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    • 专利摘要:
    A novel peroxide composition of Structure A,and use of the novel oxalic acid peroxidecomposition of Structure A as an initiator; a)for curing of unsaturated polyester resins, b)for polymerizing ethylenically unsaturatedmonomers, c) for crosslinking of polyolefins,d) for curing of elastomers, e) for modifyingpolyolefins, f) for grafting of vinyl monomersonto polymer backbones and g) for compatibilizingblends of two or more incompatible polymers aredisclosed.
    公开号:EP0850927A1
    申请号:EP97122764
    申请日:1997-12-23
    公开日:1998-07-01
    发明作者:Jose Sanchez；Daryl Lee Stein
    申请人:Elf Atochem North America Inc；
    IPC主号:C08K5-00
    专利说明:
    This Application claims priority from ProvisionalApplication S/N 60/034,526, filed December 30, 1996. BACKGROUND OF THE INVENTIONa) Field of the Invention
    This invention relates to new and novelcompositions of matter classified in the art ofchemistry as oxalic acid peroxide compositions ofStructure A,
       [The definitions of R, R1, R2, R3, Z, and nare given in the SUMMARY OF THE INVENTION]e.g., allyl 3-t-butylperoxy-1,3-dimethylbutyl oxalate, and use of the novel oxalic acid peroxide compositionsof Structure A. The compositions possess inherentapplied use characteristics making them suitable foruse as initiators a) for polymerizing ethylenicallyunsaturated monomers, b) for curing of unsaturatedpolyester resins, c) for curing of elastomers, d) forcrosslinking of polyolefins, e) for modifyingpolyolefins, f) for grafting of vinyl monomers ontopolymer backbones and g) for compatibilizing blends oftwo or more incompatible polymers.
    There is a need in the polymer industry forefficient, free-radical crosslinking agents for olefinpolymers which give longer scorch times and yet resultin faster crosslinking rates. Because of its low meltflow high density polyethylene (HDPE) must becompounded with peroxides at temperatures where thescorch time is relatively short. If the scorch timeis too short, premature crosslinking of HDPE occursduring the peroxide compounding step. This is highlyundesirable. In the crosslinking of HDPE the peroxidethat is predominantly used for crosslinking is2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne (Lupersol130; manufactured by ELF ATOCHEM North America, Inc.).Of all the commercial organic peroxides, Lupersol 130has the highest 10 hour half-life temperature (131°C).The 10 hour half-life temperature of an initiator isdefined as the temperature at which 50% of theinitiator will decompose in 10 hours. Generally, thehigher the 10 hour half-life temperature the longerthe scorch time at a given temperature.
    Although Lupersol 130 gives adequate scorch timeswhen compounded into HDPE, polymer producers complainof the noxious decomposition products that Lupersol130 produces during crosslinking of polyethylene. Thenoxious decomposition products are thought to bederived from the carbon-carbon triple bond in Lupersol130 since a similar peroxide that lacks thecarbon-carbon triple bond,2,5-dimethyl-2,5-di(t-butylperoxy)hexane, does notproduce noxious decomposition products. An efficientpolyethylene crosslinking agent which yieldslengthened scorch times and produces less noxiousdecomposition products is needed by the polyethylenecrosslinking industry.
    A novel oxalic acid peroxide composition of theinstant invention, allyl 3-t-butylperoxy-1,3-dimethylbutyloxalate, satisfied most of thesecrosslinking criteria and was found to be a moreeffective HDPE crosslinking agent than was Lupersol130. At 385°F in HDPE, allyl 3-t-butylperoxy-1,3-dimethylbutyloxalate was found to be significantlymore efficient than Lupersol 130 on an equivalentbasis and was found to crosslink HDPE much morerapidly than Lupersol 130. Hence, it was superior toLupersol 130 for crosslinking of HDPE. Because allyl3-t-butylperoxy-1,3-dimethylbutyl oxalate contains nocarbon-carbon triple bond, generation of noxiousdecomposition products during crosslinking ofpolyethylene is unlikely.
    In recent years most of the new polymeric materials that have been commercialized are polymericblends and alloys composed of two or more differentpolymers. The reasons for this trend to commercialdevelopment of polymer blends and alloys include theshort time required for development andcommercialization of these materials, the relativelylow cost involved in carrying out the R&D effortneeded to develop these materials compared todevelopment of entirely new polymers from monomers,and the ability to develop polymeric blends and alloysthat are "tailor made" to meet end use propertyspecifications, hence, they are neitherover-engineered nor under-engineered, but just right.
    The polymer property improvements achieved byblending include: Better processability Impact strength enhancement Improved flame retardance Improved barrier properties Improved tensile properties Improved adhesion Improved melt flow Enhanced heat distortion temperature (HDT) Enhanced heat resistance Improved stiffness Improved chemical resistance Improved ultraviolet light stability

    The major problem encountered in developing newblends and alloys is the inherent incompatibility or immiscibility of almost all mixtures of two or morepolymers. The consequence of incompatibility ofpolymeric blends and alloys is that they are unstableand, with sufficient time and temperature, formseparate phases, thus physical properties of thepolymeric blends and alloys suffer. Generally, resincompounders have found that block and graft copolymershaving polymeric segments that are compatible with theindividual polymer components of blends and alloysenable formation of blends and alloys having enhancedphase stabilities and physical properties.
    Low cost blends and alloys are commerciallyproduced from two or more addition polymers such asblends involving low density polyethylene (LDPE),linear low density polyethylene (LLDPE), high densitypolyethylene (HDPE) and polypropylene (PP). Thecompatibility of these low cost blends can be improvedby crosslinking with peroxides or by use ofcompatibilizing block or graft copolymers as mentionedabove.
    An important use of peroxides such as the noveloxalic acid peroxide compositions of Structure A istheir utility in preparing graft copolymers useful forcompatibilizing polymeric blends and alloys. Thenovel oxalic acid peroxide compositions of Structure Aof the instant invention, are effective in thepreparation of graft copolymer compositions. Suchgraft copolymers have utility in compatibilizingpolymer blends and alloys. b) Description of the Prior Art
    US Patent 3,236,872 (02/22/66, to LaporteChemical, Ltd.) discloses hydroxy-peroxides of thestructure:
    (wherein R- is a H-, an acyl, an aroyl or alkyl group,especially the t-butyl group, t-amyl or the hexyleneglycol residue; R'- is an H- or an acyl, aroyl oralkyl group.)
    US Patent 4,525,308 (06/25/85, to Pennwalt Corp.)and US Patent 4,634,753 (01/06/87, to Pennwalt Corp.)disclose hydroxy-peroxyesters (above structure whereR'- is H- and R- is an acyl group) having 10 hourhalf-life temperatures below about 75°C.
    US Patent 3,853,957 (12/10/74, to Pennwalt Corp.)discloses diperoxyketals and ketone peroxidescontaining hydroxy and acyloxy groups.
    US Patent 3,846,396 (11/05/74, to Pennwalt Corp.)and US Patent 3,725,455 (04/03/73, to Pennwalt Corp.)disclose coupled peroxides of the structure,R―W―R'where R- and R'- are identical and are peroxidecontaining alkoxy radicals having at least two carbonsand an oxygen atom between the peroxide groups (-OO-) of the R- and R'- groups and -W- is a diradicalselected from the class consisting of severaldiradical structures including,

    US Patent 3,846,396 and US Patent 3,725,455 areclose art when -W- is -C(O)-C(O)-. However, thestructures of this art do not anticipate thecompositions of Structure A.
    US Patent 3,706,818 (12/19/72, to Pennwalt Corp.)and US Patent 3,839,390 (10/01/74, to Pennwalt Corp.)disclose sequential polyperoxides possessing peroxidemoieties of differing structures and activities in thesame molecule. The structures of this art do notanticipate the sequential polyperoxides of StructureA.
    US Patent 3,671,651 (06/20/72, to Pennwalt Corp.)discloses peroxy compounds containing haloformate(e.g., chloroformate and carbonyl chloride) groups.Some of the novel oxalic acid peroxide compositions ofStructure A contain the chlorooxalate group,-O-C(O)-C(O)-Cl, which is different, easier toincorporate onto a hydroxy-peroxy compound than is ahaloformate group (especially when the hydroxyl groupis a secondary or a tertiary hydroxyl group) and whichis more reactive in subsequent reactions than ahaloformate (i.e., with a secondary or a tertiaryhydroxyl compound and/or in the absence of a base).Hence, the novel oxalic acid peroxide compositions of Structure A advance the art over that disclosed in USPatent 3,671,651.
    US Patent 3,660,468 (05/02/72, to Pennwalt Corp.)discloses peroxyester compounds containing carboxygroups. The carboxy compounds of Structure A containthe -O-C(O)-C(O)-OH group which is significantlydifferent than the carboxy group of thecarboxy-containing peroxyesters of USPatent 3,660,468. In addition, the carboxycompositions of Structure A are more easily producedthan are the carboxy-containing peroxyesters of USPatent 3,660,468.c) Definitions
    In the instant invention, t-cycloalkyl refers tothe monoradical structure,
    where t is 0 to 2 and Rx is a lower alkyl radical of 1to 4 carbons, t-alkynyl is the monoradical structure,
    where Ry is hydrogen or a lower alkyl radical of 1 to4 carbons, and t-aralkyl is the monoradical structure,
    where Rz is an aryl radical of 6 to 10 carbons.
