DE1092007B - Process for the preparation of polyisocyanates containing a carbodiimide isocyanate adduct - Google Patents
Process for the preparation of polyisocyanates containing a carbodiimide isocyanate adductInfo
- Publication number
- DE1092007B DE1092007B DEF29051A DEF0029051A DE1092007B DE 1092007 B DE1092007 B DE 1092007B DE F29051 A DEF29051 A DE F29051A DE F0029051 A DEF0029051 A DE F0029051A DE 1092007 B DE1092007 B DE 1092007B
- Authority
- DE
- Germany
- Prior art keywords
- carbodiimide
- isocyanate
- preparation
- isocyanate adduct
- polyisocyanates
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
- C08G18/025—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing carbodiimide groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2350/00—Acoustic or vibration damping material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2380/00—Tyres
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von ein Carbodiimid- Isocyanat -Addukt enthaltenden Polyisocyanaten Carbodiimide, die bei der thermischen Zersetzung von aromatischen Isocyanaten entstehen, sind wenig beständig (Chem. Rev., 53 [1953, S. 145). Carbodiimide aus 4,4'-Diisocyanatodiphenylmethan sind hochpolymer, unlöslich und fest (Am. Soc., 80 [1958], 5. 5496). Es ist ferner bekannt, daß Carbodiimide mit Isocyanaten Addukte bilden (deutsche Auslegeschrift 1 012 601), die beim Erhitzen wieder in Carbodiimid und Isocyanat aufspalten. Process for the preparation of a carbodiimide isocyanate adduct containing polyisocyanates carbodiimides, which in the thermal decomposition of aromatic isocyanates are not very stable (Chem. Rev., 53 [1953, P. 145). Carbodiimides made from 4,4'-diisocyanatodiphenylmethane are highly polymeric and insoluble and firm (Am. Soc., 80 [1958], pp. 5496). It is also known that carbodiimides Form adducts with isocyanates (German Auslegeschrift 1 012 601), which when heated split again into carbodiimide and isocyanate.
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von polyfunktionellen Isocyanaten der Diphenylmethanreihe, die Addukte von Carbodiimiden und Isocyanaten enthalten. The invention relates to a process for the production of polyfunctional Isocyanates of the diphenylmethane series, the adducts of carbodiimides and isocyanates contain.
Bei der Kondensation von Anilin mit Formaldehyd fallen im wesentlichen die folgenden Amine der Diphenylmethanreihe an: 2,4'-Diaminodiphenylmethan 1 bis 3010, 4,4'-Diaminodiphenylmethan 70 bis 85 0/,, 2,4-Bis-(4-aminobenzyl)-anilin 10 bis 20 °/0, tetra-, penta- und hexafunktionelle Diphenylmethanbasen 3 bis 80/o. In the condensation of aniline with formaldehyde essentially fall the following amines of the diphenylmethane series: 2,4'-diaminodiphenylmethane 1 bis 3010, 4,4'-diaminodiphenylmethane 70 to 85 0 / ,, 2,4-bis (4-aminobenzyl) aniline 10 up to 20%, tetra-, penta- and hexafunctional diphenylmethane bases 3 to 80 / o.
Man kann das Gemisch oder auch einzelne angereicherte oder in reiner Form isolierte Komponenten desselben in bekannter Weise phosgenieren bzw. Anreicherung oder Isolierung einzelner Komponenten auch erst nach erfolgter Phosgenierung vornehmen. You can use the mixture or individual enriched or pure Form isolated components of the same phosgenate in a known manner or enrichment or isolate individual components only after phosgenation has taken place.
