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WO1993011119A1 - Nouveaux polyiminoethers cycliques - Google Patents

Nouveaux polyiminoethers cycliques Download PDF

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Publication number
WO1993011119A1
WO1993011119A1 PCT/EP1992/002749 EP9202749W WO9311119A1 WO 1993011119 A1 WO1993011119 A1 WO 1993011119A1 EP 9202749 W EP9202749 W EP 9202749W WO 9311119 A1 WO9311119 A1 WO 9311119A1
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WO
WIPO (PCT)
Prior art keywords
atoms
tris
bis
polyiminoethers
group
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.)
Ceased
Application number
PCT/EP1992/002749
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German (de)
English (en)
Inventor
Ulrich Eicken
Doris Oberkobusch
Herbert Fischer
Wolfgang Gress
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of WO1993011119A1 publication Critical patent/WO1993011119A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/10—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D263/14—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with radicals substituted by oxygen atoms

Definitions

  • the present invention relates to novel compounds which contain a delta ⁇ oxazoline group two, three or four times in the molecule, a process for their preparation and their use.
  • Cyclic polyiminoethers are known as valuable intermediates and are used, for example, in accordance with EP 273 368, DE 20 29 524 or DE 35 39 593 for the production of plastics, resins and adhesives or in accordance with DE 39 24 163 for the production of coatings on solid surfaces.
  • a widespread use of these intermediates has so far stood in the way of the fact that there were only a few simple and at the same time good yields synthetic processes for polyiminoethers, as described, for example, in DE 39 15 874, and the readily accessible polyinotherms during further processing to give polymeric end products always led to the required qualities.
  • the aim of the present invention was to provide new cyclic polyiminoethers which can be easily prepared in good yields, can be further processed without problems to give polymeric end products and which give these polymeric end products overall better properties.
  • the new cyclic polyether ethers are bis-, tris- or tetrakisoxazolines of the general formula I.
  • n 2, 3 or 4
  • A Acyl residue of a di-, tri- or tetracarboxylic acid with 2 to 20 carbon atoms or the carbonyl group
  • R hydrogen or an alkyl, alkenyl or aryl group with no more than 12 carbon atoms
  • M Direct bond or double-bonded group with no more than 12 carbon atoms, selected from alkylene, alkenylene, arylene and alkylene p groups, which may optionally contain ether oxygens in its chain, R and M being linked by aloxy groups 1 to 3 carbon atoms can be substituted.
  • the new polyiminoethers can be obtained in virtually quantitative yield from polycarboxylic acid esters of the formula II
  • a and n have the meaning given above and R 'is an alkyl radical having 1 to 4 carbon atoms, by transesterification with n mol of a hydroxyoxazole ns of the formula III
  • reaction conditions can be chosen within wide limits, as long as care is taken to ensure that the oxazoline ring is not attacked during the reaction. Equivalent amounts of the reaction partners are expediently reacted with one another, but it is also readily possible to use an excess of one or the other if this excess can be separated off again after the reaction has ended or if the end product does not interfere with its further processing.
  • the transesterification is preferably carried out in the presence of neutral to alkaline transesterification catalysts, with dibutyltin dilaurate, tin octoate and titanium tetrabutylate being particularly preferred.
  • the amount of catalyst is preferably between about 0.2 and about 4 mol%, in particular 0.5 to 2 mol%, based on hydroxyoxazole n.
  • n moles of Ci- to C4-alcohol (R'-OH) are released, which can be distilled off, where appropriate is to apply a vacuum towards the end to completely separate the alcohol.
  • the course of the reaction can easily be monitored via the amount of alcohol separated off, but also, for example, by spectroscopic means by checking the reaction mixture.
  • the speed of the reaction naturally depends on the temperature and on the chosen catalyst and on its quantity; Response times in the range of a few hours are common.
