EP1467973A1 - Sels d'onium avec un anion d'imidazolidine a faible coordination utilises comme initiateurs cationiques - Google Patents

Sels d'onium avec un anion d'imidazolidine a faible coordination utilises comme initiateurs cationiques

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Publication number
EP1467973A1
EP1467973A1 EP02794080A EP02794080A EP1467973A1 EP 1467973 A1 EP1467973 A1 EP 1467973A1 EP 02794080 A EP02794080 A EP 02794080A EP 02794080 A EP02794080 A EP 02794080A EP 1467973 A1 EP1467973 A1 EP 1467973A1
Authority
EP
European Patent Office
Prior art keywords
group
formula
imidazolide
carbon atoms
onium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP02794080A
Other languages
German (de)
English (en)
Inventor
Richard Paul Eckberg
Slawomir Rubinsztajn
Douglas Neckers
John H. Malpert
Kangtai Ren
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
General Electric Co
Original Assignee
General Electric Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by General Electric Co filed Critical General Electric Co
Publication of EP1467973A1 publication Critical patent/EP1467973A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages

Definitions

  • the present invention relates to novel onium imidazolide organometallic complexes which are cationic initiators of polymerization, and to the use of such novel onium salts for the polymerization or crosslinking of functional polymers or monomers by photochemical activation, or activation under an electron beam.
  • Onium salts or salts of organometallic complexes are well known as initiators of the cationic polymerization of monomers or of polymers substituted by functional groups of the epoxy or vinyl ether type, and any other cationically polymerized media and the like (U.S. Pat. Nos. 4, 069,094; 4,450,360; 4,576,999 and 4,640,967; Canadian Patent No. 1,274, 646; European Application EP-A-203, 829). It has been observed that the best results are obtained when the anion of the initiator salt is SbF 6 " ; or tetrakis(pentafluorophenyl) borate, (C 6 F ) 4 B " .
  • the present invention relates also to ultraviolet-curable compositions containing epoxy and/or vinyl ether functional groups and onium salts as photoinitiator. More particularly, it relates to cationically polymerizable and/or crosslinkable compositions comprising novel, easily synthesized iodonium salts with high solubility and high catalytic activity.
  • compositions comprising an epoxy- functional resin and a catalytically effective amount of an onium salt such as iodonium, sulfonium, phosphonium, ferrocenium or diazonium of formula (I)
  • LN is midazolide
  • Mt is B, Ga, In or Tl
  • R 1 are identical or different and represent a monovalent aromatic hydrocarbon radical having from 6 to 14 carbon atoms with at least one electron- withdrawing element or group such as -CF 3 , -NO or -CN, or with at least two halogen atoms;
  • A is a monocarborane anion of the formula CBiiH trustX 12-n wherein X is halogen or CF 3 .
  • the onium imidazolide salts of the present invention include a cationic component and an anionic imidazolidine moiety of formula (I)
  • LN is imidazolide group
  • Mt is B, Ga, In or Tl
  • R 1 are identical or different and represent a monovalent aromatic hydrocarbon radical having from 6 to 14 carbon atoms with at least one electron-withdrawing element or group such as -CF 3 , -NO 2 or -CN, or with at least two halogen atoms.
  • the cationic moiety could be any of the cations of onium salts such as iodonium, pyrylium, thiapyrylium, sulphonium, phosphonium, ferrocenium or diazonium ions and the like.
  • Preferred onium salts are diaryliodonium salts of formula (III) [R 2 -I-R 3 ] + A " (III)
  • R 2 and R 3 are each independently a monovalent aromatic radical having from 6 to 24 carbon atoms.
  • the monovalent aromatic radicals R and R may be unsubstituted or substituted with any group that does not interfere with catalyst function.
  • Preferred substituents include CM S alkyl, CM S alkoxy, and trialkylsilane- terminated C M 8 alkyl; each of these substituents can be uninterrupted or interrupted by one or more oxygen and/or sulfur atoms.
  • iodonium imidazolide salts given by formula (IV)
  • R 4 , R 5 , R 7 and R 8 are independently an alkyl group having from 1 to 18 carbons uninterrupted or interrupted by one or more oxygen and/or sulfur atoms;
  • R 6 and R 9 are independently a divalent aliphatic hydrocarbon radical having from 1 to 18 carbon atoms per radical, which is either uninterrupted or interrupted by one or more oxygen and/or sulfur atoms;
  • R 7 , R 8 , R 9 ; R 10 , R 11 and R 12 are independently a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, which is uninterrupted or interrupted by one or more oxygen and/or sulfur atoms, or which may be further functionalized with halogen or hydroxy groups.
