EP0000893A1 - Process for the preparation of polyisocyanates and their use - Google Patents
Process for the preparation of polyisocyanates and their use Download PDFInfo
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- EP0000893A1 EP0000893A1 EP78100606A EP78100606A EP0000893A1 EP 0000893 A1 EP0000893 A1 EP 0000893A1 EP 78100606 A EP78100606 A EP 78100606A EP 78100606 A EP78100606 A EP 78100606A EP 0000893 A1 EP0000893 A1 EP 0000893A1
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- formula
- isocyanate
- polyisocyanates
- diisocyanate
- nco
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/48—Two nitrogen atoms
- C07D251/52—Two nitrogen atoms with an oxygen or sulfur atom attached to the third ring carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
- C07D251/16—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom
- C07D251/18—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom with nitrogen atoms directly attached to the two other ring carbon atoms, e.g. guanamines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/48—Two nitrogen atoms
- C07D251/50—Two nitrogen atoms with a halogen atom attached to the third ring carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
- C07D251/70—Other substituted melamines
-
- 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
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8054—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/38
- C08G18/8058—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/38 with compounds of C08G18/3819
Definitions
- the present invention relates to the polyisocyanates according to claim 1, the process for their preparation according to claim 3 and their use according to claim 5.
- the polyisocyanates according to the invention which can be obtained by the process according to the invention correspond to the general formula of claim 1, where X and Y have the meaning given there.
- X is preferably a radical having isocyanate groups, as is the case by removing the in the sense of the isocyanate addition reaction, a more reactive isocyanate group can be obtained from an aromatic diisocyanate with isocyanate groups of different reactivity.
- X particularly preferably represents a 3-isocyanato-4-methylphenyl or a 4- (o-isocyanato-benzyl) phenyl radical.
- Y preferably represents a radical of the formula -NH-CO-NH-X, where X preferably has the last-mentioned preferred or in particular the last-mentioned particularly preferred meaning.
- the compounds according to the invention are prepared by reacting amino-containing s-triazine derivatives of the formula mentioned in claim 3 with diisocyanates of the formula X-NCO, where X corresponds to the definition mentioned in claim 1 or preferably the last definitions made, and wherein Y 'is the in Claim 3 has the meaning given and preferably represents an H 2 N group.
- Diisocyanates X-NCO suitable for the process according to the invention are any organic diisocyanates which, in the sense of the isocyanate addition reaction, have isocyanate groups of different reactivity and are otherwise inert under the conditions of the process according to the invention.
- Aromatic diisocyanates corresponding to this definition are preferably used in the process according to the invention.
- the preferred aromatic diisocyanates include, in particular, those in the molecular weight range 174-400 which, in addition to a free, ie sterically unimpeded aromatically bound isocyanate group have a further aromatically bound isocyanate group which is sterically hindered by at least one substituent in the o-position.
- substituents which can lead to steric hindrance of the isocyanate group, are in particular C 1 -C S -alkyl-, C 6 -C 10 -aryl-, C 1 -C 8 -alkoxy-, C 1 -C 8 -thioethers- , C 1 -C 8 alkoxycarbonyl, chlorine, bromine or cyano groups.
- aromatic diisocyanates in the process according to the invention in which aromatic diisocyanates with isocyanate groups of the same reactivity as, for example, 4,4'-diisocyanatodiphenyl-. methane or 2,6-diisocyanatotoluene are present if the proportion of such diisocyanates with isocyanate groups of the same reactivity does not exceed an upper limit of 50, preferably 40,% by weight, based on the total mixture.
- the particularly preferred diisocyanates suitable for the process according to the invention include, for example, 2,4-diisocyanatotoluene, optionally in a mixture with up to 50% by weight, based on the total mixture of 2,6-diisocyanatotoluene, 2,4'-diisocyanatotoluene, optionally in a mixture with up to 50 wt .-% based on the total mixture of 4,4'-diisocyanatodiphenylmethane.
- 2,4'-Diisocyanatodiphenylpropan 2,4'-Diisocyanatodiphenylsulfid, 2,4'-Diisocyanatodiphenyläther, 2,4'-Diisocyanatodiphenylsulfon, 2,4'- D iisocyanatodiphenylsulfodioxid, 3-methyl-4,4'-diisocyanatodiphenylmethane , 3-ethyl-4,4'-diisocyanatodiphenylmethane, 3-isopropyl-4,4'-diisocyanatodiphenylmethane, 3,5-dimethyl-4,4'-diisocyanatodiphenylmethane, 3,5-diethyl-4,4'-diisocyanatodiphenylmethane or 3,5-diisopropyl-4,4'-diisocyanatodip
- S-triazine derivatives which have amino groups and are suitable for the process according to the invention and correspond to the above are Melamine, 6-chloro-2,4-diamino-s-triazine, benzoguanamine, acetoguanamine or caprinoguanamine. ! elamin is particularly preferred.
- the reaction partners are used in such quantitative ratios that at least 2 isocyanate groups of the diisocyanate are present in the reaction mixture for each amino group of the s-triazine derivative, this quantity indication in the case of the use of the above-mentioned mixtures exclusively relating to the diisocyanate with NCO- Groups of different reactivity relates.
- the s-triazine derivative is stirred in an excess of the initially introduced diisocyanate, and the solution or dispersion formed in the process is then heated to 60-180 ° C., preferably 100-160 ° C., optionally with the addition of known urethanization catalysts, such as zinc acetylacetonate, until the Isocyanate content of the reaction mixture shows the calculated waste.
- known urethanization catalysts such as zinc acetylacetonate
- the process products according to the invention can be obtained in pure form by filtration and washing, for example with an inert solvent such as acetone, chloroform or petroleum ether.
- an inert solvent such as acetone, chloroform or petroleum ether.
- the way of working described represents the is by far the preferred procedure, since when using an NCO / NH 2 equivalent ratio of ⁇ 2: 1, for example in the presence of inert solvents, generally no process products according to the invention but rather highly crosslinked reaction products are obtained. (The use of non-polar diluents such as mineral spirits or aromatic hydrocarbons which do not dissolve the process products would be possible, however, is generally superfluous).
- the excess of the diisocyanate component is chosen so that 5-8 NCO equivalents, based on all diisocyanates of the diisocyanate component, are present in the reaction mixture for each H2N equivalent of the s-triazine polyamine, preferably 3-10.
