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WO1989003816A1 - Ethers epoxydes divinyliques - Google Patents

Ethers epoxydes divinyliques Download PDF

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Publication number
WO1989003816A1
WO1989003816A1 PCT/US1988/003197 US8803197W WO8903816A1 WO 1989003816 A1 WO1989003816 A1 WO 1989003816A1 US 8803197 W US8803197 W US 8803197W WO 8903816 A1 WO8903816 A1 WO 8903816A1
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Prior art keywords
product
och
value
coating
formula
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
PCT/US1988/003197
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English (en)
Inventor
James A. Dougherty
Fulvio J. Vara
Lowell R. Anderson
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.)
GAF Corp
Original Assignee
GAF Corp
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
Priority claimed from US07/109,676 external-priority patent/US4766252A/en
Priority claimed from US07/194,619 external-priority patent/US4828873A/en
Application filed by GAF Corp filed Critical GAF Corp
Publication of WO1989003816A1 publication Critical patent/WO1989003816A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
    • C07D303/22—Ethers with hydroxy compounds containing no oxirane rings with monohydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/14—Unsaturated ethers
    • C07C43/15—Unsaturated ethers containing only non-aromatic carbon-to-carbon double bonds
    • C07C43/16—Vinyl ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
    • C07D303/24—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy 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
    • C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F16/12—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F16/32—Monomers containing two or more unsaturated aliphatic radicals

