CA1283425C - Diphenyliodonium hexafluoro metal salts - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Cationic polymerization of a variety of organic materials such as vinyl monomers, prepolymers, cyclic ethers, cyclic esters and organosilicon cyclics can be achieved by the use of certain radiation sensitive aromatic halonium salts. In addition, polymerizable compositions are provided which can be used as coating compounds, molding resins, adhesives etc. The salts have the general formula [(R1) I] + [MF6] -where M is an element selected from the class consisting of P, As and Sb, R1 is a divalent aromatic organic radical selected from and

Description

~ 7373A

This application is a division of Canadian application Serial Number 226,109 filed May 2, 1975.
Prior to the present invention, it was generally known that a variety of organic materials such as vinyl monomers possessing a high electron density in the double bond, were subject to cationic polymerization. A small amount of a Lewis Acid catalyst, such as SnC14, SbF5, AsF5, etc. readily polymerizes vinyl monomers such as styrene, butadiene, vinyl alkyl ethers, etc. It is often difficult, however, to generate the Lewis Acid catalyst at the appro-priate time for polymerization, or have it properly dispersed throughout the vinyl monomer to achieve uniform results.
It is also known to cure epoxy resins as "one package" systems, based on the employment of a Lewis Acid catalyst in the form of an amine complex such as boron trifluoride-monoethyl amine. The Lewis Acid is released on heating; cure takes place within 1 to 8 hours and can require a temperature of 160C. and higher. As a result, these~ package epoxy compositions cannot be employed to coat heat sensitive devices such as delicate electronic components. Nor can epoxy or other monomers having low boiling points be used due to the resulting losses to evaporation during cure.
As shown by Schlesinger, U. S. Patent 3,703,296 issued November 21, 1972, certain photosensitive aromatic diazonium salts can be employed to cure epoxy resins. When photolyzed, these aromatic diazonium salts are capable of releasing, in situ, a Lewis Acid catalyst which can initiate the rapid polymerization of the epoxy resin. However, even though these one package epoxy resin mixtures can provide fast curing compositions, a stabilizer must be use~ to minimize cure in the dark during storage of these mixtures.

~834~ RD 7373A

Despite these measures, gellation of the mixture can occur even in the absence of light. In addition, nitrogen is released during UV-cure, which can result in film imper-fections. Diazonium salts are generally thermally unstable, rendering the use of such materials hazardous because of the possibility of run-away decomposition.
Additional organic materials such as aldehydes, cyclic ethers and cyclic esters also can undergo cationic polymerization in the presence of trace amounts of Lewis Acids. Such materials when catalyzed, can be employed in coating applications, as encapsulants, and for a variety of thermoplastic applications. However, optimum results cannot be achieved because it is difficult to achieve dispersion or generation of the Lewis Acid in a desirable manner. A
further description of the principles by which cationic polymerization of the above described organic materials can be achieved with Lewis Acids is described in Principl~s of Polymer Chemistry, pp 217-222 by P. J. Flory, Cornell University Press, Ithica, New York (1953), and Polymer Reviews by J. Furukawa and T. Saegusa, Interscience Publishers, New York (1953). Another class of materials which undergoes cationic polymerization in the presence of Lewis Acids is organosilicon cyclics as shown by W. Noll, The Chemistry and Technology of Silicones, pp 219-226, Academic Press~ New York (1968~.
The present invention is based on the discovery that certain photosensitive aromatic halonium salts, as ~ 2 8 3 ~% 5 P~D 7373A

illustrat~d l,~ formula, carl be a source of Lewis Acids s~lch as boron tri1uoride~, phcs l~or ~Is ~ ~ penta~luoride, arsenic pentaEluoride, etc , ~ en exposed to radiant energy A variety of radiation poly~.eri-zable compositions are provided by incorporating the photo-sensitive aromatic halonium salt into a cationically poly-.eri~able organic material Unlike pol~Jmeriz~ble compositions containing the above described diazonium salts, the compo-: 10 sitions of the present invention, which can be in the form of a solid or liquid, do not require a stabilizer. Even after extended shelf periods, the polymerizable compositions of the present invention do not exhibit any signif-cant change in properties In addition, there is no problem ~ith ~ 15 bubbling as characterized by organic res-in compositions con-; taining diazonium salts.
The polymerizable compositions of the present inven-tion can be used as molding and extrusion resins; adhesiv~s, caulks~ coatings, printing inks~ impregnated tapes, insula-tion, sealants, blood plasma e~tenders, lubricants, etc.
The aromatic halonium salts utillzed in the compo-s-.tions of the present invention can be more particularly d~rlned by the following ~ormula, ~Z8342~

