MXPA97010519A - Peroxioxalatos novedosos derivados de hidroxi-hidroperoxi - Google Patents

Abstract

Novel compositions of Structure A are described, and use of the novel monoperoxyoxalates of Structure A as initiators for ethylenically polymerizing uurated monomers and for curing uurated polyester resins

Description

NOXIOUS PEROXIOXALATES, DERIVED FROM HYDROXY-HYDROPEROXIDES BACKGROUND OF THE INVENTION a) FIELD OF THE INVENTION This invention relates to compositions classified in the chemistry art as new and novel peroxioxalates of Structure A which can be prepared by the hydroxy¬ reaction.

O O R1 R3 II II I Q-C-C-OO-C-CH2CH-O-Z A [The Definitions of Q, R1, R2, R3 and Z are given in the SUMMARY OF THE INVENTION] hydroxy peroxides, such as 3-hydroxy-1,1-dimethylbutyl hydroperoxide and 3-hydroxy-1,1-dimethylpropyl hydroperoxide, with oxalyl halides and alkyl halooxalates, such as ethyl chlorooxalate, in the presence or absence of organic or inorganic bases, as well as processes for the preparation and use of the novel peroxioxalates of Structure A. The peroxioxalates of Structure A possess inherent applied characteristics of use making them useful as reaction intermediates and as initiators for ethylenically polymerizing unsaturated monomers and for curing unsaturated polyester resins.

There is a need in the polymer industries for free radical initiators efficient to ethylenically polymerize unsaturated monomers at low temperatures in order to obtain higher molecular weight polymers having improved stress and other mechanical properties and / or to increase polymerization rates with the order to produce current polymers at higher production speeds. In the case of the last argument, the most efficient free-radical initiators allow polymer producers to increase productivity without the need to build new and expensive production facilities. There is also a need in the polyester industry for free radical initiators to cure unsaturated polyester resins faster and / or at lower temperatures. The inherent applied characteristics of the new and novel peroxioxalate compositions of Structure A of this invention are capable of satisfying these needs of the polymer industry. b) Description of the Prior Art P.D. Bartlett, et al. (J. Am. Chem. Soc., 82, 1762-8, 1960) describe the decomposition kinetics of di-t-butyl diperoxyoxalate in solution and found that its half-life at 60 ° C in benzene is 6.8 minutes. In a subsequent document P. D. Bartlett and R.E. Pincock (J. Am. Chem. Soc., 82, 1769-73, 1960) described the decomposition kinetics of di-t-butyl diperoxyoxalate and several OO-t-butyl O-alkyl monoperoxioxalates including OO-t-butyl O -ethyl monoperoxyoxalate and OO-t-butyl O-benzyl monoperoxyoxalate. Based on the data provided in this reference the half-life temperatures of 10 h (ie the temperature at which the 50% of the peroxide is decomposed in 10 hours) were calculated to be 26 ° C, 39 ° C and 41 ° C, respectively, for the above peroxioxalates. Thus, di-t-alkyl diperoxyoxalates have half-life temperatures of 10 h of about 25 ° C while OO-t-alkyl O-alkyl monoperoxioxalates have half-life temperatures of 10 h of about 40 ° C. An OO-t-alkyl O-alkyl monoperoxyoxyalates of the present invention, ie, O-ethyl OO- (3-ethoxycarbonylcarbonyloxy-1,1-dimethylbutyl) monoperoxyoxalate (1-1), O O CH3 CH3 O O II II I I II II C2HsOC-C-OO-C-CH2CH-OC-COC2H5 (1-1) I CH3 it was found to have a half-life of 10 h at 25 ° C in trichlorethylene. Hence, the novel OO-t-alkyl O-alkyl monoperoxioxalates of the present invention are significantly more active than the OO-t-alkyl O-alkyl monoperoxioxalates of the art. R.A. Sheldon and J. K. Kochi (J. Org. Chem., 35 1233-6, 1970) reported the decomposition rates of various di-t-alkyl diperoxioxalates in the structure, O O R (CH3) 2C-OO-C-C-OO-C (CH3) 2R (where R is methyl, ethyl, isopropyl and benzyl) The data was consistent with those of Bartlett. W. Adams and J. Sanabia (J. Am. Chem. Soc., 99, 2735-9, 1977) describe the synthesis of a cyclic diperoxyoxalate, 7, 7, 10, 10-tetramethyl-1, 2,5,6-tetraoxa-3,4-dioxocyclodecane, from oxalyl chloride and the like. , 5-dimethyl-2,5-dihydroperoxyhexane in the presence of pyridine. Based on the data provided in this reference, the 10-hr half-life temperature of the cyclic diperoxyoxalate was calculated to be about 80 ° C. P.G. Griffiths, et. Al. [J. Macromol Sci., Chem., A17 (1), 45-50, 1982] describe polymerizations of alkyl methacrylates with di-t-butyl diperoxyoxalate (CAS RN 1876-22-2). European Patent Application No. EP 0049966 A1 (04/21/82, for ICI Australia, Ltd.) describes a process for polymerizing vinyl chloride monomer (VCI) using di-t-butyl diperoxyoxalate as an initiator. . M. Schulz, et al. , [J. Prakt. Chem., 324 (4), 589-95, 1982] describe the synthesis and thermolysis of azobis (isobutyl t-butyl peroxyoxalate), O O CH3 CH3 O O II II I I li li f-C4H9-OO-C-COCH2-C-N = N-C-CH2OC-C-OO-f-C4H9 I I CH3 CH3 an azo-peroxide decomposed sequentially. European Patent Application No. EP 0095860 A2 (07/12/83, for ICI Australia, Ltd.) describes a process for polymerizing a VCI monomer using as a initiator a monoperoxyoxalic acid diester of the structure, O O R1-OO-C 11-C "-OR2 a where R1 is a secondary or tertiary alkyl group, or a substituted benzyl or benzyl group and R2 is a secondary or tertiary alkyl group, or a benzyl or a substutured benzyl group. Also described in this patent application are the t-alkylperoxy chlorooxalates of the structure, O O II II R1-OO-C-C-CI which are used for preparations of the diesters of monoperoxioxalic acid. U.S. Patent 4,859,794 (08/22/89, for Berol Nobel Nacka AB) describes dialkyl esters of monoperoxioxal acid structure, O O (where R = t-alkyl of C4.o0 and R1 = primary alkyl of C? 8.2β) for example, OO-t-butyl O-docosyl monoperoxyoxalate, useful for initiating the polymerization of VCI and other monomers. Japanese Patent Applications JP 63/248806 (10/17/88, for NOFCO) and JP 63/254110 (10/20/88, for NOFCO) describe OO-t-alkyl O-alkyl monoperoxioxalates of the structure, CH; [wherein R1 = H, alkyl and R2 = C? .7 alkyl (substituted) C6H5, etc.] as initiators to produce VCI polymers having low odor and color. European Patent Specification No. 0500624 B1 (07/12/94, for Akzo Nobel N.V.) described allyl peroxide chain transfer agents of the structure, where 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 intensifying the reactivity of the olefinic unsaturation towards the addition of free radical, m is 0 or 1 and Z is selected from the structures, O O O O II II II II -C-, -C-O-, -C-C-O- If Z is one the last structure then the compounds of European Patent Specification No. 0500624 B1 can be monoperoxioxalates. However, the compositions of 0500624 B1 do not disclose the compositions of the present invention since the peroxides of Structure A are not allyl peroxides nor does the present invention cover the compositions of 0500624 B1. It should be noted that monoperoxioxalates are included in the list of peroxides on pages 5, 7 and 8 or in the preparation examples of 0500624 B1. Overall, the prior art does not disclose OO-t-alkyl O-alkyl peroxyoxalates which possess hydroxy, chlorocarbonyl-carbonyloxy, carboxycarbonyloxy or alkoxycarbonylcarbonyloxy groups in the OO-t-alkyl group such as in Structure A. US Pat. No. 3,236,872 ( 02/22/66, for Laporte Chemical, Ltd.) describes hydroxy-peroxides of the structure: CH3 | CH3-C-CH2CHCH3 I I R-OO O-R ' (wherein R is an H, an acyl group, an aroyl or an alkyl, especially the t-butyl group, t-amyl or the hexylene glycol residue, R 'is an H or an acyl, aroyl or alkyl group). U.S. Patent 4,525,308 (06/25/85, for Pennwalt Corp.) and U.S. Patent 4,634,753 (06/01/87, for Pennwalt Corp.) describe the hydroxy peroxy esters (the above structure where R 'is H and R is an acyl group) having half-life temperatures of 10 h per below about 75 ° C.

U.S. Patent 3,853,957 (10/12/74, for Pennwait Corp.) discloses diperoxyketals and ketone peroxides containing hydroxy and acyloxy groups. US Patent 3,671,651 (06/20/72, for Pennwait Corp.) discloses a hydroxy peroxy ester, t-butyl peroxy-3-hydroxypropionate, however, the product was difficult to prepare and, furthermore, the substrate used in The synthesis, that is, β-propiolactone, is a suspected agent of highly toxic cancer. The US patent 3, 706,818 (12/19/72, for Pennwait Corp.) and US Patent 3,839,390 (01/10/74, for 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 novel peroxioxalates of Structure A. c) Definitions The half-life temperature of 10 h of a free radical initiator (eg, an organic peroxide) is defined as the temperature at which half ( 50%) of the initiator decomposes in 10 hours. In the present invention, the esters of monoperoxioxalic acid, alkyl, t-alkyl Z, Q O li li Alkyl-O-C-C-OO-f-Alkyl Z they are called OO-t-alkyl O-alkyl monoperoxioxalates. t-cycloalkyl refers to the monoradical structure, where t is 0 to 2 and Rx is an alkyl radical of less than 1 to 4 carbons, t-alkynyl is the monoradical structure, Rx I Ry-C? C-C- where Ry is hydrogen or an alkyl radical of less than 1 to 4 carbons, and t-aralkyl is the monoradical structure, Rx I R2-C- I Rx where Rz is an aryl radical of 6 to 10 carbons. When any generalized functional group or indicator, 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.

