Here and in this month‘s Quarterly are
TABLE I . ORGANIC PEROXIDE DEVELOPMENT
nine papers on their handling and use
Benzoyl peroxide Lauroyl peroxide
1858 Reported by B. C. Brodie 1927 Commercially available (Luddol)
I 1937
&Butylhydroperoxide
1938 Reported by Milas and Harris 1939 Patent-Research COT. 1938 65% solution (Mass. Pharmaceutical COT.) 1943 65% solution (Union Bay State Chemical Co.)
Di-t-butyl peroxide
1946 Reported by Milas and Surgenor 1943 Pure material offered (Union Bay State Chemical Co.) 1946 PatentShell Development Co.
t -Butyl perbenzoate
1946 Reported by Milas and Surgenor 1943 Offered commercially (Union Bay State Chemical CO.) 1951 Patent-Research COT.
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rganic peroxides occur naturally as intermediates . m oxidation. The compounds which have become commercial, however, are synthetic products developed during the last century. Examples of the structural types currently used in industry are illustrated in the figure on the opposite page. The structures shown are benzoyl and acetyl peroxides (diacyl peroxides), diisopropyl peroxydicarbonate (carbonate ester), l-hydroxy-1 ’-hydroperoxydicyclohexyl peroxide and bis2,2-dihydroperoxybutane (ketones), t-butyl peroxybenzoate and t-butyl peroxyacetate (peroxyesters), cumene hydroperoxide and t-butyl hydroperoxide (hydroperoxides), and di-t-butyl peroxide and dicumyl peroxide (dialkyl peroxides), Peroxy acids, not included here because of a different area of application, might he considered as hydroperoxides. Structures of some of the newer peroxides are shown on this page. The first organic peroxide synthesized in the laboratory was of the diacyl type. B. C . Brodie reported in 1858 the preparation of benzoyl peroxide from benzoyl chloride and hydrated barium peroxide. Benzoyl peroxide was also the first to be developed commercially, and even today is one of the most widely used organic peroxides. The Dutch firm of Noury & van der Lande, in the early 1900’s, marketed this peroxide as a bleaching agent for vegetable oils. This operation was soon sold to American interests, and eventually became the Lucidol Division of Wallace & Tiernan, Inc. Table I summarizes the highlights of development in the United States. In September of 1964 a symposium entitled “Development, Stabilization, and Uses of Organic Peroxides” was presented before the 148th National Meeting of the ACS. Three articles developed from this symposium appear on the next 21 pages, while six articles appear in the concurrent issue of the I&EC Product Research and Development quarterly. These are:
Commercially available (Luddol)
Acetyl peroxide
I 1863 I
_ _ _ _ _ ~
Reported by B. C. Brodie 1944 Commercially available (in solution) (BECCO) 1949 Solution patented (BECCO)
~
Cumene hydroperoxide 1944 Reported by Hock and Lang 1948 Offered commercially (Hercules Powder Co.) Diisopropyl p e n y dicarbonate
1945 Patent-Pittsburgh Plate Glass 1947 Commercially available (PPG)
Dicumyl peroxide
1954 Patent-Hercules Powder Co. 1954 Offbed commercially (Hercules)
DETERMINATION OF DECOMPOSITION RATES OF DIACYL PEROXIDES, by J. E. Guillet, T. R. Walker, M. F. Meyer, J. P. Hawk, and E. B. T o m e
THERMAL DECOMPOSITION
AND APPLICATIONS OF 9Z-BUTYL-
s. w. Bukata, L. L. Zabrocki, M. F. McLaugblin, J. R. Kolczynski, and 0. L. Mageli 4,4-BIS(tmt-BLITYLPEROXY)VALERATE, by
tert-BUTYL.PEROXY ISOPROPYL CARBONATE-A MERIZATION CATALYST, by W. A. Strong
NEW POLY-
EVALUATION OF PEROXIDES
AS CROSSLINKING AGENTS FOR HIGH DENSITY POLYETHYLENE, by R. S. Gregorian and
R. A. Bafford INFLUENCE OF PEROXIDE
CURING SYSTEMS AND CARBON BLACKS IN ETHYLENE-PROPYLENE RUBBER, by P. LellaS
L.
CROSSLINK DENSITIES IN PEROXIDE-CURED SILICONE OUM WLCANIZATES, by W. J. Bobear.
A-t-butylperoxy. B-t-butylpnuq pivalnte, isopropyl carbonate. C2,5-dimethyl-2,5-di(t-butylperoy)haxnne. D-2,5-dimzthyl2,5-di(t-btr?r~~roxy)hcxyne-3. E-2,5-dimethlyhexyl-2,5-di(peroxybenzoate). F-n-butyl-4,4-bis(t-butylperoxy)volnafc VOL 5 6
NO. 1 2
DECEMBER 1 9 6 4
17
