# US 5,710,213 A · Process for polymerization reactions with functionalized peroxides

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- Number: US 5,710,213 A
- Document ID: US5710213A
- Status: Granted
- Kind: A
- Application number: 08/465,851
- Filed: 1995-06-06
- Granted: 1998-01-20
- Earliest claimed: 1990-09-05
- Assignees: Elf Atochem North America, Inc.
- Inventors: Daryl L. Stein
- Web page: https://patentgrep.com/patent/US5710213A

## CPC

- C08G 18/86: by peroxides
- C07C 409/38: the —O—O— group being bound between a >C=O group and a carbon atom, not further substituted by oxygen atoms, i.e. esters of peroxy acids
- C08F 283/01: on to unsaturated polyesters {(C08F283/004 takes precedence)}
- C07C 2601/14: The ring being saturated
- C07C 2602/42: the bicyclo ring system containing seven carbon atoms
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

Novel functionalized peroxides which may be used as crosslinking, grafting and curing agents, initiators for polymerization reactions and as monomers for condensation polymerizations to form peroxy-containing polymers, which in turn can be used to prepare block and graft copolymers, have the following Formula I: ##STR1## R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, X, Y.sup.1, Y.sup.2, Y.sup.3, Z.sup.1, Z.sup.2, x, y and z are as defined in the Summary of the Invention. The compounds of Formula I may be prepared by reacting hydroxy-containing tertiary hydroperoxides with diacid halides, phosgene, dichloroformates, diisocyanates, anhydrides and lactones to form the functionalized peroxides. These reaction products may be further reacted, if desired, with dialcohols, diamines, aminoalcohols, epoxides, epoxy alcohols, epoxy amines, diacid halides, dichloroformates and diisocyanates to form additional functionalized peroxides.

## Claims

### Claim 1

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.

### Claim 2 (depends on 1)

The process according to claim 1 wherein, in Formula I for the peroxide compound,
R.sup.1, R.sup.2, R.sup.6 and R.sup.7 are independently a substituted or unsubstituted alkyl diradical of 1 to 10 carbons, a substituted or unsubstituted cycloalkyl diradical of 5 to 12 carbons, a substituted or unsubstituted bicycloalkyl diradical of 7 to 10 carbons, a substituted or unsubstituted bicycloalkenyl diradical of 7 to 10 carbons, a substituted or unsubstituted alkenyl diradical of 2 to 8 carbons, a substituted or unsubstituted alkynyl diradical of 2 to 8 carbons, a substituted or unsubstituted aralkyl diradical of 7 to 12 carbons, a substituted or unsubstituted naphthyl diradical or a substituted or unsubstituted diradical of Formula II;
R.sup.3 is a substituted or unsubstituted alkyl diradical of 1 to 12 carbons, a substituted or unsubstituted aralkyl diradical of 7 to 12 carbons, a substituted or unsubstituted naphthyl diradical or a substituted or unsubstituted diradical of Formula II;
Z.sup.1 is, O.dbd.C.dbd.N--, Cl--C(.dbd.O)--, HO--C(.dbd.O)--, ##STR40## or R.sup.11 --O--C(.dbd.O)--; Z2 is, O.dbd.C.dbd.N-- or ##STR41## and substituents for any of R.sup.1, R.sup.2, R.sup.3, R.sup.6 and R.sup.7 are independently one or two of chloro, bromo, amino, carboxy, alkoxy of 1 to 6 carbons, acyloxy of 2 to 5 carbons, alkenoyloxy of 3 to 5 carbons or aroyloxy of 7 to 10 carbons.