- the new compounds according to the invention are sparingly to insoluble in practically all common organic solvents, with the exception, for example, of highly polar solvents such as dimethylformamide or dimethyl sulfoxide.
- the new compounds have a high melting point and decompose in the melt. They are suitable as an isocyanate component in powder coatings based on polyurethane and in particular as active fillers in the production of polyurethane plastics by the isocyanate polyaddition process known per se.
- the compounds according to the invention are preferably dispersed in the isocyanate component used for the production of the polyurethane plastic.
- Such dispersions of the process products according to the invention in organic polyisocyanates are then processed in a manner known per se using polyhydroxy polyethers and / or polyhydroxy polyesters, if appropriate in combination with chain extenders known per se, to give polyurethane plastics, in particular polyurethane elastomers, which then, thanks to the use of the compounds according to the invention, are improved by improved heat Stability, improved tear propagation resistance, improved elongation at break and improved tensile strength.
- the last-mentioned dispersions are reacted with the polyether polyols or polyester polyols known per se in polyurethane chemistry to form prepolymers containing NCO groups, in such proportions that the unmodified diisocyanate in the resulting NCO prepolymers originating isocyanate groups as well as the isocyanate groups of the compounds according to the invention are present.
- NCO prepolymers are then reacted with chain extenders, for example a diamine of the type exemplified in Example 10, to give the high molecular weight polyurethane polyurea, the amount of chain extender either being chosen such that for all isocyanate groups of the prepolymer including the isocyanate groups of the dispersed compounds according to the invention
- chain extenders for example a diamine of the type exemplified in Example 10
- chain extenders for example a diamine of the type exemplified in Example 10
- the amount of chain extender either being chosen such that for all isocyanate groups of the prepolymer including the isocyanate groups of the dispersed compounds according to the invention
- an isocyanate-reactive group of the chain extender is available or so that, in a first approximation Isocyanate-reactive groups of the chain extender are only available for the isocyanate groups of the prepolymer, which do not originate from the compounds according to the invention, a subsequent chemical
- the triisocyanate reacts only slowly in the cold (RT) with aliphatic amines such as di-n-butylamine.
- the NCO value can therefore only be determined at RT after a longer reaction time:
- the solids content of the prepolymer is 8.4% and its viscosity is 4500 cP (25 ° C).
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
S-Triazin-Ring aufweisende Polyisocyanate der Formel <IMAGE> in welcher X für einen Rest steht, wie er durch Entfernung der höher-reaktiven Isocyanatgruppe aus einem organischen Diisocyanat der Formel OCN-X-NCO mit Isocyanatgruppen unterschiedlicher Reaktivität im Sinne der Isocyanat-Additionsreaktion erhalten wird, und Y für einen Chlor-, Brom-, C1-C8-Alkyl-, C1-C8-Alkoxy-, C6-C10-Aryl-, C6-C10-Aroxy-Rest oder einen Rest der Formel -NH-CO-NH-X-CNO steht, ein Verfahren zu ihrer Herstellung durch Umsetzung von s-Triazin-polyaminen mit Diisocyanaten, welche Isocyanatgruppen unterschiedlicher Reaktivität aufweisen, sowie die Verwendung der neuen Verbindungen als einbaufähige Füllstoffe bei der Herstellung von Polyurethankunststoffen.S-triazine ring-containing polyisocyanates of the formula <IMAGE> in which X represents a residue such as that obtained by removing the more reactive isocyanate group from an organic diisocyanate of the formula OCN-X-NCO with isocyanate groups of different reactivity in the sense of the isocyanate addition reaction is obtained, and Y is a chlorine, bromine, C1-C8-alkyl, C1-C8-alkoxy, C6-C10-aryl, C6-C10-aroxy radical or a radical of the formula -NH-CO -NH-X-CNO is a process for their preparation by reacting s-triazine polyamines with diisocyanates which have isocyanate groups of different reactivity, and the use of the new compounds as buildable fillers in the production of polyurethane plastics.
Description
Gegenstand der vorliegenden Erfindung sind die Polyisocyanate gemäß Patentanspruch 1, das Verfahren zu ihrer Herstellung gemäß Patentanspruch 3 und ihre Verwendung gemäß Patentanspruch 5.The present invention relates to the polyisocyanates according to claim 1, the process for their preparation according to claim 3 and their use according to claim 5.
Es wurde gefunden, daß Melamin und andere Aminogruppen enthaltende s-Triazinderivate mit bestimmten, nachstehend näher beschriebenen Diisocyanaten unter bestimmten, nachstehend näher beschriebenen Reaktionsbedingungen zu neuen Harnstoffgruppen aufweisenden Polyisocyanaten umgesetzt werden können, ohne daß eine Kettenverlängerungsreaktion zu entsprechenden Polyharnstoffen eintritt.It has been found that melamine and other s-triazine derivatives containing amino groups can be reacted with certain diisocyanates, which are described in more detail below, under certain reaction conditions, which are described in more detail below, to give new urea group-containing polyisocyanates without a chain extension reaction to give corresponding polyureas.
Die nach dem erfindungsgemäßen Verfahren zugänglichen erfindungsgemäßen Polyisocyanate entsprechen der allgemeinen Formel des Patentanspruchs 1, wobei X und Y die dort genannte Bedeutung haben. Vorzugsweise steht X für einen Isocyanatgruppen aufweisenden Rest, wie er durch Entfernung der im Sinne der Isocyanat-Additionsreaktion höher reaktiven Isocyanatgruppe aus einem aromatischen Diisocyanat mit Isocyanatgruppen unterschiedlicher Reaktivität erhalten werden kann. Besonders bevorzugt steht X für einen 3-Iso- cyanato-4-methyl-phenyl- oder einen 4-(o-Isocyanato-benzyl)-phenyl-Rest. Y steht vorzugsweise für einen Rest der Formel -NH-CO-NH-X, wobei X vorzugsweise die zuletzt genannte bevorzugte bzw. insbesondere die zuletzt genannte besonders bevorzugte Bedeutung hat.The polyisocyanates according to the invention which can be obtained by the process according to the invention correspond to the general formula of claim 1, where X and Y have the meaning given there. X is preferably a radical having isocyanate groups, as is the case by removing the in the sense of the isocyanate addition reaction, a more reactive isocyanate group can be obtained from an aromatic diisocyanate with isocyanate groups of different reactivity. X particularly preferably represents a 3-isocyanato-4-methylphenyl or a 4- (o-isocyanato-benzyl) phenyl radical. Y preferably represents a radical of the formula -NH-CO-NH-X, where X preferably has the last-mentioned preferred or in particular the last-mentioned particularly preferred meaning.
