EP0986535A1 - Method for the preparation of organic isocyanates - Google Patents
Method for the preparation of organic isocyanatesInfo
- Publication number
- EP0986535A1 EP0986535A1 EP98925566A EP98925566A EP0986535A1 EP 0986535 A1 EP0986535 A1 EP 0986535A1 EP 98925566 A EP98925566 A EP 98925566A EP 98925566 A EP98925566 A EP 98925566A EP 0986535 A1 EP0986535 A1 EP 0986535A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- solvent
- decomposition
- polymeric
- monomeric
- aromatic
- 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- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/04—Preparation of derivatives of isocyanic acid from or via carbamates or carbamoyl halides
Abstract
Method for the preparation of aromatic monomeric or polymeric isocyanates by decomposing aromatic monomeric or polymeric carbamates of the formula R?1(NHCOOR2)¿x wherein x is at least 1, R1 is an aromatic radical of valency x and R2 is a monovalent organic radical, into aromatic monomeric or polymeric isocyanates of the formula R1(NCO)x and alcohols of the formula R2OH, characterised in that the radical R2 is substituted by a group containing at least one halogen group.
Description
Method for the preparation of organic isocyanates.
The present invention relates to a method for the preparation of monomeric or polymeric aromatic isocyanates by thermal decomposition of monomeric or polymeric aromatic carbamates.
EP-A 611.243 discloses the preparation of organic isocyanates by thermal decomposition of corresponding carbamates dissolved in a solvent to isocyanate and an alcohol in multiple and separate steps. In intermediate steps the solvent is treated with an inert stripping agent to remove the alcohol formed during the thermal treatment and finally an isocyanate-rich solution is recovered.
US-A 5.453.536 describes the pyrolysis of polycarbamates in the substantial absence of a solvent under reduced pressure and at a temperature of about 150 to about 270°C to form the corresponding polyisocyanate and a secondary alcohol. Alcohols containing a halogen atom are not mentioned.
In US-A 4.547.322 a method is described for manufacturing MDI from a N-phenylcarbamate which comprises methylenating a N-phenylcarbamate to produce a dinuclear diphenylmethane dicarbamate and subjecting the latter to a thermal decomposition process which involves dissolving the dinuclear diphenylmethane dicarbamate in a solvent having a boiling point between 120 and 350°C, allowing the solution to flow down in a reactor and come into counterflow contact with a carrier introduced into the reactor upwardly thereby producing an organic hydroxyl compound and recovering said hydroxyl compound as vapor and the carrier at the upper end and the isocyanate solution at the lower end of the reactor.
It is mentioned that the method can be used with, amongst others, 2,2,2-trichloroethyl and 2,2,2-trifluoroethyl substituted N-phenylcarbamates, but no such examples are given.
US-A 3.746.689 discloses the use of halogenated alcohols having 1 to 6 carbon atoms as blocking agents for polyisocyanates.
An improved method has now been found for the preparation of monomeric or polymeric isocyanates by thermolysis of corresponding monomeric or polymeric carbamates.
The invention thus concerns a method for the preparation of aromatic monomeric or polymeric isocyanates by decomposing aromatic monomeric or polymeric carbamates of the formula R1(NHCOOR2)x wherein x is at least 1 , R1 is an aromatic radical of valency x and R2 is a monovalent organic radical, into monomeric or polymeric isocyanates of the formula R1(NCO)x and alcohols of the formula R2OH, characterised in that the radical R2 is substituted by a group containing at least one halogen atom.
Organic isocyanates can be obtained at low temperatures in high yields in the absence of a solvent or from concentrated solutions.
R1 is a substituted or unsubstituted, saturated or unsaturated, aromatic hydrocarbon radical optionally containing hetero-atoms.
R2 is preferably substituted by at least one chlorine or fluorine atom.
The carbamate composition which is subjected to decomposition may be a mixture of polymeric carbamate 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 carbamate mixture. The term 'functionality' as used herein is defined as number averaged functionality.
The average value of x is generally between 1 and 15, preferably between 2 and 10 and more preferably from 2 to 3.