    When any generalized functional group or index,such as R, R1, R2, x, n, etc., appears more than oncein a general formula or structure, the meaning of eachis independent of one another. SUMMARY OF THE INVENTION
    The invention provides in a composition aspect, anovel oxalic acid peroxide composition of Structure A:
    where n is 1 or 2, and R is selected from thegroup consisting of a t-alkyl radical of 4 to 12carbons, a t-cycloalkyl radical of 6 to 13 carbons, at-alkynyl radical of 5 to 9 carbons, a t-aralkylradical of 9 to 13 carbons and the structures (a),(b), (c), (d) and (e),
    where R4 and R5 are the same or different and areselected from the group consisting of hydrogen, loweralkyl radicals of 1 to 4 carbons, alkoxy radicals of 1to 4 carbons, phenyl radicals, acyloxy radicals of 2to 8 carbons, t-alkylperoxycarbonyl radicals of 5 to 9carbons, hydroxy, fluoro, chloro or bromo, and, x is 0 or 1, R6 is a substituted or unsubstitutedalkyl radical of 1 to 18 carbons, substituents beingone or more alkyl radicals of 1 to 6 carbons,t-alkylperoxy radicals of 4 to 8 carbons, alkoxyradicals of 1 to 6 carbons, aryloxy radicals of 6 to10 carbons, hydroxy, chloro, bromo or cyano, and asubstituted or unsubstituted cycloalkyl radical of 5to 12 carbons optionally having an oxygen atom or anitrogen atom in the cycloalkane ring, withsubstituents being one or more lower alkyl radicals of1 to 4 carbons, and, R7 is selected from a substituted or unsubstituted alkylene diradical of 2 to 3 carbons,substituents being one or more lower alkyl radicals of1 to 4 carbons, and substituted or unsubstituted 1,2-,1,3- and 1,4-phenylene diradicals, substituents beingone or more lower alkyl radicals of 1 to 4 carbons,chloro, bromo, nitro or carboxy, and, R8 is a lower alkyl radical of 1 to 4 carbons,and, additionally, the two R8 radicals may beconcatenated to form an alkylene diradical of 4 to 5carbons, and, R9 is a lower alkyl radical of 1 to 4 carbons,and, R10, R11, and R12 can be the same or differentand are selected from the group consisting ofhydrogen, alkyl radicals of 1 to 8 carbons, arylradicals of 6 to 10 carbons, alkoxy radicals of 1 to 8carbons and aryloxy radicals of 6 to 10 carbons, and, R1 and R2 are lower alkyl radicals of 1 to 4carbons, and, when R is selected from a t-alkylradical of 4 to 12 carbons R2 can additionally be at-alkylperoxy radical of 4 to 12 carbons, R3 isselected from the group consisting of a substituted orunsubstituted alkylene diradical of 2 to 4 carbons anda substituted or unsubstituted alkynylene diradical of2 to 4 carbons, substituents being one or more loweralkyl radicals of 1 to 4 carbons, and, when n is 1, Z is selected from the groupconsisting of OR13, NR13R14, OO-R, Cl and Br, whereR13 and R14 are the same or different and are selectedfrom the group consisting of hydrogen, substituted or unsubstituted alkyl radicals of 1 to 18 carbons,substituents being one or more alkyl radicals of 1 to6 carbons, alkoxy radicals of 1 to 6 carbons, aryloxyradicals of 6 to 10 carbons, acryoyloxy radicals,methacryloyloxy radicals, chloro, bromo and cyano,substituted or unsubstituted alkenyl radicals of 3 to12 carbons, substituents being one or more lower alkylradicals of 1 to 4 carbons, substituted orunsubstituted aryl radicals of 6 to 10 carbons,substituents being one or more alkyl radicals of 1 to6 carbons, alkoxy radicals of 1 to 6 carbons, aryloxyradicals of 6 to 10 carbons, chloro, bromo and cyano,substituted or unsubstituted aralkyl radicals of 7 to11 carbons, substituents being one or more alkylradicals of 1 to 6 carbons, alkoxy radicals of 1 to 6carbons, aryloxy radicals of 6 to 10 carbons, chloro,bromo and cyano, and substituted or unsubstitutedcycloalkyl radicals of 5 to 12 carbons optionallyhaving an oxygen atom or a nitrogen atom in thecycloalkane ring, with substituents being one or morelower alkyl radicals of 1 to 4 carbons, and Z is alsoselected from structure (g),
    R15 is selected from the definitions of R, withthe proviso that R and R15 are not the same, and when n is 2, Z is selected from the groupconsisting of structures (h), (i), and (j), -O-R16-O- (h), -NR13-R16-NR14- (i), -NR13-R16-O- (j), R16 is selected from the group consisting ofsubstituted or unsubstituted alkylene diradicals of 2to 10 carbons, substituents being one or more loweralkyl radicals of 1 to 4 carbons, and arylenediradicals of 6 to 14 carbons, substituents being oneor more lower alkyl radicals of 1 to 4 carbons.

    B. The invention provides in a process aspect aprocess for use of the oxalic acid peroxidecompositions of Structure A as free-radicalinitiators, in effective initiating amounts, for theinitiation of free-radical reactions selected from thegroup consisting of: a. curing of unsaturated polyester resincompositions, b. polymerizing ethylenically unsaturatedmonomers (such as styrene, ethylene)compositions, c. crosslinking of olefin thermoplastic polymercompositions, d. curing of elastomer compositions, e. modifying polyolefin compositions, f. grafting of ethylenically unsaturated monomersubstrates onto olefin homo- and copolymersubstrates, and, g. compatibilizing blends of two or morenormally incompatible polymer substrates; which comprises heating said substrates in the presence of an effective initiating amount of one ormore peroxides as defined in A. above, for a timesufficient to at least partially decompose saidperoxide, to perform the free-radical reaction.
    DETAILED DESCRIPTION Novel Oxalic Acid Peroxide Compositions of Structure A -Preparative Methods
    The novel oxalic acid peroxide compositions ofStructure A can be prepared by several methods.
    One method involves reacting a hydroxy-peroxideof Structure Y with an oxalyl halide of Structure X inthe presence of an optional base and an optionalsolvent to form a novel composition of Structure A:
       [R is as previously defined and Q = Br or Cl]
    Hydroxy-peroxides of Structure Y, where R = t-alkyl,t-cycloalkyl, t-alkynyl, t-aralkyl and HO-R3-C(R1)(R2)-,are known in the art (U.S. Patent3,236,872).
    Hydroxy-peroxides of Structure Y, where R =structure (a), can be prepared by reacting asubstituted or unsubstituted benzoyl halide of Structure W with a hydroxy-hydroperoxide of StructureV in the presence of a base and an optional solvent:

    Hydroxy-peroxides of Structure Y, where R =structure (b) and x = 0, can be prepared by reactingalkyl haloformates of Structure U with a hydroxy-hydroperoxideof Structure V in the presence of a baseand an optional solvent:

    Hydroxy-peroxides of Structure Y, where R =structure (b) and x = 1, can be prepared by reactingan ester carboxylic acid halide of Structure T with ahydroxy-hydroperoxide of Structure V in the presenceof a base and an optional solvent:

    Hydroxy-peroxides of Structure Y, where R =structure (c), can be prepared by reacting anunsaturated ether of Structure S with a hydroxy-hydroperoxideof Structure V in the presence of anoptional acid and an optional solvent:
    [Where R19 contains one less methylene diradical thanR8]
    Some hydroxy-peroxides of Structure Y, where R isstructure (d) are known in the art (U.S. Patent4,525,308). This class of hydroxy-peroxides can besynthesized by reacting hydroperoxides of structure Vwith carboxylic acid halides or anhydrides of stuctureP in the presence of an optional base and an optionalsolvent:

    Non-limiting examples of suitable optionalinorganic bases that are useful in the syntheticprocesses of this invention include sodium hydroxide,sodium carbonate, sodium hydrogen carbonate, potassiumhydroxide, potassium carbonate, potassium hydrogencarbonate, calcium hydroxide, barium hydroxide,magnesium hydroxide, calcium carbonate and trisodiumphosphate. Non-limiting examples of suitable optionalorganic bases useful for preparing the peroxidecompositions of this invention include trimethylamine,triethylamine, tributylamine,1,4-diazabicyclo[2.2.2]octane, pyridine,N,N-dimethylaniline, N,N-diethylaniline,p-N,N-dimethylaminopyridine, tetramethylurea andmethylpyridines.
    Non-limiting examples of suitable optionalsolvents include pentane, hexanes, heptanes,dodecanes, odorless mineral spirits mixtures, toluene,xylenes, cumene, methylene chloride, ethyl acetate,2-ethylhexyl acetate, isobutyl isobutyrate, dimethyl adipate, dimethyl succinate, dimethyl glutarate (ormixtures thereof), dimethyl phthalate, dibutylphthalate, benzyl butyl phthalate, diethyl ether,methyl t-butyl ether, 2-methoxyethyl acetate andothers.
