WO2006051047A1 - N-substituted imides as polymerization initiators - Google Patents

N-substituted imides as polymerization initiators Download PDF

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Publication number
WO2006051047A1
WO2006051047A1 PCT/EP2005/055646 EP2005055646W WO2006051047A1 WO 2006051047 A1 WO2006051047 A1 WO 2006051047A1 EP 2005055646 W EP2005055646 W EP 2005055646W WO 2006051047 A1 WO2006051047 A1 WO 2006051047A1
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alkyl
substituted
crc
curing
ring
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PCT/EP2005/055646
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French (fr)
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Peter Nesvadba
Johannes Benkhoff
Lucienne Bugnon
Karin Powell
Tunja Jung
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Ciba Specialty Chemicals Holding Inc.
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Priority to BRPI0517622-0A priority Critical patent/BRPI0517622A/en
Priority to US11/666,887 priority patent/US7723399B2/en
Priority to EP05815624A priority patent/EP1828258B1/en
Priority to CN2005800380207A priority patent/CN101056893B/en
Priority to JP2007540627A priority patent/JP5265194B2/en
Priority to AT05815624T priority patent/ATE472560T1/en
Priority to DE602005022108T priority patent/DE602005022108D1/en
Publication of WO2006051047A1 publication Critical patent/WO2006051047A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C239/00—Compounds containing nitrogen-to-halogen bonds; Hydroxylamino compounds or ethers or esters thereof
    • C07C239/08—Hydroxylamino compounds or their ethers or esters
    • C07C239/16—Hydroxylamino compounds or their ethers or esters having nitrogen atoms of hydroxylamino groups further bound to carbon atoms of hydrocarbon radicals substituted by nitrogen atoms not being part of nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C325/00—Thioaldehydes; Thioketones; Thioquinones; Oxides thereof
    • C07C325/02—Thioketones; Oxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members 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
    • C07D207/36—Oxygen or sulfur atoms
    • C07D207/40—2,5-Pyrrolidine-diones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members 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
    • C07D207/36—Oxygen or sulfur atoms
    • C07D207/40—2,5-Pyrrolidine-diones
    • C07D207/404—2,5-Pyrrolidine-diones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. succinimide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/46—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with hetero atoms directly attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
    • C07D221/06—Ring systems of three rings
    • C07D221/14—Aza-phenalenes, e.g. 1,8-naphthalimide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts

