Process for polymerization reactions with functionalized peroxides

A process for polymerizing an unsaturated monomer or unsaturated polymer comprising reacting an unsaturated monomer or unsaturated polymer or a polymer susceptible to graft polymerization and a peroxide compound under conditions effective to polymerize the unsaturated monomer or polymer, the unsaturated monomer being selected from the group consisting of ethylenically unsaturated monomers, acrylic monomers, and mixtures thereof, and the unsaturated polymer being selected from the group consisting of unsaturated polyester resins, unsaturated elastomer resins, and mixtures therof, provided that when the polymer is one susceptible to graft polymerization, the peroxide compound is present in an amount of about 0.001% to about 50% by weight, when the unsaturated monomer is an acrylic monomer or mixture thereof, the peroxide compound is present in an amount of about 0.001% to about 15% by weight, and when the unsaturated monomer or unsaturated polymer is other than a polymer subject to graft polymerization or an acrylic monomer, the peroxide compound is present in an amount of about 0.001% to about 10% by weight, the peroxide compound having the following Formula I:

• ##STR36## wherein R.sup.1, R.sup.2, R.sup.6 and R.sup.7 are independently a substituted or unsubstituted alkyl diradical of 1 to 18 carbons, a substituted or unsubstituted cycloalkyl diradical of 5 to 18 carbons, a substituted or unsubstituted bicycloalkyl diradical of 7 to 12 carbons, a substituted or unsubstituted bicycloalkenyl diradical of 7 to 12 carbons, a substituted or unsubstituted alkenyl diradical of 2 to 18 carbons, a substituted or unsubstituted alkynyl diradical of 2 to 18 carbons, a substituted or unsubstituted aralkyl diradical of 7 to 18 carbons, a substituted or unsubstituted naphthyl diradical or a substituted or unsubstituted diradical having the following Formula II:
• ##STR37## with the proviso that when X is a direct bond, R.sup.6 is not a tertiary alkyl diradical;
• R.sup.3 is a substituted or unsubstituted alkyl diradical of 1 to 18 carbons, a substituted or unsubstituted aralkyl diradical of 7 to 18 carbons, a substituted or unsubstituted naphthyl diradical or the substituted or unsubstituted diradical having the Formula II;
• R.sup.4 and R.sup.5 are independently a substituted or unsubstituted alkyl radical of 1 to 10 carbons;
• R.sup.8 is a direct bond, --O--, --S--, --S(.dbd.O).sub.2 --, --C(.dbd.O)--, --C(.dbd.O)--O--, --O--C(.dbd.O)--, --O--C(.dbd.O)--O--, --NH--C(.dbd.O)--, --C(.dbd.O)--NH--, --NH--C(.dbd.O)--NH-- or a substituted or unsubstituted alkyl diradical of 1 to 6 carbons;
• X is a direct bond;
• Y.sup.1, Y.sup.2 and Y.sup.3 are independently --O--, --S--, --S(.dbd.O).sub.2 --, --C(.dbd.O)--, --C(.dbd.O)--O--, --O--C(.dbd.O)--, --O--C(.dbd.O)--O--, --NH--C(.dbd.O)--, --C(.dbd.O)--NH--, --NH--C(.dbd.O)--O--, --O--C(.dbd.O)--NH--, --NH--C(.dbd.O)--NH, --C(.dbd.O)--C(.dbd.O)--, --O--C(.dbd.O)--C(.dbd.O)--O--, --NH--C(.dbd.O)--C(.dbd.O)--NH--, --NH--C(.dbd.O)--C(.dbd.O)--O-- or --O--C(.dbd.O)--C(.dbd.O)--NH--;
• Z.sup.1 is H.sub.2 N--, O.dbd.C.dbd.N--, Cl--C(.dbd.O)--, Br--C(.dbd.O)--, HO--C(.dbd.O)--, ##STR38## H.sub.2 N--C(R.sup.9) (R.sup.10)--(CH.sub.2).sub.w --Y.sup.1 -- or R.sup.11 --O--C(.dbd.O)--;
• Z.sup.2 is H.sub.2 N--, O.dbd.C.dbd.N--, Cl--C(.dbd.O)--, Br--C(.dbd.O)--, ##STR39## or H.sub.2 N--C(R.sup.9) (R.sup.10)--(CH.sub.2).sub.w --Y.sup.1 --;
• R.sup.9 and R.sup.10 are independently hydrogen or a substituted or unsubstituted alkyl radical of 1 to 4 carbons;
• R.sup.11 is an alkyl radical of 1-4 carbons, benzyl or phenyl;
• t, x, y and z are independently 0 or 1;
• w is an integer from 1 to 12;
• and
• substituents for any of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9 or R.sup.10 are independently one or more of chloro, bromo, fluoro, cyano, amino, sulfo, carboxy, nitro, alkoxy of 1 to 12 carbons, alkylamino of 1 to 12 carbons, acyloxy of 1 to 12 carbons, alkenoyloxy of 3 to 12 carbons, alkenoylamino of 3 to 12 carbons, aroyloxy of 7 to 15 carbons, aroylamino of 7 to 15 carbons, phthalimido, alkoxycarbonyloxy of 2 to 13 carbons, alkoxycarbonylamino of 2 to 13 carbons, alkenyloxycarbonyloxy of 3 to 12 carbons, alkenyloxycarbonylamino of 3 to 12 carbons, aryloxycarbonyloxy of 7 to 15 carbons, alkylaminocarbonyloxy of 2 to 13 carbons, arylaminocarbonyloxy of 7 to 15 carbons, aralkylaminocarbonyloxy of 7 to 16 carbons, alkylsulfonyloxy of 1 to 8 carbons, alkylsulfonylamino of 1 to 8 carbons, arylsulfonylamino of 6 to 11 carbons or epoxyalkoxycarbonyl of 2 to 13 carbons.