    Non-limiting examples of suitable optional acidsthat are useful in the synthetic processes of thisinvention include hydrochloric acid, perchloric acid,phosphoric acid, sulfuric acid, sodium hydrogensulfate, potassium hydrogen sulfate, acetic acid,trifluoroacetic acid, methanesulfonic acid andbenzenesulfonic acid.
    Non-limiting examples of suitablehydroxy-hydroperoxides of Structure V include3-hydroxy-1,1-dimethylpropyl hydroperoxide,3-hydroxy-1,1-dimethylbutyl hydroperoxide and4-hydroxy-1,1-dimethylbutyl hydroperoxide.
    Non-limiting examples of suitable acid halides ofStructure W include benzoyl chloride, 2-methylbenzoylchloride, 2-ethylbenzoyl chloride, 2-methoxybenzoylchloride, 2,6-dimethylbenzoyl chloride,2-phenylbenzoyl chloride, 2-chlorobenzoyl chloride,2,4-dichlorobenzoyl chloride, 2-bromobenzoyl chloride,2-bromobenzoyl bromide, 2-fluorobenzoyl chloride,2-acetoxybenzoyl chloride, and2-(t-butylperoxycarbonyl)benzoyl chloride.Non-limiting examples of suitable carboxylic acidhalides and anhydrides of Structure P include pivaloylchloride, neoheptanoyl chloride, neodecanoyl chloride,neotridecanoyl chloride, 2-ethylbutyryl chloride, 2-ethylhexanoyl chloride, isobutyryl chloride,cyclohexane carboxylic acid chloride, aceticanhydride, propionic anhydride, and isobutyricanhydride
    Non-limiting examples of suitable of alkylhaloformates of Structure U include methylchloroformate, ethyl chloroformate, isopropylchloroformate, isopropyl bromoformate, butylchloroformate, 2-butyl chloroformate, neopentylchloroformate, 2-ethylhexyl chloroformate,2-ethylbutyl chloroformate, 2-butyloctylchloroformate, 4-methyl-2-pentyl chloroformate,dodecyl chloroformate, hexadecyl chloroformate,2-chloroethyl chloroformate, 2-butoxyethylchloroformate, 2-phenoxyethyl chloroformate,cyclohexyl chloroformate, 4-t-butylcyclohexylchloroformate, 3,3,5-trimethylcyclohexylchloroformate, cyclododecyl chloroformate,2,2,6,6-tetramethyl-4-piperidinyl chloroformate (andhydrochloride salt) and 1,2,2,6,6-pentamethyl-4-piperidinylchloroformate (and hydrochloridesalt). The alkyl haloformates of Structure U can beprepared by reacting the corresponding alcohols withexcess phosgene.
    Non-limiting examples of suitable acid halides ofStructure T include 2-methoxycarbonylbenzoyl chloride,2-n-butoxycarbonylbenzoyl chloride,2-(2-ethylhexoxycarbonyl)benzoyl chloride,2-cyclohexoxycarbonyl- benzoyl chloride, 3-ethoxycarbonylpropionylchloride, 4-(n-butoxycarbonyl)butyryl chloride and3,4,5,6-tetrachloro-2-methoxycarbonylbenzoyl chloride.
    The acid halides of Structures W, T, and P can beprepared by treating the corresponding carboxylicacids with acid halogenating agents such as PCl3,POCl5, PCl5, thionyl chloride, thionyl bromide,phosgene (in the presence of catalysts such asdimethylforamide, DMF), benzotrichloride and others.
    Non-limiting examples of suitable unsaturatedethers of Structure S include methyl isopropenylether, ethyl isopropenyl ether, n-butyl isopropenylether, 1-methoxy-1-cyclohexene, 1-ethoxy-1-cyclohexeneand 1-methoxy-3,3,5-trimethylcyclohexene.
    Non-limiting examples of suitable hydroxy-peroxidesof Structure Y, where R = structure (a),useful for preparing the novel oxalic acid peroxidecompositions of Structure A, include3-hydroxy-1,1-dimethylpropylperoxy-(2-chlorobenzoate), 3-hydroxy-1,1-dimethylbutylperoxybenzoate, 3-hydroxy-1,1-dimethylbutylperoxy-(2-methylbenzoate), 3-hydroxy-1,1-dimethylbutylperoxy-(2,4-dimethylbenzoate),3-hydroxy-1,1-dimethylbutylperoxy-(2,6-dimethylbenzoate),3-hydroxy-1,1-dimethylbutyl peroxy-(2-fluorobenzoate),3-hydroxy- 1,1-dimethylbutylperoxy-(2-chlorobenzoate), 3-hydroxy-1,1-dimethylbutylperoxy-(2-bromobenzoate),3-hydroxy-1,1-dimethylbutylperoxy-(2,4-dichlorobenzoate), 3-hydroxy-1,1-dimethylbutyl peroxy-(2-phenylbenzoate),3-hydroxy-1,1-dimethylbutyl peroxy(2-methoxybenzoate)and 3-hydroxy-1,1-dimethylbutyl peroxy-(2-acetoxybenzoate).
    Non-limiting examples of suitable hydroxy-peroxidesof Structure Y, where R = structure (b) andx = 0, useful for preparing the novel oxalic acidperoxide compositions of Structure A, includeOO-(3-hydroxy-1,1-dimethylpropyl) O-(2-ethylhexyl)monoperoxycarbonate, OO-(3-hydroxy-1,1-dimethylbutyl)O-isopropyl monoperoxycarbonate,OO-(3-hydroxy-1,1-dimethylbutyl) O-(2-butyl)monoperoxycarbonate, OO-(3-hydroxy-1,1-dimethylbutyl)O-(2-ethylhexyl) monoperoxycarbonate,OO-(3-hydroxy-1,1-dimethylbutyl) O-(2-butyloctyl)monoperoxycarbonate, OO-(3-hydroxy-1,1-dimethylbutyl)O-cyclohexyl monoperoxycarbonate,OO-(3-hydroxy-1,1-dimethylbutyl) O-cyclododecyl)monoperoxycarbonate, OO-(3-hydroxy-1,1-dimethylbutyl)O-(4-t-butylcyclohexyl) monoperoxycarbonate,OO-(3-hydroxy-1,1-dimethylbutyl)O-(2,2,6,6-tetramethyl-4-piperidinyl)monoperoxycarbonate (and salts) and OO-(3-hydroxy-1,1-dimethylbutyl)O-(1,2,2,6,6-pentamethyl-4-piperidinyl)monoperoxycarbonate (and salts).
    Non-limiting examples of suitable hydroxy-peroxidesof Structure Y, where R = structure (b) andx = 1, useful for preparing the novel oxalic acidperoxide compositions of Structure A, include OO-(3-hydroxy-1,1-dimethylbutyl) O-methylmonoperoxyphthalate, OO-(3-hydroxy-1,1-dimethylbutyl)O-n-butyl monoperoxyphthalate,OO-(3-hydroxy-1,1-dimethylbutyl) O-ethylmonoperoxsuccinate andOO-(3-hydroxy-1,1-dimethylbutyl) O-n-butylmonoperoxglutarate.
    Non-limiting examples of suitable hydroxy-peroxidesof Structure Y, where R = structure (c),useful for preparing the novel oxalic acid peroxidecompositions of Structure A, include2-methoxy-2-(3-hydroxy-1,1-dimethylpropylperoxy)propane,2-methoxy-2-(3-hydroxy-1,1-dimethylbutylperoxy)propaneand 1-methoxy-1-(3-hydroxy-1,1-dimethylbutylperoxy)cyclohexane.
    Non-limiting examples of suitable hydroxy-peroxidesof Structure Y, where R = structure (d),useful for preparing the novel oxalic acid peroxidecompositions of Structure A, include3-hydroxy-1,1-dimethylbutyl 2-ethylperoxyhexanoate,3-hydroxy-1,1-dimethylbutyl 2-ethylperoxybutyrate,3-hydroxy-1,1-dimethylbutyl peroxypivalate,3-hydroxy-1,1-dimethylbutyl peroxyneoheptanoate,3-hydroxy-1,1-dimethylbutyl peroxyneodecanoate,3-hydroxy-1,1-dimethylbutyl peroxyisobutyrate,3-hydroxy-1,1-dimethylbutyl peroxypropionate, and3-hydroxy-1,1-dimethylbutyl peroxyacetate.
