MXPA97010512A - Bis (mono-y di-peroxioxalatos) novedosos derived from dihydroperoxides and halo-oxalatos of alkyls and peroxialqui - Google Patents

Abstract

A novel composition of bis (mono- or di-peroxyoxalate) of Structure A, and use of the novel bis (mono- or di-peroxy-oxalate) composition as an initiator for curing unsaturated polyester resins and for ethylenically polymerizing insaturad monomers

Description

BISf MONO- AND DI-PEROXIOXALATOS) NOVEDOUS DERIVATIVES OF ALKYL AND PEROXYALKYL DIHYDROPHOXIDES AND HALO-OXALATES This application claims priority of the provisional request S / N 60 / 034,528, filed December 30, 1996.

BACKGROUND OF THE INVENTION FIELD OF THE INVENTION This invention relates to new and novel compositions of matter classified in the field of chemistry as bis (mono- and diperoxioxalates) of Structure A which can be prepared through the reaction of: O O R1 R2 O O Q-C p-C-OO-C i R5 C i -OO-C? -C? -Q1 A.

. { The definitions of Q, Q1, R1, R2 R3, R4 and Rs are presented in the DIGEST OF THE I NVENTION]. dihydroperoxides, such as 2,5-dimethyl-2,5-dihydroperoxyhexane and 2,5-dimethyl, 2,5-dihydroperoxy-3-hexane, with alkyl haloalkoxy and alkylperoxy, such as chloro-oxalate of ethyl and chlorine t-butylperoxy oxalate, in the presence of inorganic and organic bases, as well as procedures for its preparation and use. The compositions of the invention possess inherent applied use characteristics which make them suitable as synthetic intermediates and as initiators for polymerizing ethylenically unsaturated monomers and for curing unsaturated polyester resin compositions. There is a need in the polymer industries for free radical initiators, efficient to polymerize ethylenically unsaturated monomers at lower temperatures in order to obtain higher molecular weight polymers having improved properties to stress and other mechanical properties and / or increase the polymerization rates to be able to produce real polymers at higher production speeds. Thus reducing production costs. In the case of the last scenario, the most efficient free-radical initiators allow polymer producers to increase productivity without the need to develop new and expensive production facilities. There is also a need in the polyester industry for free radical initiators that cure unsaturated polyester resins faster and / or at lower temperatures. The novel bis (mono- and diperoxyoxalate) compositions of Structure A and of this invention are capable of meeting these needs of the polymer industry.

DESCRIPTION OF THE PREVIOUS TECHNIQUE P. D. Bartlett, et al. (J. Am. Chem. Soc, 82. 1762-8, 1960) describe the decomposition kinetics of di-t-butyl diperoxyoxalate (CAS RN 1876-22-2) in solution and found its half life at 60 ° C in benzene which is 6.8 minutes. In a subsequent paper by PD Bartlett and RE Pincock (J. Am. Che. Soc, 82., 1769, 73, 1969) describe the decomposition kinetics of di-t-butyl diperoxyoxalate and various OO-t-butyl monoperoxioxalates. and O-alkyl including OO-t-butyl and O-ethyl monoperoxioxalate and OO-t-butyl monoperoxyoxalate and O-benzyl monoperoxioxalate. Based on the data provided in this reference, the half-life temperatures of 10 hours (ie, the temperature at which 50% of the peroxide decomposes in 10 hours) were calculated to be 26 ° C, 39 ° C and 41 ° C, respectively, for the above peroxioxalates. Thus, the di-t-alkyl diperoxyoxalates have half-life temperatures of 10 hours of about 25 ° C, while the monoperoxyoxalates of OO-t-alkyl and O-alkyl have half-life temperatures of about 10 hours of about 40 hours. ° C. A bis (monoperoxy oxalate) of the present invention, that is, 2,5-d i methyl-2, 5-di (isobornyloxycarbonylcarbonyl peroxy) hexane (I -4), CH3 CH3 was found to have a half-life of 10 hours at 20 ° C in trichlorethylene. Therefore, the novel bis (mono- and diperoxyoxalates) of the present invention are significantly more active than the monoperoxyoxalates of OO-t-alkyl and O-alkyl. R.A. Sheldon and J. K. Kochi (J. Org. Chem., 35 1223-6, 1970) reported at the rates of decomposition of various di-t-alkyl diperoxyoxalates of the structure, O O R (CH3) 2C-0O-C I-C I-0O-C (CH3) 2R (wherein R is methyl, ethyl, isopropyl and benzyl). The data was consistent with those of Bartlett. W. Adam and J. Sanabia (J. Am. Chem. Soc, 99, 2735-9, 1977) describe the synthesis of a cyclic diperoxyoxalate, 7,7, 10, 10-tetra-methyl-1, 2, 5,6-tetroxa-3, 4-dioxocyclodecane, 0 OC-C / \ O or CH3 - C C - CH3 / \ / \ CH3 H2CH2 CH3 from oxalyl chloride and 2,5-dimethyl-2,5-dihydroperoxyhexane in the presence of pyridine. Based on the data provided in this reference, the 10-hour half-life temperature of the cyclic diperoxyoxalate was calculated to be approximately 80 ° C. It should be noted that the peroxide of Adam and Sanabia is cyclic diperoxioxalate not a bis (monoperoxioxalate). P.G. Griffiths, and others [J. Macromol, Sci. , Chem., A17 (1), 45-50, 1982] describe polymerizations of alkyl methacrylates with di-t-butyl diperoxyoxalate. European Patent Application No. EP 0049966 A1 (04/21/82, from ICI Australia, LTD.) Describes a process for polymerizing a vinyl chloride monomer (VCI), using di-t-diperoxyoxalate as an initiator. butyl. M. Schultz, and others [J. Prakt. Chem., 324 (4), 589-95, 1982] describe the synthesis and thermolysis of azobis (isobutyl peroxyoxalate and t-butyl), OO CH CH-, OOII lili t_C4H9-00 - C - COCH2-C --N »NC - CH2? C - C-00-t - C4H9 CH3 CH3 an azo-peroxide sequentially of decomposition. European Patent Application No. EP 0095860 A2 (07/12/83, from ICI Australia, Ltd.) describes a process for the polymerization of the VCI monomer using as a initiator a monoperoxioxal acid diester of the structure, 0 O 1 I R 1 -O 0 -C-C-OR 2 wherein R 1 is a secondary or tertiary alkyl group, or a substituted benzyl or benzyl group, and R 2 is a secondary or tertiary alkyl group, or a substituted benzyl or benzyl group. Also described in this patent application are t-peroxyalkyl chloro-oxalates of the structure, These intermediates are used for the preparations of the monoperoxioxalic acid diesters. The patent of E. U.A. 4, 859, 794 (08/22/89, Berol Nobel Nack AB) describes dialkyl esters of monoperoxioxalic acid structure, (wherein R = t-alkyl of C. 0 and R. = primary alkyl of C? 8-28). for example, OO-t-butyl-P-docosyl monoperoxioxalate, useful for initiating the polymerization of VCI and other monomers. Japanese Patent Applications JP 63/248806 (10/17/88, of NFCO) and Japanese Patent 63/2541 10 (10/20/88, of NFCO) describe monoperoxyoxalates of OO-t-alkyl-O-alkyl of the structure, CH- > O O R2-C l-00-Cl-Cl-OCH2R! ^ [wherein Ri = H, alkyl and R2 = C? .7 alkyl, C? H5 (substituted), etc.], as initiators to produce VCI polymers having a low odor and color. European Patent Specification No. 0500624 B1 (07/12/94, Akzo Nobel N .V.) Described peroxide chain transfer agents of the structure, wherein n is an integer of 1 -4, Ri and R2 may be the same or different and are selected from hydrogen or lower alkyl, R3 is selected from alkyl of 4-8 carbons, alkenyl of 5-18 carbons, etc. , X is an activation group capable of improving the reactivity of the olefinic unsaturation towards the addition of free radical, m is 0 or 1 and Z is selected from the structures, If z is the last structure, then the compounds of European Patent Specification No. 0500624 B1 can be monoperoxioxalates. However, the compositions of 0500624 B 1 do not disclose the compositions of the present invention, since the peroxides of Structure A are neither allyl peroxides nor the present invention covers the compositions of 0500624 B1. It should be noted that no monoperoxioxalate is included in the list of peroxides on pages 5, 7 and 8 or in the preparative examples of 0500624 B1. As a whole, the prior art does not disclose the bis (mono- and diperoxyoxalate) compositions of Structure A. The patent of E. U.A. 3, 17, 166 (01/07/64, Wallace & Tiernan) describes 2,5-dimethyl-2,5-dihydroperoxyhexane diperoxy ester derivatives such as 2,5-dimethyl-2,5-di (acetylperoxy) hexane, 2,5-dimethyl-2,5-di (2-carboxybenzoylperoxy) hexane and 2,5-dimethyl-2,5-di (ethoxycarbonyl I peroxy) hexane. The patent of E. U.A. 3,297, 738 (01/10/67, Wallace &Tiernan) discloses bis (monoperoxycarbonates) acetylenics derived from alkyl chloroformates and dihydroperoxides containing portions -C = - and -C = CC = C-, such as 2, 5 -dimethyl-2,5-di (ethoxycarbonylperoxy) -3-hexyne, 3,6-dimethyl-3,6-di (ethoxy carbon il-peroxy) -4-octino and 2,7-dimethyl-2,7-di (ethoxycarbonylperoxy) -3,5-octanediin. The patent of E. U.A. 3,264,274 (08/02/66, Witco Chemical Corporation) describes diperoxyesters of the structure, R5 R6 R2 R4 wherein n is from 1 to 5, R R2, R3 and R4 are selected from hydrogen and alkyl radicals from 1 to 5 carbons and R5 and R6 are alkyl radicals, branched at position a, from 3 to 20 carbons . The patent of E. U.A. 3, 574,696 (04/13/71, Witco Chemical Corporation) describes acetylenic diperoxyesters of the structure, O Ri R3 O R5-C I-00-OI- (C «C) m- (CH2) p- (C» C) nC I-00-CI-Rg R2 R4 wherein p is from 1 to 7, m and n are 0 or 1, Rt, R 2, R 3 and R 4 are selected from lower alkyl radicals of 1 to 5 carbons and Rs and Rβ are alkyl radicals of 1 to 12 carbons, provided that R5 and Rβ are secondary or primary alkyl radicals. The sum of m and n must be at least 1. The patent of E. U.A. 3,624, 123 (1 1/30/71, from Witco Chemical Corporation) describes bis (neoperoxyesters of the structure: R4 in I, m, n, o and p are 0 to 5, provided that the sum of I, m, n, o and p is at least 1, Ri and R2 are alkyl radicals of 1 to 7 carbons, phenyl radicals or are attached to form, together with the C atom, to which they are attached, a cyclohexane ring, R3, R and Rs are alkyl radicals of 1 to 8 carbons, provided that no more than one of the radicals R3, R4 and R5 is a methyl radical , and R R2 \ R3 \ R4 \ and R5 each are equal to Rt, R2, R3, R4 and R5, respectively. The diperoxy ester structures of this technique do not anticipate the novel bis (mono- and diperoxioxalates) of Structure A.