Definitions

  • this invention relates to novel compounds of the vinyl ether type.
  • the invention in another aspect relates to the preparation of said vinyl ethers and in a third aspect the invention pertains to the use of said vinyl ethers in an adhesive and protective coating formulations including formulation for metal and plastic materials.
  • polyepoxy compounds such as the cycloaliphatic diepoxides, monoepoxides and glycol ethers. These compounds are generally formulated in solvents or emulsified with water and reacted with typical epoxy hardeners such as epoxy polyamides, polyamines, anhydrides, melamines, imidazoles and acids.
  • typical epoxy hardeners such as epoxy polyamides, polyamines, anhydrides, melamines, imidazoles and acids.
  • these formulations pollute the atmosphere since the solvent must be evaporated in order to form a usable coating.
  • the alternative of solvent recovery is found to be uneconomical and therefore not widely practiced.
  • Water emulsified epoxy coatings also reguire evaporation which, due to the high heat of water vaporization, is also uneconomical and difficult to drive to completion.
  • a solvent free coating formulation comprising a cross-linkable base resin, a cycloaliphatic epoxy diluent and a cross-linking initiator.
  • a solvent free coating formulation comprising a cross-linkable base resin, a cycloaliphatic epoxy diluent and a cross-linking initiator.
  • the cycloaliphatic epoxy compounds react slowly with the polyepoxy resin resulting in a lack of resistance to common polar solvents such as methyl ethyl ketone, acetone, alcohols, etc.
  • the polyepoxy compounds produce brittle coatings unless substantial amounts of a flexibilizing agent, such as tripropylene glycol is added to the formulation.
  • Another object of this invention is to provide an adhesive protective coating suitable for thin layer application which shows high resistance to chemical solvents.
  • Still another object of the invention is to provide a formulation which will accept a high level of pigment loading and which possesses good wear resistance for lettering and designs which may be printed on an uncoated surface.
  • Still another object is to provide a formulation which possesses wear and slip resistance for lettering and/or decorative designs which may be imprinted on the surface of a substrate over which the formulation is coated.
  • Another object is to provide an economical and commercially feasible method for preparing the compounds of the present invention.
  • Yet another object is to provide new and novel compounds of the vinyl ether type.
  • R is hydrogen or methyl
  • x and x' have a value of from 0 to 3; with the proviso that when n and n' are positive integers, x and x' are zero and when x and x' are positive integers, n and n' are zero.
  • the compounds of this invention are prepared by a transvinylation reaction according to the general equation
  • x" is an integer having a value of from 1 to 3;
  • R is hydrogen or methyl;
  • y is an integer having a value of from 3 to 5;
  • y' , y" and y"' are integers the sum of which is from 4 to 24, and
  • x and x' are integers having a value of from 0 to 3.
  • the alcoholic reactant (F) is mixed with the vinyl ether coreactant (G) or (H) in an amount at least sufficient to convert all of the hydroxy sites in compound (F) to vinylether groups. More specifically, a ratio of hydroxy group to vinyl ether group between about 1:1 and 1:5, preferably 1:1.5 to 1:3 for each hydroxylated site in reactant (F) at which transvinylation is to be effected can be employed.
  • These coreactants are required to have low volatility so that they will not be vaporized under the ensuing reaction conditions.
  • Preferred coreactants have a volatility less than 55°C. at 1.5 mm Hg and a boiling point greater than 250°C.
  • a soluble mercury salt catalyst, between about 1 and about 10% of the total mixture is added to initiate the reaction.
  • mercuric acetate is the preferred catalyst
  • other mercury or palladium compounds such as mercuric sulfate, mercuric nitrate, mercuric chloride and dibenzonitrilodichloro palladium (II) i.e. (C 6 H 5 CN) 2 PdCl 2
  • II dibenzonitrilodichloro palladium
  • the resulting mixture is reacted at a temperature between about 25°C. and 250°C, preferably between about 60oC. and about 150°C. and below the decomposition temperature of the epoxide and then vacuum distilled to recover product.
  • the distillation pressures employed may range between about 0.5 and about 50 mm Hg, preferably between about 1 and about 10 mm Hg.
  • the reaction is conducted over a period of from about 1 to about 3 hours; however, the process may be carried out in a continuous manner or with intermittent product removal. In either case the product removal shifts the equilibrium of the product lean reaction mixture to the production of more product.
  • the distillation can be halted and the reaction mixture allowed to re-equilibrate for about 5 to 30 minutes, after which the distillation and product take-off is resumed and additional product collected. This operation can be repeated as many times as desired to drive the reaction toward completion.
  • the desired product and a small amount of hydroxy ether by-product withdrawn from the reaction zone is subjected to closely controlled fractional distillation using from 10 to 30 plates, preferably from 12 to 25 plates under vacuum and at a temperature between about 40°C. and about 100°C. Close temperature control is particularly important in the production of each of the divinyl ethers herein disclosed since there is a very small difference in boiling point between the product and the unreacted alcohol component.
  • reaction for the most preferred epoxy product .of this invention may be represented as follows.
  • the mole ratio of the epoxydiol to the divinylated coreactant is between about 1:1 and about 1:2.
  • the most preferred divinyl alkene products of the present reaction may be represented as follows.
  • w and w' have a value of from 0 to 4 and the mole ratio of hydroxyl group to vinyl moiety is between about 1:1 and about 1:2.
  • each of Z and Z ' is independently vinyl , hydroxy, or the same as C and C" depending on the transvinylation (-OH) sites in the alcoholic reactant (F) and the terminal groups in the coreactant (G) or (H) and B, C, C', C", R, n, n', x, x', x", y, y' , y" and y"' are as defined above.
  • the product of the above reaction is obtained in at least 80% purity and can be further purified by extraction with a polar solvent or selective solubilization of by-product with for example, ether, followed by evaporation.
  • the divinyl co-reactant is a liquid having low volatility, for example less than 1.5 mm Hg at 55oC. and a boiling point greater than 250°C.
  • a large molar excess of a volatile vinyl ether may be combined with the precursor alcohol to promote the transvinylation reaction.
  • the volatile alcohol and unreacted volatile vinyl ether are then removed by distillation to leave the non-volatile vinyl ether behind.