The term "polymeric'' as used herein refers to any functionality higher than 1.
Preferred as R are tolylene, methyiene diphenylene or polymethylene polyphenylene radicals or mixtures thereof.
Alcohols which may be formed include, for example, 2,2,2-trifluoroethanol, 2,2,2-trichloroethanol, trichloromethanol, 1 ,1 ,1 ,3,3,3-hexafluoroisopropanol, nonafluoro tert.butanol, fluorophenols, chlorophenols and polysubstituted halogenated phenols.
Representative monomeric isocyanates which may be formed include phenylisocyanate, 4-chlorophenylisocyanate, 2-fluorophenylisocyanate, 3,4-dichlorophenyl isocyanate, tolylisocyanate and diisopropylphenylisocyanate.
Examples of 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'-diphenylmethane diisocyanate and mixtures thereof, toluene diisocyanates such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and mixtures thereof, m-phenylene diisocyanate and 1 ,5-naphthylene diisocyanate.
The method of the present invention can advantageously be used for the preparation of diphenylmethane diisocyanates, toluene diisocyanates, polymethylene polyphenylene
polyisocyanates, or mixtures of any of these.
Trifunctional and higher functional isocyanates which can be made include 2,4,6-toluene triisocyanate and polymethylene polyphenylene polyisocyanates.
As already mentioned above, any mixtures of mono-, di- and polyfunctional isocyanates may be obtained depending on the composition of the starting carbamate mixture.
The reaction may be carried out in an inert solvent, i.e. any solvent not interacting with isocyanates or alcohols under the applied reaction conditions. However, 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.
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 alcohol without forming a chemical bond with it.
Mixtures of at least one of the above solvents with a lower boiling inert solvent used as carrier gas may also be used.
Exemplary of such additional lower boiling 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.
However, in the absence of a solvent, the reaction preferably takes place under reduced pressure. In such case, the pressure is preferably reduced to between 10"* and 50 mbar, and more preferably to between 0.1 and 10 mbar.
Superatmospheric pressures may sometimes be required, depending on the type of solvents
used.
The reaction time is dependent on the temperature and on the type and quantity of the carbamate compound, but will normally not exceed 5 hours Reaction times of less than 3 hours are common, 5 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. Generally, it will be between 50 and 350°C In a solvent-free method the temperatures will normally be between the melting point of the carbamate and 350°C, whereas in the presence of a solvent the temperature will preferably be between 100 and 200°C and more preferably between 120 and 10 190°C
With the method of the present invention yields of isocyanates of more than 90% can readily be obtained Yields of at least 95% are possible
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 15 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
The order of addition of the reactants may be varied to suit the particular apparatus and/or reactants employed
20 The presence of any other compounds, such as catalysts or co-reactants, in addition to the carbamate compound and optionally the solvent is generally not required
The isocyanates and alcohols 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
25 If a particularly high grade of purity is required, the reaction products formed may be subjected to known purification methods, such as filtration, extraction, recrystallisation or distillation
The invention is illustrated by, but not limited to, the following examples
Examples
Example 1
Into a suitable flask equipped with a condenser, were placed 3 g of diphenylmethane bis (1J J ,3,3,3-hexafluoroisopropylcarbamate). The carbamate was heated to a temperature of 5 240°C. After the carbamate was molten, the pressure was reduced to 0.1 mbar. 1 ,1 ,1 ,3,3,3-Hexafluoroisopropanol was removed from the system as the reaction proceeded. After 25 minutes at 240°C diphenylmethane diisocyanate containing 33.6% by weight NCO-groups remained in the pyrolysis flask.
Example 2
0 Example 1 was repeated, but 4.2 g of polyphenylene polymethylene poly (1 ,1 ,1 ,3,3,3-hexafluoroisopropylcarbamate) was used instead of diphenylmethane bis (1 ,1 ,1 ,3,3,3-hexafluoroisopropylcarbamate). The carbamate was heated to a temperature of 220°C. After the carbamate was molten, the pressure was reduced to 2 mbar. 1 JJ,3,3,3-Hexafluoroisopropanol was removed from the system as the reaction proceeded. 5 After 20 minutes at 220°C polyphenylene polymethylene polyisocyanate containing 30% by weight NCO-groups remained in the pyrolysis flask.