DEFINITIONS The half-life temperature of an organic peroxide is defined as the temperature at which half (50%) of the peroxide decomposes in 10 hours. The t-cycloalkyl refers to the mono-radical structure, CH2CH2 Rx / \ / (CH2) C C \ / \ CH2CH2 wherein t is 0 to 2 and R is a lower alkyl radical of 1 to 4 carbons, t-alkynyl is the mono-radical structure, R * I Ry-c «c- - I R * where Ry is hydrogen or a lower alkyl radical of 1 to 4 carbons, t-aralkyl is the mono-radical structure, Rx Ar-C I- wherein Z is equal to or different from Rx and is a lower alkyl radical of 1 to 4 carbons, and Ar is an aryl radical of 6 to 10 carbons. When any group or generalized functional index, such as R, R1, R2, x, n, etc. , appears more than once in a general formula or structure, the meaning of each is independent of the other.

COMPENDIUM OF THE INVENTION The invention provides in a compositional aspect, a novel bis (mono- or diperoxioxalate) of Structure A: 1 x? wherein R1, R2, R3 and R4 are the same or different and are alkyl radicals of 1 to 4 carbons, preferably alkyl radicals of 1 to 2 carbons, most preferably methyl radicals, R5 is a di-radical selected from - (CH2 ) -, where n is 1 to 6, -C = C-, -C = CC = C-, 1, 4-phenylene, 1, 3-phenyl substituted or unsubstituted, the substituent being of the structure, preferably, Rs is a di-radical selected from - (CH2) n-, wherein n is 1 to 2, and -C = C-, most preferably R5 is - (CH2) 2-, Q and Q1 are independently selected from group consisting of chlorine, bromine, RO and R6-OO, wherein R is selected from the group consisting of H, a substituted or unsubstituted alkyl radical of 1 to 24 carbon, the substituents being one or more alkyl radicals of 1 to 6 carbons, alkoxy radicals of 1 to 6 carbons, aryloxy radicals of 6 to 10 carbons, fluoro, chloro, bromo, carboxy and cyano, a substituted or unsubstituted alkenyl radical of 3 to 12 carbons, the substituents being one or more lower alkyl radicals of 1 to 4 carbons, a substituted or unsubstituted aryl radical of 6 to 10 carbons, the substituents being one or more alkyl radicals of 1 to 6 carbons, alkoxy radicals of 1 to 6 carbons, aryloxy radicals of 6 to 10 carbons, chlorine, bromine and cyano, a substituted or unsubstituted aralkyl radical of 7 to 13 carbons, the substituents being one or more alkyl radicals of 1 to 6 carbons, a substituted or unsubstituted cycloalkyl radical of 5 to 12 carbon optionally having one or more carbon atoms oxygen or nitrogen in the cycloalkane ring, with the substituents being one or more lower alkyl radicals of 1 to 4 carbons, a substituted or unsubstituted bicycloalkyl radical of 6 to 14 carbons, with the substituents being one or more lower alkyl radicals of 1 to 4 carbons, a substituted or unsubstituted tricycloalkyl radical of 7 to 16 carbons, the substituents being one or more lower alkyl radicals of 1 to 4 carbons, and, R may also be of the structure (a), (a) wherein R10 is a non-substituted alkylene radical of 1 to 3 carbons or a substituted alkylene radical of 1 to 3 carbons, the substituents being one or more lower alkyl radicals of 1 to 4 carbons , R7 and R8 are alkyl radicals of 1 to 4 carbons, R9 is selected from unsubstituted t-alkyl radicals of 4 to 12 carbons, substituted t-alkyl radicals of 4 to 12 carbons, t-cycloalkyl radicals of 6 s 13 carbons, t-alkynyl radicals of 5 to 9 carbons, t-aralkyl radicals of 9 to 13 carbons, unsubstituted aroyl radicals of 7 to 11 carbons, substituted aroyl radicals of 7 to 1 1 carbons, wherein the substituent for the t-alkyl radicals is a radical t-peroxialquiio of 4 to 8 carbons and what substituents for the aroyl radicals are one or more lower alkyl radicals of 1 to 4 carbons, alkoxy radicals of 1 to 4 carbons, phenyl radicals, acyloxy radicals of 2 to 8 carbons, t-peroxyalkyl-carbonyl radicals of 5 to 9 carbons, fluorine, chlorine or bromine, and R9 could also be structures (b), (c) and (d), (b) (O (d) wherein x is 0 or 1, R1 1 is a substituted or unsubstituted alkyl radical of 1 to 8 carbons, the substituents being one or more alkyl radicals of 1 to 6 carbons, t-peroxyalkyl radicals from 4 to 8 carbons, alkoxy radicals of 1 to 6 carbons, aryloxy radicals of 6 to 10 carbons, hydroxy, chlorine, bromine, or cyano or a substituted or unsubstituted radical of 5 to 12 carbons optionally having one or more oxygen atoms or nitrogen in the cycloalkane ring, the substituents being one or more lower alkyl radicals of 1 to 4 carbons, and, R 12 is selected from a substituted or unsubstituted alkylene radical of 2 to 3 carbons, the substituents being one or more radicals alkyl of 1 to 4 carbons, or a substituted, unsubstituted or substituted 1, 2-, 1, 3- or 1, 4-phenylene, the substituents being one or more lower alkyl radicals of 1 to 4 carbons, chlorine, bromine , nitro or carboxy, and, R13 is a lower alkyl radical of 1 to 4 carbons, and, addition ally, the two radicals R13 can be joined to form a alkylene di-radical of 4 to 5 carbons, R14 is a lower alkyl radical of 1 to 4 carbons, R1 S, R16 and R17 are selected from hydrogens, alkyl radicals from 1 to 8 carbons, aryl radicals of 6 to 10 carbons, alkoxy radicals of 1 to 8 carbons and aryloxy radicals of 6 to 10 carbons, preferably R is selected from the group consisting of H, a substituted or unsubstituted alkyl radical of 1 to 22 carbons, the substituents being one or more alkyl radicals of 1 to 6 carbons, alkoxy radicals of 1 to 6 carbons, aryloxy radicals of 6 to 10 carbons, fluoro, chloro, bromo, carboxy and cyano, a substituted or unsubstituted aralkyl radical of 7 to 13 carbons, the substituents being one or more alkyl radicals of 1 to 6 carbons, a substituted or unsubstituted cycloalkyl radical of 5 to 12 carbons, the substituents being one or more lower alkyl radicals of 1 to 4 carbons, a bicycloalkyl radical substi unsubstituted or substituted of 6 to 14 carbons, the substituents being one or more lower alkyl radicals of 1 to 4 carbons, a substituted or substituted tricycloalkyl radical of 7 to 16 carbons, the substituents being one or more alkyl radicals of 1 to 4 carbons , and structure (a), most preferably, R is selected from the group consisting of H, a substituted or unsubstituted alkyl radical of 1 to 22 carbons, the substituents being one or more alkyl radicals of 1 to 6 carbons, alkoxy radicals from 1 to 6 carbons, aryloxy radicals of 6 to 10 carbons, chlorine, bromine, carboxy and cyano, a substituted or unsubstituted cycloalkyl radical of 5 to 12 carbons, the substituents being one or more lower alkyl radicals of 1 to 4 carbons, a substituted or unsubstituted bicycloalkyl radical of 6 to 14 carbons, the substituents being one or more lower alkyl radicals of 1 to 4 carbons, and structure (a), and, R6 is selected from a non-substituted t-alkyi radical gone from 4 to 12 carbons, a substituted t-alkyl radical of 4 to 12 carbons, a t-cycloalkyl radical of 6 to 13 carbons, a t-alkynyl radical of 5 to 9 carbons, and a t-aralkyl radical of 9 to 13 carbons, wherein the substituent for the alkyl radical is a t-peroxyalkyl radical of 4 to 8 carbons, preferably, Q and Q1 are the same or different and are selected from the group consisting of chlorine, bromine and RO, most preferably, Q and Q1 are the same and are selected from the group consisting of chlorine and RO. The invention provides in a process aspect, a process for the initiation of the free radical addition of olefinically unsaturated substrates selected from: novel procedures using a peroxide composition of Structure A as a curing agent for curing resin compositions of unsaturated polyester by heating said resins in the presence of initiator amounts of the peroxide composition of Structure A at appropriate temperatures, and, novel methods using a peroxide composition of Structure A as a free radical initiator to polymerize ethylenically unsaturated monomers (such such as styrene, ethylene, vinyl chloride, allyl diglycol carbonate (ADC), etc.), through the use of initiator amounts of the peroxide composition of Structure A at appropriate temperatures.

DETAILED DESCRIPTION Novel compositions of Bísfmono- and diperoxioxalato) of Structure A - Method Preparations The novel bis (mono- and diperoxyoxalate) compositions of Structure A can be prepared by reacting dihydroperoxides of Structure B, with oxalyl halides, alkyl halo-oxalates or peroxyalkyl halo-oxalates of Structure C, [where X = Br or Cl; Q (or Q1) = Br, Cl, R-O, or R6-OO], at -90 ° C to 50 ° C, optionally in the presence of an inorganic or organic base, and optionally in the presence of one or more solvents. The compositions of Structure C are oxalyl halides, for example, oxalyl bromide and oxalyl chloride, when A and Q are Br and Cl. The compositions of Structure C are alkyl halo oxalates, when X is Br or Cl and Q is RO. The compositions of Structure C are t-peroxyalkyl halo-oxalates, when X is Br or Cl and Q is R6-OO.

Non-limiting examples of optional suitable solvents include pentane, hexanes, heptanes, dodecanes, mixtures of odorless mineral spirits, toluene, xylenes, cumene, methylene chloride, ethyl acetate, 2-ethylhexyl acetate, isobutyl isobutyrate, dimethyl adipate , dimethyl succinate, dimethyl glutarate (or mixtures thereof), dimethyl phthalate, dibutyl phthalate, benzyl butyl phthalate, diethyl ether, methyl t-butyl ether, 2-methoxyethyl acetate and others. Non-limiting examples of optional suitable bases include triethylamine, tributylamine, N, N-diisopropylethylamine, 2,2,6,6-tetramethyl piperidine, N, N-dimethylaniline, N, N-dimethylaminopyridine, 2,4,6-collidine, urea , tetramethylurea, sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium hydroxide, potassium carbonate, potassium hydrogen carbonate, calcium hydroxide, magnesium hydroxide, barium hydroxide, calcium carbonate and trisodium phosphate.