    Non-limiting examples of suitable oxalyl halides of Structure X, useful for preparing the novel oxalicacid peroxide compositions of Structure A, includeoxalyl bromide, oxalyl chloride, methyl chlorooxalate,ethyl chlorooxalate, butyl chlorooxalate, dodecylchlorooxalate, allyl chlorooxalate, phenylchlorooxalate, cyclohexyl chlorooxalate and benzylchlorooxalate. Novel oxalic acid peroxidecompositions of Structure A', a reactive set ofcompounds of Structure A when n is 1 and Z is Cl orBr, are useful oxalyl halides in the syntheticprocesses of this invention. Compounds of StructureA' can react with water or alcohols (HO-R13) in thepresence of bases and optional solvents (followed byacidification when water is reacted) to form noveloxalate peroxides possessing the oxalate group[-O-C(O)C(O)-O-R13]:
    Structure A'[Z = Br or Cl]
    or A' can react with glycols (HOR16OH) in the presenceof optional bases and optional solvents to form noveloxalate peroxides possessing bis(oxalate) groups[-OC(O)C(O)-OR16O-C(O)C(O)O-]:
    or A' can react with amines (HNR13R14) in the presenceof optional bases and optional solvents to form novelperoxides possessing the oxamate group [-O-C(O)C(O)-NR13R14]:
    or A' can react with diamines (HNR13R16R14NH) in thepresence of optional bases and optional solvents toform novel peroxides possessing bis(oxamate) groups[-OC(O)C(O)-N(R13)R16N(R14)-C(O)C(O)O-]:
    or A' can react with amino-alcohols (HNR13R16OH) inthe presence of optional bases and optional solventsto form novel peroxides possessing oxamate-oxalategroups [-OC(O)C(O)-N(R13)R16-O-C(O)C(O)O-]:
    or A' can react with hydroperoxides (HOO-R) in the presence of bases and optional solvents to form novelperoxides possessing the monoperoxyoxalate group[-O-C(O)C(O)-OO-R]:
    or A' can react with a hydroxy-peroxide of StructureN,
    in the presence of bases and optional solvents, toform novel unsymmetrical diperoxide oxalates:


    Non-limiting examples of suitable oxalyl halidesof Structure A', useful for preparing the noveloxalate peroxides, oxamate peroxides,monoperoxyoxalate peroxides and unsymmetricaldiperoxide oxalates of this invention, include3-t-butylperoxy-1,1-dimethylbutyl chlorooxalate, 3-t-butylperoxy-1,1-dimethylpropylchlorooxalate,3-t-butylperoxy-1,1-dimethylbutyl bromooxalate,di-(3-chlorocarbonylcarbonyloxy-1,1-dimethylbutyl)peroxide, 3-chlorocarbonylcarbonyloxy-1,1-dimethylbutyl peroxy-2-ethylhexanoate,3-chlorocarbonylcarbonyloxy-1,1-dimethylbutylperoxyneoheptanoate, 3-chlorocarbonylcarbonyloxy-1,1-dimethylbutylperoxy-2-methylbenzoate, OO-(3-chlorocarbonylcarbonyloxy-1,1-dimethylbutyl)O-ethylmonoperoxysuccinate and2-(3-chlorocarbonylcarbonyloxy-1,1-dimethylbutylperoxy)-2-methoxypropane.
    Non-limiting examples of suitable alcohols (HO-R13),useful for reacting with A' to prepare the noveloxalate peroxides of Structure A, include methanol,isopropanol, butanol, dodecanol, cyclohexanol, allylalcohol, methallyl alcohol, phenol, benzyl alcohol, 2-hydroxyethylacrylate and methacrylate, ethyleneglycol and butylene glycol.
    Non-limiting examples of suitable diols (HO-R16-OH),useful for reacting with A' to prepare the novelbis(oxalate) peroxides of Structure A, includeethylene 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 thenovel oxamate peroxides of Structure A, includemethylamine, isopropylamine, butylamine, t-butylamine,dodecylamine, cyclohexylamine, allylamine, aniline andbenzylamine.
    Non-limiting examples of suitable diamines(HNR13R16R14NH), useful for reacting with A' toprepare 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 preparethe novel oxamate-oxalate peroxides of Structure A,include ethanolamine, N-methylethanolamine andpropanolamine.
    Non-limiting examples of suitable hydroperoxides(HOO-R), useful for reacting with A' to prepare thenovel monoperoxyoxalate peroxides of Structure A,include t-butyl hydroperoxide, t-amyl hydroperoxide,t-hexyl hydroperoxide, 1,1,3,3-tetramethylbutylhydroperoxide, 4-(t-butylperoxy)-1,1,4,4-tetramethylbutylhydroperoxide, paramenthanehydroperoxide, and α-cumyl hydroperoxide. Novel Oxalic Acid Peroxide Compositions of Structure A -Illustrative Examples
    Non-limiting examples of the novel oxalic acidperoxide compositions of Structure A, in addition tothose in the working examples, include the following:3-t-Butylperoxy-1,1-dimethylpropyl chlorooxalate,3-t-butylperoxy-1,1-dimethylbutyl bromooxalate,3-chlorocarbonylcarbonyloxy-1,1-dimethylbutyl peroxy-2-ethylhexanoate,3-chlorocarbonylcarbonyloxy-1,1-dimethylbutylperoxyneoheptanoate, 3-chlorocarbonylcarbonyloxy-1,1-dimethylbutylperoxy-2-methylbenzoate,OO-(3-chlorocarbonylcarbonyloxy-1,1-dimethylbutyl) O-ethyl monoperoxysuccinate,2-(3-chlorocarbonylcarbonyloxy-1,1-dimethylbutylperoxy)-2-methoxypropane,3-t-butylperoxy-1,1-dimethylpropyl hydrogen oxalate,3-hydroxycarbonylcarbonyloxy-1,1-dimethylbutyl peroxy-2-ethylhexanoate,3-hydroxycarbonylcarbonyloxy-1,1-dimethylbutylperoxyneoheptanoate, 3-hydroxycarbonylcarbonyloxy-1,1-dimethylbutylperoxy-2-methylbenzoate,OO-(3-hydroxycarbonylcarbonyloxy-1,1-dimethylbutyl) O-ethylmonoperoxysuccinate,di-(3-hydroxycarbonylcarbonyloxy-1,1-dimethylbutyl)peroxide,3-t-butylperoxy-1,1-dimethylbutyl butyl oxalate,3-t-butylperoxy-1,1-dimethylpropyl butyl oxalate,allyl 3-t-butylperoxy-1,1-dimethylpropyl oxalate,3-t-butylperoxy-1,1-dimethylbutyl methyl oxalate,3-t-butylperoxy-1,1-dimethylbutyl dodecyl oxalate,3-t-butylperoxy-1,1-dimethylbutyl cyclohexyl oxalate,3-t-butylperoxy-1,1-dimethylbutyl phenyl oxalate,3-t-butylperoxy-1,1-dimethylbutyl 2-acryloyloxyethyloxalate,3-t-butylperoxy-1,1-dimethylbutyl benzyl oxalate,di-(3-ethoxycarbonylcarbonyloxy-1,1-dimethylbutyl)peroxide,di-(3-allyloxycarbonylcarbonyloxy-1,1-dimethylbutyl)peroxide,OO-(3-butoxycarbonylcarbonyloxy-1,1-dimethylbutyl) O-ethylmonoperoxysuccinate,N-butyl 3-t-butylperoxy-1,1-dimethylbutyl oxamate, N-butyl 3-t-butylperoxy-1,1-dimethylpropyl oxamate,N-allyl 3-t-butylperoxy-1,1-dimethylpropyl oxamate,N-methyl 3-t-butylperoxy-1,1-dimethylbutyl oxamate,N-dodecyl 3-t-butylperoxy-1,1-dimethylbutyl oxamate,N-cyclohexyl 3-t-butylperoxy-1,1-dimethylbutyloxamate,N-phenyl 3-t-butylperoxy-1,1-dimethylbutyl phenyloxamate,3-t-butylperoxy-1,1-dimethylbutyl oxamate,di-(3-allylaminocarbonylcarbonyloxy-1,1-dimethylbutyl)peroxide,OO-(3-butylaminocarbonylcarbonyloxy-1,1-dimethylbutyl)O-ethyl monoperoxysuccinate,OO-t-butyl O-(3-t-butylperoxy-1,1-dimethylbutyl)monoperoxyoxalate, OO-t-amyl O-(3-t-butylperoxy-1,1-dimethylbutyl)monoperoxyoxalate, OO-t-butylO-(3-t-butylperoxy-1,1-dimethylpropyl)monoperoxyoxalate,OO-α-cumyl O-(3-t-butylperoxy-1,1-dimethylbutyl)monoperoxyoxalate, OO-(4-t-butylperoxy-1,1,4,4-tetramethylbutyl)O-(3-t-butylperoxy-1,1-dimethylbutyl)monoperoxyoxalate,3-t-butylperoxy-1,1-dimethylbutyl3-(2-ethylhexanoylperoxy)-1,1-dimethylbutyl oxalate,and3-t-butylperoxy-1,1-dimethylbutyl3-(2-methylbenzoylperoxy)-1,1-dimethylbutyl oxalate,and the structures:
    Novel Oxalic Acid Peroxide Compositions of Structure A - UtilityA. Polymerization of Ethylenically Unsaturated Monomers
    In the free-radical polymerizations ofethylenically unsaturated monomers at suitabletemperatures and pressures the novel oxalic acidperoxide compositions of Structure A of this inventionwere found to be effective initiators with respect toefficiency (reduced initiator requirements, etc.).Ethylenically unsaturated monomers include olefins,such as ethylene, propylene, styrene,alpha-methylstyrene, p-methylstyrene, chlorostyrenes,bromostyrenes, vinylbenzyl chloride, vinylpyridine anddivinylbenzene; diolefins, such as 1,3-butadiene,isoprene and chloroprene; vinyl esters, such as vinyl acetate, vinyl propionate, vinyl laurate, vinylbenzoate and divinyl carbonate; unsaturated nitriles,such as acrylonitrile and methacrylonitrile; acrylicacid and methacrylic acid and their anhydrides, estersand amides, such as acrylic acid anhydride, alkyl,methyl, ethyl, n-butyl, 2-hydroxyethyl, glycidyl,lauryl and 2-ethylhexyl acrylates and methacrylates,and acrylamide and methacrylamide; maleic anhydrideand itaconic anhydride; maleic, itaconic and fumaricacids and their esters; vinyl halo and vinylidenedihalo compounds, such as vinyl chloride, vinylbromide, vinyl fluoride, vinylidene chloride andvinylidene fluoride; perhalo olefins, such astetrafluoroethylene, hexafluoropropylene andchlorotrifluoroethylene; vinyl ethers, such as methylvinyl ether, ethyl vinyl ether and n-butyl vinylether; allyl esters, such as allyl acetate, allylbenzoate, allyl ethyl carbonate, triallyl phosphate,diallyl phthalate, diallyl fumarate, diallylglutarate, diallyl adipate, diallyl carbonatediethylene glycol bis(allyl carbonate) (i.e., ADC);acrolein; methyl vinyl ketone; or mixtures thereof.