Die erfindungsgemäßen Verbindungen werden hergestellt durch Umsetzung von Aminogruppen aufweisenden s-Triazinderivaten der in Anspruch 3 genannten Formel mit Diisocyanaten der Formel X-NCO, wobei X der in Anspruch 1 genannten Definition bzw. vorzugsweise den zuletzt gemachten Definitionen entspricht, und wobei Y' die in Anspruch 3 genannte Bedeutung hat und vorzugsweise für eine H2N-Gruppe steht.The compounds according to the invention are prepared by reacting amino-containing s-triazine derivatives of the formula mentioned in claim 3 with diisocyanates of the formula X-NCO, where X corresponds to the definition mentioned in claim 1 or preferably the last definitions made, and wherein Y 'is the in Claim 3 has the meaning given and preferably represents an H 2 N group.
Für das erfindungsgemäße Verfahren geeignete Diisocyanate X-NCO sind alle beliebigen organischen Diisocyanate, die im Sinne der Isocyanat-Additionsreaktion Isocyanatgruppen unterschiedlicher Reaktivität aufweisen und ansonsten unter den Bedingungen des erfindungsgemäßen Verfahrens inert sind.Diisocyanates X-NCO suitable for the process according to the invention are any organic diisocyanates which, in the sense of the isocyanate addition reaction, have isocyanate groups of different reactivity and are otherwise inert under the conditions of the process according to the invention.
Vorzugsweise werden beim erfindungsgemäßen Verfahren dieser Definition entsprechende aromatische Diisocyanate eingesetzt.Aromatic diisocyanates corresponding to this definition are preferably used in the process according to the invention.
Zu den bevorzugten aromatischen Diisocyanaten gehören insbesondere solche des Molekulargewichtsbereichs 174-400, welche neben einer freien, d.h. sterisch ungehinderten aromatisch gebundenen Isocyanatgruppe eine weitere aromatisch gebundene Isocyanatgruppe aufweisen, welche durch mindestens einen Substituenten in o-Stellung sterisch gehindert ist. Derartige Substituenten, die zu einer sterischen Hinderung der Isocyanatgruppe führen können, sind insbesondere C1-CS-Alkyl-, C6-C10-Aryl-, C1-C8-Alkoxy-, C1-C8-Thioäther-, C1-C8-Alkoxycarbonyl-, Chlor-, Brom-, oder Cyano-Gruppen. Desweiteren ist eine sterische Hinderung der aromatisch gebundenen Isocyanatgruppen dann gegeben, wenn das Grundgerüst des Diisocyanats ein ggf. über Brückenglieder wie Alkylen-, Äther-, Thioäther-, Sulfoxid-oder Sulfongruppen verknüpftes System mehrerer aromatischer Ringe darstellt und die (sterisch gehinderte) Isocyanatgruppe in ortho-Stellung zu dem 2 aromatische Ringe verknüpfenden Brückenglied angeordnet ist.The preferred aromatic diisocyanates include, in particular, those in the molecular weight range 174-400 which, in addition to a free, ie sterically unimpeded aromatically bound isocyanate group have a further aromatically bound isocyanate group which is sterically hindered by at least one substituent in the o-position. Such substituents, which can lead to steric hindrance of the isocyanate group, are in particular C 1 -C S -alkyl-, C 6 -C 10 -aryl-, C 1 -C 8 -alkoxy-, C 1 -C 8 -thioethers- , C 1 -C 8 alkoxycarbonyl, chlorine, bromine or cyano groups. Furthermore, there is a steric hindrance to the aromatically bound isocyanate groups when the basic structure of the diisocyanate is a system of several aromatic rings which may be linked via bridge members such as alkylene, ether, thioether, sulfoxide or sulfone groups and the (sterically hindered) isocyanate group in ortho position to the bridge link linking 2 aromatic rings is arranged.
Geeignete aromatische Diisocyanate sind demzufolge beispielsweise solche der Formeln (I) und (II).
- R' und R" für gleiche oder verschiedene Reste stehen und eine die sterische Hinderung der Isocyanatgruppe bewirkende Gruppe der oben beispielhaft genannten Art darstellen, wobei bei den Produkten der Formel (II) einer der Reste R' bzw. R" auch für Wasserstoff stehen kann, bzw. wobei in der Formel (II) auch beide R' und R" für Wasserstoff stehen können, falls die Isocyanatgruppe ortho-ständig zur Brücke R"' bzw. im Falle von n = 0 ortho-ständig zum linken aromatischen Ring angeordnet ist;
- R"' für eine die aromatischen Ringe verknüpfende Brücke der oben beispielhaft genannten Art und
- n für 0 oder 1 steht.
- R 'and R "stand for the same or different radicals and represent a group which effects the steric hindrance of the isocyanate group of the type exemplified above, it being possible for one of the radicals R' or R" in the products of the formula (II) to also stand for hydrogen , or in the formula (II) both R 'and R "can also be hydrogen if the isocyanate group is arranged ortho to the bridge R"' or in the case of n = 0 to the left aromatic ring;
- R "'for a bridge linking the aromatic rings of the type exemplified above and
- n stands for 0 or 1.
Es ist auch möglich, beim erfindungsgemäßen Verfahren Gemische aromatischer Diisocyanate einzusetzen, in welchen aromatische Diisocyanate mit Isocyanatgruppen gleicher Reaktivität wie beispielsweise 4,4'-Diisocyanatodiphenyl-. methan oder 2,6-Diisocyanatotoluol vorliegen, falls der Anteil derartiger Diisocyanate mit Isocyanatgruppen gleicher Reaktivität eine obere Grenze von 50, vorzugsweise von 40, Gew.-% bezogen auf das Gesamtgemisch nicht übersteigt.It is also possible to use mixtures of aromatic diisocyanates in the process according to the invention in which aromatic diisocyanates with isocyanate groups of the same reactivity as, for example, 4,4'-diisocyanatodiphenyl-. methane or 2,6-diisocyanatotoluene are present if the proportion of such diisocyanates with isocyanate groups of the same reactivity does not exceed an upper limit of 50, preferably 40,% by weight, based on the total mixture.
