MXPA97010520A - Novedous compositions of oxalic acid peroxide and u - Google Patents

Abstract

A novel peroxide composition of Structure A is described, and use of the novel oxalic peroxide composition of Structure A as an initiator, a) to cure unsaturated polyester resins, b) to polymerize ethylenically unsaturated monomers, c) to interlacing polyolefins, d) to cure elastomers, e) to modify polyolefins, f) to graft vinyl monomers into polymer base structures and g) to compatibilize mixtures of two or more incompatible polymers

Description

NOVEDOUS COMPOSITIONS OF OXALIC ACID PEROXIDE AND USES This request claims priority of the Provisional Application S / N 60/034, 526, filed on December 30, 1996.

BACKGROUND OF THE INVENTION a) Field of the Invention This invention relates to new and novel compositions of matter classified in the field of chemistry as oxalic acid peroxide compositions of Structure A, [The definitions of R, R1, R2, R3, Z and n are given in the COM P DIO N OF THE I NVENTION]. for example, 3-t-butylperoxy-1,3-dimethylbutyl oxalate, and the use of the novel oxalic acid peroxide compositions of Structure A. The compositions have inherent applied application characteristics that make them suitable for use as initiators, a) for polymerizing ethylenically unsaturated monomers, b) for curing unsaturated polyester resins, c) for curing elastomers, d) for crosslinking polyolefins, e) for modifying polyolefins, f) for ging vinyl monomers onto the base structures of the polymer and g) for compatibilizing mixtures of two or more incompatible polymers. There is a need in the industry for polymers for free radical entanglement agents, efficient for olefin polymer, which give longer sintering times and still result in faster entanglement rates. Because of its low melt flow, high density polyethylene (HPE) must be mixed with peroxide at temperatures where the scorching time is relatively short. If the scorching time is too short, premature entanglement of H DPE occurs during the mixing step of the peroxide. This is highly undesirable. In the interlacing of H DPE, the peroxide which is predominantly used for interlacing is 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexane (Lupersol 130, manufactured by ELF ATOCHEM North America, Inc.) . Of all the commercial organic peroxides, Lupersol 1 30 has the longest half-life temperature of 10 hours (13 ° C). The half-life temperature of 10 hours of an initiator is defined as the temperature at which 50% of the initiator will decompose in 10 hours. Generally, the higher the half-life temperature of 10 hours, the greater the scorching time at a given temperature. Although Lu persol 130 gives adequate scorch times when mixed in the HDPE, the polymer producers complain about the harmful decomposition products that the Lupersol 130 produces during the interlacing of the polyethylene. Harmful decomposition products are believed to be derived from the carbon-carbon triple bond in LUPERSOL 130, since a similar peroxide lacking the triple carbon-carbon bond, 2,5-dimethyl-2,5-di (t-) Butylperoxy) hexane, does not produce harmful decomposition products. An efficient polyethylene interlacing agent, which produces elongated sintering times and produces less harmful decomposition products, is needed by the polyethylene interlacing industry. A novel oxalic acid peroxide composition of the present invention, 3-t-butylperoxy-l, 3-dimethylbutyl oxalate oxalate, satisfies most of these entanglement criteria and has been found to be the most effective HDPE crosslinking agent. than LUPERSOL 130. At 196.1 ° C in HDPE, allyl 3-t-butylperoxy-1,3-dimethylbutyl oxalate was found to be significantly more efficient than LUPERSOL 130 on an equivalent basis and was found to interlace HDPE much more quickly than the LUPERSOL 130. Therefore, it was superior to LUPERSOL 130 for the interlacing of HDPE. Since allyl 3-t-butylperoxy-l, 3-dimethylbutyl oxalate does not contain a carbon-carbon triple bond, the generation of harmful decomposition products during the entanglement of polyethylene is unlikely. In recent years, most of the new polymeric materials that have been commercialized are polymer blends and alloys composed of two or more different polymers. The reasons for this trend to the commercial development of polymer and alloy mixtures include the short time required for the development and commercialization of these materials, the relatively low cost to perform the R & amp;; D necessary to develop these materials, compared to the development of completely new polymers from monomers, and the ability to develop polymer blends and alloys that are "made by design" to meet end-use property specifications, therefore, not They are over-designed through engineering or under-designed through engineering, but just fine. Improvements in polymer property obtained through mixing include: Better processability Improved impact resistance Improved flame retardancy Improved barrier properties Improved stress properties Improved adhesion Improved flow under melting Improved temperature of thermal distortion (HDT) Improved resistance thermal Improved rigidity Improved chemical resistance Improved stability to ultraviolet light. The main problem encountered in the development of new mixtures and alloys is the inherent compatibility or non-miscible capacity of almost all mixtures of two or more polymers. The consequence of incompatibility of polymer mixtures and alloys is that they are unstable and, with sufficient time and temperature, form separate phases, in this way the physical properties of the polymer mixtures are affected. Generally, it has been found that resin compounds that block and graft copolymers having polymer segments that are compatible with the individual polymer components of blends and alloys allow the formation of blends and alloys that have improved physical stabilities and physical properties. Low cost blends and alloys are commercially produced from two or more addition polymers such as blends involving low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE) and polypropylene. (PP) The compatibility of these low cost blends can be improved through entanglement with peroxides or through the use of block copolymers or compatibilization graft c, as mentioned above. An important use of peroxides such as novel oxalic acid peroxide compositions of Structure A is their utility in the preparation of graft copolymers useful for compatibilizing mixtures and polymeric alloys. The novel oxalic acid peroxide compositions of structure A of the present invention are effective in the preparation of graft copolymer compositions. Said graft copolymers have utility in the compatibilization of mixtures and polymer alloys. b) Description of the Prior Art U.S. Patent 3,236,872 (02/22/96, Laporte Chemical, Ltd.) discloses hydroxy-peroxides of the structure: CH :, I (wherein R- is H-, an acyl, aroyl or alkyl group, especially the t-butyl group, t-amyl or the hexyllenic glycol residue, R'- is H- or an acyl, aroyl or alkyl group). The patent of E.U.A. 4,525,308 (06/25/85, of Pennwait Corp.) and the patent of E.U.A. 4,634,753 (06/01/87 from Pennwait Corp.) describe hydroxy peroxy esters (above structure, wherein R'- is H- and R- is an acyl group) having half-life temperatures of 10 hours below about 75 ° C. The patent of E.U.A. 3,853, 957 (10/12/74, Pennwait Corp.) describes diperoxyacetals and ketone peroxides containing hydroxy and acyloxy groups.

The patent of E.U.A. 3,846,396 (05/11/74, of Pennwait Corp.) and the patent of E.U.A. 3,725,455 (03/04/73, from Pennwait Corp.) describe coupled peroxides of the structure, R W R ' wherein R- and R'- are the same and are peroxide containing alkoxy radicals having at least two carbons and an oxygen atom between the peroxide groups (-OO-) of the groups R- and R'- and -W- is a di-radical selected from the class consisting of several di-radical structures that include, OOOOO -C i-, -C pC-, ~ C iC? _t2_C i- The patent of E.U.A. 3,846,396 and the patent of E.U.A. 3,725,455 are related technique when -W- is - (O) -C (O) -. However, the structures of this technique do not anticipate the compositions of Structure A. The patent of E.U.A. 3,706,818 (12/19/72, of Pennwait Corp.) and the patent of E.U.A. 3,839,390 (10/01/74, of Pennwait Corp.) describe sequential polyperoxides that possess peroxide moieties of different structures and activities in the same molecule. The structures of this technique do not anticipate the polypeptides sequences of Structure A. The US patent. 3,671, 651 (06/20/72, of Pennwait Corp.) discloses peroxy compounds containing haloformate groups (e.g., chloroformate and carbonyl chloride). Some of the novel oxalic acid peroxide compositions of Structure A contain the chloro oxalate group, -OC (O) -C (O) -CI, which is different, easier to incorporate on a hydroxy-peroxy compound than is a haloformate group (especially when the hydroxyl group is a secondary or tertiary hydroxyl group) and which is more reactive in subsequent reactions than a haloformate (i.e., with a secondary or tertiary hydroxyl compound and / or in the absence of a base) . Therefore, the novel oxalic acid peroxide compositions of Structure A are ahead of the art with respect to that described in the U.S.A. 3,671,651. The patent of E.U.A. 3,660,468 (02/05/72, of Pennwait Corp.) discloses peroxyester compounds containing carboxy groups. The carboxy compounds of Structure A contain the -O-C (l) -C (O) -OH group, which is significantly different from the carboxy group of the carboxy-containing polyesters of the U.S.A. 3,660,468. In addition, the carboxy compositions of Structure A are more readily produced than are the carboxy-containing peroxyesters of the U.S. patent. 3,660,468. s) Definitions In the present invention, t-cycloalkyl refers to the mono-radical structure, CH2CH2 Rx / \ / (CH2) t C \ / \ CH2CH2 wherein t is from 0 to 2 and R "is a lower alkyl radical of 1 to 4 carbon atoms, t-alkynyl is the mono-radical structure, R * I RV-C * C-C- I Rx wherein Ry is hydrogen or a lower alkyl radical of 1 to 4 carbon atoms, and t-aralkyl is the mono-radical structure, Rx I Rz - C - Rx wherein Rz 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 formula or general structure, the meaning of each is independent of the other.