where R is a monovalent aromatic organic radical; Rl is a divalent aromatic organic radical; X is a halogen; M is a metal or a metalloid; Q is a halogen, such as Cl, F, Br, I, etc.; a is an integer equal to O or 2, b is an integer equal to O or 1, and the sum of a + 2b is equal to 2;
e is the valence of M and is an integer equal to 2 to 6 inclusive;
d is greater than e and is an integer having a value up to 7; and c = d - e.
Radicals included by R can be the same or different, aromatic carbocyclic or heterocyclic radical having from 6 to 20 carbon atoms, which can be substituted with from 1 to 4 monovalent radicals selected from C(l 8) alkoxy, C(l 8) alkyl, nitro, chloro, etc., R
is more particularly, phenyl, chlorophenyl, nitrophenyl, methoxyphenyl, pyridyl, etc. Radicals included by Rl are divalent radicals such as (CH2)n where n is an integer. Complex anions included by MQd(d e~ of formula I are, for example, BF4 , PF6 , AsF6 , SbF6 , FeC14 , SnC16 , SbC16 , BiC15 , AlF6 GaC14 , InF4 , TiF6 ~ ZrF~ , etc. Metal or metalloids included by M of formula I are transition metals such as Sb, Fe, Sn, Bi, Al, Ga, Irl, Ti, Zr, Sc, V, Cr, ~n, Cs, rare earth elements such as the lanthanides, - 4 ~

~34Z5 RD 7373A

for example, Cd, Pr, Nd, etc. actinides such as Th, Pa, U, Np, etc. and metalliods such as B, P, As, etc.
Halonium salts included by formula I are, for example, CH
o 3 I + _ ~ _ I BF4 ~ PF6 ~ GJ ~
~J

I BF4 II SbF6 ~ +
~ = I BF4 There is provided by the present in~ention, poly-merizable compositions comprising, (A) a monomeric or prepolymeric cationically polymerizable organic material free of oxirane oxygen selected from vinyl organic monomers, vinyl organic prepolymers, cyclic organic ethers, cyclic organic esters, cyclic organic sulfides, organosilicon cyclics and cyclic amines, and _ 5 -~8342~ RD 7373A

(Bj an 2f:~ ective amount or a radiation sen3itive aromatic haloniun~ salt capable of e~ecting the pol~nerization of (A) by release~ of a Le~lis Acid catalyst ~1hen exposed to radiant energy.
The halonium salts o~ formula L are well kno~m and call be made by the procedures described by O A
Ptitsyna~ M. E. Pudecva~ et al, Dokl, Adad Nauk, SSSR, 163, 383 (1965); Dokl, ~hem., 163, 671 (1965). F. ~Iarshall Beringer, ~I. Drexler, E. ~I. Gindler, J. Am. Chem. Soc., 75, ~705 (1953). ~J. Coll.ette, D. McGreer, R. Cra~ord, et ~1, J. Am. Chem. Soc. 78, 3819 (1956).
Included by the vinyl organic monomers which can be used in the practice of the invention to make polymerizable compositions which are convertible to thermoplastic polymers are, for example, styrene, vinyl acetam-ide, ~-methyl styrene, isobutyl vinylether, n-octyl vinylether, acrolein, l,l-di-. phenylethylene, ~-pinene; vinyl arenes such as 4-vinyl biphenyl j l-vinyl pyrene, ~-vinyl fluorene, acenaphthylene, ~ 1 and 2-vinyl naphthylene; 9-vinyl carbazole~ vinyl pyrroli-done, 3-~.e~hyl-1-butene; vinyl cycloaliphatics such as vinyl-cyclohexane, vinylcyclopropane~ l-phenylvinylcyclopropane;
dienGs such as isobutylene, isoprene, butadiene, 1,4-penta-diene~ etc.
Some of the vinyl organic prepolymers which can be used to make the polymerizable compositions of the present ~28~ RD 737~A

invention are, for example, CH2=CH-O-(CH2-CH20) -CH=CH2, where n is a positive integer having a value up to about 1000 or higher; multi-functional vinylethers, such as 1,2,3-propane trivinyl ether, trimethylolpropane tri~Jinyl ether, prepolymers having the formula, ~~~r ~ CH ;