Zu den besonders bevorzugten, für das erfindungsgemäße Verfahren geeigneten Diisocyanaten gehören z.B. 2,4-Diisocyanatotoluol, gegebenenfalls im Gemisch mit bis zu 50 Gew.-% bezogen auf Gesamtgemisch an 2,6-Diisocyanatotoluol, 2,4'-Diisocyanatotoluol, gegebenenfalls im Gemisch mit bis zu 50 Gew.-% bezogen auf Gesamtgemisch an 4,4'-Diisocyanatodiphenylmethan. Weiterhin geeignet sind z.B. 2,4'-Diisocyanatodiphenylpropan, 2,4'-Diisocyanatodiphenylsulfid, 2,4'-Diisocyanatodiphenyläther, 2,4'-Diisocyanatodiphenylsulfon, 2,4'-Diisocyanatodiphenylsulfodioxid, 3-Methyl-4,4'-diisocyanatodiphenylmethan, 3-Äthyl-4,4'-diisocyanatodiphenylmethan, 3-Isopropyl-4,4'-diisocyanatodiphenylmethan, 3,5-Dimethyl-4,4'-diisocyanatodiphenylmethan, 3,5-Diäthyl-4,4'-diisocyanatodiphenylmethan oder 3,5-Diisopropyl-4,4'-diisocyanatodiphenylmethan, 3-Carboxymethyl-4,4'-diisocyanatodiphenylmethan, 3-Carboxyäthyl-4,4'-diisocyanatodiphenylmethanThe particularly preferred diisocyanates suitable for the process according to the invention include, for example, 2,4-diisocyanatotoluene, optionally in a mixture with up to 50% by weight, based on the total mixture of 2,6-diisocyanatotoluene, 2,4'-diisocyanatotoluene, optionally in a mixture with up to 50 wt .-% based on the total mixture of 4,4'-diisocyanatodiphenylmethane. Also suitable are, for example, 2,4'-Diisocyanatodiphenylpropan, 2,4'-Diisocyanatodiphenylsulfid, 2,4'-Diisocyanatodiphenyläther, 2,4'-Diisocyanatodiphenylsulfon, 2,4'- D iisocyanatodiphenylsulfodioxid, 3-methyl-4,4'-diisocyanatodiphenylmethane , 3-ethyl-4,4'-diisocyanatodiphenylmethane, 3-isopropyl-4,4'-diisocyanatodiphenylmethane, 3,5-dimethyl-4,4'-diisocyanatodiphenylmethane, 3,5-diethyl-4,4'-diisocyanatodiphenylmethane or 3,5-diisopropyl-4,4'-diisocyanatodiphenylmethane, 3-carboxymethyl-4,4'-diisocyanatodiphenylmethane, 3-carboxyethyl-4,4'-diisocyanatodiphenylmethane
Für das erfindungsgemäße Verfahren geeignete, obigen Ausführungen entsprechende Aminogruppen aufweisende s-Triazinderivate sind z.B. Melamin, 6-Chlor-2,4-diamino-s-triazin, Benzoguanamin, Acetoguanamin oder Caprinoguanamin. !!elamin ist besonders bevorzugt.S-triazine derivatives which have amino groups and are suitable for the process according to the invention and correspond to the above are Melamine, 6-chloro-2,4-diamino-s-triazine, benzoguanamine, acetoguanamine or caprinoguanamine. !! elamin is particularly preferred.
Bei der Durchführung des erfindungsgemäßen Verfahrens kommen die Rekationspartner in solchen Mengenverhältnissen zum Einsatz, daß für jede Aminogruppe des s-Triazinderivats mindestens 2 Isocyanatgruppen des Diisocyanats im Reaktionsgemisch vorliegen, wobei sich diese Mengenangabe im Falle der Verwendung der obengenannten Gemische ausschließlich auf das Diisocyanat mit NCO-Gruppen unterschiedlicher Reaktivität bezieht. Im allgemeinen wird das s-Triazinderivat in einem Überschuß des vorgelegten Diisocyanats eingerührt und die hierbei entstehende Lösung bzw. Dispersion anschließend auf 60-180°C, vorzugsweise 100-160°C, gegebenenfalls unter Zusatz bekannter Urethanisierungskatalysatoren, wie Zinkacetylacetonat, erhitzt, bis der Isocyanatgehalt des Reaktionsansatzes den berechneten Abfall zeigt. Das erfindungsgemäße Verfahrensprodukt fällt hierbei als im überschüssigen Diisocyanat unlöslicher Niederschlag aus.When carrying out the process according to the invention, the reaction partners are used in such quantitative ratios that at least 2 isocyanate groups of the diisocyanate are present in the reaction mixture for each amino group of the s-triazine derivative, this quantity indication in the case of the use of the above-mentioned mixtures exclusively relating to the diisocyanate with NCO- Groups of different reactivity relates. In general, the s-triazine derivative is stirred in an excess of the initially introduced diisocyanate, and the solution or dispersion formed in the process is then heated to 60-180 ° C., preferably 100-160 ° C., optionally with the addition of known urethanization catalysts, such as zinc acetylacetonate, until the Isocyanate content of the reaction mixture shows the calculated waste. The process product according to the invention precipitates as a precipitate which is insoluble in the excess diisocyanate.