SUMMARY OF THE INVENTION The invention provides in a compositional aspect a peroxyoxalate of Structure A: O O R1 R3 I Q-C-C-OO-C-CH2CH-O-Z R2 wherein R1, R2 and R3 are alkyl radicals of 1 to 4 carbons, and additionally, R3 can be hydrogen and, Q is selected from the group consisting of chlorine, bromine, R-O, and R -OO, wherein R is selected from the group consisting of H, a substituted or unsubstituted alkyl radical of 1 to 24 carbons, the substituents being one or more alkyl radicals of 1 to 6 carbons, alkoxy radicals of 1 to 6 carbons, arylloxy 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 of less than 1 to 4 carbons, a substituted aryl radical or unsubstituted 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 aralkyl radical or unsubstituted from 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 optionally having one or more nitrogen or oxygen atoms in the ring c icloalkane, the substituents being one or more alkyl radicals of less than 1 to 4 carbons, a substituted or unsubstituted bicycloalkyl radical of 6 to 14 carbons, the substituents being one or more alkyl radicals less than 1 to 4 carbons, and, R- being able to be additionally the structure (a), R5 R8-OO-C-R7- R6 (to) where R5 and R6 are alkyl radicals of 1 to 4 carbons, R7 is an unsubstituted alkylene diradical of 1 to 3 carbons or a substituted alkylene diradical of 1 to 3 carbons, the substituents being one or more alkyl radicals of less than 1 to 4 carbons , R8 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 to 13 carbons, t-alkynyl radicals of 5 to 9 carbons, radicals t -aralkyl of 9 to 13 carbons, unsubstituted aroyl radicals of 7 to 11 carbons, substituted aroyl radicals of 7 to 11 carbons, wherein the substituent for the t-alkyl radicals is a t-alkylperoxy radical of 4 to 8 carbons and the Substituents for the aroyl radicals are one or more alkyl radicals less than 1 to 4 carbons, alkoxy radicals of 1 to 4 carbons, phenyl radicals, acyloxy radicals of 2 to 8 carbons, t-alkylperoxycarbonyl radicals of 5 to 9 carbons, radicals t- alkylperoxycarbonyl or from 5 to 9 carbons, fluoro, chlorine or bromine, and R8 can also be structures (b), (c) and (d) O O R 1 1 R 13 O II R 9 -O-C -O-C-, R 14 -C-fr, R 12 -C-. fifteen (B C D) where x is 0 or 1, R9 is a substituted or unsubstituted alkyl 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 6-10 carbons, hydroxy, chlorine, bromine or cyano or a substituted or unsubstituted cycloalkyl radical of 5 to 12 carbons optionally having one or more nitrogen or oxygen atoms in the cycloalkane ring, the substituents being one or more alkyl radicals less than 1 to 4 carbons, and, R10 is selected from a substituted or unsubstituted alkylene diradical of 2 to 3 carbons, the substituents being one or more alkyl radicals of less than 1 to 4 carbons, or a diradical 1, 2, 1, 3 or 1, 4-substituted or unsubstituted phenylene, the substituents being one or more alkyl radicals less than 1 to 4 carbons, chlorine, bromine, nitro or carboxy, and R 11 is an alkyl radical of less than 1 to 4 carbons, and additionally, the two radicals R11 can be concatenated to form an alkylene diradical of 4 to 5 carbons, R12 is an alkyl radical of less than 1 to 4 carbons, R13, R14 and R1 S are selected from hydrogens, alkyl radicals of 1 to 8 carbons, aryl radicals of 6 at 10 carbons, alkoxy radicals of 1 to 8 carbons and aryloxy radicals of 6 to 10 carbons, and, R 4 is selected from an unsubstituted t-alkyl radical of 4 to 12 carbons, 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, and a t-aralkyl radical of 9 to 13 carbons, wherein the substituent for the t-alkyl radical is a t-aliperoxy radical of 4 to 8 carbons, preferably R is selected from the group consisting of H, a substituted alkyl radical or unsubstituted from 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, fluoro, chloro, bromo carboxy and cyano, a radical substituted or unsubstituted aralkyl 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, one or more alkyl radicals being less than 1 to 4 carbons , and structure (a), more preferably, R is selection of the group consisting of H, a substituted or unsubstituted alkyl radical 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 , fluoro, chloro, bromo, carboxy and cyano, a substituted or unsubstituted cycloalkyl radical of 5 to 12 carbons, the substituents being one or more alkyl radicals less than 1 to 4 carbons, and structure (a), and, Z is selected of the group consisting of hydrogen and the structures (e), (f) and (g), O O O II II II -C-C-Q, -C-O-. 16 -C-R16 (e) (f) (g) wherein R16 is selected from the group consisting of a substituted or unsubstituted alkyl radical of 1 to 24 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 19 carbons, chlorine, bromine, carboxy and cyano, a substituted or unsubstituted alkenyl radical of 3 to 12 carbons, the substituents being one or more alkyl radicals of less than 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 carbons optionally having one or more nitrogen or oxygen atoms in the cycloalkane ring, the substituents one or more alkyl radicals less than 1 to 4 carbons, and a bicycloalkyl substituted or unsubstituted radical of 6 to 10 carbons, the substituents being one or more alkyl radicals less than 1 to 4 carbons, preferably Z is hydrogen or the structure (e), more preferably, Z is the structure (e).

The invention provides in a process aspect, a process for the induced addition of the free radical of unsaturated substrates selected from the group consisting of: Processes using a peroxide composition of Structure A as a curing agent for curing free radical unsaturated polyester resin compositions by heating such resins in the presence of initiator amounts of the peroxide composition of Structure A at the appropriate temperatures, and, Processes using a peroxide composition of Structure A as a free radical initiator for ethylenically polymerizing unsaturated monomers (such as styrene, ethylene, etc.) by using initiator amounts of the peroxide composition of Structure A at the appropriate temperatures.