Definitions

  • the invention relates to novel N-substituted imides and polymerizable compositions com ⁇ prising these N-substituted imides.
  • the invention further relates to the use of N-substituted imides as polymerization initiators.
  • Free-radical polymerization is among the most important methods of building up a relatively long carbon chain. It is employed in process technology for preparing commercially important polymers such as polystyrene, PVC, poly(meth)acrylates, PAN and other polymers. For technical details, reference may be made to the still relevant standard work G. Odian, Principles of Polymerization, McGraw-Hill New York 1991.
  • Free-radical polymerizations are started using initiators.
  • Initiators which have become estab ⁇ lished in process technology are azo compounds, dialkyl peroxides, diacyl peroxides, hy ⁇ droperoxides, thermolabile C-C-dimers, redox systems and photoinitiators.
  • J. D. Druliner describes in J.Phys.Org. Chem. 8, 316-324 (1995) the polymerization of acrylates and methacrylates to make homopolymers and block copolymers initiated by N- alkoxyphthalimides and succinimides.
  • US2,872,450 describes the manufacture of thio-and dithiocarboxylic acid esters by reaction of cyclic oximides and thio-or dithiocarboxylic acid ester chlorides and their use as fungicides.
  • dicarboxylic acid imides are particularly suitable as poly ⁇ merization initiators if they are esterified by thio-acyl-, or imino radicals.
  • the invention provides compounds of the formula I and Il
  • R 1 and R 2 are each, independently of one another, hydrogen, Ci-Ci 8 alkyl, Ci-Ci 8 alkenyl, C 6 -Ci 4 aryl, aralkyl, C 5 -Ci 2 cycloalkyl, each of which may be substituted by halogen, CrC 4 -alkyl, hydroxy, CrC 6 alkoxy, carbonyl, CrC 6 alkoxycarbonyl; or R 1 and R 2 together with the adjacent -CO-N-CO- group may form a monocyclic, bicyclic or polycyclic ring, said ring having up to 50 non hydrogen atoms and wherein said ring
  • ⁇ ' may contain the structural element N-O- more than once;
  • R 3 if n is 1 is CrCi 8 alkyl, CrCi 8 alkenyl, C 6 -Ci 4 aryl, aralkyl, C 5 -Ci 2 cycloalkyl, each of which may be substituted by halogen, C r C 4 -alkyl, hydroxy, CrC 6 alkoxy, carbonyl, CrC 6 alkoxycarbonyl; or R 3 is ORi 0 or SRn, NR i2 Ri 3 ; wherein R 10 is C r Ci 8 alkyl, C 6 -Ci 4 aryl, aralkyl, C 5 -Ci 2 cycloalkyl, each of which may be substituted by halogen, C r C 4 -alkyl, hydroxy, CrC 6 alkoxy, carbonyl, d-C 6 alkoxycarbonyl; and Rn is CrCi 8 alkyl, C 6 -Ci 4 aryl, aralkyl, C 5 -C
  • Ri 2 and Ri 3 independently of one another are hydrogen, CrCi 8 alkyl, C 6 -Ci 4 aryl, aralkyl, C 5 -Ci 2 cycloalkyl, each of which may be substituted by halogen, CrC 4 -alkyl, hydroxy, Ci-C 6 alkoxy, carbonyl, C r C 6 alkoxycarbonyl; or R 12 and R i3 form together with the N atom to which they are attached a 5 or 6 membered ring, optionally interrupted by -NH-, -N(Ci-C 8 alkyl)-, -O- and/or S-atoms,
  • R 3 if n is 2, is C 2 -Ci 2 alkylene, C 2 -Ci 2 alkenylene, C 6 -Ci 4 arylene, xylylene ; with the proviso, that the following compounds disclosed in US2, 872,450 as fungicides are excluded,
  • R 4 and R 5 are each, independently of one another, hydrogen, CrCi 8 alkyl, C r Ci 8 alkenyl
  • R 6 if n is 1, is hydrogen, CrCi 8 alkyl, C r Ci 8 alkenyl, C 6 -Ci 4 aryl, aralkyl, C 5 -Ci 2 cycloalkyl, each of which may be substituted by halogen, C r C 4 -alkyl, hydroxy, CrC 6 alkoxy, carbonyl, CrC 6 alkoxycarbonyl; or R 6 is NR 14 R 15 ; wherein R i4 and R i5 independently of one another are hydrogen, C r Ci 8 alkyl, C 6 -Ci 4 aryl, aralkyl, C 5 -Ci 2 cycloalkyl, each of which may be substituted by halogen, CrC 4 -alkyl, hydroxy, CrC 6 alkoxy, carbonyl, d- C 6 alkoxycarbonyl; or R 14 and Ri 5 form together with the N atom to which they are attached a 5 or 6 membered ring, optionally
  • R 6 if n is 2, is C 2 -Ci 2 alkylene, C 2 -Ci 2 alkenylene, C 6 -Ci 4 arylene, xylylene;
  • R 7 is hydrogen, C r Ci 8 alkyl, C 6 -Ci 4 aryl, aralkyl, C 5 -Ci 2 cycloalkyl, each of which may be substituted by halogen, C r C 4 -alkyl, hydroxy, CrC 6 alkoxy, carbonyl, C r C 6 alkoxy- carbonyl; or R 7 and Ri 4 or R 7 and Ri 5 form together with the N-atom attached to R 7 a 5- 6 membered ring, optionally interrupted by -NH-, -N(C r C 8 alkyl)-, -O- and/or S-atoms. Definitions
  • Ci-Ci 8 alkyl includes, for example, Ci-C 6 alkyl, e.g. methyl, ethyl, n-propyl or isopropyl or n-, sec- or tert-butyl or straight-chain or branched pentyl or hexyl, or C 7 -Ci 8 alkyl, e.g.
  • Ci 4 -C 2 o-alkanoyl having an even number of C-atoms, e.g. lauroyl (C12), myristoyl (C14), palmitoyl (C16) or stearoyl (C 18).
  • Ci-Ci 8 alkenyl means an unsaturated, linear or branched hydrocarbon group as defined above under alkyl with one or more carbon-carbon double bonds, such as a vinyl group.
  • C 2 -Ci 2 alkylene means a divalent group derived from a straight or branched chain hydrocarbon of from 1 to 12 carbon atoms.
  • alkylene groups may include ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
  • Ce-Cuaryl refers to an optionally substituted benzene ring or to an optionally substituted benzene ring fused to one or more optionally substituted benzene rings to form a ring system.
  • Preferred aryl groups are phenyl, 2-naphthyl, tetrahydronaphthyl, 1-naphthyl, biphenyl, indanyl, anthracyl, phenanthr ⁇ l, as well as substituted derivatives thereof.
  • substituents are: CrCi 8 alkyl, C 6 -Ci 4 aryl, aralkyl, C 5 -Ci 2 cycloalkyl, halogen, OH, CrCi 8 alkoxy, CrCi 8 alkylthio, carboxy, CrCi 8 alkoxycarbonyl, carbamoyl (C(O)NH 2 ), Ci-Ci 8 alkylcarbamoyl, di-C r Ci 8 alkylcarbamoyl, acyl, nitro, amino, C r Ci 8 alkylamino or di- Ci-Ci 8 alkylamino, -CH 2 -X-CH 2 - wherein X is O, NH, N(C r Ci 8 alkyl).
  • C 6 -Ci 4 arylene refers to an optionally substituted benzene ring diradical or to a benzene ring system diradical containing an optionally substituted benzene ring fused to one or more optionally substituted benzene rings. Examples correspond to the aryl groups above.
  • aralkyl includes a radical RaRb, where Ra is an alkylene (a bivalent alkyl) group and Rb is an aryl group as defined above. Preferred are C 7 -C 8 aralkyl groups such as 2- phenylethyl or benzyl.
  • C 5 -Ci 2 cycloalkyl includes a monovalent, alicyclic, saturated hydrocarbon radical having three or more carbon atoms forming the ring. While the cycloalkyl compounds may have up to 12 carbon atoms, generally there will be three to seven carbon atoms in the ring. The latter include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclo- heptyl.
  • the term "monocyclic ring” includes a 5 to 9 membered ring system such as, for example, dioxo pyrrolidine, dioxo piperidine, dioxo morpholine, dioxo thiomorpholine or a derivative derived from trihydroxyisocyanuric acid,
  • the monocyclic ring system is preferably a residue
  • A is unsubstituted ethylene or propylene, ethylene or propylene substituted by CrCi 8 alkyl, C 6 -Ci 4 aryl, aralkyl, C 5 -Ci 2 cycloalkyl, halogen, OH, d- Ci 8 alkoxy, CrCi 8 alkylthio, carboxy, C r Ci 8 alkoxycarbonyl, carbamoyl (C(O)NH 2 ), C r Ci 8 alkylcarbamoyl, di-Ci-Ciealkylcarbamoyl, acyl, nitro, amino, Ci-Ci 8 alkylamino or i-Ci- Ci 8 alkylamino, -CH 2 -X-CH 2 - wherein X is O, NH, N(C r Ci 8 alkyl); or -N(OH)-CO-N(OH)-.
  • a monocyclic ring derived from trihydroxyisocyanuric acid is e.g.
  • acyl refers to the group RaC(O)-, where Ra is CrCi 8 alkyl, C 5 -Ci 2 cycloalkyl, or heterocyclyl as defined herein.
  • heterocyclic moieties include, for example, tetrahydrofuran, pyran, 1,4-dioxane, 1,3-dioxane, piperidine, pyrrolidine, morpholine, tetrahydrothiopyran, tetrahydrothiophene.
  • tricyclic ring means a 5 to 12 membered fused ring system.
  • fused ring system pertains to a system comprising in addition to the monocyclic core ring defined above, one or more aromatic rings, or one or more aliphatic rings.
  • the aromatic ring as well as the aliphatic ring may comprise solely carbon atoms, or may comprise carbon atoms and one or more heteroatoms, including nitrogen, oxygen, and sulfur atoms.
  • the aromatic ring is preferably a benzene ring resulting in dioxo-dihydro-isoindol rings or a naphthene ring resulting in dioxo-benzoisoquinoline rings.
  • the aliphatic ring is e.g. an C 3 -C 7 cycloalkylene ring, an oxirane ring, a cyclohexenyl ring or a norbomene ring or
  • bicyclo[2.2.2]octane or bicyclo[3.2.1]octane or a group of the form
  • the aromatic ring(s) may optionally be substituted by substituted by CrCi 8 alkyl, C 6 -Ci 4 aryl, aralkyl, C 5 -Ci 2 cycloalkyl, halogen, OH, CrCi 8 alkoxy, CrCi 8 alkylthio, carboxy, Ci-Ci 8 alkoxy- carbonyl, carbamoyl (C(O)NH 2 ), Ci-Ciealkylcarbamoyl, di-Ci-Ci 8 alkylcarbamoyl, acyl, nitro, amino, Ci-Ci 8 alkylamino or di-Ci-Ci 8 alkylamino, -CH 2 -X-CH 2 - wherein X is O, NH, N(d-Ci ⁇ alkyl).
  • the bicyclic ring system is preferably a residue of the formula
  • A is phenylene, cyclohexylene, cyclohexenylene, 1,8-naphthylene, pyridinylene or wherein A is ethylene or propylene or ethylene or propylene substituted CrC 4 alkyl, or ethenylene or propenylene or ethenylene or propenylene substituted C r C 4 alkyl.
  • polycyclic ring system refers to ring systems having more than two cyclic compounds bonded.
  • a polycyclic ring system as used herein may be aromatic or non- aromatic, or may be composed of separate aromatic and non-aromatic moieties.
  • An example is adamantane or 1 ,3,5,7-tetra-aza-adamantane (urotropine), cubane, twistane,
  • Polycyclic ring systems are also compounds of the formula I 1 and II 1 wherein R 3 ,
  • R 6 and R 7 are as defined above.
  • polycyclic residues may be:
  • non hydrogen atoms includes C-Atoms and hetero atoms like N, S, O and P atoms.
  • the ring is, for example, a saturated or unsaturated ring, for example aziridine, piperazine, pyrrole, thiophene, pyrrolidine, oxazole, pyridine, 1 ,3-diazine, 1,2-diazine, piperidine or morpholine; morpholinyl, piperidyl or piperazinyl rings, especially, are formed.
  • A is unsubstituted ethylene or propylene, ethylene or propylene substituted by
  • CrCi 8 alkyl C 6 -Ci 4 aryl, aralkyl, C 5 -Ci 2 cycloalkyl, halogen, OH, CrCi 8 alkoxy, d- Ci 8 alkylthio, carboxy, C r Ci 8 alkoxycarbonyl, carbamoyl (C(O)NH 2 ), C r Ci 8 alkyl- carbamoyl, di-Ci-Ciealkylcarbamoyl, acyl, nitro, amino, Ci-Ci 8 alkylamino or di-Ci- Ci 8 alkylamino; or A is ethenylene or propenylene or ethenylene or propenylene substituted C r C 4 alkyl; or A Js-CH 2 -X-CH 2 - wherein X is O, NH, N(C r Ci 8 alkyl); or -N(OH)-CO-N(OH)-.; or A together with the
  • said ring may contain the structural element N-O- more than once;
  • Ri 2 and Ri 3 independently of one another are hydrogen, CrCi 8 alkyl, cyclohexyl, phenyl, benzyl, or R 12 and R i3 form together with the N atom to which they are attached a 5 or 6 membered ring, optionally interrupted by -NH-, -N(C r C 8 alkyl)-, -O- and/or S-atoms,
  • a 1 is unsubstituted ethylene or propylene, ethylene or propylene substituted by
  • said ring may contain the structural element N-O- more than once;
  • R 6 is hydrogen, C r Ci 8 alkyl, cyclohexyl, phenyl, benzyl, NR 14 R 15 ; wherein
  • R 14 and R 15 independently of one another are hydrogen, Ci-d 8 alkyl, cyclohexyl, phenyl or R i4 and R i5 form together with the N atom to which they are attached a 5 or 6 membered ring, optionally interrupted by -NH-, -N(C r C 8 alkyl)-, -O- and/or S-atoms,
  • R 7 is hydrogen, CrCi 8 alkyl, cyclohexyl, phenyl;or R 7 and Ri 4 or R 7 and Ri 5 form together with the N-atom attached to R 7 a 5-6 membered ring, optionally interrupted by -NH-, - N(CrC 8 alkyl)-, -O- and/or S-atoms.
  • Ri 2 and R i3 each, independently of one another, are hydrogen or C r C 8 alkyl or cyclohexyl, or Ri 2 and Ri 3 form together with the N atom to which they are attached a 5 or 6 membered ring, optionally interrupted by -NH-, -N(C r C 8 alkyl)- and/or -0-atoms,
  • Ri 6 and Ri 7 each, independently of one another, are hydrogen, d-C 8 alkyl, cyclohexyl, benzyl, phenyl, halogen, OH, Ci-C 8 alkoxy, Ci-C 8 alkylthio, carboxy, Ci-C 8 alkoxy- carbonyl, carbamoyl (C(O)NH 2 ), CrC ⁇ alkylcarbamoyl, di-Ci-Csalkylcarbannoyl, d-
  • Ri 8 and R i9 each, independently of one another, are hydrogen, C r C 8 alkyl, cyclohexyl, benzyl, phenyl, halogen, OH, Ci-C 8 alkoxy, Ci-C 8 alkylthio, carboxy, Ci-C 8 alkoxy- carbonyl, carbamoyl (C(O)NH 2 ), C r C 8 alkylcarbamoyl, di-Ci-Cealkylcarbamoyl, C r
  • a further preparation route is the reaction of thiophosgene with a N-hydroxyimide obtaining a thiocarboxylic acid chloride which is further reacted with an amine or an alcohol according to the following scheme:
  • the imide chloride may be prepared as described in J. C. S. Perkin II, 1318 (1980).
  • Suitable tricarboxylic acids include, for example, succinic acid, Ci-Ci 8 alkylsuccinic acid, C 2 -Ci 8 alkenylsuccinic acid, maleic acid, dimethylmaleic acid, glutaric acid, thioglycolic acid, imido diacetic acid, citric acid, 5-norbomene-2,3-dicarboxylic acid, 3,6-epoxy-1 ,2,3,6-tetra- hydrophthalic acid, phthalic acid, substituted phthalic acid (halogen, COOR, nitro etc, as defined above) homophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, 1 ,8-naphthalene dicarboxylic, pyridine-2,3-dicarboxylic acid, naphthalene-1 ,4,5,8-tetra- carboxylic acid, 3,4,9, 10-perylene t
  • the N-substituted imides may be used as polymerization initiators, especially as thermal radical initiators (TRI) in a curing agent for coatings that cure by free radical polymerisation.
  • the coating may be a thermal curable coating composition, a double- (thermal and UV radiation) curable coating composition or a dual-(thermal curable) coating composition comprising at least a second crosslinkable resins.
  • the thermal curing is carried out using NIR-curing or IR-curing or convection heat. It is also possible to use microwave heating.
  • the double curing composition comprises in addition to the thermal initiator a photoinitiator.
  • the double curing is carried out using NIR-curing or IR-curing followed by UV-curing or vice versa.
  • the invention further relates to thermal curable coating composition, comprising a) at least an ethylenically unsaturated compound; b) a thermal initiator effective to enable IR-curing or NIR-curing or to enable microwave curing or to enable ultrasound curing or to enable the convection heat curing of the ethylenically unsaturated compound, wherein the thermal initiator is a N-substituted imide of the formula (I) and/or (II).
  • the invention further relates to a dual curable coating composition, comprising a) at least an ethylenically unsaturated compound and a second thermal crosslinkable compound; b) a thermal initiator effective to enable IR-curing or NIR-curing or to enable microwave curing or to enable ultrasound curing or to enable the convection heat curing of the ethylenically unsaturated compound, wherein the thermal initiator is a N-substituted imide of the formula (I) and/or (II).
  • the invention further relates to a double (thermal and UV) curable coating composition, comprising a) at least an ethylenically unsaturated compound; b) a thermal initiator effective to enable IR-curing or NIR-curing curing or to enable microwave curing or to enable ultrasound curing or to enable the convection heat curing of the ethylenically unsaturated compound, wherein the thermal initiator is a N- substituted imide of the formula (I) and/or (II); c) a photoinitiator effective to enable UV-curing of the ethylenically unsaturated compound.
  • a double (thermal and UV) curable coating composition comprising a) at least an ethylenically unsaturated compound; b) a thermal initiator effective to enable IR-curing or NIR-curing curing or to enable microwave curing or to enable ultrasound curing or to enable the convection heat curing of the ethylenically unsaturated compound,
  • Thermal curing refers to the application of convection heat or IR- or NIR-radiation or microwave irradiation or ultrasound exposure after the mixture has been applied to substrate.
  • the adhered powder coating is first melted to form a surface layer preferably by convection heat. Suitable temperatures to initiate and complete free-radical polymerization are 60-180 0 C.
  • the NIR radiation used in the process according to the invention is short-wave infrared radiation in the wavelength range from about 750 nm to about 1500 nm, preferably 750 nm to 1200 nm.
  • Radiation sources for NIR radiation include, for example, conventional NIR radiation emitters, which are available commercially (for example, from Adphos).
  • the IR radiation used in the process according to the invention is medium wave radiation in the wave length range from about 1500 nm to about 3000 nm and/or longer-wave infra-red radiation in the wave length range above 3000 nm.
  • IR radiation emitters of this kind are available commercially (for example, from Heraeus).
  • the microwave radiation used in this process according to the invention is electro magnetic radiation in the wavelength range from about 1 mm to 30 cm.
  • Ultrasound used in this process according to the invention is sound with a frequency above
  • the photochemical curing step is carried out usually using light of wavelengths from about 200 nm to about 600 nm, especially from 200 to 450 nm.
