Hydrolytically Stable, Hydrophilic Adhesion-Promoting Monomers and Polymers Made Therefrom

A method for bonding a surface comprising applying a composition comprising:

• at least one derivatized cyclodextrin, wherein said cyclodextrin contains at least one ether-linked copolymerizable vinylarylalkylene functional group on substantially every derivatized cyclodextrin molecule;
• and
• at least one or more reactive copolymerizable monomer or monomers;
• at least one stabilizer;
• and
• at least one polymerization initiator;
• in a manner that induces polymerization of said compositions to thereby form adhesive bonding to said surface or surfaces.

A composition comprising:

• at least one reactive copolymerizable monomer, wherein said composition does not contain polymerizable cyclodextrin derivatives, and
• wherein said at least one reactive copolymerizable monomer contains one or more polymerizable vinylarylalkylene group selected from the group comprising para-vinylbenzyl, meta-vinylbenzyl, ortho-vinylbenzyl, 1-vinyl-naphthalene-4-methyl, 4-vinyl-3-chlorobenzyl, 2-vinyl-4-methoxybenzyl, 2-vinyl-4-phenoxybenzyl, ortho-methyl styrene, 1-methylene-2-vinylnaphthalene, 2-methylene-1-vinylnaphthalene, 1-methylene-5-vinylnaphthalene, and 2-vinyl-1-biphenylmethyl groups that are connected to their backbone moieties via ether linkages, and
• wherein said backbone moieties comprise derivatized sugar alcohols, ethyleneglycol, diethyleneglycol, triethylene glycol, oligo-ethylene glycols, sorbitol, and other derivatized oligohydroxy compounds,
• wherein said at least one reactive copolymerizable monomer is further derivatized with substantially one or more ether-linked adhesion-promoting ligand groups selected from the group comprising undissociated carboxyl groups, dissociated anions of carboxyl groups, amides of carboxyl groups, amide-containing groups, amide-attached amino acid groups, ether-linked oligopeptide-containing groups, amide-attached oligopeptide groups, and aldehyde-containing groups,
• wherein said composition contains at least one stabilizer selected from the group comprising di-tert-butyl sulfide, the monomethyl ether of hydroquinone, 4-tert-butylcatechol, butylated hydroxytoluene, butylated hydroxyanisole, 4-tert-butylcatechol, ascorbic acid, ascorbic acid salts, ascorbic acid anionic derivatives, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, ethylenediaminetetraacidic acid, salts of ethylenediaminetetraacidic acid, anionic derivatives of ethylenediaminetetraacidic acid, phytic acid, salts of phytic acid, anionic derivatives of phytic acid, oxalic acid, salts of oxalic acid, anionic derivatives of oxalic acid, citric acid, citric acid salts, and anionic derivatives of citric acid,
• wherein said composition contains at least one polymerization initiator, selected from the group comprising phenylbis(2,4,6-trimethylbenzoyl)phosphineoxide, camphorquinone, camphorquinone-10-sulfonic acid, a salt of N-vinylarylalkylene-N-phenylglycine, a salt of N-vinylarylalkylene-N-tolylglycine, a salt of N-vinylarylalkylene-N-methylglycine, ethyl-4-dimethylaminobenzoate, diphenyliodoniumhexafluorophosphate, benzoyl peroxide, N,N-dihydroxyethyl-para-toluidine, 4-dimethylaminophenethylalcohol, 3-dimethylaminobenzoic acid, p-toluenesulfinic acid lithium salt, p-toluenesulfinic acid sodium salt hydrate, phenacylpyridiniumoxalate, 1-phenacylpyridinium bromide, phenacyltriphenylphosphonium bromide, 3,3′-carbonylbis[7-(diethylamino)coumarin], meso-tetraphenylporphine, benzene-1,2,4,5-tetracarboxylic diimide, naphthalene diimide, 2,2′-azo-bis(amidinopropane) 2(HCl), N,N′-bis-vinlbenzyl-1,4,5,8-naphthalenediimide, 2-benzoylmethylene-1-methyl-beta-naphthothiazoline, water-soluble derivatives thereof, and mixtures thereof.

A method for derivatizing a cyclodextrin comprising:

• reacting a cyclodextrin selected from the group consisting of alpha-cyclodextrin, beta-cyclodextrin, and gamma-cyclodextrin with one or more reagents selected from the group comprising para-vinylbenzyl halide or tosylate, meta-vinylbenzyl halide or tosylate, ortho-vinylbenzyl halide or tosylate, 1-vinyl-naphthalene-4-methyl halide or tosylate (1-vinyl-4-methylenenaphthalene halide or tosylate), 4-vinyl-3-chlorobenzyl halide or tosylate, 2-vinyl-4-methoxybenzyl halide or tosylate, 2-vinyl-4-phenoxybenzyl halide or tosylate, o-methyl styrene halide or tosylate (o-styrenemethyl halide or tosylate), 1-methylene-2-vinylnaphthalene halide or tosylate, 2-methylene-1-vinylnaphthalene halide or tosylate, 1-methylene-5-vinylnaphthalene halide or tosylate, and 2-vinyl-1-biphenylmethyl halide or tosylate, wherein para-vinylbenzyl halide or tosylate, and/or meta-vinylbenzyl halide or tosylate are preferred, and with one or more reagents selected from the group comprising 2-haloacetic acid, 3-halopropionic acid, 4-halobutyric acid, 5-halovaleric acid, 6-halocaproic acid, 7-enanthic acid, 8-halocaprylic acid, 9-halopelargonic acid, 10-halocapric acid, 12-halolauric acid, 16-halopalmitic acid, 2-halopropionamide, 4-halobutanal, 5-halopentanal, 6-halohexanal, 6-(halomethyl)uracil, 2-(halomethyl)pyridine, 3-(halomethyl)pyridine, 4-(halomethyl)pyridine, 4-(halomethyl)benzoic acid, 3-(halomethyl)benzoic acid, and 4-vinyl-3-carboxybenzylhalide, wherein said halides comprise Cl, Br, and I, and wherein the iodide reagents are formed from the chloride or bromide reagents by exchange with an alkaline element halide by incorporation of sodium iodide into the reaction mixtures, said reactions being further catalyzed by one or more compounds selected from the group comprising DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), 1,4-diazabicyclo[2.2.2]octane, hexamethylenetetramine, N,N-di-isopropyl ethylamine, triethylamine, tripropylamine, tributylamine, N,N-dimethylbenzylamine, tribenzylamine, N,N,N′,N′-tetramethyl-1,4-phenylenediamine, N,N-dimethylaniline, triphenylamine, pyridine, poly(4-vinylpyridine), sodium-tert-butoxide, cross-linked poly(4-vinylpyridine), 4-(dimethylamino)pyridine, triphenylantimony, triphenylphosphine, oxides of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, La, hydroxides of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, La, carbonates of Li, Na, K, Rb, and Cs, said reactions being conducted in one or more polar aprotic solvent or solvents containing one or more stabilizers.

A kit comprising:

• At least first and second containers, said first container containing at least one derivatized cyclodextrin, said cyclodextrin being at least partially derivatized with ether-linked vinylbenzyl groups;
• and
• at least said second container containing at least one reactive copolymerizable monomer or monomers, said copolymerizable monomer or monomers comprising a dentally compatible compound that includes
• at least one unsaturated functional group, said copolymerizable monomer or monomers being capable of reacting with said derivatized cyclodextrin to form a dentally compatible reaction product.