WO1986007073A1 - Esterification d'acide acrylique et compositions photopolymerisables contenant les produits acrylates - Google Patents

Esterification d'acide acrylique et compositions photopolymerisables contenant les produits acrylates Download PDF

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Publication number
WO1986007073A1
WO1986007073A1 PCT/US1986/000964 US8600964W WO8607073A1 WO 1986007073 A1 WO1986007073 A1 WO 1986007073A1 US 8600964 W US8600964 W US 8600964W WO 8607073 A1 WO8607073 A1 WO 8607073A1
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Prior art keywords
recited
reaction
amine
acid
tertiary amine
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PCT/US1986/000964
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English (en)
Inventor
George Pasternack
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Desoto, Inc.
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Publication of WO1986007073A1 publication Critical patent/WO1986007073A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461—Unsaturated monoacids
    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/026—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from the reaction products of polyepoxides and unsaturated monocarboxylic acids, their anhydrides, halogenides or esters with low molecular weight
    • C08F299/028—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from the reaction products of polyepoxides and unsaturated monocarboxylic acids, their anhydrides, halogenides or esters with low molecular weight photopolymerisable compositions

Definitions

  • the present invention relates to the preparation of polyethyleni ⁇ ally unsaturated esters of epox ⁇ -functional compounds including polyepoxides having reduced odor and exhibiting improved utility in photopolymerizable coating compositions, especially those curable by exposure to ultraviolet radiation.
  • Tertiary alkyl amines typically triethylamine
  • acrylation of epoxides i.e., the formation of an acrylate ester from acrylic acid and an epoxy- functional compound.
  • an alkaline catalyst such as pyridine or triethylamine
  • One advantage of using a relatively volatile tertiary amine, such as triethylamine, as the catalyst is that once the reaction is completed, the amine can be removed from the reaction product, along with any solvent used to dissolve the reactants, by distillation under vacuum. However, even if substantially all of- the tertiary amine is removed by vacuum distillation (or some similar procedure) , enough of the amine remains to impart an objectionable odor to the reaction product.
  • One objective of this invention is to obtain a tertiary amine catalyst that imparts little or no residual odor to the reaction product.
  • Tertiary amines are also known to facilitate or promote photopolymerization reactions including, for example, the formation of radiation-curable coatings. Again, however, typically utilized tertiary amines-are volatile and create an objectionable odor. This odor can persist in the cured coating, for example to contaminate the contents of a container, such as a metal can, when the cured coating is on the inside surface of the can.
  • Another objective of this invention is to provide photopolymerizable polyacrylate-containing compositions including a tertiary amine promoter which compositions polymerize to form cured coatings which are substantially free of amine odor.
  • an ethylenically unsaturated ester reaction product is prepared by a method comprising the steps of:
  • the epoxy-functional compounds are preferably polyepoxides, and enough of the acid is used so that the esterification process provides polyethylenically unsaturated este * r reaction products.
  • the reaction products formed by the method of this invention are substantially free of amine odor, and can be used directly in a radiation-curable coating composition. These reaction products are not purified to remove the catalyst used in their production, and thus contain the tertiary amine catalyst used to prepare it. This catalyst is effective to enhance the radiation cure when that cure is achieved by exposure to ultraviolet radiation. Just as catalytic amounts of the adduct are effective to catalyze the esterification reaction, these same catalytic amounts are effective to speed the ultraviolet cure.
  • a radiation-curable coating composition in this invention includes the ethylenically unsaturated ester, the low volatile tertiary amine catalyst used to prepare it, and other radiation-curable 'ethylenically unsaturated materials which one may wish to have present*
  • Ancillary materials may also be present, for example, typical ketonic photoinitiators, such as benzophenone, acetophenone and thioxanthone, which are used to render the composition sensitive to ultraviolet light.
  • the coating composition will be free of volatile organic solvent, but in some instances such solvents may be present. When a volatile solvent is present, it is normally allowed to evaporate before exposure to the radiation used to effect cure.
  • a method of forming a cured coating upon a substrate is also contemplated herein.
  • a radiation-curable coating composition as described above is applied to a surface of the substrate to form a coated substrate.
  • the coated substrate is thereafter irradiated, as with ultraviolet light, at an intensity and for a time period sufficient to cure the coating, and the tertiary amine adduct present in the coating composition promotes the rate at which the photochemically-induced cure occurs.
  • the cured, coated substrate so produced is substantially free from an amine.odor.
  • the tertiary amine adduct is relatively non-volatile and imparts substantially no odor to the polyethylenically unsaturated polyester, the coating composition containing that polyester or a cured coating prepared from the composition.
  • the present invention also provides the advantage that the substance used to catalyze the preparation of the polyethylenically unsaturated polyester also promotes the ultraviolet cure to which the polyester is subsequently subjected.