  • light sources there are used a large number of the most varied types. Both point sources and planiform projectors (lamp carpets) are suitable. Examples are: carbon arc lamps, xenon arc lamps, medium-, high- and low-pressure mercury lamps, optionally doped with metal halides (metal halide lamps), microwave-excited metal-vapor lamps, excimer lamps, super actinic fluorescent tubes, fluorescent lamps, argon filament lamps, electronic flash lamps, photographic flood lights, electron beams and X-rays generated by means of synchrotrons or laser plasma.
  • Double curable systems comprise ethylenically unsaturated monomers, which can be polymerized by UV radiation or which can be polymerized thermally induced by IR or NIR radiation or microwave irradiation or ultrasound exposure or by convection heat.
  • the thermal curing is preferably followed by UV-curing.
  • the UV-curing follows the thermal curing.
  • Dual curable systems comprise ethylenically unsaturated monomers, which can be polymerized thermally induced by IR or NIR radiation or microwave irradiation or ultrasound exposure or by convection heat. Furthermore, at least one second thermal crosslinkable compound is present. The second compound preferably crosslinks via a polyol-isocyanate reaction to form a polyurethane. Definition of the ethylenically unsaturated compound
  • Suitable compounds with olefinic double bonds are all compounds that can be crosslinked by free radical polymerization of the double bond.
  • the ethylenically unsaturated compound may be a monomer, an oligomer or a prepolymer, a mixture thereof or a copolymer thereof.
  • Monomers suitable for free-radical polymerization are, for example, ethylenically unsaturated polymerizable monomers selected from the group consisting of (meth)acrylates, alkenes, conjugated dienes, styrenes, acrolein, vinyl acetate, vinylpyrrolidone, vinylimidazole, maleic anhydride, fumaric anhydride, (meth)acrylic acid, (meth)acrylic acid derivatives such as esters and amides, vinyl halides and vinylidene halides.
  • (meth)acrylates selected from the group consisting of (meth)acrylates, alkenes, conjugated dienes, styrenes, acrolein, vinyl acetate, vinylpyrrolidone, vinylimidazole, maleic anhydride, fumaric anhydride, (meth)acrylic acid, (meth)acrylic acid derivatives such as esters and amides, vinyl halides and vinylidene halides.
  • Compounds which contain free-radically polymerizable double bonds in the form of the preferred (meth)acryloyl groups may be produced in accordance with conventional methods. This may proceed, for example, by: transesterifying OH-functional resins, such as OH- functional polyesters, polyacrylates, polyurethanes, polyethers or epoxy resins, with alkyl esters of (meth)acrylic acid; esterifying the stated OH-functional resins with (meth)acrylic acid; reacting the stated OH-functional resins with isocyanate-functional (meth)acrylates; reacting acid-functional resins, such as polyesters, polyacrylates, polyurethanes with epoxy- functional (meth)acrylates; reacting epoxy-functional resins, such as polyesters, poly ⁇ acrylates, epoxy resins with (meth)acrylic acid.
  • OH-functional resins such as OH- functional polyesters, polyacrylates, polyurethanes, polyethers or epoxy resins
  • prepolymers or oligomers examples include (meth)acryloyl-functional (meth)acrylic copolymers, polyurethane (meth)acrylates, polyester (meth)acrylates, unsaturated poly ⁇ esters, polyether (meth)acrylates, silicone (meth)acrylates and epoxy resin (meth)acrylates having number-average molecular masses from, for example, 500 to 10,000, preferably 500 to 5,000.
  • the (meth)acryloyl-functional prepolymers may be used in combination with reactive diluents, i.e., free-radically polymerizable low molecular weight compounds with a molar mass of below 500 g/mol.
  • the reactive diluents may be mono-, di- or polyunsaturated. Examples of monounsaturated reactive diluents are (meth)acrylic acid and the esters thereof, maleic acid and the esters thereof, vinyl acetate, vinyl ether, substituted vinyl ureas, styrene, vinyltoluene.
  • diunsaturated reactive diluents examples include di(meth)acrylates such as alkylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,3-butanediol di- (meth)acrylate, vinyl (meth)acrylate, allyl (meth)acrylate, divinylbenzene, dipropylene glycol di(meth)acrylate, hexanediol di(meth)acrylate.
  • di(meth)acrylates such as alkylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,3-butanediol di- (meth)acrylate, vinyl (meth)acrylate, allyl (meth)acrylate, divinylbenzene, dipropylene glycol di(meth)acrylate, hexanediol di(meth)acrylate.
  • polyunsaturated reactive diluents examples include glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)- acrylate, pentaerythritol tetra(meth)acrylate.
  • the reactive diluents may be used alone or in mixture.
  • Suitable salts of acrylic acid or methacrylic acid are, for example, (Ci-C 4 alkyl) 4 ammonium or (CrC 4 alkyl) 3 NH salts, e.g. the tetramethylammonium, tetraethylammonium, trimethylammo- nium or triethylammonium salt, the trimethyl-2-hydroxyethylammonium or triethyl-2-hydroxy- ethylammonium salt, the dimethyl-2-hydroxyethylammonium or diethyl-2-hydroxyethylam- monium salt.
  • (Ci-C 4 alkyl) 4 ammonium or (CrC 4 alkyl) 3 NH salts e.g. the tetramethylammonium, tetraethylammonium, trimethylammo- nium or triethylammonium salt, the trimethyl-2-hydroxyethylammonium or trieth
  • the ethylenically unsaturated compounds may contain, in addition to the olefinic double bonds, one or more further, identical or different functional groups.
  • functional groups include hydroxyl, isocyanate (optionally blocked), N-methylol, N-methylolether, ester, carbamate, epoxy, amino (optionally blocked), acetoacetyl, alkoxysilyl and carboxyl groups.
  • compositions may further comprise customary additives, which may, as an alternative, also be added after the polymerization.
  • additives can be added in small amounts, e.g. UV-absorbers or light stabilizers, e.g. compounds selected from the group consisting of hydroxyphenylbenzotriazoles, hydroxyphenylbenzophenones, oxalamides and hydroxyphenyl-s-triazines.
  • Particularly suitable light stabilizers are those selected from the group consisting of N-alkoxy-Hals compounds such as Tinuvin 123, or of sterically hindered amines Hals compounds of the 2-(2-hydroxyphenyl)-1 ,3,5-triazine or 2-hydroxyphenyl- 2H-benzotriazole type.
  • Examples of light stabilizers of the 2-(2-hydroxyphenyl)-1 ,3,5-triazine type are known from the patent literature, e.g.
  • compositions may further comprise other customary additives such as leveling agents, rheology-influencing agents, such as, fine-particle silicic acid, layer silicates, urea compounds; thickeners, e.g., based on partially cross-linked carboxy-functional polymers or polyurethanes; defoamers, wetting agents, anti-crater agents, degassing agents, e.g., benzoin, antioxidants.
  • leveling agents such as, fine-particle silicic acid, layer silicates, urea compounds
  • thickeners e.g., based on partially cross-linked carboxy-functional polymers or polyurethanes
  • defoamers e.g., wetting agents, anti-crater agents, degassing agents, e.g., benzoin, antioxidants.
  • the compounds may further comprise additives to improve the storage stability such as polymerization inhibitors on nitroxyl basis, e.g. lrgastab UV10 and 2,2,6,6-tetramethyl-4- hydroxy-piperidin-1-oxyl (4-hydroxy-TEMPO); or highly sterically hindered nitroxyl radicals or quinone methides as described in the European Patent application EO04104248.2, filed Sept. 3, 2004.
  • additives to improve the storage stability such as polymerization inhibitors on nitroxyl basis, e.g. lrgastab UV10 and 2,2,6,6-tetramethyl-4- hydroxy-piperidin-1-oxyl (4-hydroxy-TEMPO); or highly sterically hindered nitroxyl radicals or quinone methides as described in the European Patent application EO04104248.2, filed Sept. 3, 2004.
  • thermal initiator Any thermal initiator known in the art may be used in addition to the N-substituted imides
  • the additional thermal initiators are peroxides such as dialkyl peroxides, dicumyl peroxide, peroxo carboxylic acids and so one and azo initiators as disclosed in US5922473.
  • the coating agents may be unpigmented coating agents, e.g., transparent clear coats or pigmented coating agents.
  • the coating agents may contain fillers and/or transparent, color- and/or special effect- imparting pigments and/or soluble dyes.
  • inorganic or organic color-imparting pigments include titanium dioxide, micronized titanium dioxide, iron oxide pigments, carbon black, azo pigments, phthalocyanine pigments, quinacridone or pyrrolopyrrole pigments.
  • special effect-imparting pigments include metallic pigments, e.g., of aluminum, copper or other metals; interference pigments, such as, metal oxide-coated metallic pigments, e.g., titanium dioxide-coated or mixed oxide-coated aluminum, coated mica, such as, titanium dioxide-coated mica and graphite special-effect pigments.
  • suitable fillers include silica, aluminum silicate, barium sulfate, calcium carbonate and talc.
  • a photoinitiator is needed in addition to the thermal radical initiator.
  • Suitable photoinitiators are known to those skilled in the art. For example, ⁇ -hydroxyketones and Q-aminoketones, phenylglyoxalates or phospine oxides are photoinitiators commonly used in graphic arts applications.
  • HMPP 2-hydroxy-2-methyl-1-phenyl-1-propanone
  • lrgacure 184 1 -hydroxy-cyclohexyl-phenyl ketone
  • lrgacure 2959 2-hydroxy-1 -[4-(2-hydroxyethoxy)phenyl]-2-methyl-1 -propanone
  • lrgacure 369 2-benzyl-2-(dimethylamino)-1 -[4-(4-morpholinyl)phenyl]-1 -butanone
  • lrgacure 1300 lrgacure 369 + lrgacure 651 (benzildimethylketal)
  • lrgacure 379 2-(4-Methylbenzyl)-2-(dimethylamino)-1 -[4-(4-morpholinyl)phenyl]-1 -butanone
  • lrgacure 127 2-(4-Methylbenzyl)
  • Darocur EHA 2-ethylhexyl-4-dimethylamino benzoate; or mixtures of the above photoinitiators.
  • the photopolymerisable compositions comprise the photoinitiator advantageously in an amount from 0.05 to 15 % by weight, preferably from 0.1 to 8 % by weight, based on the composition.
  • At least one second thermal crosslinkable compound is present selected from
  • polyurethane surface coatings based on aliphatic or aromatic urethanes or polyurethanes and hydroxyl-group-containing acrylate, polyester or polyether resins;
  • polyurethane surface coatings based on aliphatic or aromatic urethane acrylates or polyurethane acrylates having free amine groups in the urethane structure and melamine resins or polyether resins, optionally with the addition of a curing catalyst;
  • thermoplastic polyacrylate surface coatings based on thermoplastic acrylate resins or extrinsically crosslinking acrylate resins in combination with etherified melamine resins;
  • UV-curable systems based on oligomeric urethane acrylates and/or acylate acrylates, optionally with the addition of other oligomers or monomers;
  • the resulting coating materials of the invention may be conventional coating materials, containing organic solvents, aqueous coating materials, substantially or fully solvent-free and water-free liquid coating materials (100% systems), substantially or fully solvent-free and water-free solid coating materials (powder coating materials), or substantially or fully solvent- free powder coating suspensions (powder slurries).
  • Non limiting examples of suitable substrates are, for example, wood, textiles, paper, ceramics, glass, glass fibres, plastics such as polyester, polyethylene terephthalate, polyolefins or cellulose acetate, especially in the form of films, and also metals such as Al, Cu, Ni, Fe, Zn, Mg or Co and GaAs, Si or SiO 2 .
  • the coating composition may also be an ink composition.
  • the substrate is printed with an ink composition to form an ink film on the substrate.
  • inventive compositions can be used for various purposes, for example as printing inks, such as screen printing inks, flexographic printing inks or offset printing inks, as clearcoats, gelcoats as colour coats, as white coats, e.g.
  • galvanoresists for the preparation of galvanoresists, etch or permanent resists, both liquid and dry films, as photostructurable dielectrics, and as solder stopping masks for electronic circuits, as resists for the preparation of colour filters for any type of screen or for producing structures in the production process of plasma displays and electroluminescence displays, for the production of optical switches, optical gratings (interference gratings), for the preparation of three-dimensional objects by mass curing (UV curing in transparent moulds) or by the stereolithography process, as is described, for example, in US4,575,330, for the preparation of composite materials (e.g.
  • styrenic polyesters which may contain glass fibres and/or other fibres and other auxiliaries) and other thick-layer materials, for the preparation of gel coats, for the coating or sealing of electronic components or as coatings for optical fibres.
  • the compositions are also suitable for the preparation of optical lenses, e.g. contact lenses and Fresnel lenses, and for the preparation of medical instruments, auxiliaries or implants.
  • compositions are also suitable for the preparation of gels having thermotropic properties.
  • gels having thermotropic properties.
  • Such gels are described, for example, in DE 19700064 and EP 678534.
  • compositions can be used in dry-film paints, as are described, for example, in Paint & Coatings Industry, April 1997, 72 or Plastics World, Volume 54, No. 7, page 48(5).
  • the components of the formulation and optionally further additives are applied uniformly to a substrate by means of known coating techniques, for example by spin-coating, immersion, knife coating, curtain pouring, brush application or spraying, especially by electrostatic spraying and reverse-roll coating, and also by electrophoretic deposition.
  • the quantity applied (coat thickness) and the nature of the substrate (layer support) are dependent on the desired field of application.
  • the range of coat thicknesses generally comprises values from 0.1 ⁇ m to 1mm for gel coates and more than 1mm for composites.
  • the invention further provides a process for curing a thermal curable coating composition comprising compounds of the formula I or Il as thermal initiators and using IR-curing or NIR- curing or convection heat.
  • the invention further relates to a process for curing a coating composition which process comprises a) applying a coating layer onto a substrate, whereby the coating composition is a blend of at least an ethylenically unsaturated compound and an initiator of the formula I or Il as defined above; b) thermal curing of the applied coating layer.
  • the invention further relates to a process for double curing a coating composition which process comprises a) applying a coating layer onto a substrate, whereby the coating composition is a blend of at least an ethylenically unsaturated compound and an initiator of the formula I or Il as defined above; and a photoinitiator as defined above; b) thermal curing and UV-curing of the applied coating layer.
  • the invention further relates to a process for dual curing a coating composition which process comprises a) applying a coating layer onto a substrate, whereby the coating composition is a blend of at least an ethylenically unsaturated compound and a second thermal crosslinkable compound and an initiator of the formula I or Il as defined above; b) thermal curing of the applied coating layer.
  • N-hydroxy phthalimide sodium salt 46.25 g.; 0.25 mol
  • dry DMF 220 ml
  • 38.8 g (0.25 mol) of N-methyl benzimidoyl chloride (prepared according to J. CS. Perkin II, 1324, (1980)) are slowly added at room temperature, on stirring.
  • the reaction mixture is stirred at room temperature for 19 h and then poured into 1.5 I of water.
  • the so formed precipitate is sucked off and dried in vacuo to obtain 66.06 g of a a crude product which is then taken up in 250 ml of acetonitrile.
  • Example 1 colorless crystals; Yield 73%, mp. 124-126 0 C.
  • Example 1 colorless crystals; Yield 83%, mp. 42-45 0 C.
  • Example 5 analogue to Example 5 using N-hydroxy-1 ,8-naphthalimide. colorless crystals; Yield: 33%, mp. 185-190 0 C.
  • test compound 1.00 g was dissolved in 50.00 g of Screening Formulation using a tooth wheel dissolver for 30 min.
  • Coating was applied on steel panels using a slit coater (WFT 90 ⁇ m).
  • the mixtures were applied to white coil-coat aluminum, air-dried for 5 minutes at room temperature a heated in an oven at 160 0 C for 30 minutes. A tack free dry film with a thickness of approximately 40 ⁇ m is obtained. 45 Minutes after cure, the pendulum hardness according to K ⁇ nig (DIN 53157) is measured. Pendulum Hardness 140s.
  • the mixture is applied to white coil-coat aluminum. Irradiation is carried out using a UV- processor (2X120 W/cm) Mercury medium pressure Lamps at a belt speed of 5 m/min. The sample is baked in an oven at 160°C for 30 min and a tack free dry film with a thickness of approximately 25 ⁇ m is obtained.
  • a UV- processor (2X120 W/cm) Mercury medium pressure Lamps at a belt speed of 5 m/min.
  • the sample is baked in an oven at 160°C for 30 min and a tack free dry film with a thickness of approximately 25 ⁇ m is obtained.