Non-limiting examples of suitable dihydroperoxides of the Structure B that can react with compositions of the Structure C includes 2,5-dimethyl-2,5-dihydroperoxyhexane, 2,5-dimethyl-2,5-dihydroperoxy-3-hexyne, 3,6-dimethyl-3,6-dihydroperoxy-octane, 3,6-dimethyl. -3,6-dihydroperoxy-4-octino, 2,7-dimethyl-2,7-dihydroperoxyoctane, 2,7-dimethyl-2,7-dihydroperoxy-3,5-octadiino, 1,3-diisopropylbenzene dihydroperoxide, dihydroperoxide of 1,4-diisopropylbenzene and 1,3,5-triisopropylbenzene trihydroperoxide. Non-limiting examples of suitable oxalyl halides include oxalyl bromide and oxalyl chloride. Non-limiting examples of suitable alkyl halo-oxalates of Structure C (X = Br or Cl; Q = RO) which can react with dihydroperoxides of Structure B include methyl chloro-oxalate (also known as methyl oxalyl chloride; methyl chloro-glyoxylate), ethyl bromo-oxalate, ethyl chloro-oxalate, isopropyl chloro-oxalate, n-butyl chloro-oxalate, t-butyl chloro-oxalate, 2-ethylhexyl chloro-oxalate, chlorine -dodecyl oxalate, hexadecyl chloro-oxalate, docosyl chloro-oxalate, 2,2,2-trifluoroethyl chloro-oxalate, allyl chlorooxalate, phenyl chloro-oxalate, 2-phenoxyethyl chloro-oxalate, chloro-oxalate of cyclohexyl, 4-t-butylcyclohexyl chloro-oxalate, methyl chloro-oxalate, bornyl chloro-oxalate, isobornyl chloro-oxalate, exo-norbornyl chloro-oxalate, endo-norbornyl chloro-oxalate, chloro-oxalate 1 adamantyl, 2-adamantyl chloro-oxalate, benzyl chloro-oxalate, 3-t-butylperoxy-1,3-dimethylbutyl chloro-oxalate, and 3- (2-ethylhearyl-peroxy) -1,3-dimethylbutyl chloro-oxalate. The above alkyl halo-oxalates can be prepared by reacting from 0% to 100% excess of oxalyl bromide or oxalyl chloride with the corresponding alkanol until the reaction is complete. The excess oxalyl halide can be removed by separation or by distillation. Non-limiting examples of suitable alkanols which can react with oxalyl halides to form alkyl halooxalates of Structure C include methanol, ethane, isopropanol, t-butanol, n-butanol, 2-ethylhexanol, dodecanol, hexadecanol, docosanol, hexafluoroamyl alcohol, 2,2,2-trifluoroethanol, allyl alcohol, cyclohexane, 4-t-butylcyclohexanol, menthol, exo-norborneol , endo-norborneol, borneol, isoborneol, 1-adamantol, 2-adamantol, phenol, 2-phenoxyethanol, benzyl alcohol, 3-t-butylperoxy-1,3-dimethylbutanol and 2-ethylperoxyhexanoate 3-hydroxy-1, 1 - dimethylbutyl. The t-peroxyalkyl halo-oxalates of Structure C (X = Br or Cl; Q = Rβ-OO) can be prepared by reacting an excess of oxalyl halides, for example, oxalyl bromide and oxalyl chloride, with t-alkyl hydroperoxides, optionally in the presence of one or more solvents. Excess oxalyl halide and optional solvents can be removed from the t-peroxyalkyl halooxalates by separation or by distillation. Non-limiting examples of optional suitable solvents are as given above. Non-limiting examples of t-alkyl hydroperoxides suitable for preparing the t-peroxyalkyl halooxalates of Structure C include t-butyl hydroperoxide, t-amino hydroperoxide, t-hexyl hydroperoxide, hydroperoxide 1, 1, 3.3 -tetramethylbutyl, 1-methylcyclohexyl hydroperoxide, parametane hydroperoxide, 2-hydroxy-2-methyl-3-butyne, a-cumyl hydroperoxide and diisopropylbenzene monoperoxide. Non-limiting examples of suitable t-peroxyalkyl halo-oxalates of Structure C include peroxybutyl chloro-oxalate, t-peroxyamyl chloro-oxalate, 1,1-chloro-oxalate, 3,3-peroxytetramethylbutyl, and chloro-oxalate. isopropyl-a-peroxy-methyl. An alternative two-step synthetic route for the compositions of Structure A, where Q and Q1 are RO, involves the initial reaction of dihydroperoxides of Structure B with an excess of oxalyl halides followed by the removal of excess oxalyl halide. to form the novel compositions of Structure D, and a subsequent reaction of the compositions of Structure D_ with water or an alkanol in the presence of a suitable inorganic or organic base, and optionally in the presence of one or more solvents. Non-limiting examples of suitable dihydroperoxides of Structure B_, inorganic or organic bases, optional solvents, and alkanols are as given above. Suitable novel compositions of Structure D include 2,5-dimethyl-2,5-di- (chlorocarbonylcarbonylperoxy) hexane, 2,5-dimethyl-2,5-di- (chlorocarbonylcarbonylperoxy) -3-hexin, 3, 6-dimethyl-3,6-di- (chlorocarbonylcarbonii-peroxy) octane, 3,6-dimethyl-3,6-di- (chlorocarbonylcarbonyl-peroxy) -4-octino, 2,7-di ethyl-2, 7- di- (chlorocarbonylcarbonyl-peroxy) octane, 2,7-dimethyl-2,7-di- (chlorocarbonylcarbonyl-peroxy) -3,5-octanediin, and 1,3-di (2-chlorocarbonylcarbonylperoxy-2-propyl) benzene. An alternative two-step synthetic route for the compositions of Structure A, where Q and Q1 are R6-OO, involves the initial formation of the novel compositions of Structure D or the subsequent reaction of the compositions of Structure D_ with hydroperoxides of t-alkyl in the presence of a suitable inorganic or organic base, and optionally in the presence of one or more solvents. Non-limiting examples of suitable compositions of Structure p_, inorganic or organic bases, optional solvents and t-alkyl hydroperoxide are as given above.

Novel Compositions of Bisfmono-diperoxioxalate. of Structure A - Illustrative examples Non-limiting examples of the novel bis (mono- and diperoxyoxalate) compositions of Structure A, in addition to those of the teaching examples, include the following: 1,4-di (2-chlorocarboni I carbonyl-2-propyl) benzene, 2,5-dimethyl-2,5-di- (carboxycarbonylperoxy) -3-hexyne, 2,5-di methyl-2,5-di- (chlorocarbonyl-ca rbonylperoxy) -3-hexy, 2, 5-Di-methyl-2, 5-di- (methoxycarbon i Ica rbonyl-peroxy) hexane, 2,5-di methyl-2,5-di- (methoxycarbonylcarbonylperoxy) -3 -hexine, 3,6-dimethyl-3, 6-di- (methoxycarbonylcarbonylperoxy) octane, 3,6-dimethyl-3,6-di- (methoxycarbonylcarbonylperoxy) -4-octino, 2,7-dimethyl-2,7-di- (methoxycarbonylcarbonylperoxy) octane, 2, 7 dimethyl-2,7-di- (methoxy-carbonylcarbonylperoxy) -3,5-octadiino, [wherein the methoxycarbonylcarbonylperoxy radical has the structure, OOID CH30C-O-00-], 2,5-Di-methyl-2, 5-di- (isopropoxy carboni I carbonyl peroxy) hexane, 2,5-dimethyl-2,5-di- (n-butoxycarbonylcarbonylperoxy) hexane, 2,5-dimethyl-2,5 -di- (dodecyloxycarbonylcarbonylperoxy) hexane, 2,5-di methyl-2,5-di- (hexa-decyloxycarbonylca rbonyl peroxy) hexane, 2,5-d-methyl-2,5-d- (trifluoro-ethoxycarbonylcarbonylperoxy) hexane, 2,5-dimethyl-2,5-di - [(2-phenoxyethoxy) carbonylcarbonylperoxy] hexane, 2,5-dimethyl-2,5-di- (alloxycarbonyl-carbonylperoxy) hexane, 2,5-dimethyl-2 , 5-di- (cyclohexyloxycarbonylcarbonyl peroxy) hexane, 2,5-imethyl-2,5-di - [(4-t-butylcyclohexoxy) -carbonylcarbonylperoxy] -3-hexy, 2,5-di methyl- 2,5-di- (menthyloxycarbonyl carbonylperoxy) hexa no, 2,5-dimethyl-2,5-di - [(exo-norbornyloxy) carbonylcarbonylperoxy] hexane, 2,5-dimethyl-2,5-dihydroxycarbonyl. [(1-adamantoxy) carbonyl-carbonylperoxy] hexane, 2,5-dimethyl-2,5-di - [(2-adamantyloxy) carbonyl-carbonylperoxy] hexane, 2,5-di methyl-2,5-di- ( f-enoxycarbonylcarbonyl-peroxy) hexane, 2,7-di methyl-2,7-di- (benzyloxycarbonylcarbonylperox) i) -octane, 2,5-dimethyl-2, 5-di- (benzyloxycarbonylcarbonylperoxy) -3-hexyne, 2,5-di methyl-2, 5-d i - [(3-t-butyl peroxy-3- methyl I butoxy) carbon i Icarbonyl-peroxy] hexane, 2,5-dimethyl-2,5-di- [. { 3- (2-ethylhexanoylperoxy) -1,3-dimethylbutoxy} carbonylcarbonylperoxy] hexane, 2,7-di methyl-2,7-di- (bornyloxycarbonylcarbonylhydroxy) octane, 1,3-di- [1-methyl-1- (dodecyloxycarbonylcarbonylperoxy) ethyl] benzene, , 4-di- [1-methyl-1 - (hexanoxycarbonyl-carbonylperoxy) ethyl] benzene, 1,3,5-tri- [1-methyl-1- (decyloxycarbonylcanecarbonyl) ethyl] benzene or, 215-dimethyl -2,5-di- (t-butylperoxycarbonylcarbonylperoxy) -3-hexyne, and 2,5-di methyl 1-2,5-di- (amyl peroxycarbonylcarbonyl peroxy) hexane.

Novel Compositions of Bisfmono- and diperoxioxalate) of Structure A - Utility A. Polymerization of Ethylenically Unsaturated Monomers In the free radical polymerizations of ethylenically unsaturated monomers at suitable temperatures and pressures, the novel peroxide compositions of Structure A of this invention have been found to be effective initiators with respect to efficiency (reduced initiator requirements, etc.). Ethylenically unsaturated monomers include olefins, such as ethylene, propylene, styrene, alpha-methylstyrene, p-methylstyrene, chlorostyrenes, bromostyrenes, vinylbenzyl chloride, vinylpyridine and divinylbenzene; diolefins, such as 1,3-butadiene, isoprene and chloroprene; vinyl esters, such as vinyl acetate, vinyl propionate, vinyl laurate, vinyl benzoate, and divinyl carbonate; unsaturated nitriles, such as acrylonitrile and methacrylonitrile; acrylic acid and methacrylic acid and its anhydrides, esters and amides, such as acrylic acid anhydride, allyl acrylates and methacrylates, methyl, ethyl, n-butyl, 2-hydroxyethyl, glycidyl, lauryl and 2-ethylhexyl, and acrylamide and methacrylamide; maleic anhydride and itaconic anhydride, itaconic and fumaric acids and their esters; halo vinyl and dihalo vinylidene compounds, such as vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride and vinylidene fluoride; perhale olefins, such as tetrafluoroethylene, hexafluoropropylene and chlorotrifluoroethylene; vinyl ethers, such as methyl vinyl ether, ethyl vinyl ether and n-butyl vinyl ether; allyl esters, such as allyl acetate, allyl benzoate, allyl ethyl carbonate, triallyl phosphate, diallyl phthalate, diallyl fumarate, diallyl glutarate, diallyl adipate, diallyl carbonate, bis (allyl) carbonate diethylene glycol (ie, ADC); acrolein; methyl vinyl ketone; or mixtures thereof. Temperatures from 0 ° C to 100 ° C, preferably from 20 ° C to 90 ° C, most preferably from 30 ° C to 75 ° C, and levels of bis (mono- and diperoxioxalates) of Structure A (on a basis pure) from 0.002 to 10%, preferably from 0.005% to 2%, most preferably from 0.01% to 1% by weight of the monomer, are usually employed in conventional polymerizations and copolymerizations of ethylenically unsaturated monomers. The novel peroxide compositions of this invention can be used in combination with other free radical initiators such as those described at the end of column 4 and at the top of column 5 of the U.A. 4, 525,308 (06/25/85, of PennWalt Corporation). Using the peroxide compositions of this invention in combination with these initiators adds flexibility to the processes of polymer and alloy producers to "fine-tune" their polymerization processes.

