WO1988002879A1 - COMPOSITIONS A RADICAL LIBRE POLYMERISABLES A LA LUMIERE VISIBLE ET CONTENANT DES COMPLEXES METALLIQUES pi-ARENE - Google Patents

COMPOSITIONS A RADICAL LIBRE POLYMERISABLES A LA LUMIERE VISIBLE ET CONTENANT DES COMPLEXES METALLIQUES pi-ARENE Download PDF

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Publication number
WO1988002879A1
WO1988002879A1 PCT/US1987/002619 US8702619W WO8802879A1 WO 1988002879 A1 WO1988002879 A1 WO 1988002879A1 US 8702619 W US8702619 W US 8702619W WO 8802879 A1 WO8802879 A1 WO 8802879A1
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WIPO (PCT)
Prior art keywords
arene
composition
composition according
metal
visible light
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PCT/US1987/002619
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English (en)
Inventor
John Woods
John M. Rooney
Mary P. Coakley
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Loctite Corporation
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Publication of WO1988002879A1 publication Critical patent/WO1988002879A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
    • C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur

Definitions

  • This invention relates to free radical polymerisable compositions and to the use of ⁇ -arene metal complexes in a photoinitiator system for such compositions.
  • the invention is applicable to both light-sensitive compositions which are curable on exposure to light and light-activatable anaerobic compositions which are activated on exposure to light so that they are curable on subsequent exclusion from air.
  • At least one compound with formula I where a stands for 1 or 2 and n and q independently of each other each stand for an integer from 1 to 3, M is the cation of a monovalent to trivalent metal from groups IVb to Vllb, VIII or lb of the periodic system (CAS notation), m is an integer corresponding to tne valence of L + q, Q is a halogen and L is a metal or nonmetal with a valence of 2 or 7, R 1 is a ⁇ -arene and R 2 is a ⁇ -arene or the anion of a ⁇ -arene.
  • European Patent Application 0 109 851 Minnesota Mining and Manufacturing Company described a composition comprising a cationically polymerisable material and a catalytically effective amount of an ionic salt of an organometallic complex cation as polymerisation initiator, said ionic salt of an organometallic complex cation being capable of adding an intermediate strength nucleophile or upon photolysis of liberating at least one coordination site, said metal in said organometallic complex cation being selected from elements of Periodic Groups IVB, VB, VIB, VIIB and VIII.
  • the present invention provides a polymerisable composition
  • a polymerisable composition comprising
  • the free radically polymerisable material is preferably one or more monomers and/or prepolymers containing acrylate or methacrylate groups; or a copolymerisable monomer combination based on a polythiol and a polyene.
  • the ⁇ -arene metal complex is preferably a complex salt of a ⁇ 6 , ⁇ 5 iron arene cation and a non-nucleophilic anion, which is of the formula:
  • R 6 is a ⁇ 6 arene such as benzene, alkylbenzenes (e.g. toluene, xylene, mesitylene, and cumene), alkoxybenzene (e.g. methoxybenzene), halobenzenes (e.g. chlorobenzene), haloalkylbenzenes (e.g. p-chlorotoluene), naphthalene, alkoxynaphthalenes, alkylnaphthalenes, halonaphthalenes (e.g.
  • alkylbenzenes e.g. toluene, xylene, mesitylene, and cumene
  • alkoxybenzene e.g. methoxybenzene
  • halobenzenes e.g. chlorobenzene
  • haloalkylbenzenes e.g. p-chlorotoluene
  • R 7 is the anion of a cyclopentadienyl compound such as cyclopentadiene, acetylcyclopentadiene, benzoyl cyclopentadiene, butylcyclopentadiene, amylcylopentadiene, indene and the like, L is di- to heptavalent metal or metaloid, Z is a halogen and k is equal to 1 Plus the valence of L. Examples of the i ons LZ k - include SbF 6 -, BF 4 -, AsF 6 -, and PF 6 -. Examples of such compounds include:
  • the cumyl compound is available from Ciba-Geigy Ltd., Basle, Switzerland, under the number CG 24-61.
  • the other three compounds are described in
  • the free radical polymerisation initiator is most suitably a peroxide or hydroperoxide compound such as benzoyl peroxide, cumene hydroperoxide, methylethylketone peroxide and the like.
  • Both the ⁇ -arene metal complex and initiator are suitably employed at levels of 0.01 - 10%, preferably 0.1 - 8% , and more particularly 0.5 - 5% by weight of the composition.
  • the compositions according to the invention include photosensitive compositions which are curable on exposure to visible or UV light and anaerobic compositions which are activatable on exposure to visible or UV light.
  • the composition may also incorporate one or more cationically polymerisable monomers of the kind described in European Patent 0094915.
