EP0000893B1 - Procédé pour la préparation de polyisocyanates et leur utilisation - Google Patents

Procédé pour la préparation de polyisocyanates et leur utilisation Download PDF

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Publication number
EP0000893B1
EP0000893B1 EP78100606A EP78100606A EP0000893B1 EP 0000893 B1 EP0000893 B1 EP 0000893B1 EP 78100606 A EP78100606 A EP 78100606A EP 78100606 A EP78100606 A EP 78100606A EP 0000893 B1 EP0000893 B1 EP 0000893B1
Authority
EP
European Patent Office
Prior art keywords
groups
melamine
polyisocyanates
diisocyanate
optionally
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
Application number
EP78100606A
Other languages
German (de)
English (en)
Other versions
EP0000893A1 (fr
Inventor
Gerhard Dr. Grögler
Holger Dr. Meyborg
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0000893A1 publication Critical patent/EP0000893A1/fr
Application granted granted Critical
Publication of EP0000893B1 publication Critical patent/EP0000893B1/fr
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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 invention relates to a new process for the production of novel polyisocyanates which are suitable as buildable fillers in the production of polyurethane plastics, and to the use of the process products as buildable fillers in the production of polyurethane plastics.
  • polyamides - melamine can be regarded formally as the triamide of cyanuric acid - which is known to have a significantly reduced reactivity with isocyanates.
  • Any conclusions from the known processes for the production of polyisocyanates containing urea groups by reacting polyamines with polyisocyanates see, for example, DE-AS 2 032 547) for the production of polyisocyanates containing urea groups (and s-triazine groups), as described below for the first time, are therefore not possible for this reason alone.
  • the products of the process according to the invention have a number of remarkable properties which are not inherent in the conventional polyisocyanates in polyurethane chemistry, including the solutions of urea polyisocyanates in unmodified polyisocyanates known, for example, from the aforementioned prior publication.
  • the process products described in more detail below are largely sparingly to insoluble in organic media and therefore, and because of their high melting point, represent particularly interesting polyisocyanates for the production of special polyurethane plastics.
  • the process products are particularly suitable as active fillers for the production of polyurethane elastomers which do not react with the polymer until they are at an elevated temperature React active hydrogen atoms present in the polyurethane, so that when using the process products, for example as a dispersion in the isocyanate component used for the polyurethane plastic, selective curing is made possible by selective temperature control.
  • a thermoplastic polyurethane can be produced in a manner known per se, which is thermoplastic deformable and can be converted into a thermosetting plastic by tempering at elevated temperature.
  • their flame retardancy is significantly improved.
  • the invention also relates to the use of the polyisocyanates containing urea and s-triazine groups obtained in the process according to the invention as buildable fillers in the production of polyurethane plastics.
  • Aromatic diisocyanates suitable for the process according to the invention are those of the molecular weight range 174-400 which, in addition to a free, ie sterically unrestricted, hindered 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 a steric hindrance of the isocyanate group, are in particular C, -Ce alkyl, C 6 -C 10 aryl, C 1 -C 8 alkoxy, C 1 -C 8 thioether, C 1 -C 8 alkoxycarbonyl, chlorine, bromine or cyano groups.
  • 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 (steric hindered) isocyanate group is arranged in the ortho position to the bridge member linking 2 aromatic rings.
  • aromatic diisocyanates in the process according to the invention in which aromatic diisocyanates with isocyanate groups of the same reactivity, such as 4,4'-diisocyanatodiphenylmethane or 2,6-diisocyanatotoluene, are present if the proportion of such diisocyanates with isocyanate groups of the same reactivity has an upper limit of 50, preferably of 40 wt .-%, based on the total mixture, does not exceed.
  • aromatic diisocyanates with isocyanate groups of the same reactivity such as 4,4'-diisocyanatodiphenylmethane or 2,6-diisocyanatotoluene
  • the particularly preferred diisocyanates suitable for the process according to the invention include e.g. 2,4-diisocyanatotoluene, optionally in a mixture with up to 50% by weight, based on the total mixture of 2,6-diisocyanatotoluene, 2,4'-diisocyanatodiphenylmethane, optionally in a mixture with up to 50% by weight, based on the total mixture of 4 , 4'-diisocyanatodiphenylmethane. Also suitable are e.g.
  • organic compounds containing amino groups suitable for the process according to the invention are any diamino-s-triazines, such as e.g. 6-chloro-2,4-diamino-s-triazine, benzoguanamine, acetoguanamine or caprinoguanamine. Melamine is particularly preferred.
  • the reactants are used in proportions such 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 abovementioned mixtures, exclusively relating to the diisocyanate with NCO- Groups of different reactivity relates.
  • the s-triazine derivative is stirred into an excess of the initially introduced diisocyanate and the solution or dispersion formed 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 procedure described 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 are obtained, but highly crosslinked reaction products. (However, the use of non-polar diluents such as mineral spirits or aromatic hydrocarbons which do not dissolve the process products would be possible, but 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 H 2 N equivalent of the s-triazine polyamine, preferably 3-10.
  • the new process products 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 on poly urethane base and in particular, as already stated, as active fillers in the production of polyurethane plastics by the isocyanate polyaddition process known per se. In this preferred use of the process products according to the invention, they are preferably dispersed in the isocyanate component used to produce 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, thanks to the use of the compounds according to the invention, then improve their heat resistance , 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 having NCO groups, and in proportions such that in the resulting NCO prepolymers both from unmodified diisocyanate-derived isocyanate groups and 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 in 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, with subsequent chemical incorporation of the initially dispersed compounds according to the invention is achieved by tempering the reaction products at 100-150 ° C.
  • 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
  • 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).