Die Amine der Diphenylmethanreihe lassen sich nach bekannten Verfahren, z. B. gemäß der deutschen Patentschrift 94927, in einem inerten Lösungsmittel gelöst, mit Phosgen in die entsprechenden Polyisocyanate umwandeln. Das nach dem Beseitigen des überschüssigen Phosgens und Abdampfen des Lösungsmittels zurückbleibende Rohprodukt oder auch ein reines Polyisocyanat der Diphenylmethanreihe soll mehr als 90 0/, des Gesamtstickstoffs in Form von Isocyanatgruppen enthalten. The amines of the diphenylmethane series can be obtained by known processes, z. B. according to German Patent 94927, dissolved in an inert solvent, convert with phosgene into the corresponding polyisocyanates. That after eliminating the excess phosgene and evaporation of the solvent remaining crude product or a pure polyisocyanate of the diphenylmethane series should be more than 90 0 /, of total nitrogen in the form of isocyanate groups.
Gemäß vorliegendem Verfahren ist es möglich, in einem einzigen Arbeitsgang, ausgehend von Gemischen polyfunktioneller, aromatischer Amine, wie sie bei der Kondensation von Anilin mit Formaldehyd bzw. Formaldehyd abspaltenden Substanzen in mineralsaurer Lösung gebildet werden, stabile, polyfunktionelle Isocyanate herzustellen, welche außer freien Isocyanatgruppen auch noch verkappte Isocyanatgruppen in Form von Carbodiimid-Isocyanat-Addukten enthalten. According to the present method, it is possible in a single operation, starting from mixtures of polyfunctional, aromatic amines, such as those used in condensation of aniline with formaldehyde or substances that split off formaldehyde in mineral acids Solution are formed to produce stable, polyfunctional isocyanates, which In addition to free isocyanate groups, also blocked isocyanate groups in the form of carbodiimide-isocyanate adducts contain.
Das Verfahren ist dadurch gekennzeichnet, daß man die in bekannter Weise durch Phosgenierung der entsprechenden Amine hergestellten Polyisocyanate der Diphenylmethanreihe einer Wärmebehandlung bei Temperaturen über 150"C unterwirft, bis im Höchstfall 330/0 der vorhandenen Isocyanatgruppen durch Carbodiimidbildung verbraucht worden sind, und anschließend auf Raumtemperatur abkühlt. The process is characterized in that the known in Way, polyisocyanates prepared by phosgenation of the corresponding amines subjecting the diphenylmethane series to a heat treatment at temperatures above 150 "C, up to a maximum of 330/0 of the isocyanate groups present due to carbodiimide formation have been consumed, and then cooled to room temperature.
Das oder die Polyisocyanate werden bei normalem oder vermindertem Druck auf 150 bis 3000 C, bevorzugt 180 bis 220"C, erwärmt, wobei Abspaltung von Kohlendioxyd zu beobachten ist. Es bilden sich in geringem Ausmaß nach der Gleichung RNCO+OCNR+RN=C=NR+CO2 R = substituierter Phenylrest unter Molekülvergrößerung Carbodiimide. The polyisocyanate (s) are at normal or reduced Pressure from 150 to 3000 C, preferred 180 to 220 "C, heated, with cleavage of Carbon dioxide is observed. They are formed to a small extent according to the equation RNCO + OCNR + RN = C = NR + CO2 R = substituted phenyl radical with enlarged molecules Carbodiimide.
Die Reaktion läuft autokatalytisch ab, d. h., die sich bildenden Carbodiimide katalysieren die weitere Zersetzung von Isocyanatgruppen. Die Zeitabhängigkeit der Carbodiimidbildung läßt sich annähernd durch eine Parabel darstellen: g = 100 t2 worin g den Anteil nicht umgesetzter Isocyanatgruppen, bezogen auf die Ausgangskonzentration = 100, t die Zeit in Stunden und a einen im wesentlichen von der Zersetzungstemperatur und zum geringeren Teil von der Zusammensetzung des Isocyanatgemisches abhängigen Faktor bedeutet. The reaction takes place autocatalytically, i. i.e., the forming Carbodiimides catalyze the further decomposition of isocyanate groups. The time dependency the carbodiimide formation can approximately be represented by a parabola: g = 100 t2 where g is the proportion of unreacted isocyanate groups, based on the initial concentration = 100, t is the time in hours and a essentially depends on the decomposition temperature and to a lesser extent dependent on the composition of the isocyanate mixture Factor means.