COMPENDIUM OF THE INVENTION The invention provides in one aspect of composition, a novel oxalic acid peroxide composition of Structure A: O O 00-C 1-R 3-0-C - C - - - Z & n wherein n is 1 or 2, and R is selected from the group consisting of a 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 , a t-aralkyl radical of 9 to 13 carbons and structures (a), (b), (c), (d) and (e), \ CC O, 8, 10 or / \ ICO CC- R6-0-C- [-R7-C-] R9-0-CR 11. \ / CCR 12 (H) 3 \ (b) (c) ( gives) (and) wherein R 4 and R 5 are the same or different and are selected from the group consisting of hydrogen, lower alkyl radicals of 1 to 4 carbons, alkoxy radicals of 1 to 4 carbons, phenyl radicals, acyloxy radicals of 2 to 8 carbons, radicals t- alkylperoxycarbonyl of 5 to 9 carbons, hydroxy, fluoro, chloro or bromo, and, x is 0 or 1, R6 is a substituted or unsubstituted radical of 1 to 18 carbons, the substituents being one or more alkyl radicals of 1 to 6 carbons , t-alkylperoxy radicals of 4 to 8 carbons, alkoxy radicals of 1 to 6 carbons, aryloxy radicals of 6 to 10 carbons, hydroxy, chlorine, bromine or cyano, and a substituted or unsubstituted cycloalkyl radical of 5 to 12 carbons, having optionally an oxygen atom or a nitrogen atom in the cycloalkane ring, with the substituents being one or more alkyl radicals of 1 to 4 carbons, and, R7 is selected from a substituted or unsubstituted alkylene di-radical of 2 to 3 carbons , the substituents being one or more alkyl radicals of 1 to 4 carbons, and substituted and unsubstituted 1,2-, 1,3- and 1,4-phenylene di-radicals, the substituents being one or more lower alkyl radicals of 1 to 4 carbons, chlorine , R8 is a lower alkyl radical of 1 to 4 carbons, and, additionally, the two radicals R8 can be chained to form an alkylene di-radical of 4 to 5 carbons, and, R9 is a alkyl radical of 1 to 4 carbons, and, R, R 1 and R 12 may be the same or different and are selected from the group consisting of hydrogen, 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, and, R1 and R2 are alkyl radicals of 1 to 4 carbons, and, when R is selected from a t-alkyl radical of 4 to 12 carbons, R2 may additionally be a radical t-alkylperoxy of 4 to 12 carbons, R3 is selected from the group consisting of a substituted or unsubstituted alkylene di-radical or 2 to 4 carbons and a substituted or unsubstituted alkynylene di-radical of 2 to 4 carbons, the substituents being one or more lower alkyl radicals of 1 to 4 carbons, and, when n is 1, Z is selected from the group consists of OR13, NR13R14, OO-R, Cl and Br, wherein R13 and R14 are the same or different and are selected from the group consisting of hydrogen, substituted or unsubstituted alkyl radicals of 1 to 18 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, acryloxy radicals, methacryloxy, chlorine, bromine and cyano radicals, substituted or unsubstituted alkenyl radicals of 3 to 12 carbons, substituents with one or more lower alkyl radicals of 1 to 4 carbons, substituted or unsubstituted aryl radicals of 6 to 19 carbons, the substituents being one or more radicals of 1 to 6 carbons, alkoxy radicals of 1 to 6 carbons, aryloxy radicals of 6 to 10 carb Ones, chlorine, bromine and cyano, substituted or unsubstituted aralkyl radicals of 7 to 11 carbons, the substituents being one or more alkyl radicals of 1 to 6 carbon, alkoxy radicals of 1 to 6 carbons, aryloxy radicals of 6 to 10 carbons, chlorine, bromine and cyano, and substituted or unsubstituted cycloalkyl radicals of 5 to 12 carbons, optionally having an oxygen atom or a nitrogen atom in the cycloalkane ring, with the substituents one or more lower alkyl radicals being from 1 to 4 carbons, and Z is also selected from the structure (g), -0-R3-C-00-R15 (g) i »R15 is selected from the definitions of R, provided that R and R15 are not equal, and when n is 2, Z is selected from the group consisting of the structures ( h), (i), (j), -0-R16-O- (h), -NR13-R16-NR14- (i), -NR13-R16-O- (j), R16 is selected from the group consists of substituted or unsubstituted alkylene diols of 2 to 10 carbons, the substituents being one or more lower alkyl radicals of 1 to 4 carbons, and arylene di-radicals of 6 to 14 carbons, the substituents being one or more alkyl radicals lower of 1 to 4 carbons. B. the invention provides in a process aspect, a method for using the oxalic acid peroxide compositions of Structure A as free radical initiators, in effective starter amounts, for the initiation of free radical reactions, selected from the group consists of: a. cure unsaturated polyester resin compositions, b. polymerizing compositions of ethylenically unsaturated monomers (such as styrene, ethylene), c. interlacing olefin thermoplastic polymer compositions, d. curing elastomer compositions, e. modify polyolefin compositions, f. grafting ethylenically unsaturated substrates onto homo-, and olefin copolymer substrates, and g. compatibilizing mixtures of two or more substrates of normally incompatible polymer; which comprises heating said substrates in the presence of an effective initiating amount of one more peroxides as defined in A., above, for a time sufficient to at least partially decompose said peroxide, to perform the free radical reaction.

DETAILED DESCRIPTION OF THE INVENTION Novel Compositions of Oxalic Acid Peroxide of Structure A - Preparative Methods The novel oxalic acid peroxide compositions of Structure A can be prepared by various methods. One method involves reacting a hydroxy peroxide of Structure Y with an oxalyl halide of structure X in the presence of an optional base and an optional solvent to form a novel composition of Structure A: R-00- Z [R is as previously defined and Q = Br or Cl]. The hydroxy peroxides of Structure Y, wherein R = t-alkyl, t-cycloalkyl, t-alkynyl, t-aralkyl and HO-R3-C (R1) (R2), as known in the art (US patent 3,236,872). The hydroxy peroxides of Structure Y, where R = structure (a), can be prepared by reacting a substituted or unsubstituted benzoyl halide of the Structure W with a hydroxy hydroperoxide of Structure V in the presence of a base and an optional solvent: R5 R5 [C-C] O R1 [C-C] O R1 / [II] I / [II I C O C-C-Q + HOO-C-R3-OH * C O C-C-OO-C-R3 -OH \ / | Base \ / | / C-C R2 / C-C R2 (H) 3 \ (H) 3 \ R4 AND R4 H The hydroxy peroxides of Structure Y, wherein R = structure (b) and x = O, can be prepared by reacting alkyl haloformates of Structure U with a hydroxy hydroperoxide of Structure V in the presence of a base and a optional solvent: O R1 OR R1 R6_0_C I_Q + HOO-C I-R 33-OH R2-0-C? -00-C? -RJs-OH Base The hydroxy peroxides of Structure Y, wherein R = structure (b) and x = 1, can be prepared by reacting a carboxylic acid ester halide of structure T with a hydroxy hydroperoxide of Structure V in the presence of a base and an optional solvent: O O R1 O O R1 R6.0_C.R7_C_Q + H00-C-R3-OH Rb-0-C-R -C-00-C-RJ-OH | Base | R2 R2 The hydroxy peroxides of Structure Y, wherein R = structure (c), can be prepared by reacting an unsaturated ether of Structure S with a hydroxy hydroperoxide of Structure V in the presence of an optional acid and an optional solvent: , 3-0H [Where R19 contains a methylene di-radical less than R8]. Some hydroxy peroxides of Structure Y, wherein R is structure (d) are known in the art (U.S. Patent 4,425, 308). This class of hydroxy peroxides can be synthesized by reacting hydroperoxides of Structure V with carboxylic acid halides or anhydrides of Structure P_ in the presence of an optional base and an optional solvent: R10 or R1 R10 OR R1 I II I., Optional,, I «', R11_C cQ' + HOO-C-R3-OH - •• R1: LC C-OO-C-R3 -0H II Base II R12 R2 R12 R2 £ Y. 0 R10 [Q - = Br, Cl, or OC 1-C '- R 1? 1í] R12 Optional non-limiting examples of optional norwegian bases which are useful in the synthetic processes of this invention include sodium hydroxide, carbonate of sodium, sodium acid carbonate, potassium hydroxide, potassium carbonate, potassium hydrogen carbonate, calcium hydroxide, calcium hydroxide, barium hydroxide, magnesium hydroxide, calcium carbonate and trisodium phosphate. Non-limiting examples of suitable optional organic bases useful for preparing the peroxide compositions of this invention include trimethylamine, triethylamine, tributylamine, 1,4 [2.2.2] octane, pyridine, N, N-dimethylaniline, N, N-diethylaniline, pN , N-dimethylamino-pyridine, tetramethylurea and methylpyridines.