  • the alkoxylated divinylethers of the present invention can be prepared by direct vinylation wherein the alkoxylated diol and an alkali metal hydroxide catalyst, e.g. KOH or NaOH, are introduced into an autoclave, the autoclave is purged with nitrogen and pressured to about 100 pounds with acetylene. The reaction is effected at about 150°C. for a period of from about 6 to 8 hours after which the autoclave is opened and the liquid contents distilled under a vacuum of from about 1 to about 10 mm Hg to recover the alkoxylated divinylether product.
  • an alkali metal hydroxide catalyst e.g. KOH or NaOH
  • the product obtained from the fractional distillation of the transvinylation reaction can be directly formulated into a composition suitable for coating metal or plastic surfaces.
  • the present compounds have high cross-linking capability which takes place at the multiple unsaturated sites and are characterized by rapid curability by heat or radiant energy. It has been found that the speed of curing for formulations containing the present compounds is seven times faster than those consisting of epoxides.
  • the present compounds possess high adhesion to metals such as for example aluminum surfaces and impart excellent abrasion resistance.
  • a surface protected with this compound in a cross-linkable formulation is provided with a pigment loadable coating which can be used on plastic food bags or metal cans andone which is resistant to solvent deterioration. These coatings also protect against metal corrosion and moisture penetration.
  • Another advantage realized by the incorporation of the present vinyl ethers is their ability to impart flexibility to the coating material so that no extraneous flexibilizing agent need be added to the coating composition. This represents an improvement over coatings employing saturated counterparts.
  • n and n' have a value of from about 0 to about 4 over others is their resistance to common solvents including ketones, alcohols, esters and aromatic solvents. As the value of n or n' increases, the coatings in which the compound is formulated become more flexible; although somewhat lowered in solvent resistance.
  • compositions of the present invention include between about 30 wt. % and about 55 wt. % of the present compound; between about 65 wt. % and about 45 wt. % of an adhesive base resin such as an epoxy resin or a cyclo aliphatic epoxide; between about 0.5 wt. % and about 6 wt. % of a cross-linking initiator and between about 0 and about 3 wt. % of a surfactant.
  • the base resins of the present compositions are cross-linkable components which impart adhesion and hardness to the composition and are preferably those which contain one or more epoxy and/or olefinically unsaturated groups.
  • Suitable examples of such compounds include diglycidyl ethers of bisphenol A having an epoxy equivalent weight between about 150 and about 10,000, polyglycidyl ethers of phenol formaldehyde resin (novolac), and cycloaliphatic epoxides, and the like. Those which contain olefinic unsaturation include unsaturated polyesters and polyethers.
  • the present compound is mixed at a temperature of from about 20oC. to about 50°C. under atmospheric pressure with the adhesive base resin in a mole ratio of between about 20:80 and about 80:20, preferably in a mole ratio of from about 35:65 to about 65:35 until a homogeneous mixture is obtained.
  • the surfactant and the photoinitiator are then added to the resulting mixture which can be then coated on a surface such as a surface of aluminum, steel, chromium, copper, tin-plate, brass, bronze, tin-free steel as used in cans for beer or beverages or on a plastic substrate such as a surface of polyester, polystyrene, acrylic and methacrylic polymer and the like.
  • Suitable photoinitiators used to induce cross-linking between the vinyl ether and the base resin include triphenyl sulfonium hexafluorophosphate, fluoroarsenate, fluoroammoniate, diazonium salts, aryl ferrocene and fluorophosphate.
  • deblockable acids such as onium salts, iron-arene complexes or para-toluene sulfonic acid complexes can be employed as cross-linking initiators. Specific initiators for electron beam curing are illustrated in the following Table A.
  • sulfonium salts may be employed for UV curing. Structural features associated with the cationic portion of the photoinitiator determine its absorption characteristics, its photosensitivity, and ultimately, the rate of generation of the initiating acidic species. In the polymerization of the present divinyl ether monomers where the rates of both initiation and propagation are very rapid, the overall rate of UV-cure will be determined by the photosensitivity of the particular photoinitiator used. Altering the structure of the cation by introduction of appropriate chromophors on the aromatic rings can affect the cure rates.
  • photosensitizers Another means of increasing the efficiency of cationic photoinitiators is by the use of photosensitizers. These compounds absorb light in a region of the spectrum in which the photoinitiator is transparent and then transfer that energy to the photoinitiator, inducing its photolysis. In addition to improving the overall efficiency of these photoinitiators by increasing their effective light absorption, photosensitizers make it possible to carry out the photopolymerization of the multifunctional vinyl ethers using visible light. For example, a solution of 0.5% triphenylsulfonium hexafluorophosphate in diethyleneglycol divinyl ether containing 0.05% perylene will cure to a tack-free 2 mil film in 5 seconds when exposed to a G.E. DWY photoflood lamp. The emission of this lamp lies entirely in the visible region. However, when perylene is omitted, no curing is observed even after 1 minute irradiation.
  • thermoset curing boron trifluoride complexes, para-toluene sulfonic acid complexes and trifluoromethane sulfonic acid complexes are particularly recommended.
  • composition containing the present vinyl ether, the base resin, the cross-linking initiator and optionally surfactant is coated on a substrate in a thickness between about 0.02 and about 30 mils, preferably between about 0.1 to 3 mils and most preferably between about 0.2 to 1 mil.
  • the coated substrate is cured to a tack-free state at an energy for light radiation of between about 0.15 joules/cm 2 and about 225 joules/cm 2 , preferably between about 6 joules/cm 2 and about 105 joules/cm 2 .
  • an energy of between about 0.1 and about 5 megarads is employed. Any source of radiation curing can be employed for the present process.
  • Rapid transformation to a tack free state is particularly important on continuous coating lines in order that tack free parts can be conveniently unloaded and stacked or fabricated before post baking.
  • the present vinyl ether formulations become tack free about 7 times faster than other vinyl ether formulations.