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Abstract

The invention relates to novel N-substituted imides and polymerizable compositions com¬ prising these N-substituted imides. The invention further relates to the use of N-substituted imides as polymerization initiators. The imides are compounds of the formula (I) and (II) wherein n is 1 or 2; m is 1 or 2; R1 and R2 are each, independently of one another, hydrogen, C1-C18alkyl, C1-C-18alkenyl C6-C14aryl, aralkyl, C5-C12cycloalkyl, each of which may be substituted by halogen, C1-C4-alkyl, hydroxy, C1-C6alkoxy, carbonyl, C1-C6alkoxycarbonyl; or R1 and R2 together with the adjacent -CO-N-CO- group may form a monocyclic, bicyclic or polycyclic ring, said ring having up to 50 non hydrogen atoms and wherein said ring may contain the structural element (formula III) more than once; R3 if n is 1, is C1-C18alkyl, C6-C14aryl, aralkyl, C5-C12cycloalkyl, OR10 or SR11, NR12R13; wherein R3 if n is 2, is C2-C12alkylene, C6-C14arylene, xylylene R4 and R5, correspond to R1 and R2; R6 if n is 1, is hydrogen, C1-C18alkyl, C6-C14aryl, aralkyl, C5-C12cycloalkyl, NR14R15; wherein R6 if n is 2, is C2-C12alkylene, C6-C14arylene, xylylene; R7 is hydrogen, C1-C18alkyl, C6-C14aryl, aralkyl, C5-C12cycloalkyl, each of which may be substituted by halogen, C1-C4-alkyl, hydroxy, C1-C6alkoxy, carbonyl, C1-C6alkoxy- carbonyl; or R7 and R14 or R7 and R15 form together with the N-atom attached to R7 a 5- 6 membered ring, optionally interrupted by -NH-, -N(C1-C8alkyl)-, -O- and/or S-atoms.

