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EP0462222A4 - Free-radical curable compositions - Google Patents

Free-radical curable compositions

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Publication number
EP0462222A4
EP0462222A4 EP19900905332 EP90905332A EP0462222A4 EP 0462222 A4 EP0462222 A4 EP 0462222A4 EP 19900905332 EP19900905332 EP 19900905332 EP 90905332 A EP90905332 A EP 90905332A EP 0462222 A4 EP0462222 A4 EP 0462222A4
Authority
EP
European Patent Office
Prior art keywords
group
accordance
electron
meth
oligomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP19900905332
Other languages
English (en)
Other versions
EP0462222A1 (fr
Inventor
John T. Vandeberg
John J. Krajewski
Gerry K. Noren
Danny C. Thompson
Sami A. Shama
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.)
Koninklijke DSM NV
Original Assignee
DeSoto Inc
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 DeSoto Inc filed Critical DeSoto Inc
Publication of EP0462222A1 publication Critical patent/EP0462222A1/fr
Publication of EP0462222A4 publication Critical patent/EP0462222A4/en
Ceased legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06—Unsaturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C11/00—Surface finishing of leather
    • C14C11/003—Surface finishing of leather using macromolecular compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/16—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising curable or polymerisable compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/46—Non-macromolecular organic compounds
    • D21H19/48—Diolefins, e.g. butadiene; Aromatic vinyl monomers, e.g. styrene; Polymerisable unsaturated acids or derivatives thereof, e.g. acrylic acid