  • the curing is completed by a post-bake for a period of from about 2 to about 20 minutes at a temperature of from about 50° to about 200°C., preferably from about 5 to about 15 minutes at a temperature of from about 125° to about 175°C.
  • curing can be effected at a temperature of between about 25°C. and about 35°C. for a period of from about 3 to about 14 days, preferably from about 6 to about 9 days.
  • thermoset process When curing speed is not important, a thermoset process can be employed. In this process, merely heating to between about 25°C. and about 250°C, preferably between about 50°C. and about 200°C, for a period of 5 to about 30 minutes in the presence of a Lewis acid, e.g. trifluoromethyl sulfonic acid or any of those mentioned above, is sufficient to provide a tack-free protective coating.
  • a Lewis acid e.g. trifluoromethyl sulfonic acid or any of those mentioned above
  • the present formulations function as reactive diluents when used with printing ink, pigment and the like. These coloring materials are uniformly dispersed in the coating mix, applied in a predetermined pattern in one or more colors and in one or more applications and then subjected to curing as described above. During curing the coating is internally cross-linked which involves bonding between epoxy and vinyl, vinyl and vinyl and vinyl and hydroxy. Under optimum conditions with preferred initiators, the present composition is capable of immediate cure such that 700 feet per minute of film can be cured to a tack-free condition. Such rapidity in curing represents a great improvement over prior UV curable compositions which require at least 1 minute per 100 feet of film.
  • the vinyl ethers of this invention are their resistance to common solvents including ketones, alcohols, esters and aromatic solvents. Also, because of the alkoxylation, the coatings also exhibit a high degree of flexibility which may be enhanced by the presence of alkyleneoxy groups lacking from other somewhat relatedcompositions and have improved substrate substantivity, as well as excellent solvent resistance. These properties make the present ethers useful in any coating formulation including radiation cured or heat cured coatings.
  • the distillation can be halted and the reaction mixture allowed to re-equilibrate for the formation of additional product.
  • the distillation and product take-off is then resumed and additional product collected. Re-equilibration can be repeated as many times as desired to maximize product yield.
  • Example 1 is repeated, except that the 200 g. of the propoxylated coreactant
  • Example 1 is repeated, except that 65 g. of mono-vinylated epoxybutanol having the formula
  • Example 2 The same product in about the same amount and purity as in Example 1 is obtained.
  • the by-product in this case is the corresponding ethoxylated glycerol derivative.
  • Example 1 is repeated except that 66 g. of the epoxydiol
  • Example 5 is repeated, except that the 205 g. of the propoxylated coreactant
  • Example 5 is repeated, except that 68 g. of 1-hydroxy-4-vinyl-butene-2 was reacted with 880 g. of an ethoxylated mono vinyl glycerol having the formula
  • Example 5 in about the same amount and purity as in Example 5 is obtained; however the by-product in this case is the corresponding ethoxylated glycerol derivative.
  • Example 5 is repeated except that 502 g. of
  • the above formulations were individually coated on aluminum panels by hand draw-down using a number 3 Mayer bar to give a coating thickness of about 6.5 microns.
  • the panels were then subjected to a UV light exposure of 15 joules/cm by passing them under two 200 watt/inch UV lamps at 100 feet/minute. This was followed by a thermal bake at 177°C. for 10 minutes.
  • the coatings were then subjected to a Cross-Cut Tape Test (ASTM D-3359-K-B), a Boiling Water Immersion Test and a solvent resistance test. For the water immersion, the coated panel was immersed in boiling water for 30 minutes, after which it was removed, dried and subjected to adhesion test ASTM D-3359-K-B.
  • Composition No. 3 was significantly less viscous than Composition 1. Accordingly, thin films of the type shown in Composition 3, suitable for coating magnetic tapes and other recording media, could be produced. This property, together with the markedly increased flexibility and solvent resistance of the compositions incorporating the present divinyl epoxy ethers render them excellent candidates for coating electron beam recording films and wire like filaments.
  • Example 9 was repeated except that diethoxylated 2-butene-1,4-divinylether was substituted for compound 5 in Composition No. 13 (Compositions 4, 5 and 6 below corresponding to 1, 2 and 13 respectively in Example 9).
  • the 6.5 micron coatings on aluminum panels were subjected to the adhesion, boiling water submersion reverse impact and solvent resistance tests described above and the results are reported in following Table III.
  • Example 10 was repeated with the same formulations except that the percent sulfonium salt initiator was reduced to 1.5 wt. % (Compositions 7, 8 and 9 below corresponding to 4, 5 and 6 respectively). Coatings of 6.5 microns were applied to aluminum panels as in Example 10 and were cured by an electron beam exposure of 1.5 Mrad. After a thermal bake of 10 minutes at 177°C. the coated panels were subjected to the same tests as set forth in Example 10. The results are as reported in Table IV.
  • Example 10 was again repeated with the same formulations except that the sulfonium salt photoinitiator was replaced with 1.5 wt. % of the diethylammonium salt of trifluoromethanesulfonic acid (Compositions 10, 11 and 12 below corresponding to 4, 5 and 6 respectively). Coatings of 6.5 micron were applied on aluminum panels as in Example 10, were cured with a thermal bake of 15 minutes at 177°C. and the coatings subjected to the same tests as in Example 10. The results are as reported in following Table V. TABLE V
  • Example 9 was repeated with the same formulations except that the percent sulfonium salt initiator was reduced to 1.5 wt. % (Compositions 14, 15 and 16 below corresponding to 1, 2 and 3 respectively). Coatings of 6.5 microns were applied to aluminum panels as in Example 9 and were cured by an electron beam exposure of 1.5 Mrad. After a thermal bake of 10 minutes at 177°C. panels were subjected to the same tests as set forth in Example 9. The results are as reported in Table VI.
  • Example 9 was again repeated with the same formulations except that the sulfonium salt photoinitiator was replaced with 1.5 wt. % of the diethylammonium salt of trifluoromethanesulfonic acid (Compositions 17, 18 and 19 below corresponding to 1, 2 and 3 respectively). Coatings of 6.5 micron were applied on aluminum panels as in Example 9, were cured with a thermal bake of 15 minutes at 177°C. and the coatings subjected to the same tests as in Example 9. The results are as reported in following Table VII.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)

