Allyl disulfide-containing addition-fragmentation oligomers
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.
1. An addition-fragmentation oligomer of the formula:
wherein
R A is a (hetero)hydrocarbyl group;
R B is each independently a (hetero)hydrocarbyl group;
R C is each independently a (hetero)hydrocarbyl group;
subscript a is greater than 1;
FG 1 , FG 2 and FG 3 are each independently functional groups connected the depicted R A , R B and R C groups; and
Z comprises an ethylenically unsaturated polymerizable group.
2. The addition-fragmentation agent of claim 1 wherein R A , R B and R C are each independently alkylene of 2 to 10 carbon atoms.
3. The addition-fragmentation agent of claim 1 wherein FG 1 , FG 2 and FG 3 are selected from ester, amide, urea, urethane, ether, amine, anhydride, thioester, thioether functional groups.
4. The addition-fragmentation agent of claim 1 wherein Z—R C — is selected from H 2 C═CH—CH 2 —O—C 3 H 6 —, H 2 C═CH—CH 2 —C 6 H 12 —, H 2 C═CH-cyclo-C 6 H 10 —, H 2 C═CH-phenyl-, H 2 C═C(CH 3 )C(O)—O—CH 2 —CH(OH)—CH 2 —, H 2 C═C(CH 3 )C(O)—O—CH 2 —CH(O—(O)C(CH 3 )═CH 2 )—CH 2 —, H 2 C═C(CH 3 )C(O)—O—CH(CH 2 OPh)-CH 2 —, H 2 C═C(CH 3 )C(O)—O—CH 2 CH 2 —N(H)—C(O)—O—CH(CH 2 OPh)-CH 2 —, H 2 C═C(CH 3 )C(O)—O—CH 2 —CH(O—(O)C—N(H)—CH 2 CH 2 —O—(O)C(CH 3 )C═CH 2 )—CH 2 —, H 2 C═C(H)C(O)—O—(CH 2 ) 4 —O—CH 2 —CH(OH)—CH 2 —, H 2 C═C(CH 3 )C(O)—O—CH 2 —CH(O—(O)C—N(H)—CH 2 CH 2 —O—(O)C(CH 3 )C═CH 2 )—CH 2 —, CH 3 —(CH 2 ) 7 —CH(O—(O)C—N(H)—CH 2 CH 2 —O—(O)C(CH 3 )C═CH 2 )—CH 2 —, H 2 C═C(H)C(O)—O—(CH 2 ) 4 —O—CH 2 —CH(—O—(O)C(H)═CH 2 )—CH 2 — and H 2 C═C(H)C(O)—O—CH 2 —CH(OH)—CH 2 —, H 2 C═C(H)C(O)—O—(CH 2 ) 4 —O—CH 2 —CH(—O—(O)C(H)═CH 2 )—CH 2 —, and CH 3 —(CH 2 ) 7 —CH(O—(O)C—N(H)—CH 2 CH 2 —O—(O)C(CH 3 )C═CH 2 )—CH 2 —.
5. A method of making the addition-fragmentation agent of claim 1 comprising the steps of
reacting compounds of the formula:
where R A is a (hetero)hydrocarbyl group, and Y 1 is a nucleophilic or electrophilic functional group; with compounds of the formula:
Y 2 —R B —Y 2 ,
where R B is each independently a (hetero)hydrocarbyl group and Y 2 is a nucleophilic or electrophilic functional group co-reactive with the Y 1 group; and with compounds of the formula:
Z—R C —Y 3 ,
where R C is each independently a (hetero)hydrocarbyl group and Y 3 is a nucleophilic or electrophilic functional, co-reactive with the Y 2 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; and
e) 0 to 100 parts of a multifunctional (meth)acrylate;
based on 100 parts by weight total monomer a) to d), and
f) 0.1 to 20 parts by weight of the addition-fragmentation oligomer, based on 100 parts by weight of a) to e), and
g) 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, and
d) 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 ; and
d) 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); and
d) 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.