Abstract: Enhancement of the rates of cationic polymerizations initiated by onium salts has been achieved through the use of oligomeric and polymeric electron-transfer photosensitizers derived from a polymerizable compound substituted with a polynuclear aromatic group, including epoxides, oxetanes, and ethylenically unsaturated compounds. The polymerizable compound is substituted with residues derived from anthracene, naphthalene, perylene, pyrene, fluorene, carbazole, indole, benzocarbazole, acridone, phenothiazine, and thianthrene, particularly carbazole.

Abstract: Diaryliodonium salts are disclosed, as well as a method for preparing them, in which one of the aryl groups bonded to the positively-charged iodine ion contains a methyl substituent, and the other one contains a hydroxyl-substituted alkoxy group. The salts are synthesized from (o, m, or p)- iodotoluene, as opposed to iodobenzene, and therefore do not pose a carcinogenic risk. In addition, the present salts are unexpectedly more soluble in most organic solvents, as well as in nonpolar monomers, than the corresponding benzene catalysts. The salts are useful as cationic photoinitiators, cationic thermal initiators (often combined with a cocatalyst, e.g. copper), and as starting materials in the synthesis of urethane-containing iodonium salts.

Abstract: Unsaturated or polyunsaturated, conjugated or nonconjugated hydrocarbons are reacted with an oxidizing agent including hydroperoxides and monopersulfate compounds in the presence of phase-transfer catalysts. Suitable hydrocarbons include ricinic compounds such as castor oil and dehydrated castor oil. The phase-transfer catalysts include novel tungsten peroxo complexes, such as quaternary ammonium tetrakis (diperoxotungsto) phosphates, and crown ethers. Other additives utilized include pH buffers and alkaline compounds including alkali metal and alkaline earth metal carbonates, and solvents.

Abstract: Enhancement of the rates of cationic polymerizations initiated by onium salts has been achieved through the use of oligomeric and polymeric electron-transfer photosensitizers derived from a polymerizable compound substituted with a polynuclear aromatic group, including epoxides, oxetanes, and ethylenically unsaturated compounds. The polymerizable compound is substituted with residues derived from anthracene, naphthalene, perylene, pyrene, fluorene, carbazole, indole, benzocarbazole, acridone, phenothiazine, and thianthrene, particularly carbazole.

Abstract: A method of accelerating the cure rate of an epoxy curing composition includes combining a cycloaliphatic epoxyalcohol monomer, a non-hydroxyl-containing epoxy monomer and a cationic photoinitiator to form an epoxy curing composition, and exposing the curing composition to a source of radiation. The resulting polymers and copolymers are branched polyethers containing hydroxyl functionality.

Abstract: Disclosed are compounds of the formulas which are useful as monomers in photopolymerizable compositions. Also disclosed are methods of polymerizing these monomers, and polymers produced thereby.

Abstract: Disclosed are compounds of the formulas ##STR1## which are useful as monomers in photopolymerizable compositions. Also disclosed are methods of polymerizing these monomers, and polymers produced thereby.

Abstract: Unsaturated or polyunsaturated, conjugated or nonconjugated hydrocarbons are reacted with an oxidizing agent including hydroperoxides and monopersulfate compounds in the presence of phase-transfer catalysts. Suitable hydrocarbons include ricinic compounds such as castor oil and dehydrated castor oil. The phase-transfer catalysts include novel tungsten peroxo complexes, such as quaternary ammonium tetrakis (diperoxotungsto) phosphates, and crown ethers. Other additives opionally utilized include pH buffers, alkaline compounds, and solvents.

Abstract: Cationic polymerization initiators of formula ##STR1## are disclosed. The acyl sulfonium salts of the present invention differ from known acyl sulfonium initiators in that the substituents R.sup.2 and R.sup.3 on the sulfur are larger and more complex than the lower alkyl and lower alkylene of known photoinitiators. Processes for the synthesis of the novel acyl sulfonium salts and prepolymer compositions containing them are also disclosed.

Abstract: A process for the direct polymerization of allyl ethers, crotyl ethers and allyl alcohols is disclosed. The process comprises bringing into reactive proximity an allyl ether, crotyl ether or allyl alcohol compound; a transition metal carbonyl complex catalyst; and a cocatalyst bearing at least one silicon-hydrogen bond. Preferably, the catalyst is a cobalt carbonyl complex, and most preferably, the catalyst is dicobalt octacarbonyl. While virtually any compound bearing at least one silicon-hydrogen bond can be used as cocatalyst, phenylsilane is the most preferred. The process promotes the polymerization of allyl alcohols, mono-, di-, tri-, tetra- and multifunctional allyl and crotyl ether monomers, as well as terminal and pendent allyl and crotyl ether functional groups within oligomers and polymers.

Abstract: Silicone release agents comprising propenyl-ether functionalized silicones exhibit a rapid cationic induce photo-cure. Such propenyl-ether functionalized silicones are synthesized by the hydrosilation of various .alpha.-allyloxy-.omega.-(1-propenoxy) alkanes with various linear and cyclic hydrogen functional siloxanes.