B. Curing of Unsaturated Polyester Resins In the curing of unsaturated resin compositions by heating at suitable cure temperatures in the presence of free radical curing agents, the novel bis (mono- and diperoxyoxalate) compositions of Structure A of this invention exhibit improved curing activity in the curable unsaturated polyester resin compositions. The unsaturated polyester resins that can be cured by the novel bis (mono- and diperoxyoxalate) compositions of this invention usually include an unsaturated polyester and one or more ethylenically unsaturated monomers. The unsaturated polyesters are, for example, polyesters which are obtained by esterifying at least one ethylenically unsaturated di- or polycarboxylic acid, anhydride or acid halide, such as maleic acid, fumaric acid, glutaconic acid, itaconic acid, mesaconic acid, citraconic acid, allylmalonic acid, tetrahydrophthalic acid, and others, with di- or saturated or unsaturated polyols, such as ethylene glycol, diethylene glycol, triethylene glycol, 1, 2- and 1, 3-propanediols, 1, 2-, 1, 3- and 1,4-butanediols, 2,2-dimethyl-l, 3-propanediol, 2-hydroxymethyl-2-methyl -1,3-propanediol, 2-buten-1,4-diol, 2-butyl-1,4-diol, 2,4,4-trimethyi, 3-pentanediol, glycerol, pentaerythritol, mannitol and others. Mixtures of said di- or polyacids and / or mixtures of said diols or polyols can also be used. The di- or polycarboxylic acids can be partially replaced by di- or polycarboxylic acids, such as adipic acid, succinic acid, sebacic acid and others, and / or by aromatic di- or polycarboxylic acids, such as phthalic acid, trimethyl, pyromethyl acid, isphthalic acid and terephthalic acid. The acids used can be replaced by groups such as halogen. Examples of suitable halogenated acids are, for example, tetrachlorophthalic acid, tetra bromophosphonic acid, 5,6-dicarboxy-1, 2,3,4,7,7-hexachlorobicyclo (2.2.1) -2-heptane and others. . The other component of the unsaturated polyester resin composition, the polymerizable monomer or monomers, may preferably be ethylenically unsaturated monomers, such as styrene, alpha-methylstyrene, p-methylstyrene, chlorostyrenes, bromostyrenes, vinylbenzyl chloride, divinylbenzene, diallyl maleate. , dibutyl fumarate, triallyl phosphate, triallyl cyanurate, diallyl phthalate, diallyl fumarate, methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, ethyl acrylate, and others, or mixtures thereof, which are copolymerizable with said unsaturated polyesters. A preferred unsaturated polyester resin composition contains as the unsaturated polyester component, the esterification product of 1,2-propanediol (a polyol), maleic anhydride (an unsaturated polycarboxylic acid anhydride) and phthalic anhydride (an anhydride of an acid). aromatic dicarboxylic acid) as well as the monomer component, styrene.

Other types of unsaturated polyester resin compositions can be cured using the novel peroxide compositions of this invention as cure catalysts. These resins, termed unsaturated vinyl ester resins, consist of a portion of vinyl ester resin and one or more polymerizable monomers. The vinyl ester resin component can be formed by reacting a chloroperoxide, such as epichlorohydrin, with appropriate amounts of a bisphenol to such as Bisphenol A [2,2- (4-hydroxyphenyl) propapo], in the presence of a base, such as hydroxide. of sodium, to produce a condensation product having terminal epoxy groups derived from chloroepoxide. Subsequent reaction of the condensation product with polymerizable unsaturated carboxylic acids, such as acrylic acid and methacrylic acid, in the presence or absence of acidic or basic catalysts, results in the formation of the vinyl ester resin component. Typically, styrene is added as the polymerizable monomer component to complete the preparation of the unsaturated vinyl ester resin composition.

Temperatures of about 20 ° C to 200 ° C and levels of novel bis (mono- and diperoxyoxalate) compositions of Structure A from about 0.05% to 5% or more, preferably from 0.10% to 4%, most preferably 0.25. % to 3% by weight of the curable unsaturated polyester resin composition are normally employed. The unsaturated polyester resin compositions described above can be filled with various materials, such as sulfur, glass fibers, carbon, and boron, carbon black, silicas, metal silicates, clays, metal carbonates, antioxidants (AO's), thermal stabilizers, ultraviolet light (UV) and light, sensitizers, dyes, pigments, accelerators, metal oxides, such as zinc oxide, blowing agents, nucleating agents and others.

C. Healing of Allyl-diallyl Carbonate Resins (ADC) In the curing or polymerization of bis (allyl carbonate) -glycolic diethylene glycol (ADC), by heating the ADC monomer to suitable cure temperatures in the presence of free radical curing agents, the novel bis (mono- and diperoxyoxalate) compositions of Structure A of this invention exhibit improved polymerization or curing activity for the compositions of ADC monomer. ADC was commercially introduced as monomer CR-38 (CAS Reg. No. 142-22-3) by Pittsburg Piet Glass Company (PPG) and is produced by reacting bis (chloroformate) diethylene glycol with allyl alcohol in the presence of alkali ( R. Dowbenko, in J. L. Kroschwitz and M. Howe-Grant, eds Kirk-Othmer - Encyclopedia of Chemical Technology, "Allyl Monomers and Polymers", Fourth Edition, Vol. 2, Wiley-lnterscience Publication, John Wiley & amp; Sons, Inc., New York, 1992, pp. 163-168). The ADC monomer can be cured or polymerized alone or with other co-monomers such as acrylic acid esters, methacrylic acid esters, allyl esters, diallyl dicarboxylates (e.g., diallyl phthalate), maleic anhydride and other monomers to produce castings or clear lenses that are transparent, strong, resistant to rupture and resistant to solvent. The curing or polymerization of the ADC monomer compositions are carried out in bulk (without solvent present). In general, the curing or polymerization of the ADC monomer compositions to form cast sheets or lenses is carried out in two stages. The first stage involves most of the polymerization and occurs in the presence of the curing initiator, usually dialkyl peroxydicarbonate, at temperatures of 35 ° C to 120 ° C. The curing or polymerization times vary from about 5 hours to 50 hours. Generally, a time-temperature profile is used in the first stage. An example of a time-temperature profile is given below: TYPICAL CURING TEMPERATURE PROGRAM TO CURE ADC TI EMPO (HOURS) TEMPERATU RA (° C) __ _ 1.0 62 3.0 64 7.0 68 8.0 69 8.5 74 9.0 79 9.5 86.5 10.0 96.5 10.5 1 15 10.75 85 1 1 .0 60 1 1.25 40 1 1 .5 30 The second step of curing or polymerizing the ADC monomer compositions involves post-curing or annealing the ADC resin for one to several hours at 100 ° C to 150 ° C. An example of the post-cure of the ADC resin could be 2 hours at 1 15 ° C. Levels of the novel bis (mono- and diperoxyoxalate) compositions are typically from about 1% to 6% or more, preferably from 2% to 5%, most preferably from 2.5% to 4% by weight of the monomer composition. of curable or polymerizable ADC. The ADC resin compositions described above can be filled with various materials, such as antioxidants (AO's), thermal stabilizers, ultraviolet light (UV) and light stabilizers, dyes, photochromic additives and colorants. In addition, the ADC resin compositions may contain additives such as acrylic polymers and the low molecular weight shrinkage resins described in the U.A. 4,217,433 (12/08/80, from Pennwait Corporation, now Elf Atochem North America, Inc.). Said anti shrinkage additives are employed to represent 14% shrinkage occurring when the ADC monomer is polymerized.

Novel Compositions of Bisfmono-diperoxioxalate) of Structure A - Preparative Examples v Utility The following examples further illustrate the best mode contemplated by the inventors for practicing the present invention, and are presented to provide detailed preparative and useful illustrations of the invention and are not intended to limit the scope and scope of the invention.

EXAMPLE 1 Preparation of 2.5-Dimethyl-2,5-di (ethoxycarbonylcarbonylperoxy) hexane fl-1) C2H5O 2H5 (1 -1) CHi CH3 In this example, ethyl chloro-oxalate was reacted with 2,5-dimethyl-2,5-dihydroperoxyhexane, in the presence of pyridine, to produce the product: A water jacket reactor 500 ml, equipped with a mechanical stirrer, a thermometer and an addition funnel, was charged with 200 ml of methylene chloride, 7.2 g (40.0 mmoles) of 98% of 2,5-dimethyl-2,5-dihydroperoxyhexane and 7.0 g (88.0 mmol) of pyridine. The stirred mixture was cooled to 0 ° C and a solution of 1 1 .8 g (82.0 mmoles) of 98% ethyl chloro-oxalate in 40 ml of methylene chloride was slowly added over a period of 10-15 minutes. . After the addition was started, a solid of pyridinium chloride was formed. After the addition was complete, the reaction mass was stirred for 60 minutes at 0 ° C to 10 ° C, after which 50 ml of water was added and the reaction mass was stirred for an additional 10 minutes at 5 ° C. The upper aqueous layer was then separated and the organic layer was washed with 40 ml of an aqueous solution of 5% HCl and then twice with 100 ml portions of water. The product solution was dried over 5% by weight of anhydrous MgSO 4, and, after separation of the spent desiccant through filtration, the solvent was removed under vacuum leaving 12.7 g of a colorless liquid (84.1% theory, not corrected ). An IR spectrum of the product showed a small OH band in the 3500 cm * 1 region. A larger monoperoxioxalate carbonyl band was present at 1780 cm "1 and a larger oxalate carbonyl band was present at approximately 1735 cm" 1. The product had a rapid thermal test [J. Varjavandi and O. L. Mageli, J. Chem. Ed. 48, A451 (1971)] which resulted in 45 ° C, which confirmed that the product was an extremely low temperature peroxide. The product contained 7.47% active oxygen (theory, 8.46%) according to the peroxy ester active oxygen method, therefore, the product analysis was 88.3% and the corrected yield was 74.3%. Based on the preparation method, the performance data (analysis and corrected performance), the rapid thermal test data and the infrared spectral data, the product obtained in this reaction was the product of the desired titer.

