Abstract: A treatment method for polythiol compounds used in thiol-ene formulations, especially formulations employing norbornene resins, significantly improves cure speed retention on aging of thiol-ene formulations which include hydroxylamine salts, such as N-nitrosoarylhydroxylamine aluminum salts, as shelf-life stabilizers. The treatment comprises contacting the polythiol with an amphoteric treating agent selected from the group consisting of silicated magnesium oxide, magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, barium oxide, and barium hydroxide, and then separating the resin from the treating agent prior to mixture with a polyene to form a thiol-ene composition. In formulations employing phenolic compounds having an alkenyl group in conjugation with the phenyl group thereof as shelf-life co-stabilizers the treatment method also significantly enhances the shelf-life stability of the formulation compared to formulations made from untreated polythiol.

Abstract: A process comprising the steps of:1) reacting a norbornene compound of the formula: ##STR1## where R is H or methyl, R.sup.1 is a direct bond or --C(.dbd.O)O-- and R.sup.2 is vinyl, ethynyl, allyl or propargyl, with a silicon hydride functional compound in the presence of hydrosilation catalyst at a temperature of at least 60 degrees; and2) recovering a product which consists essentially of the addition products of the silicon hydride functional compound to the R.sup.2 group of the norbornene compound and which is substantially free of addition products of the silicon hydride functional compound to the internal ring double bond of the norbornene compound.The products of this process can be used to produce norbornene functional prepolymers which are useful in cureable silicone formulations based on thiolene or hydrosilation cure chemistry.

Abstract: A method of forming liquid crystal alignment layers of high tilt angle, said method comprising preparing a polymeric film of a monomer of the formula IV: ##STR1## wherein X and Y are strong electron withdrawing groups, optionally substituted with or containing Si or Ti, and A is --H or --CH.dbd.CH.sub.2 or, provided that X and Y are both --CN, A may be --R.sup.2 or --CH.dbd.CHR.sup.2 wherein R.sup.2 is hydrocarbyl, aryl or alkaryl; exposing said polymeric film to ultraviolet radiation for sufficient period of time to photochemically modify the polymer and, thereafter, subjecting the modified polymer to a heat treatment in the range of 100.degree.-400.degree. C. for at least 5 seconds.

Abstract: Tris(norbornenyl) isocyanurate compounds of the formula: ##STR1## wherein R.sup.1 is either H or methyl group, are prepared from the base-catalyzed trimerization of norbornenyl isocyanate. Tris(norbornenyl) isocyanurate is suitable for use as a crosslinker in thiol-ene formulations containing a difunctional thiol oligomer or in systems containing norbornene-difunctional oligomers and polyfunctional thiols, producing improved high temperature properties for the cured compositions.

Abstract: A composition cureable to a solid crosslinked polyorganosiloxane comprises:a) a norbornene functional silicone prepolymer having a plurality of groups of the formula: ##STR1## bound to silicon atoms thereof, where R is H or methyl, R.sup.1 is a direct bond or --C(.dbd.O)O-- and R.sup.4 is ethylene, ethenylene, propylene or propenylene,b) a coreactive silicone prepolymer selected from SiH functional silicones, and alkylthiol functional silicones, said polyorganosiloxanes (a) and (b) being present in an equivalent ratio of between 2:1 and 1:2 norbornene to silicon hydride or alkyl thiol groups, andc) an effective amount of a hydrosilation or thiol-ene cure catalyst, respectively.

Abstract: An improved stereolithography method for building a three-dimensional article including the steps of patternwise curing successive layers of a bath of curable liquid resin formulation until the article has been completely built up, removing the article from the liquid resin bath and then post-curing the article, wherein the liquid resin is a "thiol/nene" formulation including:(a) a first compound having a plurality of norbornene groups thereon;(b) a second compound having a plurality of thiol groups therein; and(c) a free radical photoinitiator,the total functionality of the formulation being greater than 4.

Abstract: A composition cureable to a solid crosslinked polyorganosiloxane comprises:a) a norbornene functional silicone prepolymer having a plurality of groups of the formula: ##STR1## bound to silicone atoms thereof, where R is H or methyl, R.sup.1 is a direct bond of --C(.dbd.O)O-- and R.sup.4 is ethylene, ethenylene, propylene or propenylene,b) a coreactive silicone prepolymer selected from SiH functional silicones, and alkylthiol functional silicones, said polyorganosiloxanes (a) and (b) being present in an equivalent ratio of between 2:1 and 1:2 norbornene to silicon hydride or alkyl thiol groups, andc) an effective amount of a hydrosilation or thiol-ene cure catalyst, respectively.