  • compositions of the invention may also contain compatible imides.
  • a curable thiol-ene formulation comprising: a) a polythiol b) a polyene compound having a plurality of groups of the formula
  • the composition may also contain another organometallic complex, particularly a metallocene such as ferrocene in an amount of 0.1-10% by weight of the composition.
  • a metallocene such as ferrocene
  • compositions of the present invention are so sensitive to visible light.
  • Current visible-light sensitive coating compositions based on free radical polymerisable monomers and sensitizers or photoinitiators selected from fluorenone peresters or 1,2-diketone/amine combinations will not cure when exposed to light from low intensity fluorescent tubes (approx. 30 W) or from high intensity tungsten halogen lamps (e.g. Philips 650 W PF 813).
  • Compositions of the present invention cure rapidly on exposure to such light sources and (in the case of acrylic monomers) give tack-free surfaces at the high intensities, and even at low intensities on long exposures.
  • Anaerobic compositions according to the present invention may be activated by visible light, e.g. high intensity tungsten/halogen lamps or low intensity fluorescent lighting tubes.
  • Imide-contai ning compositions cannot be photocured with conventional photoinitiators in thick sections due to light screening by the imide.
  • the present invention overcomes that problem; sections of imide-contai ning compositions according to the invention, with a thickness of several mm's, have been success ful ly cured wi th visi ble l ight. DESCRIPTION OF THE PREFERRED EMBODIMENT
  • UVA LOC 1000W fitted with poly- (L2) 20 60 secs. carbonate filter 650W Tungsten Halogen Lamp (L3) 6 60 secs.
  • Light source (L1) produces high intensity ultraviolet light over the wavelength spectrum 200-400 nm along with high intensity visible light at wavelengths > 400 nm.
  • (L2) produces visible light only at wavelengths > 400 nm.
  • (L3) produces high intensity vi sible light at wavelengths > 400 nm along with lower outputs in the UV region principally between 300 and 400 nm.
  • (L4) is a low intensity source of visible light. It produces no UV radiation.
  • a photosensitive composition was prepared by dissolving the following ingredients together:
  • Blend A (Example 3) 96 ( ⁇ 6 -mesitylene)( ⁇ 5 cyclopentadienyl) iron hexafluorophosphate (Example 1) 2
  • a photosensitive composition was prepared by blending the following ingredients together:
  • Blend A (Example 3) 96
  • compositions similar to that described in Example 3 were prepared except that the ( ⁇ 6 -cumene) ( ⁇ 5 -cyclopentadienyl) iron hexafluorophosphate ( ⁇ -arene) and cumene hydroperoxide (CHP) were independently omitted.
  • the compositions were exposed to light sources (L1) - (L4) and cure examined as described in Example 3. The results obtained are as follows:
  • UV sensitive free radical photoinitiators 2,2-Dimethoxy-2-phenylacetophenone (IRGACURE 651, Ciba Geigy) and 2-methyl-1-[4-(methylthio) phenyl]-2-morpholinopropan-1-one (IRGACURE 907, Ciba Geigy) are well known commercially-available UV sensitive free radical photoinitiators.
  • UVE-10H GeneralElectric is a well known commerically-available triarylsulfonium salt cationic photoinitiator. Compositions containing these photoinitiators were prepared as follows:
  • t-BPF 4-tert-butylperoxy ester of fluoren-9-one
  • 1,2 diketones such as benzil or camphorquinone (CQ)
  • CQ camphorquinone
  • composition in parts by weight
  • L1 10 (*20) 5 secs 5 secs * 7 secs
  • L2 10 (*20) > 60 secs > 60 secs * > 180 secs
  • L3 6 > 60 secs > 60 secs > 120 secs
  • L4 1 > 5 hrs > 2.5 hrs > 3.5 hrs
  • a radiation activatable anaerobic composi tion was prepared by mixing the followi ng ingredi ents together in the fol lowing weight percentages :
  • Cumene hydroperoxide 2.0 ( ⁇ 6 -cumene)( ⁇ 5 -cyclopentadienyl) iron- hexafluorophosphate 1.0
  • Monomer X is the urethane acrylate reaction product of toluene diisocyanate and the hydroxypolyoxypropylene derivative of trimethylolpropane (commercially available under the trade name Pluracol TP 2450) having unreacted isocyanate functionality capped with hydroxyethyl methacrylate.
  • Monomer Y is the urethane acrylate prepared by reacting two moles of toluene diisocyanate with one mole of hydrogenated bisphenol A, diluting the reaction mixture with methyl methacrylate and further reacting it with two moles of hydroxyethyl methacrylate in the manner disclosed in Example V of US Patent No. 3,452,988.
  • the coated lapshears were then exposed to visible light from a Thorn 30W, Warmwhite fluorescent light tube for different periods of time.