Definitions

  • This invention is directed to free-radical curable compositions that are useful as coatings for various substrates.
  • Background of the Invention There are many applications that require a rapidly curable coating composition that adheres to a substrate, is flexible, does not discolor and has low toxicity.
  • optical glass fibers are frequently coated with two superposed coatings.
  • the coating that contacts the glass is a relatively soft, primary coating that must satisfactorily adhere to the fiber and be soft enough to resist microbending especially at low service temperatures.
  • the outer, exposed coating is a much harder secondary coating that provides the desired resistance to handling forces yet must be flexible enough to enable the coated fiber to withstand repeated bending without cracking the coating.
  • Other applications, e.g., optical fabrication, coatings for substrates including glass, metal, wood, plastic, rubber, paper, concrete, and fabrics, and adhesives also require compositions that are fast curing, have low toxicity and provide good physical properties.
  • compositions that include low molecular weight (meth)acrylate diluents have been utilized for many of these applications.
  • these (meth)acrylate diluents are hazardous to human health. Therefore, it is desirable to eliminate or reduce the amount of low molecular weight (meth) crylate diluents present in a composition.
  • Vinyl ether compositions have been utilized as replacements for (meth)acrylates. Although vinyl ethers rapidly cure when exposed to ultraviolet light in the presence of a cationic curing catalyst, their cure under cationic conditions leaves catalyst residues that discolor the cured compositions and cause them to be sensitive to water. Furthermore, vinyl ether containing oligomers having relatively high equivalent weights, e.g., an equivalent weight in excess of about 500, do not cationically cure upon exposure to dosages of energy less than 3 Joules per square centimeter. Vinyl ethers do not homopoly erize in the presence of free-radical initiators. Therefore, vinyl ethers are not suitable replacements for (meth)acrylates.
  • Unsaturated polyesters e.g., maleates and fumarates
  • European Patent Application No. 0 322 808 published on 05.07.89 discloses a radiation curable composition that comprises an ethylenically unsaturated polyester component and a vinyl ether component having an average of at least two vinyl ether groups per molecule of the vinyl ether component.
  • the unsaturated polyester component can be a polymer, oligomer or mixture thereof.
  • Coatings produced from this composition are brittle and hard because of the large amount of electron deficient ethylenically unsaturated groups in the backbone of the polyester component which leads to short chain segments between cross-links.
  • the vinyl ether component reacts with the unsaturated group and results in a high degree of cross-linking that causes the cured composition to be brittle, inflexible and hard.
  • coatings produced from the composition of this European Patent Application do not possess the needed flexibility and softness for applications, such as optical glass fiber coatings, that require a flexible and soft coating.
  • the invention is directed to free-radical curable compositions that comprise a (meth)acrylate oligomer; and at least one of a single functionality diluent, a mixture of single functionality diluents, and a dual functional monomer, wherein the ratio of electron-rich double bonds to electron deficient double bonds in the compositions is in the range of about 5:1 to about 1:5.
  • compositions of the present invention can further comprise at least one of a reactant having a saturated backbone and an average of at least one electron deficient ethylenically unsaturated end group per molecule of reactant and an oligomer having an average of at least one electron-rich ethylenically unsaturated group per molecule of oligomer.
  • the electron deficient group of the reactant is preferably an ethylenically unsaturated dicarboxylate group.
  • the electron-rich group of this oligomer is preferably a vinyl ether group.
  • the (meth)acrylate oligomer has a number average molecular weight of at least about 1000 daltons and preferably constitutes a minor amount of the composition.
  • the single functionality diluent has only one type of reactive group, e.g., an electron-rich ethylenically unsaturated group such as a preferred vinyl ether group or an electron deficient ethylenically unsaturated group such as a preferred dicarboxylate group on the same molecule of diluent.
  • an electron-rich ethylenically unsaturated group such as a preferred vinyl ether group
  • an electron deficient ethylenically unsaturated group such as a preferred dicarboxylate group
  • the dual functional monomer has at least one electron-rich ethylenically unsaturated group such as a vinyl ether group and at least one electron deficient ethylenically unsaturated group such as an unsaturated dicarboxylate group.
  • the saturated reactant is the reaction product of a polyester backbone containing component and/or a non-polyester backbone containing component and an electron deficient ethylenically unsaturated end group containing component.
  • the vinyl ether containing oligomer is the reaction product of a saturated backbone containing component and a vinyl ether having a hydroxyl group or an a ine group.
  • compositions of the present invention are curable upon exposure to ionizing radiation, actinic energy and heat.
  • the cured compositions exhibit good flexibility, tensile strength, percent elongation, toughness, abrasion resistance, tear resistance and adhesion to substrates.
  • the (meth)acrylate oligomers are relatively inexpensive and their use can lower the cost of the compositions. Suitable uses for these compositions include optical glass fiber coatings, paper coatings, coatings for the metallization of non-metallic substrates, e.g.
  • plastics plastics, coatings for rubber, metal, wood, concrete, leather, fabric and glass, optical fabrication, lamination of glass and other materials, i.e., composites, dentistry, pro ⁇ thetics, adhesives, inks, flexigraphic printing plates, and the like.
  • compositions of the present invention that contain the vinyl ether containing oligo ers are curable by a free-radical mechanism. Cationic curing of these oligomers is not practical.
  • the present invention is directed to free-radical curable compositions that comprise a (meth)acrylate oligomer and at least one of a single functionality diluent, a mixture of single functionality diluents and a dual functional monomer, wherein the ratio of electron-rich double bond to electron deficient double bonds in the compositions is in the range of about 5:1 to about 1:5.
  • the free-radical curable compositions of the present invention can further comprise at least one of a saturated reactant having a saturated backbone and an average of at least one electron deficient ethylenically unsaturated end group per molecule of saturated reactant and an oligomer having an average of at least one electron-rich ethylenically unsaturated group per molecule of oligomer.
  • the electron deficient ethylenically unsaturated end group of the saturated reactant is preferably a dicarboxylate group.
  • the electron-rich ethylenically unsaturated group of the oligomer having at least one electron-rich group is preferably a vinyl ether group.
  • (meth)acrylate and various grammatical forms thereof, identifies esters that are the reaction product of acrylic or methacrylic acid with a hydroxy group-containing compound.
  • single functionality diluent defines a diluent having only one type of reactive group, e.g. , an electron-rich ethylenically unsaturated group such as a vinyl ether group or an electron deficient ethylenically unsaturated group such as a maleate on the same molecule of diluent.
  • this diluent can be polyfunctional, i.e., a molecule can have more than one reactive group provided all reactive groups are of the same type.
  • An admixture of single functionality diluents can have electron-rich groups and electron deficient groups.
  • the single functionality diluent including admixtures thereof, is preferably selected, i.e., both the type of reactive group(s) of the single functionality diluent(s) and the amount utilized are chosen, to provide in the composition a ratio of electron-rich double bonds to electron deficient double bonds of about 5:1 to about 1:5, preferably about 2:1 to about 1:2. Most preferably this ratio is about 1:1.
  • the term "dual functional monomer”, as used herein, defines a monomer having at least one electron-rich ethylenically unsaturated group that preferably is a vinyl ether group and at least one electron deficient ethylenically unsaturated group that preferably is a dicarboxylate group.
  • the ratio of electron-rich groups to electron deficient groups in the monomer can be selected to achieve the desired ratio of electron-rich double bonds to electron deficient double bonds in the composition.
  • vinyl ether in its various grammatical forms, refers to a vinyl group bound to an oxygen atom which is bound to a carbon atom.
  • the (meth)acrylate oligomers suitable for use in the present invention preferably contain an average of at least about 1.2, more preferably about 2 to about 4, (meth)acrylate groups per oligomer.
  • These (meth)acrylate oligomers are illustrated by Cargill 1570, a diacrylate ester of Bisphenol A epichlorohydrin epoxide resin having a number average molecular weight of about 700 daltons that is commercially available from Cargill, Carpentersville, IL.
  • the (meth)acrylate oligomer can be a poly(meth)acrylate of an epoxy functional resin. These poly(meth)acrylates preferably contain an average of more than about two (meth)acrylate groups per oligomer and are exemplified by the commercial product Novacure 3700 available from Interez, Inc., Louisville, KY, which is the die ⁇ ter of Epon 828 and acrylic acid.
  • Epon 828 is an epoxy functional resin that is a diglycidyl ether of Bisphenol A that is commercially available from Shell Chemicals, New York, NY.
  • the number average molecular weight of Novacure 3700 is about 500 daltons and of Epon 828 is about 390 daltons.
  • Diacrylate-modified polyurethanes are also useful as the (meth)acrylate oligomers, especially those that employ a polyester base.
  • Particularly preferred are acrylate-capped polyurethanes that are the urethane reaction products of a hydroxy-functional polyester, especially one having an average of about 2 to about 5 hydroxy groups per molecule, with a monoacrylate monoisocyanate.
