DE895902C - Process for the production of organic isocyanates containing a urethane group - Google Patents
Process for the production of organic isocyanates containing a urethane groupInfo
- Publication number
- DE895902C DE895902C DEW6307A DEW0006307A DE895902C DE 895902 C DE895902 C DE 895902C DE W6307 A DEW6307 A DE W6307A DE W0006307 A DEW0006307 A DE W0006307A DE 895902 C DE895902 C DE 895902C
- Authority
- DE
- Germany
- Prior art keywords
- diisocyanate
- production
- tert
- urethane group
- alcohol
- 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.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von organischen Isocyanaten, die eine Urethangruppe enthalten Die Erfindung betrifft die Herstellung von organischen Isocyanaten, die eine Urethangruppe enthalten, durch Umsetzung von Polyisocyanaten mit tertiären Alkoholen in etwa äquimolaren Mengen. Einige von diesen können zur Modifizierung von Polyestern und Polyesteramiden verwendet werden.Process for the preparation of organic isocyanates containing a urethane group The invention relates to the production of organic isocyanates that contain contain a urethane group by reacting polyisocyanates with tertiary Alcohols in approximately equimolar amounts. Some of these can be modified of polyesters and polyester amides can be used.
Die Herstellung der neuen Verbindungen kann durch die folgende Formel ausgedrückt werden: In dieser Formel sind R, R' und R" organische Radikale und R"' ein organisches Radikal, das wenigstens eine -N C O-Gruppe enthält.The preparation of the new compounds can be expressed by the following formula: In this formula, R, R 'and R "are organic radicals and R"' is an organic radical containing at least one -NC O- group.
Es sei bemerkt, daß die Reaktion zwischen dem Polyisocyanat und dem tertiären Alkohol reversibel ist, wobei die Reaktion durch die Temperatur gesteuert werden kann.It should be noted that the reaction between the polyisocyanate and the tertiary alcohol is reversible, the reaction being controlled by temperature can be.
Das Monoadditionsprodukt des Polyisocyanats und des tertiären Alkohols wird bei verhältnismäßig niedrigen Temperaturen gebildet und wird bei verhältnismäßig hohen Temperaturen im Bereich von ioo bis 15o° wieder in das Polyisocyanat und den Alkohol dissoziiert. Diese Temperaturabhängigkeit macht die Verfahrensprodukte besonders zur Modifizierung von Polyestern und Polyesteramiden geeignet. Das Monoadditionsprodukt dissoziiert nicht in das reaktionsfähige Polyisocyanat, wenn nicht zu hohe Temperaturen erreicht werden. Deshalb bleibt bei normalen Verfahrensbedingungen das Monoadditionsprodukt stabil und vermindert daher die Zahl der Querverbindungen der zu modifizierenden Linearpolymeren. Die Monoadditionsprodukte sind weiter als Mittel zur Steuerung der Neigung von Polyisocyanaten zur Selbstpolymerisation geeignet.The monoaddition product of the polyisocyanate and the tertiary alcohol is formed at relatively low temperatures and is at relatively high Temperatures in the range from 100 to 150 ° back into the polyisocyanate and the alcohol dissociated. This temperature dependence makes the process products special suitable for modifying polyesters and polyester amides. The monoaddition product does not dissociate into the reactive polyisocyanate unless temperatures are too high can be achieved. Therefore, under normal process conditions, the monoaddition product remains stable and therefore reduces the number of cross-connections to be modified Linear polymers. The monoadducts are useful as a means of control the tendency of polyisocyanates to self-polymerize.