~ C~=CH2 ~ n and low molecular weight polybutadiene having a viscosity of from 200 to 10,000 centipoises at 25C., etc. Products resulting from the cure of such compositions can be used as potting resins, crosslinked coatings, printing inks and other applications typical of thermosetting or network resins.
A further category of the organic materials which can be used to make the polymerizable compositions are cyclic ethers which are convertible to thermoplastics. Included by such cyclic ethers are, for example, any monomeric, dimeric or oligomeric or polymeric epoxy material containing one or a plurality of epoxy functional groups. For example, those resins which result from the reaction of bisphenol-A (4,4'-isopropylidenediphenol) and epichlorohydrin, or by the reaction of low molecular weight phenol-formaldehyde resins (Novolak resins) wi~h epichlorohydrin, can be used alone or in combination with an epoxy containing compound as a reactive diluent. Such diluents as phenyl glycidyl ether, 4-vinylccylo-hexene dioxide, limonene dioxide, l,2-cyclohexene oxide, glycidyl acrylate, glycidyl methacrylate, styrene oxide, allyl glycidyl ether, etc., may be added as viscosity modifying agents.

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In addition, the range of these compounds can be extended to include polymeric materials containing terminal or pendant epoxy groups. Examples of these compounds are ~inyl copolymers containing glycidyl acrylate or methacrylate a5 one of the comonomers. Other classes of epoxy containing polymers amenable to cure using the above catalysts are epoxy-siloxane resins, epoxy-polyurethanes and epoxy-polyesters. Such polymers usually have epoxy functional groups at the ends of their chains. Epoxy-siloxane resins and method for making are more particularly shown by E. P.
Plueddemann and G. Fanger, J. Am. Chem. Soc. 81 632-5 (1959).
As described in the literature, epoxy resins can also be modified in a number of standard ways such as reactions with amines, carboxylic acids, thiols, phenols, alcohols, etc. as shown in U. S. patents 2,935,488 issued May 3, 1960; 3,235,620 issued February 15, 1966; 3,369,055 issued February 13, 1968;
3,379,653 issued April 23, 1968; 3,398,211 issued August 2~, 1968; 3,403,199 issued September 24, 1968; 3,563,850 issued February 16, 1971; 3,567,797 issued March 2, 1971; 3,677,995 issued July 18, 1972, etc. Further examples of epoxy resins which can be used are shown in the Encyclopedia of Polymer Science and Technology, Vol. 6, 1967, Interscience Publishers, New York, pp 209-271. The term epoxy resin as hereinafter employed may signify both curable epoxy polymers, prepolymers and monomers or mixtures thereof. Also included as cyclic ethers are oxetanes such as 3,3-bis-chloromethyloxetane alkoxy-oxetanes as shown by Schroe~er U.S. Patent 3,673,216 issued June 27, 1972, assigned to the same assignee as the present invention; oxolanes such as tetrahydrofuran, oxepanes, oxygen containing spiro compounds, trioxane, dioxolane, etc.

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In addition to cyclic ethers, there are also included cyclic esters such as~?"~ -lactones, for example, propiolactone, cyclic amines, such as 1,3,3-trimethylazetidine and organo-silicone cyclics, for example, materials included by the R;SlO - ~-m where R" can be the same or different monovalent organic radicals such as methyl or phenyl and m is an integer to 3 to 8 inclusive. An example of an organosilicon cyclic is he~amethyl trisiloxane, octamethyl tetrasiloxane, etc.
The products made in accordance with the present invention are high molecular weight oils and gums.
The curable compositions of the present invention can be made by blending the polymeri~able organic material with an effective amount of the halonium salt. The resulting curable composition which can be in the form of a varnish having a viscosity of from 1 centipoise to 100,000 centipoises at 25C can be applied to a variety of substrates by conven-tional means and cured to the tack-free state within l second or less to lO minutes or more. In other instances, for example, where a solid epoxy resin is employed, the curable composition can be a free flowing powder.
In particular instances, depending upon the compata-bility of the halonium salt with the organic material, the halonium salt can be dissolved or dispersed in an organic solvent such as nitromethane, acetonitrile, methylene chloride, etc., prior to its incorporation into the organic material.
Where the polymerizable organic material is a solid, e.g.

~Z~3342~;
certain of the higher molecular weight bisphenol or novola1.
based epoxy resins, incorporation of the onium salt may be achieved by dry milling or melt mixing where the melting point of the resin is suitably low. EYperience has sho,Jn khat the proportion of halonium salt to organic material san vary widely inasmuch as the salt is substantially inert, unless activated. Effective results can be achieved, for example, if a proportion of from 0.1% to 15~ by weight of halonium salt is employed, based on the weight of polymerizable composition. Higher or lower amounts can be used, however, depending upon factors such as the nature of organic material, intensity of radiation, polymerization time desired, etc.
It has been found the halonium salt of formula I
also can be generated ln situ in the presence of the organic material if desired. For example, an onium salt of the formula, L(R) a(R ~b J Y I