Landscapes

  • 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)

Claims (3)

1. Procédé pour la préparation de polyisocyanates portant des groupes urée et s-triazine par réaction de composés organiques portant des groupes amino avec des diisocyanates dans un rapport molaire NCO/NH2 d'au moins 2:1, caractérisé en ce que:
a) on utilise en tant que composé organique portant des groupes amino une diamino-s-triazine portant des substituants chloro-, bromo-, alkyle en C1-C8, alcoxy en C,-C8, aryle en C6-C10 ou aroxy en C6-C10, ou la mélamine, et
b) on utilise en tant que diisocyanates des diisocyanates aromatiques dont le poids moléculaire se situe dans l'intervalle de 174 à 400 et qui, en plus d'un groupe isocyanate à liaison aromatique ne faisant pas l'objet d'un empêchement stérique, portent un autre groupe isocyanate à liaison aromatique faisant l'objet d'un empêchement stérique par au moins un substituant en position ortho, éventuellement en mélange avec une proportion allant jusqu'a à 50% en poids, par rapport au mélange total, de diisocyanates aromatiques dont les groupes isocyanate ont la même réactivité.
2. Procédé selon la revendication 1, caractérisé en ce que l'on utilise en tant que composé portant des groupes amino la mélamine et, en tant que diisocyanate, le 2,4-diisocyanato-toluène, éventuellement en mélange avec le 2,6-diisocyanato-toluène, et/ou le 2,4'-diisocyanato-diphénylméthane, éventuellement en mélange avec le 4,4'-diisocyanato- diphénylméthane.
3. Utilisation des polyisocyanates portant des groupes urée et s-triazine, obtenus selon les revendications 1 et 2, en tant que matières de charge incorporables chimiquement à la préparation de résines synthétiques de polyuréthannes.
EP78100606A 1977-08-19 1978-08-07 Procédé pour la préparation de polyisocyanates et leur utilisation Expired EP0000893B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19772737402 DE2737402A1 (de) 1977-08-19 1977-08-19 Polyisocyanate, ein verfahren zu ihrer herstellung und ihre verwendung
DE2737402 1977-08-19

Publications (2)

Publication Number Publication Date
EP0000893A1 EP0000893A1 (fr) 1979-03-07
EP0000893B1 true EP0000893B1 (fr) 1980-09-17

Family

ID=6016781

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100606A Expired EP0000893B1 (fr) 1977-08-19 1978-08-07 Procédé pour la préparation de polyisocyanates et leur utilisation

Country Status (4)

Country Link
US (2) US4255570A (fr)
EP (1) EP0000893B1 (fr)
DE (2) DE2737402A1 (fr)
IT (1) IT1106886B (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3045470A1 (de) * 1980-12-02 1982-07-01 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von s-triazineinheiten und isocyanatgruppen oder gegenueber isocyanatgruppen reaktionsfaehige gruppen aufweisenden verbindungen und ihre verwendung als einbaufaehige fuellstoffe bei der herstellung von polyurethanen
DE3100355A1 (de) * 1981-01-08 1982-08-05 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von s-triazin-einheiten und epoxidgruppen aufweisenden verbindungen und ihre verwendung als einbaufaehige fuellstoffe bei der herstellung von polyurethan-kunststoffen
US4931487A (en) * 1988-03-04 1990-06-05 Dow Chemical Company Chain extenders for polyurethanes
DE3932168A1 (de) * 1989-09-27 1991-04-04 Bayer Ag Lackpolyisocyanate, ein verfahren zu ihrer herstellung und ihre verwendung
DE4022663C2 (de) * 1990-07-17 1999-11-04 Bayer Ag Verfahren zur Herstellung von Polyurethanformkörpern
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
KR0179461B1 (ko) 1992-10-30 1999-05-15 리타 버그스트롬 산 내식성 필름을 제공하는 아미노플라스트 경화성 필름 형성 조성물
TW242644B (fr) * 1992-10-30 1995-03-11 Ppg Industries Inc
US6235858B1 (en) 1992-10-30 2001-05-22 Ppg Industries Ohio, Inc. Aminoplast curable film-forming compositions providing films having resistance to acid etching

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2838511A (en) * 1955-10-31 1958-06-10 Du Pont Preparation of triaryl isocyanates
BE617033A (fr) 1961-04-28
US3210339A (en) * 1962-08-01 1965-10-05 Dentsche Gold Und Silber Schei Diamino-s-triazine derivatives
BE755460A (fr) * 1969-08-28 1971-02-01 Bayer Ag Isocyanates de s-triazinyle, leur preparation et leur utilisation dans la fabrication de resines de polyurethanes
DE2032547B2 (de) * 1970-07-01 1976-06-16 Bayer Ag, 5090 Leverkusen Herstellung von harnstoffgruppen aufweisenden polyisocyanaten und deren verwendung
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 (de) * 1974-07-30 1976-02-12 Bayer Ag Verfahren zur herstellung von polyharnstoffen
DE2507682A1 (de) * 1975-02-22 1976-09-02 Bayer Ag Isocyanate
US4026890A (en) * 1975-11-26 1977-05-31 Shell Oil Company Triazine-urea grease thickeners

Also Published As

Publication number Publication date
EP0000893A1 (fr) 1979-03-07
US4255570A (en) 1981-03-10
IT1106886B (it) 1985-11-18
IT7850756A0 (it) 1978-08-17
DE2737402A1 (de) 1979-02-22
DE2860170D1 (en) 1980-12-18
US4348512A (en) 1982-09-07

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