2007-07-26 | Basf Se | Method for producing isocyanates |
WO2012163894A2 (en) | 2011-05-30 | 2012-12-06 | Basf Se | Process for preparing polyisocyanates |
WO2014082910A1 (en) * | 2012-11-28 | 2014-06-05 | Basf Se | Method for producing polyisocyanates |
US8772527B2 (en) | 2012-04-27 | 2014-07-08 | Basf Se | Process for isomerization of cis-2-pentenenitrile to 3-pentenenitriles |
US8871969B2 (en) | 2011-05-30 | 2014-10-28 | Basf Se | Process for the production of polyisocyanates |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0391716A1 (en) * | 1989-04-06 | 1990-10-10 | Arco Chemical Technology, Inc. | An integrated process for the preparation of aromatic mono- and polyisocyanates from aromatic amines |
-
1998
- 1998-05-11 AU AU77634/98A patent/AU7763498A/en not_active Abandoned
- 1998-05-11 EP EP98925567A patent/EP0986536A1/en not_active Withdrawn
- 1998-05-11 WO PCT/EP1998/002734 patent/WO1998054129A1/en not_active Application Discontinuation
- 1998-05-26 ZA ZA984489A patent/ZA984489B/en unknown
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0391716A1 (en) * | 1989-04-06 | 1990-10-10 | Arco Chemical Technology, Inc. | An integrated process for the preparation of aromatic mono- and polyisocyanates from aromatic amines |
Non-Patent Citations (1)
Title |
---|
J.C. STOWELL ET AL.: "Urea dissociation. A measure of steric hindrance in secondary amines", JOURNAL OF ORGANIC CHEMISTRY, vol. 39, 1974, EASTON US, pages 2448 - 2449, XP002052020 * |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007082818A1 (en) * | 2006-01-13 | 2007-07-26 | Basf Se | Method for producing isocyanates |
JP2009523153A (en) * | 2006-01-13 | 2009-06-18 | ビーエーエスエフ ソシエタス・ヨーロピア | Isocyanate production method |
US8026387B2 (en) | 2006-01-13 | 2011-09-27 | Basf Aktiengesellschaft | Method for producing isocyanates |
JP2013173784A (en) * | 2006-01-13 | 2013-09-05 | Basf Se | Method for producing isocyanate |
WO2012163894A2 (en) | 2011-05-30 | 2012-12-06 | Basf Se | Process for preparing polyisocyanates |
WO2012163894A3 (en) * | 2011-05-30 | 2013-07-18 | Basf Se | Process for preparing polyisocyanates |
CN103596920A (en) * | 2011-05-30 | 2014-02-19 | 巴斯夫欧洲公司 | Process for preparing polyisocyanates |
US8871969B2 (en) | 2011-05-30 | 2014-10-28 | Basf Se | Process for the production of polyisocyanates |
US8772527B2 (en) | 2012-04-27 | 2014-07-08 | Basf Se | Process for isomerization of cis-2-pentenenitrile to 3-pentenenitriles |
WO2014082910A1 (en) * | 2012-11-28 | 2014-06-05 | Basf Se | Method for producing polyisocyanates |
Also Published As
Publication number | Publication date |
---|---|
AU7763498A (en) | 1998-12-30 |
EP0986536A1 (en) | 2000-03-22 |
ZA984489B (en) | 1998-11-30 |
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