EXAMPLE 2 Preparation of 2,5-Dimethyl-2,5-d docosyloxycarbonylcarbonylperoxy) hexane (I-2) CH3 CH3 In this example, the product was prepared in two synthetic steps. In the first step, docosanol was reacted with 50% molar excess of oxalyl chloride. After the reaction ends. The excess oxalyl chloride was removed from the product under reduced pressure to produce docosyl chloro-oxalate having an analysis of 91.4% and a corrected yield of 92.5%. In the second step, docosyl chloro-oxalate was reacted with 2,5-dimethyl-2,5-dihydroperoxyhexane, in the presence of pyridine, to produce the product: A 3-neck 500 ml reactor, equipped with a bar magnetic stirring, a condenser, a thermometer and an addition funnel was charged with 60 ml of pentane, 2.0 g (11.0 mmol) of 98% of 2,5-dimethyl-2,5-dihydroperoxyhexane and 2.4 g ( 30.0 mmoles) of pyridine. The stirred mixture was cooled to 0 ° C and a solution of 10.0 g (22.0 mmoles) of 91.4% docosyl chloro-oxalate in 250 ml of pentane was added slowly over a period of 20 minutes. After the addition was complete, the reaction mass was stirred for 90 minutes at 0 ° C, after which 100 ml of water and 100 ml of hexane were added, and the reaction mass was stirred for an additional 10 minutes at 5 ° C. C. The lower aqueous layer was then separated and the organic layer was washed with an aqueous solution of 5% HCl and with water until the pH of the washings of spent water was 7.0. The product solution was dried over 5% by weight of anhydrous MgSO, and, after separation of the spent desiccant through filtration, the solvent was removed under vacuum leaving 6.7 g of a white solid (65% theory, not corrected ) that had a melting point of 71 ° C. An I R spectrum of the product as a "nujol mull" did not show any OH band in the region 3500 cm "1. A larger band of monoperoxioxalate carbonyl appeared in 1775 cm" 1. The product had a rapid thermal test result of 72 ° C, which confirmed that the product was a very low temperature peroxide. The product contained 3.21% active oxygen (theory, 3.41%) according to a peroxy ester active oxygen method, therefore, the product analysis was 94.1% and the corrected yield was 61.2%. Based on the preparation method, the performance data, the rapid thermal test data and the infrared spectral data, the product obtained in this reaction was the product of the desired titer.

EXAMPLE 3 Preparation of 2,5-Dimethyl-2,5-rdi (4-t-butyl-cyclohexoxy) carbonylcarbonylperoxylhexane (1-3) CH 3 CH 2 OO CS-. CH 3 O O CH 2 CH 2 / I I I I I I / CC-C4HQ-CH "H0C-C-00-C-CH2CH2-C-OO-C- < : 0CH CH-t-C4H9 (1-3) \ / I I \ / CH2CH2 CH3 CH3 CH2CH2 In this example, the product was prepared in two synthetic steps. In the first step, 4-t-butylcyclohexanol was reacted with 50% molar excess of oxalyl chloride. After completion of the reaction, the excess oxalyl chloride was removed from the product under reduced pressure to produce 4-t-butylcyclohexyl chloro-oxalate having an analysis of 96.9% and a corrected yield of 95.3%. In the second step, butylcyclohexyl chlorooxalate was reacted with 2,5-dimethyl-2,5-dihydro-eroxyhexane, in the presence of pyridine, to produce the product: A 500 ml water jacketed reactor, equipped with a mechanical bar, thermometer and addition funnel, was charged with 75 ml of methylene chloride, 3.6 g (20.0 mmoles) of 95% of 2,5-dimethyl- 2,5-dihydroperoxyhexane and 3.5 g (44.0 mmoles) of pyridine. The stirred mixture was cooled to 0 ° C and a solution of 9.9 g (40.0 moles) of 96.9% 4-t-butylcyclohexyl chloro-oxalate in 25 ml of methylene chloride was added slowly over a period of 10-15. minutes After the addition was complete, the reaction mass was stirred for 60 minutes at 0 ° C to 10 ° C, after which 50 ml of water was added and the reaction mass was stirred for an additional 10 minutes at 5 ° C. The upper aqueous layer was then separated and the organic layer was washed with 20 ml of an aqueous solution of 5% HCl and then twice with 50 ml portions of water. The product solution was dried over 5% by weight of anhydrous MgSO 4, and, after separation of the spent desiccant through filtration, the solvent was removed under vacuum leaving 13.7 g of a colorless liquid (>; 100% theory, not corrected). An IR spectrum of the product showed a larger band of monoperoxioxalate carbonyl at 1790 cm "1 and a greater band of oxalate carbonyl at approximately 1750 cm" 1. The product had a rapid thermal test result of 57 ° C, which confirmed that the product was a very low temperature peroxide. The product contained 3.88% active oxygen (theory, 5.34%) according to a peroxy ester active oxygen method, therefore, the product analysis was 72.7% and the corrected yield was 83.0%.

Based on the preparation method, the performance data, the rapid thermal test data and the infrared spectral data, the product obtained in this reaction was the product of the desired titer.

EXAMPLE 4 Preparation of 2.5-Dimethyl-2,5-di (isobornyloxycarbonylcarbonyl-peroxyhexane (1-4) In this example, the product was prepared in two synthetic steps. In the first step, isoborneol was reacted with 50% molar excess of oxalyl chloride. After completion of the reaction, the excess oxatyl chloride was removed from the product under reduced pressure to produce isobornyl chloro-oxalate having an analysis of 95.2% and a corrected yield of 91.3%. In the second step, isobornyl chloro-oxalate was reacted with 2,5-dimethyl-2,5-dihydroperoxyhexane, in the presence of pyridine, to produce the product as described below: A 500 ml water-jacketed reactor , equipped with a mechanical bar, a thermometer and an addition funnel, was charged with 100 ml of methylene chloride, 3.6 g (20.0 mmoles) of 98% of 2,5-dimethyl-2,5-dihydro-eroxyhexane and 3.5 g (44.0 mmoles) of pyridine. The stirred mixture was cooled to 0 ° C and a solution of 10.3 g (40.0 moles) of 95.2% isobornyl chloro-oxalate in 20 ml of methylene chloride was added slowly over a period of 10-15 minutes. After the addition was complete, the reaction mass was stirred for 60 minutes at 0 ° C to 10 ° C, after which 50 ml of water was added and the reaction mass was stirred for an additional 10 minutes at 5 ° C. The upper aqueous layer was then separated and the organic layer was washed with 20 ml of an aqueous solution of 5% HCl and then twice with 50 ml portions of water. The product solution was dried over 5% by weight of anhydrous MgSO 4, and, after separation of the spent desiccant through filtration, the solvent was removed under vacuum leaving 20 g of a colorless liquid. To this product was added 50 ml of pentane, which resulted in the precipitation of a solid product. The mixture was cooled to -20 ° and the solid was separated through filtration and air dried. 7.2 g of a white solid (60.5% theory, uncorrected) having a melting point of 78-80 ° C were obtained. An IR spectrum of the product as a "nujol mull" showed no OH band in the region of 3500 cm "1 and a larger band of monoperoxioxalate carbonyl was present at 1785 cm'1 and a larger band of oxalate carbonyl appeared at approximately 1735 cm "1. The product had a rapid thermal test result of 63 ° C, which confirmed that the product was a very low temperature peroxide. The product contained 5.08% active oxygen (theory, 5.38%) according to a peroxy ester active oxygen method, therefore, the product analysis was 94.4% and the corrected yield was 57.1%. Based on the preparation method, the performance data, the rapid thermal test data and the infrared spectral data, the product obtained in this reaction was the product of the desired titer. It was found that 2,5-dimethyl-2,5-di (isobornyloxycarbonyl-carbonylperoxy) hexane (I-4) has a half-life temperature of hours at 20 ° C in trichlorethylene, therefore, I-4 was an extremely peroxide at < compared to the monoperoxioxalates of OO-t-alkyl and O-alkyl of the art.

EXAMPLE 5 Preparation of 2,5-Dimethyl-2,5-di (neopentyloxycarbonylcarbonyl peroxy) hexane (1-5) CH- »O O CH3 CH3 O O CH3 l l l I l l l I CH3-: - < -? 2? C ^ -? > - < ? 2 (-? 2 ^ - ^^ í 1"5 * CH3 CH3 CH3 CH3 In this example, the product was prepared in two synthetic steps. In the first step, neopentyl alcohol was reacted with 50% molar excess of oxalyl chloride. After completion of the reaction, the excess oxalyl chloride was removed from the product under reduced pressure to produce isobornyl chloro-oxalate having a 100% analysis and a corrected yield of 92.7%.

In the second step, neopentyl chloro-oxalate was reacted with 2,5-dimethyl-2,5-dihydroperoxyhexane, in the presence of pyridine, to produce the product as described below: A 250 ml three neck flask, equipped with a bar of magnetic stirring, a thermometer and an addition funnel, and cooled with an ice water bath, was charged with 60 ml of MTBE, 3.6 g (20.0 mmoles) of 98% of 2,5-dimethyl-2,5- dihydroperoxyhexane and 4.5 g (57.0 mmoles) of pyridine. The stirred mixture was cooled to 0 ° C and a solution of 7.5 g (42.0 moles) of 100% neopentyl chloro-oxalate in 10 ml of MTBE was added slowly over a period of 10-15 minutes. After starting the addition, a solid of pyridinium chloride was immediately formed. After the addition was complete, the reaction mass was stirred for 60 minutes at 2 ° C, after which 10 ml of water was added and the reaction mass was stirred for an additional 10 minutes at 3-4 ° C. The upper aqueous layer was then separated and the organic layer was washed three times with 35 ml of an aqueous solution of 5% HCl and then twice with 75 ml portions of water. The product solution was dried over 5% by weight of anhydrous MgSO 4, and, after removal of the spent desiccant through filtration, the solvent was removed under vacuum leaving 9.1 g of a white solid (97.8% theory, not corrected ) that had a melting point of 35-37 ° C. An IR spectrum of the product as a "nujol muir" showed no OH band in the 3500 cm region "1. A larger band of monoperoxioxalate carbonyl was present at 1790 cm "1 and a larger oxalate carbonyl band was present at approximately 1740 cm" 1. The product had a rapid thermal test result of 54 ° C, which confirmed that the product was a very low temperature peroxide. The product contained 6.66% active oxygen (theory, 6.92%) according to a peroxy ester active oxygen method, therefore, the product analysis was 96.2% and the corrected yield was 94.2%. Based on the preparation method, the performance data, the rapid thermal test data and the infrared spectral data, the product obtained in this reaction was the product of the desired titer.