DETAILED DESCRIPTION OF THE PREFERRED MODALITIES Compositions of peroxioxalate from Structure A - Preparation methods The novel peroxioxalate compositions of Structure A can be prepared by reacting hydroxy-hydroperoxides from Structure B, R1 R3 I I B HOO-C-CH2CH-OH With oxalyl halides, alkyl halooxalates or t-alkylperoxy halooxalates of Structure C, O O II II X-C-C-Q [where X = Br or Cl; C Q = Br, Cl, R-O or R4-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 X and Q are Br and Cl. The compositions of Structure C are alkyl halooxalates when X is Br or Cl and Q is R-O. The compositions of Structure C are t-alkylperoxy halooxalates when X is Br or Cl and Q is R4-OO. Non-limiting examples of suitable optional solvents include pentane, hexanes, heptanes, dodecanes, mixtures of odorless mineral essences, toluene, xylenes, cumene, methylene chloride, ethyl acetate, 2-ethylhexyl acetate, isobutyl isobutyrate, dimetal 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 suitable optional bases include triethylamine, tributylamine, N, N-diisopropylethylamine, 2,2,6,6-tetramethylpiperidine, N, N-dimethylaninoline, N, N-dimethylaminopyridine, 2,4,6-collidine, urea , tetramethylurea, sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, potassium bicarbonate, calcium hydroxide, magnesium hydroxide, barium hydroxide, calcium carbonate and trisodium phosphate. Non-limiting examples of hydroxy hydroperoxides of Structure B which can be reacted with alkyl halooxalates of Structure C include 3-hydroxy-1,1-dimethylpropyl hydroperoxide and 3-hydroxy-1,1-dimethylbutyl hydroperoxide. Non-limiting examples of suitable oxalyl halides include oxalyl bromide and oxalyl chloride. Non-limiting examples of suitable alkyl halooxalates of Structure C (X = Br or Cl; Q = RO) which can be reacted with hydroxy-hydroperoxides of Structure B include ethyl bromooxalate, methyl chloroaxalate, ethyl chloroaxalate, n-butyl chloroaxalate, t- butyl chlorooxalate, 2-ethylhexyl chlorooxalate, dodecyl chlorooxalate, docosyl chlorooxalate, hexafluoroamyl chlorooxalate, allyl chlorooxalate, phenyl chlorooxalate, 2-phenoxyethyl chloroaxlate, cyclohexyl chloroaxalate, 4-t-butylcyclohexyl chloroaxalate, isobornyl chloroxalate, bornyloxalalate, benzyl chloroaxalate, 3-t -butylperoxy-1,3-dimethylbutyl chloroaxalate and 3- (2-ethylhexanoylperoxy) -1,3-dimethylbutyl chloroaxalate. The above alkyl halooxalates can be prepared by reacting oxalyl chloride or oxalyl bromide with 0% to 100% excess with the corresponding alkanol until the reaction is complete. Oxalyl halide in excess is removed by separation or distillation. Non-limiting examples of suitable alkanols that react with oxalyl halides to form alkyl halooxalates of Structure C include methanol, ethanol, n-butanol, t-butanol, 2-ethylhexanol, dodecanol, docosanol, hexafluroamyl alcohol, allyl alcohol, cyclohexanol, 4- t-butylcyclohexanol, menthol, isoborneol, borneol, phenol, 2-phenoxyethanol, benzyl alcohol, 3-t-butylperoxy-1,3-dimethylbutanol and 3-hydroxy-1,1-dimethylbutyl 2-ethylperoxyhexanoate. Non-limiting examples of suitable t-alkylperoxy halooxalates of Structure C (X = Br or Cl; Q = R4-OO) which can be reacted with hydroxy hydroperoxides of Structure B include t-butylperoxy chlorooxalate, t-amylperoxy chlorooxalate, 1, 1, 3,3-tetramethyl-butylperoxy-chlorooxalate, and isopropyl-a-cumylperoxy-chlorooxalate. The t-alkylperoxy halooxalates of Structure C can be prepared by reacting excess 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-alkylperoxy halooxalates by separation or by distillation. Non-limiting examples of suitable optional solvents are those given previously. Non-limiting examples of t-alkyl hydroperoxides suitable for preparing the t-alkyl peroxy halooxalates of Structure C include t-butyl hydroperoxide, t-amyl hydroperoxide, t-hexyl hydroperoxide, 1,1, 3,3-tetramethylbutyl hydroperoxide, 1- methylcyclohexyl hydroperoxide, paramentane hydroperoxide, 2-hydroperoxy- 2-methyl-3-butyne, α-cumyl hydroperoxide, and diisopropylbenzene monohydroperoxide. The novel O-alkyl OO- (hydroxy-t-alkyl) peroxioxalates of Structure D that can be prepared by the synthetic process of this O O R1 R3 II II I I ROC-C-OO-C-CH2CH? H invention can be further reacted with alkyl halooxalates (or oxalyl halides or t-alkylperoxy halooxalates), alkyl haloformates and carboxylic acid halides (or carboxylic acid anhydrides), optionally in the presence of an organic or inorganic base, and optionally in the presence of a solvent, to form the novel monoperoxioxalates of Structure A where Z is the structure (e), (f) and (g), respectively. Non-limiting examples of suitable oxalyl halides, alkyl halooxalates, organic or inorganic bases and optional solvents are listed above. Non-limiting examples of alkyl haloformates include isopropyl bromoformate, methyl chloroformate, cyclohexyl chloroformate, 4-t-butylcyclohexyl chloroformate, 2-phenoxyethyl chloroformate, 3-t-butylperoxy-1,3-dimethylbutyl chloroformate, phenyl chloroformate and benzyl chloroformate. Non-limiting examples of suitable carboxylic acid halides or carboxylic acid anhydrides include acetyl chloride, benzoyl chloride, isobutyryl chloride, lauroyl chloride, pivaloyl chloride, neodecanoyl chloride, acetic anhydride, propionic anhydride and succinic anhydride. Novel peroxioxalates from Structure E can be prepared O O R1 O O II II X-C-C-OO-C-CH2CHOC-C-X (where X = Br or Cl) by reacting hydroxy hydroperoxides with oxalyl halides such as oxalyl bromide and oxalyl chloride. The novel peroxioxalates of Structure E provide substrates to alternate synthetic routes for some of the novel monoperoxioxalates of Structure A. For example, monoperoxioxalates of Structure E can be further reacted with excess water, alkanols or excess t-alkyl hydroperoxides, in the presence of an organic or inorganic base, and optionally in the presence of a solvent, to produce novel peroxioxalates of Structure E.

O O R1 R3 O O li li I II II Q-C-C-OO-C-CH2CHO-C-C-Q (where Q = R-O or R4-OO) F | R2 Non-limiting examples of suitable organic or inorganic bases, optional solvents, alkanols and t-alkyl hydroperoxides are listed above.

Novel Peroxioxalate Compositions of Structure A - Illustrative Examples The non-limiting examples of the novel peroxioxalates of Structure A, in addition to those in the teaching examples, include the following: 1-methyl-3- (chlorocarbonylcarbonylperoxy) butyl chlorooxalate, O-methyl OO- (3-hydroxy-1,1-dimethylpropyl) monoperoxyoxalate, O-cyclohexyl OO- (3-hydroxy-1,1-dimethylbutyl) monoperoxyoxalate, O- octyl OO- (3-hydroxy-1,1-dimethylbutyl) monoperoxyoxalate, O-dodecyl OO- (3-hydroxy-1-dimethylbuty monoperoxyoxalate, O- (4-t-butylcyclohexyl) OO- (3-hydroxy-1) -dimethylbuty monoperoxyoxalate, O- (2-phenoxyethyl) OO- (3-hydroxy-1-dimethylbuty monoperoxyoxalate, O-allyl OO- (3-hydroxy-1-dimethylbuty monoperoxyoxalate, O-phenyl OO- (3-hydroxy) 1-dimethylbutyne monoperoxyoxalate, O-benzyl OO- (3-hydroxy-1-dimethylbuty monoperoxyoxalate, O- (3-t-butylperoxy-1,1-dimethylbutyl) OO- (3-hydroxy-1,1-dimethylbutyl) monoperoxyoxalate, O-methyl OO- (3-methoxycarbonylcarbonyloxy-1,1-dimethylbutyl) monoperoxyoxalate, O-cyclohexyl OO- (3-cyclohexoxycarbonylcarbonyloxy-1,1-dimethylbutyl) monoperoxyoxalate, O-bornyl OO- (3-bornyloxycarbonylcarbonyloxy-1, 1-dimethylbutyl) monoperoxyoxalate, O-bornil OO- (3-bornyloxycarbon) nylcarbonyloxy-1,1-dimethylbutyl) monoperoxyoxalate, O-butyl O - (3-butoxycarbonylcarbonyloxy-1,1-dimethylbutyl) monoperoxyoxalate, O-octyl OO- (3-octoxycarbonylcarbonyloxy) 1,1-dimethylbutyl) monoperoxyoxalate, O- (2-ethylhexyl) OO- [3- (2-ethylhexoxycarbonylcarbonyloxy) -1, 1-dimethylbutyl] monoperoxyoxalate, O- (4-t-butylcyclohexyl) OO- [3- (4 -t-butylcyclohexyloxycarbonylcarbonyloxy) - 1, 1-dimethylbutyl] monoperoxyoxalate, O-phenyl OO- (3-phenoxycarbonylcarbonyloxy-1,1-dimethylbutyl) monoperoxyoxalate, O-benzyl OO- (3-benzyloxycarbonylcarbonyloxy-1,1-dimethylbutyl) monoperoxyoxalate, O- (2-phenoxyethyl) OO- [3- (2-phenoxyethoxycarbonylcarbonyloxy) -1,1-dimethylbutyl] monoperoxyoxalate and O-allyl OO- (3-allyloxycarbonylcarbonyloxy-1,1-dimethylbutyl) monoperoxyoxalate, O-cyclohexyl OO- (3-methoxycarbonyloxy-1, 1) -dimethylbutyl) monoperoxyoxalate, O-cyclohexyl OO- (3-ethoxycarbonylcarbonyloxy-1,1-dimethylbutyl) monoperoxyoxalate, O- (2-ethylhexyl) OO- (3-acetoxy-1,1-dimethylbutyl) monoperoxyoxalate, t-butyl 3- t-butylperoxycarbonylcarbonyloxy-1,1-dimethylpropyl diperoxyoxalate, and t-amyl 3-t-amylperoxycarbonylcarbonyloxy-1,1-dimethylbutyl diperoxyoxalate.

Novel Structure Peroxyoxalate Compositions A -Utility A. Polymerization of Ethylenically Unsaturated Monomers In free radical polymerizations of ethylenically unsaturated monomers at appropriate pressures and temperatures the novel peroxioxalate compositions of Structure A of this invention were 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; maleic, itaconic and fumaric acids and their esters; vinyl halo and vinylidene dihalo 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 diethylene glycol bis (allyl carbonate) (i.e., ADC); acrolein, methyl vinyl ketone; or mixtures thereof. Temperatures from 0 ° C to 100 ° C, preferably 20 ° C to 90 ° C, more preferably 30 ° C to 75 ° C, and peroxioxalate levels of Structure A (on a pure basis) from 0.002 to 10% or more , preferably 0.005% to 2%, more preferably 0.01% to 1% by weight based on the monomer, are normally 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 the upper part of column 5 of US Pat. No. 4,525,308. Using the peroxide compositions of this invention in combination with these initiators adds flexibility to the processes of the polymer producers and allows them 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 peroxioxalate compositions of Structure A of this invention exhibit the activity of intensified cure in curable unsaturated polyester resin compositions. The unsaturated polyester resins that can be cured by the novel peroxioxalate compositions of this invention usually include an unsaturated polyester and one or more ethylenically unsaturated monomers. Unsaturated polyesters are, for example, polyesters as obtained by esterification of 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-1,3-propanediol, 2-hydroxymethyl-2- methyl-1, 3-propanediol, 2-buten-1,4-diol, 2-butin-1,4-diol, 2,4,4-trimethyl-1,3-pentanediol, glycerol, pentaerythritol, mannitol and others. Mixtures of such di- or polyacids and / or mixtures of such di- or polyols may also be used. The di- or polycarboxylic acids can be partially replaced by saturated 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, trimellitic acid, pyromellitic acid, isophthalic 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-hexachlorobicyclo (2.2.1) -2-heptene 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 anhydride of an acid unsaturated polycarboxylic acid) and phthalic anhydride (an aromatic dicarboxylic acid anhydride) 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, called unsaturated vinyl ester resins, consist of a portion of vinyl ester resin and one or more polymerizable monomer components. The vinyl ester resin component can be made by reacting a chloroepoxide, such as epichlorohydrin, with the appropriate amounts of a bisphenol such as Bisphenol A [2,2- (4-hydroxyphenyl) propane], in the presence of a base, such as sodium hydroxide, to produce a condensation product having terminal epoxy groups derived from chloroepoxide. The 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, the 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 peroxioxalates of Structure A from about 0.05% to 5% or more, preferably 0.10% to 4%, more preferably 0.25% to 3% by weight of resin composition of curable unsaturated polyester are normally employed.