Der Faktor a liegt bei einer Zersetzungstemperatur von 220"C zwischen 0,1 und 0,6 und bei einer Zersetzungstemperatur von 1800 C zwischen 0,01 und 0,06, entsprechend einer 100/0eigen Zersetzung bei 2200 C in 4 bis 10 Stunden und bei 1800 C in 13 bis 32 Stunden. At a decomposition temperature of 220 "C, the factor a is between 0.1 and 0.6 and at a decomposition temperature of 1800 C between 0.01 and 0.06, corresponding to a 100/0 decomposition at 2200 C in 4 to 10 hours and at 1800 C in 13 to 32 hours.
Um noch flüssige oder zumindest schmelzbare Produkte zu erhalten, dürfen höchstens 50 0/, der ursprünglich vorhandenen Isocyanatgruppen zu Carbodiimid-Isocyanat-Addukten umgesetzt werden. In order to obtain still liquid or at least meltable products, may not exceed 50% of the isocyanate groups originally present to form carbodiimide-isocyanate adducts implemented.
Sobald daher im Höchstfall 330/, der umzusetzenden Isocyanatgruppen von der Carbodiimidreaktion verbraucht worden sind, wird das Polyisocyanat-Carbodiimid -Gemisch auf Raumtemperatur abgekühlt. Bei Raumtemperatur reagieren Carbodiimidgruppen mit freien Isocyanatgruppen im molaren Verhältnis 1:1, wobei eine weitere Molekülvergrößerung eintritt, so daß dann die obengenannten höchstens 500/0 der ursprünglich vorhandenen Isocyanatgruppen verbraucht sind. As soon as a maximum of 330 /, of the isocyanate groups to be converted have been consumed by the carbodiimide reaction, the polyisocyanate becomes carbodiimide -Mixture cooled to room temperature. Carbodiimide groups react at room temperature free isocyanate groups in a molar ratio of 1: 1, with a further increase in the size of the molecule occurs, so that the above-mentioned at most 500/0 of the originally existing Isocyanate groups are consumed.
Die Carbodiimid-Isocyanat-Addukte absorbieren Licht im infraroten Bereich bei 5,76 bis 5,78 p und bei 7,24 bis 7,22 p. The carbodiimide isocyanate adducts absorb light in the infrared Range at 5.76 to 5.78 p and at 7.24 to 7.22 p.
Die erhaltenen Produkte haben folgende Vorzüge: Sie sind hervorragend geeignet für die Herstellung von Schaumstoffen, speziell von Hartschaumstoffen. The products obtained have the following advantages: They are excellent suitable for the production of foams, especially rigid foams.
Sie haben einen äußerst niedrigen Dampfdruck, praktisch keinen Geruch und sind ungiftig. They have an extremely low vapor pressure, practically no odor and are non-toxic.
Sie zeigen gegenüber nicht modifiziertem 4,4'-Diisocyanatodiphenylmethan eine verbesserte Lagerfähigkeit und geringere oder keine Neigung zur Kristallisation. They show against unmodified 4,4'-diisocyanatodiphenylmethane improved shelf life and less or no tendency to crystallize.
Beispiel 1 Aus einem Amingemisch, bestehend aus 2 Teilen 2,4'-Diaminodiphenylmethan, 85 Teilen 4,4'-Diaminodiphenylmethan, 12 Teilen 2,4-Bis-(4-aminobenzyl)-anilin und 3 Teilen mehr als dreifunktionelle Diphenylmethanbasen, wird durch Umsetzung mit Phosgen in chiorbenzolischer Lösung ein Gemisch von Polyisocyanaten erhalten, dessen Gesamtstickstoff - nach dem Abdampfen des Lösungsmittels - zu 95,8 0!o in den Isocyanatgruppen enthalten ist. Example 1 From an amine mixture consisting of 2 parts of 2,4'-diaminodiphenylmethane, 85 parts of 4,4'-diaminodiphenylmethane, 12 parts of 2,4-bis- (4-aminobenzyl) -aniline and 3 parts of more than three-functional diphenylmethane bases are reacted with Phosgene obtained in chlorobenzene solution, a mixture of polyisocyanates whose Total nitrogen - after evaporation of the solvent - to 95.8% in the isocyanate groups is included.