where R, R , X, a and b are as previously defined, and Y is an anion such as Cl , Br , I , F , HSO4 and NO3 , etc. can be separately or simultaneously introduced into the organic material with a Lewis Acid of the formula, ~ Q) where M and Q are as previously defined and M' is a metal cation such as an alkali ~etal, for example, Na , K , etc., alkaline earth, such as Ca , Mg or an organic cation such as quaternary ammonium, pyridinium, etc.
The curable compositions may contain inactive ingredients such as inorganic fillers, dyes, pigments, extenders, viscoosity control agents, process aids, W -screens, etc~ in amounts of up to 100 parts filler per 100 of epoxy resin. The ~2~34Z~
curable compositions can be applied to such substrates as metal, rubber, plastic, molded parts or films, paper, ~700d, glass cloth, concrete, ceramic, etc.
Some of the applications in which the curable compositions of the present invention can be used are, for example, protective, decorative and insulating coatings, potting compounds, printing inks, sealants, adhesives, photoresists, wire insulation, textile coatings, laminates, impregnated tapes, etc.
Polymerization can be achieved by activating the halonium salt to provide the release of the Lewis Acid catalyst. Activation of the halonium salt can be achieved by heating the composition at a temperature in the range of from 150C to 250C. Preferably, polymerization can be achieved by exposing the composition to radiant energy such as electron beam or ultraviolet light. Electron beam cure can be effected at an accelerator voltage of from about 100 to lO00 KV. Polymerization is preferably achieved by the use of UV irradiation having a wavelength of from A
~0 4000~A. The lamp systems used to generate such radiation can consist of ultraviolet lamps such as from 1 to 50 discharge lamps, for example, xenon, metallic halide, ~D 7373A

metallic arc, such as a low, medium or high pressure mercury vapor discharge lamp, etc. having an operating pressure of from a few millimeters to about 10 atmos-pheres, etc., can be employed. The lamps can include envelopes capable of transmitting light of a wave-length preferably of 2400 A to 4000 A. The lamp envelope can consist of quartz, such as Spectrocil ~ or Pyrex ~-, etc. Typical lamps which can be employed for providing ultraviolet radiation are, for example, medium pressure mercury arcs, such as the GE H3T7 arc and the Hanovia 450 W arc lamp. Polymerization may be carried out with a combination of various lamps, some or all of which can operate in an inert atmosphere. When using UV lamps, the irradiation flux in the substrate can be at least 0.01 watts per square inch to effect polymerization of the organic material within 1 to 20 seconds and permit the cure to be carried on continuously as, for example, in the curing of a multifunctional vinyl ether or epoxy resin coated steel strip, or paper web, to be taken up at a rate of from 100 to 600 feet per minute. The web can be cut to a predetermined width for use as printed material. A combination of heat and light may be used to cure reactive compositions. Such a combina-~28342~ RD 7373A

tion of heat and light may se~rve to reduce the overall cure time, In order that those skilled in the art will be better able to practice the invention~ the following examples are given by ~ay of illustration and not by way o limita-tion, All parts are by weight, EX~h~LE 1 -A curabLe mixture was prepared by adding under a nitrogen atmosphere 0,2 part of diphenyli~donium hexa-fluorophosphate to 39 parts of tetrahydrofuran, The result-ing mixture was exposed for 10 minutes to ultraviolet light from a GE H3T7 lamp, The resulting product was allowed to stand for 3 hours, A highly viscous product was obtained, The polymer was then poured into water to destroy the catalys~ and then was filtered off and dissolved in tetra- --hydrofuran, On pouring the highly viscous polymer into me~hanol, a fibrous, tough polymer was obtained, The poly-mer was washed with methanol and dryed to give a pale yellow material having an lntrinsic viscosity of 3,9 dl/g. This indicates a molecular weight of greater than 350,000, The polymer ~Jas pressed into an exceedingly ~ough film. It could be hea~-pressed to a particular sha~ .
The procedure is repeated except`a portion of the mixture is allowfd to remain under normal daylight conditions ~13-~

~ ~ ~ 3 ~2 ~

ror several days at ambient temperature, ;~lo ch~nge in viscosity is noted.

E,~PLE 2 A mixture o 0.1 part o~ diphenyliodonium ~uoro-borate and a solution o~ 13,3 parts of N-vinylcarbazole in 39.9 parts of methylene chloride was irradiated for 10 min.
at a distance of 3 inches from a 450 W Hanovia læmp, Irradiation was performed under nitrogen while ~he mixture ~Jas in a vial. There was observed rapid exothermic poly-merization of the monomer to give a viscous pol~.er. After standing in the dark for 3 hours, the polymer was isolated by pouring it into methanol. There was obtained after filtering, washing and drying 13,1 parts of a dry, powdery polymer, Based on method o preparation, the poly-mer was polyvinylcarbazole use~ul as a molding compound.