### Claim 3 (depends on 1)

The process according to claim 1 wherein, in Formula I for the peroxide compound,
R.sup.1, R.sup.2, R.sup.6 and R.sup.7 are independently a substituted or unsubstituted alkyl diradical of 1 to 6 carbons, a substituted or unsubstituted cycloalkyl diradical of 5 to 7 carbons, a substituted or unsubstituted bicycloalkyl diradical of 7 to 8 carbons, a substituted or unsubstituted bicycloalkenyl diradical of 7 to 8 carbons, a substituted or unsubstituted alkenyl diradical of 2 to 4 carbons, a substituted or unsubstituted aralkyl diradical of 7 to 12 carbons or a substituted or unsubstituted diradical of Formula II;
R.sup.3 is an alkyl diradical of 1 to 8 carbons;
R.sup.4 and R.sup.5 are independently alkyl of 1 to 3 carbons;
Y.sup.1, Y.sup.2 and Y.sup.3 are independently --C(.dbd.O)--O-- or --O--C(.dbd.O)--;
Z.sup.1 is, O.dbd.C.dbd.N--, Cl--C(.dbd.O)-- or HO--C(.dbd.O)--;
Z.sup.2 is, O.dbd.C.dbd.N-- or Cl--C(.dbd.O)--; and
substituents for any of R.sup.1, R.sup.2, R.sup.3, R.sup.6 and R.sup.7 are independently chloro, carboxy, alkoxy of 1 to 4 carbons, acyloxy of 2 to 3 carbons or alkenoyloxy of 3 to 5 carbons.

### Claim 4 (depends on 1)

The process according to claim 1 wherein the peroxide compound is ##STR42##

### Claim 5 (depends on 1)

The process according to claim 1, for polymerizing an ethylenically unsaturated monomer or monomer blend, comprising mixing an ethylenically unsaturated monomer or blend of two or more ethylenically unsaturated monomers with about 0.001% by weight to about 10% by weight of the peroxide compound at a temperature effective to initiate free radical polymerization of the monomer or monomer blend.

### Claim 6 (depends on 5)

The process of claim 5 wherein the ethylenically unsaturated monomer is selected from the group consisting of ethylene, propylene, styrene, p-methylstyrene, p-chlorostyrene, alpha-methylstyrene, butadiene, isoprene, chloroprene, vinyl acetate, vinyl chloride, vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, methyl vinyl ether, ethyl vinyl ether, allyl alcohol, acrylonitrile, acrylic acid, methyl acrylate, butyl acrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, acrylamide, acrolein and mixtures thereof.

### Claim 7 (depends on 1)

The process according to claim 1, for curing an unsaturated polyester resin, comprising heating an unsaturated polyester resin and about 0.001% by weight to about 10% by weight of the peroxide compound at a temperature effective to cure the polyester resin.

### Claim 8 (depends on 1)

The process according to claim 1, for curing an unsaturated elastomer resin, comprising heating an elastomer resin containing unsaturation and about 0.001% by weight to about 10% by weight of the peroxide compound at a temperature effective to cure the elastomer resin.

### Claim 9 (depends on 1)

The process according to claim 1, for graft polymerizing at least one monomer onto a polymer, comprising reacting a monomer with a polymer susceptible to graft polymerization in the presence of about 0.001% by weight to about 50% by weight of the peroxide compound under conditions effective to graft polymerize the monomer onto the polymer.

### Claim 10 (depends on 1)

The process according to claim 1, resulting in a hydroxy functionalized acrylic resin or a carboxy functionalized acrylic resin, comprising heating a blend of acrylic monomers and about 0.001% by weight to about 15% by weight of the peroxide compound at a temperature effective to initiate free radical polymerization of the monomer blend.

### Claim 11 (depends on 10)

The process of claim 10 wherein the monomers in the blend of acrylic monomers are selected from the group consisting of branched or unbranched alkyl acrylate or branched or unbranched alkyl methacrylate or mixtures thereof, where the alkyl group is substituted or unsubstituted alkyl of 1 to 18 carbons, the substituents being selected from the group consisting of alkoxy of 1 to 4 carbons, chloro, phenyl and dialkylamino of 2 to 4 carbons; hydroxyalkyl methacrylate and hydroxyalkyl acrylate, where the alkyl group is substituted or unsubstituted alkyl of 2 to 8 carbons, the substituents being selected from the group consisting of alkyl of 1 to 4 carbons, alkoxy of 1 to 4 carbons, chloro and hydroxy.

### Claim 12 (depends on 10)

The process of claim 10 further comprising conducting the polymerization reaction in the presence of at least one ethylenically unsaturated monomer.

### Claim 13 (depends on 12)

The process of claim 12 wherein the ethylenically unsaturated monomer is selected from the group consisting of styrene, maleic anhydride, acrylic acid, methacrylic acid, 5-norbornene-2,3-dicarboxylic anhydride, glycidyl acrylate, glycidyl methacrylate, isocyanatoethyl acrylate, isocyanatoethyl methacrylate and mixtures thereof.