  • R 13 are identical or different and selected from the group of substituted phenyls consisting of-C 6 F 5 , -C 6 H (CF 3 ), and -C 6 H 3 (CF 3 ) ;
  • c, d, g, h, i and 1 are independently 0, 1, 2, 3, 4 or 5, with the proviso that each of the sums c+d+g and h+i+1 not exceed 5.
  • the initiator salts of the present invention are useful for polymerizing or crosslinking, by radiation (especially under ultraviolet light or electron beam) monomers or polymers bearing functional groups such as epoxy groups, oxetane groups, vinyl ether groups, or any other cationically polymerizable monomers and the like.
  • radiation especially under ultraviolet light or electron beam
  • monomers or polymers bearing functional groups such as epoxy groups, oxetane groups, vinyl ether groups, or any other cationically polymerizable monomers and the like.
  • cationically polymerizable monomers and prepolymers are disclosed in U.S. Pat. No. 5, 639,802, which is incorporated herein be reference.
  • the monomers can be made monofunctional, difunctional, or multifunctional. These may also be high molecular weight prepolymers and oligomers.
  • Examples of cationically polymerizable compounds further include epoxy compounds, vinyl or allyl monomers, vinyl or allylic prepolymers, vinyl ethers, vinyl ether functional prepolymers, cyclic ethers including oxetanes, cyclic esters, cyclic sulfides, melamine formaldehyde, phenolic formaldehyde, cyclic organosiloxanes, lactanes and lactones, cyclic acetals, epoxy functional silicone oligomers, vinyl ether functional silicone oligomers, and oxetane functional silicone oligomers.
  • the onium imidazolide salts can additionally be used as thermal polymerization initiators, or as combination ultraviolet light or electron beam and thermal polymerization initiators.
  • compositions that may be polymerized using the onium imidazolide salts of the present invention are described in U.S. Pat. No. 5,639,802.
  • these may also include bis-phenol-A-epoxy resins, cycloaliphatic epoxides, oxetanes, epoxidized olefms such as polybutadiene epoxide, epoxidized organic oils such as epoxidized soybean oil and the like.
  • the onium imidazolidine salt is added to the cationically polymerizable material in an amount sufficient to initiate polymerization or crosslinking and generally ranges from about 0.01 to 20 parts by weight per 100 parts by weight of the polymerizable material.
  • compositions of the invention are useful as radiation polymerizable coatings for paper, metal, plastic or glass and are particularly useful in applications where the properties of a silicone coating are desired.
  • Photosensitizers allow one to utilize the onium imidazolides of the present invention for photopolymerization on exposure to longer wavelengths of light.
  • the iodonium imidazolides may employ separate photosensitizers or sensitizers and accelerators described in the prior art for sensitizing and accelerating cationic polymerization reactions. If a compound is serving as a photosensitizer only it must absorb light energy that can, in some form, be transferred to imidazolide reacting species that does not absorb light energy of the same wavelength.
  • photosensitizers that may be used include benzophenones, acetophenone acetals, benzoin ethers, substituted or nonsubstituted thioxanthones, fluorones, etc. Additionally, photosensitizers may function as electron transfer donors in an oxidative chain as shown in U.S. Patent Application filed on even date herewith claiming priority of U.S. Provisional Application Ser. No. 60/137,115 "Accelerator/Sensitizers for Cationic Systems". In this embodiment, the crucial step is the formation of an excited state of the photosensitizer that is capable of electron donation to the ground state of the onium imidazolide.
  • sensitizer/accelerators useful in the invention include naphthols, dihydroxynaphthalenes; polyhydroxy phenols, such as cresols, gallols, pyrogallols, etc.; di (Cl- C10)alkoxynaphthalenes; C1-C10 alkoxyhydroxynaphthalenes; naphthyl glycidyl ethers and the like.
  • free radical polymerizable monomers include both monomers having one or more ethylenically unsaturated groups, such as vinyl or allyl groups, and polymers having terminal or pendant ethylenic unsaturation. Such compounds are easily identifiable to those skilled in the art and include acrylates.
  • solvents are used to dissolve the photosensitizer/accelerator or an onium imidazolide they may be selected from the group yielding ⁇ -hydroxy alkylsubstituted carbon centered radicals upon UV induced cleavage. These radicals will further deprotonate to form a ketone. The proton released will participate in the cationic polymerization. Thus, the solvent may act as an accelerator as well.
  • the useful solvents include diacetone alcohol, 2-hydroxy-2-mefhyl-l-phenyl- propan-1 -one and the like.