Description

N-substituted imides as polymerization initiators
The invention relates to novel N-substituted imides and polymerizable compositions com¬ prising these N-substituted imides. The invention further relates to the use of N-substituted imides as polymerization initiators.
Free-radical polymerization is among the most important methods of building up a relatively long carbon chain. It is employed in process technology for preparing commercially important polymers such as polystyrene, PVC, poly(meth)acrylates, PAN and other polymers. For technical details, reference may be made to the still relevant standard work G. Odian, Principles of Polymerization, McGraw-Hill New York 1991.
Free-radical polymerizations are started using initiators. Initiators which have become estab¬ lished in process technology are azo compounds, dialkyl peroxides, diacyl peroxides, hy¬ droperoxides, thermolabile C-C-dimers, redox systems and photoinitiators. Reference is made to the "Handbook of Free Radical Initiators", (ET. Denisov, T.G. Denisova, T.S. Pokidova, J. Wiley & Sons, Inc. Hoboken, New Jersey, 2003).
Despite their widespread use, these initiators have various disadvantages. Thus, for exam¬ ple, peroxides are extremely readily ignitable and sustain fire. Other classes of substances are potential explosion hazards, so that their use, storage and transport has to involve costly safety precautions. Some initiators generate toxic products, as e.g.AIBN. There is therefore a general need for advantageous initiators useful in process technology which have a satisfactory safety profile for free-radical polymerization processes.
J. D. Druliner describes in J.Phys.Org. Chem. 8, 316-324 (1995) the polymerization of acrylates and methacrylates to make homopolymers and block copolymers initiated by N- alkoxyphthalimides and succinimides.
US2,872,450 describes the manufacture of thio-and dithiocarboxylic acid esters by reaction of cyclic oximides and thio-or dithiocarboxylic acid ester chlorides and their use as fungicides. US 6,667,376 describes compounds of the general formula RrS-C(=S)-O-NR2R3 used as control agents for living type free radical polymerization.
It has been found that certain dicarboxylic acid imides are particularly suitable as poly¬ merization initiators if they are esterified by thio-acyl-, or imino radicals.
The invention provides compounds of the formula I and Il
Figure imgf000003_0001
wherein n is 1 or 2; m is 1 or 2;
R1 and R2 are each, independently of one another, hydrogen, Ci-Ci8alkyl, Ci-Ci8alkenyl, C6-Ci4aryl, aralkyl, C5-Ci2cycloalkyl, each of which may be substituted by halogen, CrC4-alkyl, hydroxy, CrC6alkoxy, carbonyl, CrC6alkoxycarbonyl; or R1 and R2 together with the adjacent -CO-N-CO- group may form a monocyclic, bicyclic or polycyclic ring, said ring having up to 50 non hydrogen atoms and wherein said ring
O
<' may contain the structural element N-O- more than once;
(\ O
R3 if n is 1 , is CrCi8alkyl, CrCi8alkenyl, C6-Ci4aryl, aralkyl, C5-Ci2cycloalkyl, each of which may be substituted by halogen, CrC4-alkyl, hydroxy, CrC6alkoxy, carbonyl, CrC6alkoxycarbonyl; or R3 is ORi0 or SRn, NRi2Ri3; wherein R10 is CrCi8alkyl, C6-Ci4aryl, aralkyl, C5-Ci2cycloalkyl, each of which may be substituted by halogen, Cr C4-alkyl, hydroxy, CrC6alkoxy, carbonyl, d-C6alkoxycarbonyl; and Rn is CrCi8alkyl, C6-Ci4aryl, aralkyl, C5-Ci2cycloalkyl, each of which may be substituted by halogen, CrC4-alkyl, hydroxy, CrC6alkoxy, carbonyl, CrC6alkoxy- carbonyl; and
Ri2 and Ri3 independently of one another are hydrogen, CrCi8alkyl, C6-Ci4aryl, aralkyl, C5-Ci2cycloalkyl, each of which may be substituted by halogen, CrC4-alkyl, hydroxy, Ci-C6alkoxy, carbonyl, CrC6alkoxycarbonyl; or R12 and Ri3 form together with the N atom to which they are attached a 5 or 6 membered ring, optionally interrupted by -NH-, -N(Ci-C8alkyl)-, -O- and/or S-atoms,
R3 if n is 2, is C2-Ci2alkylene, C2-Ci2alkenylene, C6-Ci4arylene, xylylene ; with the proviso, that the following compounds disclosed in US2, 872,450 as fungicides are excluded,
Figure imgf000004_0001
R4 and R5 are each, independently of one another, hydrogen, CrCi8alkyl, CrCi8alkenyl
C6-Ci4aryl, aralkyl, C5-Ci2cycloalkyl, each of which may be substituted by halogen, Cr C4-alkyl, hydroxy, CrC6alkoxy, carbonyl, CrC6alkoxycarbonyl; or R4 and R5 together with the adjacent -CO-N-CO- group may form a monocyclic, bicyclic or polycyclic ring, said ring having up to 50 non hydrogen atoms and wherein said ring may contain the O
<' structural element N-O- more than once;
(\ O
R6 if n is 1, is hydrogen, CrCi8alkyl, CrCi8alkenyl, C6-Ci4aryl, aralkyl, C5-Ci2cycloalkyl, each of which may be substituted by halogen, CrC4-alkyl, hydroxy, CrC6alkoxy, carbonyl, CrC6alkoxycarbonyl; or R6 is NR14R15; wherein Ri4 and Ri5 independently of one another are hydrogen, CrCi8alkyl, C6-Ci4aryl, aralkyl, C5-Ci2cycloalkyl, each of which may be substituted by halogen, CrC4-alkyl, hydroxy, CrC6alkoxy, carbonyl, d- C6alkoxycarbonyl; or R14 and Ri5 form together with the N atom to which they are attached a 5 or 6 membered ring, optionally interrupted by -NH-, -N(CrC8alkyl)-, -O- and/or S-atoms,
R6 if n is 2, is C2-Ci2alkylene, C2-Ci2alkenylene, C6-Ci4arylene, xylylene;
R7 is hydrogen, CrCi8alkyl, C6-Ci4aryl, aralkyl, C5-Ci2cycloalkyl, each of which may be substituted by halogen, CrC4-alkyl, hydroxy, CrC6alkoxy, carbonyl, CrC6alkoxy- carbonyl; or R7 and Ri4 or R7 and Ri5 form together with the N-atom attached to R7 a 5- 6 membered ring, optionally interrupted by -NH-, -N(CrC8alkyl)-, -O- and/or S-atoms. Definitions
The term "Ci-Ci8alkyl" includes, for example, Ci-C6alkyl, e.g. methyl, ethyl, n-propyl or isopropyl or n-, sec- or tert-butyl or straight-chain or branched pentyl or hexyl, or C7-Ci8alkyl, e.g. straight-chain or branched heptyl, octyl, isooctyl, nonyl, tert-nonyl, decyl or undecyl, or straight-chain Cn-Ci8alkyl, which together with the -(C=O)- radical forms Ci4-C2o-alkanoyl having an even number of C-atoms, e.g. lauroyl (C12), myristoyl (C14), palmitoyl (C16) or stearoyl (C 18).
The term "Ci-Ci8alkenyl" means an unsaturated, linear or branched hydrocarbon group as defined above under alkyl with one or more carbon-carbon double bonds, such as a vinyl group.
The term "C2-Ci2alkylene" means a divalent group derived from a straight or branched chain hydrocarbon of from 1 to 12 carbon atoms. Examples of alkylene groups may include ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
The term "Ce-Cuaryl" refers to an optionally substituted benzene ring or to an optionally substituted benzene ring fused to one or more optionally substituted benzene rings to form a ring system. Preferred aryl groups are phenyl, 2-naphthyl, tetrahydronaphthyl, 1-naphthyl, biphenyl, indanyl, anthracyl, phenanthrγl, as well as substituted derivatives thereof. Examples of substituents are: CrCi8alkyl, C6-Ci4aryl, aralkyl, C5-Ci2cycloalkyl, halogen, OH, CrCi8alkoxy, CrCi8alkylthio, carboxy, CrCi8alkoxycarbonyl, carbamoyl (C(O)NH2), Ci-Ci8alkylcarbamoyl, di-CrCi8alkylcarbamoyl, acyl, nitro, amino, CrCi8alkylamino or di- Ci-Ci8alkylamino, -CH2-X-CH2- wherein X is O, NH, N(CrCi8alkyl).
The term "C6-Ci4arylene" refers to an optionally substituted benzene ring diradical or to a benzene ring system diradical containing an optionally substituted benzene ring fused to one or more optionally substituted benzene rings. Examples correspond to the aryl groups above. The term "aralkyl" includes a radical RaRb, where Ra is an alkylene (a bivalent alkyl) group and Rb is an aryl group as defined above. Preferred are C7-C8aralkyl groups such as 2- phenylethyl or benzyl.
The term "C5-Ci2cycloalkyl" includes a monovalent, alicyclic, saturated hydrocarbon radical having three or more carbon atoms forming the ring. While the cycloalkyl compounds may have up to 12 carbon atoms, generally there will be three to seven carbon atoms in the ring. The latter include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclo- heptyl.
The term "monocyclic ring" includes a 5 to 9 membered ring system such as, for example, dioxo pyrrolidine, dioxo piperidine, dioxo morpholine, dioxo thiomorpholine or a derivative derived from trihydroxyisocyanuric acid, The monocyclic ring system is preferably a residue
of the formula, wherein A is unsubstituted ethylene or propylene, ethylene or
Figure imgf000006_0001
propylene substituted by CrCi8alkyl, C6-Ci4aryl, aralkyl, C5-Ci2cycloalkyl, halogen, OH, d- Ci8alkoxy, CrCi8alkylthio, carboxy, CrCi8alkoxycarbonyl, carbamoyl (C(O)NH2), Cr Ci8alkylcarbamoyl, di-Ci-Ciealkylcarbamoyl, acyl, nitro, amino, Ci-Ci8alkylamino or i-Ci- Ci8alkylamino, -CH2-X-CH2- wherein X is O, NH, N(CrCi8alkyl); or -N(OH)-CO-N(OH)-.
A monocyclic ring derived from trihydroxyisocyanuric acid is e.g.
Figure imgf000006_0002
The term "acyl" refers to the group RaC(O)-, where Ra is CrCi8alkyl, C5-Ci2cycloalkyl, or heterocyclyl as defined herein. Examples of "heterocyclic" moieties include, for example, tetrahydrofuran, pyran, 1,4-dioxane, 1,3-dioxane, piperidine, pyrrolidine, morpholine, tetrahydrothiopyran, tetrahydrothiophene. The term "tricyclic ring" means a 5 to 12 membered fused ring system.
The term "fused ring system" pertains to a system comprising in addition to the monocyclic core ring defined above, one or more aromatic rings, or one or more aliphatic rings. The aromatic ring as well as the aliphatic ring may comprise solely carbon atoms, or may comprise carbon atoms and one or more heteroatoms, including nitrogen, oxygen, and sulfur atoms. The aromatic ring is preferably a benzene ring resulting in dioxo-dihydro-isoindol rings or a naphthene ring resulting in dioxo-benzoisoquinoline rings. The aliphatic ring is e.g. an C3-C7cycloalkylene ring, an oxirane ring, a cyclohexenyl ring or a norbomene ring or
bicyclo[2.2.2]octane or bicyclo[3.2.1]octane, or a group of the form
Figure imgf000007_0001
The aromatic ring(s) may optionally be substituted by substituted by CrCi8alkyl, C6-Ci4aryl, aralkyl, C5-Ci2cycloalkyl, halogen, OH, CrCi8alkoxy, CrCi8alkylthio, carboxy, Ci-Ci8alkoxy- carbonyl, carbamoyl (C(O)NH2), Ci-Ciealkylcarbamoyl, di-Ci-Ci8alkylcarbamoyl, acyl, nitro, amino, Ci-Ci8alkylamino or di-Ci-Ci8alkylamino, -CH2-X-CH2- wherein X is O, NH, N(d-Ciβalkyl).
The bicyclic ring system is preferably a residue of the formula
Figure imgf000007_0002
wherein A is phenylene, cyclohexylene, cyclohexenylene, 1,8-naphthylene, pyridinylene or wherein A is ethylene or propylene or ethylene or propylene substituted CrC4alkyl, or ethenylene or propenylene or ethenylene or propenylene substituted CrC4alkyl.
The term "polycyclic ring system" refers to ring systems having more than two cyclic compounds bonded. A polycyclic ring system as used herein may be aromatic or non- aromatic, or may be composed of separate aromatic and non-aromatic moieties. An example is adamantane or 1 ,3,5,7-tetra-aza-adamantane (urotropine), cubane, twistane, Polycyclic ring systems are also compounds of the formula I1 and II1
Figure imgf000008_0001
wherein R3,
R6 and R7 are as defined above.
Further examples of polycyclic residues may be:
Figure imgf000008_0002
derived from 1 ,8 naphthalene dicarboxylic acid imide
Figure imgf000008_0003
derived from naphthalene-1 ,4,5,8-tetracarboxylic acid diimide
Figure imgf000008_0004
derived from 3,4,9, 10-perylene tetracarboxylic acid diimide
Figure imgf000008_0005
derived from bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid diimide
Figure imgf000008_0006
derived from5-norbomene-2,3- dicarboxylic acid imide. The term " non hydrogen atoms" includes C-Atoms and hetero atoms like N, S, O and P atoms.
When R12 and Ri3 or R14 and Ri5 or R7 and Ri4 or R7 and Ri5 together with the nitrogen atom to which they are attached, form a 5- or 6-membered ring that in addition may be interrupted by -NH-, -N(Ci-C8alkyl)-, -O- and/or S-atoms, the ring is, for example, a saturated or unsaturated ring, for example aziridine, piperazine, pyrrole, thiophene, pyrrolidine, oxazole, pyridine, 1 ,3-diazine, 1,2-diazine, piperidine or morpholine; morpholinyl, piperidyl or piperazinyl rings, especially, are formed.
Preferences
Preferred are compounds of the formula I and II, wherein Ri and R2 and R3 and R4 together with the adjacent -CO-N-CO- group form a monocyclic, bicyclic or polycyclic ring, resulting in compounds of the formula
Figure imgf000009_0001
wherein
A is unsubstituted ethylene or propylene, ethylene or propylene substituted by
CrCi8alkyl, C6-Ci4aryl, aralkyl, C5-Ci2cycloalkyl, halogen, OH, CrCi8alkoxy, d- Ci8alkylthio, carboxy, CrCi8alkoxycarbonyl, carbamoyl (C(O)NH2), CrCi8alkyl- carbamoyl, di-Ci-Ciealkylcarbamoyl, acyl, nitro, amino, Ci-Ci8alkylamino or di-Ci- Ci8alkylamino; or A is ethenylene or propenylene or ethenylene or propenylene substituted CrC4alkyl; or A Js-CH2-X-CH2- wherein X is O, NH, N(CrCi8alkyl); or -N(OH)-CO-N(OH)-.; or A together with the adjacent -CO-N-CO- group may form a bicyclic or polycyclic ring, said ring having up to 20 non hydrogen atoms, and wherein
O
<' said ring may contain the structural element N-O- more than once;
(\ O
Ri2 and Ri3 independently of one another are hydrogen, CrCi8alkyl, cyclohexyl, phenyl, benzyl, or R12 and Ri3 form together with the N atom to which they are attached a 5 or 6 membered ring, optionally interrupted by -NH-, -N(CrC8alkyl)-, -O- and/or S-atoms, A1 is unsubstituted ethylene or propylene, ethylene or propylene substituted by
Ci-Ci8alkyl, C6-Ci4aryl, aralkyl, C5-Ci2cycloalkyl, halogen, OH, Ci-Ci8alkoxy, d- Ci8alkylthio, carboxy, CrCi8alkoxycarbonyl, carbamoyl (C(O)NH2), CrCi8alkyl- carbamoyl, di-Ci-Clealkylcarbamoyl, acyl, nitro, amino, Ci-Ci8alkylamino or di-d- Ci8alkylamino; or A1 is ethenylene or propenylene or ethenylene or propenylene substituted CrC4alkyl; or A' Js-CH2-X-CH2- wherein X is O, NH, N(CrCi8alkyl); or -N(OH)-CO-N(OH)-. or A1 together with the adjacent -CO-N-CO- group may form a bicyclic or polycyclic ring, said ring having up to 20 non hydrogen atoms, and wherein
O
<' said ring may contain the structural element N-O- more than once;
(\ O
R6 is hydrogen, CrCi8alkyl, cyclohexyl, phenyl, benzyl, NR14R15; wherein
R14 and R15 independently of one another are hydrogen, Ci-d8alkyl, cyclohexyl, phenyl or Ri4 and Ri5 form together with the N atom to which they are attached a 5 or 6 membered ring, optionally interrupted by -NH-, -N(CrC8alkyl)-, -O- and/or S-atoms,
R7 is hydrogen, CrCi8alkyl, cyclohexyl, phenyl;or R7 and Ri4 or R7 and Ri5 form together with the N-atom attached to R7 a 5-6 membered ring, optionally interrupted by -NH-, - N(CrC8alkyl)-, -O- and/or S-atoms.
Compounds of the formula I and II, wherein Ri and R2 and R3 and R4 together with the adjacent -CO-N-CO- group form a bicyclic ring resulting in compounds of the formula Ib and Nb
Figure imgf000010_0001
wherein
Ri2 and Ri3 each, independently of one another, are hydrogen or CrC8alkyl or cyclohexyl, or Ri2 and Ri3 form together with the N atom to which they are attached a 5 or 6 membered ring, optionally interrupted by -NH-, -N(CrC8alkyl)- and/or -0-atoms,
Ri6 and Ri7 each, independently of one another, are hydrogen, d-C8alkyl, cyclohexyl, benzyl, phenyl, halogen, OH, Ci-C8alkoxy, Ci-C8alkylthio, carboxy, Ci-C8alkoxy- carbonyl, carbamoyl (C(O)NH2), CrCβalkylcarbamoyl, di-Ci-Csalkylcarbannoyl, d-
C8acyl, nitro, amino, Ci-C8alkylamino or di-Ci-C8alkylamino; R7 CrC8alkyl, cyclohexyl, benzyl, phenyl; R6 CrC8alkyl, cyclohexyl, benzyl, phenyl; Ri8 and Ri9 each, independently of one another, are hydrogen, CrC8alkyl, cyclohexyl, benzyl, phenyl, halogen, OH, Ci-C8alkoxy, Ci-C8alkylthio, carboxy, Ci-C8alkoxy- carbonyl, carbamoyl (C(O)NH2), CrC8alkylcarbamoyl, di-Ci-Cealkylcarbamoyl, Cr
C8acyl, nitro, amino, Ci-C8alkylamino or di-Ci-C8alkylamino.
Preparation of the compounds
The above-described compounds of the formula (I) or (II) can be prepared by methods known per se.
Compounds of the formula (I) can be prepared as described in US2, 872,450 by reaction of cyclic oximides and tricarboxylic acid ester chlorides according to the following scheme:
Figure imgf000011_0001
A further preparation route is the reaction of thiophosgene with a N-hydroxyimide obtaining a thiocarboxylic acid chloride which is further reacted with an amine or an alcohol according to the following scheme:
Figure imgf000011_0002
Compounds of the formula (II) may be prepared reacting an N-hydroxyimide or a salt thereof with an imide chloride according to the following scheme:
Figure imgf000011_0003
The imide chloride may be prepared as described in J. C. S. Perkin II, 1318 (1980).
The above referenced preparation routes are only examples, other routes may be possible. Suitable tricarboxylic acids include, for example, succinic acid, Ci-Ci8 alkylsuccinic acid, C2-Ci8 alkenylsuccinic acid, maleic acid, dimethylmaleic acid, glutaric acid, thioglycolic acid, imido diacetic acid, citric acid, 5-norbomene-2,3-dicarboxylic acid, 3,6-epoxy-1 ,2,3,6-tetra- hydrophthalic acid, phthalic acid, substituted phthalic acid (halogen, COOR, nitro etc, as defined above) homophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, 1 ,8-naphthalene dicarboxylic, pyridine-2,3-dicarboxylic acid, naphthalene-1 ,4,5,8-tetra- carboxylic acid, 3,4,9, 10-perylene tetracarboxylic acid, bicyclo[2.2.2]oct-7-ene-2,3,5,6- tetra car boxy lie acid.
Use
The N-substituted imides may be used as polymerization initiators, especially as thermal radical initiators (TRI) in a curing agent for coatings that cure by free radical polymerisation. The coating may be a thermal curable coating composition, a double- (thermal and UV radiation) curable coating composition or a dual-(thermal curable) coating composition comprising at least a second crosslinkable resins. The thermal curing is carried out using NIR-curing or IR-curing or convection heat. It is also possible to use microwave heating. The double curing composition comprises in addition to the thermal initiator a photoinitiator. The double curing is carried out using NIR-curing or IR-curing followed by UV-curing or vice versa.
The invention further relates to thermal curable coating composition, comprising a) at least an ethylenically unsaturated compound; b) a thermal initiator effective to enable IR-curing or NIR-curing or to enable microwave curing or to enable ultrasound curing or to enable the convection heat curing of the ethylenically unsaturated compound, wherein the thermal initiator is a N-substituted imide of the formula (I) and/or (II).
The invention further relates to a dual curable coating composition, comprising a) at least an ethylenically unsaturated compound and a second thermal crosslinkable compound; b) a thermal initiator effective to enable IR-curing or NIR-curing or to enable microwave curing or to enable ultrasound curing or to enable the convection heat curing of the ethylenically unsaturated compound, wherein the thermal initiator is a N-substituted imide of the formula (I) and/or (II).
The invention further relates to a double (thermal and UV) curable coating composition, comprising a) at least an ethylenically unsaturated compound; b) a thermal initiator effective to enable IR-curing or NIR-curing curing or to enable microwave curing or to enable ultrasound curing or to enable the convection heat curing of the ethylenically unsaturated compound, wherein the thermal initiator is a N- substituted imide of the formula (I) and/or (II); c) a photoinitiator effective to enable UV-curing of the ethylenically unsaturated compound.
Definitions: Thermal curing:
Thermal curing refers to the application of convection heat or IR- or NIR-radiation or microwave irradiation or ultrasound exposure after the mixture has been applied to substrate. In case of powder coatings the adhered powder coating is first melted to form a surface layer preferably by convection heat. Suitable temperatures to initiate and complete free-radical polymerization are 60-1800C.
NIR-curing
The NIR radiation used in the process according to the invention is short-wave infrared radiation in the wavelength range from about 750 nm to about 1500 nm, preferably 750 nm to 1200 nm. Radiation sources for NIR radiation include, for example, conventional NIR radiation emitters, which are available commercially (for example, from Adphos).
IR-curing
The IR radiation used in the process according to the invention is medium wave radiation in the wave length range from about 1500 nm to about 3000 nm and/or longer-wave infra-red radiation in the wave length range above 3000 nm. IR radiation emitters of this kind are available commercially (for example, from Heraeus). Microwave curing:
The microwave radiation used in this process according to the invention is electro magnetic radiation in the wavelength range from about 1 mm to 30 cm.
Ultrasound Curing:
Ultrasound used in this process according to the invention is sound with a frequency above
20 kHz.
UV-cu ring
The photochemical curing step is carried out usually using light of wavelengths from about 200 nm to about 600 nm, especially from 200 to 450 nm. As light sources there are used a large number of the most varied types. Both point sources and planiform projectors (lamp carpets) are suitable. Examples are: carbon arc lamps, xenon arc lamps, medium-, high- and low-pressure mercury lamps, optionally doped with metal halides (metal halide lamps), microwave-excited metal-vapor lamps, excimer lamps, super actinic fluorescent tubes, fluorescent lamps, argon filament lamps, electronic flash lamps, photographic flood lights, electron beams and X-rays generated by means of synchrotrons or laser plasma.
Double-curing
Double curable systems comprise ethylenically unsaturated monomers, which can be polymerized by UV radiation or which can be polymerized thermally induced by IR or NIR radiation or microwave irradiation or ultrasound exposure or by convection heat. In a double cure system the thermal curing is preferably followed by UV-curing. However, it is also possible that the UV-curing follows the thermal curing.
Dual-curing
Dual curable systems comprise ethylenically unsaturated monomers, which can be polymerized thermally induced by IR or NIR radiation or microwave irradiation or ultrasound exposure or by convection heat. Furthermore, at least one second thermal crosslinkable compound is present. The second compound preferably crosslinks via a polyol-isocyanate reaction to form a polyurethane. Definition of the ethylenically unsaturated compound
Suitable compounds with olefinic double bonds are all compounds that can be crosslinked by free radical polymerization of the double bond. The ethylenically unsaturated compound may be a monomer, an oligomer or a prepolymer, a mixture thereof or a copolymer thereof.
Monomers suitable for free-radical polymerization are, for example, ethylenically unsaturated polymerizable monomers selected from the group consisting of (meth)acrylates, alkenes, conjugated dienes, styrenes, acrolein, vinyl acetate, vinylpyrrolidone, vinylimidazole, maleic anhydride, fumaric anhydride, (meth)acrylic acid, (meth)acrylic acid derivatives such as esters and amides, vinyl halides and vinylidene halides. Preferred are compounds having (meth)acryloyl, vinyl and/or maleinate groups. Especially preferred are (meth)acrylates.
Compounds which contain free-radically polymerizable double bonds in the form of the preferred (meth)acryloyl groups may be produced in accordance with conventional methods. This may proceed, for example, by: transesterifying OH-functional resins, such as OH- functional polyesters, polyacrylates, polyurethanes, polyethers or epoxy resins, with alkyl esters of (meth)acrylic acid; esterifying the stated OH-functional resins with (meth)acrylic acid; reacting the stated OH-functional resins with isocyanate-functional (meth)acrylates; reacting acid-functional resins, such as polyesters, polyacrylates, polyurethanes with epoxy- functional (meth)acrylates; reacting epoxy-functional resins, such as polyesters, poly¬ acrylates, epoxy resins with (meth)acrylic acid. These production methods stated by way of example are described in the literature and known to the person skilled in the art.
Examples of prepolymers or oligomers include (meth)acryloyl-functional (meth)acrylic copolymers, polyurethane (meth)acrylates, polyester (meth)acrylates, unsaturated poly¬ esters, polyether (meth)acrylates, silicone (meth)acrylates and epoxy resin (meth)acrylates having number-average molecular masses from, for example, 500 to 10,000, preferably 500 to 5,000.
The (meth)acryloyl-functional prepolymers may be used in combination with reactive diluents, i.e., free-radically polymerizable low molecular weight compounds with a molar mass of below 500 g/mol. The reactive diluents may be mono-, di- or polyunsaturated. Examples of monounsaturated reactive diluents are (meth)acrylic acid and the esters thereof, maleic acid and the esters thereof, vinyl acetate, vinyl ether, substituted vinyl ureas, styrene, vinyltoluene. Examples of diunsaturated reactive diluents are di(meth)acrylates such as alkylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,3-butanediol di- (meth)acrylate, vinyl (meth)acrylate, allyl (meth)acrylate, divinylbenzene, dipropylene glycol di(meth)acrylate, hexanediol di(meth)acrylate. Examples of polyunsaturated reactive diluents are glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)- acrylate, pentaerythritol tetra(meth)acrylate. The reactive diluents may be used alone or in mixture.
Suitable salts of acrylic acid or methacrylic acid are, for example, (Ci-C4alkyl)4ammonium or (CrC4alkyl)3NH salts, e.g. the tetramethylammonium, tetraethylammonium, trimethylammo- nium or triethylammonium salt, the trimethyl-2-hydroxyethylammonium or triethyl-2-hydroxy- ethylammonium salt, the dimethyl-2-hydroxyethylammonium or diethyl-2-hydroxyethylam- monium salt.
The ethylenically unsaturated compounds may contain, in addition to the olefinic double bonds, one or more further, identical or different functional groups. Examples of functional groups include hydroxyl, isocyanate (optionally blocked), N-methylol, N-methylolether, ester, carbamate, epoxy, amino (optionally blocked), acetoacetyl, alkoxysilyl and carboxyl groups. Examples are polyurethane resins with (meth)acryloyl groups and glycerol mono-and di- (meth)acrylate, trimethylol propane mono-and di(meth)acrylate or pentaerythritol tri(meth)- acrylate.
Additives
The above-described compositions may further comprise customary additives, which may, as an alternative, also be added after the polymerization. Such additives can be added in small amounts, e.g. UV-absorbers or light stabilizers, e.g. compounds selected from the group consisting of hydroxyphenylbenzotriazoles, hydroxyphenylbenzophenones, oxalamides and hydroxyphenyl-s-triazines. Particularly suitable light stabilizers are those selected from the group consisting of N-alkoxy-Hals compounds such as Tinuvin 123, or of sterically hindered amines Hals compounds of the 2-(2-hydroxyphenyl)-1 ,3,5-triazine or 2-hydroxyphenyl- 2H-benzotriazole type. Examples of light stabilizers of the 2-(2-hydroxyphenyl)-1 ,3,5-triazine type are known from the patent literature, e.g. US4,619,956, EP-A-434 608, US5, 198,498, US5,322,868, 1185,369,140, 1185,298,067, WO-94/18278, EP-A-704 437, GB-A-2,297,091 or WO-96/28431. 3,3,5,5 polysubstituted morpholin-2-one derivatives as described in US6, 140,326 are well established light stabilizers for coatings.
The compositions may further comprise other customary additives such as leveling agents, rheology-influencing agents, such as, fine-particle silicic acid, layer silicates, urea compounds; thickeners, e.g., based on partially cross-linked carboxy-functional polymers or polyurethanes; defoamers, wetting agents, anti-crater agents, degassing agents, e.g., benzoin, antioxidants.
The compounds may further comprise additives to improve the storage stability such as polymerization inhibitors on nitroxyl basis, e.g. lrgastab UV10 and 2,2,6,6-tetramethyl-4- hydroxy-piperidin-1-oxyl (4-hydroxy-TEMPO); or highly sterically hindered nitroxyl radicals or quinone methides as described in the European Patent application EO04104248.2, filed Sept. 3, 2004.
Any thermal initiator known in the art may be used in addition to the N-substituted imides Preferably, the additional thermal initiators are peroxides such as dialkyl peroxides, dicumyl peroxide, peroxo carboxylic acids and so one and azo initiators as disclosed in US5922473. The coating agents may be unpigmented coating agents, e.g., transparent clear coats or pigmented coating agents.
The coating agents may contain fillers and/or transparent, color- and/or special effect- imparting pigments and/or soluble dyes. Examples of inorganic or organic color-imparting pigments include titanium dioxide, micronized titanium dioxide, iron oxide pigments, carbon black, azo pigments, phthalocyanine pigments, quinacridone or pyrrolopyrrole pigments. Examples of special effect-imparting pigments include metallic pigments, e.g., of aluminum, copper or other metals; interference pigments, such as, metal oxide-coated metallic pigments, e.g., titanium dioxide-coated or mixed oxide-coated aluminum, coated mica, such as, titanium dioxide-coated mica and graphite special-effect pigments. Examples of suitable fillers include silica, aluminum silicate, barium sulfate, calcium carbonate and talc.
In double cure systems a photoinitiator is needed in addition to the thermal radical initiator. Suitable photoinitiators are known to those skilled in the art. For example, α-hydroxyketones and Q-aminoketones, phenylglyoxalates or phospine oxides are photoinitiators commonly used in graphic arts applications.
Especially preferred are, for example, the following commercially available photoinitiators:
Darocur 1173: 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP) and Oligomeric HMPP, lrgacure 184: 1 -hydroxy-cyclohexyl-phenyl ketone, lrgacure 2959: 2-hydroxy-1 -[4-(2-hydroxyethoxy)phenyl]-2-methyl-1 -propanone, lrgacure 369: 2-benzyl-2-(dimethylamino)-1 -[4-(4-morpholinyl)phenyl]-1 -butanone, lrgacure 1300: lrgacure 369 + lrgacure 651 (benzildimethylketal), lrgacure 379: 2-(4-Methylbenzyl)-2-(dimethylamino)-1 -[4-(4-morpholinyl)phenyl]-1 -butanone, lrgacure 127: 2-Hydroxy-1 -{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl- propan-1-one, lrgacure 754: oxo-phenyl-acetic acid 1-methyl-2-[2-(2-oxo-2-phenyl-acetoxy)-propoxy]-ethyl ester, lrgacure 819: bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, lrgacur 250: 4-isobutylphenyl-4'-methylphenyl iodonium hexafluorophosphate, Darocur ITX: 2-isopropylthioxanthone and 4-isopropylthioxanthone, Darocur EDB: ethyl-4-dimethylamino benzoate,
Darocur EHA: 2-ethylhexyl-4-dimethylamino benzoate; or mixtures of the above photoinitiators.
The photopolymerisable compositions comprise the photoinitiator advantageously in an amount from 0.05 to 15 % by weight, preferably from 0.1 to 8 % by weight, based on the composition.
In dual curing systems at least one second thermal crosslinkable compound is present selected from
1. surface coatings based on cold- or hot-crosslinkable alkyd, acrylate, polyester, epoxy or melamine resins or mixtures of such resins, optionally with the addition of a curing catalyst;
2. two-component polyurethane surface coatings based on hydroxyl-group-containing acrylate, polyester or polyether resins and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;
3. two-component polyurethane surface coatings based on thiol-group-containing acrylate, polyester or polyether resins and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates; 4. one-component polyurethane surface coatings based on blocked isocyanates, isocyanurates or polyisocyanates which are deblocked during stoving; the addition of melamine resins is also possible, if desired;
5. one-component polyurethane surface coatings based on aliphatic or aromatic urethanes or polyurethanes and hydroxyl-group-containing acrylate, polyester or polyether resins;
6. one-component polyurethane surface coatings based on aliphatic or aromatic urethane acrylates or polyurethane acrylates having free amine groups in the urethane structure and melamine resins or polyether resins, optionally with the addition of a curing catalyst;
7. two-component surface coatings based on (poly)ketimines and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;
8. two-component surface coatings based on (poly)ketimines and an unsaturated acrylate resin or a polyacetoacetate resin or a methacrylamidoglycolate methyl ester;