Das Rohisocyanat wird unter Rühren auf 1890 C erhitzt. Nach 41/2 Stunden sind noch 89,8 01o des Gesamtstickstoffs in NCO-Gruppen zu finden. Die Mischung wird auf 20"C gekühlt. Nach lOstündiger Nachreaktion liegen nur noch 86,20/0 des Gesamtstickstoffs in freien NCO-Gruppen vor. The crude isocyanate is heated to 1890 ° C. while stirring. After 41/2 Hours are still 89.8 01o of the total nitrogen to be found in NCO groups. The mixture is cooled to 20 ° C. After a post-reaction period of 10 hours, only 86.20 / 0 des are left Total nitrogen in free NCO groups.
Das Produkt bleibt bei Raumtemperatur flüssig. The product remains liquid at room temperature.
Beispiel 2 Ein Amingemisch aus 1 Teil 2,4'-Diaminodiphenylmethan, 76 Teilen 4,4'-Diaminodiphenylmethan, 15 Teilen 2,4-Bis-(4-aminobenzyl)-anilin, 8 Teilen tetra-, penta- und hexafunktionellen Diphenylmethanbasen läßt sich mit einer Ausbeute von 96,50/,, bezogen auf eingesetzte Aminogruppen, zu dem entsprechenden Isocyanatgemisch umsetzen. Das vom Lösungsmittel befreite Konzentrat wird unter einem Vakuum von 50 Torr 3 Stunden auf 2000 C erhitzt, wobei der Isocyanatstickstoff auf 91,00/0 vom Gesamtstickstoff sinkt. 15 Stunden später wird in der auf Raumtemperatur gehaltenen Probe ein Isocyanatstickstoff von 89,5°/o festgestellt. Das Produkt kristallisiert nicht mehr. Example 2 An amine mixture of 1 part 2,4'-diaminodiphenylmethane, 76 parts of 4,4'-diaminodiphenylmethane, 15 parts of 2,4-bis (4-aminobenzyl) aniline, 8 parts of tetra-, penta- and hexafunctional diphenylmethane bases can be used with a yield of 96.50 / ,, based on the amino groups used, to the corresponding React isocyanate mixture. The concentrate freed from the solvent is under heated to 2000 C for 3 hours in a vacuum of 50 torr, the isocyanate nitrogen drops to 91.00 / 0 of total nitrogen. 15 hours later it is at room temperature An isocyanate nitrogen of 89.5% was found in the sample held. The product crystallizes no longer.
Beispiel 3 Reines, destilliertes 4,4'-Diisocyanatodiphenylmethan wird 11 Stunden lang auf 2200 C erhitzt, wobei der N CO-Gehalt, ausgedrückt in Teilen vom Äquivalentgewicht 42, von 33,5 auf 25,80:, zurückgeht. Nach 24stündigem Stehen bei Raumtemperatur enthält das kristallin erstarrte Endprodukt noch 22,8 0/o freie NCO-Gruppen. Example 3 Pure, distilled 4,4'-diisocyanatodiphenylmethane is heated for 11 hours at 2200 C, the N CO content, expressed in parts from the equivalent weight 42, from 33.5 to 25.80 :, decreases. After standing for 24 hours At room temperature the crystalline solidified end product still contains 22.8% free NCO groups.