  • Iodonium imidazolide salts of the present invention are preferred photo-initiators for epoxy-functionalized siloxane resins due to their excellent solubility in the siloxane polymers.
  • Epoxy-functionalized siloxane polymers suitable for curing by iodonium salts of the present invention are described in US Patent Nos. 4,279,717, 5,397,813 and 5,583,195 of Eckberg et al., which are incorporated herein by reference.
  • Preferred epoxy-functionalized siloxane polymers and silane monomers include ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxy silane, dialkylepoxysiloxy- chain- stopped polydialkyl-alkylepoxysiloxane copolymers (such as materials sold as UV9315 and UV9400 by General Electric Sili cones), and trialkylsiloxy- chain- stopped polydialkyl-alkylepoxysiloxane copolymers (such as the material sold as UV9300 by General Electric Sili cones), epoxy functional siloxane resin (such as the material sold as UV9430 by General Electric Silicones, and further described in US Patent No. 5,360,833 to Eckberg et al.), blends of epoxy functional siloxane copolymers with vinyl and/or propenyl ethers (such as those described in US Patent No. 5,650,453 to Eckberg et al.).
  • the siloxane compositions can additionally contain other additives and adjuvants, such as adherence modulators (linear silicone polymers or resins bearing vinyl, epoxy, vinyl ether, alcohol and the like functional groups), reactive diluents, pigments, photosensitizing agents, anchorage additives, fungicidal, bactericidal and antimicrobial agents, corrosion inhibitors and the like.
  • adherence modulators linear silicone polymers or resins bearing vinyl, epoxy, vinyl ether, alcohol and the like functional groups
  • reactive diluents pigments
  • photosensitizing agents include anchorage additives, fungicidal, bactericidal and antimicrobial agents, corrosion inhibitors and the like.
  • compositions according to the invention can be used as such or in solution in an organic solvent.
  • the compositions advantageously exhibit a viscosity not exceeding 5,000 mPa.sec, preferably not exceeding 2000 mPa.sec at 25°C. They are useful for providing antiadherent coatings on cellulosic materials, films, paints, for encapsulation of electrical and electronic components, for coatings on textiles and for sheathing optical fibers. They are very particularly advantageous when they are used, as such, to produce a material, such as metal sheet, glass, plastic or paper that is nonadherent to other materials to which it would normally adhere.
  • the present invention also features a process for the production of articles (sheets for example) that are nonadherent to surfaces to which they normally adhere, comprising coating an amount of the subject composition, generally from 0.1 to 5 g/m 2 , onto at least one face surface thereof, and crosslinking the composition by supplying energy, as, for example, UV radiation or electron beam.
  • the present invention also features the final articles (sheets for example) comprising a solid material (metal, glass, plastic, paper, and the like), at least one surface of which is coated with a composition as described above, which composition is photocrosslinked or cross-linked by an electron beam.
  • a solid material metal, glass, plastic, paper, and the like
  • iodonium imidazolide salts of the invention can be prepared by synthetic procedures such as those described in the synthetic examples, below.
  • Tris(pentafluorophenyl)borane (3.008 g, 5.88 mmol), 0.2 g of imidazole (2.94 mmol) and added 0.297 mg (2.94 mmol) of triethylamine were partly dissolved in 50 mL of toluene. This mixture was refluxed for 5 hours to give a white powder. The white solid was collected on the frit, washed with hexane, and dried under reduced pressure to give 3.22 g of product. Yield 91.9%.
  • the comparative iodonium salts are as follows:
  • each iodonium salt was evaluated visually at 0.25% weight percent in UV9315.
  • the same catalyst concentration was used for the photoactivity determination.
  • Borate (compound 4) was dissolved at 0.25 % by weight in an epoxy silicone resin (GE Sili cones UV9315) and used as a standard.
  • the other iodonium salts were prepared at molar concentrations equal to borate 4.
  • a 0.5 mil film of these solutions was applied onto PK paper, and the sample was passed under a focused UV lamp (System LC-06-T3 from American Ultraviolet Co.) using a conveyor belt capable of operation at variable speed. The intensity of the UV lamp was 125 Watts/in".
  • iodonium salts were prepared at molar concentrations equal to gallate 5. A drop of
  • compositions of the invention provide good catalyst solubility and photoactivity in organic epoxy and especially epoxy-functional siloxane systems.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Polymerization Catalysts (AREA)