Example 3 (comparative)
Example 1 was repeated, but 2 g of diphenylmethane bis (isopropylcarbamate) was used instead of diphenylmethane bis (1 ,1 ,1 ,3,3,3-hexafluoroisopropyl carbamate). The carbamate was heated 0 to a temperature of 220°C. After the carbamate was molten, the pressure was reduced to 1-3 mbar. isopropanol was removed from the system as the reaction proceeded. After 20 minutes at 220°C diphenylmethane diisocyanate containing 5.7% by weight NCO-groups remained in the pyrolysis flask.
25 Example 4 (comparative)
Example 1 was repeated, but 2.1 g of diphenylmethane bis (1-methoxy-2-propyl carbamate) was used instead of diphenylmethane bis (1 ,1 ,1 ,3,3,3-hexafluoro isopropylcarbamate). The carbamate was heated to a temperature of 220°C. After the carbamate was molten, the pressure was
reduced to 1-5 mbar.
1 -Methoxy-2-propanol was removed from the system as the reaction proceeded. After 25 minutes at 220°C diphenylmethane diisocyanate containing 23.5% by weight NCO-groups remained in the pyrolysis flask.
Comparative examples 3 and 4 show that a significantly lower yield is obtained in comparison with example 1 when the alcohol formed does not contain a halogen atom.
Example 5
Into a suitable flask equipped with a condenser and an addition funnel, a 5% dispersion of diphenylmethane bis (1 ,1 ,1 ,3,3,3-hexafluoroisopropyl carbamate) in chlorobenzene (MCB) was placed. The dispersion was heated to about 134°C and the solvent/alcohol mixture was distilled off. The volume was kept constant in the pyrolysis flask by addition of MCB. After 1 hour at 134°C diphenylmethane diisocyanate containing 30.5% by weight NCO-groups was obtained.
Example 6
Example 5 was repeated, but a 10% dispersion of polyphenylene polymethylene poly (1 ,1 J ,3,3,3-hexafluoroisopropylcarbamate) in MCB was used. The dispersion was heated to about 134°C and the solvent/alcohol mixture was distilled off. The volume was kept constant in the pyrolysis flask by addition of MCB. After 1 hour at 134°C polyphenylene polymethylene polyisocyanate containing 31.2% by weight NCO-groups was obtained.
Example 7
Example 5 was repeated, but a 5% dispersion of diphenylmethane bis (2,2,2-trifluoroethylcarbamate) in ortho-dichlorobenzene (ODCB) was used. The dispersion was heated to about 180°C and the solvent/alcohol mixture was distilled off. The volume was kept constant in the pyrolysis flask by addition of ODCB.
After 1 hour at 180°C diphenylmethane diisocyanate containing 27.4% by weight NCO-groups was obtained.
Example 8
Example 5 was repeated, but a 5% dispersion of polyphenylene polymethylene poly (2,2,2-trifluoroethylcarbamate) in a MCB/ODCB mixture was used. The dispersion was heated to about 180°C. The volume was kept constant in the pyrolysis flask by addition of ODCB. After 1 hour at 180°C polyphenylene polymethylene polyisocyanate containing 28.2% by weight NCO-groups was obtained.
Example 9 (comparative)
Example 5 was repeated, but a 5% dispersion of diphenylmethane bis (isopropylcarbamate) in a MCB/ODCB mixture was used. The dispersion was heated to about 180°C. The volume was kept constant in the pyrolysis flask by addition of ODCB. After 2 hours at 180°C diphenylmethane diisocyanate containing 8.6% by weight NCO-groups was obtained.
Compared with example 5, this comparative example shows that a much lower yield is obtained when an alcohol not having a halogen atom is split off.
Example 10 (comparative)
Example 5 was repeated, but a 10% dispersion of polyphenylene polymethylene poly (1-methoxy-2-propylcarbamate) in ODCB was used. The dispersion was heated to about 180°C. The volume was kept constant in the pyrolysis flask by addition of ODCB. After 2Vι hours at 180°C polyphenylene polymethylene polyisocyanate containing 9% by weight NCO-groups was obtained.
