Pennwalt Corporation

Orville L Mageli

Antonio Joseph D'Angelo

Wilbur H McKellin

William A Swarts

Chester Stephen Sheppard

Richard A Bafford

David C Noller

James R Kolczynski

A polyperoxyketal having at least one carboxy group--an acid, hydrocarbon ester, a metal ion, or as part of an anhydride. Illustrations are: n-Butyl .gamma.,.gamma.-bis-(t-butylperoxy) valerate and Barium .gamma.,.gamma.-bis(t-butylperoxy) valerate. These polyperoxyketals are vulcanizing agents for thermoplastic polymers such as rubber and ethylenepropylene rubber.

Polyperoxy compounds

A polyperoxyketal compound is provided having at least one carboxy group, a hydrocarbon ester. An example of this compound is n-butyl gamma,gamma-bis(t-butylperoxy)valerate. This polyperoxyketal compound is used as a vulcanizing agent for thermoplastic polymers such as rubber and ethylene-propylene rubber.

Polymers of the formula [(A.sub.n.sbsb.1 -R-D.sub.n.sbsb.2).sub.v P.sub.n.sbsb.3 ].sub.w Z.sub.n.sbsb.4 where A is a peroxy-containing group; R is a 2-4 valent aliphatic, cycloaliphatic or aromatic radical; P is a polyvalent polymeric residue; D is a carbonyl-containing connecting group; and Z is a terminal group, such polymers being useful with vinyl monomers in the formation of block and graft polymers.

Polymer from peroxy compounds containing acylating groups

A novel class of compounds having the formula ##STR1## where Z is a substituted carbonate or carbamate, D is alkynyl or an alkyl, and the R's may be alkyl.

Peroxy compounds and vulcanizable compositions thereof

An aliphatic or cycloaliphatic hydroperoxide, an olefin such as a 1-aromatic-1-substituted ethylene and a halide corresponding to the ethylene are reacted under essentially anhydrous conditions, in the absence of a free acid, at a temperature below the decomposition temperature of the halide to obtain a peroxide corresponding to the hydroperoxide and the ethylene. Preferably the product peroxide is recovered by treating the reaction product mixture with aqueous alkali metal hydroxide to destroy the halide and hydroperoxide therein; then distilling the treated mixture in the presence of a substantial amount of liquid water at sub-atmospheric pressure to remove overhead impurities. Example: Dicumyl peroxide is prepared by reacting at about 30.degree. C. for about 5 hours cumene hydroperoxide, .alpha.-methylstyrene and cumyl chloride, which compounds has been charged to the reaction zone in a mole ratio of 1.25:0.86:0.14 and treating the reaction product mixture with aqueous alkali metal hydroxide to remove cumyl chloride and cumene hydroperoxide to obtain a product mixture including dicumyl peroxide; and adding 2-10 parts of liquid water to the product mixture in a distillation zone and vaporizing water and impurities at a temperature of about 30.degree.-80.degree. C. at a pressure of about 0.01-0.5 atmospheres and continuing said vaporization until essentially no oily liquid is obtained in a condensor receiving vapors from said zone, under conditions such that a substantial amount of liquid water is present in said zone in contact with peroxide product.

Process for di-organic peroxides

A novel class of compounds having the formula ##STR1## where Z is a substituted carbonate or carbamate, D is an alkynyl or an alkyl, and the R's may be alkyl.

Peroxy compounds

An aliphatic or cycloaliphatic hydroperoxide, an olefin such as a 1-aromatic-1-substituted ethylene and a halide corresponding to the ethylene are reacted under essentially anhydrous conditions, in the absence of a free acid, at a temperature below the decomposition temperature of the halide to obtain a peroxide corresponding to the hydroperoxide and the ethylene. Preferably the product peroxide is recovered by treating the reaction product mixture with aqueous alkali metal hydroxide to destroy the halide and hydroperoxide therein; then distilling the treated mixture in the presence of a substantial amount of liquid water at sub-atmospheric pressure to remove overhead impurities. Example: Dicumyl peroxide is prepared by reacting at about 30.degree. C for about 5 hours cumene hydroperoxide, .alpha.-methylstyrene and cumyl chloride, which compounds has been charged to the reaction zone in a mole ratio of 1.25: 0.86: 0.14 and treating the reaction product mixture with aqueous alkali metal hydroxide to remove cumyl chloride and cumene hydroperoxide to obtain a product mixture including dicumyl peroxide; and adding 2-10 parts of liquid water to the product mixture in a distillation zone and vaporizing water and impurities at a temperature of about 30-80.degree. C at a pressure of about 0.01-0.5 atmospheres and continuing said vaporization until essentially no oily liquid is obtained in a condensor receiving vapors from said zone, under conditions such that a substantial amount of liquid water is present in said zone in contact with peroxide product.