The unsaturated polyester resin compositions described above can be filled with various materials, such as boron, carbon, glass, and sulfur fibers, carbon black, silicas, metal silicates, clays, metal carbonates, antioxidants (AO's), stabilizers of light, ultraviolet (UV) and heat, sensitizers, dyes, pigments, accelerators, metal oxides, such as zinc oxide, blowing agents, core forming agents and others.

C. Healing of Allyl Diglycol Carbonate Resins (ADC) In the curing or polymerization of diethylene glycol bis (allyl carbonate) (ADC), O O II CH2 = CHCH2? -C-OCH2CH2OCH2CH2O-C-OCH2CH = CH2 ADC by heating the ADC monomer to suitable cure temperatures in the presence of free radical curing agents, the novel peroxyoxalate compositions of Structure A of this invention exhibit enhanced polymerization or curing activity for ADC monomer compositions. The ADC was commercially introduced as monomer CR-39 (CAS Reg. No. 142-22-3) by Pittsburgh Piet Glass Company (PPG) and is produced by reacting diethylene glycol bis (chloroformate) with allyl alcohol in the presence of alkali ( R. Dowbenko, in Jl Krowchwitz and M. Howe-Grant, eds., Kirk-Othmer - Encyclopedia of Chemical Technology, "Allyl Monomers and Polymers," Fourth Edition, Vol. 2, Wiley-lnterscience Publication, John Wiley &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 clear castings or lenses They are transparent, hard, resistant to breakage and resistant to solvents. The curing or polymerization of ADC monomer compositions are carried out in bulk (without solvent present). In general, the curing or polymerization of ADC monomer compositions to form lenses or sheets of casting is carried out in two stages. The first stage involves the main part of the polymerization and occurs in the presence of the curing initiator, usually a lower 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: PROGRAM OF TEMPERATURE OF TYPICAL CURE FOR THE CURE OF ADC TIME (HOURS) TEMPERATURE (° 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 stage of the curing or polymerization of ADC monomer compositions involves post-curing or tempering the ADC resin for one to several hours at 100 ° C to 150 ° C. An example of post-cure of the ADC resin would be 2 hours at 115 ° C. Levels of the novel peroxioxalate compositions of from about 1% to 6% or more, preferably 2% to 5%, more preferably 2.5% to 4% by weight of polymerizable or curable ADC monomer composition, are normally employed. The ADC resin compositions described above can be filled with various metals, such as antioxidants (AO's), light stabilizers, ultraviolet (UV) and heat, dyes, photochromic additives and colorants. In addition, the ADC resin compositions may contain additives such as acrylic polymers and the low molecular weight, anti-shrinkage acrylic resins described in U.S. Patent 4,217,433.

Such anti-shrinkage additives are employed to counteract the 14% shrinkage that occurs when the ADC monomer is polymerized.

Novel Peroxioxalate Compositions of Structure A - Examples of usefulness and preparation The following examples further illustrate the best mode contemplated by the inventors for practicing the present invention, and are presented to provide detailed usefulness and preparation illustrations of the invention and are not intended to limit the scope and scope of the invention.

Example 1 Preparation of O-ethyl OO- (3-ethoxycarbonyl-carbonyloxy-1,1-dimethylbutyl) Monoperoxy-oxalate (1-1) O O CH3 CH3 O O li li I li li C2H5? C-C-OO-C-CH2CH-OC-COC2H5 (1- 1) I CH3 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 4.3 g (30.0 mmoles) of 94.4% 3-hydroxy -1, 1 -dimethylbutyl hydroperoxide dry, 6.7 g (85.0 mmoles) of dry pyridine and 60 ml of methyl t-butyl ether (MTBE). The contents of the flask were cooled to 1 ° C. Then to the resulting vigorously stirred solution at 5-8 ° C was slowly added a solution of 8.8 g (63.0 mmol) of 98% ethyl oxalyl chloride in 10 ml of MTBE. A solid pyridinium chloride, formed just after the addition began. After the addition was complete, the reaction mass was stirred for 45 minutes at 2 ° C after which 10 ml of water were added and the reaction mass was stirred an additional 20 minutes at 3-4 ° C. The aqueous layer was then separated and the organic layer was washed three times with 35 ml portions of 5% aqueous HCl solution and then washed 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 desiccant employed by filtration, the solvent was removed in vacuo leaving 11.3 g (> 100% theory, uncorrected) of a colorless liquid . An infrared (IR) spectrum of the product showed a light OH band in the 3500 cm'1 region. A larger carbonyl monoperoxioxalate band was present at 1791.1 cm'1, a large carbonyl oxalate band was present at 1741.6 cm "1 and one band of peroxide (-OO-) was present at approximately 860 cm" 1. The product had a rapid heat test result [J. Chem. Ed. 48, 1451 (1970)] of 62 ° C, which confirmed that the product was a very low temperature peroxide. The product contained 4.77% active oxygen (theory, 4.79%) according to a peroxy ester active oxygen method, consequently, the product test had 99.6% and the corrected yield was 100%. Based on the preparation method, production data, fast heat data and infrared spectrum data, the product obtained in this reaction was the desired product of the title.

O-ethyl OO- (3-ethoxycarbonyl-carbonyloxy-1,1-dimethylbutyl) monoperoxyoxalate (1-1) was found to have a half-life of 10 h at 25 ° C in trichlorethylene, consequently, 1-1 was a peroxide extremely active compared to the OO-t-alkyl O-alkyl monoperoxioxalates of the art.

Example 2 Preparation of 1,3-dimethyl-3- (chlorocarbonylcarbonylperoxy) butylchlorooxalate (I-2) O O CH3 CH3 O O II II I I II II CIC-C-OCCHCH2-C-OO-C-CCI (1-2) I CH3 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 38.1 g (300 mmol) of oxalyl chloride and 80 ml of MTBE . The contents of the flask were then cooled to 1 ° C. Then 4.3 g (30 mmol) of 94.4% dry 3-hydroxy-1,1-dimethylbutyl hydroperoxide and 9.5 g of methoxyethyl ether (diglyme) in 20 ml of MTBE were added slowly to the contents of the flask over a period of 30 minutes at 1 C. The diglyme was used as a safety diluent for the product. Then the reaction mass was further stirred for 120 minutes at 0 ° C after which the MTBE and excess oxalyl chloride were removed in vacuo using a water aspirator at 0 ° C leaving 23.5 g (> 100% theory) , uncorrected, expected yield = 19 g of diluted product of diglima) of a slightly yellow liquid. An IR spectrum of the product showed only one trace of an OH band in the 3500 cm "1 region A larger carbonyl monoperoxioxalate band was presented at 1790 cm" 1 and a larger carbonyl oxalate band appeared at approximately 1750 cm'1 . The product had a rapid heat test result of 66 ° C which confirmed that the product was a very low temperature peroxide. Based on the preparation method, raw yield data, fast heat data and infrared spectrum data the product obtained in this reaction was the desired product of the title. A second preparation of the title peroxide was performed in a similar manner except that only 4.0 g of diglyme safety diluent were employed. In this experiment 16.8 g (> 100% theory, uncorrected, expected yield = 13.5 diluted product of diglyme) of a slightly yellow liquid product were obtained. An IR spectrum of the product showed only one trace of an OH band in the 3500 cm "region.1 A larger carbonyl monoperoxioxalate band was present at 1795 cm" 1 and a higher carbonyl oxalate band was present at approximately 1750 cm "1. The product had a rapid heat test result of 63 ° C (strong burst) which again confirmed that the product was a very low temperature peroxide.The desired peroxide product was prepared in this experiment based on the preparation method, Raw performance data, fast heat data and infrared spectrum data were obtained.A third preparation of the title peroxide was performed in a similar manner except that no safety diluent was used. diglima. In this experiment 9.5 g (100% theory, uncorrected, expected yield = 9.5 g of undiluted product) of a slightly yellow liquid product was obtained. An IR spectrum of the product showed only one trace of an OH band in the 3500 crn'1 region, a higher monoperoxioxalate carbonyl band at approximately 1795 cm "1 and a higher carbonyl oxalate band at approximately 1750 cm" 1. The product had a rapid heat test result of 51 ° C which again confirmed that the product was a very low temperature peroxide. Based on the preparation method, raw performance data, fast heat data and infrared spectrum data, the desired peroxide product was prepared in this experiment.