  • These acrylate-capped polyurethanes are illustrated by a polyester made by reacting trimethylol propane with a caprolactone to a number average molecular weight of about 600 daltons followed by reaction with three molar proportions of the reaction product of 1 ol of 2-hydroxyethyl acrylate with 1 mol of isophorone diisocyanate.
  • the end product is a polyurethane triacrylate.
  • the urethane-forming reaction is conventionally performed at about 60°C in the presence of about 1 percent by weight of dibutyltin dilaurate.
  • a commercial, polyester-based polyacrylate- modified polyurethane that is useful herein is Uvithane 893 available from Thiokol Chemical Corp., Trenton, NJ.
  • the polyester in the Uvithane 893 product is a polyester of adipic acid with about 1.2 molar proportions of ethylene glycol polyesterified to an acid number of less than about 5.
  • This polyester is converted as described above to a polyacrylate-modified polyurethane that is a semi-solid at room temperature and that has an average unsaturation equivalent of about 0.15 to about 0.175 ethylenically unsaturated groups per 100 grams of resin.
  • the acid number defined as the number of milligrams of base required to neutralize one gram of polyester, is used to monitor the progress of the reaction. The lower the acid number, the further the reaction has progressed.
  • a polyacrylate-modified polyurethane that is suitable as the (meth)acrylate oligomer is the reaction product of 1 mol of diisocyanate, 1 mol of 2-hydroxyethyl acrylate (HEA) and about 1 weight percent dibutyltin dilaurate reacted at a temperature of about 40°C for a time period of 4 hours that is subsequently reacted at a temperature of about 60°C for a time period of about 2 hours with 1 mol of a commercial hydroxy end-functional caprolactone polyester.
  • a suitable caprolactone polyester is the reaction product of 2 mol ⁇ caprolactone and 1 mol of ethylene glycol reacted at a temperature of about 60°C for a time period of 4 hours.
  • a suitable commercial caprolactone polyester is available from Union Carbide Corp., Danbury, CT, under the trade designation Tone M-100 which has a number average molecular weight of about 345 daltons.
  • the number average molecular weight of the (meth)acrylate oligomers is preferably about 1,000 to about 15,000, more preferably about 1,200 to about 6,000, daltons.
  • the equivalent weight of the (meth)acrylate oligomers is preferably about 500 to about 5,000, more preferably about 600 to about 3,000.
  • the single functionality diluents suitable for use herein include vinyl ether diluents, vinyl amides, divinyl ethers, ethylenically unsaturated monocarboxylates and dicarboxylates that are not acrylates, the like and mixtures thereof.
  • N-vinyl pyrrolidinone N-vinyl imidazole, 2-vinylpyridine, N-vinyl carbazole, N-vinyl caprolactam, the like, and mixtures thereof.
  • diluents are the divinyl ethers of triethylene glycol or of any other diol, such as 1,6-hexane diol or dibutylene glycol.
  • polyvinylates of other polyhydric alcohols such as glycerin or trimethylol propane.
  • Polyhydric polyethers can be used, such as ethylene oxide, propylene oxide or butylene oxide adduct ⁇ of polyhydric alcohols, illustrated by ethylene glycol, butylene glycol, glycerin, trimethylol propane or pentaerythritol.
  • Preferred single functionality diluents are triethylene glycol divinyl ether commercially available from GAF under the trade designation Rapicure DVE-3, diethyl maleate, butane diol divinyl ether, 1,4-cyclo- hexane dimethanol divinyl ether, octyl vinyl ether, diethyl furmarate dimethyl maleate, the like, and mixtures thereof.
  • the single functionality diluents can have an average of about 1 to about , preferably about 1 to about 3, reactive groups per molecule.
  • the dual functional monomer can be represented by the following Formula I:
  • R a is selected from the group con ⁇ i ⁇ ting of H, C, to C 10 alkyl or allyl groups, C 5 to C 10 aryl groups, metal ion ⁇ , heteroato s and combinations of carbon and heteroatoms;
  • each R d i ⁇ independently selected from the group consi ⁇ ting of H, C 1 to C 4 alkyl group ⁇ , C 5 to C 10 aryl group ⁇ and electron withdrawing group ⁇ .
  • heteroatoms that can be present in the dual functional monomer include non-carbon atom ⁇ ⁇ uch as oxygen, nitrogen, sulfur, ⁇ ilicon, pho ⁇ phorus and the like.
  • the saturated reactant is the reaction product of a polyester backbone containing component and/or a non-polyester backbone containing component and an electron deficient ethylenically unsaturated end group containing component.
  • the saturated polyester backbone containing component can be repre ⁇ ented by hydroxy functional saturated dicarboxylates, polycarbonates, polycaprolactones and the like.
  • dicarboxylates are the reaction products of saturated polycarboxylic acids, or their anhydrides, and diols.
  • Suitable saturated polycarboxylic acid ⁇ and anhydride ⁇ include phthalic acid, isophthalic acid, terephthalic acid, trimetillitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, tetrachlorophthalic acid, adipic acid, azelaic acid, sebacic acid, succinic acid, glutaric acid, malonic acid, pimelic acid, suberic acid, 2,2-dimethylsuccinic acid, 3,3-dimethylglutaric acid, 2,2-dimethylglutaric acid, the like, anhydride ⁇ thereof, and mixture ⁇ thereof.
  • Suitable diol ⁇ include 1,4-butane diol, 1,8-octane diol and the like.
  • saturated polycarbonates are polyhexamethylene carbonate commercially available from PPG Industries under the trade designation Duracarb 120 and polycyclohexane dimethylene carbonate commercially available from PPG Industries under the trade designation Duracarb 140.
  • Tone Polyol series of products e.g., Tone 0200
  • the saturated, non-polyester backbone containing component can be represented by hydroxy functional polyethers, Bisphenol-A alkoxylates, and siloxane ⁇ and organic polyisocyanates, the like and mixture ⁇ thereof.
  • the group linking the ethylenically unsaturated group to the saturated non-polyester backbone can be a urethane, urea, ether, or thio group and the like.
  • the linking group can be an ester when the ethylenically unsaturated end group containing component i ⁇ a preferred dicarboxylate, dicarboxylic acid or dicarboxylic anhydride.
  • Repre ⁇ entative of the ⁇ aturated polyethers are polyalkylene oxides, alkyl ⁇ ub ⁇ tituted poly(tetrahydrofuran ⁇ ) , and copolymer ⁇ of the alkyl ⁇ ub ⁇ tituted tetrahydrofuran ⁇ and a cyclic ether.
  • Repre ⁇ entative of the polyalkylene oxide ⁇ are poly(propylene oxide), commercially available from Union Carbide under the trade de ⁇ ignation Niax PPG 1025 and poly(tetramethylene glycol), commercially available from DuPont under the trade de ⁇ ignation Terathane 1000.
  • the alkyl substituted poly(tetrahydrofuran ⁇ ) have ring structures that open during polymerization.
  • the alkyl group of the alkyl substituted poly(tetrahydrofuran ⁇ ) ha ⁇ about 1 to about 4 carbon atom ⁇ .
  • Representative of the alkyl ⁇ ub ⁇ tituted poly(tetrahydrofuran ⁇ ) are poly(2-methyltetrahydrofuran) and poly(3-methyltetrahydrofuran) .
  • Repre ⁇ entative of the cyclic ethers with which the alkyl substituted tetrahydrofurans can be copolymerized are ethylene oxide, propylene oxide, tetrahydrofuran and the like.
  • Repre ⁇ entative of the Bisphenol-A alkoxylates are those wherein the alkoxy group contains about 2 to about 4 carbon atoms, e.g., ethoxy.
  • a commercial Bisphenol-A alkoxylate is the Bi ⁇ phenol-A diethyoxlate available under the trade de ⁇ ignation Dianol 22 from Akzo Research, The Netherlands.
  • siloxanes is poly(dimethylsiloxane) commercially available from Dow Corning under the trade designation DC 193.
  • diisocyanates include isophorone diisocyanate (IPDI) , toluene diisocyanate (TDI) , diphenylmethylene diisocyanate, hexamethylene dii ⁇ ocyanate, cyclohexylene dii ⁇ ocyanate, methylene dicyclohexane dii ⁇ ocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, m-phenylene diisocyanate, 4-chloro-l,3-phenylene diisocyanate, 4,4'-biphenylene dii ⁇ ocyanate, 1,5-naphthalene dii ⁇ ocyanate, 1,4-tetramethylene dii ⁇ ocyanate, 1,6-hexamethylene dii ⁇ ocyan
  • the polyester backbone containing component and/or the non-polye ⁇ ter backbone containing component are reacted with an ethylenically unsaturated group containing component that can be the reaction product of an ethylenically unsaturated dicarboxylic acid and a monohydric alcohol or an aforementioned cyclic ether.
  • Representative unsaturated dicarboxylic acid ⁇ are maleic acid, aleic anhydride, fu aric acid, and itaconic acid.
  • the monohydric alcohols are the C, to C 10 alcohols, e.g., ethanol, decanol, the like and mixtures thereof.
  • the ester produced by the reaction of the dicarboxylic acid, or anhydride, and the alcohol, or cyclic ether has unreacted carboxyl group ⁇
  • the ester can be conventionally reacted with a material having a group that is reactive with the carboxyl groups of the ester, e.g., hydroxy groups and epoxy groups.
  • this material i ⁇ re ⁇ inous and has a number average molecular weight of about 300 to about 5000, more preferably about 500 to about 3,500 daltons.
  • the saturated reactant preferably has an average of about 1 to about 10, more preferably about 2 to about 5, electron deficient ethylenically unsaturated end groups per molecule of reactant.
  • the equivalent weight of the saturated reactant having electron deficient ethylenically unsaturated end groups is preferably about 100 to about 10,000, more preferably about 200 to about 1,000.
  • Oligomer ⁇ having an average of at lea ⁇ t one electron-rich ethylenically un ⁇ aturated end group per molecule of oligomer, preferably a vinyl ether containing oligomer, can be utilized in addition to, or in place of, the ⁇ aturated reactant in the compositions of the present invention.
  • the vinyl ether containing oligomer can be produced by conventionally reacting a monohydric or monoamine vinyl ether and a ⁇ aturated backbone moiety containing component.
  • the backbone containing component i ⁇ repre ⁇ ented by hydroxy functional polye ⁇ ter ⁇ , polycarbonates, siloxanes, polycaprolactone ⁇ , Bisphenol-A alkoxylates, polyethers, and organic polyisocyanates, the like and mixtures thereof.
  • the backbone of the vinyl ether containing oligomer can contain repeating backbone units.
  • the group linking the vinyl ether group to the saturated backbone (linking group) can be a urethane, urea, ester, ether, or thio group and the like.
