S,S′-BIS-(α, α′-DISUBSTITUTED-α-ACETIC ACID)-TRITHIOCARBONATES AND DERIVATIVES AS INITIATOR-CHAIN TRANSFER AGENT-TERMINATOR FOR CONTROLLED RADICAL POLYMERIZATIONS AND THE PROCESS FOR MAKING THE SAME
View Patent ↗A s,s′-bis-(α, α′-disubstituted-α″-acetic acid)-trithiocarbonate and derivatives thereof can be used as an initiator, chain transfer agent, or terminator for polymerization of monomers such as free radical polymerizable monomers. Homopolymers, copolymers, and the like as well as block copolymers can be made utilizing the trithio carbonate compound such as in a living free radical polymerization as well as to form telechelic polymers.
1. A polymer, comprising:
repeat units derived from the free radical polymerization of at least one vinyl monomer, or at least one conjugated diene monomer, or combinations thereof, in the presence of a s,s′-bis-(α, α′-disubstituted-α″-acetic acid)-trithiocarbonate compound having the formula:
wherein R 1 and R 2 , independently, is an alkyl having from 1 to about 6 carbon atoms, or a substituted C 1 to about C 6 alkyl having one or more substituents, or one or more aryls, or a substituted aryls having from 1 to 6 substituents on the aryl ring; wherein said one or more substituents, independently, are selected from an alkyl having from 1 to 6 carbon atoms, an aryl, a halogen which can be the same or different, a cyano, an ether having a total of from 2 to about 20 carbon atoms, a nitro, and combinations thereof; and wherein R 1 and R 2 are part of a cyclic ring having from about 5 to about 12 total carbon atoms.
2. A polymer according to claim 1 , wherein said conjugated diene monomer has from 4 to 12 carbon atoms, and wherein said one vinyl monomer has the formula:
where R 3 is selected from hydrogen, halogen, C 1 -C 4 alkyl, substituted C 1 -C 4 alkyl wherein said substituents, independently, are selected from one or more hydroxy, alkoxy, aryloxy(OR 5 ), carboxy, acyloxy, aroyloxy(O 2 CR 5 ), alkoxy-carbonyl(CO 2 R 5 , and aryloxy-carbonyl;
wherein R 4 is selected from hydrogen, R 5 , CO 2 H, CO 2 R 5 , COR 5 , CN, CONH 2 , CONHR 5 , O 2 CR 5 , OR 5 and halogen; and
wherein R 5 is selected from C 1 -C 18 alkyl, substituted C 1 -C 18 alkyl, C 2 -C 18 alkenyl, aryl, heterocyclyl, aralkyl, and alkaryl, and wherein said substituents, independently, are selected from one or more epoxy, hydroxy, alkoxy, acyl, acyloxy, carboxy, sulfonic acid, alkoxy- or aryloxy-carbonyl, cyanato, cyano, silyl, halo and dialkylamino.
3. A polymer according to claim 2 , wherein said one or more monomers are selected from an acrylate having from 1 to 8 carbon atoms, a methacrylate having form 1 to 8 carbon atoms, styrene, butadiene, isoprene, acrylonitrile, and combinations thereof, and wherein R 1 and R 2 , independently, are methyl or phenyl.
4. A polymer according to claim 1 , wherein said s,s′-bis-(α, α′-disubstituted-α″-acetic acid)-trithiocarbonate is an initiator, or a chain transfer agent, or both.
5. A polymer according to claim 2 , wherein said s,s′-bis-(α, α′-disubstituted-α″-acetic acid)-trithiocarbonate is an initiator, a chain transfer agent, or both.
6. A polymer according to claim 3 , wherein said s,s′-bis-(α, α′-disubstituted-α″-acetic acid)-trithiocarbonate is an initiator, a chain transfer agent, or both.
7. A polymer according to claim 4 , including a free radical initiator.
8. A polymer according to claim 5 , including a free radical initiator.
9. A polymer according to claim 6 , including a free radical initiator.
10. A polymer according to claim 7 , wherein said free radical initiator is 2,2′-azobis(isobutyronitrile)(AIBN); or 4,4′-azobis(4-cyanopentanoic acid); 2,2′-azobis(2-cyano-2-butane); or 1, 1′-azobis(cyclohexanecarbanitrile), or combinations thereof.
11. A polymer according to claim 8 , wherein said free radical initiator is 2,2′-azobis(isobutyronitrile)(AIBN); or 4,4′-azobis(4-cyanopentanoic acid); 2,2′-azobis(2-cyano-2-butane); or 1, 1′-azobis(cyclohexanecarbanitrile); or combinations thereof, and wherein the amount of free radical initiator is from about 0.01 to about 25 mole percent based upon the total number of moles of said s,s′-bis-(α, α′-disubstituted-α″-acetic acid)-trithiocarbonate compound.
12. A polymer according to claim 9 , wherein said free radical initiator is 2,2′-azobis(isobutyronitrile)(AIBN); or 4,4′-azobis(4-cyanopentanoic acid); 2,2′-azobis(2-cyano-2-butane); or 1, 1′-azobis(cyclohexanecarbanitrile); or combinations thereof, and
wherein the amount of free radical initiator is from about 0.1 to about 10 mole percent based upon the total number of moles of said s,s′-bis-(α, α′-disubstituted-α″-acetic acid)-trithiocarbonate compound.
13. A polymer according to claim 4 , wherein the polydispersity of said polymer is 1.75 or less.
14. A polymer according to claim 5 , wherein the polydispersity of said polymer is 1.75 or less.
15. A polymer according to claim 6 , wherein the polydispersity of said polymer is 1.50 or less.
16. A polymer according to claim 1 , wherein the polydispersity of said polymer is 1.50 or less.