Abstract: Compounds useful as adhesion promoters for thermally cured thiolene adhesives include a) acrylic or norbornene acid phosphate esters such as ##STR1## b) maleic, acrylic, methacrylic, norbornene dicarboxylic, and fumaric acids and half acid esters and peresters of maleic fumaric and norbornene dicarboxylic acids; and c) norbornene, acrylic or methacrylic silanes having two or three hydrolyzable groups bound to the silicon atom thereof, such as 5-(triacetoxysilyl) norbornene.The adhesion promoters may be employed as surface primers for conventional thiolene compositions. Alternatively the thiolene compositions themselves may be modified by addition of 0.1 to 10% by weight of the adhesion promoter. Preferred thiolene compositions employ norbornene functional ene ingredients.

Abstract: A composition curable to a solid crosslinked polyorganosiloxane comprises:(a) an acrylic functional silicone prepolymer having a plurality of acrylic groups of the formula: ##STR1## bound to silicon atoms thereof, where R is H or methyl, and R.sup.1 is a divalent olefinically unsaturated hydrocarbon group,(b) a silicone prepolymer having a plurality of organothiol groups thereon, and(c) an effective amount of a thiol-ene cure catalyst.Particularly preferred formulations are photoinitiated formulations employing alkylthiol functional silicones in which the total number of thiol groups is between 0.5 and 1.5 times the total number of ene groups counting both the acrylic and the linking group R.sup.1 as ene groups.

Abstract: A curable thiol-ene formulation comprising(a) a polythiol(b) a 'ene compound having a plurality of groups of the formula: ##STR1## where Q is CH.sub.2, CHCH.sub.3, C(Ch.sub.3).sub.2, O, S, NR.sup.1 or SO.sub.2 R.sup.1 is H or alkyl, and m is 0-10, and(c) an effective amount of a free radical initiator.

Abstract: A curable composition including a monomer having at least one curable acrylic functionality, an accelerator and optionally a free radical initiator, wherein the accelerator is a compound of the formula ##STR1## wherein R' is H or alkyl; when R' is H, R is substituted or unsubstituted cyclohexyl, alkenylamino, or C.sub.3 -C.sub.10 branched alkyl; andwhen R' is alkyl, R is aralkyl.Such compositions are useful as fixturing (e.g., threadlocking) compositions, and overcome the problems of poor solubility in organic non-polar media and temperature constraints associated with the use of saccharin per se as an accelerator in such compositions.Also disclosed is a corresponding method of polymerizing compositions containing acrylic-functional compounds, and a method of making the substituted saccharin compounds from the corresponding substituted benzene sulfonamide.Alkenylamido-substituted saccharin compounds and alkyl, aralkyl-disubstituted saccharin compounds are specifically disclosed.

Abstract: Polyorganosiloxane polymers which include at least one group of the formula: ##STR1## where R.sup.1 is an organo group; R.sup.2 is alkylene or alkenylene; G is a n+1 valent hydrocarbon, oxyhydrocarbon or poly(oxyhydrocarbon) radical in which some or all of the hydrogen atoms may optionally be substituted by halogen atoms; R.sup.3 is H or an organic functional group, particularly polymerizable groups, polymerization accelerating groups or polymerization initiating groups; n is an integer of 2 or more provided that when n is 2 and one of R.sup.3 is H, the other R.sup.3 group is also H; and a is 0, 1 or 2.Additional polyorganosiloxane polymers include at least one group of the formula: ##STR2## where R.sup.4 R.sup.5 are H or a mono valent hydrocarbon group.

Abstract: Products formed from chlorosulfonyl isocyanate either by sequentially reaction of a hydroxy functional compound followed by reaction of the sulfonyl chloride group with a primary or secondary amine, or by reaction of chlorosulfonyl isocyanate with an excess of primary or secondary amine, are cure accelerators for acrylic compositions. Depending on the choice of alcohol or amine, the accelerator may be functionalized so that it is bound or bindable to an organic or silicone polymer backbone or contains other desirable functionality such as peroxy, photosensitizer, or acrylic groups.