  • Preferred linking group ⁇ are urethane, urea and ester groups. Mixtures of linking groups can be used.
  • vinyl ethers suitable as reactants in the production of the vinyl ether containing oligomer are conventional vinyl ethers including triethylene glycol monovinyl ether and 1,4-cyclohexane dimethylol monovinyl ether.
  • saturated polyesters Representative of the saturated polyesters, polyethers, polycaprolactones, Bisphenol-A alkoxylates, and siloxanes are those utilized in producing the saturated reactant.
  • the oligomers containing vinyl ether group ⁇ can be the reaction product of an organic polyi ⁇ ocyanate, preferably a dii ⁇ ocyanate (e ⁇ pecially a diphenylalkane dii ⁇ ocyanate in which the alkane group contain ⁇ l to 8 carbon atom ⁇ ) , and a tran ⁇ vinylated polyhydric alcohol mixture containing hydroxy group ⁇ that i ⁇ the transvinylation reaction product of (1) at lea ⁇ t one vinyl ether and (2) at lea ⁇ t one polyhydric alcohol having an average of more than 2 hydroxy group ⁇ per molecule.
  • the polyi ⁇ ocyanate i ⁇ pre ⁇ ent in an amount effective to consume sub ⁇ tantially all of the available hydroxy group ⁇ in the tran ⁇ vinylation mixture.
  • transvinylation a ⁇ used in its variou ⁇ grammatical form ⁇ , means that the vinyl ether group of the vinyl ether and the hydroxy group of the alcohol are exchanged.
  • tran ⁇ vinylation mixture and "tran ⁇ vinylation polyhydric alcohol mixture”, a ⁇ used in their variou ⁇ grammatical form ⁇ , mean unreacted polyhydric alcohol, partially tran ⁇ vinylated polyhydric alcohol and fully tran ⁇ vinylated polyhydric alcohol are present in the transvinylation reaction product of the vinyl ether and the polyhydric alcohol.
  • the transvinylation mixture is preferably, but not necessarily, an equilibrium mixture.
  • substantially all in its various grammatical forms, when u ⁇ ed in reference to the isocyanate consuming the hydroxy groups (hydroxy functionality) , means that if the vinyl ether containing oligomer has hydroxy groups, they are not present in an amount that adversely affects the properties of the composition ⁇ .
  • the tran ⁇ vinylated aliphatic polyhydric alcohol mixture can contain partially vinylated polyhydric alcohol ⁇ and at lea ⁇ t about 3 percent to about 90 percent by weight of unreacted polyhydric alcohol ⁇ .
  • the polyi ⁇ ocyanate con ⁇ umes substantially all of the available hydroxy functionality.
  • Simple monohydric alcohols (which are formed when a C, to C 4 alkyl vinyl ether is u ⁇ ed) are preferably removed to provide a tran ⁇ vinylation mixture that i ⁇ ⁇ ub ⁇ tantially free of ⁇ imple monohydric alcohol.
  • Such an alcohol functions to terminate the vinyl ether containing oligomer which is formed, an action that is unde ⁇ irable, but tolerable in ⁇ ome in ⁇ tance ⁇ .
  • the transvinylated mixture is produced by transvinylating a vinyl ether with at lea ⁇ t one polyhydric alcohol which preferably contains an average of more than 2 hydroxy groups per molecule, whereafter any simple monohydric alcohol by-product of the transvinylation reaction and the tran ⁇ vinylation cataly ⁇ t are normally removed. More particularly, the vinyl ether containing oligomer ⁇ are prepared from the transvinylation reaction product of an arylalkyl polyhydric alcohol, which o ⁇ t preferably contains or consists of polyhydric alcohols having an average of 3 or more hydroxy groups per molecule, and a vinyl ether which can contain one or more vinyl ether groups per molecule.
  • the transvinylated reaction product contains partially transvinylated polyhydric alcohols as well as unreacted polyhydric alcohols, and it can also contain fully transvinylated polyhydric alcohols.
  • the tran ⁇ vinylation reaction i ⁇ conveniently carried out in the presence of a catalyst that is known for use in this reaction. While it is not es ⁇ ential, the cataly ⁇ t and the ⁇ imple monohydric alcohol by-product ⁇ of the reaction can both be optionally removed, and thi ⁇ u ⁇ ually al ⁇ o remove ⁇ any unreacted monovinyl ether which may be present.
  • the catalyst is conventionally removed by filtration, which is a particularly ⁇ imple operation.
  • Any ⁇ imple monohydric alcohol ⁇ and any unreacted monovinyl ether which can be pre ⁇ ent when a monovinyl ether i ⁇ u ⁇ ed in the transvinylation reaction are highly volatile and easily removed by evaporation from the reaction product, leaving the balance of the tran ⁇ vinylation reaction product intact.
  • Thi ⁇ method of operation eliminates the need to distill off the monohydric vinyl ether utilized in conventional compositions, and other components that are distilled off with this monohydric vinyl ether, from the pota ⁇ ium hydroxide cataly ⁇ t u ⁇ ed in the reaction with acetylene.
  • the distillation step utilized in the prior art is a difficult operation involving elevated temperature which causes undesired side reactions.
  • the catalyst utilized herein is a conventional transvinylation catalyst and is illustrated by the elements of Group ⁇ IB, IIB, IVB, VB, VIB, VIIB, and VIII of the Periodic Table of Element ⁇ .
  • Repre ⁇ entative cataly ⁇ t ⁇ include palladium, mercury, copper, zinc, magne ⁇ ium, cobalt, mercuric acetate, mercury (II) salts, lithium chloropalladite (I) dialkylpyridine ⁇ , pho ⁇ phate ⁇ of thallium, vanadium, chromium, manganese, iron; cobalt, nickel, Group VI oxyacid salt ⁇ and mixture ⁇ thereof.
  • a pre ⁇ ently preferred cataly ⁇ t i ⁇ palladium (II) .
  • the cataly ⁇ t u ⁇ ed herein can be a finely divided powder and can be removed by filtration.
  • the addition of charcoal to the tran ⁇ vinylation mixture can a ⁇ ist the filtration proces ⁇ , e.g., when a finely divided powder form of the cataly ⁇ t i ⁇ utilized.
  • the catalyst can be bound to a ⁇ olid matrix such as charcoal, nickel, alumina, ion exchange resins, molecular sieves, zeolites, or similar materials.
  • a ⁇ olid matrix such as charcoal, nickel, alumina, ion exchange resins, molecular sieves, zeolites, or similar materials.
  • the ⁇ olid matrix having cataly ⁇ t bound thereto can be in the shape of bead ⁇ , filing ⁇ , part of the walls of a column, and the like.
  • the solid matrix having catalyst bound thereto can be packed in a column.
  • the product of the transvinylation reaction i ⁇ a mixture containing partially tran ⁇ vinylated polyhydric alcohol ⁇ .
  • ⁇ o the tran ⁇ vinylation mixture tend ⁇ to deteriorate with time and expo ⁇ ure to elevated temperature, at least partially by the formation of acetal group ⁇ .
  • Reaction with a polyi ⁇ ocyanate in accordance with thi ⁇ invention ⁇ ignificantly reduces the hydroxy content to minimize or largely avoid this deterioration.
  • the pre ⁇ ent transvinylation mixture does not require an elevated temperature distillation operation. The elimination of thi ⁇ distillation operation further minimizes this deterioration of the transvinylation mixture.
  • the tran ⁇ vinylation mixture will normally contain some unreacted polyhydric alcohol ⁇ and ⁇ ome fully vinylated polyvinyl alcohol ⁇ , a ⁇ previou ⁇ ly indicated, and these are not removed.
  • Thi ⁇ introduce ⁇ an important economy at the ⁇ ame time that it enable ⁇ one to increase the molecular weight and the vinyl ether functionality by reaction of the transvinylation mixture with organic polyisocyanates.
  • Increased molecular weight, the pre ⁇ ence of internal urethane or urea groups, and the increased vinyl ether functionality all introduce physical toughness into the cured products.
  • the partially transvinylated polyhydric alcohol ⁇ in this invention contain from 3 percent to 25 percent unreacted polyhydric alcohols, about 30 to about 94 percent partially transvinylated polyhydric alcohols, and from 3 percent to 25 percent fully transvinylated polyhydric alcohols. This is particularly preferred when the polyhydric alcohol that is transvinylated contains 3 or 4 hydroxy group ⁇ .
  • the tran ⁇ vinylation mixture can u ⁇ e a diol as the polyhydric alcohol, it preferably employs triols and tetrols (mo ⁇ t preferably triol ⁇ ) .
  • diol ⁇ are u ⁇ ed some higher functional polyol is preferably added to the mixture that is transvinylated or to the transvinylation mixture that is reacted with the diisocyanate.
  • Suitable higher functional polyols include the triols and higher hydroxy functional polyols referred to herein.
  • the polyhydric alcohol can be a mixture of alcohols and has an average hydroxy functionality per molecule of more than 2.
  • transvinylation reaction form ⁇ unrefined tran ⁇ vinylation mixture ⁇ which are further reacted to enhance stability of the tran ⁇ vinylation mixture by the formation of vinyl ether containing oligomers in which the molecular weight and vinyl ether functionality are both increased.
  • Suitable polyhydric alcohols for use in thi ⁇ transvinylation reaction can be arylalkyl or aliphatic polyhydric alcohols having an average of more than 2, preferably at least 3, hydroxy groups per molecule on the aliphatic or alkyl portion thereof. It is presently preferred that the polyhydric alcohols can have up to about an average of about 10 hydroxy group ⁇ per molecule.
  • the polyhydric alcohol utilized is preferably soluble in the vinyl ether and has a number average molecular weight of up to about 2,000 dalton ⁇ .
  • the alkyl group of the ⁇ e arylalkyl polyhydric alcohol ⁇ preferably contain ⁇ about 2 to about 10, more preferably about 3 to about 6, carbon atom ⁇ .
  • the aryl group of the ⁇ e polyhydric alcohols preferably contains up to about 20, more preferably up to about 10, carbon atom ⁇ .
  • Illustrative arylalkyl polyhydric alcohols include ethoxylated polyhydric phenols, hydroxy substituted ring structures, e.g., phenol, naphthol, and the like, that are alkoxylated, trimethylol benzene, and the like, and mixtures thereof.
  • Preferred polyhydric alcohols are aliphatic polyhydric alcohols that contain 2 to 10 carbon atoms, more preferably 3 to about 6 carbon atoms, and are illustrated by ethylene glycol, butylene glycol, ester diol, 1,6-hexane diol, glycerol, trimethylol propane, pentaerythritol, and sorbitol. Trimethylol propane i ⁇ particularly preferred.
  • the polyhydric alcohol can be a polyether, ⁇ uch a ⁇ the ethylene oxide or propylene oxide adduct ⁇ of the polyhydric alcohol ⁇ noted previously. These are illu ⁇ trated by the propylene oxide adduct of trimethylol propane that ha ⁇ a number average molecular weight of about 1500 dalton ⁇ .