Nach Abkühlung des Reaktionsansatzes auf Raumtemperatur können die erfindungsgemäßen Verfahrensprodukte durch Filtration und Waschen, beispielsweise mit einem inerten Lösungsmittel wie Aceton, Chloroform oder Petroläther, in reiner Form erhalten. Die geschilderte Arbeitsweise stellt die mit Abstand bevorzugte Verfahrensweise dar, da bei Verwendung eines NCO/NH2-Aquivalentverhältnisses von ≥ 2:1, beispielsweise in Gegenwart inerter Lösungsmittel im allge-meinen keine erfindungsgemäßen Verfahrensprodukte, sondern hochvernetzte Umsetzungsprodukte erhalten werden. (Die Mitverwendung von die Verfahrensprodukte nicht lösenden unpolaren Verdünnungsmittel wie z.B. Lösungsbenzinen oder aromatischen Kohlenwasserstoffen wäre allerdings möglich, ist im allgemeinen jedoch überflüssig). Im allgemeinen wird der Überschuß der Diisocyanat-Komponente hierbei so gewählt, daß im Reaktionsgemisch für jedes H2N-Äquivalent des s-Triazin-Polyamins 3-10 vorzugsweise 5-8 NCO-Äquivalente bezogen auf alle Diisocyanate der Diisocyanat-Komponente vorliegen.After the reaction mixture has cooled to room temperature, the process products according to the invention can be obtained in pure form by filtration and washing, for example with an inert solvent such as acetone, chloroform or petroleum ether. The way of working described represents the is by far the preferred procedure, since when using an NCO / NH 2 equivalent ratio of ≥ 2: 1, for example in the presence of inert solvents, generally no process products according to the invention but rather highly crosslinked reaction products are obtained. (The use of non-polar diluents such as mineral spirits or aromatic hydrocarbons which do not dissolve the process products would be possible, however, is generally superfluous). In general, the excess of the diisocyanate component is chosen so that 5-8 NCO equivalents, based on all diisocyanates of the diisocyanate component, are present in the reaction mixture for each H2N equivalent of the s-triazine polyamine, preferably 3-10.
Die neuen erfindungsgemäßen Verbindungen sind in praktisch allen gängigen organischen Lösungsmitteln schwer- bis unlöslich, ausgenommen z.B. hochpolare, wie Dimethylformamid oder Dimethylsulfoxid. Die neuen Verbindungen sind hochschmelzend und zersetzen sich in der Schmelze. Sie eignen sich als Isocyanat-komponente in Pulverlacken auf Polyurethanbasis und insbesondere als aktive Füllstoffe bei der Herstellung von Polyurethankunststoffen nach dem an sich bekannten Isocyanat-Polyadditionsverfahren. Bei dieser bevorzugten Verwendung der erfindungsgemäßen Verbindungen werden die erfindungsgemäßen Verbindungen vorzugsweise in der zur Herstellung des Polyurethankunststoffes eingesetzten Isocyanat-Komponente dispergiert. Derartige Dispersionen der erfindungsgemäßen Verfahrensprodukte in organischen Polyisocyanaten werden dann in an sich bekannter Weise mit Polyhydroxypolyäthern und/oder Polyhydroxypolyestern gegebenenfalls in Kombination mit an sich bekannten Kettenverlängerungsmitteln zu Polyurethankunststoffen,insbesondere Polyurethanelastomeren, verarbeitet, die sich dann dank der Mitverwendung der erfindungsgemäßen Verbindungen durch eine verbesserte Wärmestandfestigkeit, eine verbesserte Weiterreißfestigkeit, eine verbesserte Bruchdehnung und eine verbesserte Zugfestigkeit auszeichnen.The new compounds according to the invention are sparingly to insoluble in practically all common organic solvents, with the exception, for example, of highly polar solvents such as dimethylformamide or dimethyl sulfoxide. The new compounds have a high melting point and decompose in the melt. They are suitable as an isocyanate component in powder coatings based on polyurethane and in particular as active fillers in the production of polyurethane plastics by the isocyanate polyaddition process known per se. In this preferred use of the compounds according to the invention, the compounds according to the invention are preferably dispersed in the isocyanate component used for the production of the polyurethane plastic. Such dispersions of the process products according to the invention in organic polyisocyanates are then processed in a manner known per se using polyhydroxy polyethers and / or polyhydroxy polyesters, if appropriate in combination with chain extenders known per se, to give polyurethane plastics, in particular polyurethane elastomers, which then, thanks to the use of the compounds according to the invention, are improved by improved heat Stability, improved tear propagation resistance, improved elongation at break and improved tensile strength.
Falls die Verwendung der erfindungsgemäßen Verbindungen zur Herstellung derartiger verbesserter Polyurethankunststoffe beabsichtigt ist, erübrigt sich oft ein Entfernen des bei der Herstellung der erfindungsgemäßen Verfahrensprodukte im Uberschuß eingesetzten Diisocyanats. Vielmehr kann die bei der erfindungsgemäßen Umsetzung anfallende Dispersion der erfindungsgemäßen Verfahrensprodukte im im Überschuß eingesetzten Ausgangsdiisocyanat direkt zur Herstellung der Polyurethankunststoffe eingesetzt werden. Gemäß einer bevorzugten Ausführungsform der erfindungsgemäßen Verwendung der erfindungsgemäßen Verbindungen werden die zuletzt genannten Dispersionen mit den in der Polyurethanchemie an sich bekannten Polyätherpolyolen oder Polyesterpolyolen zu NCO-Gruppen aufweisenden Präpolymeren umgesetzt und zwar in solchen Mengenverhältnissen, daß in den entstehenden NCO-Präpolymeren sowohl vom unmodifizierten Diisocyanat herrührende Isocyanatgruppen als auch die Isocyanatgruppen der erfindungsgemäßen Verbindungen vorliegen. Diese NCO-Präpolymeren werden dann mit Kettenverlängerungsmitteln beispielsweise einem Diamin der in Beispiel 10 beispielhaft genannten Art zum hochmolekularen Polyurethan-Polyharnstoff umgesetzt, wobei die Menge des Kettenverlängerungsmittels entweder so gewählt wird, daß für alle Isocyanatgruppen des Präpolymeren inkl. den Isocyanatgruppen der dispergierten erfindungsgemäßen Verbindungen in erster Näherung eine Isocyanat-reaktive Gruppe des Kettenverlängerungsmittels zur Verfügung steht oder aber so, daß in erster Näherung lediglich für die Isocyanatgruppen des Präpolymeren, welche nicht von den erfindungsgemäßen Verbindungen herrühren,Isocyanat-reaktive Gruppen des Kettenverlängerungsmittels zur Verfügung stehen, wobei ein nachträglicher chemischer Einbau der zunächst dispergierten erfindungsgemäßen Verbindungen durch Tempern der Umsetzungsprodukte bei 100 - 150°C erreicht wird (vgl. Beispiel 10). Insbesondere im erstgenannten Falle der Verwendung in etwa äquivalenter Mengen des Kettenverlängerungsmittels bezogen auf die Gesamtmenge der vorliegenden Isocyanatgruppen empfiehlt sich die Mitverwendung der bekannten Polyurethan-Katalysatoren wie z.B. Dibutylzinndilaurat, Zinndioctoat, Diazobicyclooctan und/oder Dimethyltetrahydropyrimidin.If the use of the compounds according to the invention for the production of such improved polyurethane plastics is intended, it is often unnecessary to remove the excess diisocyanate used in the production of the process products according to the invention. Rather, the dispersion of the process products according to the invention in the starting diisocyanate used in excess in the reaction according to the invention can be used directly for the production of the polyurethane plastics. According to a preferred embodiment of the use according to the invention of the compounds according to the invention, the last-mentioned dispersions are reacted with the polyether polyols or polyester polyols known per se in polyurethane chemistry to form prepolymers containing NCO groups, in such proportions that the unmodified diisocyanate in the resulting NCO prepolymers originating isocyanate groups as well as the isocyanate groups of the compounds according to the invention are present. These NCO prepolymers are then reacted with chain extenders, for example a diamine of the type exemplified in Example 10, to give the high molecular weight polyurethane polyurea, the amount of chain extender either being chosen such that for all isocyanate groups of the prepolymer including the isocyanate groups of the dispersed compounds according to the invention First approximation, an isocyanate-reactive group of the chain extender is available or so that, in a first approximation Isocyanate-reactive groups of the chain extender are only available for the isocyanate groups of the prepolymer, which do not originate from the compounds according to the invention, a subsequent chemical incorporation of the initially dispersed compounds according to the invention being achieved by tempering the reaction products at 100-150 ° C. (cf. Example 10). Particularly in the first-mentioned case of using approximately equivalent amounts of the chain extender based on the total amount of the isocyanate groups present, it is advisable to use the known polyurethane catalysts such as, for example, dibutyltin dilaurate, tin dioctoate, diazobicyclooctane and / or dimethyltetrahydropyrimidine.