Comparative example 10 again illustrates, by comparison with example 6, that the yield is significantly lower when an alcohol not according to the invention is formed in the decomposition.
Example 11
Into a suitable flask equipped with a condenser and an addition funnel, a 10% dispersion of toluene 2,4 bis(2,2,2-trifluoroethylcarbamate) in ortho-dichlorobenzene (ODCB) was placed. The dispersion was heated to about 180°C and the solvent/alcohol mixture was distilled off. The volume was kept constant in the pyrolysis flask by addition of ODCB. After 90 minutes at about 180°C toluene diisocyanate containing more than 43% by weight NCO-groups, corresponding to more than 89% yield, was obtained.
Example 12
Into a suitable flask equipped with a condenser and an addition funnel, a 10% dispersion of toluene 2,4 bis(1 J,1 ,3,3,3-hexafluoroisopropylcarbamate) in ortho-dichlorobenzene (ODCB) was placed. The dispersion was heated to about 180°C and the solvent/alcohol mixture was distilled off. The volume was kept constant in the pyrolysis flask by addition of ODCB. After 90 minutes at about 180°C toluene diisocyanate containing more than 47% by weight NCO-groups, corresponding to about 99% yield, was obtained.
Claims
1. Method for the preparation of aromatic monomeric or polymeric isocyanates by decomposing aromatic monomeric or polymeric carbamates of the formula R1(NHCOOR2)x wherein x is at least 1 , R is an aromatic radical of valency x and R2 is a monovalent organic radical, into aromatic monomeric or polymeric isocyanates of the formula R1(NCO)x and alcohols of the formula R2OH, characterised in that the radical R2 is substituted by a group containing at least one halogen group.
2. Method according to claim 1 wherein R2 is substituted by at least one chlorine or fluorine atom.
3. Method according to any one of the preceding claims wherein R1 comprises methylene diphenylene or polymethylene polyphenylene radicals or mixtures thereof.
4. Method according to any one of the claims 1 to 3 wherein R1 comprises tolylene radicals.
5. Method according to any one of the preceding claims wherein the decomposition is carried out in the presence of a solvent.
6. Method according to claim 5 wherein the solvent comprises monochlorobenzene or ortho-dichlorobenzene.
7. Method according to claim 5 or 6 wherein the decomposition temperature is between 100 and 200┬░C.
8. Method according to claim 7 wherein the decomposition temperature is between 120 and 190┬░C.
9. Method according any one of the claims 1 to 8 wherein the solvent is mixed with a lower boiling solvent used to generate a carrier gas.
10. Method according to any one of the claims 1 to 4 wherein the decomposition is carried out in the absence of a solvent.
11. Method according to claim 10 wherein the decomposition is carried out at a temperature between the melting point of the monomeric or polymeric carbamate and 350┬░C.