EXA~LE 3 Three parts of p-methoxydiphenyliodonium fluo-roborate were added to 97 parts diethyleneglycol di-vinyl ether, This blend was thoroughly mixed by stirring for one hour. Then the sensitized mixture was applied to a glass plate as a 1 mil coating, Exposure of this compo-sition to ultraviolet light from an H3T7 lamp at a distance of four inches for 2-3 seconds in air gave a completely cured, hard coating which could not be removed by rubbing with ace~one, P~D 7373A
~Z~3~5 A portion of the above sensitized mixture ~tas combined with 2 parts by weight Cabosil ~ M-5 silica iller and knife coated to provide a 2 mil coating. The film ~t7as cured as before and required 3 seconds irradiation to be converted to a hard translucent coating.

A mixture of 0.32 part of diphenyliodonium chloride, 10 parts of ethylene glycol divinyl ether and 0.21 part of NaAsF6 was heated under sealed conditions for 5 hours at 50C. All suspended salts were then allowed to settle and the clear solution was knife coated onto a 3 in x 6 in steel panel to provide a 0.2 mil coating. Cure was performed as in Example 3. Three seconds were required to give a highly cured, acetone resistant coating.

There were added 0.3 part di-p-tolyliodonium fluoroborate and 0.4 part carbon black to 15 parts trimethylolpropane trivinyl ether. The mixture was agitated for 3 hours in a ball mill and then applied to white print paper. Exposure of the treated paper to ultraviolet light from a H3T7 lamp at a distance o~
3 inches cured the ink in 1-2 seconds.

2~

E~AMPLE 6 There was added 0.1 part of p-methoxyphenylphenyl-iodonium hexafluorophosphate to a mixture o~ 6 parts hexa-methylcyclotrisiloxane and 4 parts octamethyltetrasiloxane.
The mixture of monomers and sensitizer was sealed under nitrogen. The mixture was then placed 3 inches from a Hanovia 450 watt lamp and irradiated for 10 minutes to activate the catalyst. After allowing the mixture to stand for 16 hours during which the contents became very viscous, the product was poured into methanol. Based on method of preparation, the product was a polydimethyl siloxane oil.
It was recovered by decanting the methanol layer, washing with more methanol and then drying in vacuo at 60C. The polydimethyl siloxane oil was useful ~or imparting improved surface characteristics to fibrous substrates.

A mixture was prepared composed of 2% diphenyl-iodonium tetrafluoroborate, 97.5% ethyleneglycol divinyl ether and 0~5% of a surface active agent. The mixture was stirred until homogeneous and then coated onto a 3 in x 6 in steel panel using a 0.2 mil drawblade. After exposing the panel for a period of 1 second to ultraviolet radiation, the film became hard. The film could not be removed by rubbing with acetone nor was it affected by immersion in boiling ~5 water for one hour.

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A mixture of 0.26 part of 4-methoxydiphenyl-iodonium fluoroborate, 28.8 parts of freshly distilled styrene and 13 parts of methylene chloride was flushed with nitrogen and sealed. The mixture was exposed six minutes to a 450 watt Hanovia lamp. Rapid polymerization took place and the polymerization product was allowed to stand in the dark for 2 hours. A highly viscous reaction product was obtained whizh was poured into methanol and the solid product was filtered and washed. The product was dried in a vacuum oven. There was obtained 25.7 g of product. Based on method of preparation, the product was polystyrene.

A mixture of 22.8 parts of recrystallized acenaphthalene, 0O~3 part of 4-methoxydiphenyliodonium fluoroborate and 58.6 parts of methylene chloride was purged with nitrogen and sealed. It was then irraaiated for 8 hours in accordance with Example 8. A powdery tan precipitate of polyacenaphthalene was obtained on pouring the solution into methanol. Aftex drying overnight in a vacuum oven at 60C, there was obtained 22.2 parts of polymer.

; EXAMPLE 10 A mixture of 11.4 parts of ~-methylstyrene, 0.11 part of 4-methoxydiphenyliodonium fluoroborate and 13 parts iJ

~D 7373A
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of methylene chloride was flushed with nitrogen and seal~d.
While using a methanol dry ice bath, the mixture ~7as irradiated as in Example 8. The resulting highly viscous polymer solution was quenched by adding a small amount of methanol and the polymer isolated by pouring the solution into a large amount of methanol. After drying, 11 parts of poly~ methylstyrene were obtained.

