A Addition-fragmentation oligomers containing allylic disulfide groups are described. The oligomers may be added to polymerizable compositions to provide labile crosslinks that can cleave and reform during the polymerization process.
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1. An addition-fragmentation oligomer of the formula: whereinRA is a (hetero)hydrocarbyl group;RB is each independently a (hetero)hydrocarbyl group;RC is each independently a (hetero)hydrocarbyl group;subscript a is greater than 1;FG1, FG2 and FG3 are each independently functional groups connected t
1. An addition-fragmentation oligomer of the formula: whereinRA is a (hetero)hydrocarbyl group;RB is each independently a (hetero)hydrocarbyl group;RC is each independently a (hetero)hydrocarbyl group;subscript a is greater than 1;FG1, FG2 and FG3 are each independently functional groups connected the depicted RA, RB and RC groups; andZ comprises an ethylenically unsaturated polymerizable group. 2. The addition-fragmentation agent of claim 1 wherein RA, RB and RC are each independently alkylene of 2 to 10 carbon atoms. 3. The addition-fragmentation agent of claim 1 wherein FG1, FG2 and FG3 are selected from ester, amide, urea, urethane, ether, amine, anhydride, thioester, thioether functional groups. 4. The addition-fragmentation agent of claim 1 wherein Z—RC— is selected from H2C═CH—CH2—O—C3H6—, H2C═CH—CH2—C6H12—, H2C═CH-cyclo-C6H10—, H2C═CH-phenyl-, H2C═C(CH3)C(O)—O—CH2—CH(OH)—CH2—, H2C═C(CH3)C(O)—O—CH2—CH(O—(O)C(CH3)═CH2)—CH2—, H2C═C(CH3)C(O)—O—CH(CH2OPh)-CH2—, H2C═C(CH3)C(O)—O—CH2CH2—N(H)—C(O)—O—CH(CH2OPh)-CH2—, H2C═C(CH3)C(O)—O—CH2—CH(O—(O)C—N(H)—CH2CH2—O—(O)C(CH3)C═CH2)—CH2—, H2C═C(H)C(O)—O—(CH2)4—O—CH2—CH(OH)—CH2—, H2C═C(CH3)C(O)—O—CH2—CH(O—(O)C—N(H)—CH2CH2—O—(O)C(CH3)C═CH2)—CH2—, CH3—(CH2)7—CH(O—(O)C—N(H)—CH2CH2—O—(O)C(CH3)C═CH2)—CH2—, H2C═C(H)C(O)—O—(CH2)4—O—CH2—CH(—O—(O)C(H)═CH2)—CH2— and H2C═C(H)C(O)—O—CH2—CH(OH)—CH2—, H2C═C(H)C(O)—O—(CH2)4—O—CH2—CH(—O—(O)C(H)═CH2)—CH2—, and CH3—(CH2)7—CH(O—(O)C—N(H)—CH2CH2—O—(O)C(CH3)C═CH2)—CH2—. 5. A method of making the addition-fragmentation agent of claim 1 comprising the steps of reacting compounds of the formula: where RA is a (hetero)hydrocarbyl group, and Y1 is a nucleophilic or electrophilic functional group; with compounds of the formula: Y2—RB—Y2,where RB is each independently a (hetero)hydrocarbyl group and Y2 is a nucleophilic or electrophilic functional group co-reactive with the Y1 group; and with compounds of the formula: Z—RC—Y3,where RC is each independently a (hetero)hydrocarbyl group and Y3 is a nucleophilic or electrophilic functional, co-reactive with the Y2 group. 6. A polymerizable composition comprising the addition-fragmentation oligomer of claim 1, at least one free-radically polymerizable monomer, and an initiator. 7. The polymerizable composition of claim 6 comprising: a) 85 to 100 parts by weight of an (meth)acrylic acid ester;b) 0 to 15 parts by weight of an acid functional ethylenically unsaturated monomer;c) 0 to 10 parts by weight of a non-acid functional, ethylenically unsaturated polar monomer;d) 0 to 5 parts vinyl monomer; ande) 0 to 100 parts of a multifunctional (meth)acrylate; based on 100 parts by weight total monomer a) to d), andf) 0.1 to 20 parts by weight of the addition-fragmentation oligomer, based on 100 parts by weight of a) to e), andg) an initiator. 8. The polymerizable composition of claim 6 further comprising 0.01 to 100 parts of a multifunctional (meth)acrylate. 9. The polymerizable composition of claim 6 further comprising an inorganic filler. 10. The polymerizable composition of claim 6 further comprising a toughening agent. 11. An article comprising a layer of the polymerizable composition of claim 6 on a substrate. 12. An article comprising the cured polymerizable composition of claim 6 on a substrate. 13. A hardcoat composition comprising one or more multifunctional (meth)acrylate monomers or (meth)acrylate oligomers, and the addition-fragmentation agent of claim 1. 14. The hardcoat composition of claim 13 comprising: a) 0.1-10 wt. % of the addition fragmentation oligomer of Formula I;b) 20-80 wt. % of multifunctional (meth)acrylate monomers and/or multifunctional (meth)acrylate oligomers,c) 0 to 25 wt. % range of (meth)acrylate diluent, andd) 20 to 75 wt. % of silica. 15. A curable dental composition comprising: a) at least one dental resin comprising at least two ethylenically unsaturated groups;b) an addition fragmentation oligomer of claim 1; andd) optionally an inorganic oxide filler. 16. The curable dental composition of claim 15 wherein the dental resin further comprises a high refractive index monomer. 17. The curable dental composition of claim 16 comprising: a) 100 parts of at least one dental resin comprising at least two ethylenically unsaturated groups;b) 1 to 50 parts the high refractive index monomer, relative to the dental resin;c) at least 0.1 parts by weight of addition-fragmentation agent(s); andd) optionally an inorganic oxide filler. 18. The curable dental composition of claim 15 further comprising at least 1 part inorganic filler relative to 100 parts of dental resin.
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