Bei der Herstellung der Verfahrensprodukte kann jedes Polyisocyanat verwendet werden. Beispiele hierfür sind aliphatische Verbindungen, wie Äthylen-, Trimethylen-, Tetramethylen-, Pentamethylen-, Hexamethylen-, Propylen-i, 2-, Butylen-i, 2-, Butylen-2, 3-, Butylen-i, 3-, Äthyliden- und Butylidendiisocyanate; Cycloalkylenverbindungen, wie Cyclopentan-i, 3-, Cyclohexan-i, 4- und Cyclohexan-i, 2-diisocyanate; aromatische Verbindungen, wie m-Phenylen-, p-Phenylen-, 4, 4'-Diphenyl-, i, 5-Naphthalin- und i, 4-Naphthalin-diisocyanate; aliphatisch-aromatische Verbindungen, wie 4, 4'-Diphenylmethan-, 2, 4-Toluylen-, 3, 3'-Dimethyldiphenyl-4, 4'-diisocyanate und i, 4-Xylylen-düsocyanate; kernsubstituierte aromatische Verbindungen, wie Dianisidindüsocyanat, 4, 4'-Diphenylätherdiisocyanat und Chlordiphenyldiisocyanat ; Trüsocyanate, wie 4, 4', 4"-Triisocyanattriphenylmethan, i, 3, 5-Trüsocyanatbenzol und 2, 4, 6-Trüsocyanattoluol, und Tetraisocyanate, wie 4, 4'-Dimethyldiphenylmethan-2, 2', 5, 5'-tetraisocyanat.Any polyisocyanate can be used in the production of the process products be used. Examples are aliphatic compounds such as ethylene, Trimethylene, tetramethylene, pentamethylene, hexamethylene, propylene-i, 2-, butylene-i, 2-, butylene-2, 3-, butylene-i, 3-, ethylidene and butylidene diisocyanates; Cycloalkylene compounds, such as cyclopentane-i, 3-, cyclohexane-i, 4- and cyclohexane-i, 2-diisocyanates; aromatic Compounds such as m-phenylene, p-phenylene, 4, 4'-diphenyl, i, 5-naphthalene and i, 4-naphthalene diisocyanate; aliphatic-aromatic compounds, such as 4, 4'-diphenylmethane, 2,4-toluylene, 3, 3'-dimethyldiphenyl-4, 4'-diisocyanate and i, 4-xylylene diisocyanate; ring-substituted aromatic compounds, such as dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate and chlorodiphenyl diisocyanate; Trisocyanates, such as 4, 4 ', 4 "-triisocyanate triphenylmethane, i, 3, 5-tri-cyanate benzene and 2, 4, 6-tri-cyanate toluene, and tetraisocyanates, such as 4,4'-Dimethyldiphenylmethane-2, 2 ', 5, 5'-tetraisocyanate.
Jeder tertiäre Alkohol kann zur Bildung der Monoadditionsprodukte verwendet werden. Beispiele hierfür sind tert. Butylalkohol, tert. Amylalkohol, Dimethyläthinylcarbinol, Dimethylphenylcarbinol, Methyldiphenylcarbinol, Triphenylcarbinol, tert. i-Nitrobutylalkohol und tert. i-Chlorbutylalkohol.Any tertiary alcohol can lead to the formation of the monoadducts be used. Examples are tert. Butyl alcohol, tert. Amyl alcohol, Dimethyläthinylcarbinol, Dimethylphenylcarbinol, Methyldiphenylcarbinol, Triphenylcarbinol, tert. i-nitrobutyl alcohol and tert. i-chlorobutyl alcohol.
Besonders bevorzugte Urethanisocyanate erhält man durch die Reaktion von: i. tert. Butylalkohol und 4, 4'-Diphenyldiisocyanat, 2. tert. Butylalkohol und 2, 4-Toluylendiisocyanat, 3. tert. Butylalkohol und i, 5-Naphthalindüsocyanat, 4. tert. Butylalkohol und Hexamethylendiisocyanat, 5. tert. Amylalkohol und 4, 4'-Diphenyldiisocyanat, 6. tert. Amylalkohol und 2, 4-Toluylendiisocyanat, 7. tert. Amylalkohol und i, 5-Naphthalindiisocyanat, B. tert. Amylalkohol und Hexamethylendüsocyanat, g. Dimethyläthinylcarbinol und 4, 4'-Diphenyldüsocyanat, io. Dimethyläthinylcarbinol und 2, 4-Toluylendüsocyanat, ii. Dimethyläthinylcarbinol und i, 5-NaphthaEndiisocyanat, 12. Dimethyläthinylcarbinol und Hexamethylendiisocyanat.Particularly preferred urethane isocyanates are obtained by the reaction of: i. tert. Butyl alcohol and 4, 4'-diphenyl diisocyanate, 2nd tert. Butyl alcohol and 2, 4-tolylene diisocyanate, 3rd tert. Butyl alcohol and i, 5-naphthalene diisocyanate, 4th tert. Butyl alcohol and hexamethylene diisocyanate, 5th tert. Amyl alcohol and 4, 4'-diphenyl diisocyanate, 6th tert. Amyl alcohol and 2, 4-tolylene diisocyanate, 7th tert. Amyl alcohol and i, 5-naphthalene diisocyanate, B. tert. Amyl alcohol and hexamethylene diisocyanate, g. Dimethyläthinylcarbinol and 4, 4'-Diphenyldüsocyanat, io. Dimethyläthinylcarbinol and 2,4-toluene diisocyanate, ii. Dimethylethinylcarbinol and i, 5-naphtha end diisocyanate, 12. Dimethyläthinylcarbinol and hexamethylene diisocyanate.