Non-limiting examples of suitable optional solvents include pentane, hexanes, heptanes, dodecanes, mixtures of odorless mineral spirits, toluene, xylenes, eumeno, 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 optional optional acids which are useful in the synthetic processes of this invention include hydrochloric acid, perchloric acid, phosphoric acid, sulfuric acid, sodium acid sulfate, potassium acid sulfate, acetic acid, trifluoroacetic acid, methanesulfonic acid and benzenesulfonic acid. Non-limiting examples of suitable hydroxyhydroperoxides of Structure V include 3-hydroxy-1,1-dimethylpropyl hydroperoxide, 3-hydroxy-1,1-dimethylbutyl hydroperoxide and 4-hydroxy-1,1-dihydroxy-hydroperoxide. but i lo. Non-limiting examples of suitable acid halides of Structure W include benzoyl chloride, 2-methylbenzoyl chloride, 2-ethylbenzoyl chloride, 2-methoxybenzoyl chloride, 2,6-dimethylbenzoyl chloride, 2-phenylbenzoyl chloride, chloride of 2-chlorobenzoyl, 2,4-dichlorobenzoyl chloride, 2-bromobenzoyl chloride, 2-bromobenzoyl bromide, 2-fluorobenzoyl chloride, 2-acetoxybenzoyl chloride, and 2- (t-butylperoxycarbonyl) benzoyl chloride). Non-limiting examples of suitable carboxylic acid halides and anhydrides of Structure P include pivaloyl chloride, neoheptanoyl chloride, neodecanoyl chloride, neotridecanoyl chloride, 2-ethylbutyryl chloride, 2-ethylhexanoyl chloride, isobutyryl chloride, cyclohexane carboxylic acid, acetic anhydride, propionic anhydride, and isobutyric anhydride. Non-limiting examples of alkyl haloformates of Structure U_ include methyl chloroformate, ethyl chloroformate, isopropyl chloroformate, isopropyl bromoformate, butyl chloroformate, 2-butyl chloroformate, neopentyl chloroformate, 2-ethylhexyl chloroformate, chloroformate 2-eti Ibuti lo, 2-butyloctyl chloroformate, 4-methyl-2-pentyl chloroformate, dodecyl chloroformate, hexadecyl chloroformate, 2-chloroethyl chloroformate, 2-butoxyethyl chloroformate, 2-phenoxyethyl chloroformate, chloroformate cyclohexyl, 4-t-butylcyclohexyl chloroformate, 3,3,5-trimethylcyclohexyl chloroformate, cyclododecyl chloroformate, 2,2,6,6-tetramethyl-4-piperidinyl chloroformate (and hydrochloride salt) and chloroformate of 1, 2,2,6,6-penta methyl-4-piperidinyl (and hydrochloride salt). The alkyl haloformates of Structure IJ can be prepared by reacting the corresponding alcohols with excess phosgene. Non-limiting examples of suitable acid halides of Structure T include 2-methoxycarbonylbenzoyl chloride, 2-n-butoxycarbonylbenzoyl chloride, 2- (2-ethylhexoxycarbonyl) benzoyl chloride, 2-cyclohexyloxycarbonyl-benzoyl chloride, 3-ethoxycarbonylpropionyl chloride, 4- (n-butoxycarbonyl) butyryl chloride and 3,4,5,6-tetrachloro-2-chloride -methoxycarbonylbenzoyl. The acid halides of Structures W, T and P can be prepared by treating the corresponding carboxylic acids with acid halogenating agents such as PCI3, POC, PCIS, thionyl chloride, thionyl bromide, phosgene (in the presence of catalysts such as dimethylformamide, DMF), benzotrichloride and others. Non-limiting examples of suitable unsaturated ethers of Structure S_ include methyl isopropenyl ether, ethyl isopropenyl ether, n-butyl isopropentyl ether, 1-methoxy-1-cyclohexane, 1-ethoxy-1-cyclohexane and 1-methoxy-3,3, 5-trimethylcyclohexene. Non-limiting examples of hydroxy peroxides of Structure X, wherein R = structure (a), useful for preparing the novel oxalic acid peroxide compositions of Structure A include peroxy- (2-chlorobenzoate) 3-hydroxy-1 , 1-dimethylpropyl, 3-hydroxy-1,1-dimethylbutyl peroxybenzoate, 3-hydroxy-1,1-dimethylbutyl peroxy- (2-methylbenzoate), 3-hydroxy peroxy- (2,4-dimethylbenzoate) -1, 1-dimethylbutyl, peroxy- (2,6-dimethylbenzoate of 3-hydroxy-1,1-dimethylbutyl, peroxy- (2-fluorobenzoate) of 3-hydroxy-1,1-dimethylbutyl, peroxy- (2- chlorobenzoate) of 3-hydroxy-1,1-dimethylbutyl, peroxy- (2-bromobenzoate) of 3-hydroxy-1,1-dimethylbutyl,? -roxy- (2,4-dichlorobenzoate) of 3-hydroxy-1, 1- dimethyl butyl, peroxy- (2-phenylbenzoate) of 3-hydroxy-1,1-dimethylbutyl, peroxy (2-methoxy-benzoate) of 3-hydroxy-1,1-dimethylbutyl, and peroxy- (2-acetoxybenzoate) of 3- hydroxy-1,1-dimethylbutyl, non-limiting examples of suitable hydroxy peroxides of Structure Y, wherein R = structure (b) and x = 0, useful for preparing the novel oxalic acid peroxide compositions of Structure A, include CO- (3-hydroxy-1,1-dimethylpropyl) O- (2-ethexyl) monoperoxycarbonate, monoperoxycarbonate of OO- (3-hydroxy-1,1-dimethylbutyl) O-isopropyl, OO- (3-hydroxy-1,1-dimethylbutyl) O- (2-butyl) monoperoxycarbonate, OO- (3-hydroxy) monoperoxycarbonate 1, 1-dimethylbutyl) O- (2-ethylhexyl), OO- (3-hydroxy-1,1-dimethylbutyl) O- (2-butyloctyl) monoperoxycarbonate, OO- (3-hydroxy-1, 1- monoperoxycarbonate dimethylbutyl) O- (cyclohexyl), monoperoxycarbonate of OO- (3-hydroxy-1,1-dimethylbutyl) O-cyclododecyl, monoperoxycarbonate of OO- (3-hydroxy-1,1-dimethylbutyl) O- (4-t) -butylcyclohexyl), monoperoxycarbonate of OO- (3-hydroxy-1,1-dimethylbutyl) O- (2, 2,6,6-tetramethyl-4-piperidinyl) (and salts) and monoperoxycarbonate of OO- (3-h roxy-1,1-dimethylbutyl) O- (1,2,2,6,6-pentamethyl-4-piperidinyl). Non-limiting examples of suitable hydroxy peroxides of Structure Y, wherein R = structure (b) and x = 1, useful for preparing the novel oxalic acid peroxide compositions of Structure A, include OO- (3-hydroxy) monoperoxyphthalate -1, 1-dimethylbutyl) O-methyl, OO- (3-hydroxy-1,1-dimethylbutyl) On-butyl monoperoxyphthalate, OO- (3-hydroxy-1,1-dimethylbutyl) O-ethyl monoperoxysuccinate and monoperoxyglutarate of OO- (3-hydroxy-1, 1-dimethylbutyl) On-butyl. Non-limiting examples of suitable hydroxy peroxides of Structure X, wherein R = structure (c), useful for preparing the novel oxalic acid peroxide compositions of structure A, include 2-methoxy-2- (3-hydroxy) 1,1-dimethylpropylperoxy) propane, 2-methoxy-2- (3-hydroxy-1,1-dimethylbutylperoxy) propane and 1-methoxy-1- (3-hydroxy-1,1-dimethylbutyl peroxy) cyclohexane. Non-limiting examples of suitable hydroxy peroxides of Structure Y, wherein R = structure (d), useful for preparing the novel oxalic acid peroxide compositions of Structure A, include 3-hydroxy-1-ethylperoxyhexanoate. -dimethyl-butyl, 3-hydroxy-1,1-dimethylbutyl 2-ethylperoxybutyrate, 3-hydroxy-1,1-dimethylbutyl peroxivalate, 3-hydroxy-1-peroxyheptanoate, 1-dimethylbutyl, 3-hydroxy-1,1-dimethylbutyl peroxydecanoate, 3-hydroxy-1,1-dimethylbutyl peroxybutyrate, 3-hydroxy-1,1-dimethylbutyl peroxypropionate and 3-hydroxybutylacetate 1,1-dimethylbutyl. Non-limiting examples of suitable oxalyl halides of Structure X, useful for preparing the novel oxalic peroxide compositions of Structure A, include oxalyl bromide, oxalyl chloride, methyl chloro-oxalate, ethyl chloro-oxalate, butyl chloro-oxalate, dodecyl chloro-oxalate, allyl chloro-oxalate, phenyl chloro-oxalate, cyclohexyl chloro-oxalate, and benzyl chloro-oxalate. The novel oxalic acid peroxide compositions of Structure A ', a reactive group of compounds of Structure A, when n is 1 and Z is Cl or Br, are oxalyl halides useful in the synthetic processes of this invention. The compounds of Structure A 'can react with water or alcohols (HO-R13) in the presence of bases and optional solvents (followed by acidification when water is reacted) to form novel oxalate peroxides possessing the oxalate group,? o o R1 or o R-00-C I-R3, -0-C II-C I-Z + HO-R "13 • >; R-OO-C '-R 33 -OC! -C "-OR 113-1 I Base I ¿R2 Structure A' [Z = Br or Cl], or A 'can react with glycols (HOR16OH) in the presence of bases optional and optional solvents for forming novel oxalate peroxides having bis (oxalate) groups, [-OC (O) C (O) -OR16O-C (O) C (O) O-]: R1 O O O R1 2 A1 + HOR16OH »R-O0-C I-R -0-C I-C II-OR160-C I-CI-0-R3-C-O0-R l2 R2 R2 or A 'can react with amines (HNR13R14) in the presence of optional bases and optional solvents to form novel peroxides possessing the oxamate group [-O-C (O) C (O) -NR13R14]: R1 0 0,, .. Optional ', "», n. A' HNR 13R14.R-00-C-R3-0-CC-NR13R14 Base R2 or A 'can react with diamines (HNR RR NH) in the presence of optional bases and optional solvents for forming novel peroxides having bis (oxamate) groups [OC- (O) C (O) -N (R13) R16N (R1) -C (O) C (O) O-]: R1 OO R13 R14 0 0 R1 2 ?' + HN (R13) R16N (R14) H »R-00-C I-R30-C 1-C1-N1R, 16N1 C I-CI-0R 33-C 1 -OO-R i2 R2 or A 'can react with amino-alcohols (HNR13R16OH) in the presence of optional bases and optional solvents to form novel peroxides possessing oxamate-oxalate groups [-OC (O) C (O) -N (R13) R16-OC (O) C (O) O -]: or A 'can react with hydroperoxides (HOO-R) in the presence of bases and optional solvents to form novel peroxides possessing the monoperoxyoxalate [-O-C (O) C (O) -OO-R] group: R1 0 0 I II II A '+ H O -R »• R-OO-C-RJ-O-C-C-0O-R Base | R2 or A 'can react with a hydroxy peroxide of Structure N_, l H0-R3-C-O0-R15 H l2 R2 in the presence of bases and optional solvents, to form novel non-symmetric oxalate oxalates: Rl R1 O 0 R1 A '+ H0-R3-C I-00-R15 »R-00-C 1 -R3, -0-C1-C1-0-R3, -C1-00-Rl I Base | A 2 R2 Non-limiting examples of oxalyl halides of Structure A ', useful for preparing the oxalate peroxides, oxamate peroxides, monoperoxioxalate peroxides and novel diperoxide oxalates of this invention, include 3-t-chloro-oxalate butylperoxy-1,1-dimethylbutyl, 3-t-butylperoxy-1,1-dimethylpropyl chloro-oxalate, 3-t-butylperoxy-1,1-dimethylbutyl bromo oxalate, di- (3-chlorocarbonylcarbonyloxy) peroxide 1,1-dimethylbutyl), 3-chlorocarbonylcarbonyloxy-1,1-dimethylbutyl peroxy-2-ethylhexanoate, 3-chlorocarbonylcarbonyloxy-1,1-dimethylbutyl peroxy neoheptanoate, 3-chlorocarbonylcarbonyloxy-1-methyl-2-methylbenzoate dimethylbutyl, (3-chlorocarbonylcarbonyloxy-1,1-dimethylbutyl) O-ethyl monobutylsuccinate and 2- (3-chlorocarbonylcarbonyloxy-1,1-diethylbutylperoxy) -2-methoxypropane. Non-limiting examples of suitable alcohols (HO-R13), useful for reacting with A 'to prepare the novel peroxides oxalate of Structure A, include methanol, isopropanol, butanol, dodecanol, cyclohexanol, allyl alcohol, metal alcohol, phenol, benzyl alcohol , acrylate and methacrylate of 2-hydroxyethyl, ethylene glycol, and butylene glycol. Non-limiting examples of suitable diols (HO-R16-OH), useful for reacting with A 'to prepare the novel bis (oxalate) peroxides of Structure A', include ethylene glycol, 1,2-propanediol, 1,3-propanediol , 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, resorcinol and catechol. Non-limiting examples of suitable amines (HNR13R14), useful for reacting with A 'to prepare the novel peroxides of Structure A, include methylamine, isopropylamine, butylamine, t-butylamine, dodecylamine, cyclohexylamine, allylamine, aniline and benzylamine. Non-limiting examples of suitable diamines (HNR13R16R14NH), useful for reacting with A 'to prepare the novel bis (oxamate) peroxides of Structure A, include ethylene diamine and 1,6-diaminohexane. Non-limiting examples of suitable amino alcohols (HNR13R16OH), useful for reacting with A 'to prepare the novel peroxaze oxamate oxalates of Structure A, include ethanolamine, N-methylethanolamine and propanolamine. Non-limiting examples of suitable hydroperoxides (HOO-R), useful for reacting with A 'to prepare the novel peroxides monoperoxyoxalate of Structure A, include t-butyl hydroperoxide, t-amyl hydroperoxide, t-hexyl hydroperoxide, hydroperoxide 1, 1,3,3-tetramethylbutyl, 4- (t-butylperoxy) -1,4,4-tetramethylbutyl hydroperoxide, parametane hydroperoxide, and a-cumyl hydroperoxide.