  • the tertiary amine catalyst used in polyester preparation need not be removed from the polyester prior to the compound's later use, and this is a distinct advantage in the production procedure.
  • the tertiary amine catalyst compounds useful in the present invention comprise an addition reaction product (adduct) of an aliphatic or aromatic amine containing at least one amino hydrogen atom (primary or secondary amine) and (i) an ethylenically unsaturated material whose ethylenic bond is polarized and is capable of undergoing a Michael-type addition reaction, or (ii) an epoxide compound.
  • an addition reaction product adduct
  • an aliphatic or aromatic amine containing at least one amino hydrogen atom primary or secondary amine
  • an ethylenically unsaturated material whose ethylenic bond is polarized and is capable of undergoing a Michael-type addition reaction
  • an epoxide compound Such products are known in the art.
  • Primary and secondary amines i.e., amines containing at least one amino hydrogen atom, as a class, and especially aliphatic amines, are known to participate in Michael-type addition reactions. Accordingly, any amine capable of undergoing a Michael-type addition reaction is broadly suitable for use in this invention.
  • Monofunctional amines e.g., those which contain a single amino hydrogen atom, can be illustrated by diethylamine, but other amines like dibutyl amine and dioctyl amine are also useful.
  • the amines are aliphatic and include from 2-30 carbon atoms per molecule.
  • aliphatic amines useful herein may be further illustrated by piperidine, morpholine, piperazine, di- (hydrogenated-coco)amine, and diallylamine.
  • Hydroxy-functional amines such as monoethanolamine, monoisopropanolamine, diethanolamine and. iisopropanolamine are also useful herein.
  • Amines containing a plurality of amino hydrogen atoms are also useful in this invention.
  • monobutylamine can be reacted with pentaerythritol triacrylate to form mono-, di-, or tri-tertiary a ine-containing reaction products, as well as mixtures thereof, depending upon the stoichiometry of the reaction mixture, as is known.
  • pentaerythritol triacrylate can be reacted with pentaerythritol triacrylate to form mono-, di-, or tri-tertiary a ine-containing reaction products, as well as mixtures thereof, depending upon the stoichiometry of the reaction mixture, as is known.
  • the unsaturated products are especially useful because these polymerize together with the unsaturated esters which are the prime products of this invention. This more permanently incorporates the tertiary amine products used in this invention into the cured coatings which are formed.
  • An amine containing a plurality of amino hydrogen atoms for example ethylamine. butylamine or ethylene diamine, can be used to provide higher molecular weight tertiary amine adducts. These may retain polarized ethylenic bonds.
  • neopentyl glycol diacrylate is reacted with one-half molar proportion of ethylamine or butylamine, the reaction of these two difunctional reactants leads to the production of polymers.
  • These polymers will have progressively higher molecular weight as the stoichiometric relation of amino hydrogen atoms to polarized monoethylenic unsaturated groups approaches 1:1.
  • the catalysts used in this invention have been illustrated to this point by the use of simple amines, such as monoamines, which may be primary or secondary monoamines.
  • polyamines are also useful. When a highly branched structure is desired, it is appropriate to employ polyamines having a high functionality.
  • Such polyamines are illustrated by diethylenetriamine, triethylenetetramine and tetraethylenepentamine. These include terminal two primary amine groups and one or more secondary amine groups spaced along the length of the chain. The presence of amine groups along the length of the chain is not required, as is illustrated by the usefulness of hexamethylenediamine which contains only terminal amine groups.
  • polyamides having terminal amino groups are also quite useful as illustrated by the commercial material Versamid 125 (commercially available from General Mills, Inc, Minneapolis, Minnesota) which is an amine-terminated fatty polyamide.
  • Versamid 125 commercially available from General Mills, Inc, Minneapolis, Minnesota
  • the above-described amines can be used alone or in any desired combination, but it will be understood that when the higher functional amines, and especially those of higher molecular weight, are reacted with an ethylenically unsaturated material or with an epoxide (as discussed hereinafter) , the products are frequently solid and, therefore, must be dissolved for use.
  • a polyacrylate is used in combination with a polyamine of high functionality, this can lead to the production of insoluble, gelled products that are not desired in this invention.
  • the preferred catalysts are soluble in common organic solvents such as acetone, ethyl acetate, methyl cyclohexane and the like.
  • a polyacrylate can be used in admixture with a liquid monoacrylate or in admixture with another liquid monoethylenic monomer having a polarized ethylenic bond, such as acrylonitrile, diacetone acrylamide, and the like, to either minimize the cross-link density obtained directly by the Michael-type addition reaction, or as a solvent to dissolve the normally solid Michael-type addition product, or for both purposes.
  • a polyacrylate can be used in admixture with a liquid monoacrylate or in admixture with another liquid monoethylenic monomer having a polarized ethylenic bond, such as acrylonitrile, diacetone acrylamide, and the like, to either minimize the cross-link density obtained directly by the Michael-type addition reaction, or as a solvent to dissolve the normally solid Michael-type addition product, or for both purposes.
  • ethylenically unsaturated compounds useful herein may be represented by the formula:
  • R is a polarizing, strongly electron withdrawing group, and can be:
  • R is H or a lower alkyl group that contains 1-4 carbon atoms
