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WO2008142100A1 - Procédé de fabrication d'uréthanes à terminaison carbonate - Google Patents

Procédé de fabrication d'uréthanes à terminaison carbonate Download PDF

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Publication number
WO2008142100A1
WO2008142100A1 PCT/EP2008/056241 EP2008056241W WO2008142100A1 WO 2008142100 A1 WO2008142100 A1 WO 2008142100A1 EP 2008056241 W EP2008056241 W EP 2008056241W WO 2008142100 A1 WO2008142100 A1 WO 2008142100A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
general formula
alkylene
compounds
iii
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/EP2008/056241
Other languages
German (de)
English (en)
Inventor
Andreas Job
Lars Rodefeld
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.)
Saltigo GmbH
Original Assignee
Saltigo GmbH
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 Saltigo GmbH filed Critical Saltigo GmbH
Priority to EP08759843A priority Critical patent/EP2152774A1/fr
Publication of WO2008142100A1 publication Critical patent/WO2008142100A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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
    • C08G18/06—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
    • C08G18/71—Monoisocyanates or monoisothiocyanates
    • C08G18/711—Monoisocyanates or monoisothiocyanates containing oxygen in addition to isocyanate oxygen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/34—Oxygen atoms
    • C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
    • C07D317/38—Ethylene carbonate

