WO1989003816A1

WO1989003816A1 - Divinyl epoxy ethers

Info

Publication number: WO1989003816A1
Application number: PCT/US1988/003197
Authority: WO
Inventors: James A. Dougherty; Fulvio J. Vara; Lowell R. Anderson
Original assignee: GAF Corp
Current assignee: GAF Corp
Priority date: 1987-10-16
Filing date: 1988-09-19
Publication date: 1989-05-05
Anticipated expiration: 1990-04-16
Also published as: IL87827A0; IL87827A; AU2723588A

Abstract

This invention relates to vinyl ethers having formula (I) wherein R is hydrogen or methyl; Y is the divalent radical (1) or (2); n and n' have a value of from 0 to 24 and n and n' are positive integers when Y is (1); 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 invention also relates to the preparation and use of the above divinyl epoxy ethers for metal, wood or plastic coatings which possess high resistance to solvents and improved flexibility over somewhat similar saturated compounds.

Description

DIVINYL EPOXY ETHERS

In one aspect this invention relates to novel compounds of the vinyl ether type.

In another aspect the invention 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.

BACKGROUND OF THE INVENTION

Many formulations have been proposed for coating metal and plastic surfaces, including 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. However, 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. To avoid these disadvantages, the use of a solvent free coating formulation comprising a cross-linkable base resin, a cycloaliphatic epoxy diluent and a cross-linking initiator has been proposed. Although such a formulation would be acceptable from an economical and environmental standpoint, it is known that 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. Still further, the polyepoxy compounds produce brittle coatings unless substantial amounts of a flexibilizing agent, such as tripropylene glycol is added to the formulation.

Another deficiency of the above formulated compounds is their inability to accept high levels of pigment loading before an unmanageable viscosity is reached.

Accordingly, it is an object of this invention to overcome the deficiencies of the coatings described above.

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. THE INVENTION

According to this invention there is provided novel ether compounds having the formula:

wherein

R is hydrogen or methyl;

Y is the divalent radical -CH=CH- or

n and n' have a value of from 0 to 24 and n and n' are positive integers when Y is -CH=CH-;

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.

Of the above compounds, those wherein n and n' are positive integers when Y is -CH=CH- and those wherein x and x' have a value of 4 when Y are

are preferred.

The compounds of this invention are prepared by a transvinylation reaction according to the general equation

+ a coreactant high boiling mono- or poly- vinyl ether reactant having the structure G or H.

wherein B is -OH or -OCH=CH₂; C, C' and C" are each hydrogen, C₁ to C₄ alkyl, C₁ to C₄ alkoxy or -(CH₂)_x"OCH=CH₂; 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. In the case where Y is -CH=CH- involving coreactant (H), it is essential that the vinyl groups be separated by more than 4 carbon atoms. If they are not, the monovinylated compound may undergo internal addition of the hydroxy group to the vinyl group and form a 5 or 6 membered ring; thus failing to provide the divinylated compound and destroying the cross-linking potential of the vinyl group.

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. Although 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. (C₆H₅CN)₂PdCl₂, may be substituted in whole or in part to induce transvinylation. 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.

In a batch process, 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. Thus, to maximize product yield, 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.

The reaction for the most preferred epoxy product .of this invention may be represented as follows.

wherein 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.

wherein 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.

The more general reaction can be expressed as follows:

wherein 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. In the most preferred embodiment, 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.

Alternatively, where the product vinyl ether is too non-volatile to distill, 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.

In another alternative when Y is -CH=CH- and n and n' are positive integers, 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.

Although purification of product may be required for some uses, e.g. in medicinal or cosmetic uses, removal of by-product to levels below about 15% is usually not required. Accordingly, 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. As can be seen from the product structural formula, 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.

A principal advantage of the alkoxylated divinylether alkenes wherein 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.

Generally coating 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. Generally, for radiation curing, 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.

For UV curing, sulfonium salts may be employed. 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. A comparison between the UV-cure rates of diethylene-glycol divinyl ether using three different triarylsulfonium salts having identical anions but varying in the structure of their cations is shown in Table B. For the same molar concentration of photoinitiators, the diphenyl-[(4-phenylthio)phenyl]. sulfonium salt, V, is considerably more efficient in cationic polymerization of the present divinyl ether monomers than other triarylsulfonium salts, due to its better UV absorption characteristics.

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.

For thermoset curing, boron trifluoride complexes, para-toluene sulfonic acid complexes and trifluoromethane sulfonic acid complexes are particularly recommended.

The 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. In radiation curing, the coated substrate is cured to a tack-free state at an energy for light radiation of between about 0.15 joules/cm² and about 225 joules/cm², preferably between about 6 joules/cm² and about 105 joules/cm². For electron beam radiation, 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.

After the tack-free state is achieved, 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. Alternatively, 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.

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.

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. One of the principal advantages of the vinyl ethers of this invention over others is 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.

Having thus generally described the invention, reference is now had to the following Examples. However it is to be understood that the scope of this invention is not intended to be limited to these embodiments but is extended to the general discussion above with modifications and alterations normally apparent to the skilled artisan and to the appended claims.