Novel Compositions of Oxalic Acid Peroxide of Structure A - Illustrative Examples Non-limiting examples of novel oxalic acid peroxide compositions of Structure A, in addition to those in the working examples, include the following: 3-t-butylperoxy-1,1-dimethylpropyl chloro-oxalate, 3-bromo-oxalate chloro-oxalate -t-butylperoxy-1,1-dimethylbutyl, 3-chloro-3-ethylhexanoate, 3-chlorocarbonyl, 1-carbonyl, 1,1-dimethylbutyl, 3-chlorocarbonylcarbonyloxy-1,1-dimethylbutyl peroxyhetanoate, peroxy- 2-methylobenzoate of 3-cl or rboni rock Ica rbon i loxi-1, 1-imethylbutyl, monoperoxysuccinate of OO- (3-chlorocarbonylcarbonyloxy-1,1-dimethylbutyl) ethyl, oxalate acid of 2- (3-chlorocarbonylcarbonyloxy) -1, 1-d imeti lbutilperoxi) -2-methoxypropane, 3-t-butylperoxy-1,1-di-meti I pro pyl, 3-hydroxycarbonylcarbonyloxy-1-dimethylbutyl peroxy-2-ethylhexanoate, 3-hydroxycarbonylcarbonyloxyperoxyheptanoate -1, 1-dimethylbutyl, 3-hydroxycarbonylcarbonyloxy-1,1-dimethylbutyl peroxy-2-methylbenzoate, OO- (3-hydroxycarbon) monoperoxysuccinate [alpha] -carbonyloxy-1,1-dimethylbutyl) O-ethyl, di- (3-hydroxycarbonylcarbonyloxy-1,1-dimethylbutyl) peroxide, 3-t-butylperoxy-1,1-dimethyl butyl butyl oxalate, 3-oxalate -t-butylperoxy-1, 1-dimethylpropyl butyl, 3-t-butylperoxy-1,1-dimethylpropyl oxalate allyl, 3-t-butylperoxy-1,1-dimethylbutyl methyl oxalate, 3-t-butylperoxy- oxalate 1,1-dimethylbutyl, 3-t-butyl-eroxy-1,1-dimethylbutylcyclohexyl oxalate, 3-t-butylperoxy-1,1-dimethylbutylphenol oxalate, 3-t-butylperoxy-1-oxalate , 1-dimethylbutyl 2-acryloyloxyethyl, 3-t-butylperoxy-1,1-dimethylbutyl benzyl oxalate, di- (3-ethoxycarbonylcarbonyloxy-1,1-dimethylbutyl) peroxide, di- (3-allyloxycarbonylcarbonyloxy-) peroxide 1,1-dimethylbutyl), OO- (3-butoxycarbonylcarbonyloxy-1,1-dimethylbutyl O-ethyl, 3-t-butylperoxy-1,1-dimethylbutyl oxamate, N-butyl, 3-t-butylperoxy-1 monoperoxysuccinate, N-butyl 1-dimethylpropyl oxamate, 3-t-butylperoxy-1,1-dimethylpropyl oxamate N-allyl, 3-t-butylpe N-methyl roxy-1, 1-dimethylbutyl oxamate, N-dodecyl 3-t-butylperoxy-1,1-dimethylbutyl oxamate, 3-t-butylperoxy-1,1-dimethylbutyl oxamate of N-cyclohexyl, 3- N-phenyl t-butylperoxy-l, 1-dimethylbutyl oxamate, 3-t-butylperoxy-1,1-dimethylbutyl oxamate, di- (3-allylaminocarbonylcarbonyloxy-1,1-dimethylbutyl) peroxide, OO- monoperoxysuccinate ( 3-Butylaminocarbonylcarbonyloxy-1,1-dimethylbutyl) O-ethyl, O- (3-t-butylperoxy-1, 1-dimethylbutyl) monoperoxyoxalate of OO-t-butyl, 0- (3-t-butylperoxy-1, 1 -dimethyl) monoperoxioxalate of OO-t-amyl, O- (3-t-butylperoxy-1,1-dimethylpropyl) monoperoxyoxalate of OO-t-butyl, 0- (3-t-butylperoxy-1,1-dimethylbutyl) OO-α-cumyl monoperoxyoxalate, 0- (3-t-butylperoxy-1,1-dimethylbutyl) monoperoxyoxalate of OO- (4-t-butylperoxy-1,1,4,4-tetramethylbutyl), 3- (2- ethylhexanoylperoxy) -1, 1-dimethylbutyl oxalate of 3-t-butylperoxy-1,1-dimethylbutyl, and 3- (2-methyl benzoylperoxy) -1, 1-dimethylbutyl oxalate of 3-t-butylperoxy-1, -dimethylbutyl and the structures: CH-, CH3 0 0 OO CH-, CH-, t-C4H9-00-C I-CH2CIH-0-C I-CI-0CH2CH2? -C11-Cfl-OC IHCH2-C I-OO -t-C4H9. t-C4HQ-00- -t-C4H9, CH-, CH, OO 0 0 CH3CH3 t-c4Hq-0O-C l -CH2CiH-0-Cl-Ci-? mCH2CH2O-C l-Cl-0-ClHCH2- C i-0O-t-D4H9, an II CH 3 H 3 CH 3 CH 3 00 CH 3 CH 3 O C, H 5 t-C 4 H 9-0s-C 1 -CH 2 ClH-O-Cl-Ci-O-C IHCH 2 -C 1 -OO-Cl-ClH (CH 2) 3 CH 3. CH3 CH3 Novel Compositions of Oxalic Acid Peroxide 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 oxalic acid peroxide compositions of Structure A of this invention has 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 180 ° C, preferably from 20 ° C to 160 ° C, most preferably from 30 ° C to 150 ° C, and levels of novel oxalic acid peroxide compositions from Structure A (on a basis pure) from 0.002 to 3%, preferably from 0.005% to 1%, most preferably from 0.01% to 0.75% by weight of the monomer, are normally employed in conventional polymerizations and copolymerizations of ethylenically unsaturated monomers. The novel oxalic acid 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 US patent. 4,525,308. 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 to suitable cure temperatures in the presence of free radical curing agents, the novel oxalic acid peroxide compositions of Structure A of this invention exhibit improved activity of cure in the curable unsaturated polyester resin compositions. The unsaturated polyester resins that can be cured by the novel oxalic acid peroxide 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-1-1, 3- propanediol, 2-hydroxymethyl-2-methyl-1,3-propanediol, 2-buten-1,4-diol, 2-butyl-1, 4-diol, 2,4,4-trimethyl-1,3-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, 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, tetrabromophthalic acid, 5,6-dicarboxy-1, 2, 3, 4, 7, 7- hexa chloro bicyclo (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 with 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 oxalic acid 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) propane], 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 oxalic acid peroxide compositions of the Structure A from about 0.05% to 5% or more, preferably from 0.10% to 4%, most preferably from 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. Elastomer Cure and Interlacing of Thermoplastic Polymers In the curing of elastomeric compositions, and the entanglement of polymer compositions, by heating to suitable curing and entanglement temperatures in the presence of curing and free radical entangling agents, the novel compositions of oxalic acid peroxide of this invention exhibit healing and entanglement activities. Elastomeric resin compositions that can be cured through the novel oxalic acid peroxide compositions of this invention include elastomers such as ethylene-propylene copolymers (EPR), ethylene-propylene-diene terpolymers (EPDM), polybutadiene (PBD) ), silicone rubber (SR), nitrile rubber (NR), neoprene, fluoroelastomers and ethylene-vinyl acetate (EVA) copolymer. Polymer compositions that can be entangled through the novel oxalic acid peroxide compositions of this invention include olefin thermoplastics such as chlorinated polyethylene (CPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE). , and high density polyethylene (HDPE). The temperatures of about 80 ° C to 310 ° C and the levels of the novel oxalic acid peroxide composition of from about 0.1% to 10%, preferably from 0.5% to 5%, based on weight of the elastomeric resin composition The curable or crosslinkable olefin polymer composition are usually employed. The curable elastomeric resin composition or the crosslinkable polymer composition may optionally be filled with the materials listed above for use with conventional unsaturated polyester resin compositions.