  • the coated panels were placed 1 cm directly under the light tube. After the irradiation period, small pieces of stainless steel wire, 0.125 mm diameter and bent in a U-shape were embedded into the adhesive coating of one panel of the pair.
  • the coated surfaces of each pair were then firmly placed in contact to give in each case a 1 ⁇ 2 inch overlap in the length direction of the lapshears for an adhesive bond to develop.
  • the bondline gap of the joint was determined by the wire diameter, viz. 0.125 mm.
  • the bonds were left for 84 hours at room temperature to cure.
  • the bond strengths were measured in a tensile shear mode using conventional tensile testing equipment. The results are summarised as follows:
  • Light sensitive c ⁇ npositions were prepared by blending together the following ingredients in parts by weight:
  • Composition 8A of the present invention is clearly polymerisable to a tackfree coating by irradiation with visible light, whereas prior art composition 8B is sensitive only to ultraviolet light.
  • 4-allyloxy-3-methoxypropenylbenzene was prepared by refluxing a stirred mixture of isoeugenol (164 g), allylbromide (133 g) and potassium carbonate (278 g) in dry acetone (700 mis) for 18 hours. Removal of the solids and solvent gave a crude product (208 g) which was vacuum distilled to yield 130 g of pure 4-allyloxy-3-methoxy-prop-1-enylbenzene (b.p. 104-118°C at 0.1 mbar).
  • composition 10A of the present invention is clearly superior to prior art composition 10C.
  • the results obtained with composition 10B demonstrate the advantage of incorporating a peroxidic material into the formulation.
  • Composition 10A is not suitable as a UV sensitive material however due probably to a UV light induced acid catalysed dimerization of the s-methyl substituted styrene function of the diene component. The development of an intense green colour in this composition during UV irradiation is an indication of this reaction.
  • a light sensitive thiol/ene composition was prepared by dissolving together the following material s:
  • SPILAC T-510-7 Showa Highpolymer Co., Tokyo
  • 96 ⁇ 6 -cumene
  • ⁇ 5 -cyclopentadienyl
  • a light sensitive thiol/ene composition was prepared by blending together the following ingredients in parts by weight:
  • a coating of the composition was prepared and the cure examined following irradiation 1 cm under the visible light source L4 as described in Example 3. The coating was found to be fully cured after 90 secs exposure. A similar composition but wi thout the ⁇ -arene and hydroperoxide ingredients fai led to cure under the same conditions.
  • the resin was dissolved in 90 mis of dichloromethane, washed with 2 x 100 ml portions of water and dried over sodium sulphate. Removal of the solvent under reduced pressure yielded 18. 3 g of a brown viscous resin which was shown by gel permeation chromatography to consist of one major component, higher in molecular weight than either of the starting compounds and a minor component identified as the starting anhydride.
  • the major component is believed to be the bis(norborn ene imide) having the formula:
  • a light sensitive composition was prepared by dissolving the following ingredients together:
  • Blend A (Example 3) 96
  • Coatings of the composition were prepared as described in Example 3. Tackfree and through curing times were measured following irradiation from the various light sources as described also in Example 3. The results obtained are as follows: Light Source Distance from Source (cms) Cure Time
  • Light sensitive compositions were prepared by blending together the following ingredients in parts by weight:
  • Blend A (Example 3) 80 80 bis(norbornene imide) of Example 15 20 20 ( ⁇ 6 -cumene)( ⁇ 5 -cyclopentadienyl) iron hexafluorophosphate 2 - Cumene hydroperoxide 2 2 2,2-dimethoxy-2-phenylacetophenone - 2
  • composition 17A was poured into an open-topped cylindrical mould as described in Example 16 and irradiated under light source L1, 30 cms from the lamp, for 60 secs. After this time composition 17A was found to have completely gelled through the 4 mm depth whereas composition 17B had cured only to a depth of 0.5 mm, the rest of the material remaining liquid.
  • a similar result was obtained when the samples were poured into an open-topped cylindrical mould 8mm in diameter and 4mm in depth and the filled mould exposed to UV/visible light from a SUPERLITE 201 (high pressure mercury light source supplied by Lumatec GmbH, Kunststoff, W. Germany) through a 1m long light guide. The light system was fitted with a filter which cut-off all visible light with wavelengths greater than 530nm. Thesamples were placed 10 mm directly below the tip of the lightguide. After 3 mins. exposure, sample 17A had completely cured through 4mm depth forming a solvent insoluble hard gel, whereas Sample 17B had cured only in a surface layer.