Example 3 Preparation of O-ethyl OO- (3-ethoxycarbonyl-carbonyloxy-1,1-dimethylbutyl) Monoperoxyoxalate (1-1) from (I-2) 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 2.8 g (60 mmol) of ethanol, 3.4 g (43 mmol) of dry pyridine and 60 ml of MTBE. The contents of the flask were cooled to 0CC. Then to the resulting vigorously stirred solution at 0 ° C was added 4.8 g (15 mmol) of 1,3-dimethyl-3- (chlorocarbonylcarbonylperoxy) butyl chlorooxalate (I-2) in 10 mL of MTBE. After the addition was complete, the reaction mass was stirred for 60 minutes at 2 ° C after which 20 ml of water were added and the reaction mass was stirred an additional 5 minutes at 3-4 ° C. The aqueous layer was then separated and the organic layer was washed three times with 50 ml portions of water. The product solution was dried over 5% by weight of anhydrous MgSO 4, and after removal of the desiccant employed by filtration, the solvent was removed in vacuo using a vacuum pump / water aspirator at 0 ° C leaving 3.6 g (72 % theory, uncorrected) of a colorless liquid. An IR spectrum of the product showed a band of light OH in the region 3500 cm "1, a greater band of carbonyl monoperoxioxalate at 1791.1 cm'1 and a greater band of carbonyl oxalate was present at 1741.6 cm" 1. There was a peroxide band (-OO-) at approximately 860 cm "1. The product was given a rapid heat test result of 60 ° C which confirmed that the product was a very low temperature peroxide. preparation, performance data, fast heat data and infrared spectrum data, the product obtained in this reaction was the desired product of the title, 1-1 The IR spectrum of the product of this example was exactly the same as the IR spectrum of the product of Example 1. Hence, two different synthetic methods were used to prepare O-ethyl OO- (3-ethoxycarbonylcarbonyloxy-1,1-dimethylbutyl) monoperoxyoxalate, ie, the method of this example and the method of Example 1.

Example 4 Preparation of O-ethyl OO- (3-hydroxy-1,1-dimethylbutyl) Monoperoxyoxalate (I-3) O O CH3 CH3 li li I I C2H5OC-C-OO-C-CH2CHOH (I-3) I CH3 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 6.0 g (44.0 mmol) of 98% 3-hydroxy- 1, 1-dimethylbutyl hydroperoxide, 9.8 g (80.0 mmoles) of dry 2,4,6-collidine and 50 ml of methylene chloride. The contents of the flask were cooled to -78 ° C. Then to the resulting vigorously stirred solution at -78 ° C a solution of 5.6 g (40 mmoles) of 98% ethyl oxalyl chloride in 40 ml of methylene chloride was added slowly over a period of 15-20 minutes. After the addition was complete, the reaction mass was stirred for 4 hours at -78 ° C, then for 60 minutes at 25 ° C, after which 100 ml of water were added and the reaction mass was stirred. additional minutes at 25 ° C. The aqueous layer was then separated and the organic layer was washed twice with 50 ml portions of 5% aqueous HCl solution and then with 50 ml portions of water until the washings were neutral. The product solution was dried over 5% by weight of anhydrous MgSO, and, after removal of the desiccant used by filtration, the solvent was removed in vacuo leaving 5.5 g (59% theory, uncorrected) of an oil without color . An IR spectrum of product showed a large band of OH in the region 3500 cm "1, a greater band of carbonyl monoperoxioxalate at 1790 cm'1 and a greater band of carbonyl oxalate at approximately 1735 cm * 1. The product had a rapid heat test result of 55 ° C which confirmed that the product was a very low temperature peroxide.The product contained 3.71% active oxygen (theory, 6.38%) according to a peroxy ester active oxygen method, consequently, the product test was 54% and the corrected yield was 32% Based on the preparation method, active oxygen content, fast heat data and infrared spectrum data, the product obtained in this reaction was the desired product of the title.

Example 5 Preparation of O- (2-ethylhexyl) OO- (3-hydroxy-1,1-dimethylbutyl) Monoperoxyoxalate (1-4) O O CH3 CH3 li li I I CH3 (CH2) 3CHCH2OC-C-OO-C-CH2CHOH (1-4) 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 6.4 g (44.0 mmoles) of 92% 3-hydroxy- Dry 1, 1-dimethylbutyl hydroperoxide, 9.8 g (80.0 mmoles) of dry 2,4,6-collidine and 50 ml of methylene chloride. The contents of the flask were cooled to -78 ° C. Then to the resulting vigorously stirred solution at -78 ° C was slowly added a solution of 9.0 g (40.0 mmoles) of 98% 2-ethylhexyl oxalyl chloride (prepared by reacting excess oxalyl chloride with 2-ethylhexanol, followed by rem of the excess oxalyl chloride) in 40 ml of methylene chloride over a period of 15-20 minutes. After the addition was complete the reaction mass was stirred for 4 hours at -78 ° C, then for 60 minutes at 25 ° C, after which 100 ml of water were added and the reaction mass was stirred 5 minutes additional at 25 ° C. The aqueous layer was then separated and the organic layer was washed twice with 50 ml portions of 5% aqueous HCl solution and then with 50 ml portions of water until the washings were neutral. The product solution was dried over 5% by weight of anhydrous MgSO 4, and, after rem of the desiccant used by filtration, the solvent was removed under vacuum leaving 10.0 g (79% theory, uncorrected) of a colorless oil . An IR spectrum of the product showed a large OH band in the 3500 cm "1 region.The product had a rapid heat test result of 58 ° C which confirmed that the product was a low temperature peroxide.The product contained 3.98. % of active oxygen (theory, 5.02%) according to a peroxy ester active oxygen method, consequently, the product test was 79% and the corrected yield was 62%, based on the preparation method, yield data, Fast heat data and infrared spectrum data, the product obtained in this reaction was the desired product of the title.

Example 6 Preparation of O- (2-ethylhexyl) OO-f3- (2-ethylhexyloxycarbonylcarbonyloxy) -1.1-dimethylbutyl Monoperoxy-oxalate (I-5) O O CH3 O O CH3 (CH2) H2) 3CH3 (I-5) An open top, jacketed reactor (ca. 250 ml) equipped with a mechanical stirrer, a thermometer and an addition funnel and cooled with circulating ice water was charged with 2.9 g (20 mmol) of 91.7%. dry hydroxy-1, 1-dimethylbutyl hydroperoxide, 3.5 g (44 mmoles) of dry pyridine and 75 ml of methylene chloride. The contents of the flask were cooled to 0 ° C. Then a solution of 8.8 g (40.0 mmol? S) of 98% 2-ethylhexyl chlorooxalate (previously prepared by reacting excess oxalyl chloride with 2-ethylhexanol, followed by rem) was added slowly to the resulting vigorously stirred solution at 0 ° C. of oxalyl chloride in excess) in 25 ml of methylene chloride. After the addition was complete the reaction mass was stirred for 60 minutes at 0 ° C after which 50 ml of water were added and the reaction mass was stirred an additional 10 minutes at 5 ° C. The aqueous layer was then separated and the organic layer was washed with a 20 ml portion of 5% aqueous HCl solution and then twice with 50 ml portions of water. The product solution was dried over 5% by weight of anhydrous MgSO, and, after separation of the desiccant employed by filtration, the solvent was removed under vacuum leaving 10.5 g (> 100% theory, uncorrected) of a colorless liquid. A IR spectrum of the product showed an important carbonyl monoperoxioxalate band at approximately 1790 cm "1 and a carbonyl oxalate band at approximately 1750 cm" 1. The product had a rapid heat test result of 72-75 ° C which confirmed that the product was a very low temperature peroxide. The product contained 2.86% active oxygen (theory, 3.18%) according to a peroxy ester active oxygen method, consequently, the product test was 90% and the corrected yield was 94%. Based on the preparation method, performance data, fast heat data and infrared spectrum data, the product obtained in this reaction was the desired product of the title.

Example 7 Preparation of OO-f3- (4-methyl-2-pentoxycarbonylcarbonyloxy) -1, 1-dimethylbutyl O- (4-methyl-2-pentyl) Monoperoxy-oxalate (1-6) CH3 CH3 O O CH3 CH3 O O CH3 CH3 I I II II I I li li I I CH3CHCH2CHOC-C-OO-C-CH2-CH-OC-CO-CHCH2CHCH3 (1-6) I CH3 In this example the product was prepared in two synthetic steps. In the first step, 4-methyl-2-pentanol was reacted with 50 mol% excess oxalyl chloride. Upon completion of the reaction the excess oxalyl chloride was removed from the product under reduced pressure to produce 4-methyl-2-pentyl chlorooxalate having a 96.2% test and a corrected yield of 88.2%. In the second step, 4-methyl-2-pentyl chlorooxalate was reacted with 3-hydroxy-1,1-dimethylbutyl hydroperoxide in the presence of pyridine to produce the product as described below: 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 4.3 g (30.0 mmol) of 94.4% dry 3-hydroxy-1,1-dimethylbutyl hydroperoxide, 6.7 g (85.0 mmol) of dry pyridine and 50 ml of methyl t-butyl ether (MTBE). The contents of the flask were cooled to 3 ° C. Then to the resulting vigorously stirred solution at 3-8 ° C a solution of 1 1.9 g (59.4 mmoles) of 96.2% 4-methyl-2-pentyl chlorooxalate in 25 ml of MTBE was slowly added over a period of 30 minutes. The reaction mass was stirred for 60 minutes at 0-5 ° C, after which it was washed with 100 ml of water, two 50 ml portions of 5% aqueous HCl solution and a pH of 7 with portions of 100. ml of water. The product solution was dried over 5% by weight of anhydrous MgSO 4, and, after removal of the desiccant used by filtration, the solvent was removed under vacuum leaving 12.6 g (95% theory, uncorrected) of a colorless liquid . An IR spectrum of the product did not show any significant OH band in the 3500 cm "region.1 A larger monoperoxioxalate carbonyl band was present at 1795 cm" 1 and a larger band of carbonyl oxalate occurred at approximately 1740 cm "1. The product had a rapid heat test result of 48 ° C which confirmed that the product was a low temperature peroxide.