Eine Mischung aus 1000 g (5,75 Mol) Toluylenaiisocyanat (2,4-und 2,6-Isomere im Verhältnis 80:20) und 72,5 g (0,575 Mol) Melamin werden unter kräftigem Rühren 3 Stunden auf 120 bis 130°C erhitzt. Nach dem Abkühlen der Reaktionsmischung wird das Reaktionsprodukt abgesaugt und mit Aceton isocyanatfrei gewaschen. Nach Trocknung im Vakuum fallen 373 g eines farblosen, in organischen Lösungsmitteln extrem schwerlöslichen Produkts an. Ausbeute, berechnet auf ein Additionsprodukt von Melamin und Toluylendiisocyanat im Mol-Verhältnis 1:3, 98 %, Fp = 350-380 (Z).
Das Triisocyanat reagiert in der Kälte (RT) nur langsam mit aliphatischen Aminen wie Di-n-butylamin. Der NCO-Wert ist deshalb bei RT erst nach längerer Reaktionszeit feststellbar:
Wenn die Titration bei 50-70°C durchgeführt wird, findet man hingegen schon nach 3 bis 5 Minuten einen NCO-Wert von 19,3 % (berechnet 19,5 %).If the titration is carried out at 50-70 ° C, on the other hand, an NCO value of 19.3% (calculated 19.5%) is found after only 3 to 5 minutes.
Eine Mischung aus 63 g (0,5 Mol) Melamin und 313 g (1,8 Mol) des Toluylendiisocyanat des Beispiels 1 in 1 1 Nitrobenzol wird auf 140°C erhitzt. Nach 45 Minuten ist der Reaktionsansatz nicht mehr rührbar. Er wird mit Aceton verdünnt und abgesaugt. Der getrocknete Niederschlag weist einen NCO-Wert von 2,5 % auf (berechnet 19,5 %).A mixture of 63 g (0.5 mol) of melamine and 313 g (1.8 mol) of the tolylene diisocyanate of Example 1 in 1 liter of nitrobenzene is heated to 140 ° C. After 45 minutes, the reaction mixture can no longer be stirred. It is diluted with acetone and suction filtered. The dried precipitate has an NCO value of 2.5% (calculated 19.5%).
31,5 g (0,25 Mol) Melamin und 480 g (3 Mol) 1,3-Phenylendiisocyanat werden 7 Stunden unter kräftigem Rühren auf 100-140°C erhitzt. Anschließend wird der Reaktionsansatz mit Chloroform verdünnt und abgesaugt. Der im Vakuum getrocknete Niederschlag weist einen NCO-Wert von 10,9 % auf (berechnet 20,8 %).31.5 g (0.25 mol) of melamine and 480 g (3 mol) of 1,3-phenylene diisocyanate are heated to 100-140 ° C. for 7 hours with vigorous stirring. The reaction mixture is then diluted with chloroform and suction filtered. The precipitate, dried in vacuo, has an NCO value of 10.9% (calculated 20.8%).
31,5 g (0,25 Mol) Melamin und 500 g (2 Mol) eines Diphenylmethandiisocyanats mit ca. 40 % 4,4'-Isomeren und 60 % 2,4'-Isomeren werden 4 Stunden unter kräftigem Rühren auf 100°C erhitzt. Anschließend wird der Reaktionsansatz mit Chloroform /Petroläther verdünnt und abgesaugt. Der Niederschlag wird im Vakuum getrocknet. Ausbeute 200 g (91 %). Festpunkt 252-60°C (Zersetzung).
Eine Mischung aus 12,6 g (0,1 Mol) Melamin und 250 g (1 Mol) geschmolzenem 4,4'-Diphenylmethandiisocyanat wird auf 120°C erhitzt. Nach 30 Minuten ist der Reaktionsansatz fest.A mixture of 12.6 g (0.1 mol) of melamine and 250 g (1 mol) of melted 4,4'-diphenylmethane diisocyanate is heated to 120 ° C. The reaction mixture is solid after 30 minutes.
7,6 g (0,06 Mol) Melamin und 252 g (1 Mol) 2,4'-Diisocyanatodiphenyläther werden 4 Stunden auf 100°C erhitzt. Anschließend wird der Reaktionsansatz mit Methylenchlorid/Petroläther verdünnt und abgesaugt. Der Niederschlag wird im Vakuum getrocknet. Ausbeute 48 g (91 %). Festpunkt 265-68°C.