    Temperatures of 0°C to 180°C, preferably 20°C to160°C, more preferably 30°C to 150°C and levels ofnovel oxalic acid peroxide compositions of Structure A(on a pure basis) of 0.002 to 3%, preferably 0.005% to1%, more preferably 0.01% to 0.75% by weight based onmonomer, are normally employed in conventionalpolymerizations and copolymerizations of ethylenicallyunsaturated monomers. The novel oxalic acid peroxide compositions of this invention can be used incombination with other free-radical initiators such asthose disclosed at the bottom of column 4 and the topof column 5 of U.S. Patent 4,525,308. Using theperoxide compositions of this invention in combinationwith these initiators adds flexibility to theprocesses of polymer producers and allows them to"fine tune" their polymerization processes.B. Curing of Unsaturated Polyester Resins
    In the curing of unsaturated resin compositionsby heating at suitable curing temperatures in thepresence of free-radical curing agents, the noveloxalic acid peroxide compositions of Structure A ofthis invention exhibit enhanced curing activity in thecurable unsaturated polyester resin compositions.Unsaturated polyester resins that can be cured by thenovel oxalic acid peroxide compositions of thisinvention usually include an unsaturated polyester andone or more ethylenically unsaturated monomers.
    The unsaturated polyesters are, for instance,polyesters as they are obtained by esterifying atleast one ethylenically unsaturated di- orpolycarboxylic acid, anhydride or acid halide, such asmaleic acid, fumaric acid, glutaconic acid, itaconicacid, mesaconic acid, citraconic acid, allylmalonicacid, tetrahydrophthalic acid, and others, withsaturated and unsaturated di- or polyols, such asethylene glycol, diethylene glycol, triethylene glycol, 1,2- and 1,3-propanediols, 1,2-, 1,3- and1,4-butanediols, 2,2-dimethyl-1,3-propanediol,2-hydroxymethyl-2-methyl-1,3-propanediol,2-buten-1,4-diol, 2-butyn-1,4-diol,2,4,4-trimethyl-1,3-pentanediol, glycerol, pentaerythritol,mannitol and others. Mixtures of such di- orpolyacids and/or mixtures of such di- or polyolsmay also be used. The di- or polycarboxylic acids maybe partially replaced by saturated di- orpolycarboxylic acids, such as adipic acid, succinicacid, sebacic acid and other, and/or by aromatic di- orpolycarboxylic acids, such as phthalic acid,trimellitic acid, pyromellitic acid, isophthalic acidand terephthalic acid. The acids used may besubstituted by groups such as halogen. Examples ofsuch suitable halogenated acids are, for instance,tetrachlorophthalic acid, tetrabromophthalic acid,5,6-dicarboxy-1,2,3,4,7,7-hexachlorobicyclo(2.2.1)-2-hepteneandothers.
    The other component of the unsaturated polyesterresin composition, the polymerizable monomer ormonomers, can preferably be ethylenically unsaturatedmonomers, such as styrene, alpha-methylstyrene,p-methylstyrene, chlorostyrenes, bromostyrenes,vinylbenzyl chloride, divinylbenzene, diallyl maleate,dibutyl fumarate, triallyl phosphate, triallylcyanurate, diallyl phthalate, diallyl fumarate, methylacrylate, methyl methacrylate, n-butyl acrylate,n-butyl methacrylate, ethyl acrylate, and others, or mixtures thereof, which are copolymerizable with saidunsaturated polyesters.
    A preferred unsaturated polyester resincomposition contains as the unsaturated polyestercomponent the esterification product of1,2-propanediol (a polyol), maleic anhydride (ananhydride of an unsaturated polycarboxylic acid) andphthalic anhydride (an anhydride of an aromaticdicarboxylic acid) as well as the monomer component,styrene.
    Other types of unsaturated polyester resincompositions can be cured using the novel oxalic acidperoxide compositions of this invention as curingcatalysts. These resins, called unsaturated vinylester resins, consist of a vinyl ester resin portionand one or more polymerizable monomer components. Thevinyl ester resin component can be made by reacting achloroepoxide, such as epichlorohydrin, withappropriate amounts of a bisphenol such as Bisphenol A[2,2-(4-hydroxyphenyl)propane], in the presence of abase, such as sodium hydroxide, to yield acondensation product having terminal epoxy groupsderived from the chloroepoxide. Subsequent reactionof the condensation product with polymerizableunsaturated carboxylic acids, such as acrylic acid andmethacrylic acid, in the presence or absence of acidicor basic catalysts, results in formation of the vinylester resin component. Normally, styrene is added asthe polymerizable monomer component to complete thepreparation of the unsaturated vinyl ester resin composition.
    Temperatures of about 20°C to 200°C and levels ofnovel oxalic acid peroxide compositions of Structure Aof about 0.05% to 5% or more, preferably 0.10% to 4%,more preferably 0.25% to 3% by weight of curableunsaturated polyester resin composition are normallyemployed.
    The unsaturated polyester resin compositionsdescribed above can be filled with various materials,such as sulfur, glass, carbon and boron fibers, carbonblacks, silicas, metal silicates, clays, metalcarbonates, antioxidants (AO's), heat, ultraviolet(UV) and light stabilizers, sensitizers, dyes,pigments, accelerators, metal oxides, such as zincoxide, blowing agents, nucleating agents and others.C. Curing of Elastomers and Crosslinking of ThermoplasticPolymers
    In the curing of elastomeric compositions, andthe crosslinking of polymer compositions, by heatingat suitable curing and crosslinking temperatures inthe presence of free-radical curing and crosslinkingagents, the novel oxalic acid peroxide compositions ofthis invention exhibit curing and crosslinkingactivities.Elastomeric resin compositions that can be cured
    by the novel oxalic acid peroxide compositions of thisinvention include elastomers such asethylene-propylene copolymers (EPR), ethylene-propylene-diene terpolymers (EPDM),polybutadiene (PBD), silicone rubber (SR), nitrilerubber (NR), neoprene, fluoroelastomers andethylene-vinyl acetate copolymer (EVA).
    Polymer compositions that can be crosslinked bythe novel oxalic acid peroxide compositions of thisinvention include olefin thermoplastics such aschlorinated polyethylene (CPE), low densitypolyethylene (LDPE), linear-low density polyethylene(LLDPE), and high density polyethylene (HDPE).
    Temperatures of about 80°C to 310°C and noveloxalic acid peroxide composition levels of about 0.1%to 10%, preferably 0.5% to 5%, based on weight ofcurable elastomeric resin composition or crosslinkableolefin polymer composition, are normally employed.
    The curable elastomeric resin composition orcrosslinkable polymer composition can be optionallyfilled with the materials listed above for use withthe conventional unsaturated polyester resincompositions.D. Modification of Propylene Homo- and Copolymers
    In the processes for modifying propylenehomopolymers and propylene copolymers (e.g.,beneficial degradation of polypropylene (PP) byreducing the polymer molecular weight and the polymermolecular weight distribution), the novel oxalic acidperoxide compositions of this invention exhibitpolypropylene modification activity.