Based on the preparation method, performance data, fast heat data and infrared spectrum data, the product obtained in this reaction was the desired product of the title.

Example 8 Preparation of O-t-butyl OO- (3-t-butoxycarbonylcarbonyloxy-1, 1- Dimethylbutyl Monoperoxyoxalate (I-7) O O CH3 CH3 O O li li I li li t-C4H9-OC-C-OO-C-CH2CH-OC-CO-t-C4H9 (1-7) I CH3 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 4.3 g (30.0 mmol) of 94.4% 3-hydroxyl. 1, 1-dimethylbutyl hydroperoxide dry, 6.7 g (85.0 mmoles) of dry pyridine and 60 ml of MTBE. The contents of the flask were cooled to 0 ° C. Then a solution of 10.4 g (63.0 mmoles) of 100% t-butyl chlorooxalate (previously prepared by reacting excess oxalyl chloride with 2-t-butanol) was slowly added to the resulting vigorously stirred solution at 5-8 ° C. by removal of excess oxalyl chloride) in 10 ml of MTBE. After the addition was complete the reaction mass was stirred for 45 minutes at 0 ° C, after which 10 ml of water were added and the reaction mass was stirred an additional 20 minutes at 3-4 ° C. The aqueous layer was then separated and the organic layer was washed three times with 35 ml portions of 5% aqueous HCl solution and then two times with 75 ml portions of water. The product solution was dried over 5% by weight of anhydrous MgSO 4, and, after removal of the desiccant used by filtration, the solvent was removed under vacuum leaving 1.0 g (94% theory, uncorrected) of a liquid colorless. An IR spectrum of the product did not show any significant OH band in the 3500 cm * 1 region. A larger carbonyl monoperoxioxalate band appeared at 1790 cm "1 and a carbonyl oxalate band appeared at approximately 1735 cm '1. The product had a result of rapid heat test (36 ° C) which confirmed that the product was a very low temperature peroxide based on the preparation method, performance data, fast heat data and infrared spectrum data, the product obtained in this reaction was the desired product of the title.

Example 9 Preparation of O-neopentyl OO- (3-neopentoxycarbonyl-carbonyloxy-1,1-dimethylbutyl) Monoperoxyoxalate (I-8) CH3 O O CH3 CH3 O O CH3 I li li I li li I CH3CCH2OC-C-OO-C-CH2CH-OC-COCH2CCH3 (I-8) I I I CH3 CH3 CH3 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 2.9 g (20 mmol) of 94.4% 3-hydroxyl. 1, 1 -dimethylbutyl hydroperoxide dry, 4.5 g (57 mmoles) of dry pyridine and 60 ml of MTBE. The contents of the flask were cooled to 0 ° C. Then a solution of 7.5 g (42 mmol) of 100% neopentyl chlorooxalate (previously prepared by reacting excess oxalyl chloride with neopentyl alcohol, followed by removal of the oxalyl chloride in the solution) was added slowly to the resulting vigorously stirred solution at about 0 ° C. excess) in 10 ml of MTBE. After the addition was complete, the reaction mass was stirred for 45 minutes at 0 ° C, after which 10 ml of water were added and the reaction mass was stirred an additional 20 minutes at 3-4 ° C. The aqueous layer was then separated and the organic layer was washed three times with 35 ml portions of 5% aqueous HCl solution 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 desiccant employed by filtration, the solvent was removed under vacuum leaving 9.0 g (> 100% theory, uncorrected) of a colorless liquid. An IR spectrum of the product showed a small band of OH in the 3500 cm'1 region. A larger carbonyl monoperoxioxalate band was present at approximately 1790 cm'l and a carbonyl oxalate band appeared at approximately 1735 cm "1 The product had a rapid heat test result of 75 ° C which confirmed that the product was a very low temperature peroxide The product contained 3.61% active oxygen (theory, 3.82%) according to a peroxy ester active oxygen method, consequently, the product test was 95% and the corrected yield was 100%.

Based on the preparation method, performance data, fast heat data and infrared spectrum data, the product obtained in this reaction was the desired product of the title.

Example 10 Preparation of O-benzyl OO- (3-benzyloxycarbonylcarbonyloxy-1,1-dimethylbutyl) Monoperoxyoxalate (I-9) O O CH3 CH3 O O C6H5CH2OC-C-OO-C-CH2CH-OC-COCH2C6H5 (1-9) I CH3 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 2.9 g (20 mmol) of 94.4% 3-hydroxyl. Dry 1, 1-dimethylbutyl hydroperoxide, 4.5 g (57 mmol) of dry pyridine and 60 ml of MTBE. The contents of the flask were cooled to 1 ° C. Then a solution of 8.6 g (42 mmol) of 96.6% benzyl chlorooxalate (previously prepared by reacting excess oxalyl chloride with benzyl alcohol, followed by removal of excess oxalyl chloride) was added slowly to the resulting vigorously stirred solution at 0 ° C. ) in 10 ml MTBE. After the addition was complete, the reaction mass was stirred for 45 minutes at 2 ° C, after which 10 ml of water were added and the reaction mass was stirred an additional 20 minutes at 3-4 ° C. The aqueous layer was then separated and the organic layer was washed three times with 35 ml portions of 5% aqueous HCl solution and then twice with 75 ml portions of water. The product solution was dried over 5% by weight of anhydrous MgSO, and, after removal of the desiccant employed by filtration, the solvent was removed under vacuum leaving 9.1 g (99% theory, uncorrected) of a colorless liquid . An IR spectrum of the product showed a slight band of OH in the region 3500 cm "1 A larger band of carbonyl monoperoxioxalate was presented at 1790 cm" 1 and one band of carbonyl oxalate was presented at approximately 1740 cm "1. a result of the rapid heat test of 73 ° C which confirmed that the product was a very low temperature peroxide.The product contained 3.02% active oxygen (theory, 3.49%) according to a peroxy ester active oxygen method, consequently, the product test was 87% and the corrected yield was 86%. Based on the preparation method, performance data, fast heat data and infrared spectrum data, the product obtained in this reaction was the desired product of the title.

EXAMPLE 11 Preparation of O-hexafluoroamyl OO- (3-hexafluoro-amyloxycarbonylcarbonyloxy-1,1-dimethylbutyl) Monoperoxy-oxalate (1-10) CH 3 O O CH 3 CH 3 O O CH 3 I li li I li li I CF 3 CHFCF 2 CH-OC-C-OO-C-CH 2 CH-OC-COCHCF 2 CHFCR 3 (1-10) CH.

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 1.5 g (10 mmol) of 94.4% dry 3-hydroxy-1,1-dimethylbutyl hydroperoxide, 2.3 g (29 mmol) of dry pyridine and 60 ml of MTBE. The contents of the flask were cooled to 1 ° C. Then a solution of 6.6 g (21 mmol) of 91.3% hexafluoroamyl chlorooxalate (previously prepared by reacting excess oxalyl chloride with hexafluoroamyl alcohol, followed by removal of the oxalyl chloride in the resulting vigorously stirred solution at about 0 ° C) was slowly added. excess) in 10 ml MTBE. After the addition was complete, the reaction mass was stirred for 45 minutes at 0 ° C, after which 10 ml of water were added and the reaction mass was stirred an additional 20 minutes at 3-4 ° C. The aqueous layer was then separated and the organic layer was washed three times with 35 ml portions of 5% aqueous HCl solution 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 desiccant employed by filtration, the solvent was removed in vacuo leaving 7.3 g (> 100% theory, uncorrected) of a colorless liquid. An IR spectrum of the product showed a large OH band in the 3500 cm'1 region. The product contained 1.77% active oxygen (theory, 2.52%) according to a peroxy ester active oxygen method, consequently, the product test was 70% and the corrected yield was 81%. The product had a rapid heat test result of 93 ° C which confirmed that the product was a low temperature peroxide. The higher rapid heat temperature compared to other similar monoperoxioxalates was due to the lower active oxygen content of the product compared to those of other monoperoxyoxalates.

Based on the preparation method, performance data, fast heat data and infrared spectrum data, the product obtained in this reaction was the desired product of the title.