EXAr~PLE 1 1 A solution of diethyleneglycol divinyl ether containing 2% by weight 4-methoxydiphenyliodonium fluoro-borate was coated onto a 3 in x 6 in steel plate. A
perforated mask was placed over the coating and this assembly was exposed to ultraviolet light using a GE
H3T7 medium pressure mercury arc lamp at a distance of four inches. After a 5 second exposure, the mask was removed and the plate was washed with i-propanoi. A
clear, raised negative image of the mask was formed.
These results showed that this photo-imaging procedure was useful in printing plate applications and in printed circuits for semiconductor devices.

There was added a cooled solution of about 100 ml of acetic anhydride and 70 ml of concentrated sulfuric acid to a suspension of 100 g of potassium iodate in 100 ml of acetic anhydride and 90 ml of benzene. During the addition, the mixture the mixture was stirred and maintained below 5C. When the addition was complete, the reaction mixture was allowed to warm at room temperature and stirred for 48 hours. There was then add~d 400 ml of distilled water. The aqueous portion of the reaction mixture was extracted three times with diethyl ether and petroleum ether to remove unreacted organic materials.
A pale yellow crystalline product formed upon addition of ~D 7373A
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ammonium chloride to the aqueous reaction mixture. There was obtained a 48% yield of diphenyliodonium chloride having a m.p. of 1~0-185C. The pure salt had a m.p.
of 22~-229C.
A mixture of 20 g of moist, freshly prepared Ag2O, 10 ml of water and 31.6 g of diphenyliodonium chloride was ground together in a slurry. The wet mixture was filtered and ashed with water to produce 360 ml of filtrate.
The filtrate was cooled until a substantial amount of the solution had frozen. There was slowly added 25 ml 45-50~ HBF4 cooled to -15C. The cold solution was stirred and allowed to warm to room temperature. A white crystalline solid separated and was collected by filtration. There was obtained a 60% yield of diphenyliodonium fluoroborate, m.p.
136C when the solid was dried overnight in vacuo at 60C.
A curable composition was prepared by dissolving 0.05 part of diphenyliodonium tetrafluoroborate in a small amount of acetonitrile and mixing the resulting solution in 5 parts of 4-vinylcyclohexene dioxide.
The viscosity of the resulting curable composition was found to be initially about 6 centipoises at 25C. It did not change substantially after several months exposure under normal room liyhting.
A portion of the curable compositions was applied as a 0.1 mil film onto a steel strip. The treated steel surface was exposed 15 seconds to the ultraviolet radiation of an H3T7 lamp at a distance of 2 inches. A clear tack-free film was formed which showed no signs of bubbles or other Lmperfections.
The above treated strip was then immersed in lOC
hydrocarbon oil for ~8 hours at 120C to detenmine its ydrolytic stability in accordance with IFT t~st AST~I D971-50 ~Z~334Z5 Interfacial Tension of Oil Against Water shown on page 322 of the 1972 Annual Book of ASTM Standards, part 17 (November). The initial reading of the oil ~as about 39.0 dynes/cm. After the test the oil sh~ed an inter-facial tension reading of 38. In order to pass, a reading of at least 30 is required.

The procedure of Example 1 was repeated for preparing an aromatic halonium salt using diphenylio-donium chloride. In this preparation, fluoroboricacid was replaced by 25 ml (60%) hexafluorophosphoric acid. There was obtained a 74% yield of diphenyliodonium hexafluorophosphate having a m.p. of 139-141C.
A curable composition was prepared following the same procedure as Example 1. Comparable results were achieved with respect to its ability to resist change in viscosity over an extended period of time under normal atmospheric conditions. In addition, satisfactory IFT
values were also obtained.

A curable composition was prepared using a 40:60 ~'~l33~Z5 solution of 4-vinylcyclohene dioxide and a novolak-epoxy resin and adding 2% by weight of diphenyliodonium tetra-fluoroborate in a small amount of nitromethane.
The curable compositon was spread on a glass plate. A mask was then used to cover the treated gla~s.
After irradiation under an H3T7 lamp for 1.5 minutes, the glass was washed with isopropanol. The unexposed portions were washed completely away leaving a negative image of the mask. When the same procedure is repeated using a steel plate as the substrate, the product is useful for the fabrication of printing plates.

Several curable compositions were prepared in accordance with the procedure shown in Example 1 using 4-vinylcyclohexene dioxide and about 3% by weight of the halonium salt. Various cure times were experienced when the compositions were applied onto a glass substrate and cured at a distance of four inches from a GE H3T7 lamp. The following shows the halonium salt used, its m.p. and the cure times.