Abstract: An organopolysiloxane photoinitiator having an average of at least two siloxane units, of which at least an average of one siloxane unit per organopolysiloxane molecule has the formula:X.sub.a R.sub.b SiO.sub.(4-a-b)/2wherein a is an integer of 1-3, b is a integer of 0-2 and a plus b equals 1-3; R is C.sub.1 -C.sub.10 hydrocarbyl or halogen substituted C.sub.1 -C.sub.10 hydrocarbyl; and X is substituted acetophenone photomoiety of the formula: ##STR1## where R.sup.1 is any substitutent which will not interfere with hydrosilation, n is an integer between 0 and 4; R.sup.2 is organosilyl substituted alkyl or alkenyl; R.sup.3 is H, alkyl or aryl; and R.sup.4 is a divalent hydrocarbon group having between 2 and 10 carbon atoms.The silicones are prepared by hydrosilation of the corresponding olefinically or acetylenically .alpha.,.alpha.-dialkenylacetophenones or .alpha.,.alpha.-dialkynylacetophenones.

Abstract: An organopolysiloxane photoinitiator having an average of at least two siloxane units, of which at least an average of one siloxane unit per organopolysiloxane molecule has the formula:X.sub.a R.sub.b SiO(.sub.4-a-b)/2 (I)wherein a is an integer of 1-3, b is an integer of 0-2 and a plus b equals 1-3; R is C.sub.1 -C.sub.10 hydrocarbyl or halogen substituted C.sub.1 -C.sub.10 hydrocarbyl; and X is a substituted acetophenone photomoiety selected from: ##STR1## where R.sup.1 is any substituent which will not interfere with hydrosilation, n is an integer between 0 and 5 in formulas (II), (IIa), (III), (IIIa), (IV) and (IVa) and between 0 and 4 in formula (III) and (IIIa); m is 0 or 1; R.sup.2 is alkyl or substituted alkyl; R.sup.3 is H, alkyl or aryl; R.sup.4 is a divalent hydrocarbon group having between 2 and 10 carbon atoms or an alkylene oxy alkylene group; R.sup.

Abstract: The photopolymerization of ethylenically unsaturated compounds is effected using a combination of an aromatic ketone photosensitizer and a tetrasubstituted urea (e.g. N,N,N',N'-tetramethylurea) or N,N-disubstituted acid amide. Storage stable liquid photoinitiator compositions comprising an aromatic ketone sensitizer (e.g. benzophenone) and a tetrasubstituted urea (e.g. N,N,N',N'-tetramethylurea) are also disclosed. The use of the tetrasubstituted urea or N,N-disubstituted amide possesses advantages (storage stability, lack of discoloration on curing) over photosensitizers such as Michler's ketone which have been used previously in combination with aromatic ketone photosensitizers.

Abstract: Free radically curable monomer compositions, particularly anaerobic compositions, which include an accelerator compound of the formula: ##STR1## where n is an integer; G is an n valent radical providing compatibility of the accelerator with the curable monomer; X is 0, 0--0, S or NR"; R' is an aromatic group which may be substituted or unsubstituted; and, R" is H, alkyl or aryl.The accelerator compounds are readily prepared by reacting an aromatic sulfonyl isocyanate with a compound having an isocyanate reactive hydrogen atom.

Abstract: Polyorganosiloxane photoinitiators containing aryoyl formate photomoieties bonded to silicon atoms via non-hydrolyzable Si-C bonds. They may be prepared from alkenyl or alkynyl aryoyl formates and polyorganosiloxanes containing silicon hydride groups via hydrosilation. They are effective photoinitiators for photocurable silicone resins and for ethylenically unsaturated monomers, producing cured films with good weatherability and low temperature flexibility.

Abstract: The photopolymerization of ethylenically unsaturated compounds is effected using a combination of an aromatic ketone photosensitizer and a tetrasubstituted urea (e.g. N,N,N',N'-tetramethylurea) or N,N-disubstituted acid amide. Storage stable liquid photoinitiator compositions comprising an aromatic ketone sensitizer (e.g. benzophenone) and a tetrasubstituted urea (e.g. N,N,N',N'-tetramethylurea) are also disclosed. The use of the tetrasubstituted urea or N,N-disubstituted amide possesses advantages (storage stability, lack of discoloration on curing) over photosensitizers such as Michler's ketone which have been used previously in combination with aromatic ketone photosensitizers.

Abstract: The photopolymerization of ethylenically unsaturated compounds is effected using a combination of an aromatic ketone photosensitizer and a tetrasubstituted urea (e.g. N,N,N',N'-tetramethylurea) or N,N-disubstituted acid amide. Storage stable liquid photoinitiator compositions comprising an aromatic ketone sensitizer (e.g. benzophenone) and a tetrasubstituted urea (e.g. N,N,N',N'-tetramethylurea) are also disclosed. The use of the tetrasubstituted urea or N,N-disubstituted amide possesses advantages (storage stability, lack of discoloration on curing) over photosensitizers such as Michler's ketone which have been used previously in combination with aromatic ketone photosensitizers.