Example 12 Preparation of OO-r3- (3-t-burylperoxy-1,3-dimethylbutoxycarbonylcarbonyloxy) -1, 1-dimethylbutyne O- (3-t-butylperoxy-1,3-dimethylbutyl) Monoperoxyoxalate (1-11) CH3 O O CH3 O O CH3 I li li I II II I CH3CCH2CHOC-C-OO-C-CH2CHOC-COCHCH2CCH3 (1-11) I I I I I t-C4H9-OO CH3 CH3 CH3 CH3 OO-t-C4H9 In this example the product was prepared in two synthetic steps. In the first step 3-t-butylperoxy-1,3-dimethylbutanol was reacted with 100% molar of excess oxalyl chloride. Upon completion of the reaction the excess oxalyl chloride was removed from the product under reduced pressure to produce 3-t-butylperoxy-1,3-dimethylbutyl chloroaxalate having a 98.1% test and in a corrected yield of 98.4%. In the second step 3-t-butylperoxy-1,3-diethylbutyl chlorooxalate was reacted with 3-hydroperoxy-1,3-dimethylbutanol in the presence of pyridine to produce the product as described below: A 3-neck flask of 250 ml equipped with a magnetic stirring bar, a condenser, a thermometer and an addition funnel and cooled with an ice bath was charged with 2.9 g (20 mmol) of 94.1% 3-hydroxy-1,1-dimethylbutyl hydroperoxide dry, 4.8 g (61.0 mmoles) of dry pyridine and 40 ml of MTBE. The contents of the flask were cooled to 3 ° C. Then to the resulting vigorously stirred solution at 3-7 ° C a solution of 11.5 g (40.0 mmoles) of 98.1% 3-t-butylperoxy-1,3-dimethylbutyl chloroaxalate in 10 ml MTBE over a period of 30 minutes was slowly added. The reaction mass was stirred for 120 minutes at 0-10 ° C, after which it was washed with 100 ml of water, two 50 ml portions of 5% aqueous HCl solution and a pH of 7 with 100 ml portions of water. The product solution was dried over 5% by weight of anhydrous MgSO 4, and, after removal of the desiccant employed by filtration, the solvent was removed under vacuum leaving 12.1 g (97% theory, uncorrected) of a colorless liquid . An IR spectrum of the product did not show an important OH band in the 3500 cm "region.1 A larger carbonyl monoperoxioxalate band was presented at 1800 cm * 1 and a carbonyl oxalate band appeared at approximately 1750 cm" 1. Based on the active oxygen content of monoperoxioxalate (2.08%) the product test was 80% and the corrected yield was approximately 78%. Based on the preparation method, performance data, fast heat data and infrared spectrum data, the product obtained in this reaction was the desired product of the title.

Example 13 Preparation of t-butyl 3-t-Butylperoxycarbonylcarbonyloxy-1,1-dimethylbutyl) Monoperoxyoxalate (1-12) O O CH; O O t-C4H9-OO-C-C-OO-C-CH2CHOC-C-OO-t-C4H9 d-12) I I CH3 CH3 In this example the product was prepared in two synthetic steps. In the first step the t-butyl hydroperoxide was reacted with 100 mol% excess oxalyl chloride to form t-butylperoxy chlorooxalate (A-1).

O O II II CI-C-C-OO-t-C4H9 (A-1) In the second step the t-butylperoxy chlorooxalate (A-1) was reacted with 3-hydroxy-1,1-dimethylbutyl hydroperoxide 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 of pentane and 3 g of anhydrous MgSO 4 at room temperature. The contents were stirred for 30 minutes after which the contents were filtered and the desiccant used was washed with 25 ml of pentane and the washes of the pentane were combined with the filtrate. A 3-neck flask equipped with a magnetic stir bar, a condenser, a thermometer and an addition funnel and cooled with an ice 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 slowly added to the stirred oxalyl chloride / pentane solution over a period of 60 minutes at 0 ° C. The reaction was stirred for an additional 3 hours at 0 ° C. Then pentane and excess oxalyl chloride were removed by separating at ice water temperature, leaving 18.5 g (> 100% theory, uncorrected, theoretical yield = 18.1 g) of a liquid product. An IR spectrum of the product showed an OH band very light in the region 3500 cm'1 and a band of carbonyl monoperoxioxalato major, simple at 1797 cm'1. The product had a result of the rapid heat test of 45 ° C (very strong burst) which confirmed that the product, t-butylperoxy chlorooxalate, was a very low temperature peroxide. The shock effect test [J. Chem. Ed. 48, A 451 (1971)] showed that the product was sensitive to shock at 7.62 cm and not sensitive to shock at 2.54 cm. Because the shock and thermal sensitivities of the product were diluted with an equal weight of diglyme before subsequent use. The product diluted with diglima had a rapid heat test result of 60 ° C (mild decomposition) and a shock sensitivity of approximately 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 1.4 g (10.0 mmol) of 94.4 Dry 3-hydroxy-1,1-dimethylbutyl hydroperoxide, 2.3 g (29.0 mmoles) 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 0 ° C was slowly added a solution of 7.7 g (21.0 mmol) of approximately a 50% diglyme solution of t-butylperoxy chlorooxalate in 10 ml of MTBE. After the addition was complete, the reaction mass was stirred for 60 minutes at 0 ° C, after which 10 ml of water were added and the reaction mass was stirred an additional 20 minutes at 0 ° C. The aqueous layer was then separated and the organic layer was washed three times with 35 ml portions of 5% aqueous HCl solution and then twice with 75 ml portions of aqueous solution of 5% NaHCO3. The product solution was dried over 5% by weight of anhydrous MgSO 4, and, after separation of the desiccant used by filtration, the solvent was removed under vacuum leaving 3.9 g (91% theory, uncorrected, theoretical yield = 4.3 g) of a colorless liquid. An IR spectrum of the product showed a slight OH band in the 3500 cm'1 region, a higher carbonyl monoperoxioxalate band was presented at 1797 cm '1, a carbonyl oxalate band it was presented at approximately 1750 cm'1 and a peroxide band (-OO-) appeared at approximately 845 cm "1. The shock effect test showed that the product was sensitive to shock at 7.62 cm and not sensitive to shock. 2.54 cm The product was diluted with an equal weight of diglyme (at approximately 50% active) in order to suppress the sensitivity of the product's shock effect The product diluted with diglyme had a sensitivity to shock above 50.8 cm and a rapid heat test result of 45-48 ° C. The last result confirmed that the product was an extremely low temperature peroxide., performance data, fast heat data and infrared spectrum data, the product obtained in this reaction was the desired product of the title.

Example 14 Polymerization of methyl methacrylate using OO-r3- (4-methyl-2-pentoxycarbonyl-carbonyloxy) -1,1-dimethylbutyn O- (4-methyl-2-pentyl) monoperoxy-oxalate (I-6) as an initiator A 250 ml 3-necked flask equipped with a magnetic stir bar, a condenser, a thermometer was charged with 75 g of methyl ethyl ketone (MEK) and 30 g of methyl methacrylate (MMA). To the resulting vigorously stirred solution at 53-56X was slowly added a solution of 2.4 g (ca. 5.0 mmole) of OO- [3- (4-methyl-2-pentoxycarbonyl-carbonyloxy) -1, 1-dimethylbutyl] O- (4-methyl-2-pentyl) monoperoxyoxalate (I-6) in 25 ml of MEK over a period of about 30 minutes. The reaction mass was stirred for 15 minutes at 55 ° C and then for approximately 120 minutes at 65-70 ° C. The polymer solution was then cooled to about 30 ° C and emptied into about 1500 ml of vigorously stirred water to precipitate the poly (methyl methacrylate) (PMMA). The paste was allowed to stabilize overnight after which the solid PMMA was separated by filtration and air dried for 3 hours at 20-25 ° C. The polymer was washed with 50 ml of pentane, filtered and dried. 11.3 g of PMMA polymer were obtained (ca. 35% theory, uncorrected). This example showed that a novel monoperoxyoxalate composition of this invention was an effective free radical initiator for ethylenically polymerizing unsaturated monomers such as MMA.

Example 15 Preparation of methyl methacrylate polymer with peroxide end groups using OO-f3- (3-t-Butylperoxy-1,3-dimethylbutoxycarbonylcarbonyloxy-1,1-dimethylbutyn O- (3-t-butyl-peroxy-1,3-dimethylbutyl) Monoperoxyoxylate (1-11) as an initiator A 250 ml 3-neck flask equipped with a magnetic stir bar, a condenser, a thermometer was charged with 75 g of MEK and 30 g of MMA. To the resulting vigorously stirred solution at 53-56 ° C a solution of 4.0 g (ca. 5.1 mmole) of OO- [3- (3-t-butylperoxy-1,3-dimethylbutoxycarbonylcarbonyloxy) -1, 1- was slowly added. dimethylbutyl] O- (3-t-butylperoxy-1,3-dimethylbutyl) monoperoxyoxalate (1-1 1) in 25 ml of MEK over a period of about 30 minutes. The reaction mass was stirred for 15 minutes at 55 ° C and then for approximately 120 minutes at 65-70 ° C. The polymer solution was then cooled to about 30 ° C and evacuated to about 1500 ml of vigorously stirred water to precipitate the PMMA. The pulp was allowed to settle overnight after which the solid PMMA was separated by filtration and air dried for 2-3 hours at 20-25 ° C. The polymer was washed with 50 ml of pentane, filtered and dried. 12.8 g of PMMA polymer (ca. 39% theory, uncorrected) having terminal peroxide groups were obtained. The analysis of the product by differential scanning calorimetry (DSC) showed an exotherm of decomposition of peroxide important at approximately 190 ° C, which confirmed the presence of peroxide groups covalently bound to the ends of the chains of polymer. The peroxide polymer was found to have molecular weights and molecular weight distribution as follows: Mn - 4,000 Mw - 6,000 Mz - 11,000 This example showed that a novel monoperoxyoxalate composition of this invention was an effective free radical initiator for polymerizing ethylenically unsaturated monomers such as MMA.