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To 10 g limonene dioxide were added 0.32 g diphenyliodonium chloride and 0.21 g sodium hexa~luoro-arsenate. ~his mixture was heated for 20 minutes a~ 50~C to achieve metathesis. The salts were allowed to s~ttle and the clear supernatent liquid was drawn off. The sensitized epoxy compound was applied to a steel strip to a thickness of 2 mil and exposed to W light as described aboYe. Cure took place in 30 seconds. A tough film having good adhesion to the steel plate was ohtained.

Three parts of diphenyliodonium fluoroborate were ground to a fine powder and tumbled for 30 minutes with 97 parts of Reichhold Epotuf ~ 37-834 powder coating resin.
The powder blend was then electrostatically sprayed onto 3 in x 6 in steel samples to form a 2 mil coating using a GEMA
model 171 spray gun. Subsequently, the samples were heated briefly to 150C to fuse the powder and then exposed while hot to a GE H3T7 medium pressury mercury arc lamp at a distance of 3 inches. Cured samples were obtained after 30 seconds exposure.

a8~ 1E_18 Three parts by weight of di-p-tolyl iodonium fluoroborate were added to 97 parts of (3,4-epoxycyclohexyl)-methyl-3,4-epoxycyclohexanecarboxylate. The epoxy resin was then used to impregnate a 1 inch woven glass tape After winding two turns of the tape onto a 4 in diameter drum, the tape was c-ured to a rigid glass band by rotating the drum under a GE H3T7 lamp at a distance of 4 inches S for 2 minutes. The banding tapes thus prepared can be used as restraining bands in motors and generators.
Ihe above resin was used to impregnate woven glass cloth, Two 6 in x 6 in squares of the glass cloth were stacked on top of one another and cured for 1 mir.-~te on each side. A rigid composite was obtained which is use-ful for circuit ~oard applications.
A portion of the above mixture was used to impreg-nate glass roving. The treated glass was then wound onto a 3 in dia. drum to a thickness of about 5 mils. The drum was then rotated beneath a GE H3T7 lamp at a distance of 3 inches for 5 minutes. A measurement of the intensity of ~- - the lamp showed that it was approximately 200 watts/sq.
inch. When the cured wlnding was removed from the drum, it - was rigid and fully cured. A typical use for such a cured winding is as a spool for electrically conducting wire.

A mixture was prepared consisting of 14.5 g (0.25 mole) glycidyl allyl ether9 10 mg. t-butyl-catechol, and 3 drops chloroplatinic acid in octyl alcohol. The reaction P.D 7373A

mixture was heated to 50C in a water bath and then 13.0 g of a polydimethyl siloxane resin containing 0.89% by ~Jeight Si-H groups was added dropwise by means of a dropping funnel. Immediate exothermic reaction took place with the temperature rising to 65C. Reaction proceeded smoothly at this temperature giving a clear resin.
Three parts by weight of 4-methoxydiphenyl-iod~nium fluoroborate dissolved in a small amount of methylene chloride was added to 97 parts of the above silicone epoxy resin. A 2 mil film of the sensitized resin was drawn on a steel plate and then exposed to W light from ; a GE H3T7 lamp at a distance of six inches. The film was tack-free within 10-15 seconds. A small amount of silica was added to the sensitized resin to produce a thixotropic mixture and the resin cured as described previously. A
tough, rubbery coating resulted.

A solution of 3 parts of 4-methoxydipehnyliodonium fluoroborate dissolved in 20 parts of 4-vinyl-cyclohexene dioxide was added to 80 parts of a glycidyl methacrylate-methyl methacrylate copolymer having a molecular weight of 8,500 and a glycidyl acrylate content of 5% by weight.
This mixture was mixed by rolling it in a glass bottle on a ball mill overnight. The viscous solution was knife ~ 3~Z5 coated onto a glass plate to give a 2 mil film whicll ~Jllcn irradiated at a distance of six inches from a GE H3r7 lamp, gave a clear hard coating in 10 seconds. The film was highly crosslinked and ir~;~luble in all common solvents, . .~ . .
Three parts of diphenyliodonium hexafluoro-arsenate were dissolved in 6.7 parts of methylene chloride and the solution added to 97 parts glycidyl acrylate. A 3 part aliquot of this highly fluld mixture was placed in an ~luminum cup and then exposed to the ultr~vlolet lrradiation of a ~13T7 lamp using a water fllter. The cure time was 15 seconds~. Subsequent analysis showed that the conversion to polymer was greater than 95%. A hard glossy resin was obtained.