  • the polyhydric alcohol can. also be a saturated polyester of the polyhydric alcohols noted previously, ⁇ uch a ⁇ the reaction product of trimethylol propane with ep ⁇ ilon caprolactone having a number average molecular weight of about 600 and the reaction product of two mols of ethylene glycol with one mol of adipic acid. Still other polyhydric alcohol ⁇ are illustrated by resinous materials that contain hydroxy group ⁇ , ⁇ uch a ⁇ ⁇ tyrene-allyl alcohol copolymer ⁇ , acrylic copolymers containing 2 percent to 20 percent of copolymerized 2-hydroxyethyl acrylate, and even starch or cellulo ⁇ e. However, the ⁇ e have a higher hydroxy functionality than i ⁇ now preferred.
  • the polyhydric alcohol can also be amine sub ⁇ tituted, e.g., triethanolamine.
  • Polyesters and polycarbonates such as 1,6-hexane diol polycarbonate having a molecular weight of about 1,000 dalton ⁇ , are degraded by the potassium hydroxide catalyst used in reaction with acetylene, but can be transvinylated in accordance with the present transvinylation process.
  • Suitable vinyl ethers can be represented by the following general Formula II:
  • R e ,-R , R 9 , R h , and R 1 are each independently selected from the group of hydrogen and lower alkyl groups containing 1 to 4 carbon atom ⁇ ; R e , or R , and R 9 joined together can be part of a ring ⁇ tructure; R e , or R , and R h , or R 1 , joined together can be part of a ring ⁇ tructure; and R 9 and R h , or R c , joined together can be part of a ring ⁇ tructure;
  • R J is an aromatic or aliphatic group that is reactive only at the ⁇ ite(s) where a vinyl ether containing radical i ⁇ bound; x i ⁇ 0 or 1; and n i ⁇ equal to 1 to 10, preferably 1 to 4, with the proviso that n is les ⁇ than or equal to the number of reactive sites of R j .
  • R 1 can contain heteroatom ⁇ , i.e., atom ⁇ other than carbon atom ⁇ , such a ⁇ oxygen, nitrogen, ⁇ ulfur, silicon, phosphorus, and mixtures of heteroatoms alone or in combination with carbon atom ⁇ .
  • R J can contain 1 to about 20, preferably 1 to about 10, atom ⁇ .
  • R j i ⁇ preferably a straight or branched carbon containing group containing 1 to about 8, more preferably 1 to about 4, carbon atoms and can preferably contain oxygen atoms.
  • Repre ⁇ entative of vinyl ethers of Formula II are dihydropyran and dimethylol benzene divinyl ether.
  • Preferred vinyl ether ⁇ for u ⁇ e in the tran ⁇ vinylation reaction can be represented by the following general Formula III:
  • R k i ⁇ an aliphatic group that i ⁇ reactive only at the site( ⁇ ) where a vinyl ether containing radical i ⁇ bound and n i ⁇ equal to l to 4.
  • R contain ⁇ at lea ⁇ t one carbon atom and can contain heteroatoms and mixtures of heteroatoms.
  • R k contains 1 to about 4 carbon atoms and can contain oxygen atom ⁇ .
  • Vinyl ethers having the structure of Formula
  • polyvinyl ether ⁇ of higher functionality are illu ⁇ trated by trimethylol propane trivinyl ether and pentaerythritol tetravinyl ether.
  • Illustrative monovinyl ethers having the structure of Formula III are ethyl vinyl ether, methyl vinyl ether, n-butyl vinyl ether, and the like, including phenyl vinyl ether.
  • the presently preferred monovinyl ether is ethyl vinyl ether which releases ethanol on reaction.
  • the equivalent ratio of the vinyl ether to the hydroxy groups in the polyhydric alcohol is in the range of about 0.5:1 to about 5:1, preferably 0.8:1 to 2:1.
  • the polyhydric alcohol is transvinylated to react with from 10 percent to 90 percent, preferably from 30 percent to 80 percent, of the hydroxy group ⁇ which are present thereon.
  • a palladium (II) catalyst can be utilized.
  • Illustrative palladium catalysts are PdCl 2 , (PhCN) 2 PdCl 2 , diacetato- (2, '-bipyridyl)palladium (II), diacetato- (1,10-phenanthroline)palladium (II), diacetato- (N,N,N' ,N'-tetramethylenediamine)palladium (II) , diacetato(P,P' ,P'-tetraphenyl-1,2-di- pho ⁇ phino-ethane) palladium (II) , and the like.
  • the cataly ⁇ t i ⁇ u ⁇ ually pre ⁇ ent in a range of about 0.001 to about 1 percent, preferably about 0.1 percent, by weight based on the total weight of the polyhydric alcohol and vinyl ether.
  • the transvinylation reaction i ⁇ a conventional one, a ⁇ previou ⁇ ly indicated, and i ⁇ de ⁇ cribed in the article ⁇ noted previously.
  • a closed vessel which is charged with the appropriate amounts of the polyhydric alcohol, vinyl ether and catalyst and the mixture i ⁇ ⁇ tirred and reacted at a temperature of from about room temperature up to about 45°C.
  • the reaction proceed ⁇ slowly, and we usually permit it to proceed for an extended period of time up to about 3 days to obtain the desired equilibrium composition. After about 2 days we find that using a 20 percent ⁇ toichiometric exce ⁇ s of vinyl ether with respect to hydroxy functionality cau ⁇ e ⁇ about half of the hydroxy 29, to be con ⁇ umed in the reaction.
  • a preferred method of performing the tran ⁇ vinylation reaction i ⁇ to utilize ultrasonic energy to enhance the transvinylation In thi ⁇ method an admixture of the vinyl ether, the polyhydric alcohol and the cataly ⁇ t is exposed to ultrasonic energy for a time period effective to produce the transvinylation mixture.
  • the frequency of the ultrasonic energy is about 10 to about 850 kilohertz (kHz) .
  • the ultrasonic transvinylation reaction is preferably performed at room temperature and pressure, i.e., about one atmosphere.
  • An illustrative device for supplying ultrasonic energy is a Model B220 ultrasonic cleaner, commercially available from Branson Corp. , Shelton, CT.
  • Thi ⁇ cleaner ha ⁇ 125 watt ⁇ of power and provide ⁇ a frequency of about 30 to about 50 kHz at thi ⁇ power level.
  • the reactant ⁇ are placed into a ⁇ uitable ve ⁇ el which i ⁇ then placed in the water bath of the cleaner.
  • the cleaner i ⁇ then activated to enhance the tran ⁇ vinylation reaction.
  • the tran ⁇ vinylation reaction can be run for a time period sufficient to obtain the desired tran ⁇ vinylation mixture.
  • the tran ⁇ vinylation polyhydric alcohol mixture be liquid at room temperature, but thi ⁇ is not es ⁇ ential since reactive liquid materials can be added, e.g., the aforementioned vinyl ether ⁇ ⁇ uch a ⁇ ethyl vinyl ether or a polyvinyl ether ⁇ uch as ethylene glycol divinyl ether, to permit the further reactions contemplated herein to be carried out.
  • any residual alkyl monovinyl ether and simple monohydric alcohol by-product can be retained a ⁇ a reactive liquid material, but thi ⁇ i ⁇ u ⁇ ually unde ⁇ irable since the monohydric alcohol is independently reactive with polyisocyanate and function ⁇ a ⁇ a chain-terminating agent and limit ⁇ the attainment of the de ⁇ ired molecular weight.
  • Other conventional diluent ⁇ e.g., N-vinyl pyrrolidone, N-vinyl caprolactam, and the like can al ⁇ o be present.
  • the unreacted polyhydric alcohol and partially transvinylated polyhydric alcohol are then converted into a vinyl ether containing oligomer by reaction with the dii ⁇ ocyanate to form a vinyl ether containing oligomer preferably having an average of 1 to about 10, more preferably about 2 to about 5, vinyl ether group ⁇ per molecule.
  • the polyi ⁇ ocyanate i ⁇ utilized in an amount ⁇ ufficient to ⁇ ub ⁇ tantially eliminate unreacted hydroxy group ⁇ pre ⁇ ent in the tran ⁇ vinylation mixture.
  • the i ⁇ ocyanate con ⁇ umes ⁇ ub ⁇ tantially all of the available hydroxy group ⁇ of the transvinylation mixture, i.e., les ⁇ than about 0.1 percent by weight of hydroxy group ⁇ are present in the vinyl ether containing oligomer.
  • the vinyl ester containing oligomer has a hydroxy number below about 10.
  • the reaction with organic polyisocyanates increase ⁇ the number average molecular weight and the vinyl ether functionality of the re ⁇ ultant vinyl ether containing oligomer.
  • Thi ⁇ is especially true to the extent that polyhydric alcohols having a hydroxy functionality in exces ⁇ of 2 are u ⁇ ed ⁇ ince thi ⁇ introduce ⁇ branching or an increa ⁇ e in the number of vinyl ether or divinyl ether group ⁇ .
  • the polyi ⁇ ocyanate can have a functionality higher than two, it i ⁇ preferred to utilize dii ⁇ ocyante ⁇ becau ⁇ e of their availability and al ⁇ o becau ⁇ e thi ⁇ minimize ⁇ the tendency to gel when ⁇ ub ⁇ tantially all of the hydroxy functionality i ⁇ con ⁇ umed.
  • a ⁇ toichiometric exce ⁇ of i ⁇ ocyanate group ⁇ , ba ⁇ ed on hydroxy group ⁇ , can be u ⁇ ed, but a ⁇ toichiometric proportion is preferred.
  • Exces ⁇ i ⁇ ocyanate group ⁇ , when pre ⁇ ent, can be later con ⁇ umed by reaction with any i ⁇ ocyanate reactive group. Thu ⁇ , one can po ⁇ t-react the exce ⁇ i ⁇ ocyanate group ⁇ of the vinyl ether containing oligomer with an alcohol or amine-functional reagent that can be monofunctional or polyfunctional depending upon whether a further increa ⁇ e in molecular weight or functionality i ⁇ de ⁇ ired.
  • the aforementioned polyi ⁇ ocyanate ⁇ utilized in the production of the saturated reactant are suitable for use in producing the vinyl ether containing oligomers.
  • Thi ⁇ also indicate ⁇ the hydroxy functionality is similarly consumed.
  • diisocyanates are preferably used herein, this means that the polyhydric alcohol u ⁇ ed should contain a proportion of polyol having at least three hydroxy groups.
  • tran ⁇ vinylation provide ⁇ a monovinyl ether having two hydroxy group ⁇ that is reacted with diisocyanate ⁇ to provide vinyl ether functionality along the length of the oligomer.
  • Tran ⁇ vinylation al ⁇ o provides a monohydric divinyl ether which acts a ⁇ a capping agent. Such a capping agent supplies two vinyl ether groups wherever it appears in the vinyl ether containing oligomer.
  • Both of the ⁇ e triol derivative ⁇ increa ⁇ e the vinyl ether functionality of the vinyl ether containing oligomer ⁇ .
  • unreacted triol ha ⁇ the ⁇ ame function, for it provide ⁇ three branche ⁇ which mu ⁇ t be capped by the vinyl ether-containing capping agent.
  • chain exten ⁇ ion, and hence increa ⁇ ed molecular weight can be achieved by the addition of conventional chain extenders including amine functional chain extenders.
  • Illustrative amine functional chain extender ⁇ include polyoxyalkylene amine ⁇ and the Jeffamine line of products, commercially available from Jefferson Chemicals.
  • a monohydric capping agent can al ⁇ o be present to prevent gelation.
  • the use, and amount required, of this agent is conventional.
  • the internal urethane or urea group ⁇ are provided by the ⁇ toichiometry of the ⁇ y ⁇ tem.