EXAMPLE 6 Preparation of 2,5-Dimethyl-2,5-di (neopentyloxycarbonylcarbonyl peroxy) -3-hexyne (l-ß) CH-, 0 0 CH-, CH 3 0 0 CH 3 III I CH3-C-CH2OC-C- 0- C - C «C - C-00-C-COCH2-C-CH3 (1-6) CH3 CH3 CH3 CH3 In this example, the product was prepared initially by drying a solution of 78% wet 2, 5-dimethyl-2,5-dihydroperoxy-3-hexyne in MTBE with anhydrous MgSO 4 and separating the spent desiccant through filtration, then reaction of the dry solution of 2,5-dimethyl-2,5-dihydroperoxy-3-hexyne with neopentyl chloro-oxalate in the presence of pyridine, as described below: A solution of 4.5 g (0.020 moles) of 78% of 2,5-dimethyl-2,5-dihydroperoxy-3-hexyne wet in 60 ml of MTBE, dried over 5% by weight of MgSO 4. After filtering the solution and washing the spent MgSO 4 in the filter with three 10 ml portions of fresh MTBE, the combined MTBE solution was then charged to a 250 ml three neck flask, equipped with a magnetic stir bar, a condenser, a thermometer and an addition funnel and cooled with an ice water bath. Then, 4.5 g (0.057 mole) of dry pyridine was added. The contents of the flask were cooled to 0 ° C. After the resulting vigorously stirred solution at about 0 ° C was slowly added a solution of 7.5 g (0.042 mole) of 100% neopentyl chloro-oxalate in 10 ml of MTBE. A solid of pyridinium chloride was formed after the addition was started. After the addition was complete, the reaction mass was stirred for 60 minutes at 2 ° C, after which 10 ml of water was added and the reaction mass was stirred for an additional 10 minutes at 3-4 ° C. The upper aqueous layer was then separated and the organic layer was washed three times with 35 ml of an aqueous solution of 5% HCl and then twice with 75 ml portions of water. The product solution was dried over 5% by weight of anhydrous MgSO 4, and, after separation of the spent desiccant through filtration, the solvent was removed under vacuum leaving 10.0 g of a liquid (> 100% theory, no corrected). An IR spectrum of the product a small OH band in the region of 3500 cm "1, a larger band of monoperoxioxalate carbonyl was present at 1800 cm '1 and a larger band of oxalate carbonyl at approximately 1750 cm" 1. The product had a result of rapid thermal test of 54 ° C, which confirmed that the product was a very low temperature peroxide. The product contained 6.39% active oxygen (theory, 6.98%) according to a peroxy ester active oxygen method, therefore, the product analysis was 91.5% and the corrected yield was 99.5%. Based on the preparation method, the performance data, the rapid thermal test data and the infrared spectral data, the product obtained in this reaction was the product of the desired title.

EXAMPLE 7 Preparation of 2,5-Dimethyl-2,5-di (bornyloxycarbonylcarbonyl peroxOhexane (I-7) OO CH-, CH 3 OO] = IORNIL-OC I-CI-00-C I - CH 2 CH 2 -C 1 - 00- Cl - ClO-BORNIL (I - 7) CH3 CH3 In this example, the product was prepared by reacting 98% of 2,5-dimethyl-2,5-dihydroperoxyhexane in MTBE with 96.6% of boron-chloro-oxalate in the presence of pyridine. Bornyl chloro-oxalate was prepared by reacting an excess of oxalyl chloride with borneol followed by removal of HCl and excess oxalyl chloride. The procedure is described below: A 250 ml three neck flask, equipped with a magnetic stir bar, a thermometer and an addition funnel, and cooled with an ice water bath, was charged with 60 ml of MTBE, 3.6 g (20.0 mmoles) of 98% of 2,5-dimethyl-2,5-dihydroperoxyhexane and 4.5 g (57.0 mmoles) of pyridine. The stirred mixture was cooled to 0 ° C and a solution of 10.6 g (42.0 moles) of 96.6% boronyl chloro-oxalate in 10 ml of MTBE was added slowly over a period of 10-15 minutes. After starting the addition, a solid of pyridinium chloride was immediately formed. After completing the addition, the reaction mass was stirred for 60 minutes at 2 ° C, after which 10 ml of water was added and the reaction mass was stirred for an additional 10 minutes at 3-4 ° C. The upper aqueous layer was then separated and the organic layer was washed three times with 35 ml of an aqueous solution of 5% HCl and then twice with 75 ml portions of water. The product solution was dried over 5% by weight of anhydrous MgSO, and, after separation of the spent desiccant through filtration, the solvent was removed under vacuum leaving 7.4 g of a white solid (62.2% theory, not corrected ) that had a melting point of 80 ° C. An IR spectrum of the product as a "nujol mull" showed no OH band in the region of 3500 cm "1 A larger band of monoperoxioxalate carbonyl was present at 1790 cm'1 and a larger band of oxalate carbonyl appeared at about 1745 cm'1 The product had a rapid thermal test result of 54 ° C, which confirmed that the product was a very low temperature peroxide.The product contained 5.02% active oxygen (theory, 5.38%) according to a peroxy ester active oxygen method, therefore, the product analysis was 93.3% and the corrected yield was 58.8% Based on the preparation method, the performance data, the rapid thermal test data and the data infrared spectral, the product obtained in this reaction was the product of the desired titer.

EXAMPLE 8 Preparation of 2,5-Dimethyl-2,5-di (benzyloxycarbonylcarbonyl peroxy) hexane (1-8) In this example, the product was prepared in two synthetic steps. In the first step, benzylic alcohol was reacted with 50% molar excess of oxalyl chloride. After completion of the reaction, the excess oxalyl chloride was removed from the product under reduced pressure to produce benzyl chloro-oxalate having an analysis of 96.6% and a corrected yield of 92.1%. In the second step, the benzyl chloro-oxalate was reacted with 2,5-dimethyl-2,5-dihydroperoxyhexane in the presence of pyridine to produce the product as described below: A 250 ml three neck flask, equipped with a magnetic stir bar, a thermometer and an addition funnel, and cooled with an ice water bath, was charged with 60 ml of MTBE, 3.6 g (20.0 mmol) of 98% of 2,5-dimethyl-2,5-dihydroperoxyhexane and 4.5 g (57.0 mmol) of pyridine. The stirred mixture was cooled to 0 ° C and a solution of 8.6 g (42.0 moles) of 96.6% benzyl chloro-oxalate in 10 ml of MTBE was added slowly over a period of 10-15 minutes. After starting the addition, a solid of pyridinium chloride was immediately formed. After the addition was complete, the reaction mass was stirred for 60 minutes at 2 ° C, after which 10 ml of water was added and the reaction mass was stirred for an additional 10 minutes at 3-4 ° C. The upper aqueous layer was then separated and the organic layer was washed three times with 35 ml of an aqueous solution of 5% HCl and then twice with 75 ml portions of water. The product solution was dried over 5% by weight of anhydrous MgSO 4, and, after separation of the spent desiccant through filtration, the solvent was removed under vacuum leaving 6.2 g of a white solid (61.4% theory, not corrected ) that had a melting point of 60-61 ° C. An IR spectrum of the product as a "nujol mull" showed no OH band in the 3500 cm '1 region. A larger band of monoperoxioxalate carbonyl was present at 1785 cm "1 and a larger oxalate carbonyl band was present at approximately 1740 cm'1 The product had a rapid thermal test result of 72 ° C, which confirmed that the product was a very low temperature peroxide.The product contained 6.14% active oxygen (theory, 6.37%) according to a peroxy ester active oxygen method, therefore, the product analysis was 96.4% and the corrected yield was 59.2% Based on the preparation method, the performance data, the rapid thermal test data and the data infrared spectral, the product obtained in this reaction was the product of the desired titer.

EXAMPLE 9 Preparation of 2,5-Dimethyl-2,5-di (t-butoxycarbonylcarbonyl peroxy) hexane (I-9) CH3 O O CH3 CH3 O O CH3 l l l l l l l CH3-C-0C-C-00-C-CH2CH2-C-OO-: -C0-C-CH3 (I-9) CH3 CH3 CH3 CH3 In this example, the product was prepared in two synthetic steps. In the first step, t-butyl alcohol was reacted with 50% molar excess of oxalyl chloride. After completing the reaction, the excess oxalyl chloride was removed from the product under reduced pressure to produce t-butyl chloro-oxalate having a 100% analysis and a corrected yield of 90.8%. In the second step, the t-butyl chloro-oxalate was reacted with 2,5-dimethyl-2,5-dihydroperoxyhexane, in the presence of pyridine, to produce the product as described below: A 250 ml three neck flask, equipped with a magnetic stir bar, a thermometer and an addition funnel, and cooled with an ice water bath, was charged with 60 ml of MTBE, 3.6 g (20.0 mmol) of 98% of 2,5-dimethyl-2,5-dihydroperoxyhexane and 4.5 g (57.0 mmol) of pyridine. The stirred mixture was cooled to 0 ° C and a solution of 6.9 g (42.0 moles) of 100% t-butyl chloro-oxalate in 10 ml of MTBE was added slowly over a period of 10-15 minutes. After starting the addition, a solid of pyridinium chloride was formed immediately. After the addition was complete, the reaction mass was stirred for 60 minutes at 2 ° C, after which 10 ml of water was added and the reaction mass was stirred for an additional 10 minutes at 3-4 ° C. The upper aqueous layer was then separated and the organic layer was washed three times with 35 ml of an aqueous solution of 5% HCl and then twice with 75 ml portions of water. The product solution was dried over 5% by weight of anhydrous MgSO, and, after separation of the spent desiccant through filtration, the solvent was removed under vacuum leaving 4.5 g (51.7% theory, uncorrected) of a liquid product An IR spectrum of the product as a "nujol mull" showed no OH band in the region of 3500 cm "1. A larger band of monoperoxioxalate carbonyl was present at 1785 cm" 1 and a larger band of oxalate carbonyl appeared at about 1740 cm "1. The product had a rapid thermal test result of 33 ° C, which confirmed that the product was a very low temperature peroxide, based on the preparation method, performance data, thermal test data fast and the infrared spectral data, the product obtained in this reaction was the product of the desired titer.

EXAMPLE 10 Preparation 2.5-Dimethyl-2,5-dihexafluoroamyl-oxocarbonylcarbonyl peroxylhexane (1-10) CH-, O O CH3 CH3 O O CH3 l l l l i l i CF3CHFCP2CHO-: - '^ 0-: - -H2CH2-C-00 - C-C-OCHCF2CHPCF3 (I-10) CH3 CH3 3 3 In this example, the product was prepared in two synthetic steps. In the first step, hexafluoroamyl alcohol was reacted with 100% molar excess of oxalyl chloride.

After completion of the reaction, excess oxalyl chloride was removed from the product under reduced pressure to produce hexafluoroamyl chloro-oxalate having an analysis of 91.3% and a corrected yield of 52.8%. In the second step, the hexafluoroamyl chlorooxalate was reacted with 2,5-dimethyl-2,5-dihydroperoxyhexane, in the presence of pyridine, to produce the product as described below: A 250 ml three neck flask , equipped with a magnetic stir bar, a thermometer and an addition funnel, and cooled with an ice water bath, was charged with 60 ml of MTBE, 1.8 g (10.0 mmol) of 98% of 2.5 -dimethyl-2, 5-dihydroperoxyhexane and 2.3 g (29.0 mmoles) of pyridine. The stirred mixture was cooled to 0 ° C and a solution of 6.6 g (21.0 moles) of 91.3% hexafluoroamyl chloro-oxalate in 10 ml of MTBE was added slowly over a period of 10-15 minutes. After the addition was complete, the reaction mass was stirred for 60 minutes at 2 ° C, after which 10 ml of water was added and the reaction mass was stirred for an additional 10 minutes at 3-4 ° C. The upper aqueous layer was then separated and the organic layer was washed three times with 35 ml of an aqueous solution of 5% HCl and then twice with 75 ml portions of water. The product solution was dried over 5% by weight of anhydrous MgSO 4, and, after separation of the spent desiccant through filtration, the solvent was removed under vacuum leaving 5.5 g (80.9% theory, uncorrected) of a solid White. An IR spectrum of the product showed a larger band of monoperoxioxalate carbonyl was present at 1785 cm "1 and a larger band of oxalate carbonyl appeared at approximately 1755 cm" 1. The product had a rapid thermal test result of 90 ° C, indicating that the product was a very low temperature peroxide. The product contained 3.64% active oxygen (theory, 4.72%) according to a peroxy ester active oxygen method, therefore, the product analysis was 77.1% and the corrected yield was 62.4%. Based on the preparation method, the performance data, the rapid thermal test data and the infrared spectral data, the product obtained in this reaction was the product of the desired titer.