Claims (1)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEF29051A DE1092007B (en) | 1959-07-29 | 1959-07-29 | Process for the preparation of polyisocyanates containing a carbodiimide isocyanate adduct |
GB26167/60A GB899036A (en) | 1959-07-29 | 1960-07-27 | Process for the production of carbodiimide polyisocyanate adducts |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEF29051A DE1092007B (en) | 1959-07-29 | 1959-07-29 | Process for the preparation of polyisocyanates containing a carbodiimide isocyanate adduct |
Publications (1)
Publication Number | Publication Date |
---|---|
DE1092007B true DE1092007B (en) | 1960-11-03 |
Family
ID=7093136
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DEF29051A Pending DE1092007B (en) | 1959-07-29 | 1959-07-29 | Process for the preparation of polyisocyanates containing a carbodiimide isocyanate adduct |
Country Status (2)
Country | Link |
---|---|
DE (1) | DE1092007B (en) |
GB (1) | GB899036A (en) |
Cited By (38)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1145353B (en) * | 1961-05-24 | 1963-03-14 | Bayer Ag | Process for the production of homogeneous plastics including surface structures according to the isocyanate polyaddition process |
DE2325926A1 (en) * | 1973-05-22 | 1974-12-12 | Bayer Ag | PROCESS FOR MANUFACTURING MATERIALS CONTAINING LIGNOCELLULOSE |
FR2350137A1 (en) * | 1976-05-03 | 1977-12-02 | Bayer Ag | MICROCAPSULES PRODUCTION |
US4271087A (en) * | 1979-11-08 | 1981-06-02 | Basf Wyandotte Corporation | Carbamylbiuret-modified polyisocyanates |
US4294951A (en) | 1980-07-14 | 1981-10-13 | Mitsui-Nisso Corporation | Rapid curing polyurethane elastomer prepared from a diphenylmethanediisocyanate based liquid prepolymer and a curing agent containing a polytetramethylene ether glycol, a diol and an organometallic catalyst |
US4330636A (en) * | 1979-11-08 | 1982-05-18 | Basf Wyandotte Corporation | Carbamylbiuret-modified polyisocyanates |
US4331810A (en) * | 1979-11-08 | 1982-05-25 | Basf Wyandotte Corporation | Carbamylbiuret-modified polyisocyanates |
US4331809A (en) | 1979-11-08 | 1982-05-25 | Basf Wyandotte Corporation | Carbamylbiuret-modified polyisocyanates |
US4332953A (en) | 1979-11-08 | 1982-06-01 | Basf Wyandotte Corporation | Carbamylbiuret-modified polyisocyanates |
EP0699696A1 (en) | 1994-08-29 | 1996-03-06 | Bayer Corporation | Polyisocyanate/polyamine mixtures and their use for the production of polyurea coatings |
EP0718333A1 (en) | 1994-12-21 | 1996-06-26 | Bayer Corporation | Coating compositions based on aldimines and polyisocyanates containing uretdione groups |
EP0744425A2 (en) | 1995-05-23 | 1996-11-27 | Bayer Corporation | Blocked polyisocyanates with improved thermal stability |
US5610260A (en) * | 1994-02-03 | 1997-03-11 | Bayer Aktiengesellschaft | Polyisocyanate mixtures which are liquid at greater than 5° C |
US6005062A (en) * | 1998-07-02 | 1999-12-21 | 3M Innovative Properties Company | Secondary aspartic acid amide esters |
WO2008157013A1 (en) | 2007-06-13 | 2008-12-24 | Hontek Corporation | Method and coating for protecting and repairing an airfoil surface using molded boots, sheet or tape |
US7736745B2 (en) | 2004-05-24 | 2010-06-15 | Hontek Corporation | Abrasion resistant coatings |
WO2010083024A2 (en) | 2009-01-14 | 2010-07-22 | Bayer Materialscience Llc | Long-fiber thermoset composite with low orange peel |