D. Modification of Homo- and Propylene Copolymers In the processes for modifying propylene homopolymers and propylene copolymers (eg, beneficial degradation of polypropylene (PP) by reducing the molecular weight of the polymer and the molecular weight distribution of the polymer), the novel oxalic acid peroxide compositions of this invention exhibit polypropylene modification activity.

Normally temperatures of about 140 ° C to 340 ° C and levels of the novel oxalic acid peroxide composition of about 0.01% to 1.0% based on the weight of the modifiable propylene Jhomopolymers and propylene copolymers are employed. Optionally, up to 1% by weight of molecular oxygen can be used as a modification co-catalyst.

Novel Compositions of Oxalic Acid Peroxide of Structure A - Preparative Examples and 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 breathing and scope of the invention.

EXAMPLE 1 Oxalate Preparation of 3-t-Butylperoxy-1,3-dimethylbutyl ethyl (1-1) A 125 ml Erlenmeyer flask equipped with a magnetic stir bar was charged with 10.0 g (48.4 mmoles) of 92% 3-t-butylperoxy-1,3-dimethylbutanol, 7.8 (77.2 mmole) of triethylamine, 0. 1 g (0.08 mmol) of 4-dimethylaminopyridine and 30 g of dry ethyl acetate. A clear solution resulted at room temperature. To this vigorously stirred solution at room temperature was slowly added a solution consisting of 7.0 g (50.2 mmol) of ethyl oxalyl chloride and 10 g of dry ethyl acetate over a period of 20 minutes. Immediately a precipitate formed and the flask was heated. It was necessary to cool the flask in order to maintain the temperature around room temperature. After a total reaction period of 60 minutes, the reaction mass was transferred to a separatory funnel, 100 ml of water was added to the reaction mass and stirred. The aqueous phase was separated and discarded. The organic phase was washed once with an aqueous solution of 10% HCl, twice with water and once with a dilute aqueous solution of NaHCO3. The resulting solution was dried over about 10% by weight of anhydrous MgSO 4, and, after it was separated from the spent desiccant through filtration, the solvent was removed under vacuum leaving 13.9 g (99% theory, not corrected) of a yellow liquid Clear. The product contained 5.79% active oxygen (theory, 5.51%), therefore, it was obtained from compound 1-1, with a 100% analysis and a corrected yield of 99%. Gas chromatographic analysis showed that the product contained less than 0.1% 3-t-butylperoxy-1,3-dimethylbutanol, the starting material. An infrared (IR) spectrum of the product showed carbonyl bands at 1770 cm'1 and 1745 cm "1 and a band of peroxide (-OO-) at 870 cm" 1.

EXAMPLE 2 Preparation of 3-t-Butylperoxy-1,3-dimethylbutyl Chloro-oxolate A 250 ml three neck flask equipped with a magnetic stirrer, thermometer and addition funnel was charged with 25.4 g (200 mmol) of oxalyl chloride and 75 ml of methyl t-butyl ether (MTBE). Then to the resulting solution was added 20.6 g (100 mmol) of 93% 3-t-butylperoxy-1,3-dimethylbutanol over a period of 30 minutes at 22-28 ° C. The addition funnel was then replaced with a nitrogen gas tube and dry nitrogen gas was slowly bubbled through the reaction mass in order to remove the HCl for a period of 4 hours at 25-30 ° C. MTBE, excess oxalyl chloride, and any remaining gas were removed under vacuum using a water aspirator. 28.3 g (101% theory, uncorrected) of a yellow liquid were obtained. An IR spectrum of the product did not show any OH band and showed carbonyl bands at 1800 cm * 1 and 1760 cm "1. The analysis of I-2, based on the content of hydrolysable chloride (theory, 12.63%; 12.37%), was 97.9% and the corrected yield was 98.6%.

EXAMPLE 3 Preparation of Oxalate Acid of 3-t-butylperoxy-1,3-dimethylbutyll-3) A 50 ml Erlenmeyer flask equipped with a magnetic stirrer and a thermometer was charged with 50 g of water and 2.8 g (10 mmol) of 3-t-butylperoxy-1,3-dimethylbutyl chloro-oxalate and the resulting mixture it was stirred at room temperature. No reaction appeared to occur, therefore, 2.1 g (23 mmoles) of NaHCO3 were added. The gas development was presented and the organic liquid was dissolved in the aqueous phase at room temperature. The pH of the solution was approximately 9. The aqueous solution was washed twice with 30 ml portions of MTBE in order to remove neutral impurities. Then, the aqueous solution was acidified with 20 g (27 mmol) of an aqueous solution of 5% HCl and a yellow organic liquid was formed. The resulting mixture was extracted twice with 30 ml portions of MTBE. The MTBE extracts were combined, washed once with 50 ml of water, dried over 5% by weight of anhydrous MgSO, and, after separation of the spent desiccant through filtration, the solvent was removed under vacuum leaving 2.2 g. (85% theory, uncorrected) of a clear liquid. An IR spectrum of the product showed an acid OH band at approximately 3200 cm "1, a very strong carbonyl band at 1740 cm" 1 and a peroxide band (-OO-) at approximately 875 cm "1.