    Temperatures of about 140°C to 340°C and noveloxalic acid peroxide composition levels of about 0.01%to 1.0% based on weight of modifiable propylenehomopolymers and propylene copolymers are normallyemployed. Optionally, up to 1% by weight of molecularoxygen can be employed as a modification co-catalyst. Novel Oxalic Acid Peroxide Compositions of Structure A -Preparative and Utility Examples
    The following examples further illustrate thebest mode contemplated by the inventors for practicingthe instant invention, and are presented to providedetailed preparative and utility illustrations of theinvention and are not intended to limit the breadthand scope of the invention. Example 1 Preparation of3-t-Butylperoxy-1,3-dimethylbutyl EthylOxalate (I-1)
    A 125 mL Erlenmeyer flask equipped with amagnetic stirring bar was charged with 10.0 g (48.4mmoles) of 92% 3-t-butylperoxy-1,3-dimethylbutanol,7.8 g (77.2 mmoles) of triethylamine, 0.1 g (0.08mmole) of 4-dimethylaminopyridine and 30 g of dryethyl acetate. A clear solution resulted at roomtemperature. To this vigorously stirred solution atroom temperature was slowly added a solutionconsisting of 7.0 g (50.2 mmoles) of ethyl oxalylchloride and 10 g of dry ethyl acetate over a periodof 20 minutes. A precipitate immediately formed andthe flask became warm. It was necessary to cool theflask in order to maintain the temperature around roomtemperature. After a total reaction period of 60minutes, the reaction mass was transferred to a separatory funnel, 100 mL of water was added to thereaction mass and shaken. The aqueous phase wasseparated and discarded. The organic phase was washedonce with aqueous 10% HCl solution, twice with waterand once with dilute aqueous NaHCO3 solution. Theresulting solution was dried over about 10% by weightof anhydrous MgSO4, and, after separation of the spentdesiccant by filtration, the solvent was removed in vacuoleaving 13.9 g (99% of theory, uncorrected) of aclear yellow liquid. The product contained 5.79%active oxygen (theory, 5.51%), therefore, compound I-1,was obtained with an assay of 100% and in acorrected yield of 99%. Gas chromatographic analysisshowed that the product contained less than 0.1% of3-t-butylperoxy-1,3-dimethylbutanol, the startingmaterial. An infrared (IR) spectrum of the productshowed carbonyl bands at 1770 cm-1 and 1745 cm-1 and aperoxide (-OO-) band at 870 cm-1. Example 2. Preparation of3-t-Butylperoxy-1,3-dimethylbutylChlorooxalate (I-2)
    A 250 mL three-neck flask equipped with amagnetic stirrer, a thermometer and an addition funnelwas charged with 25.4 g (200 mmoles) of oxalylchloride and 75 mL of methyl t-butyl ether (MTBE).Then to the resulting solution was added 20.6 g (100mmoles) of 93% 3-t-butylperoxy-1,3-dimethylbutanolover a period of 30 minutes at 22-28°C. The addition funnel was then replaced with a nitrogen gas tube anddry nitrogen gas was slowly bubbled through thereaction mass in order to remove HCl over a period of4 hours at 25-30°C. The MTBE, excess oxalyl chloride,and any remaining gas were removed in vacuo using awater aspirator. Obtained was 28.3 g (101% of theory,uncorrected) of a yellow liquid. An IR spectrum ofthe product showed no OH bands and showed carbonylbands at 1800 cm-1 and 1760 cm-1. The assay of I-2,based upon hydrolyzable chloride content (theory,12.63%; found, 12.37%), was 97.9% and the correctedyield was 98.6%. Example 3. Preparation of3-t-Butylperoxy-1,3-dimethylbutylHydrogen Oxalate (I-3)
    A 50 mL Erlenmeyer flask equipped with a magneticstirrer and a thermometer was charged with 50 g ofwater and 2.8 g (10 mmoles) of3-t-butylperoxy-1,3-dimethylbutyl chlorooxalate andthe resulting mixture was stirred at room temperature.No reaction appeared to be occurring, therefore, 2.1 g(23 mmoles) of NaHCO3 was added. Gas evolutionoccurred and the organic liquid dissolved in theaqueous phase at room temperature. The pH of thesolution was about 9. The aqueous solution was washedtwice with 30 mL portions of MTBE in order to removeneutral impurities. Then the aqueous solution wasacidified with 20 g (27 mmoles) of aqueous 5% HCl solution and a yellow organic liquid formed. Theresulting mixture was extracted twice with 30 mLportions of MTBE. The MTBE extracts were combined,washed once with 50 mL of water, dried over 5% byweight of anhydrous MgSO4, and, after separation ofthe spent desiccant by filtration, the solvent wasremoved in vacuo leaving 2.2 g (85% of theory,uncorrected) of a clear yellow liquid. An IR spectrumof the product showed an acid OH band at about 3200cm-1, a very strong carbonyl band at 1740 cm-1 and aperoxide (-OO-) band at about 875 cm-1.
    Based on the method of preparation, yield data,and IR data the product obtained in this reaction wasI-3. Example 4. Preparation of Allyl3-t-Butylperoxy-1,3-dimethylbutylOxalate (I-4)
    A 100 mL 3-necked flask equipped with a magneticstirring bar, a nitrogen inlet line, a thermometer andan addition funnel was charged with 12.6 g (97.3mmoles) of oxalyl chloride and the flask contents werecooled to 0°C. Then 10.0 g (48.7 mmoles) of 92.6%3-t-butylperoxy-1,3-dimethylbutanol was added dropwiseover 30 minutes while the flask was swept with asteady stream of dry nitrogen. After the addition wascompleted the reaction mass was stirred for 60 minutesat room temperature. A vacuum line was then attachedto the flask in order to distill off the excess oxalyl chloride, however, this was only partially successful.The contents in the flask were diluted with dry ethylacetate and the contents were then transferred to aone-necked flask. The solvent and excess oxalylchloride were then removed using a rotary evaporator.Obtained was a light yellow oil which was cooled to10°C and to it was added 3.0 g (51.7 mmoles) of allylalcohol over a period of 10 minutes while a vigorousstream of dry nitrogen was swept through the reactionmass. The reaction mixture was then diluted withethyl acetate and the solution was stripped on arotary evaporator to remove solvent, HCl and residualallyl alcohol. Obtained was 11.9 g (81% of theory,uncorrected of a light yellow liquid. Gaschromatography (GC) showed a single large peak havingan area % of 98.6. An IR spectrum of the productshowed carbonyl bands at 1770 cm-1 and 1750 cm-1 and aperoxide (-OO-) band at 875 cm-1.
    Based on the method of preparation, yield data,GC data, and IR data the product obtained in thisreaction was I-4.
    A second preparation of I-4 was carried out. A100 mL 3-necked flask equipped with a magneticstirring bar, a nitrogen inlet line, a thermometer andan addition funnel with a side arm was charged with25.9 g (200 mmoles) of oxalyl chloride, dry nitrogengas was bubbled through the oxalyl chloride and theflask contents were cooled to 0°C. Then 20.0 g (97.3mmoles) of 92.6% 3-t-butylperoxy-1,3-dimethylbutanolwas added dropwise at such a rate that the temperature remained below 15°C. The addition took 30 minutes tocomplete. The reaction mass was then stirred for 60minutes at 15°C after which 50 mL of dry ethyl acetatewas added. The contents were then transferred to aone-necked flask and the solvent and excess oxalylchloride were then removed using a rotary evaporator.Obtained was 29.3 g of a light yellow oil. The oilwas cooled to 10°C and to it was added 6.0 g (103.3mmoles) of allyl alcohol over a period of 15 minuteswhile a vigorous stream of dry nitrogen was sweptthrough the reaction mass. The temperature was heldbelow 20°C during the addition of allyl alcohol. Thereaction mixture was then stirred for 60 minutes at15-20°C after which it was stripped on a rotaryevaporator. Obtained was 31.7 g (>100% of theory,uncorrected) of a light yellow liquid. GC showed asingle large peak, 93% by area. An IR spectrum of theproduct showed carbonyl bands at 1770 cm-1 and 1750cm-1 and a peroxide (-OO-) band at 875 cm-1.
    In order to prepare a high purity sample of I-4,11.9 g of the first preparation and 23 g of the secondpreparation were combined and purified by preparativeliquid chromatography using a Walters Prep 500 LiquidChromatograph. Obtained was 30.3 g of I-4 having apurity of 97.6% according to GC analysis. Example 5. Preparation of a mixture of DiallylOxalateDi-(3-t-Butylperoxy-1,3-dimethylbutyl)Oxalate and Allyl 3-t-Butylperoxy-1,3-dimethylbutylOxalate (I-4)
    A 250 mL 3-necked flask equipped with a magneticstirring bar, a nitrogen inlet line, a thermometer andan addition funnel was charged with 4.3 g (30.2mmoles) of oxalyl chloride and 75 mL of MTBE and theflask contents were cooled to 0°C. Then a solution of6.8 g (33.1 mmoles) of 92.6%3-t-butylperoxy-1,3-dimethylbutanol and 3.4 g (33.6mmoles) of triethylamine in 10 mL of MTBE was addeddropwise over 60 minutes at 0-5°C and the solution wasstirred for an additional 30 minutes after theaddition was completed. Then a solution of 1.9 g(32.4 mmoles) of allyl alcohol and 3.4 g (33.6 mmoles)of triethylamine in 10 mL of MTBE was added to theflask contents over a period of 30 minutes. Thereaction mixture was then stirred at room temperaturefor 120 minutes after which the reaction was quenchedwith water. The aqueous phase was separated anddiscarded. The organic phase was washed once withaqueous 10% HCl solution, three times with water andonce with dilute aqueous NaHCO3 solution. The productsolution was dried over 5% by weight of anhydrousMgSO4, and, after separation of the spent desiccant byfiltration, the solvent was removed in vacuo leaving9.4 g (96% of theory, uncorrected) of a clear yellow liquid. An IR spectrum of the product showed carbonylbands at 1770 cm-1 and 1750 cm-1 and a peroxide (-OO-)band at 875 cm-1. GC showed three product peaks atretention times of 21.6 minutes (6% by area, assignedto diallyl oxalate), 33.4 minutes (65% by area,assigned to allyl 3-t-butylperoxy-1,3-dimethylbutyloxalate) and 43.6 minutes [15% by area, assigned todi-(3-t-butylperoxy-1,3-dimethylbutyl) oxalate]. GCalso showed that the product mixture contained lessthan 0.1% allyl alcohol and only 0.2%3-t-butylperoxy-1,3-dimethylbutanol.