  • the new cyclic polyiminoethers remain in the form of low-melting solids or as viscous liquids. They are characterized by NMR and IR spectra, in which the absence of the R 'group and the 0H group and the maintenance of the oxazoline ring are particularly noticeable.
  • the cyclic polyiminoethers formed can be further processed in the form obtained, ie together with the traces of catalyst. If necessary, the catalyst can also be removed in the usual way.
  • Preferred in the context of the invention are those polyiminoethers in which n has the value 2 and A represents the acyl radical of a dicarboxylic acid or the carbonyl group.
  • Acyl radicals which are derived from a benzene dicarboxylic acid or an aliphatic alpha-, omega-dicarboxylic acid having 2 to 13 carbon atoms are particularly preferred.
  • cyclic polyiminoethers derived from an oxazoline of the formula III in which the molecular part HO-CHR-M- is a hydroxyalkyl or hydroxyalkenyl radical having 1 to 17 carbon atoms, in particular the 5-hydroxypentyl radical, the 11-hy- droxyheptadec-8-enylrest or the 11-hydroxyheptadecylrest means.
  • esters of di-, tri- and tetracarbon acids used as starting material are generally commercially available substances or can easily be prepared from the commercially available acids by esterification with the alcohols R'-OH.
  • esters are: diethyl isophthalate, dimethyl terephthalate, dimethyl 2,6-naphthalenedicarboxylate, diethyl carbonic acid, diethyl oxalate and diethyl adipate, and also the esters of diphenylmethane-4,4'-benzophenone, dicarone -dicarboxylic acid, 4,4'-stilbenedicarboxylic acid and Diphenylsulfone-4. '-dicarboxylic acid.
  • the oxazolines of the formula III which serve as starting material and carry hydroxyl groups are also in a manner known per se, for example by cyclization of derivatives of the hydroxycarboxylic acids H0-CHR-M-C0 2 H, for example according to the process of patent applications EP 315856, DE 39 14 133 and DE 3914159 or according to the method of Litt and Levy (J. Polym. Sei. AI, 6., 1883 (1968)) or other customary synthetic methods for cyclic iminoethers (e.g. DE 1 445 642 or S. Kobayashi and T Saegusa in "Ring-opening Polymerization” Vol. 2, London 1984, page 762 following) is easily accessible.
  • Oxazolines which are derived from ricinoleic acid, dihydroricinoleic acid, caprolactone or from epoxidized unsaturated fatty acids which are ring-opened with monohydric lower alcohols are particularly preferred.
  • the 2-alkyl radical of the cyclic imino ether III consists of the 11-hydroxy-8-heptadecenyl radical f
  • the 11-hydroxyheptadecyl radical in the third case the 5-hydroxypentyl radical and in the latter case preferably a straight-chain 17 alkyl radical containing up to 21 C atoms, ⁇ er internally substituted by a hydroxyl and an alkoxyl group (preferably having 1 to 3 C atoms).
  • the new polyiminoethers are versatile intermediates.
  • An advantageous area of application is processes for the production of crosslinked polymers, the polyiminoethers being used alone, but preferably together with other low molecular weight or polymeric starting materials.
  • the polymers are prepared from the new polyiminoethers either together with reactants which, such as polyfunctional alcohols, amines or carboxylic acids, are able to react with the oxazoline rings or with those reactants which, like the polyiminoethers themselves, are cationic Poly routes in the presence of strong mineral acids, Lewis acids or alkylating agents. Examples of the latter reactants are monofunctional cycl * zhe imino ethers and lactones.
  • the hydroxyalkyloxazolines of the formula III which served as starting material had been prepared in accordance with the information in EP 315 856.
  • the esters and the transesterification catalysts were commercially available compounds.
  • Ric 2- (ll-hydroxyheptadec-8-enyl) oxazoline (ricinoloxazoline)
  • HOC5 2- (5-hydroxypentyl) oxazoline
  • a mixture of 10 g of the bisoxazoline obtained from diethyl carbonate and 5-hydroxypentyloxazole n was prepared with 0.2 g of methyl tosylate (as a polymerization catalyst) and 1 g of xylene and applied to a glass plate using a doctor knife with a gap width of 100 ⁇ m. To polymerize the film, the plate thus coated was heated to 160 ° C. for 30 minutes * * in an oven. This resulted in a festhaften._ "• Film with a pendulum hardness of 150 sec. (According to DIN 53 157), which was stable even against methyl ethyl ketone and did not yellow under UV light.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