WO2011038337A1 (en) | 2009-09-26 | 2011-03-31 | Segetis, Inc. | Ketal lactones and stereospecific adducts of oxocarboxylic ketals with trimethylol compounds, polymers containing the same, methods of manufacture, and uses thereof |
WO2011068855A1 (en) | 2009-12-04 | 2011-06-09 | Basf Coatings Gmbh | Method and composition for refinish coatings |
US8091227B2 (en) | 2005-12-14 | 2012-01-10 | Hontek Corporation | Method of repairing an airfoil surface |
WO2012054547A1 (en) | 2010-10-20 | 2012-04-26 | Basf Coatings Gmbh | Scratch-resistant refinish clearcoat |
WO2013006609A2 (en) | 2011-07-06 | 2013-01-10 | Bayer Materialscience Llc | Waterborne polyurethane coating compositions |
WO2013006606A2 (en) | 2011-07-06 | 2013-01-10 | Bayer Materialscience Llc | Free radical curable waterborne glass coating compositions |
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Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2504400A1 (en) | 1975-02-01 | 1976-08-05 | Bayer Ag | STORAGE-STABLE POLYISOCYANATE CONTAINING CARBODIIMIDE GROUPS |
-
1959
- 1959-07-29 DE DEF29051A patent/DE1092007B/en active Pending
-
1960
- 1960-07-27 GB GB26167/60A patent/GB899036A/en not_active Expired
Cited By (50)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1145353B (en) * | 1961-05-24 | 1963-03-14 | Bayer Ag | Process for the production of homogeneous plastics including surface structures according to the isocyanate polyaddition process |
DE2325926A1 (en) * | 1973-05-22 | 1974-12-12 | Bayer Ag | PROCESS FOR MANUFACTURING MATERIALS CONTAINING LIGNOCELLULOSE |
FR2350137A1 (en) * | 1976-05-03 | 1977-12-02 | Bayer Ag | MICROCAPSULES PRODUCTION |
US4271087A (en) * | 1979-11-08 | 1981-06-02 | Basf Wyandotte Corporation | Carbamylbiuret-modified polyisocyanates |
US4330636A (en) * | 1979-11-08 | 1982-05-18 | Basf Wyandotte Corporation | Carbamylbiuret-modified polyisocyanates |
US4331810A (en) * | 1979-11-08 | 1982-05-25 | Basf Wyandotte Corporation | Carbamylbiuret-modified polyisocyanates |
US4331809A (en) | 1979-11-08 | 1982-05-25 | Basf Wyandotte Corporation | Carbamylbiuret-modified polyisocyanates |
US4332953A (en) | 1979-11-08 | 1982-06-01 | Basf Wyandotte Corporation | Carbamylbiuret-modified polyisocyanates |
US4294951A (en) | 1980-07-14 | 1981-10-13 | Mitsui-Nisso Corporation | Rapid curing polyurethane elastomer prepared from a diphenylmethanediisocyanate based liquid prepolymer and a curing agent containing a polytetramethylene ether glycol, a diol and an organometallic catalyst |
US5610260A (en) * | 1994-02-03 | 1997-03-11 | Bayer Aktiengesellschaft | Polyisocyanate mixtures which are liquid at greater than 5° C |
EP0699696A1 (en) | 1994-08-29 | 1996-03-06 | Bayer Corporation | Polyisocyanate/polyamine mixtures and their use for the production of polyurea coatings |
EP0718333A1 (en) | 1994-12-21 | 1996-06-26 | Bayer Corporation | Coating compositions based on aldimines and polyisocyanates containing uretdione groups |
EP0744425A2 (en) | 1995-05-23 | 1996-11-27 | Bayer Corporation | Blocked polyisocyanates with improved thermal stability |
US6005062A (en) * | 1998-07-02 | 1999-12-21 | 3M Innovative Properties Company | Secondary aspartic acid amide esters |
US6469199B1 (en) | 1998-07-02 | 2002-10-22 | 3M Innovative Properties Company | Secondary aspartic acid amide esters |
US6573398B2 (en) | 1998-07-02 | 2003-06-03 | 3M Innovative Properties Company | Secondary aspartic acid amide esters |
US10557038B2 (en) | 2004-05-24 | 2020-02-11 | Hontek Corporation | Erosion resistant coatings |
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