Abstract

Cette invention concerne des éthers divinyliques ayant la formule (I) dans laquelle R représente l'hydrogène ou un méthyle; Y est le radical bivalent (1) ou (2); n et n' ont une valeur comprise entre 0 et 24 et n et n' sont des nombres entiers positifs lorsque Y est (1); x et x' ont une valeur comprise entre 0 et 3, à condition que lorsque n et n' sont des nombres entiers positifs, x et x' ont la valeur zéro et lorsque x et x' sont des nombres entiers positifs, n et n' ont la valeur zéro. Cette invention concerne également la préparation et l'utilisation des éthers époxydes divinyliques décrits ci-dessus pour des revêtements en métal, en bois ou en plastique qui sont d'une grande résistance aux solvants et possèdent une flexibilité améliorée par rapport à des composés saturés similaires.
PCT/US1988/003197 1987-10-16 1988-09-19 Ethers epoxydes divinyliques Ceased WO1989003816A1 (fr)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
US10938987A 1987-10-16 1987-10-16
US07/109,676 US4766252A (en) 1987-10-16 1987-10-16 Solvent and stain resistant coatings
US109,389 1987-10-16
US109,676 1987-10-16
US19436888A 1988-05-16 1988-05-16
US194,619 1988-05-16
US194,368 1988-05-16
US07/194,619 US4828873A (en) 1987-10-16 1988-05-16 Solvent and stain resistant coating

Publications (1)

Publication Number Publication Date
WO1989003816A1 true WO1989003816A1 (fr) 1989-05-05

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PCT/US1988/003197 Ceased WO1989003816A1 (fr) 1987-10-16 1988-09-19 Ethers epoxydes divinyliques