Based on the preparation method, the yield data, and the IR data of the product obtained in this reaction was 1-3.

EXAMPLE 4 Preparation of Allyl 3-t-Butylperoxy-1,3-dimethylbutyl Oxalate (I-1) A 100 ml 3-necked flask equipped with a magnetic stir bar, a nitrogen inlet line, a thermometer and an addition funnel was charged with 12.6 g (97.3 mmol) of oxalyl chloride and the contents of the flask were cooled to 0 ° C. Then, 10.0 g (48.7 mmoles) of 92.6% of 3-t-butylperoxy-1,3-dimethylbutanol were added dropwise over 30 minutes, while the flask was swept with a stable stream of dry nitrogen. After the addition was complete, the reaction mass was stirred for 60 minutes at room temperature. A vacuum line was then attached to the flask in order to distill excess oxalyl chloride, however, this was only partially successful. The contents in the flask were diluted with ethyl acetate and the contents were then transferred to a single neck flask. The solvent and excess oxalyl chloride were then removed using a rotary evaporator. A light yellow oil was obtained, which it was cooled to 10 ° C and 3.0 g (51.7 mmoles) of allylic alcohol was added over a period of 10 minutes, while a vigorous stream of dry nitrogen was swept through the reaction mass. The reaction mixture was then diluted with ethyl acetate and the solution was partitioned on a rotary evaporator to remove the solvent, HCl and the allyl alcohol. 11.9 g (81% theory, uncorrected) of a light yellow liquid were obtained. Gas chromatography (GC) showed a single large peak having a% area of 98.6. An IR spectrum of the product showed carbonyl bands at 1770 cm "1 and 1750 cm" 1 and a band of peroxide (-OO-) at 875 cm'1. Based on the preparation method, the performance data, GC data and IR data of the product obtained is this reaction was I-4. A second preparation of I-4 was performed. A 3-neck 100 ml flask equipped with a magnetic stir bar, a nitrogen inlet line, a thermometer and an addition funnel with a side arm was charged with 25.9 g (200 moles) of oxalyl chloride, it bubbled nitrogen gas through the oxalyl chloride and the contents of the flask were cooled to 0 ° C. Then, 20.0 g (97.3 mmoles) of 92.6% of 3-t-butylperoxy-1,3-dimethylbuanol was added dropwise at such a rate that the temperature remained below 15 ° C. The addition took 30 minutes to complete. The reaction mixture was then stirred for 60 minutes at 15 ° C, after which 50 ml of dry ethyl acetate were added. The contents were then transferred to a single neck flask and the solvent and excess oxalyl chloride were then removed using a rotary evaporator. 29.3 g of a light yellow oil were obtained. The oil was cooled to 10 ° C and 6.0 g (103.3 mmoles) of allylic alcohol was added over a period of 15 minutes, while a vigorous stream of dry nitrogen was swept through the reaction mass. The temperature was maintained below 20 ° C during the addition of the allyl alcohol. The reaction mixture was then stirred for 60 minutes at 15-20 ° C, after which it was divided on a rotary evaporator. 31.7 g (> 100% theory, uncorrected) of a light yellow liquid were obtained. The GC showed a single large peak, 93% per area. An IR spectrum of the product showed carbonyl bands at 1770 cm'1 and 1750 cm "1 and a band of peroxide (-OO-) at 875 cm'1.To be able to prepare a sample of high purity of I-4, they were combined 11.9 g of the first preparation and 23 g of the second preparation and purified through preparative liquid chromatography using a Walters Prep 500 Liquid Chromatography. 30.3 g of I-4 having a purity of 97.6% according to GC analysis were obtained. .

EXAMPLE 6 Preparation of a mixture of diallyl oxalate, di- (3-t-butylperoxy-1,3-dimethylbutyl) oxalate and 3-tb uti pe rox i-1, 3-di methyloxybutyl oxalate 4) A 250 ml 3-necked flask equipped with a magnetic stir bar, a nitrogen inlet line, a thermometer and an addition funnel was charged with 4.3 g (30.2 mmol) of oxalyl chloride and 75 ml of MTBE and The contents of the flask were cooled to 0 ° C. Then the solution of 6.8 g (33.1 mmoles) of 92.6% of 3-t-butylperoxy-1,3-dimethylbutanol and 3.4 g (33.6 mmoles) of triethylamine in 10 ml of MTBE was added dropwise over 60 minutes at 0 -5 ° C and the solution was stirred for an additional 30 minutes after completing the addition. Then, a solution of 1.9 g (32.4 mmol) of allyl alcohol and 3.4 g (33.6 mmol) of triethylamine in 10 ml of MTBE was added to the contents of the flask for a period of 30 minutes. The reaction mixture was then stirred at room temperature for 120 minutes, after which the reaction was quenched with water. The aqueous phase was separated and discarded. The organic phase was washed once with an aqueous solution of 10% HCl, three times with water and once with a dilute 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 9.4 g (96% theory, not corrected) of a liquid light yellow. An IR spectrum of the product showed carbonyl bands at 1770 cm "1 and 1750 cm" 1 and a band of peroxide (-OO-) at 875 cm "1. The GC showed three peaks of product at retention times of 21.6 minutes ( 6% per area, assigned to diallyl oxalate), 33.4 minutes (65% per area, assigned from 3-t-butylperoxy-1,3-dimethylbutyl allyl oxalate) and 43.6 minutes [15% per area, assigned to oxalate of di- (3-t-butylperoxy-1,3-dimethylbutyl)] The GC also showed that the product mixture contained less than 0.1% allyl alcohol and only 0.2% 3-t-butylperoxy-1,3-dimethylbutanol Based on the preparation method, the performance data, GC data and IR data that the product obtained in this reaction was the mixture of the desired title product.

EXAMPLE 6 Oxalate Preparation of 3-t-butylperoxy-1,3-dimethylbutyl-3-neoheptanoylperoxy-1,3-dimethylbutyl (I-5) A 250 ml 3-necked flask equipped with a magnetic stir bar, a nitrogen inlet line, a thermometer and an addition funnel was charged with 75 ml of MTBE and 2.5 g (19.3 mmol) of oxalyl chloride and The contents of the flask were cooled to 0 ° C. Then, a solution of 3.9 g (19 mmol) of 92.6% of 3-t-butylperoxy-1,3-dimethylbuanol and 1.5 g of 819.0 mmol) of pyridine in 10 ml of MTBE was added dropwise over 30 minutes, while the temperature was maintained at 0-5 ° C. After the addition was complete, the reaction mass was stirred for 60 minutes at 0-5 ° C. To the stirred reaction mass was added a solution of 5.0 g (19.2 mmol) of 94.4% 3-hydroxy-1,1-dimemethyl butyl peroxyheptanoate and 1.5 g (19.0 mmol) of pyridine in 10 ml of MTBE over a period of time. 15 minutes. The reaction mixture was then stirred for an additional 45 minutes at 20-25 ° C, after which it was quenched with water. After separating and discarding the aqueous phase, the organic phase was washed once with a cold aqueous solution of 10% HCl, three times with water and once with a dilute aqueous solution of NaHCO3. 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 9.3 g (100% theory, not corrected) of an oil colorless nebulous The product contained 6.78% active oxygen (theory, 6.52%), therefore, I-5 was obtained with a 100% analysis and a corrected yield of 100%. A Differential Scanning Calorimetry (DSC) scan showed two decomposition temperatures of the peroxide, one at 71 ° C for the 3-neoheptanoylperoxy-1,3-dimethylbutyl portion and one at 169 ° C for the 3-t-butylperoxy portion. -1,3-dimethylbutyl.