Abstract

La présente invention concerne des complexes organométalliques d'imidazolide d'onium qui sont des initiateurs cationiques de polymérisation, et l'utilisation de ces nouveaux sels d'onium dans la polymérisation ou la réticulation des polymères ou monomères fonctionnels par l'activation photochimique, ou l'activation par un faisceau d'électrons. L'imidazolide d'onium correspond à la formule (I): Q+ A- dans laquelle Q+ est un cation d'onium. A est un anion d'imidazolide correspondant à la formule (II) [R13Mt-LN-MtR13]- dans laquelle LN est un groupe d'imidazolide, Mt est B, Ga, In ou T1; R1 sont identiques ou différents et représentent un radical monovalent d'hydrocarbures aromatiques possédant entre 6 et 14 atomes de carbone avec au moins un élément ou groupe de retrait d'électrons tel que CF3, -NO2 ou -CN ou avec au moins deux atomes halogènes.
EP02794080A 2002-01-17 2002-11-26 Sels d'onium avec un anion d'imidazolidine a faible coordination utilises comme initiateurs cationiques Withdrawn EP1467973A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US5302902A 2002-01-17 2002-01-17
US53029 2002-01-17
PCT/US2002/038227 WO2003062208A1 (fr) 2002-01-17 2002-11-26 Sels d'onium avec un anion d'imidazolidine a faible coordination utilises comme initiateurs cationiques

Publications (1)

Publication Number Publication Date
EP1467973A1 true EP1467973A1 (fr) 2004-10-20

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EP02794080A Withdrawn EP1467973A1 (fr) 2002-01-17 2002-11-26 Sels d'onium avec un anion d'imidazolidine a faible coordination utilises comme initiateurs cationiques

Country Status (4)

Country Link
EP (1) EP1467973A1 (fr)
KR (1) KR20040075353A (fr)
CN (1) CN1622940A (fr)
WO (1) WO2003062208A1 (fr)

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Publication number Priority date Publication date Assignee Title
PL2289879T3 (pl) 2004-09-27 2015-05-29 Acadia Pharm Inc Synteza formy krystalicznej soli winianowej n-(4-fluorobenzylo)-n-(1-metylopiperydyn-4-ylo)-n'-(4-(2-metylopropyloksy)fenylometylo)karbamidu
US8048819B2 (en) 2005-06-23 2011-11-01 Momentive Performance Materials Inc. Cure catalyst, composition, electronic device and associated method
TWI480308B (zh) * 2010-11-05 2015-04-11 Nippon Catalytic Chem Ind Cationic hardening resin composition
JP6001317B2 (ja) * 2012-05-07 2016-10-05 株式会社日本触媒 カチオン硬化性樹脂組成物
JP6001318B2 (ja) * 2012-05-07 2016-10-05 株式会社日本触媒 エポキシ系硬化物
CN102863387B (zh) * 2012-09-29 2015-07-08 四川大学 一种咪唑类鎓盐的合成方法
CN103755638B (zh) * 2014-01-21 2017-01-18 四川大学 由硼酸制备咪唑类鎓盐的方法
US11891494B2 (en) * 2018-04-26 2024-02-06 Kirin Holdings Kabushiki Kaisha Antimicrobial resin and coating material
TW202212480A (zh) * 2020-09-29 2022-04-01 美商陶氏有機矽公司 可固化聚矽氧組成物及其固化產物
JPWO2023003038A1 (fr) * 2021-07-21 2023-01-26

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US4677137A (en) * 1985-05-31 1987-06-30 Minnesota Mining And Manufacturing Company Supported photoinitiator
DE69909057T2 (de) * 1998-02-20 2004-05-06 Dow Global Technologies, Inc., Midland Expandierte Anionen enthaltende Katalysatoraktivatoren

Non-Patent Citations (1)

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Title
See references of WO03062208A1 *

Also Published As

Publication number Publication date
KR20040075353A (ko) 2004-08-27
WO2003062208A1 (fr) 2003-07-31
CN1622940A (zh) 2005-06-01

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