  • Subtracting the molar proportion of the monohydric capping agent, if such an agent is present, from the number of mols of diisocyanate, the equivalent ratio of hydroxy, and/or amine from the amine functional chain extender if one is utilized, to isocyanate in the unreacted diisocyanate can be about 1:1 and can be up to about 1.2:1. This ratio increase ⁇ the molecular weight of the vinyl ether containing oligomer and introduce ⁇ internal urethane or urea group ⁇ therein.
  • Unreacted i ⁇ ocyanate groups can be present in the vinyl ether containing oligomer, but are preferably minimized to les ⁇ than about 0.1 percent by weight. More particularly, the residual isocyanate content of the vinyl ether containing oligomer obtained by reaction of the transvinylation mixture with polyisocyanate can be ⁇ ub ⁇ tantial when further reaction, e.g. , reaction with an aforementioned amine functional chain extender, is contemplated, but when the vinyl ether containing oligomer is to be u ⁇ ed for coating, it i ⁇ preferred that there be no detectable i ⁇ ocyanate pre ⁇ ent.
  • the vinyl ether containing oligomer ⁇ can compri ⁇ e the reaction product of an organic diisocyanate with a transvinylation mixture containing hydroxy group ⁇ that i ⁇ the tran ⁇ vinylation reaction product of a divinyl ether having the Formula III, above, and at lea ⁇ t one aliphatic polyhydric alcohol having an average of 3 or more hydroxy group ⁇ per molecule.
  • the dii ⁇ ocyanate con ⁇ ume ⁇ ⁇ ub ⁇ tantially all of the available hydroxy group ⁇ of the tran ⁇ vinylation mixture.
  • the equivalent ratio of vinyl ether to polyhydric alcohol i ⁇ in the range of about 0.5:1 to about 5:1.
  • ⁇ uitable vinyl ether containing oligomer ⁇ are polyvinyl ether polyurethane ⁇ and saturated polyester ⁇ ⁇ uch a ⁇ tho ⁇ e shown in U.S. Patent Nos. 4,472,019, 4,749,807, 4,751,273, and 4,775,732.
  • each R l independently can be hydrogen or an alkyl, aryl, cycloaliphatic or halogen group and m i ⁇ a number in the range of about 2 to about 10, preferably about 5 to about 6.
  • Metathe ⁇ i ⁇ which i ⁇ de ⁇ cribed in March, Advanced Organic Chemistry, Third Edition, copyright 1985 by John Wiley & Son ⁇ , Inc., pp 1036-1039 & 1115, results in the opening of the ring of the cyclic olefin ether to produce an oligomer having the following general Formula V:
  • R l and m are a ⁇ previou ⁇ ly de ⁇ cribed, y i ⁇ a number in the range of about 2 to about 50, preferably about 2 to about 25, and each Z i ⁇ a terminal group, e.g., hydrogen, a vinyl group.
  • the vinyl ether containing oligomer ⁇ of Formula V can be blended with the other vinyl ether containing oligomer ⁇ of the pre ⁇ ent invention or tho ⁇ e di ⁇ clo ⁇ ed in U.S. Patent Nos. 4,472,019; 4,749,807; 4,751,273; and 4,775,732.
  • the oligomers having an average of at lea ⁇ t one electron-rich ethylenically un ⁇ aturated group per molecule of oligomer preferably contain an average of about 1 to about 10, more preferably about 2 to about 5, electron-rich ethylenically un ⁇ aturated groups per molecule of oligomer.
  • the number average molecular weight of the oligomers having an average of at lea ⁇ t one electron- rich ethylenically un ⁇ aturated group per molecule of oligomer is preferably about 500 to about 8,000, more preferably about 1,000 to about 4,000, daltons.
  • the equivalent weight of the oligomers having an average of at least one electron-rich ethylenically unsaturated group per molecule of oligomer i ⁇ preferably about 500 to about 1,500, more preferably about 800 to about 1,200.
  • the compo ⁇ ition ⁇ of the pre ⁇ ent invention are utilized a ⁇ a secondary coating for optical glas ⁇ fiber the equivalent weight of the oligomer ⁇ having an average of at lea ⁇ t one electron-rich ethylenically un ⁇ aturated group per molecule of oligomer i ⁇ preferably about 300 to about 1,000, more preferably about 400 to about 800.
  • compositions preferably contain the (meth)acrylate oligomer in an amount in the range of about 1 to about 70, more preferably about 20 to about 40, weight percent based on the total weight of the composition.
  • the pre ⁇ ent compo ⁇ ition ⁇ preferably contain the ⁇ ingle functionality diluent in an amount in the range of about 0 to about 40, more preferably about 5 to about 30, weight percent ba ⁇ ed on the total weight of the composition.
  • the pre ⁇ ent compo ⁇ ition ⁇ preferably contain the dual functional monomer in an amount in the range of about 0 to about 40, more preferably about 5 to about 30, weight percent ba ⁇ ed on the total weight of the composition.
  • the present compo ⁇ ition ⁇ preferably contain the ⁇ aturated reactant in an amount in the range of about 0 to about 60, more preferably about 30 to about 50, weight percent ba ⁇ ed on the total weight of the composition.
  • compositions preferably contain the vinyl ether containing oligomer in an amount in the range of about 0 to about 50, more preferably about 10 to about 30, weight percent ba ⁇ ed on the total weight of the composition.
  • the viscosity of the present co position ⁇ i ⁇ preferably about 200 to about 100,000, more preferably about 500 to about 4,000, centipoi ⁇ e (cP) .
  • the compo ⁇ ition ⁇ of the pre ⁇ ent invention are preferably ⁇ olvent free.
  • the compo ⁇ ition ⁇ of the pre ⁇ ent invention can be cured upon expo ⁇ ure to energy ⁇ uch a ⁇ ionizing radiation, actinic energy, i.e., ultraviolet and vi ⁇ ible light, and heat, i.e., thermal cure.
  • Conventional ionizing radiation sources include electron beam devices.
  • the amount of ionizing radiation required for cure of a 3 mil thick film is about 1 to about 5 megarad ⁇ .
  • a photoinitiator When cure of thi ⁇ co po ⁇ ition by expo ⁇ ure to actinic energy of appropriate wavelength, ⁇ uch a ⁇ ultraviolet light, a photoinitiator can be admixed with the compo ⁇ ition.
  • the photoinitiator i ⁇ preferably ⁇ elected from the group con ⁇ i ⁇ ting of (1) hydroxy- or alkoxy-functional acetophenone derivative ⁇ , preferably hydroxyalkyl phenone ⁇ , and (2) benzoyl diaryl pho ⁇ phine oxide ⁇ .
  • the vinyl ethers do not exhibit any substantial curing re ⁇ pon ⁇ e to ultraviolet light when the ⁇ e aryl ketone photoinitiator ⁇ are utilized. Nonethele ⁇ , the ⁇ e two types of ethylenically unsaturated atoms in admixture respond to the photocure very rapidly when the photoinitiator is correctly ⁇ elected. The photocure, and the cure upon expo ⁇ ure to other type ⁇ of energy when no initiator i ⁇ pre ⁇ ent, i ⁇ e ⁇ pecially rapid and effective when both of the de ⁇ cribed type ⁇ of un ⁇ aturation are provided in polyfunctional compounds, particularly tho ⁇ e of re ⁇ inou ⁇ character. The fastest cures are obtained when the respective functionalities are present in about the same equivalent amount.-
  • Preferred photoinitiator ⁇ are (1) hydroxy- or alkoxy-functional acetophenone derivatives, more preferably hydroxyalkyl phenones, and (2) benzoyl diaryl phosphine oxide ⁇ .
  • acetophenone derivatives that may be u ⁇ ed have the Formula VI:
  • R m is an optional hydrocarbon ⁇ ubstituent containing from 1 to 10 carbon atom ⁇ and which may be alkyl or aryl, e.g., methyl, ethyl, butyl, octyl or phenyl, X i ⁇ ⁇ elected from the group consisting of hydroxy, C, to C 4 alkoxy, C, to C 8 alkyl, cycloalkyl, halogen, and phenyl, or 2 Xs together are cycloalkyl, and at least one X is ⁇ elected from the group consisting of hydroxy and C, to C ⁇ alkoxy.
  • the alkoxy groups are preferably methoxy or ethoxy, the alkyl group is preferably methyl or ethyl, the cycloalkyl group i ⁇ preferably cyclohexyl, and the halogen i ⁇ preferably chlorine.
  • the photoinitiator i ⁇ a hydroxy-functional compound
  • the hydroxyalkyl phenone ⁇ which are preferred herein have the Formula X:
  • R i ⁇ an alkylene group containing from 2-8 carbon atom ⁇ and R n i ⁇ an optional hydrocarbon sub ⁇ tituent containing from 1 to 10 carbon atom ⁇ and which may be alkyl or aryl, e.g., methyl, ethyl, butyl, octyl or phenyl.
  • the hydroxy group be in the 2-po ⁇ ition in which ca ⁇ e it i ⁇ preferably a tertiary hydroxy group which define ⁇ a hydroxy group carried by a carbon atom that has its remaining three valences connected to other carbon atoms.
  • Particularly preferred compounds have the Formula XI:
  • each R p i ⁇ independently an alkyl group containing from 1 to 4 carbon atom ⁇ .
  • each R p i ⁇ methyl.
  • Thi ⁇ provides a compound which can be described a ⁇ 2-hydroxy-2-methyl- 1-phenyl propane 1-one.
  • the "propane" i ⁇ replaced by butane or hexane to de ⁇ cribe the corre ⁇ ponding compound ⁇ , and the ⁇ e will further illu ⁇ trate preferred compounds in thi ⁇ invention.
  • the benzoyl diaryl pho ⁇ phine oxide photoinitiator ⁇ which may be u ⁇ ed herein have the Formula XII:
  • R q i ⁇ an optional hydrocarbon ⁇ ub ⁇ tituent containing from 1 to 10 carbon atom ⁇ and may be alkyl or aryl a ⁇ previou ⁇ ly noted, and each x i ⁇ independently an integer from 1 to 3.
  • a 2 ,4 ,6-trimethyl benzoyl compound i ⁇ u ⁇ ed, and the two aromatic group ⁇ connected to the pho ⁇ phorus atom are phenyl groups. This provides the compound 2, , 6-trimethyl benzoyl diphenyl pho ⁇ phine oxide which i ⁇ available from BASF under the trade de ⁇ ignation Lucirin TPO.
  • the photoinitiator i ⁇ preferably present in an amount in the range of about 0.01 to about 10.0, more preferably about 0.1 to about 6.0, weight percent ba ⁇ ed on the total weight of the compo ⁇ ition.
  • Suitable ⁇ ources of actinic energy includes lasers and other conventional light source ⁇ having an effective energy output, e.g., mercury lamp ⁇ .
  • the wavelength of the actinic energy ⁇ uitable for u ⁇ e herein extend ⁇ from the ultraviolet range through the vi ⁇ ible light range and into the infrared range.
  • Preferred wavelength ⁇ are about 200 to about 2,000, more preferably about 250 to about 1,000, nanometers (nm) .
  • the amount of actinic energy utilized to solidify a 3 mil thick film is about 0.05 to about 5.0, preferably about 0.1 to about l, Joules per square centimeter (J/sqcm) .
  • compositions also can be thermally cured in the presence of a conventional thermal free-radical initiator, e.g. , benzoyl peroxide, cyclohexanone peroxide, N,N' azobis(isobutyrylnitrite) , metallic dryer systems, redox systems, and the like.
  • a conventional thermal free-radical initiator e.g. , benzoyl peroxide, cyclohexanone peroxide, N,N' azobis(isobutyrylnitrite) , metallic dryer systems, redox systems, and the like.
  • the u ⁇ e of (meth)acrylate oligomers and the single functionality diluent and/or the dual functional monomer in the composition ⁇ of the present invention result in a reduction in toxicity as compared to conventional compositions that contain only (meth)acrylate oligomers and diluent ⁇ .