Zu 7,1 kg (40,8 Mbl) 2,4-Toluylendiisocyanat werden bei RT unter Rühren 0,567 kg (4,5 Mol) Melamin zugesetzt. Das Reaktionsgenisch wird auf 125-130°C erhitzt. Nach 2 Stunden wird auf 80-850C abgekühlt. Anschließend wird das Melamintriisocyanat in Form einer feinverteilten Aufschlämmung enthaltende überschüssige 2,4-Toluylendiisocyanat mit 27,31 kg (13,7 Mol) eines difunktionellen Polypropylenglykols (OH-Zahl 56) präpolymerisiert. Nach 4 bis 5 Stunden bei 80-850 C weist das Präpolymer einen NCO-Wert von 3,2-3,4 % auf. Wird die NCO-Bestimmung in der Hitze oder in Dimethylsulfoxid-Lösung durchgeführt, wird ein NCO-Wert von 4,4-4,6 % bestimmt, da dann auch der NCO-Gehalt des Melamin-Diisocyanat-Adduktes miterfaßt wird.0.567 kg (4.5 mol) of melamine are added to 7.1 kg (40.8 Mbl) of 2,4-tolylene diisocyanate at RT with stirring. The reaction mixture is heated to 125-130 ° C. After 2 hours, cool to 80-85 0 C. The melamine triisocyanate is then prepolymerized in the form of a finely divided slurry containing excess 2,4-tolylene diisocyanate with 27.31 kg (13.7 mol) of a difunctional polypropylene glycol (OH number 56). After 4 to 5 hours at 80-85 0 C the prepolymer has an NCO value of 3.2-3.4%. If the NCO determination is carried out in the heat or in dimethyl sulfoxide solution, an NCO value of 4.4-4.6% is determined, since the NCO content of the melamine-diisocyanate adduct is then also included.
Der Feststoffanteil des Präpolymers beträgt 8,4 %, seine Viskosität liegt bei 4500 cP (25°C).The solids content of the prepolymer is 8.4% and its viscosity is 4500 cP (25 ° C).
14,4 g (0,11 Mol) Melamin und 336 g (1,34 Mol) eines Diphenylmethandiisocyanats mit ca. 40 % 4,4'-Isomeren- und 60 % 2,4'-Isomerenanteil werden 4 Stunden unter kräftigem Rühren auf 1000C erhitzt. Anschließend werden 1000 g eines difunktionellen Polyätherdiols (OH-Zahl 28) bei 80°C zugesetzt. Nach 3 Stunden bei 90°C weist das Präpolymer einen NCO-Wert von 3,6 % auf. Sein Feststoffgehalt beträgt 7,4 %.14.4 g (0.11 mol) of melamine and 336 g (1.34 mol) of a diphenylmethane diisocyanate with about 40% of 4,4'-isomer and 60% of 2,4'-isomer are stirred for 4 hours with vigorous stirring 100 0 C heated. Then 1000 g of a difunctional polyether diol (OH number 28) are added at 80 ° C. After 3 hours at 90 ° C, the prepolymer has an NCO value of 3.6%. Its solids content is 7.4%.
27,5 g (0,24 Mol) Äthylenglykolmonobutyläther in 100 ml Chlorbenzol werden mit 50 g (0,08 Mol) der im Beispiel 1 isolierten Verbindung vermischt. Der Reaktionsansatz wird auf 130°C erhitzt. Er ist nach 90 Minuten nicht mehr rührbar. Bei Zusatz von 0,5 g Dibutylzinndilaurat unter sonst gleichen Bedingungen ist der Reaktionsansatz bereits nach 20 Minuten nicht mehr rührbar, bei Zusatz von 0,5 g Dimethyltetrahydropyrimidin schon nach 14 Minuten. Das Triisocyanat reagiert also unter den üblichen Bedingungen zum Urethan ab.27.5 g (0.24 mol) of ethylene glycol monobutyl ether in 100 ml of chlorobenzene are mixed with 50 g (0.08 mol) of the compound isolated in Example 1. The reaction mixture is heated to 130 ° C. It cannot be stirred after 90 minutes. If 0.5 g of dibutyltin dilaurate is added under otherwise identical conditions, the reaction mixture can no longer be stirred after 20 minutes, with the addition of 0.5 g of dime thyltetrahydropyrimidine after 14 minutes. The triisocyanate reacts under the usual conditions to form urethane.
100 Gew.-Teile des in Beispiel 7 hergestellten, modifizierten NCO-Präpolymeren werden bei 60 bis 80°C im Vakuum entgast und anschließend mit 6 Gew.-Teilen 3,5-Diäthyl-1-methyl-2,4-diaminobenzol innerhalb von 30 Sekunden verrührt. Je die Hälfte des.Reaktionsansatzes wird dann in eine auf 110 bzw. 130°C heiße Metallform gegossen. Die Gießzeit beträgt ca. 2 Minuten. Nach 4 bis 5 Minuten kann der Gießling entformt werden. Nach Temperung bei 110°C (24 Stunden) und bei 130°C werden jeweils die mechanischen Eigenschaften des Elastomers bestimmt:
Aus der Zunahme der Zugfestigkeit, Bruchdehnung und Weiterreißfestigkeit bei gleicher Härte ist erkennbar, daß erst nach Temperung des Elastomeren bei ≥ 130°C der Füllstoff in die PU-Matrix eingebaut wird, was in dem verstärkenden Effekt deutlich sichtbar wird.From the increase in tensile strength, elongation at break and tear resistance with the same hardness, it can be seen that the filler is only incorporated into the PU matrix after the elastomer has been tempered at ≥ 130 ° C., which is clearly visible in the reinforcing effect.