    Based on the method of preparation, yield data,GC data, and IR data the product obtained in thisreaction was the desired title product mixture. Example 6. Preparation of3-t-Butylperoxy-1,3-dimethylbutyl3-Neoheptanoylperoxy-1,3-dimethylbutylOxalate (I-5)
    A 250 mL 3-necked flask equipped with a magneticstirring bar, a nitrogen inlet line, a thermometer andan addition funnel was charged with 75 mL of MTBE and2.5 g (19.3 mmoles) of oxalyl chloride and the flaskcontents were cooled to 0°C. Then a solution of 3.9 g(19 mmoles) of 92.6% 3-t-butylperoxy-1,3-dimethylbutanoland 1.5 g (19.0 mmoles)of pyridine in10 mL of MTBE was added dropwise over 30 minutes whilethe temperature was maintained at 0-5°C. After theaddition was completed the reaction mass was stirred for 60 minutes at 0-5°C. To the stirred reaction masswas added a solution of 5.0 g (19.2 mmoles) of 94.4%3-hydroxy- 1,1-dimethylbutyl peroxyneoheptanoate and1.5 g (19.0 mmoles) of pyridine in 10 mL of MTBE overa period of 15 minutes. The reaction mixture was thenstirred for an additional 45 minutes at 20-25°C afterwhich it was quenched with water. After separatingand discarding the aqueous phase the organic waswashed once with cold aqueous 10% HCl solution, threetimes with water and once with dilute aqueous NaHCO3solution. The product solution was dried over 5% byweight of anhydrous MgSO4, and, after separation ofthe spent desiccant by filtration, the solvent wasremoved in vacuo leaving 9.3 g (100% of theory,uncorrected) of a hazy colorless oil. The productcontained 6.78% active oxygen (theory, 6.52%),therefore, I-5 was obtained with an assay of 100% andin a corrected yield of 100%. A Differential ScanningCalorimeter (DSC) scan showed two peroxidedecomposition temperatures, one at 71°C for the3-neoheptanoylperoxy-1,3-dimethylbutyl moiety and oneat 169°C for the 3-t-butylperoxy-1,3-dimethylbutylmoiety. Example 7. Preparation ofOO-(1,1,3,3-Tetramethylbutyl)O-(3-t-Butylperoxy-1,3-dimethylbutyl)Monoperoxyoxalate (I-6)
    A 250 mL 3-necked flask equipped with a magneticstirring bar, a condenser, a thermometer and anaddition funnel and cooled with an ice bath wascharged with 3.1 g (20.0 mmoles) of 94%1,1,3,3-tetramethylbutyl hydroperoxide, 2.4 g (30.0mmoles) of dry pyridine and 50 mL of MTBE. The flaskcontents were cooled to 3°C. Then to the resultingvigorously stirred solution at 3-7°C was added asolution of 5.6 g (20.0 mmoles) of3-t-butylperoxy-1,3-dimethylbutyl chlorooxalate over aperiod of 11 minutes. A solid, pyridinium chloride,formed shortly after the addition commenced. Afterthe addition was completed the reaction mass wasstirred for 90 minutes at 2°C after which 10 mL ofwater was added and the reaction mass was stirred anadditional 15 minutes. The aqueous layer was thenseparated and the organic layer was washed once with50 mL of water, three times with 40 mL portions ofaqueous 5% HCl solution and once with 50 mL ofsaturated aqueous NaHCO3 solution. The productsolution was dried over 10% by weight of anhydrousMgSO4, and, after separation of the spent desiccant byfiltration, the solvent was removed in vacuo leaving6.3 g (81% of theory, uncorrected) of a colorlessliquid. An IR spectrum of the product showed an OH band at about 3480 cm-1, a monoperoxyoxalate carbonylband at 1800 cm-1, an oxalate carbonyl band at 1750cm-1 and a peroxide (-OO-) band at about 875 cm-1.The presence of the OH band at 3480 cm-1 in the IRspectrum of the product indicated the presence of ahydroxy-containing impurity. Therefore, the productwas taken up in 60 mL of MTBE and the resultingsolution was washed with 50 mL of water containing4.0 g of NaHSO3 and once with 50 mL of saturatedaqueous NaH2PO4 solution. After drying and isolationof the product as above, 5.5 g (71% of theory,uncorrected) of colorless oil was obtained. The IRspectrum of the purified product showed no OH band inthe 3500 cm-1 region, a monoperoxyoxalate carbonylband at 1800 cm-1, an oxalate carbonyl band at 1750cm-1 and a peroxide (-OO-) band at about 880 cm-1.The IR spectrum of the purified product was thatexpected for the desired titled product. Liquidchromatographic (LC) analysis of the product showed asingle large peak. The product contained 2.33% activeoxygen according to a peroxyester active oxygen method(theory, 4.10%).
    Based on the method of preparation, yield data,LC data, and IR data the product obtained in thisreaction was I-6. The product was a sequentialdiperoxide having a dialkyl peroxide moiety with a 10Hr half-life temperature of about 120°C and amonoperoxyoxalate moiety having a 10 Hr half-lifetemperature of about 35-40°C. Example 8. Preparation of Di(3-chlorocarbonylcarbonyloxy-1,1-dimethylbutyl) Peroxide (I-7)
    A 250 mL three-neck flask equipped with amagnetic stirrer, a thermometer and an addition funnelwas charged with 50.8 g (400 mmoles) of oxalylchloride and 75 mL of MTBE. Then to the resultingsolution was slowly added 24.7 g (100 mmoles) of 95%di(3-hydroxy-1,1-dimethylbutyl) peroxide over a periodof 30 minutes at 21-30°C. The addition funnel wasthen replaced with a nitrogen gas tube and drynitrogen gas was slowly bubbled through the reactionmass in order to remove HCl over a period of 4 hoursat 25-30°C. The MTBE, excess oxalyl chloride, and anyremaining gas were removed in vacuo using a wateraspirator. Obtained was 38.2 g (97% of theory,uncorrected) of a amber liquid. An IR spectrum of theproduct showed no OH bands and showed a pair ofcarbonyl bands at 1790 cm-1 and 1755 cm-1. Based onhydrolyzable chloride content the assay of the productwas 85.0% and the corrected yield was 82.7%.
    Based on the method of preparation, assay data,yield data, and IR data the product obtained in thisreaction was I-7. Example 9. Preparation of N-t-Butyl3-t-Butylperoxy-1,3dimethylbutylOxamate (I-8)
    A 250 mL 3-necked flask equipped with a magneticstirring bar, a nitrogen inlet line, a thermometer andan addition funnel was charged with 40 mL of MTBE, 2.5g (34 mmoles) of t-butylamine and 4.0 g (50 mmoles) ofpyridine. The flask contents were cooled to 10°C.Then 5.7 g (20 mmoles) of 98.1%3-t-butylperoxy-1,3-dimethylbutyl chlorooxalate (I-2)in 10 mL of MTBE was added dropwise over 15 minutes at10-20°C to the stirred solution. After the additionwas completed the reaction mass was stirred for 60minutes at 15-20°C. Then 50 mL of water and 20 mL ofMTBE were added to the stirred reaction mass and themixture was allowed to separate into liquid phases.The aqueous layer was separated and discarded. Theorganic layer was washed twice with 50 g portions ofaqueous 5% hydrochloric acid solution and then with 50mL portions of water until the pH was about 7. Theproduct solution was dried over 5% by weight ofanhydrous MgSO4, and, after separation of the spentdesiccant by filtration, the solvent was removed in vacuoleaving 3.1 g (49% of theory, uncorrected) of aliquid product. An IR spectrum of the product showeda weak-medium pair of bands in the 3400-3500 cm-1region due to the NH group, a strong carbonyl band at1705 cm-1 and weaker carbonyl shoulder bands at about1730 cm-1 and about 1760 cm-1.