EXAMPLE 7 Preparation of OO- (1,1,3,3-tetramethylbutyl) Q- (3-t-butylperoxy-1,3-dimethylbutyl) monoperoxyoxalate (I-6) To a 250 ml 3 neck flask equipped with a magnetic stir bar, a condenser, a thermometer, and an addition funnel and cooled with an ice bath, was charged with 3.1 g (20.0 mmoles) of 94% hydroperoxide of 1, 1, 3, 3-tetramethylbutyl, 0.4 g (30.0 mmol) of dry pyridine and 50 ml of MTBE. The contents of the flask were cooled to 3 ° C. After the resulting vigorously stirred solution, at 3-7 ° C, a solution of 5.6 g (20.0 mmoles) of 3-t-butylperoxy-1,3-dimethylbutyl chloro-oxalate was added over a period of 1 1 minutes. . A solid pyridinium chloride formed briefly after the addition began. After the addition was complete, the reaction mass was stirred for 90 minutes at 2 ° C, after which 10 ml of water was added and the reaction mass was stirred for an additional 15 minutes. The aqueous layer was then separated and the organic layer was washed once with 50 ml of water, three times with 40 ml of portions of an aqueous solution of 5% HCl and once with 50 ml of a saturated aqueous solution of NaHCO3. The product solution was dried over 10% by weight of anhydrous MgSO 4, after separation of the spent desiccant through filtration, the solvent was removed in vacuo leaving 6.3 g (81% theory, uncorrected) of a colorless liquid. An IR spectrum of the product showed a band of OH at approximately 3489 cm '1, a band of monoperoxioxalate carbonyl at 1800 cm "1, a band of oxalate carbonyl at 1750 cm" 1 and a band of peroxide (-OO-) at about 875 cm'1. The presence of the OH band at 3480 cm "1 in the IR spectrum of the product indicated the presence of an impurity containing hydroxy.Therefore, the product was taken up in 60 ml of MTBE and the resulting solution was washed with 50 ml of water containing 4.0 NaHSO3 and once with 50 ml of a saturated aqueous solution of NaH2PO4 After drying and isolating the product as above, 5.5 g (71% theory, uncorrected) of a colorless oil was obtained. IR of the purified product -1 showed no OH band in the region 3500 cm ", a monoperoxioxalate carbonyl band at 1800 cm'1, an oxalate carbonyl band at 1750 cm" 1 and a peroxide band (-OO-) at approximately 880 cm "1. The IR spectrum of the purified product was that expected for the desired title product. Liquid chromatographic (LC) analysis of the product showed a single large peak. The product contained 2.33% active oxygen according to a peroxy ester active oxygen method (theory, 4.10%). Based on the preparation method, performance data, LC data, and IR data, the product obtained is this reaction was I-6. The product was a sequential diperoxide having a portion of dialkyl peroxide with a half-life of 10 hours of about 120 ° C and a portion of monoperoxioxalate having a half-life of 10 hours of about 35-40 ° C.

EXAMPLE 8 Preparation of Di (3-chlorocarbonylcarbonyloxy-1,1 dimethylbutyl) il-7 peroxide) A 250 ml three neck flask equipped with a magnetic stirrer, thermometer and addition funnel was charged with 50.8 g (400 mmol) of oxalyl chloride and 75 ml of MTBE. Then, 24.7 g (100 mmol) of 85% di (3-hydroxy-1,1-dimethylbutyl) peroxide was slowly added to the resulting solution over a period of 30 minutes at 21 -30 ° C. The addition funnel was then replaced with a tube of nitrogen gas and dry nitrogen gas was bubbled slowly through the reaction mass to remove the HCl for a period of 4 hours at 25-30 ° C. MTBE, excess oxalyl chloride and any remaining gas were removed under vacuum using a water aspirator. 38.2 g (97% theory, uncorrected) of an amber liquid were obtained. An IR spectrum of the product showed no OH band and showed a pair of carbonyl bands at 1790 cm "1 and 1755 cm" 1. Based on the content of hydrolysable chloride, the product analysis was 85.0% and the yield corrected it was 82.7%. Based on the preparation method, the analysis data, performance data and I R data, the product obtained in this reaction was I-7.

EXAMPLE 9 Preparation of 3-t-butylperoxy-1,3-dimethylbutyl oxamate of N-t-b used (I-8) A 250 ml 3 neck flask equipped with a magnetic stir bar, a nitrogen inlet line, a thermometer and an addition funnel was charged with 40 ml of MTB E, 2.5 g (34 mmole) of t-butylamine. and 4.0 g (50 mmol) of pyridine. The contents of the flask were cooled to 10 ° C. Then 5.7 g (20 mmoles) of 98.1% chloro-oxalate of 3-t-butylperoxy-l, 3-dimethylbutyl (1-2) in 10 ml of MTBE were added dropwise over 15 minutes at 10-20 ° C to the stirred solution. After the addition was complete, the reaction mass was stirred for 60 minutes at 15-20 ° C. Then, 50 ml of water and 20 ml of MTBE were added to the reaction mass, and the mixture was allowed to separate to liquid phases. The aqueous layer was separated and discarded. The organic layer was washed twice with 50 g portions of an aqueous solution of 5% hydrochloric acid and then with 50 ml portions of water until the pH was about 7. The product solution was dried over 5% on weight of anhydrous MgSO 4, and, after separation of the spent desiccant through filtration, the solvent was removed under vacuum leaving 3.1 g (49% theory, not corrected) of a liquid product. An IR spectrum of the product showed a weak medium pair of bands in the region 3400-3500 cm "1 due to the NH group, a strong carbonyl band at 1705 cm" 1 and weaker bands of carbonyl shoulder at approximately 1730 cm * 1 and approximately 1769 cm '1. Based on the preparation method and I R data, the product obtained in this reaction was I-8.

EXAMPLE 10 Effi ciency of the Oxalate Oxalate of 3-t-bu ilperoxy-1, 3-di-methyl-ethyl-ethyl-1-yl) in High Density Polyethylene (HDPE) Compound 1- 1 was evaluated for entanglement efficiency in HDPE compared to 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexane (LUPERSOL 130, manufactured by ELF ATOCHEM North America, Inc.). 1-1 and LUPERSOL 130 were individually mixed in HDPE samples (USI's LY 66000 HDPE) at 140 ° C using a Brabender for thorough mixing. The level of entanglement agent employed was 10 meq (milliequivalents of peroxide) per 100 grams of HDPE resin. This was added to 2,904 g of 1-1 per 100 grams of HDPE resin and 1.43 g of LUPERSOL 130 per 100 grams of HDPE resin. Discs of the mixed HDPE resins were pressed and these resin disks were used to determine entanglement data using a Monsanto Oscillation Disc Rheometer (ODR) at 196.1 ° C, + 3 ° arc. The interlace data are summarized in the following table: PE PEEVERING HDPE AT 196.1 ° C FORMULATION: AB LUPERSOL 130 1.43 (10 meq / 100 g HDPE) 1-1 - 2,904 (10 meq / 100 g HDPE) mh (in kg) 15.7 18.2 TC9o (min.) 8.4 5.6 Ts2 (min.) 1.8 1.4 Based on the cure times (Tc 0) and an improvement in the torque (Mh-ML), the results show that the oxalate of 3-t-butylperoxy-1,3-dimethylbutyl ethyl (1-1) was a faster and more efficient entanglement agent for HDPE than was LUPERSOL 130, the entanglement agent currently employed to interlace HDPE commercially. Consequently, the results showed that 1-1 was a very good entanglement peroxide candidate for HDPE.

EXAMPLE 11 Oxalate Interlacing Efficiency of 3-t-butylperoxy-1,3-dimethylbutyl ethyl (1-1) in Low Density Polyethylene (LDPE) Compound 1-1 was evaluated for entanglement efficiency in LDPE compared to 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (LUPERSOL 101, manufactured by ELF ATOCHEM North America, Inc.). 1-1 and LUPERSOL 101 were individually mixed in LDPE samples (Union Carbide DYNH-1) at 120 ° C using a Brabender for thorough mixing. The level of entanglement agent employed was 10 meq (milliequivalents of peroxide) per 100 grams of LDPE resin. This was added to 2,904 g of 1-1 per 100 grams of LDPE resin and 1.45 g of LUPERSOL 101 per 100 grams of LDPE resin. Discs of the mixed LDPE resins were pressed and these resin disks were used to determine entanglement data using a Monsanto Oscillation Disk Rheometer (ODR) at 196.1 ° C, + 3 ° arc. The interlace data are summarized in the following table: HDPE INTERLOCKING AT 196.1 ° C FORMULATION: A B LUPERSOL 101 1.45 (10 meq / 100 g LDPE) 1-1 - 2,904 (10 meq / 100 g LDPE) mH (in kg) 10.8 12.8 TC9o (min.) 8.9 10.4 TS2 (min.) 2.15 2.30 Based on the torque improvement (MH-ML), the results show that 1-1 was a much more efficient entanglement agent for LDPE than was LUPERSOL 101, an entanglement agent currently employed to commercially interweave LDPE. In addition, the use of an interlacing agent for LDPE advantageously resulted in a longer scorch time (TS2) than when LUPERSOL 101 was employed. Consequently, the results showed that 1-1 was a very good interlacing peroxide candidate for LDPE EXAMPLE 12 Polypropylene (PP) Modification Efficiency of 3-t-butylperoxy-1,3-dimethylbutyl ethyl oxalate (1-1) Compound 1-1 was evaluated for polypropylene (PP) modification efficiency compared to that of 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (LUPERSOL 101, manufactured by ELF ATOCH EM North America, Inc. .). 1-1 and LUPERSOL 101 were individually mixed under a blanket of nitrogen gas (to eliminate the effect of oxygen in PP modification) to PP (Himont 6501), containing: 0.1% calcium stearate 0.3% dilauryl thiodipropionate 0.1 % of Irganox 1010 (manufactured by Ciba Geigy Corp.) at 180 ° C using a Brabener plastigraphy. Mixing under the blanket of nitrogen gas was continued for a total of 10 minutes. In these experiments, the level of the modifying agent used was 0.20 meq (milliequivalents peroxide) per 100 grams of PP resin. This was added to 0.058 g of 1-1 per 100 grams of PP resin and 0.29 grams of PERSOL 101 LU per 100 grams of PP resin. The melt flow index (MFI) is a measure of the amount of degradation (modification or reduction of molecular weight) of PP. The higher the MFI of the modified PP resin under specific conditions, the lower the molecular weight of the PP resin. The MFI data for virgin PP resin and modified PP resins were determined in accordance with ASTM D-1238 (230 ° C, 2.16 kg weight). The MFI data is summarized below: MFI Peroxide Weight Agent Modification PP peroxide,% meq per 100 g of PP grams / 10 min.