EXAMPLE 1

Into the pot of a 15 plate Oldershaw distillation column was introduced 52 g. of epoxybutanediol, 115 g. of triethylene glycol divinyl ether,

CH₂=CHO (CH₂CH₂O ) ₃CH=CH₂ and 10 g. of mercuric acetate. The mixture was heated to a pot temperature of 85°C. foe a few minutes and a first cut of 12.6 g. of product having the formula

was distilled off and collected in a few minutes within a 3° temperature range including 68°C. under a pressure of 1.5 mm Hg. The product was obtained in 76.6% purity and contained a minor amount of by-product having the formula H(OCH₂CH₂)OH. The product was identified by gas chromatography, NMR and infrared spectrum.

To maximize product yield, 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 2

Example 1 is repeated, except that the 200 g. of the propoxylated coreactant

is substituted therein. The same product as in Example 1 in about the same amount and purity is obtained. The by-product in this case is the corresponding propoxylated diol derivative,

EXAMPLE 3

Example 1 is repeated, except that 65 g. of mono-vinylated epoxybutanol having the formula

is reacted with 350 g. of an ethoxylated mono vinyl glycerol having the formula

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 4

Example 1 is repeated except that 66 g. of the epoxydiol

is substituted for 52 g. of the epoxybutanediol. The distillation product of the reaction,

is obtained in at least 70% purity and the by-product of the reaction is the same as that obtained in Example 1.

EXAMPLE 5

Into the pot of a 15 plate Oldershaw distillation column was introduced 52 g. of 2-butene-1,4-diol, 115 g. of triethylene glycol divinyl ether,

CH₂=CHO ( CH₂CH₂O)₃CH=CH₂

and 10 g. of mercuric acetate. The mixture was heated to a pot temperature of 85°C. for a few minutes and a first cut of 12.6 g. of product having the formula

CH₂=CHOCH₂-CH=CH-CH₂OCH=CH₂ was distilled off and collected in a few minutes within a 3° temperature range including 68°C. under a pressure of 1.5 mm Hg. The distillation was discontinued and the reaction mixture was allowed to stand for a period of 15 minutes during which the reaction mixture re-equilibrated. The distillation under the above conditions was then resumed. This incremental draw-off of product was repeated 3 times and product collected in an overall yield of 75% and 80% purity. The product contained a minor amount of by-product having the formula H(OCH₂CH₂)OH and was identified by gas chromatography, NMR and infrared spectrum.

EXAMPLE 6

Example 5 is repeated, except that the 205 g. of the propoxylated coreactant

is substituted therein. The same product as in Example 5 in about the same amount and purity is obtained; however, the by-product in this case is the corresponding propoxylated diol derivative,

EXAMPLE 7

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

The corresponding product

CH₂=CH(OCH₂CH₂)₂₀OCH₂CH=CHCH₂O ( CH₂CH₂O ) ₂₀CH=CH₂ ,

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 8

Example 5 is repeated except that 502 g. of

H(OCH₂CH₂)₁₂OCH₂CH=CHCH₂O(CH₂CH₂O)₁₂H

is substituted for 52 g. of 2-butene-1,4-diol. The distillation product of the reaction,

CH₂=CH(OCH₂CH₂)₁₂OCH₂CH=CHCH₂O(CH₂CH₂O)₁₂CH=CH₂ is obtained in at least 70% purity and the by-product of the reaction is the same as that obtained in Example 5.

EXAMPLE 9

Two commercial coating formulations (No. 1 and No. 2) and formulations of the present invention (No. 3 and No. 13) were prepared and compared. The components of these compositions are shown in following Table I.

All amounts are reported as wt. %.

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.

For the solvent resistance test, a methylethyl ketone saturated cheesecloth was rubbed across the surface of the coated panel under a constant pressure. The number of back and forth strokes needed to break through the coating was recorded. The reverse impact test was carried out by placing a coated panel face down on a die containing a 0.640 inch hole. A 0.625 inch pin with rounded tip was placed on the back of the panel directly over the hole. A 1 lb. weight was dropped, from varying heights, onto the pin causing rapid deformation of the panel and coating and the coating was examined for cracking. or crazing. The maximum energy the coating can absorb before failure was recorded. The results of these tests are reported in following Table II.

TABLE II

TEST COMPOSITIONS 1 2 13

Adhesion 100 100 100 100

Water Submersion 100 100 100 100

Solvent Resistance 23 >200 19

Reverse Impact (lbs at failure) <8 24 24

In addition to the above results, it was found that 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 10

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.

TABLE III

Composition

Test 4 5 6

Adhesion 100 100 100

Water Submersion 100 100 16 Solvent Resistance 2 5 70 Reverse Impact <8 24 32 EXAMPLE 11

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.

TABLE IV

Composition

Test 7 8 9

Adhesion 100 100 100

Water Submersion 100 100 100

Solvent Resistance 4 50 200

EXAMPLE 12

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

Test Composition

10 11 12

Adhesion 100 100 100

Water submersion 100 100 100

Solvent resistance 3 25 200

Reverse Impact < 8 18 24

EXAMPLE 13

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.