    Based on the method of preparation and IR datathe product obtained in this reaction was I-8. Example 10. Crosslinking Efficiency of 3-t-Butylperoxy-1,3-dimethylbutylEthylOxalate (I-1) in High DensityPolyethylene (HDPE)
    Compound I-1 was evaluated for crosslinkingefficiency in HDPE compared to2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne (LUPERSOL130, manufactured by ELF ATOCHEM North America, Inc.).I-1 and LUPERSOL 130 were individually blended intosamples of HDPE (USI's LY 66000 HDPE) at 140°C using aBrabender for thorough mixing. The level ofcrosslinking agent employed was 10 meq(milliequivalents of peroxide) per hundred grams ofHDPE resin. This amounted to 2.904 grams of I-1 perhundred grams of HDPE resin and 1.43 grams of LUPERSOL130 per hundred grams of HDPE resin. Disks of thecompounded HDPE resins were pressed out and theseresin disks were used for determining crosslinkingdata using a Monsanto Oscillating Disk Rheometer (ODR)at 196.1°C (385°F), ± 3o arc. The crosslinking dataobtained are summarized in the table below: CROSSLINKING OF HDPE AT 385°F FORMULATION: A B LUPERSOL 130 (10 meq/100 g HDPE) 1.43 - I-1 (10 meq/100 g HDPE) - 2.904 MH (in-lbs) 34.6 40.3 MH-ML (in-lbs) 33.4 38.6 TC90 (mins) 8.4 5.6 TS2 (mins) 1.8 1.4
    Based on cure times (TC90) and torque enhancement(MH-ML) the results show that 3-t-butylperoxy-1,3-dimethylbutylethyl oxalate (I-1) was a faster and amuch more efficient crosslinking agent for HDPE thanwas LUPERSOL 130, the crosslinking agent currentlyemployed to commercially crosslink HDPE.Consequently, the results showed that I-1 was a verygood crosslinking peroxide candidate for HDPE. Example 11. Crosslinking Efficiency of 3-t-Butylperoxy-1,3-dimethylbutylEthylOxalate (I-1) in Low DensityPolyethylene (LDPE)
    Compound I-1 was evaluated for crosslinkingefficiency in LDPE compared to2,5-dimethyl-2,5-di(t-butylperoxy)hexane (LUPERSOL 101, manufactured by ELF ATOCHEM North America, Inc.).I-1 and LUPERSOL 101 were individually blended intosamples of LDPE (Union Carbide DYNH-1) at 120°C usinga Brabender for thorough mixing. The level ofcrosslinking agent employed was 10 meq(milliequivalents of peroxide) per hundred grams ofLDPE resin. This amounted to 2.904 grams of I-1 perhundred grams of LDPE resin and 1.45 grams of LUPERSOL101 per hundred grams of LDPE resin. Disks of thecompounded LDPE resins were pressed out and theseresin disks were used for determining crosslinkingdata using a Monsanto Oscillating Disk Rheometer (ODR)at 196.1°C (385°F), ± 3o arc. The crosslinking dataobtained are summarized in the table below: CROSSLINKING OF LDPE AT 385°F FORMULATION: A B LUPERSOL 101 (10 meq/100 g LDPE) 1.45 - I-1 (10 meq/100 g LDPE) - 2.904 MH (in-lbs) 24.0 28.3 MH-ML (in-lbs) 21.5 25.8 TC90 (mins) 8.9 10.4 TS2 (mins) 2.15 2.30
    Based on torque enhancement (MH-ML) the resultsshow that I-1 was a much more efficient crosslinkingagent for LDPE than was LUPERSOL 101, a crosslinking agent currently employed to commercially crosslinkLDPE. In addition, use of I-1 as a crosslinking agentfor LDPE advantageously resulted in a longer scorchtime (TS2) than when LUPERSOL 101 was employed.Consequently, the results showed that I-1 was a verygood crosslinking peroxide candidate for LDPE. Example 12. Polypropylene (PP) ModificationEfficiency of 3-t-Butylperoxy-1,3-dimethylbutylEthyl Oxalate (I-1)
    Compound I-1 was evaluated for polypropylene (PP)modification efficiency compared that of to2,5-dimethyl-2,5-di(t-butyl- peroxy)hexane (LUPERSOL101, manufactured by ELF ATOCHEM North America, Inc.).I-1 and LUPERSOL 101 were separately blended under ablanket of nitrogen gas (to eliminate the effect ofoxygen on modification of PP) into PP (Himont 6501),containing: 0.1% calcium stearate 0.3% dilaury thiodipropionate 0.1% Irganox 1010 (manufactured by Ciba Geigy Corp.) at 180°C using a Brabender plastigraph. Mixing underthe blanket of nitrogen gas was continued for a totalof 10 minutes. In these experiments, the level ofmodifying agent employed was 0.20 meq (milliequivalentof peroxide) per hundred grams of PP resin. Thisamounted to 0.058 grams of I-1 per hundred grams of PPresin and 0.029 grams of LUPERSOL 101 per hundred grams of PP resin. Melt flow index (MFI) is a measureof the amount of degradation (modification ormolecular weight reduction) of PP. The higher the MFIof the modified PP resin under specific conditions,the lower the molecular weight of the PP resin. TheMFI data for the virgin PP resin and the modified PPresins were determined according to ASTM D-1238(230°C, 2.16 kg weight). The MFI data are summarizedbelow: PP Modifying Agent Peroxide Weight, % Peroxide meq per 100 g PP MFI grams/10 mins. None --- --- 5.5 LUPERSOL 101 0.029 0.20 11.5 I-1 0.058 0.20 15.5 The results showed that 3-t-butylperoxy-1,3-dimethylbutylethyl oxalate (I-1) was much moreefficient for modifying PP than was LUPERSOL 101.Lupersol 101 is currently the most widely usedcommercial modifying agent for PP. Consequently, theresults showed that I-1 was a very good modifyingagent for PP.
    Example 13. Crosslinking Efficiency of Allyl 3-t-Butylperoxy-1,3-dimethylbutylOxalate(I-4) in High Density Polyethylene(HDPE)
    Compound I-4 was evaluated for crosslinkingefficiency in HDPE compared to2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne(LUPERSOL 130, manufactured by ELF ATOCHEM NorthAmerica, Inc.). I-4 and LUPERSOL 130 wereindividually blended into samples of HDPE (USI LY66000) at 140°C using a Brabender mixer. The level ofcrosslinking agent employed was 10 meq(milliequivalents of peroxide) per hundred grams ofHDPE resin. This amounted to 3.024 grams of I-4 perhundred grams of HDPE resin and 1.432 grams ofLUPERSOL 130 per hundred grams of HDPE resin. Disksof the compounded HDPE resins were pressed out andthese resin disks were used for determiningcrosslinking data using a Monsanto Oscillating DiskRheometer (ODR) at 385°F ± 3o arc. The crosslinkingdata obtained are summarized in the table below: CROSSLINKING OF HDPE AT 385°F FORMULATION: A B LUPERSOL 130 (10 meq/100 g HDPE) 1.432 - I-4 (10 meq/100 g HDPE) - 3.024 MH (in-lbs) 36.8 45.5 MH-ML (in-lbs) 35.3 43.9 TC90 (mins) 9.8 5.5 TS2 (mins) 1.9 1.5
    Based on cure times (TC90) and torque enhancement(MH-ML) the results show that I-4 was a faster and amuch more efficient crosslinking agent for HDPE thanwas LUPERSOL 130, the crosslinking agent currentlyemployed to commercially crosslink HDPE.Consequently, the results showed that I-4 was a verygood crosslinking peroxide candidate for HDPE.
    权利要求:
    Claims (9)
    [1] A peroxide composition of Structure A:
    [2] A peroxide as defined in claim 1, selected fromthe group consisting of:3-t-Butylperoxy-1,3-dimethylbutyl ethyl oxalate,3-t-butylperoxy-1,3-dimethylbutyl chlorooxalate,di-(3-chlorocarbonylcarbonyloxy-1,1-dimethylbutyl)peroxide, 3-t-butylperoxy-1,3-dimethylbutyl hydrogenoxalate, allyl 3-t-butylperoxy-1,3-dimethylbutyloxalate, N-t-butyl 3-t-butylperoxy-1,3-dimethylbutyloxamate, 3-t-butylperoxy-1,3-dimethylbutyl3-(neoheptanoylperoxy)-1,3-dimethylbutyl oxalate andOO-(1,1,3,3-tetramethylbutyl)O-(3-t-butylperoxy-1,3-dimethylbutyl)monoperoxyoxalate.
    [3] Peroxide composition as defined in claim 1wherein R is a t-alkyl radical of 4 to 12 carbons.
    [4] Peroxide composition as defined in claim 1wherein Z is Cl.
    [5] Peroxide composition as defined in claim 1wherein Z is OR13.
    [6] Peroxide composition as defined in claim 1wherein Z is NR13R14.
    [7] Peroxide composition as defined in claim 1wherein Z is OO-R.
    [8] Peroxide composition as defined in claim 1wherein Z is O-R3-C(R1)(R2)-OO-R15.
    [9] A process for use of a peroxide composition asdefined in claim 1 as a free-radical initiator, ineffective initiating amounts, for the initiation offree-radical reactions selected from the groupconsisting of:
    a. curing of unsaturated polyester resincompositions,
    b. polymerizing ethylenically unsaturatedmonomers (such as styrene, ethylene)compositions,
    c. crosslinking of olefin thermoplastic polymercompositions,
    d. curing of elastomer compositions,
    e. modifying polyolefin compositions,
    f. grafting of ethylenically unsaturated monomersubstrates onto olefin homo- and copolymersubstrates, and,
    g. compatibilizing blends of two or morenormally incompatible polymer substrates; which comprises heating said substrates in thepresence of an effective initiating amount of one ormore peroxides as defined in claim 1, for a timesufficient to at least partially decompose saidperoxide, to perform the free-radical reaction.
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    同族专利:
    公开号 | 公开日
    DE69704256T2|2001-10-18|
    TW442465B|2001-06-23|
    CA2222157A1|1998-06-30|
    BR9706504A|1999-06-08|
    AU4835897A|1998-07-02|
    EP0850927B1|2001-03-14|
    JPH10265455A|1998-10-06|
    US5866712A|1999-02-02|
    DE69704256D1|2001-04-19|
    AT199711T|2001-03-15|
    MX9710520A|1998-12-31|
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    优先权:
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    US3452696P| true| 1996-12-30|1996-12-30||
    US34526P||1996-12-30||
    US948363||1997-10-10||
    US08/948,363|US5866712A|1996-12-30|1997-10-10|Oxalic acid peroxide compositions and uses|
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