Controlled free radical polymerization process

A free radical polymerization process for the preparation of a thermoplastic resin or resins comprising the step of:

• heating from about 80° C. to about 160° C. a mixture of at least one polymerizable monomer compound and a preformed nitroxide adduct having the following formula:
• wherein X is CH2 or C═O, Y is O or N—R, R, R1, R2, R3, R4, and R5 are independently selected from the group consisting of aryl, alkyl having from 1 to about 24 carbon atoms, cycloalkyl having from 5 to about 7 carbon atoms, aralkyl having from 7 to about 20 carbon atoms, cyanoalkyl having from 2 to about 12 carbon atoms, ether having from 4 to about 18 carbon atoms, and hydroxyalkyl having from 1 to about 18 carbon atoms;
• and
• R1 and R2 together, or R3 and R4 together, or each pair, may be cyclized forming a ring having from about 5 to about 14 carbon atoms to form said thermoplastic resin or resins with a polydispersity from about 1.0 to about 3.0.

A free radical polymerization process for the preparation of a (meth)acrylate containing block copolymer comprising the steps of:

• (a) heating from about 80° to about 160° C. a first mixture of a free radical initiator, a first polymerizable monomer compound, and a stable free radical agent comprising a nitroxyl radical having the following formula:
• wherein X is CH2 or C═O, Y is O or N—R, R, R1, R2, R3, and R4 are independently selected from the group consisting of aryl, alkyl having from 1 to about 24 carbon atoms, cycloalkyl having from 5 to about 7 carbon atoms, aralkyl having from 7 to about 20 carbon atoms, cyanoalkyl having from 2 to about 12 carbon atoms, ether having from 4 to about 18 carbon atoms, and hydroxyalkyl having from 1 to about 18 carbon atoms;
• and
• R1 and R2 together, or R3 and R4 together, or each pair, may be cyclized forming a ring having from about 5 to about 14 carbon atoms to form a prepolymer;
• and
• (b) heating from about 80° C. to about 160° C. a second mixture of said prepolymer and a second polymerizable monomer compound, said second polymerizable monomer compound being different than said first polymerizable compound.

A free radical polymerization process for the preparation of a (meth)acrylate containing block copolymer comprising the steps of:

• (a) heating from about 80° C. to about 160° C. a first mixture of a first polymerizable monomer compound and a preformed nitroxide adduct having the following formula:
• wherein X is CH2 or C═O, Y is O or N—R, R, R1, R2, R3, R4, and R5 are independently selected from the group consisting of aryl, alkyl having from 1 to about 24 carbon atoms, cycloalkyl having from 5 to about 7 carbon atoms, aralkyl having from 7 to about 20 carbon atoms, cyanoalkyl having from 2 to about 12 carbon atoms, ether having from 4 to about 18 carbon atoms, and hydroxyalkyl having from 1 to about 18 carbon atoms;
• and
• R1 and R2 together, or R3 and R4 together, or each pair, may be cyclized forming a ring having from about 5 to about 14 carbon atoms to form a prepolymer;
• and
• (b) heating from about 80° C. to about 160° C. a second mixture of said prepolymer and a second polymerizable monomer compound, said second polymerizable monomer compound being different than said first polymerizable compound.

A free radical polymerization process for the preparation of a (meth)acrylate containing triblock copolymer comprising the steps of:

• (a) heating from about 80° to about 160° C. a first mixture of a free radical initiator, a first polymerizable monomer compound, and a stable free radical agent comprising a nitroxyl radical having the following formula:
• wherein X is CH2 or C═O, Y is O or N—R, R, R1, R2, R3, and R4 are independently selected from the group consisting of aryl, alkyl having from 1 to about 24 carbon atoms, cycloalkyl having from 5 to about 7 carbon atoms, aralkyl having from 7 to about 20 carbon atoms, cyanoalkyl having from 2 to about 12 carbon atoms, ether having from 4 to about 18 carbon atoms, and hydroxyalkyl having from 1 to about 18 carbon atoms;
• and
• R1 and R2 together, or R3 and R4 together, or each pair, may be cyclized forming a ring having from about 5 to about 14 carbon atoms, to form a prepolymer;
• (b) heating from about 80° C. to about 160° C. a second mixture of said prepolymer and a second polymerizable monomer compound, said second polymerizable monomer compound being different than said first polymerizable compound, to form a block copolymer;
• and
• (c) heating from about 80° C. to about 160° C. a third mixture of said block copolymer and a third polymerizable compound.

In a free radical polymerization process for the preparation of a thermoplastic resin or resins of the type comprising heating from about 80° C. to about 160° C. a mixture of a free radical initiator, a nitroxide stable free radical agent, and at least one polymerizable monomer compound, to form said thermoplastic resin or resins having a high monomer to polymer conversion and a narrow polydispersity, wherein the improvement comprises:

• said nitroxide stable free radical agent being a nitroxide radical having the following formula:
• wherein X is CH2 or C═O, Y is O or N—R, R, R1, R2, R3, R4, and R5 are independently selected from the group consisting of aryl, alkyl having from 1 to about 24 carbon atoms, cycloalkyl having from 5 to about 7 carbon atoms, aralkyl having from 7 to about 20 carbon atoms, cyanoalkyl having from 2 to about 12 carbon atoms, ether having from 4 to about 18 carbon atoms, and hydroxyalkyl having from 1 to about 18 carbon atoms;
• and
• R1 and R2 together, or R3 and R4 together, or each pair, may be cyclized forming a ring having from about 5 to about 14 carbon atoms.