EXAMPLE 1 Preparation of 2,5-Dimethyl-2,5-di (chlorocarbonylcarbonylperoxy) hexane (1-11) 0 0 CH3 CH3 0 0 CI-C? -C? -OO-C i -CH2CH2-C i- OC pC-- CI (1-11) CH3 CH3 A 250 ml three neck flask, equipped with a magnetic stir bar, a thermometer and an addition funnel, and cooled with an ice water bath, charged 12.7 g (0.100 moles) ) of oxalyl chloride and 60 ml of MTBE. The contents of the flask were cooled to 0 ° C. Then to the resulting vigorously stirred solution, at about 0 ° C, 3.6 g (0.020 mole) of 98% of 2, 5-dimethyl-2, 5-dihydroperoxyhexane was added slowly in portions over a period of 20 minutes. The reaction was then stirred for an additional 3 hours at 0 ° C. Then, 7.2 g of diglyme was added to the product solution and the solvent and excess oxalyl chloride were removed in vacuum leaving 15.6 (> 100% theory, not corrected) of a product solution (approximately 50% concentration) in diglima. An IR spectrum of the product solution showed a larger band of monoperoxioxalate carbonyl was at 1790 cm '1. The product had a rapid thermal test result of 54-57 ° C, indicating that the product was a very low temperature peroxide. Based on the preparation method, the performance data, the rapid thermal test data and the infrared spectral data, the product obtained in this reaction was the product of the desired titer.

EXAMPLE 12 Preparation of 2,5-Dimethyl-2,5-di (t-butylperoxycarbonylcarbonyl peroxy) hexane (1-12) CH3 CH3 In this example, the product was prepared in two synthetic steps. In the first step, t-butyl hydroperoxide was reacted with 100% molar excess of oxalyl chloride to form t-peroxybutyl chloro-oxalate (A-1). 0 O 1 I Cl-C-C-00-t > -C4H9 (A-l) In a second step, t-peroxybutyl chloro-oxalate was reacted with 2,5-dimethyl-2,5-dihydroperoxyhexane in the presence of pyridine to produce the product (1-12). A 125 ml flask was charged with 9.3 g (100 mmol) of 97% t-butyl hydroperoxide, 75 ml pentane and 3 g anhydrous MgSO 4 at room temperature. The contents were stirred for 30 minutes, after which the contents were filtered and the spent desiccant was washed with 25 ml of pentane and the pentane washings were combined with the filtrate. A 3-necked flask equipped with a magnetic stirring bar, a condenser, a thermometer and an addition funnel and cooled with an ice water bath was then charged with 25.4 g (200 mmol) of oxalyl chloride and 25 ml. of pentane. The solution was cooled to 0 ° C. Then, the dry pentane solution of t-butyl hydroperoxide was added slowly to the stirred solution of oxalyl chloride / pentane for a period of 60 minutes at 0 ° C. the reaction was stirred for an additional 3 hours at 0 ° C. Then, the pentane and excess oxalyl chloride were removed by separating at ice water temperature, leaving 18.5 g (> 100% theory, not corrected, theoretical yield = 18.1 g) of a liquid product. An IR spectrum of the product showed a very light OH band in the region 3500 cm "1 and a single band of monoperoxioxalate carbonyl at 1797 cm" 1. The product had a rapid thermal test result of 45 ° C (very loud noise), which confirmed that the product, t-peroxybutyl chloro-oxalate, was a very low temperature peroxide. The impact shock test [J. Varjavandi and O. L. Mageli, J. Chem. Ed. 48, A451 (19781)] showed that the product is sensitive to shock at 7.62 cm, and was not sensitive to a shock of 2.54 cm. Due to the thermal and shock sensitivities of the product, it was diluted with an equal weight of diglyme before subsequent use. The product diluted in diglima had a rapid thermal test result of 60 ° C (moderate decomposition) and a shock sensitivity above 50.8 cm. In the second step, a 250 ml 3-necked flask equipped with a magnetic stir bar, a condenser, a thermometer and an addition funnel and cooled with an ice bath was charged with 1.8 g (10.0 mmol) 98% of 2, 5-dimethyl-2,5-dihydroperoxyhexane (Luperox 2, 5-2.5 dry), 2.3 g (29.0 moles) of dry pyridine and 60 ml of MTBE. The contents of the flask were cooled to 0 ° C. Then to the resulting vigorously stirred solution, at about 0 ° C, 7.7 g (21.0 moles) of about 50% of a solution of t-peroxybutyl chloro-oxalate diglyme in 10 ml of MTBE was added slowly. After the addition was complete, the reaction mass was stirred for 60 minutes at 0 ° C, after which 10 ml of water was added and the reaction mass was stirred for an additional 20 minutes at 0-5 ° C. The aqueous layer was then separated and the organic layer was washed three times with 35 ml portions of an aqueous solution of 5% HCl and then twice with 75 ml portions of a 5% aqueous solution of NaHCO3. The product solution was dried over 5% by weight of anhydrous MgSO 4, and, after separation of the spent desiccant through filtration, 4.7 g of diglyme was added as a high boiling safety diluent and the solvent was removed under vacuum leaving 8.7 g (> 100% theory, uncorrected, pure theoretical yield = 4.7 g) of a fine slurry of the product in diglyme. An IR spectrum of the product solution showed two major bands of peroxioxalate carbonyl was at 1769 cm '1 and 1801 cm "1. The product in diglyme had a rapid thermal test result of 51 ° C, indicating that the product was a peroxide Very low temperature Based on the preparation method, the performance data, the rapid thermal test data and the infrared spectral data, the product obtained in this reaction was the product of the desired titer.

EXAMPLE 13 Preparation of 2,5-Dimethyl-2,5-di (3-t-butylperoxy-1,3-dimethylbutoxycarbonylcarbonylperoxyhexane (1-13) CH, O 0 CH 3 CH 3 OO CH 3 III I III OT3C ~ CH2CHOC ^ -OO ^ H2CH2 ^ -) C COCHCH2 - CCH3 (I - 13) t-C4Hg-00 CH3 CH3 CH3 CH3 00-t-C4H9 In this example, the product was prepared in two synthetic steps. In the first step, 3-t-butylperoxy-1,3-dimethylbutane was reacted with 100% molar excess of oxalyl chloride. After the end of the reaction, the excess oxalyl chloride was removed from the product under reduced pressure to produce 3-t-butylperoxy-1,3-dimethylbutyl chloro-oxalate, having an analysis of 97.5% and in a corrected yield of 98.5%. In the second step, 3-t-butylperoxy-1,3-dimethylbutyl chloro-oxalate was reacted with 2,5-dimethyl-2,5-dihydroperoxyhexane in the presence of pyridine to produce the product as described below : A 250 ml 3-necked flask equipped with a magnetic stir bar, a condenser, a thermometer and an addition funnel and cooled with an ice bath was charged with 1.6 g (9 mmol) of 98% 2,5-dimethyl-2,5-dihydroperoxyhexane, 2.0 g (25 moles) of dry pyridine and 60 ml of MTBE. The contents of the flask were cooled to 0 ° C. Then to the resulting vigorously stirred solution, at about 0 ° C, a solution of 5.2 g (18 moles) of 97.5% 3-t-butylperoxy-1,3-dimethylbutyl chloro-oxalate in 10 ml of a solution was slowly added. MTBE. After the addition was complete, the reaction mass was stirred for 60 minutes at 2 ° C, after which 10 ml of water was added and the reaction mass was stirred for an additional 10 minutes at 3-4 ° C. The aqueous layer was then separated and the organic layer was washed three times with 35 ml portions of an aqueous solution of 5% HCt and then twice with 75 ml portions of a 5% aqueous solution of NaHCO3. The product solution was dried over 5% by weight of anhydrous MgSO 4, and, after separation of the spent desiccant through filtration, the solvent was removed under vacuum leaving 6.5 g (> 100% theory, uncorrected) of a liquid product An IR spectrum of the product solution showed no OH band in the 3500 cm "1 region, a larger band of monoperoxioxalate carbonyl at approximately 1790 cm" 1 and a greater oxalate carbonyl band at approximately 1740 cm "1. The product in diglima had a rapid thermal test result of 54-57 ° C, which confirmed that the product was a very low temperature peroxide.The product contained 3.48% active oxygen (theory, 4.80%) according to the active oxygen method of peroxyester, therefore, the product analysis was 80.0% and the corrected yield was 86.7% Based on the preparation method, the performance data, the fast thermal test data and the infrared spectral data, the The product obtained in this reaction was the product of the desired title.

EXAMPLE 14 SPI Exotherm Data at 60 ° C for 2.5-dimethyl-2.5-di (isoboornyloxycarbonylcarbonylperoxy) hexane (I-4) The unsaturated polyester resin composition employed in this example was a mixture of an unsaturated polyester and a styrene monomer. The unsaturated polyester was an alkyd resin made by esterifying the following components: 0.013% by weight of a hydroquinone inhibitor was added to the resulting resin. The alkyd resin had an acid number of 45-50. Seven (7) parts by weight of the unsaturated polyester alkyd resin were diluted with res (3) parts by weight of the styrene monomer. The resulting unsaturated polyester resin composition had the following properties: D Viscosity (Brookfield No.2 to 20 r.p.m.) - 13.0 poises D Specific gravity - 1.14 The gelling and curing characteristics of di (4-t-butylcyclohexyl) peroxydicarbonate (A-1), (a commercially available peroxide product used to cure unsaturated polyester resin compositions), t-butyl peroxydecanoate (A-2) ), (another commercially available peroxide product used to cure unsaturated polyester resin compositions), α-cumyl peroxydecanoate (A-3) (a commercial low-temperature peroxide initiator) and 2,5-dimethyl-2,5-di (isobornyloxycarbonylcarbonylperoxy) -hexane (I-4), a novel bis (monoperoxyoxalate) composition of the present invention, were determined using the Normal SPI Exotherm Procedure (Suggested SPI Procedure for Running Exotherm Curves-Polyester Resins, published in Preprint of the 24th Annual Techinca Conference - Reinforced Plastics / Composites Division, Society of He Plastícs Industry, Inc., 1969). Using this procedure at 60 ° C, A-1 A-2, A-3 and I-4 were comparatively evaluated. The level of I-4 was 1.0 g per 100 g of resin in a pure base and the levels of A-1, A-2 and A-3 (per 100 g of resin) were equivalent in the content of active oxygen to a level of 1.0 g of I-4 (pure base). The results of this investigation are given in the Table of Example 14 and show that O-4 gelled and cured the resin much more rapidly than A-1, A-2 and A-3, therefore, I-4, a composition novel bis (monoperoxyoxalate) of the present invention, was much more active in curing the unsaturated polyester resin than the three commercial, lower temperature peroxide catalysts.