Les nouveaux polyiminoéthers cycliques concernent une bis-, tris-, ou tétrakisoxazoline, de formule (I), avec la signification suivante des symboles: n: 2, 3, ou 4; A: reste acyle d'un acide di-, tri- ou tétracarboxylique de 2 à 20 atomes de carbone, ou le groupe carbonyle; R: hydrogène ou un groupe alkyle, alcényle ou aryle n'ayant pas plus de 12 atomes de carbone; M: liaison directe ou groupe à deux liaisons, n'ayant pas plus de 12 atomes de carbone, choisi parmi les groupes alkylène, alcénylène, arylène et alkarylène, lesquels peuvent contenir, dans leurs chaînes, éventuellement un oxygène d'un éther, R et M pouvant être substitués par des groupes alcoxy de 1 à 3 atomes de carbone. Les nouveaux polyiminoéthers sont préparés, avec des rendements pratiquement quantitatifs, à partir d'esters d'acides polycarboxyliques de formule (II): A(-O-R')n, dans laquelle A et n ont les significations précitées et R' est un reste alkyle de 1 à 4 atomes de carbone, par transestérification avec n moles d'une hydroxyoxazoline de formule (III), dans laquelle tous les symboles ont les désignations précitées. Les nouveaux polyiminoéthers sont des produits intermédiaires à utilisations multiples. Comme domaine d'application avantageux, on mentionne des procédés de fabrication de polymères réticulés, dans lesquels les polyiminoéthers seuls, mais de préférence avec d'autres produits de départ polymères ou à bas poids moléculaires sont utilisés. On obtient des résultats particulièrement avantageux en produisant des revêtements polymères sur des subjectiles solides, à partir des nouvelles bis-, tris- et tétraoxazolines. Ces revêtements se sont révélés particulièrement stables à la lumière et résistants aux solvants.
PCT/EP1992/002749 1991-12-06 1992-11-27 Nouveaux polyiminoethers cycliques Ceased WO1993011119A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4140333.9 1991-12-06
DE19914140333 DE4140333A1 (de) 1991-12-06 1991-12-06 Neue cyclische polyiminoether (ii)

Publications (1)

Publication Number Publication Date
WO1993011119A1 true WO1993011119A1 (fr) 1993-06-10

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ID=6446483

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1992/002749 Ceased WO1993011119A1 (fr) 1991-12-06 1992-11-27 Nouveaux polyiminoethers cycliques

Country Status (2)

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DE (1) DE4140333A1 (fr)
WO (1) WO1993011119A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1059862A (en) * 1963-07-01 1967-02-22 Commercial Solvents Corp Ester-oxazoline compositions and their method of preparation
WO1990014341A1 (fr) * 1989-05-16 1990-11-29 Henkel Kommanditgesellschaft Auf Aktien Nouveaux polyiminoethers cycliques
WO1991001354A1 (fr) * 1989-07-21 1991-02-07 Henkel Kommanditgesellschaft Auf Aktien Procede d'enduction

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1059862A (en) * 1963-07-01 1967-02-22 Commercial Solvents Corp Ester-oxazoline compositions and their method of preparation
WO1990014341A1 (fr) * 1989-05-16 1990-11-29 Henkel Kommanditgesellschaft Auf Aktien Nouveaux polyiminoethers cycliques
WO1991001354A1 (fr) * 1989-07-21 1991-02-07 Henkel Kommanditgesellschaft Auf Aktien Procede d'enduction

Also Published As

Publication number Publication date
DE4140333A1 (de) 1993-06-09

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