Bei der Herstellung der Verfahrensprodukte werden im allgemeinen das Polyisocyanat und der tertiäre Alkohol in einem geeigneten inerten Lösungsmittel, wie Toluol, Methyläthylketon oder o-Dichlorbenzol, gelöst. Die Lösungen werden gerührt und stehengelassen. Das gebildete Monoadditionsprodukt scheidet sich aus der Lösung ab und wird durch Filtrieren oder Verdampfung des Lösungsmittels gewonnen. Die Zeit, die zu seiner Bildung nötig ist, schwankt zwischen einigen Minuten und mehreren Stunden. Sie hängt von den verwendeten Ausgangsstoffen ab. Gewöhnlich wird ein Überschuß 'des Polyisocyanats angewandt, so daß das Produkt, das sich abscheidet, im wesentlichen ein reines Monoadditionsprodukt ist. Das aus der Lösung ausgeschiedene Produkt enthält wahrscheinlich auch geringe Mengen an Diadditionsprodukt und an nicht zur Reaktion gekommenen Stoffen, die nötigenfalls durch Umkristallisation in bekannter Weise entfernt werden können.In the production of the process products are generally the Polyisocyanate and the tertiary alcohol in a suitable inert solvent, such as toluene, methyl ethyl ketone or o-dichlorobenzene, dissolved. The solutions are stirred and left standing. The monoaddition product formed separates out of the solution and is recovered by filtration or evaporation of the solvent. The time, which is necessary for its formation varies between a few minutes and several Hours. It depends on the raw materials used. Usually there will be an excess 'of the polyisocyanate applied so that the product that separates out is essentially is a pure monoaddition product. The product excreted from the solution contains probably also small amounts of diaddition product and not for the reaction substances that have come in, if necessary by recrystallization in a known manner can be removed.
Beispiel 4, 4'-Diphenyldüsocyanat (o, 15 Mol) und tert. Amylalkohol (o,io Mol) werden in 400 ccm trockenem Toluol gelöst. Die Lösung wird am Rückflußkühler 5 Stunden lang erhitzt. Das Urethanisocyanat der Formel beginnt sich aus der Lösung während der ersten Stunden auszuscheiden. Die Lösung wird abgekühlt und das Verfahrensprodukt durch Filtrieren gewonnen. Nach Umkristallisation aus Petroleumäther erhält man eine Ausbeute von 27 °/o. Das Produkt beginnt oberhalb 31o° zu sublimieren und verkohlt, ohne zu schmelzen, bei 37o bis 38o°.Example 4, 4'-diphenyl diisocyanate (0.15 mol) and tert. Amyl alcohol (0.1 moles) are dissolved in 400 ccm of dry toluene. The solution is refluxed for 5 hours. The urethane isocyanate of the formula begins to separate from the solution during the first few hours. The solution is cooled and the process product is recovered by filtration. After recrystallization from petroleum ether, a yield of 27% is obtained. The product begins to sublime above 31o ° and char without melting at 37o to 38o °.
Claims (1)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US895902XA | 1950-11-01 | 1950-11-01 |
Publications (1)
Publication Number | Publication Date |
---|---|
DE895902C true DE895902C (en) | 1953-11-09 |
Family
ID=22218480
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DEW6307A Expired DE895902C (en) | 1950-11-01 | 1951-07-21 | Process for the production of organic isocyanates containing a urethane group |
Country Status (1)
Country | Link |
---|---|
DE (1) | DE895902C (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1075830B (en) * | 1954-10-04 | 1960-02-18 | California Research Corporation San Francisco Calif (V St A) | Process for the production of rubbery hot melt and hardenable polyester urethanes |
-
1951
- 1951-07-21 DE DEW6307A patent/DE895902C/en not_active Expired
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1075830B (en) * | 1954-10-04 | 1960-02-18 | California Research Corporation San Francisco Calif (V St A) | Process for the production of rubbery hot melt and hardenable polyester urethanes |
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