  • R is H, CH- or CN, with the proviso that R 2 is not CN when R is CN, 0 2 , SO j R 3 ,
  • suitable monoethylenically unsaturated materials comprise acrylic acid esters, such as ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, hydroxy alkyl acrylate esters whose alkyl group contains 2-4 carbon atoms such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate, and the corresponding methacrylates.
  • Additional monoethylenically unsaturated materials that are suitable include crotonic acid esters, such as ethyl crotonate, and crotonate derivatives similar to the acrylate derivatives listed above.
  • monoethylenically unsaturated compounds having polarized ethylenic bonds include acrylonitrile; methacrylonitrile; acrylamide and methacrylamide as well as their N-substituted derivatives that contain one or two lower alkyl groups such as N-ethylacrylamide,
  • N,N-dimethylacrylamide, and N-hexylmethacr ⁇ lamide N,N-dimethylacrylamide, and N-hexylmethacr ⁇ lamide
  • cyanoacrylic acid and cyanomethacrylic acid as well as their lower alkyl esters such as ethyl cyanoacrylate and 2-ethylhexyl cyanomethacrylate
  • a vinyl lower alkyl sulfone such as vinyl ethyl sulfone
  • a vinyl lower alkyl ketone such as methyl vinyl ketone and hexyl vinyl ketone.
  • Polyethylenically unsaturated materials suitable for use in the present invention include polyesters of acrylic acid with polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, trimethylol propane, glycerine, pentaerythritol, sorbitol and the like.
  • polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, trimethylol propane, glycerine, pentaerythritol, sorbitol and the like.
  • ethylene glycol diacrylate, trimethylol propane diacrylate, pentaerythritol triacrylate and tris-hydroxyethyl isocyanurate di- and triacrylates may also be used.
  • Mono- or polyepoxides may also be used to form tertiary amine adducts with the amines noted previously.
  • monoepoxides such as propylene oxide, butylene oxide, or higher mono-epoxides (preferably not containing more than about 30 carbon atoms) , including olefin oxides containing from 12-16 carbon atoms, such as an epoxidized alpha olefin containing 12 carbon atoms, may be used.
  • Cyclohexene oxide further illustrates the mono-epoxides that may be used to form tertiary amine adducts which are useful herein.
  • mono-epoxides are preferred herein for use in preparing a tertiary amine catalyst.
  • Polyepoxides of any functionality and molecular weight may also be used.
  • the bisphenol-based diglycidyl ethers are all useful as are tri- and higher functional epoxides.
  • Polyoxy- propylene glycols are also suitable, these being available from Dow Chemical Co. , Midland, Michigan, under trade designations DER ' 732 and DER 736.
  • the tertiary amine catalysts described hereinbefore are used as catalysts in the esterification of epoxide compounds with an alpha, beta-monoethylenically unsaturated monocarboxylic acid, such as acrylic, methacrylic or crotonic acids, to form ethylenically unsaturated esters Cacrylation).
  • Esterification of polyepoxides to form polyethylenically unsaturated polyesters is particularly preferred.
  • the ethylenic unsaturation of the epoxy esters thus resides in the carboxylic acid portion of the molecule, as in the acrylate group.
  • approximately stoichiometric amounts of an epoxide compound such as a diglycidyl ether of propylene glycol
  • an alpha, beta-monoethylenically unsaturated monocarboxylic acid such as acrylic acid
  • a tertiary amine catalyst formed by Michael adducting one mole of diethylamine with one mole of ethyl acrylate.
  • the catalyst is used in catalytic amounts, e.g., at least about 0.05% of the weight of the reactants, and the reaction can be carried out in solvent solution, the solvent typically being benzene or toluene.
  • Suitable polyepoxide compounds are diglycidyl ethers of polyols, such as ethylene glycol, butylene glycol, and polyoxypropylene glycols. Dicyclohexyl diepoxides are preferred. Exemplary materials include diglycidyl ethers of bisphenols such as bisphenol A.
  • Epon 828 Shell Chemical Co., Houston, Texas
  • Araldite 6010 Ciba-Geigy Corp., Ardsley, New York.
  • Those polyepoxides having a molecular weight below about 1000 are particularly preferred. It is preferred to employ aliphatic polyhydric alcohols having a molecular weight below 4000 and containing 2 to 4 hydroxy groups. All the hydroxy groups need not be consumed in the reaction. though this may be done. It is particularly preferred to react glycerin, trimethylol propane or pentaerythritol, as the polyol, with acrylic acid.
  • a diglycidyl ether of a C 2 ⁇ (_ polyoxyal ylene glycol it is particularly preferred to react polyoxypropylene diglycidyl ethers containing from about 2 to about 30 oxyalkylene groups with acrylic acid.
  • Illustrative available materials of this type include those sold under the trademarks DER 732 and DER 736 by Dow Chemical Co., Midland, Michigan.
  • Epoxidized novolacs i.e., a polyglycidyl ether of a phenol-formaldehyde novolac having an average oxirane functionality greater than 2, e.g., about 2.5 to about 10, and more preferably about 3 to about 6, are also particularly preferred reactants in acrylation reactions. Such materials are well known.
  • Particularly, preferred alpha, beta-monoethylenically unsaturated monocarboxylic acids are acrylic acid and methacrylic acids. Additional useful acids include crotonic acid, itaconic acid, monobutyl fumarate, and the like.
  • a catalytic amount constitutes about 0.01% to about 3% by weight of the combined weights of the materials which are to be reacted together.
  • the catalytic amount is about 0.03% to about 1.0%.
  • a volatile organic solvent those having a boiling points of about 80°C. to about 120°C. are preferred.
  • Exemplary of such materials are cyclohexane, methyl cyclohexane, which is particularly preferred, toluene and the like.
