Bulk radical polymerization using a batch reactor

A method of free radically polymerizing vinyl monomers comprising the steps of:

• (a) providing a mixture comprising:
• (i) free radically (co)polymerizable vinyl monomers;
• (ii) optional chain transfer agent;
• (iii) optional crosslinking agent;
• (iv) at least one thermal free-radical initiator;
• (v) optionally polymer comprising polymerized free radically polymerizable monomers;
• in a batch reactor;
• (b) deoxygenating the mixture if the mixture is not already deoxygenated, wherein step (b) can optionally at least partially overlap with step (c);
• (c) heating the mixture to a sufficient temperature to generate sufficient initiator free radicals from at least one thermal free radical initiator so as to initiate polymerization;
• (d) allowing the mixture to polymerize under essentially adiabatic conditions to yield an at least partially polymerized mixture;
• (e) optionally heating the mixture to generate free radicals from some or all of any initiator that has not generated initiator free radicals, followed by allowing the mixture to polymerize under essentially adiabatic conditions to yield a further polymerized mixture;
• and
• (f) optionally repeating step (e) one or more times;
• (g) optionally cooling the mixture;
• (h) adding to the mixture in the batch reactor at least one thermal free radical initiator wherein the initiator(s) of step (h) can be the same or different than the initiator(s) of step (a), optionally free radically polymerizable monomers, optionally crosslinking agents, optionally chain transfer agent(s), optionally polymer comprising polymerized free radically polymerizable monomers, wherein the mixture optionally has a temperature below that which would generate initiator free radicals from the initiator(s) added in step (h);
• (i) deoxygenating the mixture if the mixture is not already deoxygenated;
• (j) optionally heating the mixture to generate initiator free radicals from at least one initiator to further polymerize the mixture if the mixture has a temperature below that which would generate initiator free radicals from the initiator(s) in step (h);
• (k) allowing the mixture to further polymerize under essentially adiabatic conditions to yield a further polymerized mixture;
• (l) optionally heating the mixture to generate free radicals from some or all of any initiator that has not generated initiator free radicals, followed by allowing the mixture to polymerize under essentially adiabatic conditions to yield a further polymerized mixture;
• (m) optionally repeating step (l) one or more times;
• (n) optionally repeating steps (g) through (m) one or more times.