  • the (meth)acrylate oligomer ⁇ result in improved physical properties, e.g., toughne ⁇ s, abrasion resi ⁇ tance, tear re ⁇ istance and flexibility in products produced from the compositions as compared to non (meth)acrylate containing compo ⁇ ition ⁇ .
  • compositions of the present invention as coating ⁇ for optical gla ⁇ fibers, coating ⁇ for substrates, e.g., gla ⁇ , paper, wood, rubber, metal, concrete, fabric, and pla ⁇ tic, inks, flexigraphic printing plate ⁇ , binder ⁇ in the manufacturing of composites, and the like.
  • substrates e.g., gla ⁇ , paper, wood, rubber, metal, concrete, fabric, and pla ⁇ tic, inks, flexigraphic printing plate ⁇ , binder ⁇ in the manufacturing of composites, and the like.
  • ⁇ aturated reactant and/or vinyl ether containing oligomer are pre ⁇ ent in the compositions.
  • EXAMPLE 1 Preparation of the Dual Functional Monomer Into a one liter 4-neck flask were introduced 298.3 grams (g) (1.732 equivalents) of diethylmaleate, commercially available from Aldrich Chemical Co., Milwaukee, WI, 201.2 g (1.732 equivalents) of
  • HBVE 4-hydroxybutyl vinyl ether
  • Rapicure HBVE 0.5 g of tetraoctyl titanate, a conventional esterification cataylst commercially available from DuPont under the trade designation TYZOR TOT, and 0.22 g of phenothiazine, a conventional inhibitor commercially available from ICI Chemicals, Wilmington, DE.
  • the flask was fitted with a variable speed stirrer, thermometers, a snyder column, a condenser with a trap, a nitrogen sparge and a heating mantle.
  • the temperature of the contents of the flask and the temperature at the top of the column i.e., a thermometer i ⁇ placed in the condenser at the top of the column to measure the temperature of distillate, were set to distill about 80 g of ethanol in a time period of about 2.5 hours.
  • the resultant product was the dual functional monomer that had a viscosity at 25°C. of about 36 centipoise (cP) .
  • compositions were prepared and tested. Each composition comprised a (meth)acrylate oligomer and at least one of a single functionality diluent and a dual functional monomer of EXAMPLE 1. The formulations of the compositions are present in TABLE I. TABLE I
  • Oligomer 1 60S 83.3 60.8 73.A ... ... ... ...
  • Photoinitiator 204 2.9 3.0 3.4 3.0 3.0 3.1 3.0 3.4 3.4
  • Irgacure 184 commercially available from Ciba-Geigy Corp. Ard ⁇ ley, NY.
  • (Meth)acrylate oligomer 1 wa ⁇ prepared by reacting 80.8 weight percent Adiprene L-200 commercially available from Uniroyal, Middlebury, CT, 0.1 weight percent of dibutyltin dilaurate, 0.1 weight percent butylated hydroxy toluene and 19 weight percent 2- hydroxyethyl acrylate.
  • (Meth)acrylate oligomer 2 was prepared by reacting 3 mols of IDPI and 3 mols of 2-hydroxyethyl acrylate which was then reacted with 1 mol of Jeffamine T5000, commercially available from Jefferson Chemicals.
  • (Meth)acrylate oligomer 3 was prepared by reacting 18.65 weight percent Desmondur W, commercially available from Mobay Chemical Co., 0.01 weight percent P 2 N, 0.03 weight percent butylated hydroxy toluene, 0.07 weight percent dibutyltin dilaurate and 35.9 weight percent NIAX PPG 1025 commercially available from Union Carbide which was then reacted with 4 weight percent hydroxyethyl acrylate which wa ⁇ then reacted with 30 weight percent phenoxyethyl acrylate, 7.3 weight percent N-vinyl pyrrolidone and 4 weight percent Jeffamine D230 commercially available from Jeffer ⁇ on Chemcial ⁇ .
  • the film ⁇ , cured at a do ⁇ age of 1 Joule per ⁇ quare centimeter, prepared from Compositions A to I exhibited no odor. Films prepared from Composition ⁇ A, B and C were clear and exhibited no tack and good adhe ⁇ ion and toughne ⁇ . Film ⁇ prepared from Compo ⁇ ition ⁇ D, E and F exhibited slight tack. Film prepared from Composition G exhibited ⁇ light tack, good toughne ⁇ and fair adhe ⁇ ion. Film ⁇ prepared from Compo ⁇ ition ⁇ H and I exhibited no tack, were ⁇ trong and stiff films. Appearance
  • An automatic draw down apparatus like a Gardner AG-3860 commercially available from Pacific Scientific, Gardner/Neotec Instrument Division, Silver Spring ⁇ , MD, can be utilized.
  • the coating wa ⁇ cured using a "D" lamp from Fu ⁇ ion Curing Sy ⁇ te ⁇ , Rockville, MD.
  • the "D" lamp emit ⁇ radiation having a wavelength of about 200 to about 470 nanometer ⁇ with the peak radiation being at about 380 nanometer ⁇ and the power output thereof i ⁇ about 300 watt ⁇ per linear inch.
  • the coating was cured at a do ⁇ e of about 1 J/ ⁇ qcm which provided complete cure.
  • the film wa ⁇ then conditioned at 23 ⁇ 2°C. and 50 + 3% relative humidity for a minimum time period of 16 hour ⁇ .
  • a 10 mil draw-down of the composition was made on a glas ⁇ plate utilizing a Bird bar.
  • the composition was cured utilizing the "D" lamp at a dose of 1.0 J/sqcm.
  • Three test samples each having dimensions of 1/2" x 1" x 1/2" were cut from the cured coating.
  • Each sample was weighed utilizing an analytical balance to obtain weight measurement A and then immersed in separate containers of deionized water. After a time period of 24 hours, the samples were removed from the water, blotted to remove excess water on the surface and reweighed to obtain weight measurement B.
  • a negative value obtained for % water ab ⁇ orption indicate ⁇ water ⁇ oluble, low molecular weight material ⁇ were leached out of the film.
  • Toxicity te ⁇ t ⁇ were performed on commercially available (meth)acrylate oligomer ⁇ and diluent ⁇ and on commercially available vinyl ether and maleate diluent ⁇ .
  • the re ⁇ ult ⁇ of the ⁇ e toxicity te ⁇ t ⁇ are provided in TABLE III.
  • Pentaery- thritol tri ⁇ crylate 2.46 0 of 6 10
  • Actomer products commercially available from Union Carbide, are acrylate oligomers prepared by the addition of acrylic acid to epoxidized soy or linseed oils. These are relatively high molecular weight materials containing up to three to six acrylic groups respectively per molecule.
  • Neopentylglycol diacrylate was found to be an experimental tumor causing agent.
  • the skin irritation and eye irritation tests were conducted according to the procedure to catagorize the composition ⁇ under the Federal Hazardous Substance Labeling Act (16 C.F.R. ⁇ 1500).
  • composition J A composition representing the present invention (Composition J) was tested for skin irritation and eye irritation.
  • the te ⁇ t re ⁇ ult ⁇ are pre ⁇ ented in TABLE IV, below.
  • PI Primary irritation index.
  • a PI of 1.8 indicates the compo ⁇ ition of the pre ⁇ ent invention (Compo ⁇ ition J) i ⁇ only a mild irritant.
  • Trimethylol propane (0.23 mols), 1,6-pentane diol (0.3 mols), azelaic acid (0.2 mols), Fascat 4100 a catalyst commercially available from M & T Chemical Co. (0.3%) and 40 ml of xylene were then added to the flask. The contents of the flask were heated and stirred while the water of reaction was removed by azetropic distillation. When an acid value of 16.5 wa ⁇ reached, the xylene wa ⁇ distilled out. The resulting branched maleate terminated ester had a Brookfield vi ⁇ co ⁇ ity of 392 cP.
  • Composition J comprised Novacure 8805, a urethane acrylate oligomer commercially available from Interez Inc., Louisville, KY (40 parts), Rapicure DVE-3, commercially available from GAF (14.7 part ⁇ ) , the maleate terminated e ⁇ ter de ⁇ cribed above (55.9 part ⁇ ), Darocur 1173, commercially available from E & M Company (5.0 parts), and Phenothiazine, commercially available from Eastman (0.2 parts) were blended together at room temperature under yellow ⁇ afety light ⁇ until homogeneous.
  • the resultant Composition J had a visco ⁇ ity of 1,830 cP, a weight per gallon of 8.6 pound ⁇ , and a clo ⁇ ed cup flash point of greater than 212'F.
  • Composition J was drawn down on a paper sheet with a remedy 20 wire wound rod, placed on a U.V. cure apparatus (commercially available from Fusion Sy ⁇ te ⁇ ) to cure. At an expo ⁇ ure of 1 Joule/square centimeter, the resultant coating wa ⁇ completely cured (125+ MEK Double rub ⁇ ) with a tough hard ⁇ urface. The same coating cured with 5 megarad ⁇ of electron beam expo ⁇ ure. Removal of the Darocur 1173 from Compo ⁇ ition J permitted much lower electron beam do ⁇ e ⁇ for total cure (about 2-3 megarad ⁇ ) .
  • EXAMPLE 4 Comparison of Compo ⁇ ition ⁇
  • composition K (meth)acrylate oligomer containing composition
  • Composition L a similar composition that did not include a (meth)acrylate oligomer
  • Photoinitiator 5 5.0 3.9. Phenothiazine 0.2
  • Saturated Reactant 1 wa ⁇ prepared by reacting the dii ⁇ ocyanate commercially available under the trade de ⁇ ignation De ⁇ modur W with the butyl cello ⁇ olve ester of maleic anhydride which had been reacted with propylene oxide.
  • Saturated Reactant 2 was prepared by reacting 1,5 pentane diol and maleic anhydride followed by reacting butyl carbitol therewith.
  • the surface of the film was then rubbed with a cloth soaked in methyl ethyl ketone (MEK) .
  • MEK methyl ethyl ketone
  • the number provided is the number of the double rub at which deterioration of the film was first noted.
  • the adhesion to a polycarbonate substrate wa ⁇ determined by curing a film of the composition on the substrate at a cure dose of 1 J/sqcm.
  • a first adhesion te ⁇ t wa ⁇ conducted by making a cross hatching of 10 parallel cuts, equally spaced apart, in the film down to the substrate. Then, 10 parallel cuts, al ⁇ o equally spaced apart, were made perpendicular to the first 10 cut ⁇ . The cut section was then covered with Scotch brand 610 tape commercially available from 3M Company that adhered to the ⁇ urface. The tape wa ⁇ removed and the number of squares of film remaining adhered to the sub ⁇ trate i ⁇ the percent adhe ⁇ ion. None of the film adhered to the substrate.
  • the adhesion and flexibility of the ⁇ e compo ⁇ ition ⁇ can be improved by reducing the cro ⁇ -link den ⁇ ity of the cured film ⁇ .
  • Thi ⁇ reduction can be achieved by increa ⁇ ing the amount of ⁇ ingle functionality diluent and/or dual functional monomer utilized.
  • EXAMPLE 5 Paper Coating Compo ⁇ ition ⁇ Compo ⁇ ition ⁇ ⁇ uitable a ⁇ paper coating compo ⁇ ition ⁇ were prepared and te ⁇ ted. The formulation ⁇ of the ⁇ e compo ⁇ ition ⁇ are pre ⁇ ented in TABLE VII.
  • adhe ⁇ ion to a paper ⁇ ub ⁇ trate tests was similar to the previously discu ⁇ ed adhesion test.
  • the cure dose for these adhesion test wa ⁇ 0 .5 J/sqcm.
  • a third adhesion test was conducted using scotch tape on an uncross-hatched film.
  • the MEK Double Rubs test was conducted on a film cured to an aluminum Q panel.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paints Or Removers (AREA)