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

Abstract

Une composition polymérisable à la lumière visible comprend: 1) un matériau polymérisable à radical libre tel qu'un ou plusieurs monomères et/ou prépolymères contenant des groupes acrylates ou méthacrylates ou une combinaison monomère copolymérisable basée sur un polythyol ou un polyène; 2) un complexe métallique pi-arène de formule (I) dans laquelle a représente 1 ou 2 et n et q, indépendamment l'un de l'autre, représentent un nombre entier compris entre 1 et 3, M représente le cathium d'un métal monovalent à trivalent parmi les groupes IVb, VIIb, VIII ou Ib du système périodique, m est un nombre entier correspondant à la valence de L + q, Q représente un halogène et L est un métal ou un non métal, avec une valence comprise entre 2 et 7, R1 représente pi-arène et R2 représente pi-arène ou bien l'anion de pi-arène. 3) un accélérateur à radical libre tel qu'un composé pyroxide ou hydropyroxyde. Plus particulièrement, le complexe métallique pi-arène est un sel complexe eta6, eta5 d'un cation d'arène de fer et un anion non nucléophyle de formule (VII) dans laquelle R6 reprrésente eta6 arène sélectionné parmi le benzène, des alkylbenzènes, des alkyloxybenzènes, des halobenzènes, des haloalkylbenzènes, du naphtalène, des alcoxynaphthalènes, des alkylnaphtalènes, des halonaphtalènes, le biphényle, l'indène, le pyrène ou le diphénylsulfure; R7 représente l'anion d'un composé cyclopentadiényle, L représente un métaloïde ou un métal bivalent à heptavalent, Z est un halogène et k est égal à 1 plus la valence de L.
PCT/US1987/002619 1986-10-14 1987-10-13 COMPOSITIONS A RADICAL LIBRE POLYMERISABLES A LA LUMIERE VISIBLE ET CONTENANT DES COMPLEXES METALLIQUES pi-ARENE WO1988002879A1 (fr)

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US91800586A 1986-10-14 1986-10-14
US918,005 1986-10-14

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0421512A1 (fr) * 1989-10-03 1991-04-10 Chimia Prodotti E Processi Srl Sensibilisation et stabilisation de composés organométalliques agissant comme photocatalyseurs et photosensibilisateurs dans des polymerisations radicalaires photochimiques
US5102924A (en) * 1990-08-16 1992-04-07 Minnesota Mining And Manufacturing Company Polymeric mixtures and process therefor
US5212210A (en) * 1992-03-18 1993-05-18 Minnesota Mining And Manufacturing Company Energy curable compositions having improved cure speeds
FR2686607A1 (fr) * 1992-01-24 1993-07-30 Celliose Lobo Entreprise Systeme photosensible sous irradiation visible et ultra-violette pour compositions filmogenes pigmentees photoreticulables.
US5238744A (en) * 1990-08-16 1993-08-24 Minnesota Mining And Manufacturing Company Tough polymeric mixtures
US5252694A (en) * 1992-01-22 1993-10-12 Minnesota Mining And Manufacturing Company Energy-polymerization adhesive, coating, film and process for making the same
US5462797A (en) * 1990-09-05 1995-10-31 Minneapolis Mining And Manufacturing Company Energy curable pressure-sensitive adhesive compositions
US5521227A (en) * 1990-04-23 1996-05-28 Minnesota Mining And Manufacturing Company Energy curable cationcally and free-radically polymerizable pressure-sensitive compositions
US6433036B1 (en) 1997-02-27 2002-08-13 Loctite Corporation Radiation-curable, cyanoacrylate-containing compositions
WO2006043009A1 (fr) * 2004-10-22 2006-04-27 Astrium Sas Rigidification de structures a deploiement par gonflage, en particulier a usage spatial
WO2018005416A1 (fr) * 2016-06-30 2018-01-04 3M Innovative Properties Company Composition de thiol-ène à double durcissement, comprenant un polythiol, un composé insaturé, un photoinitiateur et un hydroperoxyde organique, ainsi qu'un agent d'étanchéité polymère réticulé préparé à partir de cette dernière destiné à être utilisé dans le domaine aérospatial
WO2020128806A1 (fr) * 2018-12-20 2020-06-25 Ppg Industries Ohio, Inc. Compositions catalytiques et compositions à base de thiolène à vie en pot prolongée
US20200199300A1 (en) * 2017-06-09 2020-06-25 Prc-Desoto International, Inc. Dual Cure Sealants