9. two-component surface coatings based on carboxyl- or amino-group-containing polyacrylates and polyepoxides;
10. two-component surface coatings based on anhydride-group-containing acrylate resins and a polyhydroxy or polyamino component;
11. two-component surface coatings based on acrylate-containing anhydrides and poly¬ epoxides;
12. two-component surface coatings based on (poly)oxazolines and anhydride-group- containing acrylate resins or unsaturated acrylate resins or aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;
13. two-component surface coatings based on unsaturated (poly)acrylates and (poly)- malonates;
14. thermoplastic polyacrylate surface coatings based on thermoplastic acrylate resins or extrinsically crosslinking acrylate resins in combination with etherified melamine resins;
15. surface-coating systems, especially clearcoats, based on malonate-blocked isocyanates with melamine resins (e.g. hexamethoxymethylmelamine) as crosslinkers (acid-catalysed);
16. UV-curable systems based on oligomeric urethane acrylates and/or acylate acrylates, optionally with the addition of other oligomers or monomers;
17. dual-cure systems, which are cured first thermally and then by UV, or vice versa, the constituents of the surface-coating formulation containing double bonds that can be caused to react by UV light and photoinitiators and/or by electron-beam curing. The resulting coating materials of the invention may be conventional coating materials, containing organic solvents, aqueous coating materials, substantially or fully solvent-free and water-free liquid coating materials (100% systems), substantially or fully solvent-free and water-free solid coating materials (powder coating materials), or substantially or fully solvent- free powder coating suspensions (powder slurries).
Non limiting examples of suitable substrates are, for example, wood, textiles, paper, ceramics, glass, glass fibres, plastics such as polyester, polyethylene terephthalate, polyolefins or cellulose acetate, especially in the form of films, and also metals such as Al, Cu, Ni, Fe, Zn, Mg or Co and GaAs, Si or SiO2.
The coating composition may also be an ink composition. Thus, the substrate is printed with an ink composition to form an ink film on the substrate.
The inventive compositions can be used for various purposes, for example as printing inks, such as screen printing inks, flexographic printing inks or offset printing inks, as clearcoats, gelcoats as colour coats, as white coats, e.g. for wood or metal, as powder coatings, as paints, inter alia for paper, water, metal or plastic, as daylight-curable coatings for marking buildings and roads, for photographic reproduction processes, for holographic recording materials, for image recording processes or for the production of printing plates which can be developed using, for example, organic solvents or aqueous-alkaline media, for the production of masks for screen printing, as dental filling materials, as adhesives, as pressure-sensitive adhesives, as laminating resins, as photoresists, e.g. galvanoresists, etch or permanent resists, both liquid and dry films, as photostructurable dielectrics, and as solder stopping masks for electronic circuits, as resists for the preparation of colour filters for any type of screen or for producing structures in the production process of plasma displays and electroluminescence displays, for the production of optical switches, optical gratings (interference gratings), for the preparation of three-dimensional objects by mass curing (UV curing in transparent moulds) or by the stereolithography process, as is described, for example, in US4,575,330, for the preparation of composite materials (e.g. styrenic polyesters which may contain glass fibres and/or other fibres and other auxiliaries) and other thick-layer materials, for the preparation of gel coats, for the coating or sealing of electronic components or as coatings for optical fibres. The compositions are also suitable for the preparation of optical lenses, e.g. contact lenses and Fresnel lenses, and for the preparation of medical instruments, auxiliaries or implants.
The compositions are also suitable for the preparation of gels having thermotropic properties. Such gels are described, for example, in DE 19700064 and EP 678534.
Furthermore, the compositions can be used in dry-film paints, as are described, for example, in Paint & Coatings Industry, April 1997, 72 or Plastics World, Volume 54, No. 7, page 48(5).
Preparation of the coating
The components of the formulation and optionally further additives are applied uniformly to a substrate by means of known coating techniques, for example by spin-coating, immersion, knife coating, curtain pouring, brush application or spraying, especially by electrostatic spraying and reverse-roll coating, and also by electrophoretic deposition. The quantity applied (coat thickness) and the nature of the substrate (layer support) are dependent on the desired field of application. The range of coat thicknesses generally comprises values from 0.1 μm to 1mm for gel coates and more than 1mm for composites.
The invention further provides a process for curing a thermal curable coating composition comprising compounds of the formula I or Il as thermal initiators and using IR-curing or NIR- curing or convection heat.
The invention further relates to a process for curing a coating composition which process comprises a) applying a coating layer onto a substrate, whereby the coating composition is a blend of at least an ethylenically unsaturated compound and an initiator of the formula I or Il as defined above; b) thermal curing of the applied coating layer.
The invention further relates to a process for double curing a coating composition which process comprises a) applying a coating layer onto a substrate, whereby the coating composition is a blend of at least an ethylenically unsaturated compound and an initiator of the formula I or Il as defined above; and a photoinitiator as defined above; b) thermal curing and UV-curing of the applied coating layer.
The invention further relates to a process for dual curing a coating composition which process comprises a) applying a coating layer onto a substrate, whereby the coating composition is a blend of at least an ethylenically unsaturated compound and a second thermal crosslinkable compound and an initiator of the formula I or Il as defined above; b) thermal curing of the applied coating layer.
Examples
Example 1
Preparation of N-methyl-benzimidic acid 1,3-dioxo-1 ,3-dihydro-isoindol-2-yl ester
Figure imgf000022_0001
a) preparation of N-hydroxyphthalimide sodium salt
118 g (0.723 mol) of N-hydroxyphthalimide are suspended in 700 ml of ethanol absolute. To this suspension a solution of 16.65g (0.723 mol) of sodium in 400 ml of ethanol absolute is added dropwise under stirring. The resulting red suspension is stirred for 19 h at room temperature. The so formed red solid is sucked off, washed with 100 ml of ethanol abs. and dried in vacuo to give 133 g of a red solid.
b) preparation of the title compound
N-hydroxy phthalimide sodium salt (46.25 g.; 0.25 mol), is dissolved in dry DMF (220 ml), to the resulting suspension 38.8 g (0.25 mol) of N-methyl benzimidoyl chloride (prepared according to J. CS. Perkin II, 1324, (1980)) are slowly added at room temperature, on stirring. The reaction mixture is stirred at room temperature for 19 h and then poured into 1.5 I of water. The so formed precipitate is sucked off and dried in vacuo to obtain 66.06 g of a a crude product which is then taken up in 250 ml of acetonitrile. After filtration 58.7 g of N- methyl-benzimidic acid 1,3-dioxo-1,3-dihydro-isoindol-2-yl ester are obtained in form of colorless crystals, mp. 174-176 0C.
For Ci6H12N2O3 (280.29) calculated/found (%); C 68.56/68.54, H 4.32/4.49, N 9.99/10.00 Example 2
Preparation of N-ethyl-benzimidic acid 1,3-dioxo-1,3-dihydro-isoindol-2-yl ester
Figure imgf000023_0001
analogue to Example 1 colorless crystals; Yield 73%, mp. 124-126 0C.
For Ci7H14N2O3 (294.31) calculated/found (%); C 69.38/69.10, H 4.79/4.63, N 9.52/9.44.
Example 3
Preparation of N-butyl-benzimidic acid 1,3-dioxo-1,3-dihydro-isoindol-2-yl ester
Figure imgf000023_0002
analogue to Example 1 colorless crystals; Yield 83%, mp. 42-45 0C.
For 018H18N2O3 (322.37) Berechnet/Gefunden (%); C 70.79/70.71, H 5.63/5.64, N 8.69/8.68.
Example 4
Preparation of N-methyl-benzimidic acid 2,5-dioxo-pyrrolidine-1-yl ester
Figure imgf000023_0003
1.7 g (0.03 mol) of sodium methylate are added to a solution of 3.45 g (0.03 mol) of N- hydroxy succinimide in 25 ml of methanol. The reaction mixture is stirred for one h, concentrated under vacuo and the residue is taken up in 15 ml of DMF. 4.6 g (0.03 mol) of methyl benzimidoyl chloride are added on stirring. The reaction mixture is stirred at room temperature for 12 h and then poured into 120 ml of water. The so formed precipitate is sucked off and dried in vacuo to obtain 3.8g of a crude product which is then taken up and recrystallised in 9 ml of toluene to give 3.05 g of N-methyl-benzimidic acid 2,5-dioxo- pyrrolidine-1-yl ester in form of colorless crystals; mp. 119-120 0C.
For Ci2H12N2O3 (232.24) calculated/found (%); C 62.06/61.85, H 5.21/5.22, N 12.06/12.00
Example 5
Preparation of dimethyl-thiocarbamic acid O-(1 ,3-dioxo-1 ,3-dihydro-isoindol-2-yl) ester
Figure imgf000024_0001
97.9 g (0.6 mol) of N-hydroxy phthalimide are added to 400 ml of pyridine. Then 76 g (0.615 mol) of dimethyl thiocarbamoyl chloride are added. The reaction mixture is stirred at room temperature for 21 h and then poured into 4 I of ice water. The so formed precipitate is sucked off and dried in vacuo to obtain 145g of a a crude product which is then taken up and recrystallised in dichloromethane-hexane to give 127 g of dimethyl-thiocarbamic acid O-(1,3- dioxo-1 ,3-dihydro-isoindol-2-yl) calculated /found (%); C 52.79/52.68, H 4.03/4.14, N 11.19/11.14.
Example 6
Preparation of dimethyl-thiocarbamic acid O-(1 ,3-dioxo-benzoisochinoline-2-yl) ester
Figure imgf000024_0002
analogue to Example 5 using N-hydroxy-1 ,8-naphthalimide. colorless crystals; Yield: 33%, mp. 185-190 0C.
1 H-NMR(CDCI3, 300 MHz, ppm): 8.67 (d, J=7.5Hz, 2ArH), 8.28 (d, J=7.5Hz, 2ArH), 7.82 (t,
J=7.5 Hz, 4 ArH), 3.51 (s, 2xCH3). Example 7
Preparation of dimethyl-thiocarbamic acid O-(2,5-dioxo-pyrrolidine-1-yl) ester
Figure imgf000025_0001
colorless crystals; Yield: 68.5%, mp. 148-151 0C .
Calculated/found C7H10N2O3S (202.23), (%); C 41.57/41.61, H 4.98/4.91, N 13.85/13.76
Example 8:
Preparation of dimethyl-thiocarbamic acid -O-(1,3-dioxo-octahydro-isoindol-2-yl) ester
Figure imgf000025_0002
To a solution of 25.38 g (0.15 mol) of N-hydroxy-hexahydrophthalimide (prepared as described in Chem. Pharm. Bull., 16, (1968), 622) and 0.5 g 4-dimethylaminopyridine in 100 ml pyridine were added 18.54 g (0.15 mol) of dimethylthiocarbamoyl chloride. The mixture was stirred at room temperature during 3 h and then poured into 1000 ml of ice water. The precipitate was filtered off and recristallized from 120 ml of ethanol to give 28.38 g of white crystals, mp. 124-126 0C. Infusion MS, for CnH16N2O3S (256.33) found [M+1]+ = 257.1.
Example 9:
Preparation of N-(N',N'-dimethyl-thionocarbamoyl-oxy)-5-norbomene-2,3-dicarboximide
Figure imgf000025_0003
This compound was prepared in analogy to example 8 starting from 26.9 g (0.15 mol) of N- hydroxy-5-norbomene-2,3-dicarboximide (prepared as described in Bull. Soc. Chim. Fr., (1976), 833). Yield 36.3 g of colorless crystals after recrystallization from dichloromethane- acetonitrile, mp. 215-218 0C. Elemental analysis, for Ci2H14N2O3S calcd. /found (%): C 54.12/54.18; H 5.30/5.37; N 10.52/10.52.
Example 10
Preparation of dimethyl-thiocarbamic acid O-(3,4-dimethyl-2,5-dioxo-2,5-dihydro-pyrrol-1-yl) ester
Figure imgf000026_0001
This compound was prepared in analogy to example 8 starting from 21.17 g (0.15 mol) of N- hydroxy-3,4-dimethyl-2,5-dioxo-2,5-dihydro-pyrrole (prepared as described in J. Chem. Soc, (1955), 631). Yield 23.50 g after recrystallization from ethanol, mp. 135-138 0C . Infusion MS, for C9H12N2O3S (228.27) found [M+1]+ = 229.1
Example 11
Preparation of diisopropyl-thiocarbamic acid -O-(1,3-dioxo-1,3-dihydro-isoindol-2-yl) ester
Figure imgf000026_0002
This compound was prepared in analogy to example 8 starting from 32.35 g (0.18 mol) of diisopropyl-thiocarbamoyl chloride (prepared as described in (Chem. Ber., 101 , (1968), 113) and N-hydroxyphthalimide. Yield 21.44 g of white crystals after recrystallization from hexane, mp. 73-75 0C
1H-NMR(300 MHz, CDCI3): 7.94-7.89 (m, 2ArH), 7.82-7.78 (m, 2 ArH), 5.29-5.26 (m, 1 H), 3.89-3.86 (m, 1H), 1.59 (d, 6H), 1.32 (d, 6H). Example 12
Preparation of dicyclohexyl-thiocarbamic acid -O-(1 ,3-dioxo-1,3-dihydro-isoindol-2-yl) ester
Figure imgf000027_0001
This compound was prepared in analogy to example 8 starting from 24.94 g (0.096 mol) of dicyclohexyl-thiocarbamoyl chloride (prepared as described in (Chem. Ber., 101, (1968),113) and N-hydroxyphthalimide. Yield 9.65 g of white crystals after recrystallization from hexane, mp. 148-15O 0C. AP-CI (butane) MS, for C2IH26N2O3S (386.51) found [M+1]+ = 386.87
Application Examples Curing under NIR-lrradiation:
Screening Formulation:
Figure imgf000027_0002
Components were stirred until homogenous.
Tested Samples:
Compound of Example 5 and of Example 7.
1.00 g of the test compound was dissolved in 50.00 g of Screening Formulation using a tooth wheel dissolver for 30 min.
Application and Curing Conditions:
Coating was applied on steel panels using a slit coater (WFT 90 μm).
Curing under NIR-Lamps, with main emission between 750 - 1500 nm (eg. by Adphos) at 65% power output, distance to substrate 3 cm, line speed 3 m/min. Testing Methods:
Pendulum Hardness (Koenig) according to DIN EN ISO 1522
Cross Hatch Test according to DIN 53 151
Results:
Figure imgf000028_0001
Oven Curing:
Figure imgf000028_0002
0.4 g of the compound of the compounds of Example 5, 10, 11 or 12 (see Table below) were dissolved in 20.00 g Screening Formulation using a magnet stirring device for 30 min. The mixture is applied to white coil-coat aluminum. The sample is baked in an oven at 1600C for 30 min and a tack free dry film with a thickness of approximately 25μm is obtained. 45 Minutes after cure, the pendulum hardness according to Kόnig (DIN 53157) is measured.
Figure imgf000028_0003
Storing Stability:
Screening Formulation:
Figure imgf000029_0001
Components were stirred until homogenous.
Tested Samples:
Compounds of Ex. 5, 7, 9, 10 and 12
1.00 g were dissolved in 50.00 g Screening Formulation using a magnet stirring device for 30 min.
Testing Methods:
Measurement of viscosity on ICI Cone Plate Viscosimeter at 20°C.
Storing Stability: Initially after sample preparation viscosity was measured. Samples were split and stored in closed containers at 40°C. After a period of 4 weeks and 12 weeks, viscosity was measured again. As reference the screening formulation was treated and measured accordingly.
Results:
Figure imgf000029_0002
Dual Curing
0.26 g of the compound of Ex. 5 were dissolved in 13.4 g Component A using a magnet stirring device for 30 min Subsequent component B is added and well homogenised
Figure imgf000030_0001
The mixtures were applied to white coil-coat aluminum, air-dried for 5 minutes at room temperature a heated in an oven at 1600C for 30 minutes. A tack free dry film with a thickness of approximately 40μm is obtained. 45 Minutes after cure, the pendulum hardness according to Kόnig (DIN 53157) is measured. Pendulum Hardness 140s.
Double Curing
0.4 g of a compound of Ex. 5 and 0.4 g lrgacure 184 were dissolved in 20.00 g Screening Formulation using a magnet stirring device for 30 min
Figure imgf000030_0002
The mixture is applied to white coil-coat aluminum. Irradiation is carried out using a UV- processor (2X120 W/cm) Mercury medium pressure Lamps at a belt speed of 5 m/min. The sample is baked in an oven at 160°C for 30 min and a tack free dry film with a thickness of approximately 25μm is obtained.
45 Minutes after cure, the pendulum hardness according to Kόnig (DIN 53157) is measured. Pendulum Hardness 146s