  • the solvent be substantially removed prior to the use of the ester product in a coating composition, for these frequently contain no inert volatile solvent. Since the tertiary amine adducts used herein have little volatility, they are not removed when the solvent is evaporated, which is usually carried out under vacuum to minimize the temperature and the tendency for the unsaturated esters to polymerize.
  • composition and Method A radiation-curable coating in this invention comprises the polyethylenically unsaturated esters containing residual relatively high boiling tertiary amine adduct, as previously described.
  • This adduct is present in a catalytic amount, but this is enough to provide a useful improvement in cure speed when ultraviolet light is used for cure.
  • An appropriate photoinitiator is also preferably present, but these are themselves well known.
  • Other ethylenically unsaturated materials may also be present, and these may be solid or liquid and monoethylenic or polyethylenic.
  • the "monomers” include the be ore-described monoethylenically unsaturated materials whose ethylenic bonds are polarized, such as ethyl acrylate, butyl acrylate, phenoxyethyl acrylate, isobornyl acrylate and the corresponding methacrylates. Also included are monomers such as vinyl acetate.
  • polyethylenic polyesters of low molecular weight like ethylene glycol diacrylate. These are viewed as monomers because they are liquid at room temperature.
  • Polymers include polyethylenic polyurethanes which are well known radiation-curable materials. Since these are frequently solid or of high viscosity, they are combined with liquid materials which may be ethylenically unsaturated and copolymerizable, or with volatile solvents which enable the coating composition to be liquid to enable its application as a coating.
  • reaction mixture used in the preparation of the polyethylenic polyester may be used directly in the coating composition after removal of the solvent usually present during such reactions.
  • the relative amounts of each ingredient can also be altered by addition of one or more of the components, as may be desired.
  • the tertiary amine adduct may be present during the curing of coating compositions by radiation,- in particular, by ionizing or • - ultraviolet radiation.
  • ionizing radiation such as an electron beam
  • the tertiary amine adduct can act as a chain transmitting agent.
  • ketonic photoinitiators, and especially benzophenone, acetophenone or thioxanthone are present, the tertiary amine adducts signficantly enhance the cure speed.
  • Exemplary photoinitiators include benzophenone, acetophenone, benzoin (and methyl, butyl or isobutyl ethers of benzoin) , and are typically effective at about 0.5 to about weight 6 percent concentrations based on the total weight of the reaction mixture.
  • Thioxanthone thioxanthen- 9-one is typically effective at somewhat lower concentrations, but all of this is conventional. All proportions herein are by weight, unless otherwise stated.
  • Optimum concentrations are a function of the particular composition in which a particular photoinitiator is used as well as of the thickness of the coating, the intensity and wavelength of the ultraviolet energy source and the time of exposure.
  • the amount of particular photoinitiators to use is known to those skilled in the art, and may be referred to as an effective amount.
  • the present invention also contemplates a method of forming a substrate having a cured coating.
  • a before-described radiation-curable coating composition that preferably contains an effective amount of a photoinitiator is provided.
  • the composition is coated on a substrate, such as the surface of a metal as would be used in canning to form a coated substrate, and the coated substrate is irradiated with radiation, such as ultraviolet li ' ght or electron beam radiation, for a time period sufficient for the coating to cure.
  • a 550 watt (2 inch) -medium pressure Hanovia mercury arc quartz lamp (Canrad-Hanovia, Inc. Newark, New Jersey) in an appropriate polished aluminum reflector is suitable for stationary test.
  • Example III A one liter, three-necked flask, equipped as described in Example I, is charged with 592.64 grams (2 moles) of trimethylol propane triacrylate. With the stirrer set at medium speed, 146.28 grams (2.0 moles) of diethylamine is added dropwise to the trimethylolpropane triacrylate over a period of about one hour. The contents of the flask increase in temperature from 25 degrees C to 30 degrees C during the addition. After the addition is completed, the contents of the flask are heated at 40 degrees C for about 30 minutes to yield the diethylamine addition product of trimethylolpropane triacrylate.
  • Example III A one liter, three-necked flask, equipped as described in Example I, is charged with 592.64 grams (2 moles) of trimethylol propane triacrylate. With the stirrer set at medium speed, 146.28 grams (2.0 moles) of diethylamine is added dropwise to the trimethylolpropane triacrylate over
  • thermometer and addition funnel A one liter, three-necked flask equipped with a motor-driven stirrer, ice-water bath. thermometer and addition funnel is charged with 300.36 grams (2 moles) of phenyl gly ⁇ idyl ether. The stirrer is set at medium speed, and the contents of the flask are cooled to about 0 degrees C. Two moles of diethylamine, 146.28 grams, are slowly added to the flask over a period of about one hour. The temperature of the contents of the flask should not be allowed to exceed 10 degrees C during the addition.
  • Araldite 6010 (Ciba- 48.4 Geigy Corp., Ardsley, NY)
  • Reagents 1 through 4 are charged to a one-liter flask equipped with a motor-driven stirrer. Dean Stirk water separator, thermometer, heating mantle and air sparge. The mixture is heated to 40 degrees C at which time the sulfuric acid catalyst is added. Water is azeotropically removed at 85-98 degrees C until an acid value of about 20 is reached. Reagents 6, 7 and 8 are charged to the flask and the reaction is continued until an acid value of less than about 5 is achieved.
  • a vacuum distillation is then performed to remove the solvent.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