12. Method according to claim 10 or 11 wherein the decomposition is carried out under reduced pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP98925566A EP0986535A1 (en) | 1997-05-31 | 1998-05-11 | Method for the preparation of organic isocyanates |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP97201627 | 1997-05-31 | ||
| EP97201627 | 1997-05-31 | ||
| EP98925566A EP0986535A1 (en) | 1997-05-31 | 1998-05-11 | Method for the preparation of organic isocyanates |
| PCT/EP1998/002733 WO1998054128A1 (en) | 1997-05-31 | 1998-05-11 | Method for the preparation of organic isocyanates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0986535A1 true EP0986535A1 (en) | 2000-03-22 |
Family
ID=8228384
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP98925566A Withdrawn EP0986535A1 (en) | 1997-05-31 | 1998-05-11 | Method for the preparation of organic isocyanates |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0986535A1 (en) |
| JP (1) | JP2002500654A (en) |
| KR (1) | KR20010013096A (en) |
| CN (1) | CN1258273A (en) |
| AU (1) | AU7763398A (en) |
| CA (1) | CA2289656A1 (en) |
| HU (1) | HUP0002197A2 (en) |
| WO (1) | WO1998054128A1 (en) |
| ZA (1) | ZA984595B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE305918T1 (en) * | 2000-02-29 | 2005-10-15 | Huntsman Int Llc | METHOD FOR PRODUCING ORGANIC POLYISOCYANATES |
| US8053595B2 (en) | 2006-11-17 | 2011-11-08 | Asahi Kasei Chemicals Corporation | Process for producing isocyanates |
| CN101589022B (en) * | 2006-11-17 | 2013-08-14 | 旭化成化学株式会社 | Method for producing isocyanate |
| TW200844080A (en) | 2007-01-11 | 2008-11-16 | Asahi Kasei Chemicals Corp | Process for producing isocyanate |
| EP2147909B1 (en) | 2007-03-30 | 2016-12-14 | Asahi Kasei Kabushiki Kaisha | Method for production of isocyanate using composition comprising carbamic acid ester and aromatic hydroxy compound, and composition for transport or storage of carbamic acid ester |
| EP2036884A1 (en) | 2007-09-14 | 2009-03-18 | Repsol Ypf S.A. | Process for producing fluorinated isocyanates and carbamates |
| RU2483058C2 (en) | 2008-05-15 | 2013-05-27 | Асахи Касеи Кемикалз Корпорейшн | Method of producing isocyanate |
| EP2275405B1 (en) | 2008-05-15 | 2019-04-24 | Asahi Kasei Kabushiki Kaisha | Process for producing isocyanate using diaryl carbonate |
| WO2011125429A1 (en) | 2010-04-02 | 2011-10-13 | 旭硝子株式会社 | Method for producing carbamate compound, carbamate compound, and method for producing isocyanate compound using same |
| KR101318828B1 (en) * | 2011-03-31 | 2013-10-17 | 케이에스랩(주) | Process of preparing xylylene diisocyanates, their reaction intermediates and process of preparing them |
| CN103804331B (en) * | 2012-11-06 | 2016-08-03 | 中国科学院青岛生物能源与过程研究所 | A kind of synthetic method of difurfuryl methane diisocyanate |
| KR102618935B1 (en) | 2015-01-30 | 2023-12-27 | 바스프 에스이 | Polyphenylene polymethylene polyisocyanate with low by-product content |
| CN112125826B (en) * | 2020-09-16 | 2021-08-10 | 北京理工大学 | Preparation method of 2,4, 6-toluene triisocyanate |
| WO2023080049A1 (en) * | 2021-11-02 | 2023-05-11 | 国立大学法人神戸大学 | Production method for fluorine-containing polyurethane |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3746689A (en) * | 1972-02-11 | 1973-07-17 | Basf Wyandotte Corp | Polyisocyanates blocked with polyhaloalcohols |
-
1998
- 1998-05-11 HU HU0002197A patent/HUP0002197A2/en unknown
- 1998-05-11 CN CN98805520A patent/CN1258273A/en active Pending
- 1998-05-11 EP EP98925566A patent/EP0986535A1/en not_active Withdrawn
- 1998-05-11 JP JP50015499A patent/JP2002500654A/en active Pending
- 1998-05-11 WO PCT/EP1998/002733 patent/WO1998054128A1/en not_active Application Discontinuation
- 1998-05-11 CA CA002289656A patent/CA2289656A1/en not_active Abandoned
- 1998-05-11 KR KR19997011075A patent/KR20010013096A/en not_active Application Discontinuation
- 1998-05-11 AU AU77633/98A patent/AU7763398A/en not_active Abandoned
- 1998-05-28 ZA ZA984595A patent/ZA984595B/en unknown
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9854128A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| HUP0002197A2 (en) | 2000-10-28 |
| CN1258273A (en) | 2000-06-28 |
| KR20010013096A (en) | 2001-02-26 |
| AU7763398A (en) | 1998-12-30 |
| ZA984595B (en) | 1998-11-30 |
| WO1998054128A1 (en) | 1998-12-03 |
| CA2289656A1 (en) | 1998-12-03 |
| JP2002500654A (en) | 2002-01-08 |
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