Abstract

Des compositions durcissables à radicaux libres contiennent un oligomère de (méth)acrylate et au moins un diluant monofonctionnel, un mélange de diluants monofonctionnels et d'un monomère bifonctionnel. Le rapport entre les liaisons doubles riches en électrons et les liaisons doubles pauvres en électrons dans les compositions est compris entre 5:1 et 1:5 environ. Ces compositions peuvent en outre comprendre au moins un réactif ayant une structure saturée et en moyenne au moins un groupe terminal éthyléniquement insaturé, pauvre en électrons, par molécule de réactif saturé, et un oligomère ayant en moyenne au moins un groupe éthyléniquement insaturé, riche en électrons, par molécule d'oligomère. Ces compositions sont utiles comme revêtements de substrats divers.
EP19900905332 1989-03-07 1990-03-07 Free-radical curable compositions Ceased EP0462222A4 (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US31956689A 1989-03-07 1989-03-07
US319566 1989-03-07
US40457889A 1989-09-08 1989-09-08
US404578 1989-09-08
US43682689A 1989-11-15 1989-11-15
US436826 1989-11-15

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EP0462222A1 EP0462222A1 (fr) 1991-12-27
EP0462222A4 true EP0462222A4 (en) 1992-03-11

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AU (1) AU641152B2 (fr)
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EP0608575A1 (fr) * 1993-01-27 1994-08-03 Dsm N.V. Composition réticulée par exposition à la lumière ultra violette en l'absence de solvant
US5498782A (en) * 1993-09-08 1996-03-12 Union Carbide Chemicals & Plastics Technology Corporation Distortion control additives for ultraviolet-curable compositions
ATE268317T1 (de) * 1999-12-24 2004-06-15 Remei Gmbh & Co Kg Verfahren zur oberflächenbehandlung von bauteilen aus zementgebundenen baustoffen

Citations (1)

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Publication number Priority date Publication date Assignee Title
WO1988006973A1 (fr) * 1987-03-09 1988-09-22 Polycure Pty Limited Panneau stratifie et composition vulcanisable par faisceau d'electrons utilisee dans la fabrication dudit panneau

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US4112146A (en) * 1975-12-15 1978-09-05 Celanese Corporation Polyester resin compositions which are photocurable in the presence of oxygen and an organic hydrazone polymerization initiator
US4200762A (en) * 1976-10-29 1980-04-29 Thiokol Corporation Actinic radiation curable polymers
DE2722264C2 (de) * 1977-05-17 1984-06-28 Merck Patent Gmbh, 6100 Darmstadt Verwendung von substituierten Oxyalkylphenonen als Photosensibilisatoren
US4552830A (en) * 1978-05-09 1985-11-12 Dynachem Corporation Carbonylic halides as activators for phototropic compositions
DE3133419A1 (de) * 1981-08-24 1983-03-10 Basf Ag, 6700 Ludwigshafen Acylphosphinoxidverbindungen und ihre verwendung
DE3328285A1 (de) * 1983-08-05 1985-02-21 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von lichtgehaerteten schichten mit definierter haerte
US4749807A (en) * 1987-02-17 1988-06-07 Allied-Signal Inc. Vinyl ether terminated ester oligomers
MX169697B (es) * 1987-12-28 1993-07-19 Ppg Industries Inc Mejoras a composiciones fraguables por radiacion basadas sobre poliesteres insaturados y compuestos teniendo por lo menos dos grupos de vinil eter

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
WO1988006973A1 (fr) * 1987-03-09 1988-09-22 Polycure Pty Limited Panneau stratifie et composition vulcanisable par faisceau d'electrons utilisee dans la fabrication dudit panneau

Non-Patent Citations (1)

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Title
See also references of WO9010661A1 *

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JPH04505029A (ja) 1992-09-03
CA2047698A1 (fr) 1990-09-08
AU5345590A (en) 1990-10-09
AU641152B2 (en) 1993-09-16
EP0462222A1 (fr) 1991-12-27
WO1990010661A1 (fr) 1990-09-20

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