The subject matter considered by the applicant as his invention is particularly pointed and indistinctly claimed in the following claims.

Claims (6)

1 .- A new bis (mono- or diperoxioxalato) of Structure A: wherein R1, R2, R3 and R4 are the same or different and are alkyl radicals of 1 to 4 carbons, preferably alkyl radicals of 1 to 2 carbons, most preferably methyl radicals, R5 is a di-radical selected from - (CH2 ) n-, where n is 1 to 6, -C = C-, -C = CC = C-, 1, 4-phenylene, 1, 3-phenyl substituted or unsubstituted, the substituent being of the structure, preferably, R5 is a di-radical selected from - (CH2) p-, wherein n is 1 to 2, and -C = C-, most preferably Rs is - (CH2) 2-, Q and Q1 are independently selected from group consisting of chlorine, bromine, RO and Rβ-OO, wherein R is selected from the group consisting of H, a substituted or unsubstituted alkyl radical of 1 to 24 carbon, the substituents being one or more alkyl radicals of 1 to 6 carbons, alkoxy radicals of 1 to 6 carbons, aryloxy radicals of 6 to 10 carbons, fluoro, chloro, bromo, carboxy and cyano, a substituted or unsubstituted alkenyl radical of 3 to 12 carbons, the substituents being one or more alkyl radicals lower of 1 to 4 carbons, a substituted or unsubstituted aryl radical of 6 to 10 carbons, the substituents being one or more alkyl radicals of 1 to 6 carbons, alkoxy radicals of 1 to 6 carbons, aryloxy radicals of 6 to 10 carbons, chlorine, bromine and cyano, a substituted or unsubstituted aralkyl radical of 7 to 13 carbons, the sub With one or more alkyl radicals being from 1 to 6 carbons, a substituted or unsubstituted cycloalkyl radical from 5 to 12 carbon optionally having one or more oxygen or nitrogen atoms in the cycloalkane ring, with the substituents being one or more lower alkyl radicals of 1 to 4 carbons, a substituted or unsubstituted bicycloalkyl radical of 6 to 14 carbons, with substituents one or more lower alkyl radicals of 1 to 4 carbons, a substituted or unsubstituted tricycloalkyl radical of 7 to 16 carbons, substituents one or more lower alkyl radicals being from 1 to 4 carbons, and R may also be from structure (a), R9- 0-C-R10- (a) wherein R "1, 0u is an unsubstituted alkylene di-radical of 1 to 3 carbons or a substituted alkylene radical of 1 to 3 carbons, the substituents being one or more lower alkyl radicals of 1 to 4 carbons , R7 and Rβ are alkyl radicals of 1 to 4 carbons, Rβ is selected from unsubstituted t-alkyl radicals of 4 to 12 carbons, substituted t-alkyl radicals of 4 to 12 carbons, t-cycloalkyl radicals of 6 s 13 carbons, t-alkynyl radicals of 5 to 9 carbons, t-aralkyl radicals of 9 to 13 carbons, unsubstituted aroyl radicals of 7 to 1 carbons, substituted aroyl radicals of 7 to 1 1 carbons, wherein the substituent for the radicals t- alkyl is a t-peroxyalkyl radical of 4 to 8 carbons and the substituents for the aroyl radicals are one or more lower alkyl radicals of 1 to 4 carbons, alkoxy radicals of 1 to 4 carbons, phenyl radicals, acyloxy radicals of 2 to 8 carbons , t-peroxyalkyl-carbonyl radicals of 5 to 9 carbons, fluoro, chlorine or bromine, and R9 could also be structures (b), (c) and (d), > 15 I I R11 --- 0 --- O: -j-R12-c I-, R14-0-C- 13 17 (b) (O (d) wherein x is 0 or 1, R "1 1 is a substituted or unsubstituted alkyl radical of 1 to 8 carbons, the substituents being one or more alkyl radicals of 1 to 6 carbons, radicals t -peroxyalkyl of 4 to 8 carbons, alkoxy radicals of 1 to 6 carbons, aryloxy radicals of 6 to 10 carbons, hydroxy, chlorine, bromine, or cyano or a substituted or unsubstituted radical of 5 to 12 carbons optionally having one or more atoms of oxygen or nitrogen in the cycloalkane ring, the substituents being one or more lower alkyl radicals of 1 to 4 carbons, and, R 12 is selected from a substituted or unsubstituted alkylene radical of 2 to 3 carbons, the substituents being one or more alkyl radicals of 1 to 4 carbonsor a substituted 1, 2-, 1, 3- or 1, 4-substituted or unsubstituted phenylene, the substituents being one or more lower alkyl radicals of 1 to 4 carbons, chlorine, bromine, nitro or carboxy, and , R13 is a lower alkyl radical of 1 to 4 carbons, and, additionally, the two R13 radicals can be joined to form an alkylene di-radical of 4 to 5 carbons, R14 is a lower alkyl radical of 1 to 4 carbons, R15, R16 and R1 7 are selected from hydrogens, alkyl radicals of 1 to 8 carbons, aryl radicals of 6 to 10 carbons, alkoxy radicals of 1 to 8 carbons and aryloxy radicals of 6 to 10 carbons, preferably R is selected from the group consists of H, a substituted or unsubstituted alkyl radical of 1 to 22 carbons, the substituents being one or more alkyl radicals of 1 to 6 carbons, alkoxy radicals of 1 to 6 carbons, aryloxy radicals of 6 to 10 carbons, fluoro, chloro , bromine, carboxy and cyano, a substituted or unsubstituted aralkyl radical of 7 to 13 carbons, substituents being one or more alkyl radicals of 1 to 6 carbons, a substituted or unsubstituted cycloalkyl radical of 5 to 12 carbons, the substituents being one or more lower alkyl radicals of 1 to 4 carbons, a substituted or unsubstituted bicycloalkyl radical of 6 at 14 carbons, the substituents being one or more lower alkyl radicals of 1 to 4 carbons, a substituted or substituted tricycloalkyl radical of 7 to 16 carbons, the substituents being one or more alkyl radicals of 1 to 4 carbons, and the structure (a ), most preferably, R is selected from the group consisting of H, a substituted or unsubstituted alkyl radical of 1 to 22 carbons, the substituents being one or more alkyl radicals of 1 to 6 carbons, alkoxy radicals of 1 to 6 carbons, aryloxy radicals of 6 to 10 carbons, chlorine, bromine, carboxy and cyano, a substituted or unsubstituted cycloalkyl radical of 5 to 12 carbons, the substituents being one or more lower alkyl radicals 1 to 4 carbons, a substituted or unsubstituted bicycloalkyl radical of 6 to 14 carbons, the substituents being one or more lower alkyl radicals of 1 to 4 carbons, and structure (a), and, R6 is selected from a radical unsubstituted t-alky from 4 to 12 carbons, a substituted t-alkyl radical of 4 to 12 carbons, a t-cycloalkyl radical of 6 to 13 carbons, a t-alkynyl radical of 5 to 9 carbons, and a t-aralkyl radical of 9 to 13 carbons, in where the substituent for the alkyl radical is a t-peroxyalkyl radical of 4 to 8 carbons.

2. A bis (mono- or diperoxyoxalate) according to claim 1, which is selected from the group consisting of: 2,5-dimethyl-2,5-di (ethoxycarbonylcarbonylperoxy) hexane, 2,5-di methyl -2, 5-di (docosyloxycarbonylcarbonylperoxy) hexane, 2,5-dimethyl-2,5- [di (4-t-butylcyclohexoxy) carbonylcarbonylperoxy] hexane, 2,5-di methyl 1-2,5-di (isobornyloxycarbonylcarbonyl) I peroxy) hexane, 2,5-di methyl 1-2, 5-di (neo-pentyloxycarbonylcarbonyl I peroxy) hexane, 2,5-dimethyl-2,5-di (neopentyl-oxycarbonylcarbonylperoxy) -3 -hexine, 2,5-dimethyl-2,5-di (bornyloxy-carbonylcarbonylperoxy) hexane, 2,5-imethyl-2,5-di (benzyloxycarbonyl-carbonyl) peroxy) hexane, 2,5-dimethyl-2,5-di (t) -butoxycarbonylcarbonyl-peroxy) hexane, 2,5-di methyl-2,5-di (hexaf luoramyloxycarbonylcarboni I-peroxy) hexane, 2,5-dimethyl-2,5-di (chlorocarbonylcarbonylperoxy) hexane, 2, 5 -d im eti 1-2, 5-di (t-bu tiperoxycarbonylcarbonylperoxy) hexane, and 2,5-dimethyl-2, 5-di (t-butyl peroxy-1,3-d imethylbutoxy-carbonylca rbonylperoxy) hexane.

3. A bis (mono- or diperoxioxalate) according to claim 1, wherein Q and Q are the same and R1, R2, R3 and R4 are the same and are alkyl radicals of 1 to 2 carbons.

4. A bis (mono- or diperoxioxalate) according to claim 3, wherein Q and Q1 are selected from RO and Cl.

5.- A bis (mono- or diperoxioxalate) according to claim 4, wherein Q and Q1 are RO.

6. A bis (mono- or diperoxioxalate) according to claim 5, wherein R5 is selected from -C = C- and - (CH2) n-, and n is 2. 7 - A bis (mono- or diperoxyoxalate ) according to claim 6, wherein Rs is - (CH2) n- and n is 2. 8.- A bis (mono- or diperoxyoxalate) according to claim 7, wherein R is selected from the group consisting of H, a substituted or unsubstituted alkyl radical of 1 to 22 carbons, the substituents being one or more alkyl radicals of 1 to 6 carbons, alkoxy radicals of 1 to 6 carbons, aryloxy radicals of 6 to 10 carbons, chlorine, bromine, carboxy and cyano, a substituted or unsubstituted cycloalkyl radical of 5 to 12 carbons, the substituents being one or more alkyl radicals of 1 to 4 carbons, substituted or unsubstituted bicycloalkyl radicals of 6 to 14 carbons, the substituents being one or more alkyl radicals lower of 1 to 4 carbons, and structure (a). 9. A process for the use of the bis (mono- or diperoxyoxalate) compositions according to claim 1, as free radical initiators for the curing of unsaturated polyester resin compositions by heating said resins in the presence of initiator amounts of the novel peroxide compositions of claim 1, at appropriate temperatures. 10. A process according to claim 9, wherein the composition of bis (monoperoxyoxalate) is 2,5-dimethyl-2,5-di (isobornyloxycarbonylcarbonylperoxy) hexane. 1 .- A process for the use of bis (mono- or diperoxyoxalate) compositions according to claim 1 as free radical initiators for the polymerization of ethylenically unsaturated monomers through the use of initiator amounts of the novel compositions of peroxide of claim 1, at appropriate temperatures. 12. A process according to claim 8, wherein the ethylenically unsaturated monomer is vinyl chloride.