Definitions

  • the present invention relates to a process for the preparation of carbonate-terminated urethanes.
  • material surfaces can be made biocompatible by coating with heparin.
  • Other applications include stain-resistant and bacteriostatic finishes and improved adhesion of adhesives and paints.
  • Targeted modification of biomolecules is also desirable in many cases.
  • biomolecules For example, it is known that the biological half-life of various drugs can be improved by adding polyoxyalkylene residues
  • R ' is C 1 -C stands 2 is alkylene and R "are different organic radicals can represent.
  • These reactive cychschen carbonates can be with nucleophiles implement such as hydroxyl or primary or secondary amino groups of biomolecules, polymers, or to substrate surfaces, wherein the opening The cyan carbon ring comes with simultaneous covalent attachment to the biomolecule, the polymer or other substrate surfaces.
  • isocyanate-reactive compositions are based on the reaction product of (a) a di- or polychloroformate ester of the type Q- [X-COY] n , where X O and Y may be chlorine, n is at least 2 and Q is an organic radical, with (b) a multi-functional compound, which in addition to the functional groups which react with the di- or Polychlorformiatester (a), necessarily at least one Immo - or enum group must contain.
  • No di- or polychloroformate esters (a) are described which have cyano carbonate groups.
  • the di- or polychloroformate esters are prepared by reacting polyols with acylating agents such as phosgene. From the imino and / or enamino groups contained in the multi-functional compound (b), an isocyanate-reactive amino group can later be obtained by hydrolysis.
  • EP-A-0 328 150 discloses a process which describes the reaction of cyclocarbonate-terminated alcohols with carboxylic anhydrides. Cyclocarbonate-terminated esters are obtained which can be used for a variety of further reactions. Also described in Example 18 is the reaction of hexamethylene diisocyanate with
  • this invention Since there is a high demand for reactive cyclic carbonates for surface treatment, this invention has the object to provide an improved manufacturing process.
  • the invention relates to a process for the preparation of compounds of general formula (I),
  • R 1 is C r Ci 2 alkylene
  • R 2 is C 1 -C 30 -alkyl, C 2 -C 30 -alkenyl, Ci-C 30 haloalkyl, C 1 -C 6 -AIlCyIoXy-C 1 -C 30 - alkyl, QQ-alkylcarbonyloxy-d-q O- alkyl, di (C 1 -C 8 -alkyl) ammoCrC 3 o-alkyl, di (C 7 -C 11 -aralkyl) ammo C 1 -C 30 -alkyl, di (allyl) aminoC r C 3 o-alkyl , ammonio-C ⁇ - C 30 alkyl, polyoxyalkylene Q-Cso-alkyl, Polysiloxanyl-C r C 30 alkyl, (meth) acrylic oyloxy-QC ⁇ alkyl, di (C 1 -C 6 alkyl)
  • R 2 represents a fluoresceinyl radical or a pyrene, fluorescem, coumarin, 4,4'-bisstyrylbiphenyl, pyrazohn, hydroquinone, benzoxazole, benzisoxazole, benzimidazole bonded via a C r C 3 o-alkylene group. or flavone acid residue.
  • R 1 has the meaning given for the general formula (I), with an isocyanate of the general formula (III)
  • the advantage of the process according to the invention is the avoidance of phenol as a minor component. It is particularly advantageous that this reaction is an addition reaction in which, in principle, no further secondary components are formed. It is thus a process which provides a complete atomic economy.
  • the isocyanates of the general formula (III) are obtainable by reacting the amines of the general formula (IV)
  • alkyl is intended to include straight-chain, branched and cyclic alkyl groups, unless explicitly stated otherwise in this application, these alkyl groups each having 1 to 30, preferably 1 to 24 and particularly preferably 1 to 18 carbon atoms are suitable
  • Alkyl radicals for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-butyl
  • Pentyl 1-methylbutyl, 2-methylbutyl, 3-methylbuutyl, neo-pentyl, 1-ethylpropyl, cyclohexy ⁇ ,
  • haloalkyl accordingly means an alkyl group of the aforementioned meaning in which one or more hydrogen atoms are replaced by halogen, preferably chlorine or fluorine.
  • Al ky loxyalkyl mean, "Alky Icarbonyl oxyalky 1", “di (alkyl) on inoalkyl”',”di (aralky l) amino alky 1 ",” di (allyl) aminoalkyl “,” ammonioalkyl ",” polyoxyalkylenealkyl “,” polysiloxanylalkyl “,” (meth) acryloyloxyalkyl “ 5 and” dialkylphosphonoalkyl ",” dialkylphosphonatoalkyl "and 3-" imidazolioalkyl "means an alkyl radical, m one or more hydrogen atoms through a
  • Alkyloxy group an alkylcarbonyloxy group, eme Dialkylammo group, a Ammomo- group ((NR 5 3) T, wherein R 3 independently of one another example of Ci-C] g alkyl, C 2 -C lg alkenyl or Benzyl), a polyoxyalkylene radical, a polysüoxanyl radical, eme (meth) acryloyloxy group or an imidazolio group of the following structure
  • R 5 is hydrogen, C 1 -C 18 alkyl, C 2 -C 8 alkenyl, preferably allyl, or benzyl replaced.
  • R 2 and / or R 3 are aminoalkyl or irmdazohoalkyl, the compound is accompanied by one equivalent of an anion, preferably a physiologically acceptable anion, such as a halide, especially chloride or bromide, sulphate, bisulphate, methosulphate or nitrate.
  • alkylene means a divalent aliphatic, branched or unbranched hydrocarbon radical, preferably one - (CH 2 -CH 2 ) -, one - (CH 2 -CH (CH 3 )) -, one - (CH 2 - CH (C 2 H 5 )) - or a - (CH 2 -CH 2 -CH 2 -CH 2 ) - radical.