Procédé de préparation d'un produit de réaction d'un ester à insaturation éthylénique consistant a) à mélanger un composé à fonction époxyde, notamment un polyépoxyde, avec un acide monocarboxylique à insaturation alpha, béta-monoéthylénique, tel que l'acide acrylique, en présence d'une quantité catalytique d'un produit d'addition d'amine tertiaire d'une amine aliphatique ou aromatique possédant au moins un atome d'hydrogène amino, tel que la diéthylamine, avec i) un composé à insaturation éthylénique dont la liaison éthylénique est polarisée et qui peut subir une réaction d'addition du type Michael, ou ii) un composé époxyde; et b) à maintenir ce mélange à la température de réaction jusqu'à ce que la proportion désirée d'acide soit consommée dans une réaction d'estérification. Les compositions de revêtement vulcanisables par une radiation et contenant l'ester résultant et un catalyseur à base d'amine tertiaire possèdent une meilleure odeur, et les compositions vulcanisables aux ultraviolets contenant les mêmes composants vulcanisent plus rapidement et les revêtements ne dégagent pas l'odeur typique d'amine.
PCT/US1986/000964 1985-05-22 1986-05-05 Esterification d'acide acrylique et compositions photopolymerisables contenant les produits acrylates WO1986007073A1 (fr)