A blend was prepared using equal parts of 4-vinyl-cyclohexene dioxide and (3,4-epoxycyclohexyljmethyl-3,4-epoxycyclohcxanccarboxylate, To this blend were addcd four parts of diphenyliodonium fluoroborate. An aliquot of the above sensitized resin was spread onto a sheet of Lexan~
polycarbonate using a draw-down blade to give a 0.5 mil film.
The film was cured as described in ~xample 3 for 20 seconds giving a clear hard coa~ing which provides mar and solvent resistance for the substrate polymer.

--:~ 6--~3a~Z~

A mixture oE 50 parts bisphenol-A-diglycidyl ether arld 50 parts (3,4-epoxy-cyclohexyl)methyl-3,4-epoxycyclo-hexanecarboxylate was stirred until homogeneous and then 3 parts by weight diphenyliodonium hexaflworoantimonate in a small amount oE methylene chloride was added and the solution thoroughly mixed A portion of the above sensi-tized solution was coated onto a steel plate using a 0.2 mil drawbar. The plate was then irradiated for 10 seconds using a GE H3T7 mercury arc lamp at a distance of six inches The complttely cured, hard, glossy fllm had excellent adhesion to the steel and could not be removed by rubbing it with acetone.
.
EXAMPJ.E 24 A blend of epoxy resins consisting of 50 parts - 4-vinylcyclohexane dioxide, 40 parts of a novolak-epoxy resin having an epoxy et~uivalent weight of 172-178 and 10 part~ n-decylglycidyl cther were thoroughly mlxed~together. A
100 part aliquot was tak~n ~nd 1 part diphenyliodonium hex~l~t~r-)-phosphate was added and the resulting mixture stirred until the catalyst had dissolved. When the above mixture was coated onto a 3 in x 6 in panel and then exposed to a 450 wat~ medium pressure mercury arc lamp at a distance of 3 inches, a glossy, dry coating was obtained in 3 seconds.
. .

~Z83~2~;
The coating withstood attack by hot boiling ~7ater for four hours and could not be removed by rubbing with acetone.

EX~MPLE 2S
lhere was added 1 g o di-p-tolyliodonium 1uoro-borate to a mixture of 40 g limonene dioxide and 10 g o a solid multifunctional aromatic glycidyl ether having an epoxy equivalent weight of 210-240. The mixture-was stirred at 50C for 1 hour to produce a homogeneous solution of the --~
components. When the mixture was coated onto a glass plate using a 0 5 mil drawbar, a hard, adherent, cured film was produced by irradiating the sample for 5 seconds at a dis-tance of 3 inches from a GE H3T7 lamp which has an intensity of 200 watts/sq, inch There was added 0 2 part p-methoxydiphenyliodonium fluoroborate In 2 parts 4-vinylcycloh~xene dioxide to 10 pa~s of an epoxidized butadiene resin. After mixing, a l mil coating of the resulting mixture was applied onto a l/16 inch thick glass plate. Another plate of glass was placed on top of the first and this assembly exposed to a GE H3T7 medium pressure mercury arc lamp having an intensity of 200 watts/sq. in. at a distance of 3 inches. The total time of exposure was 1 minute. The glass plates were ~ Z~ 2~

permanently bonded together and the glass laminate could be used as a shatterproof windshield for automobiles.

A mixture was prepared consisting of by weigh~
67% of a novolak-epoxy resin having an epoxy equivalent weight of 172-178, 33% 4-vinylcyclohexene dioxide, 0.5% of a surface active agent, and 1% dipehnyliodonium hexafluoro-aresenate. The mixture was applied as a 0.1 mil film to 3 in x 6 in steel plates. The treated pla*es were exposed for 20 seconds at a distance of 4 inches from a G~ H3T7 medium pressure mercury arc lamp. Panels were subsequently immersed for 5 hrs. at room temperature in methylene chloride;
others were immersed for 4 hours in acetone. In all cases, no visible signs of attack on the coating by these agents were observed. The panels were baked for 1 hour at 160C, then tests were run separately in boiling 5% KOH
solution for 30 minutes and in boiling distilled water for 4 hours. At the end of these tests, the coatings were intac~ and showed no signs of degradation.
Although the above examples are limited to only a few of the very many polymerizable compositions and uses thereof which are included within the scope of the present invention, it should be understood that the present invention is intended to cover a much broader class of polymerizable compositions such as a mixture of the halonium salt and a cyclic organic sulfide and uses thereof. Those skilled in the art would also know that the polymerizable compositions also cover the use of onium polymers containing halonium functionality as part of the polymer backbone or in a pendant position.

2') _

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. An iodonium salt of the formula [(Rl) I] + [MF6]-where M is an element selected from the class consisting of P, As and Sb, and R1 is a divalent aromatic organic radical selected from and where n is an integer.