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DE1906701A1 (de) * 1968-02-12 1969-12-18 Gaf Corp Photopolymerisierbares Praeparat sowie dessen Verwendung bei der Herstellung von Photoaetzgruenden
FR2033674A5 (fr) * 1969-03-28 1970-12-04 Eastman Kodak Co
EP0014785A1 (fr) * 1979-02-12 1980-09-03 General Electric Company Procédé de revêtement et compositions réticulables
EP0109851A2 (fr) * 1982-11-22 1984-05-30 Minnesota Mining And Manufacturing Company Compositions polymérisables par apport d'énergie contenant des initiateurs organométalliques
EP0126712A1 (fr) * 1983-05-18 1984-11-28 Ciba-Geigy Ag Composition durcissable et son utilisation
EP0144148A2 (fr) * 1983-10-28 1985-06-12 LOCTITE (IRELAND) Ltd. Compositions photodurcissables contenant des prépolymères durcissant par deux méthodes distinctes
EP0152377A2 (fr) * 1984-02-10 1985-08-21 Ciba-Geigy Ag Compositions durcissables et leur emploi
EP0186626A2 (fr) * 1984-12-20 1986-07-02 Ciba-Geigy Ag Titanocènes et compositions polymérisables par radiation contenant ces titanocènes
EP0221010A1 (fr) * 1985-09-23 1987-05-06 Ciba-Geigy Ag Système de photo-initiation pour compositions polymérisables par vote radicalaire

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1906701A1 (de) * 1968-02-12 1969-12-18 Gaf Corp Photopolymerisierbares Praeparat sowie dessen Verwendung bei der Herstellung von Photoaetzgruenden
FR2033674A5 (fr) * 1969-03-28 1970-12-04 Eastman Kodak Co
EP0014785A1 (fr) * 1979-02-12 1980-09-03 General Electric Company Procédé de revêtement et compositions réticulables
EP0109851A2 (fr) * 1982-11-22 1984-05-30 Minnesota Mining And Manufacturing Company Compositions polymérisables par apport d'énergie contenant des initiateurs organométalliques
EP0126712A1 (fr) * 1983-05-18 1984-11-28 Ciba-Geigy Ag Composition durcissable et son utilisation
EP0144148A2 (fr) * 1983-10-28 1985-06-12 LOCTITE (IRELAND) Ltd. Compositions photodurcissables contenant des prépolymères durcissant par deux méthodes distinctes
EP0152377A2 (fr) * 1984-02-10 1985-08-21 Ciba-Geigy Ag Compositions durcissables et leur emploi
EP0186626A2 (fr) * 1984-12-20 1986-07-02 Ciba-Geigy Ag Titanocènes et compositions polymérisables par radiation contenant ces titanocènes
EP0221010A1 (fr) * 1985-09-23 1987-05-06 Ciba-Geigy Ag Système de photo-initiation pour compositions polymérisables par vote radicalaire