Claims (5)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE19772737402 DE2737402A1 (en) | 1977-08-19 | 1977-08-19 | POLYISOCYANATE, A PROCESS FOR THEIR MANUFACTURING AND USE |
DE2737402 | 1977-08-19 |
Publications (2)
Publication Number | Publication Date |
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EP0000893A1 true EP0000893A1 (en) | 1979-03-07 |
EP0000893B1 EP0000893B1 (en) | 1980-09-17 |
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ID=6016781
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EP78100606A Expired EP0000893B1 (en) | 1977-08-19 | 1978-08-07 | Process for the preparation of polyisocyanates and their use |
Country Status (4)
Country | Link |
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US (2) | US4255570A (en) |
EP (1) | EP0000893B1 (en) |
DE (2) | DE2737402A1 (en) |
IT (1) | IT1106886B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0053327A1 (en) * | 1980-12-02 | 1982-06-09 | Bayer Ag | Process for the preparation of compounds containing s-triazine units and isocyanate groups or isocyanate-reactive groups, and their use as reactive fillers in the preparation of polyurethanes |
EP0056153A2 (en) * | 1981-01-08 | 1982-07-21 | Bayer Ag | Process for producing compounds having s-triazine units and epoxy groups, and their uses as incorporable filling materials in the production of polyurethane plastic materials |
EP0419965A2 (en) * | 1989-09-27 | 1991-04-03 | Bayer Ag | Polyisocyanates for lacquers, a process for their preparation and their use |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4931487A (en) * | 1988-03-04 | 1990-06-05 | Dow Chemical Company | Chain extenders for polyurethanes |
DE4022663C2 (en) * | 1990-07-17 | 1999-11-04 | Bayer Ag | Process for the production of polyurethane moldings |
US6103816A (en) * | 1992-10-30 | 2000-08-15 | Ppg Industries Ohio, Inc. | Aqueous aminoplast curable film-forming compositions providing films having resistance to acid etching |
CA2145850C (en) | 1992-10-30 | 1999-08-10 | Shanti Swarup | Aminoplast-curable film-forming compositions providing films having resistance to acid etching |
US6235858B1 (en) | 1992-10-30 | 2001-05-22 | Ppg Industries Ohio, Inc. | Aminoplast curable film-forming compositions providing films having resistance to acid etching |
TW242644B (en) * | 1992-10-30 | 1995-03-11 | Ppg Industries Inc |
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DE1943635A1 (en) * | 1969-08-28 | 1971-03-11 | Bayer Ag | s-triazinyl isocyanate |
FR2243936A1 (en) * | 1973-09-17 | 1975-04-11 | Aries Robert | N-s-triazinyl urea herbicides - prepd from 2-amino triazine and alkyl isocyanate or carbamoyl halide |
DE2436740A1 (en) * | 1974-07-30 | 1976-02-12 | Bayer Ag | PROCESS FOR THE MANUFACTURING OF POLYURN FABRICS |
DE2032547B2 (en) * | 1970-07-01 | 1976-06-16 | Bayer Ag, 5090 Leverkusen | PREPARATION OF POLYISOCYANATES CONTAINING UREA GROUPS AND THEIR USE |
DE2507682A1 (en) * | 1975-02-22 | 1976-09-02 | Bayer Ag | ISOCYANATE |
DE2653408A1 (en) * | 1975-11-26 | 1977-06-08 | Shell Int Research | TRIAZINE-UREA COMPOUNDS, PROCESS FOR THEIR PRODUCTION AND GREASES CONTAINING THESE COMPOUNDS AS THICKENING AGENTS |
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US2838511A (en) * | 1955-10-31 | 1958-06-10 | Du Pont | Preparation of triaryl isocyanates |
NL277135A (en) | 1961-04-28 | |||
US3210339A (en) * | 1962-08-01 | 1965-10-05 | Dentsche Gold Und Silber Schei | Diamino-s-triazine derivatives |
-
1977
- 1977-08-19 DE DE19772737402 patent/DE2737402A1/en not_active Withdrawn
-
1978
- 1978-08-03 US US05/930,611 patent/US4255570A/en not_active Expired - Lifetime
- 1978-08-07 EP EP78100606A patent/EP0000893B1/en not_active Expired
- 1978-08-07 DE DE7878100606T patent/DE2860170D1/en not_active Expired
- 1978-08-17 IT IT50756/78A patent/IT1106886B/en active
-
1980
- 1980-11-12 US US06/206,115 patent/US4348512A/en not_active Expired - Lifetime
Patent Citations (6)
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DE1943635A1 (en) * | 1969-08-28 | 1971-03-11 | Bayer Ag | s-triazinyl isocyanate |
DE2032547B2 (en) * | 1970-07-01 | 1976-06-16 | Bayer Ag, 5090 Leverkusen | PREPARATION OF POLYISOCYANATES CONTAINING UREA GROUPS AND THEIR USE |
FR2243936A1 (en) * | 1973-09-17 | 1975-04-11 | Aries Robert | N-s-triazinyl urea herbicides - prepd from 2-amino triazine and alkyl isocyanate or carbamoyl halide |
DE2436740A1 (en) * | 1974-07-30 | 1976-02-12 | Bayer Ag | PROCESS FOR THE MANUFACTURING OF POLYURN FABRICS |
DE2507682A1 (en) * | 1975-02-22 | 1976-09-02 | Bayer Ag | ISOCYANATE |
DE2653408A1 (en) * | 1975-11-26 | 1977-06-08 | Shell Int Research | TRIAZINE-UREA COMPOUNDS, PROCESS FOR THEIR PRODUCTION AND GREASES CONTAINING THESE COMPOUNDS AS THICKENING AGENTS |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0053327A1 (en) * | 1980-12-02 | 1982-06-09 | Bayer Ag | Process for the preparation of compounds containing s-triazine units and isocyanate groups or isocyanate-reactive groups, and their use as reactive fillers in the preparation of polyurethanes |
EP0056153A2 (en) * | 1981-01-08 | 1982-07-21 | Bayer Ag | Process for producing compounds having s-triazine units and epoxy groups, and their uses as incorporable filling materials in the production of polyurethane plastic materials |
EP0056153A3 (en) * | 1981-01-08 | 1982-10-27 | Bayer Ag | Process for producing compounds having s-triazine units and epoxy groups, and their uses as incorporable filling materials in the production of polyurethane plastic materials |
EP0419965A2 (en) * | 1989-09-27 | 1991-04-03 | Bayer Ag | Polyisocyanates for lacquers, a process for their preparation and their use |
EP0419965A3 (en) * | 1989-09-27 | 1992-01-15 | Bayer Ag | Polyisocyanates for lacquers, a process for their preparation and their use |
Also Published As
Publication number | Publication date |
---|---|
DE2860170D1 (en) | 1980-12-18 |
US4348512A (en) | 1982-09-07 |
US4255570A (en) | 1981-03-10 |
IT1106886B (en) | 1985-11-18 |
DE2737402A1 (en) | 1979-02-22 |
IT7850756A0 (en) | 1978-08-17 |
EP0000893B1 (en) | 1980-09-17 |
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