Example 16 SPI exotherm data at 60 ° C for O-ethyl OO- (3-ethoxycarbonylcarbonyloxy-1-, 1-dimethylbutyl) Monoperoxyoxalate (1-1) 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 esterification of the following components: 0. 013% by weight of 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 three (3) parts by weight of styrene monomer. The resulting unsaturated polyester composition had the following properties: • Viscosity (Brookfield No. 2 at 20 rpm) - 13.0 poises • Specific gravity - 1.14 The gelation and cure characteristics of di (4-t-butylcyclohexyl) peroxydicarbonate (A-1) ), (a commercially available peroxide product used to cure unsaturated polyester resin compositions), t-butyl peroxydeodecanoate (A-2), (another commercially available peroxide product used to cure unsaturated polyester resin compositions), a-cumyl peroxydeodecanoate (A-3) (a commercial low temperature peroxide initiator) and O-ethyl OO- (3-ethoxycarbonylcarbonyloxy-1,1-dimethylbutyl) monoperoxyoxalate (1-1), a novel monoperoxyoxalate composition of the present invention, were determined using the Standard SPI Exotherm Procedure (Suggested SPI Procedure for Running Exotherm Curves-Polyester Resins, published in the preprint of 24th Annual Technical Conference - Reinforced Plasti cs / Composites Division, Society of the Plastics Industry, Inc., 1969). Using this procedure at 60CC, A-1, A-2, A-3 and 1-1 were evaluated comparatively. The level of 1-1 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 active oxygen content for a 1.0 g level of 1-1 (pure base). The results of this investigation are given in the Table of Example 16 and show that 1-1 gelled and cured the resin much more rapidly than A-1, A-2 and A-3, hence, 1-1, a novel composition of monoperoxioxalate of the present invention, it was much more active to cure the unsaturated polyester resin than the three commercial, lower temperature peroxide catalysts.

Claims (5)

1. Peroxyoxalates from Structure A: O O R1 R3 II II I Q-C-C-OO-C-CH2CH-O-Z R ' wherein R1, R2 and R3 are alkyl radicals of 1 to 4 carbons, and additionally, R3 can be hydrogen and, Q is selected from the group consisting of chlorine, bromine, RO, and R-OO, where R is selected from the group that consists of H, a substituted or unsubstituted alkyl radical of 1 to 24 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 alkenyl radical of 3 to 12 carbons, the substituents being one or more alkyl radicals of less than 1 to 4 carbons, a substituted or unsubstituted aryl radical of 6 to 10 carbons, the substituents 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 carbons optionally having one or more nitrogen or oxygen atoms in the cycloalkane ring, the substituents being one or more lower alkyl radicals from 1 to 4 carbons, a substituted or unsubstituted bicycloalkyl radical of 6 to 14 carbons, the substituents being one or more alkyl radicals of less than 1 to 4 carbons, and, R- being able to be additionally structure (a), Rs R8-OO-C 1 -R 77- R6 (to) where R5 and R6 are alkyl radicals of 1 to 4 carbons, R7 is an unsubstituted alkylene diradical of 1 to 3 carbons or a substituted alkylene diradical of 1 to 3 carbons, the substituents being one or more alkyl radicals of less than 1 to 4 carbons , R8 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 to 13 carbons, t-alkynyl radicals of 5 to 9 carbons, radicals t -aralkyl of 9 to 13 carbons, unsubstituted aroyl radicals of 7 to 11 carbons, substituted aroyl radicals of 7 to 11 carbons, wherein the substituent for the t-alkyl radicals is a t-alkylperoxy radical of 4 to 8 carbons and the substituents for the aroyl radicals are one or more alkyl radicals of less than 1 to 4 carbons, alkoxy radicals of 1 to 4 carbons, phenyl radicals, acyloxy radicals of 2 to 8 carbons, t-alkylperoxycarbonyl radicals of 5 to 9 carbons, t-alkylperoxycarbonyl radicals from 5 to 9 carbons, fluoro, chlorine or bromine, and R8 can also be structures (b), (c) and (d) O O R11 R 13 O II C 1! 1X-L rRR? 1I00 ° -CC "'i | Ì, R12-O-C-, R14-C- -C- 1 J x R11 R 15 (B C D) where x is O or 1, Rs is a substituted or unsubstituted alkyl 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 6-10 carbons, hydroxy, chlorine, bromine or cyano or a substituted or unsubstituted cycloalkyl radical of 5 to 12 carbons optionally having one or more nitrogen or oxygen atoms in the cycloalkane ring, the substituents being one or more alkyl radicals less than 1 to 4 carbons, and, R 10 is selected from a substituted or unsubstituted alkylene diradical of 2 to 3 carbons, the substituents being one or more alkyl radicals less than 1 to 4 carbons, or a diradical 1 , 2-, 1, 3- or 1,4-substituted or unsubstituted phenylene, the substituents being one or more alkyl radicals less than 1 to 4 carbons, chlorine, bromine, nitro or carboxy, and R 11 is a minor alkyl radical of 1 to 4 carbons, and additionally, the two radicals R11 can be concatenated to form a diradical alkylene of 4 to 5 carbons, R12 is an alkyl radical of less than 1 to 4 carbons, R13, R14 and R15 are selected from hydrogens, alkyl radicals of 1 to 8 carbons, aryl radicals from 6 to 10 carbons, alkoxy radicals of 1 to 8 carbons and aryloxy radicals of 6 to 10 carbons, and, R 4 is selected from an unsubstituted t-alkyl radical of 4 to 12 carbons, 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, and a t-aralkyl radical of 9 to 13 carbons, wherein the substituent for the t-alkyl radical is a t-aliperoxy radical of 4 to 8 carbons, preferably R is selected from the group consisting of H, a substituted alkyl radical or unsubstituted from 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, fluoro, chloro, bromo carboxy and cyano, a radical substituted or unsubstituted aralkyl 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, one or more alkyl radicals being less than 1 to 4 carbons , and structure (a), more preferably, R is selection of the group consisting of H, a substituted or unsubstituted alkyl radical 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 , fluoro, chloro, bromo, carboxy and cyano, a substituted or unsubstituted cycloalkyl radical of 5 to 12 carbons, the substituents being one or more alkyl radicals less than 1 to 4 carbons, and structure (a), and, Z is selected of the group consisting of hydrogen and the structures (e), (f) and (g), O O O O II II -C-C-Q, -C-O-R16, -C-R1β (e) (f) (g) wherein R1ß is selected from the group consisting of a substituted or unsubstituted alkyl radical of 1 to 24 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 19 carbons, chlorine, bromine, carboxy and cyano, a substituted or unsubstituted alkenyl radical of 3 to 12 carbons, the substituents being one or more alkyl radicals of less than 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 carbons optionally having one or more nitrogen or oxygen atoms in the cycloalkane ring, The substituents include one or more alkyl radicals of less than 1 to 4 carbons, and a bicycloalkyl substituted or unsubstituted radical of 6 to 10 carbons, the substituents being one or more alkyl radicals of less than 1 to 4 carbons.

2. A monoperoxioxalate as defined in claim 1 selected from the group consisting of: O -ethyl OO- (3-ethoxycarbonyloxycarbonyloxy-1,1-dimethylbutyl) monoperoxyoxalate, OO- [3- (4-methyl-2-pentoxycarbonylcarbonyloxy) -1, 1-dimethylbutyl] O- (4-methyl-2-pentyl) monoperoxioxalate, OO- [3- (3-t-butylperoxy-1,3-dimethyl-butoxycarbonylcarbonyloxy) -1, 1-dimethylbutyl] O- (3-t-butylperoxy-1,3-dimethylbutyl) monoperoxyoxalate, 1,3-dimet L-3- (chlorocarbonylcarbonylperoxy) butyl chlorooxalate, O -ethyl OO- (3-hydroxy-1,1-dimethylbutyl) monoperoxyoxalate, O- (2-ethylhexyl) OO- (3-hydroxy-1,1-dimethylbutyl) monoperoxyoxalate, O- (2-ethylhexyl) OO- [3- (2-ethylhexoycarbonyl-carbonyloxy) -1, 1-dimethylbutyl] monoperoxyoxalate, Ot-butyl OO- (3-t-butoxycarbonylcarbonyloxy) -1, 1-dimethylbutyl] monoperoxyoxalate, O-neopentyl OO- (3-neopentoxycarbonylcarbonyloxy-1,1-dimethylbutyl) monoperoxyoxalate, O-benzyl O- (3-benzyloxycarbonylcarbonyloxy-1,1-dimethylbutyl) monoperoxyoxalate, O-hexafluoroamyl OO- (3-hexafluoroaminoxycarbonylcarbonyloxy-1, 1-dimethylbutyl) monoperoxioxalate, and t-butyl 3-t-butylperoxy rbonylcarbonyloxy-1,1-dimethylbutyl diperoxyoxalate.

3. A monoperoxioxalate as defined in claim 1 wherein Z is the structure (e).

4. A monoperoxioxalate as defined in claim 1 wherein Z is hydrogen.

5. A process for the use of monoperoxyoxalates as defined in claim 1 as free radical initiators for the curing of unsaturated polyester resin compositions by heating such resins in the presence of amounts initiators of the novel peroxide compositions of claim 1 at the appropriate temperatures. A process for the use of the monoperoxioxalates as defined in claim 1 as free radical initiators for ethylenically polymerizing unsaturated monomers (such as styrene, ethylene, etc.) by using initiator amounts of the novel peroxide compositions of claim 1 at the appropriate temperatures.