  • the polyoxyalkylene radical is preferably derived from ethylene oxide, propylene oxide, butylene oxide or
  • Tetrahydrofuran more preferably of ethylene oxide or propylene oxide. It is terminated at the distal end by a radical which is hydrogen or a C 1 -C 6 alkyl radical.
  • the Polysiloxanylrest is preferably derived from Porydrniethylsüoxanen and may be straight-chain or branched.
  • the saccharide residue is e.g. to a Glucoxy ⁇ rest.
  • R 1 represents a C 1 -C 6 -alkylene radical, particularly preferably a methylene, ethylene, n-propylene, n-butylene or n-hexamethylene radical ,
  • R 2 is a fluoresceinyl radical or a pyrene, fluorescein, coumarin or 4,4'-bis-styrylbiphenyl bonded via a C 1 -C 30 -alkylene group, Pyrazolm, hydroquinone,
  • Benzoxazole, benzisoxazole, benzimidazole or flavonic acid radical, so the aforementioned radicals R 2 may also be mono- or polysubstituted.
  • exemplary here are the
  • Formula (IV) contain no further, reactive with phosgene groups.
  • R 2 is C r C 30 alkyl, C r C 6 alkyloxy-C, -C 3 O-alkyl, C iC 6 alkylcarbonyloxy-C iC 30 - alkyl , Di (C 1 -C 6 -alkyl) aminoC 1 -C 3 0-alkyl, di (C 7 -C 5 aralkyl) aminoC 1 -C 30 -alkyl, di (allyl) arninoCrC 30 -alkyl, ammonium ci C 30 -alkyl s polyoxyalkylene-C 1 -C 30 -alkyl, polysiloxanyl-C 1 -C 30 -alkyl, (meth) acryloyloxy-C 1 -C 30 -alkyl, 3-imidazolio-C 1 -C 30 -
  • R 2 is Ci-Ci S alkyl, C JC 6 - alkylcarbonyloxy-Q -C 18 - -alkyl, di (C -C 6 alkyl!) A ⁇ mno-C; -C g alkyl, di (C 7 -C u -ar alkyl) amino-C ⁇ C 18 alkyl, di (allyl) amino-Ci-C 8 alkyl, Ammomo-Ci -C 18 alkyl, polyoxyalkylene Ci-C lg -alkyl, polysiloxanyl-Ci -C j g -alkyl, (meth) acryloyloxy-C i -Ci 8 alkyl, 3 -imidazolio-C i -C 30 -alkyl or [C 2 -C 6 - Alkylene-O] x - [C 2 -C 6 -alkylene-O] y -C I -C
  • R 4 is Ci-C ⁇ - alkylene
  • R 5 is hydrogen, C 1 -C 13 alkyl, C 2 -C 18 alkenyl, preferably AHyI, or benzyl,
  • R 6 is hydrogen or methyl
  • R 7 is C r C 6 -alkyl
  • Y is one equivalent of an anion, preferably chloride, bromide
  • n, m, o are independently an integer from 0 to 17
  • p is an integer from 1 to 12
  • q is an integer from 1 to 100, preferably 2 to 50
  • the amines of the general formula (IV) which can be used for the preparation of the compounds of the general formula (III) are either available commercially or can be prepared by methods familiar to the person skilled in the art.
  • Suitable amines of the general formula (IV) are, for example:
  • 1-butylimidiazoliummethyl sulfate 3-aminopropyl-1-methylimidazolium chloride, 3-aminopropyl-1-butylimidazolium chloride, 3-aminopropyl-1-methylimidazolium bromide, 3-aminopropyl-1-butyl-imidiazohumbromide, 3-aminoethyl-1-methylimidazolium chloride, 3-aminomethyl - 1-butyl-imidiazolmmchlo ⁇ d, 3-ammoethyl-l-methylimidiazoliumbromid and 3-aminoethyl-1-butyl imidiazolmmbromid.
  • Polyetheramines of formula (IV) may be in the form of commercial products of the Huntsman Corporation, e.g. Jeffamm M-600, Jeffamm M-1000, Jeffamm M-2005 and Jeffarmn M-2070.
  • the inventive method is usually at a temperature in the range of 0 0 C to
  • the erfmdungswashe method can be carried out so that the isocyanate of the general formula (III), optionally dissolved in an inert solvent, and then the compound of general formula (II), optionally also dissolved in the same or in a different inert solvent to which isocyanate is added.
  • the compound of the general formula (II) is initially charged and then the isocyanate of the general formula (III) is added, where both substances may optionally be diluted with the same or different inert solvent.
  • the method according to the invention can also be operated continuously.
  • the addition of the isocyanate of the general formula (III) takes place simultaneously with the addition of the compound of the general formula (II) in a suitable apparatus.
  • Suitable solvents are, for example, toluene, xylene, chlorobenzene, 1, 2-dichlorobenzene,
  • the isolation of the compounds of the general formula (I) can be carried out by distillation, crystallization, chromatography or freeze-drying.
  • the compounds of the general formula (I) obtained by the process according to the invention can be reacted with functional groups, e.g. Hydroxy groups or primary or secondary
  • biomolecule is intended to encompass all molecules which can be isolated from biological systems and / or which can interact with biological systems or parts thereof, in particular peptides, proteins, proteoglycans, enzymes, markers, antibodies, receptor molecules, Antigens and drugs Specific examples are heparin, tissue plasminogen activator, streptokinase and prostaglandins.
  • polyamines or polyols can be used as polymers.
  • polyamines are polyvinylamine, polyallylamine, polyethyleneimines, chitosan, polyamide-epichlorohydrin resins (available as "Hercosett®” products), polyaminostyrene, peptides or proteins such as gelatin.
  • the surfaces of materials are suitable which have amino and / or hydroxyl groups, or surfaces which have been treated by amino acid methods known per se.
  • Glycerol (90%) 75 g m submitted chlorobenzene via the dropping funnel 98.95 g of the isocyanate from Example 1 dissolved in 75 ml of chlorobenzene at 20 0 C are added dropwise. The mixture was then heated to boiling (134 ° C). The conversion was monitored by IR spectroscopy. After a reaction time of 4 hours, no NCO band was detectable by IR spectroscopy. The mixture was heated to 130 0 C and all volatile