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AU (1) AU2723588A (fr)
IL (1) IL87827A (fr)
WO (1) WO1989003816A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0646580A3 (fr) * 1993-09-16 1995-10-11 Ciba Geigy Ag Composés de vinyléther avec des groupes fonctionnels additionnels différents de vinyléther et leur utilisation dans la formulation de compositions durcissables.
JP2008163314A (ja) * 2006-12-07 2008-07-17 Nippon Carbide Ind Co Inc ポリプロピレングリコールジビニルエーテル
JP2014065665A (ja) * 2012-09-24 2014-04-17 Nippon Shokubai Co Ltd 不飽和ポリアルキレングリコール誘導体、その製造方法及び中間体
CN110483838A (zh) * 2015-05-29 2019-11-22 赛鲁斯股份有限公司 包封的聚合引发剂、聚合体系以及使用所述体系的方法

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US2201074A (en) * 1939-01-28 1940-05-14 Dow Chemical Co Unsaturated ethers and method of making same
US2841621A (en) * 1956-05-22 1958-07-01 Rohm & Haas Alkenyloxypolyethoxyethyl alkyl ethers
CA621813A (en) * 1961-06-13 Union Carbide And Carbon Corporation Process for the production of diethers of polyglycols
CA682727A (en) * 1964-03-24 I. Hoaglin Raymond Process for the production of diethers of polyglycols
US3594243A (en) * 1967-02-07 1971-07-20 Gen Aniline & Film Corp Formation of polymeric resists
US3786102A (en) * 1971-08-09 1974-01-15 Grace W R & Co Transvinylation catalyst
US4163809A (en) * 1975-10-06 1979-08-07 Scm Corporation Radiation polymerization of polymeric binder coating compositions
US4291087A (en) * 1979-06-12 1981-09-22 Rohm And Haas Company Non-woven fabrics bonded by radiation-curable, hazard-free binders

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA621813A (en) * 1961-06-13 Union Carbide And Carbon Corporation Process for the production of diethers of polyglycols
CA682727A (en) * 1964-03-24 I. Hoaglin Raymond Process for the production of diethers of polyglycols
US2201074A (en) * 1939-01-28 1940-05-14 Dow Chemical Co Unsaturated ethers and method of making same
US2841621A (en) * 1956-05-22 1958-07-01 Rohm & Haas Alkenyloxypolyethoxyethyl alkyl ethers
US3594243A (en) * 1967-02-07 1971-07-20 Gen Aniline & Film Corp Formation of polymeric resists
US3786102A (en) * 1971-08-09 1974-01-15 Grace W R & Co Transvinylation catalyst
US4163809A (en) * 1975-10-06 1979-08-07 Scm Corporation Radiation polymerization of polymeric binder coating compositions
US4291087A (en) * 1979-06-12 1981-09-22 Rohm And Haas Company Non-woven fabrics bonded by radiation-curable, hazard-free binders

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0646580A3 (fr) * 1993-09-16 1995-10-11 Ciba Geigy Ag Composés de vinyléther avec des groupes fonctionnels additionnels différents de vinyléther et leur utilisation dans la formulation de compositions durcissables.
US5605941A (en) * 1993-09-16 1997-02-25 Steinmann; Bettina Vinyl ether compounds having additional functional groups other than vinyl ether groups and the use thereof in the formulation of curable compositions
US5705316A (en) * 1993-09-16 1998-01-06 Ciba Specialty Chemicals Corporation Vinyl ether compounds having additional functional groups other than vinyl ether groups and the use thereof in the formulation of curable compositions
US5783615A (en) * 1993-09-16 1998-07-21 Ciba Specialty Chemicals Corporation Vinyl ether compounds having additional functional groups other than vinyl ether groups and the use thereof in the formulation of curable compositions
US5783712A (en) * 1993-09-16 1998-07-21 Ciba Specialty Chemicals Corporation Vinyl ether compounds having additional functional groups other than vinyl ether groups and the use thereof in the formulation of curable compositions
JP2008163314A (ja) * 2006-12-07 2008-07-17 Nippon Carbide Ind Co Inc ポリプロピレングリコールジビニルエーテル
JP2014065665A (ja) * 2012-09-24 2014-04-17 Nippon Shokubai Co Ltd 不飽和ポリアルキレングリコール誘導体、その製造方法及び中間体
CN110483838A (zh) * 2015-05-29 2019-11-22 赛鲁斯股份有限公司 包封的聚合引发剂、聚合体系以及使用所述体系的方法

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