Claims

Claims
1. Compounds of the formula I and
Figure imgf000032_0001
wherein n is 1 or 2; m is 1 or 2;
R1 and R2 are each, independently of one another, hydrogen, Ci-Ci8alkyl, Ci-Ci8alkenyl, C6-Ci4aryl, aralkyl, C5-Ci2cycloalkyl, each of which may be substituted by halogen, CrC4-alkyl, hydroxy, Ci-C6alkoxy, carbonyl, CrC6alkoxycarbonyl; or R1 and R2 together with the adjacent -CO-N-CO- group may form a monocyclic, bicyclic or polycyclic ring, said ring having up to 50 non hydrogen atoms and wherein said ring
O
<' may contain the structural element N-O- more than once;
(\ O
R3 if n is 1 , is CrCi8alkyl, CrCi8alkenyl, C6-Ci4aryl, aralkyl, C5-Ci2cycloalkyl, each of which may be substituted by halogen, CrC4-alkyl, hydroxy, CrC6alkoxy, carbonyl, CrC6alkoxycarbonyl; or R3 is ORi0 or SRn, NRi2Ri3; wherein R10 is CrCi8alkyl, C6-Ci4aryl, aralkyl, C5-Ci2cycloalkyl, each of which may be substituted by halogen, d- C4-alkyl, hydroxy, CrC6alkoxy, carbonyl, CrC6alkoxycarbonyl; and Rn is CrCi8alkyl, C6-Ci4aryl, aralkyl, C5-Ci2cycloalkyl, each of which may be substituted by halogen, CrC4-alkyl, hydroxy, CrC6alkoxy, carbonyl, CrC6alkoxy- carbonyl; and
Ri2 and Ri3 independently of one another are hydrogen, CrCi8alkyl, C6-Ci4aryl, aralkyl, C5-Ci2cycloalkyl, each of which may be substituted by halogen, CrC4-alkyl, hydroxy, CrC6alkoxy, carbonyl, Ci-C6alkoxycarbonyl; or Ri2 and Ri3 form together with the N atom to which they are attached a 5 or 6 membered ring, optionally interrupted by -NH-, -N(CrC8alkyl)-, -O- and/or S-atoms, R3 if n is 2, is C2-Ci2alkylene, C2-Ci2alkenylene, C6-Ci4arylene, xylylene ; with the proviso, that the following compounds disclosed in US2,872,450 as fungicides are excluded,
Figure imgf000033_0001
R4 and R5 are each, independently of one another, hydrogen, Ci-Ci8alkyl, CrCi8alkenyl
C6-Ci4aryl, aralkyl, C5-Ci2cycloalkyl, each of which may be substituted by halogen, Cr C4-alkyl, hydroxy, CrC6alkoxy, carbonyl, CrC6alkoxycarbonyl; or R4 and R5 together with the adjacent -CO-N-CO- group may form a monocyclic, bicyclic or polycyclic ring, said ring having up to 50 non hydrogen atoms and wherein said ring may contain the O
<' structural element N-O- more than once;
(\ O
R6 if n is 1, is hydrogen, CrCi8alkyl, CrCi8alkenyl, C6-Ci4aryl, aralkyl, C5-Ci2cycloalkyl, each of which may be substituted by halogen, CrC4-alkyl, hydroxy, CrC6alkoxy, carbonyl, CrC6alkoxycarbonyl; or R6 is NR14R15; wherein Ri4 and Ri5 independently of one another are hydrogen, CrCi8alkyl, C6-Ci4aryl, aralkyl, C5-Ci2cycloalkyl, each of which may be substituted by halogen, CrC4-alkyl, hydroxy, CrC6alkoxy, carbonyl, d- C6alkoxycarbonyl; or R14 and Ri5 form together with the N atom to which they are attached a 5 or 6 membered ring, optionally interrupted by -NH-, -N(CrC8alkyl)-, -O- and/or S-atoms,
R6 if n is 2, is C2-Ci2alkylene, C2-Ci2alkenylene, C6-Ci4arylene, xylylene;
R7 is hydrogen, CrCi8alkyl, C6-Ci4aryl, aralkyl, C5-Ci2cycloalkyl, each of which may be substituted by halogen, CrC4-alkyl, hydroxy, CrC6alkoxy, carbonyl, CrC6alkoxy- carbonyl; or R7 and Ri4 or R7 and Ri5 form together with the N-atom attached to R7 a 5- 6 membered ring, optionally interrupted by -NH-, -N(CrC8alkyl)-, -O- and/or S-atoms.
2. Compounds according to claim 1 , wherein (R1, R2) and (R3, R4) together with the adjacent -CO-N-CO- group form a monocyclic, bicyclic or polycyclic ring, resulting in compounds of the formula Ia or Na
Figure imgf000034_0001
wherein
A is unsubstituted ethylene or propylene, ethylene or propylene substituted by
CrCi8alkyl, C6-Ci4aryl, aralkyl, C5-Ci2cycloalkyl, halogen, OH, CrCi8alkoxy, d- Ci8alkylthio, carboxy, Ci-Cisalkoxycarbonyl, carbamoyl (C(O)NH2), d-Ci8alkyl- carbamoyl, di-Ci-Cisalkylcarbamoyl, acyl, nitro, amino, Ci-Ci8alkylamino or di-Ci- Ci8alkylamino; or A is ethenylene or propenylene or ethenylene or propenylene substituted CrC4alkyl; or A Js-CH2-X-CH2- wherein X is O, NH, N(CrCi8alkyl); or -N(OH)-CO-N(OH)-; or A together with the adjacent -CO-N-CO- group may form a bicyclic or polycyclic ring, said ring having up to 20 non hydrogen atoms, and wherein
O
<' said ring may contain the structural element N-O- more than once;
(\ O
Ri2 and Ri3 independently of one another are hydrogen, CrCi8alkyl, cyclohexyl, phenyl, benzyl, or R12 and R13 form together with the N atom to which they are attached a 5 or 6 membered ring, optionally interrupted by -NH-, -N(CrC8alkyl)-, -O- and/or S-atoms,
A1 is unsubstituted ethylene or propylene, ethylene or propylene substituted by
CrCi8alkyl, C6-Ci4aryl, aralkyl, C5-Ci2cycloalkyl, halogen, OH, CrCi8alkoxy, d- Ci8alkylthio, carboxy, CrCi8alkoxycarbonyl, carbamoyl (C(O)NH2), Ci-Ci8alkyl- carbamoyl, di-CrCi8alkylcarbamoyl, acyl, nitro, amino, CrCi8alkylamino or di-d- Ci8alkylamino; or A is ethenylene or propenylene or ethenylene or propenylene substituted CrC4alkyl; or A' Js-CH2-X-CH2- wherein X is O, NH, N(CrCi8alkyl); or -N(OH)-CO-N(OH)-; or A" together with the adjacent -CO-N-CO- group may form a bicyclic or polycyclic ring, said ring having up to 20 non hydrogen atoms, and wherein
O
<' said ring may contain the structural element N-O- more than once;
(\ O
R6 is hydrogen, CrCi8alkyl, cyclohexyl, phenyl, benzyl, NR14R15; wherein
R14 and R15 independently of one another are hydrogen, Ci-d8alkyl, cyclohexyl, phenyl or R14 and Ri5 form together with the N atom to which they are attached a 5 or 6 membered ring, optionally interrupted by -NH-, -N(Ci-C8alkyl)-, -O- and/or S-atoms, R7 is hydrogen, Ci-Ci8alkyl,cyclohexyl, phenyl;or R7 and Ri4 or R7 and Ri5 form together with the N-atom attached to R7 a 5-6 membered ring, optionally interrupted by -NH-, - N(Ci-C8alkyl)-, -O- and/or S-atoms.
3. Compounds according to claim 1 , wherein (Ri, R2) and (R3, R4) together with the adjacent -CO-N-CO- group form a bicyclic ring resulting in compounds of the formula Ib and Nb
Figure imgf000035_0001
wherein
Ri2 and Ri3 each, independently of one another, are hydrogen or d-C8alkyl or cyclohexyl, or Ri2 and Ri3 form together with the N atom to which they are attached a 5 or 6 membered ring, optionally interrupted by -NH-, -N(Ci-C8alkyl)- and/or -0-atoms,
Ri6 and Ri7 each, independently of one another, are hydrogen, CrC8alkyl, cyclohexyl, benzyl, phenyl, halogen, OH, CrC8alkoxy, CrC8alkylthio, carboxy, d-C8alkoxy- carbonyl, carbamoyl (C(O)NH2), CrC8alkylcarbamoyl, di-Ci-Cealkylcarbamoyl, d- C8acyl, nitro, amino, CrC8alkylamino or di-CrC8alkylamino;
R7 CrC8alkyl, cyclohexyl, benzyl, phenyl;
R6 CrC8alkyl, cyclohexyl, benzyl, phenyl;
Ri8 and Ri9 each, independently of one another, are hydrogen, d-C8alkyl, cyclohexyl, benzyl, phenyl, halogen, OH, Ci-C8alkoxy, Ci-C8alkylthio, carboxy, Ci-C8alkoxy- carbonyl, carbamoyl (C(O)NH2), CrC8alkylcarbamoyl, di-Ci-Cealkylcarbamoyl, d- C8acyl, nitro, amino, Ci-C8alkylamino or di-Ci-C8alkylamino.
4. Compounds according to claim 2, wherein A and A' independently are phenylene, cyclohexylene, cyclohexenylene, 1,8-naphthylene or pyridinylene.
5. Compounds according to claim 2, wherein A and A' independently are ethylene or propylene or ethylene or propylene substituted d-C4alkyl or ethenylene or propenylene or ethenylene or propenylene substituted d-C4alkyl.
6. A thermally curable coating composition, comprising a) at least an ethylenically unsaturated compound; b) a thermal initiator effective to enable IR-curing or NIR-curing or to enable microwave curing or to enable ultrasound curing or to enable the convection heat curing of the ethylenically unsaturated compound, wherein the thermal initiator is a N-substituted imide of the formula (I) and/or (II) according to claim 1.
7. A dual curable coating composition, comprising a) at least an ethylenically unsaturated compound and a second thermal crosslinkable compound; b) a thermal initiator effective to enable IR-curing or NIR-curing or to enable microwave curing or to enable ultrasound curing or to enable the convection heat curing of the ethylenically unsaturated compound, wherein the thermal initiator is a N-substituted imide of the formula (I) and/or (II) according to claim 1.
8. A double curable coating composition, comprising a) at least an ethylenically unsaturated compound; b) a thermal initiator effective to enable IR-curing or NIR-curing or to enable microwave curing or to enable ultrasound curing or to enable the convection heat curing of the ethylenically unsaturated compound, wherein the thermal initiator is a N-substituted imide of the formula (I) and/or (II) according to claim 1 ; c) a photoinitiator effective to enable UV-curing of the ethylenically unsaturated compound.
9. Use of the polymerization initiators according to claim 1-5 as thermal radical initiators (TRI) in a curing agent for coatings that cure by free radical polymerisation.
PCT/EP2005/055646 2004-11-09 2005-10-31 N-substituted imides as polymerization initiators WO2006051047A1 (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010079102A1 (en) 2009-01-08 2010-07-15 Basf Se Polymerisation initiator
WO2010112410A1 (en) 2009-03-30 2010-10-07 Basf Se Polymerizable compositions
WO2010128062A1 (en) * 2009-05-07 2010-11-11 Basf Se O-imino-iso-urea compounds and polymerizable compositions thereof
WO2014064064A1 (en) 2012-10-23 2014-05-01 Basf Se Iminoxytriazines as radical generators
WO2016042043A1 (en) * 2014-09-18 2016-03-24 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Use of organic oxyimide salts as flame retardants, flame-retardant plastic compositions, method for the production thereof and moulded part, paint or coating

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4979641B2 (en) * 2007-06-20 2012-07-18 キヤノン株式会社 Method for manufacturing liquid discharge head
FR2939795B1 (en) * 2008-12-17 2010-12-17 Sanofi Aventis PROCESS FOR PREPARING ACTIVE ESTERS
AR086709A1 (en) * 2011-06-22 2014-01-15 Purdue Pharma Lp TRPV1 ANTAGONISTS INCLUDING SUBSTITUTES DIHIDROXI AND ITS USES
US9827321B2 (en) 2012-08-14 2017-11-28 The Trustees Of The University Of Pennsylvania Stabilizing shear-thinning hydrogels
DE102015015143A1 (en) 2015-11-25 2017-06-01 Durst Phototechnik Digital Technology Gmbh Water-based hybrid ink and process for making an article printed with this ink
CN106496383B (en) * 2016-11-28 2019-04-26 湖南理工学院 A kind of acid imide is the method that the reversible addion-fragmentation chain transfer polymerization reaction of photoinitiator prepares polymer

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2872450A (en) * 1955-12-06 1959-02-03 Bayer Ag Thio- and dithio-carboxylic acid esters and a process for their manufacture
US3928493A (en) * 1964-11-05 1975-12-23 Pennwalt Corp Curing and polymerization processes initiated by tertiary-aliphatic-alpha-(imido)-azo compounds
WO2002015939A2 (en) * 2000-08-24 2002-02-28 University Of Leeds Calycins
US20030204034A1 (en) * 2002-03-22 2003-10-30 Symyx Technologies, Inc. Control agents for living-type free radical polymerization and methods of polymerizing

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5415958A (en) * 1977-07-06 1979-02-06 Mitsubishi Paper Mills Ltd Method of curing gelatin
GB8628003D0 (en) * 1986-11-22 1986-12-31 Ciba Geigy Ag Polymerisable compounds
AUPQ014699A0 (en) * 1999-05-04 1999-05-27 Access Pharmaceuticals Australia Pty Limited Amplification of folate-mediated targeting to tumor cells using nanoparticles

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2872450A (en) * 1955-12-06 1959-02-03 Bayer Ag Thio- and dithio-carboxylic acid esters and a process for their manufacture
US3928493A (en) * 1964-11-05 1975-12-23 Pennwalt Corp Curing and polymerization processes initiated by tertiary-aliphatic-alpha-(imido)-azo compounds
WO2002015939A2 (en) * 2000-08-24 2002-02-28 University Of Leeds Calycins
US20030204034A1 (en) * 2002-03-22 2003-10-30 Symyx Technologies, Inc. Control agents for living-type free radical polymerization and methods of polymerizing

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
CHINCHILLA, RAFAEL ET AL: "Uronium salts from polymeric N-hydroxysuccinimide (P-HOSu) as new solid-supported peptide coupling reagents", ARKIVOC (GAINESVILLE, FL, UNITED STATES) , (10), 41-47 CODEN: AGFUAR URL: HTTP://WWW.ARKAT-USA.ORG/ARK/JOURNAL/2003/RUVEDA_ROSSI/RR- 758C/758C.PDF, 2003, XP002368296 *
DATABASE BEILSTEIN [online] XP002368473, Database accession no. Beilstein RN : 6932217 *
GLOWKA M.L., SOBANSKA A.W., ACTA CRYSTALLOGR. SECT. C: CRYST. STRUCT.COMMUN., vol. 50, 1994, pages 1124 - 1126 *
J. DE ABAJO, A.G. BRUNET, S.G. BABE, J. FONTAN: "poliamida-imidas a partir de diisocianatos", ANALES DE QUIMICA, vol. 70, 1974, pages 908 - 913, XP009062111 *
LI, P. ET AL: "The development of highly efficient onium-type peptide coupling reagents based upon rational molecular design", JOURNAL OF PEPTIDE RESEARCH , 58(2), 129-139 CODEN: JPERFA; ISSN: 1397-002X, 2001, XP001039108 *
N.I. NAKANO, M. KISE, E.E. SMISSMAN, K. WIDIGER, R.L. SCHOWEN: "transition-state structure and reactivity in the acid-base catalysed hydrolysis of a model intermediate for corn-plant herbicide resistance", J. ORG. CHEM., vol. 40, no. 15, 1975, pages 2215 - 2220, XP002368471 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010079102A1 (en) 2009-01-08 2010-07-15 Basf Se Polymerisation initiator
JP2012514619A (en) * 2009-01-08 2012-06-28 ビーエーエスエフ ソシエタス・ヨーロピア Polymerization initiator
US8669398B2 (en) 2009-01-08 2014-03-11 Basf Se Polymerisation initiator
WO2010112410A1 (en) 2009-03-30 2010-10-07 Basf Se Polymerizable compositions
US8940806B2 (en) 2009-03-30 2015-01-27 Basf Se Polymerizable compositions
WO2010128062A1 (en) * 2009-05-07 2010-11-11 Basf Se O-imino-iso-urea compounds and polymerizable compositions thereof
US8664288B2 (en) 2009-05-07 2014-03-04 Basf Se O-imino-iso-urea compounds and polymerizable compositions thereof
US9127098B2 (en) 2009-05-07 2015-09-08 Basf Se O-imino-iso-urea compounds and polymerizable compositions thereof
WO2014064064A1 (en) 2012-10-23 2014-05-01 Basf Se Iminoxytriazines as radical generators
US9255217B2 (en) 2012-10-23 2016-02-09 Basf Se Iminoxytriazines as radical generators
WO2016042043A1 (en) * 2014-09-18 2016-03-24 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Use of organic oxyimide salts as flame retardants, flame-retardant plastic compositions, method for the production thereof and moulded part, paint or coating
US10450442B2 (en) 2014-09-18 2019-10-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Use of organic oxyimide salts as flame retardants, flame-retardant plastic compositions, method for the production thereof and moulded part, paint or coating

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