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyethers (AREA)

Abstract

L'invention concerne un procédé amélioré de fabrication d'uréthanes à terminaison carbonate au moyen d'isocyanates. Ledit procédé se caractérise par des rendements élevés et par l'absence de production de phénols en tant que composants secondaires.
PCT/EP2008/056241 2007-05-21 2008-05-21 Procédé de fabrication d'uréthanes à terminaison carbonate Ceased WO2008142100A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08759843A EP2152774A1 (fr) 2007-05-21 2008-05-21 Procédé de fabrication d'uréthanes à terminaison carbonate

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200710023866 DE102007023866A1 (de) 2007-05-21 2007-05-21 Verfahren zur Herstellung Carbonat-terminierter Urethane
DE102007023866.7 2007-05-21

Publications (1)

Publication Number Publication Date
WO2008142100A1 true WO2008142100A1 (fr) 2008-11-27

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Application Number Title Priority Date Filing Date
PCT/EP2008/056241 Ceased WO2008142100A1 (fr) 2007-05-21 2008-05-21 Procédé de fabrication d'uréthanes à terminaison carbonate

Country Status (3)

Country Link
EP (1) EP2152774A1 (fr)
DE (1) DE102007023866A1 (fr)
WO (1) WO2008142100A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002042383A1 (fr) * 2000-11-22 2002-05-30 Dsm N.V. Compositions durcissables par rayonnement
JP2006232673A (ja) * 2005-02-22 2006-09-07 Nof Corp ウレタン結合含有グリセロールカーボネート（メタ）アクリレート化合物、その製造方法、及び重合体

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4002598A (en) 1975-03-06 1977-01-11 Texaco Development Corporation Polyether urea epoxy curing agent
DE3804820A1 (de) 1988-02-12 1989-08-17 Dainippon Ink & Chemicals Cyclocarbonathaltige ester und verfahren zu ihrer herstellung
GB8905768D0 (en) 1989-03-13 1989-04-26 Ici Plc Compositions of matter
EP1541568A1 (fr) 2003-12-09 2005-06-15 Deutsches Wollforschungsinstitut an der Rheinisch-Westfälischen Technischen Hochschule Aachen e.V. Carbonates et urées cycliques et réactifs pour la modification de biomolecules, polymères et surfaces
AU2004319385A1 (en) 2004-04-05 2005-11-17 Lanxess Deutschland Gmbh Method for marking terrain

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002042383A1 (fr) * 2000-11-22 2002-05-30 Dsm N.V. Compositions durcissables par rayonnement
JP2006232673A (ja) * 2005-02-22 2006-09-07 Nof Corp ウレタン結合含有グリセロールカーボネート（メタ）アクリレート化合物、その製造方法、及び重合体

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PASQUIER N ET AL: "POLYMERS WITH SPECIFIC ADHESION PROPERTIES FOR SURFACE MODIFICATION: SYNTHESIS, CHARACTERIZATION AND APPLICATIONS", DESIGNED MONOMERS AND POLYMERS, VSP, UTRECHT, NL, vol. 8, no. 6, 1 January 2005 (2005-01-01), pages 679 - 703, XP009074721, ISSN: 1385-772X *

Also Published As

Publication number Publication date
DE102007023866A1 (de) 2008-11-27
EP2152774A1 (fr) 2010-02-17

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