TABLE VI

Test Composition

14 15 16

Adhesion 100 100 100

Water Submersion 100 100 100

Solvent Resistance 4 50 >200 EXAMPLE 14

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.

TABLE VII

Test Composition

17 18 19

Adhesion 100 100 100

Water submersion 100 100 100

Solvent resistance 25 > 200

EXAMPLE 15

The cure speed in feet per minute and number of seconds to achieve a tack free conditions of coating compositions 1, 2, 13, 4, 5 and 6 reported in Examples 9 and 10 above, were calculated. The tack free state was determined by non-adhesion after touching the coated surface with a cottonball. The results of this determination are reported in following Table VIII. TABLE- VIII

Coating Composition 13

cure speed 100 700 700 100 700 700 tack free time 60 < 1 <1 60 <1 <1

Many alterations and variations of the above description and disclosure will become apparent to those skilled in the art. However, it is intended that such modifications and alterations be included within the scope of this invention.

Claims

DIVINYL EPOXY ETHERSWHAT IS CLAIMED IS:

1. The compound having the formula:

H₂C=CH(OCH₂CH)_nOCH₂(CH₂)_χ-Y-(CH₂)_χ'CH₂O(CHCH₂O)_n'CH=CH₂ | | R R

wherein

R is hydrogen or methyl;

Y is the divalent radical -CH=CH- or

2. The compound of Claim 1 wherein Y is -CH=CH- and n and n' each have a value of from 1 to 4.

3. The compound of Claim 1 wherein Y is

and x and x' each have a value of 2.

4. The process which comprises contacting, in the presence of a mercuric salt catalyst, a hydroxy compound having the formula

wherein Y is the divalent radical -CH=CH- or

R is hydrogen or methyl; B is hydrogen or -CH=CH₂, n" and n"' each have a value of from 0 to 24 when Y is -CH=CH-; x and x' each have a value of from 0 to

3 when Y is

with the proviso that n" and n" ' are zero when x and z' are positive integers and x and x' are zero when n" and n" ' are positive integers; reacting said hydroxy compound with a liquid vinyl ether reactant having the formulae

or a mixture thereof wherein D, D' and D" are each independently hydrogen, C₁ to C-₄, C₁ to C₄ alkoxy or -(CH₂)_x"OCH=CH₂;

x" is an integer having a value of from 1 to 4;

y has a value of from 3 to 5 and the sum of y' + y" + y"' is 4 to 24; conducting said reaction at a temperature between about 25° and about 250°C. and fractionally distilling the resulting reacted mixture at a temperature between about 40° and about 100°C. under from about 0.5 to about 50 mm Hg to recover a divinyl ether product having the formula

wherein n and n' each have a value of from 0 to 24 and R, Y, x and x' are as defined above.

5. The process of Claim 4 wherein the boiling point of said vinyl ether reactant is higher than that of said product.

6. The process of Claim 4 wherein reaction by-product is vaporized and separated from a higher boiling liquid product.

7. The process of Claim 4 wherein said hydroxy compound is added to said vinyl ether reactant.

8. The process of Claim 4 wherein the ratio of hydroxy compound to vinyl group of said vinyl ether reactant is between about 1:1 and about 1:5.

9. The process of Claim 4 wherein said vinyl ether reactant has the formula

CH₂=CH(OCH₂CH₂)₃OCH=CH₂

and Y in the product of the reaction is

10. The process of formulating a coating composition which comprises combining a crosslinkable base resin, a crosslinking initiator and an effective crosslinking amount of the divinyl ether product of Claim 4.

11. The process of Claim 10 wherein said formulation is coated on substrate in a thickness of between about 0.02 mil and about 30 mil and is cured thereon at a temperature of between about 25°C. and about 250°C.

12. The process of Claim 11 wherein said formulation is coated on a metal substrate in a thickness of between about 0.5 mil and about 5 mils and is cured thereon at a temperature of between about 25°C. and about 200°C.

13. The process of Claim 12 wherein said coating is cured on the substrate by exposure to a source of radiation or heat.

14. The process of Claim 13 wherein said coating is cured on the substrate by exposure to an electron beam at from about 0.5 to about 5 megarads.

15. The process of Claim 13 wherein said coating is cured by exposure to UV light at between about 0.15 joules/cm² and about 225 joules/cm².

16. The process of Claim 15 wherein said coating is cured at between about 6 joules/cm² and about 150 joules/cm².

17. The process of Claim 10 wherein the product of Claim 4 has the formula

CH₂=CH(OCH₂CH₂)_xOCH₂CH=CHCH₂O(CH₂CH₂O)_x'CH=CH₂ .

18. The process of Claim 17 wherein the product of Claim 4 is 2-butene-1,4 divinylether.

19. The process of Claim 1 wherein the product of Claim 4 has the formula

CH₂=CH(OCH₂CH₂)_xOCH₂CH-CHCH₂O(CH₂CH₂O)_x'CH=CH₂

20. The process of Claim 19 wherein the product of Claim 4 is 2-epoxybutane-1,4-divinylether.

21. The process of formulating a coating composition which comprises combining a crosslinkable base resin, a crosslinking initiator and an effective amount of the compound of Claim 1.