Process for bi-organic peroxides

A new class of compounds: R-W-R' where R and R' are identical oxy radicals containing peroxide functions such as dialkyl or diaralkyl peroxide, peroxyketal, peroxyester, or monoperoxycarbonate, and W is a carbonyl group, or carbonyl containing group, or an alkylidene or aralkylidene group, or a phosphorus containing group. Examples: Di[1,3-dimethyl-3-(t-butylperoxy)butyl] carbonate; Di[1,3-dimethyl-3-(n-butoxycarbonylperoxy)butyl] carbonate; 2,2-Bis[3,3-di(t-butylperoxy)butoxy] propane; Di[1,3-dimethyl-3-(t-butylperoxy)butyl] ethyl phosphate. They are free radical affording compounds useful in crosslinking of polyolefins and unsaturated polymers, and for the polymerization of vinyl monomers and diolefinic monomers.

Coupled peroxides

Vulcanizable compositions containing a polyperoxyketal having at least one carboxy group as an acid, hydrocarbon ester, a metal ion salt or as part of an anhydride. Illustrations are rubber or ethylene-propylene rubber containing n-butyl .gamma., .gamma.-bis(t-butylperoxy) valerate, barium .gamma., .gamma.-bis(t-butylperoxy)valerate or .gamma., .gamma.-bis(t-butylperoxy) valeric acid anhydride. Also embodied are the cross-linked compositions and methods of crosslinking.

Vulcanizable and vulcanized compositions containing polyperoxide

I. A novel class of compounds X.sub.n --R.sub.p --Y.sub.m where R is a 2-4 valence aliphatic, cycloaliphatic or aromatic radical, X is an acylating function; Y is a peroxy containing group and n and m are each equal to 1-2 and p is at least 1. Ii. a novel class of polymers [A.sub.n -(R-D.sub.n).sub.n ].sub.v -P.sub.w -Z where A is a peroxy containing group; R is a 2-4 valence aliphatic, cycloaliphatic or aromatic radical, P is a polyvalent polymeric residue; D is a carbonyl containing connecting group; Z is H, OH, NH.sub.2, NHR.sub.2, SH or R.sub.2 O group; v and w are each equal to 1-100; and n is equal to 1-2. Iii. polymers II are useful with vinyl monomers in the formation of block and graft polymers. Iv. peroxides having an acylating function are prepared by reacting at 0.degree.-80.degree. C an organic peroxide having an hydroxyl or carboxyl group with a defined acylating reactant. V. peroxides having at least one acylating function are prepared by peroxidizing a compound having at least two acylating functions as the only peroxidizable substituents.

Diacyl peroxy compounds

A new class of compounds: R--W--R' were R and R' are identical oxy radicals containing peroxide functions such as dialkyl or diaralkyl peroxide, peroxyketal, peroxyester, or monoperoxycarbonate, and W is a carbonyl group, or carbonyl containing group, or an alkylidene or aralkylidene group, or a phosphorus containing group.

A new class of compounds: R-W-R' where R and R' are identical oxy radicals containing peroxide functions such as dialkyl or diaralkyl peroxide, proxyketal, peroxyester, or monoperoxycarbonate, and W is a carbonyl group, or carbonyl containing group, or an alkylidene or aralkylidene group, or a phosphorous containing group. Examples:

Polymer crosslinking with coupled peroxides

A safe peroxide solution composition consisting essentially of a diacyl peroxide having 1-5 carbon atoms in each aliphatic group and an aliphatic hydrocarbon, ketone, ester, ether, or alcohol characterized by a vapor pressure substantially that of the peroxide. Example: Equal parts by weight of diacetyl peroxide and ethyl butyl ketone.

Growing community of inventors

Kenmore, NY, United States of America

Orville L Mageli