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0421512A1 (fr) * 1989-10-03 1991-04-10 Chimia Prodotti E Processi Srl Sensibilisation et stabilisation de composés organométalliques agissant comme photocatalyseurs et photosensibilisateurs dans des polymerisations radicalaires photochimiques
US5521227A (en) * 1990-04-23 1996-05-28 Minnesota Mining And Manufacturing Company Energy curable cationcally and free-radically polymerizable pressure-sensitive compositions
US5102924A (en) * 1990-08-16 1992-04-07 Minnesota Mining And Manufacturing Company Polymeric mixtures and process therefor
US5238744A (en) * 1990-08-16 1993-08-24 Minnesota Mining And Manufacturing Company Tough polymeric mixtures
US5462797A (en) * 1990-09-05 1995-10-31 Minneapolis Mining And Manufacturing Company Energy curable pressure-sensitive adhesive compositions
US5252694A (en) * 1992-01-22 1993-10-12 Minnesota Mining And Manufacturing Company Energy-polymerization adhesive, coating, film and process for making the same
US5310840A (en) * 1992-01-22 1994-05-10 Minnesota Mining And Manufacturing Company Energy-polymerizable adhesive, coating and film
US5399637A (en) * 1992-01-22 1995-03-21 Minnesota Mining And Manufacturing Company Energy-polymerizable adhesive, coating, and film
FR2686607A1 (fr) * 1992-01-24 1993-07-30 Celliose Lobo Entreprise Systeme photosensible sous irradiation visible et ultra-violette pour compositions filmogenes pigmentees photoreticulables.
US5212210A (en) * 1992-03-18 1993-05-18 Minnesota Mining And Manufacturing Company Energy curable compositions having improved cure speeds
US6906112B1 (en) 1997-02-27 2005-06-14 Henkel Corporation Radiation-curable, cyanoacrylate-containing compositions
US6433036B1 (en) 1997-02-27 2002-08-13 Loctite Corporation Radiation-curable, cyanoacrylate-containing compositions
US6726795B1 (en) 1997-02-27 2004-04-27 Stan Wojciak Radiation-curable, cyanoacrylate-containing compositions
WO2006043009A1 (fr) * 2004-10-22 2006-04-27 Astrium Sas Rigidification de structures a deploiement par gonflage, en particulier a usage spatial
US8025942B2 (en) 2004-10-22 2011-09-27 Astrium Sas Rigidification of structures to be deployed by inflating, particularly for use in space
US11041049B2 (en) 2016-06-30 2021-06-22 3M Innovative Properties Company Dual curable thiol-ene composition, comprising a polythiol, an unsaturated compound, a photoinitiator and an organic hydroperoxide, as well as a cross-linked polymer sealant prepared therefrom for use in aerospace
WO2018005416A1 (fr) * 2016-06-30 2018-01-04 3M Innovative Properties Company Composition de thiol-ène à double durcissement, comprenant un polythiol, un composé insaturé, un photoinitiateur et un hydroperoxyde organique, ainsi qu'un agent d'étanchéité polymère réticulé préparé à partir de cette dernière destiné à être utilisé dans le domaine aérospatial
CN109451742A (zh) * 2016-06-30 2019-03-08 3M创新有限公司 包含多硫醇、不饱和化合物、光引发剂和有机氢过氧化物的可双重固化的硫醇-烯组合物以及在航空航天中使用的由其制备的交联聚合物密封剂
US11655340B2 (en) * 2017-06-09 2023-05-23 Prc-Desoto International, Inc. Dual cure sealants
US20200199300A1 (en) * 2017-06-09 2020-06-25 Prc-Desoto International, Inc. Dual Cure Sealants
US10981158B2 (en) 2018-12-20 2021-04-20 Ppg Industries Ohio, Inc. Catalytic compositions and thiolene-based compositions with extended pot life
US20210170382A1 (en) * 2018-12-20 2021-06-10 Ppg Industries Ohio, Inc. Catalytic compositions and thiolene-based compositions with extended pot life
CN113227213A (zh) * 2018-12-20 2021-08-06 Ppg工业俄亥俄公司 催化组合物和具有延长的适用期的基于硫醇烯的组合物
AU2019407129B2 (en) * 2018-12-20 2022-04-21 Ppg Industries Ohio, Inc. Catalytic compositions and thiolene-based compositions with extended pot life
US11628431B2 (en) 2018-12-20 2023-04-18 Ppg Industries Ohio, Inc. Catalytic compositions and thiolene-based compositions with extended pot life
WO2020128806A1 (fr) * 2018-12-20 2020-06-25 Ppg Industries Ohio, Inc. Compositions catalytiques et compositions à base de thiolène à vie en pot prolongée
CN113227213B (zh) * 2018-12-20 2023-09-05 Ppg工业俄亥俄公司 催化组合物和具有延长的适用期的基于硫醇烯的组合物

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