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US736,674 1991-07-26

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3623718A1 (de) * 1985-07-13 1987-01-15 Canon Kk Fluessigkeitsstrahl-aufzeichnungskopf
EP1978048A1 (fr) * 2007-04-05 2008-10-08 Uppc Ag Durcisseur pour résine époxy, procédé de durcissement d'une résine époxy tout comme utilisation du durcisseur

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3844916A (en) * 1972-09-18 1974-10-29 Desoto Inc Radiation curable non-gelled michael addition reaction products
US3903322A (en) * 1974-03-07 1975-09-02 Continental Can Co Photopolymerizable ethylenically unsaturated compounds photoinitiated with benzoyl derivatives of diphenyl sulfide and an organic amine compound
US3914165A (en) * 1972-09-18 1975-10-21 Desoto Inc Radiation curable non-gelled michael addition reaction products
US3925349A (en) * 1972-09-18 1975-12-09 Desoto Inc Radiation curable non-gelled michael addition reaction products
US4358477A (en) * 1978-09-07 1982-11-09 Akzo N.V. Process of curing unsaturated epoxy coating composition with radiation and epoxy curing agent, and coated substrate

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3844916A (en) * 1972-09-18 1974-10-29 Desoto Inc Radiation curable non-gelled michael addition reaction products
US3914165A (en) * 1972-09-18 1975-10-21 Desoto Inc Radiation curable non-gelled michael addition reaction products
US3925349A (en) * 1972-09-18 1975-12-09 Desoto Inc Radiation curable non-gelled michael addition reaction products
US3903322A (en) * 1974-03-07 1975-09-02 Continental Can Co Photopolymerizable ethylenically unsaturated compounds photoinitiated with benzoyl derivatives of diphenyl sulfide and an organic amine compound
US4358477A (en) * 1978-09-07 1982-11-09 Akzo N.V. Process of curing unsaturated epoxy coating composition with radiation and epoxy curing agent, and coated substrate

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3623718A1 (de) * 1985-07-13 1987-01-15 Canon Kk Fluessigkeitsstrahl-aufzeichnungskopf
EP1978048A1 (fr) * 2007-04-05 2008-10-08 Uppc Ag Durcisseur pour résine époxy, procédé de durcissement d'une résine époxy tout comme utilisation du durcisseur

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