Abstract: The invention provides a method for making a curable epoxysilicone composition through the hydrosilation reaction between an ethylenically unsaturated epoxide and an SiH-containing silicone to produce an epoxysilicone product, and catalyzed by a quaternary ammonium, phosphonium or arsonium hexahaloplatinate which does not promote the oxirane ring-opening reaction of either the ethylenically unsaturated epoxide starting material or the epoxysilicone product. The invention also provides for a curable epoxysilicone composition made by the above method.

Abstract: Propenyl ether monomers of formula VA(OCH.dbd.CHCH.sub.3).sub.nwherein n is an integer from one to six and A is selected from cyclic ethers, polyether and alkanes are disclosed. The monomers are readily polymerized in the presence of cationic photoinitiators, when exposed to actinic radiation, to form poly(propenyl ethers) that are useful for coatings, sealants, varnishes and adhesives. Compositions for preparing polymeric coatings comprising the compounds of formula V together with particular cationic photoinitiators are also disclosed, as are processes for making the monomers from allyl halides and readily available alcohols. The process involves rearranging the resulting allyl ethers to propenyl ethers.

Abstract: Propenyl ether monomers of formula VA(OCH.dbd.CHCH.sub.3).sub.nwherein n is an integer from one to six and A is selected from cyclic ethers, polyether and alkanes are disclosed. The monomers are readily polymerized in the presence of cationic photoinitiators, when exposed to actinic radiation, to form poly(propenyl ethers) that are useful for coatings, sealants, varnishes and adhesives. Compositions for preparing polymeric coatings comprising the compounds of formula V together with particular cationic photoinitiators are also disclosed, as are processes for making the monomers from allyl halides and readily available alcohols. The process involves rearranging the resulting allyl ethers to propenyl ethers.

Abstract: A process for the selective monoadditon of an olefin or acetylene to a siloxane which contains two reactive Si--H bonds to produce a product in which only one of the two Si--H functions has added across the olefin or acetylene is disclosed. A process for making unsymmetrical siloxanes from symmetrical dihydrosiloxanes and products of both of these processes are also disclosed. Products are represented by the formula I in which R.sup.1 and R.sup.

Abstract: A photochemical grafting process permits the attachment of free radically polymerizable monomers to the surface of aryl polysulfone membranes. The process, which does not use sensitizers, results in membrane compositions which can be used for ultrafiltration and microfiltration membranes and which exhibit low or non-fouling characteristics.

Abstract: Novel 3-substituted oxetane monomers for photoinitiated cationic polymerization, compositions for polymerization containing these oxetanes, processes for polymerizing the monomers, and polymers produced thereby are disclosed.A class of oxetane monomers have the formula ##STR1## wherein R.sup.1 is hydrogen, alkyl of 1 to 6 carbons, fluorine, fluoroalkyl of 1 to 6 carbons, allyl, aryl, furan or thiophene; R.sup.2 is a polyvalent radical chosen from the group consisting of linear or branched alkylene, linear or branched poly(alkyleneoxy), xylylene, and silicones; Z is oxygen or sulfur; and m is 2, 3 or 4.

Abstract: A method for making a triarylsulfonium hexafluoro metal or metalloid salt is provided by effecting reaction between a diarylsulfoxide and an aromatic substrate, such as an arylalkylether in the presence of a solution of phosphorus pentoxide and methanesulfonic acid to produce a triarylsulfonium complex. A metathesis of the resulting triarylsulfonium complex is effected with an alkali metal hexafluoro metal or metalloid salt.

Abstract: The invention provides a method for making a curable epoxysilicone composition through the hydrosilation reaction between an ethylenically unsaturated epoxide and an SiH-containing silicone to produce an epoxysilicone product, and catalyzed by a rhodium containing selective catalyst which does not promote the oxirane ring-opening reaction of either the ethylenically unsaturated epoxide starting material or the epoxysilicone product. The rhodium containing selective catalyst has the general formula[R.sub.4 M].sup.+ [RhCl.sub.3 Br].sup.-wherein M is phosphorous or nitrogen and R is an organic radical comprising a C.sub.1-18 linear alkyl radical, aryl, alkaryl or aralkyl radical.

Abstract: A catalyst: mixture for ring-opening polymerization of heterocyclic monomers and polymers includes a catalyst composed of a cobalt carbonyl complex; and a cocatalyst composed of at least one Si-H-containing compound. A curable composition, which may be a two-part kit, is also disclosed and includes the catalyst; the cocatalyst; and at least one polymerizable compound which is a monomer or polymer containing a heterocyclic ring. A method of producing a polymeric product by ring-opening polymerization of heterocyclic monomers and polymers is also disclosed which includes the steps of preparing a mixture including a catalyst composed of a cobalt carbonyl complex, a cocatalyst composed of at least one Si-H-containing compound, and at least one polymerizable compound which is a monomer or polymer containing a heterocyclic ring; and reacting the mixture, preferably at about room temperature, to promote ring-opening polymerization of the at least one polymerizable compound to produce the polymeric product.