None - --- 5.5 LUPERSOL 101 0.029 0.20 11.5 1-1 0.058 0.20 15.5 The results showed that oxalate of 3-t-butylperoxy-1,3-dimethylbutyl ethyl (1-1) was much more efficient to modify PP than was LUPERSOL 101. Lupersol 101 is currently the most widely used commercial modifying agent used for PP. Consequently, the results showed that 1-1 was a very good modifying agent for PP.

EXAMPLE 13 Entanglement Efficiency of Allyl 3-t-butylperoxy-1,3-dimethylbutyl oxalate (I-4) in High Density Polyethylene (HDPE) Compound I-4 was evaluated for entanglement efficiency in HDPE compared to 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexane (LUPERSOL 130, manufactured by ELF ATOCHEM North America, Inc.). I-4 and LUPERSOL 130 were individually mixed in HDPE samples (USI's LY 66000 HDPE) at 140 ° C using a Brabender for thorough mixing. The level of entanglement agent employed was 10 meq (milliequivalents of peroxide) per 100 grams of HDPE resin. This was added to 3,024 g of I-4 per 100 grams of HDPE resin and 1,432 g of LUPERSOL 130 per 100 grams of HDPE resin. Discs of the mixed HDPE resins were pressed and these resin disks were used to determine entanglement data using a Monsanto Oscillation Disc Rheometer (ODR) at 196.1 ° C, + 3 ° arc. The interlace data are summarized in the following table: HDPE INTERLOCKING AT 196.1 ° C FORMULATION: AB LUPERSOL 130 1.432 (10 meq / 100 g of HDPE) 1-1 - 3.024 (10 meq / 100 g of HDPE) mh (in kg) 16.7 20.6 MH-ML (in kg) 16.02 19.9 Ts2 (min.) 1.9 1.5 Based on cure times (Tc90) and an improvement in torque (Mh-ML), the results show I-4 was a faster and more efficient entanglement agent for HDPE than was LUPERSOL 130, the entanglement agent currently employed to commercially interweave HDPE. Consequently, the results showed that I-4 was a very good interlacing peroxide candidate for HDPE. The subject matter considered by the applicants as their invention is particularly pointed and indistinctly claimed as follows.

Claims (5)

1. - A peroxide composition of Structure A: wherein n is 1 or 2, and R is selected from the group consisting of a 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, a t-aralkyl radical of 9 to 13 carbons and structures (a), (b), (c), (d) and (e), \ C-C O O O 8 R10 O / \ I C C-C Rb-O-C- [-R'-C-] v- Ry-0-C- RU-C- \ / / C-C Rd R 12 (H) 3 \? (b) (O (d) (a) (e) wherein R4 and R5 are the same or different and are selected from the group consisting of hydrogen, lower alkyl radicals of 1 to 4 carbons, alkoxy radicals of 1 to 4 carbons, phenyl radicals, acyloxy radicals of 2 to 8 carbons, radicals t-alquilperoxicarbonilo 5 to 9 carbons, hydroxy, fluoro, chloro or bromo, and, x is 0 or 1, R6 is a substituted radical or unsubstituted 1 to 18 carbons, substituents being one or more alkyl radicals of 1 to 6 carbons, t-alkylperoxy radicals of 4 to 8 carbons, alkoxy radicals of 1 to 6 carbons, aryloxy radicals of 6 to 10 carbons, hydroxy, chlorine, bromine or cyano, and a substituted or unsubstituted cycloalkyl radical of 5 to 12 carbons optionally having an oxygen atom or a nitrogen atom in the cycloalkane ring, with substituents being one or more alkyl radicals of 1 to 4 carbons, and R7 is selected from a substituted alkylene diradical or unsubstituted 2 at 3 carbons, the substituents are One or more alkyl radicals of 1 to 4 carbons, and substituted, unsubstituted 1, 2, 1, 3, and 1, 4-phenylene radicals, the substituents being one or more lower alkyl radicals of 1 to 4 carbons , chlorine, bromine, nitro or carboxy, and, R8 is a lower alkyl radical of 1 to 4 carbons, and, additionally, the two radicals R8 can be chained to form an alkylene di-radical of 4 to 5 carbons, and, R9 is an alkyl radical of 1 to 4 carbons, and, R 10, R 1 1 and R 12 may be the same or different and are selected from the group consisting of hydrogen, 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, and, R 1 and R 2 are alkyl radicals of 1 to 4 carbons, and, when R is selected from a t-alkyl radical of 4 to 12 carbons, R it may additionally be a t-alkylperoxy radical of 4 to 12 carbons, R3 is selected from the group consisting of a substituted alkylene di-radical or unsubstituted of 2 to 4 carbons and a substituted or unsubstituted alkynylene di-radical of 2 to 4 carbons, the substituents being one or more lower alkyl radicals of 1 to 4 carbons, and, when n is 1, Z is selected from group consisting of OR13, NR13R14, OO-R, Cl and Br, wherein R13 and R14 are identical or different and are selected from the group consisting of hydrogen, substituted alkyl radicals or unsubstituted 1 to 18 carbons, 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, acryloxy radicals, methacryloxy, chloro, bromo and cyano radicals, substituted or unsubstituted alkenyl radicals of 3 to 12 carbons the substituents being one or more lower alkyl radicals of 1 to 4 carbons, substituted aryl or unsubstituted 6 to 19 carbons, substituents being one or more radicals of 1 to 6 carbons, alkoxy radicals of 1 to 6 carbons, radicals arilox i of 6 to 10 carbons, chlorine, bromine and cyano, substituted or unsubstituted aralkyl radicals of 7 to 11 carbons, the substituents being one or more alkyl radicals of 1 to 6 carbon, alkoxy radicals of 1 to 6 carbons, aryloxy radicals of 6 to 10 carbons, chlorine, bromine and cyano, and substituted or unsubstituted cycloalkyl radicals of 5 to 12 carbons, optionally having an oxygen atom or a nitrogen atom in the cycloalkane ring, with the substituents being one or more alkyl radicals lower of 1 to 4 carbons, and Z is also selected from the structure (g), ol -0-R3 -C-00-R15 (g) I R is selected from the definitions of R, provided that R and R 1 5 are not equal, and when n is 2, Z is selected from the group consisting of structures (h), (i), (j), -0-R16 -0- (h), -NR13 -R16-R14- (i), -NR13-R16-0- (j), R, 16 is selected from the group consisting of substituted or unsubstituted alkylene diols of 2 to 10 carbons, the substituents being one or more lower alkyl radicals of 1 to 4 carbons, and arylene di-radicals of 6 to 14 carbons, the substituents being one or more lower alkyl radicals of 1 to 4 carbons.

2. A peroxide according to claim 1, wherein it is selected from the group consisting of: 3-t-butylperoxy-1,3-dimethylbutyl ethyl oxalate, 3-t-butylperoxy-1, 3- chloro-oxalate ethyl dimethylbutyl, di- (3-chlorocarbonylcarbonyloxy-1,1-dimethylbutyl) oxalate, 3-t-butylperoxy-1,3-dimethylbutyl acid oxalate, allyl 3-t-butylperoxy-1,3-dimethylbutyl oxalate peroxide, 3- N-butyl t-butylperoxy-1,3-dimethylbutyl oxamate, 3-t-butylperoxy-1,3-dimethylbutyl 3- (neoheptanoylperoxy) -1,3-dimethylbutyl oxalate, and O- (3-t-butylperoxy) - 1, 3-dimethylbutyl) OO- (1, 1, 3,3-tetramethylbutyl) monoperoxyoxalate 3.- A peroxide composition according to claim 1, wherein R is a t-alkyl radical of 4 to 12. carbons 4 - A peroxide composition according to claim 1, wherein Z is Cl. 5.- A peroxide composition according to claim 1, wherein Z is OR 1

3. 6.- A peroxide composition according to with the Claim 1, wherein Z is NR 13R1

4. 7. A peroxide composition according to claim 1, wherein Z is OO-R. 8. A peroxide composition according to claim 1, wherein Z is O-R3-C (R1) (R2) -OO-R1

5. 9. A process for the use of a peroxide composition according to claim 1, as a free radical initiator, in effective starter amounts, for the initiation of free radical reactions selected from the group consisting of: a. cure unsaturated polyester resin compositions, b. polymerizing compositions of ethylenically unsaturated monomers (such as styrene, ethylene), c. interlacing olefin thermoplastic polymer compositions, d. curing elastomer compositions, e. modify polyolefin compositions, f. grafting ethylenically unsaturated substrates onto homo-, and olefin copolymer substrates, and g. compatibilize mixtures of two or more substrates of normally incompatible polymer; which comprises heating said substrates in the presence of an effective initiating amount of one more peroxides as defined in claim 1, for a time sufficient to at least partially decompose said peroxide, to perform the free radical reaction.