CA2080456A1

CA2080456A1 - Fluxed composites

Info

Publication number: CA2080456A1
Application number: CA002080456A
Authority: CA
Inventors: Richard D. Cortelezzi; Clifford C. Martin
Original assignee: Richard D. Cortelezzi; Clifford C. Martin; Elastochem, Inc.
Current assignee: Elastochem Inc
Priority date: 1991-10-10
Filing date: 1992-10-13
Publication date: 1993-04-11
Also published as: US6515057B1; EP0537006A2; US5621032A; EP0537006A3; US6214913B1; MX9205838A

Abstract

ABSTRACT

A method and product which provides a solid, non-powdered homogeneous form to liquid and low melting point solid compounds which facili-tates stability, storage, dispersability and handling and which may be added directly to formu-lations requiring the liquid compound or low melting point solid compound. The liquid or low melting point solid ingredient is combined with a binder which is comprised of at least a wax and thermoplastic polymer. During the method of forming the product, both the binder and the liquid compound (or low melting point solid com-pound) pass through a liquid phase during which they are mixed. The product is then formed and cooled.

Description

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The large sca]e industrial and commercial uses of liquid and low melting point solid bulk materials pose a multitude of practical problems. Such materials are difficult to handle;
their physical properties lead to inaccurate meas-urements. Their physical form frequently results in a significant percentage of waste due to mate-rials adhering to containers and handling equip-ment. Frequently, such materials have a limited shelf life due to decomposition. Decomposition presents a particular problem with organic peroxides which over time, become unstable and present an explosive hazard. Low melting point solids, those solids having a melting point below 120F, become semi-solid and usually tacky, as they approach their melting point. While this may not present a significant problem at room tempera-ture, the ambient temperature in many plant operations may exceed 100F and approach the melting point of the low melting point solids.
Even if the ambient temperature is well below the melting point of the low melting point solid, if the solid has been previously e~posed to tempera~
tures near the melting point, the product may have partlally melted and "coalesced" into a large agglomerate.
~ ttempts have been made to address these problems by mixing certain li~uid or low melting point solid materials with solid compounds thereby giving such materials an interim solid form so that they will remain solid over a wider tempera-ture range. The resulting product is then added to formulations which call for the liquid or low melting point solid. ~owever, the products that result from such attempts have significant draw-backs. Frequently, the dispersion o~ the liquid or ~ , .
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2 ~ 6 low melting solid material is not uniform; this results in a wide variability in the concentration of the material within the product. Variability is a particular problem in products which use mineral fillers, such as clay, as a binder component.
Where the liquid or low melting point solid is ab-sorbed or adsorbed onto a mineral :Eiller like clay, there is a strong tendency toward particle agglomeration, especially if the product experiences wide temperature variation cluring transportation and storage. Where a mineral such as clay is mixed into a liquid, the clay tends to settle out be~ore the product fully solidifies, resultin~ in a stratified product. This stratifi-cation produces an uneven concentration o~ the liquid or low melting point solid throughout the final product. Also, products that have a mineral filler as a binder, present a dispersion problem during the products incorporation into the end formulation, such as into a rubber formulation.
Also, such products frequently ha~e a low '7activity", that is, the product contains a low percentage of the desired liquid or low melting point solid ingredient. ~ higher activity is desired by the purchasers since Eirst, more o~
the desired liquid or low melting point solid is available ~or the money, and, second, since the product will have correspondingly less binder, there are fewer compatibility problems between the binder and the purchaser's formulation which requires the liquid or low melting point solid.
In addition, such products are frequently powdered. Powders may present a respi-ratory hazard ~or persons handlin~ the product and may present an e~plosive hazard as well. Further-more, many products ~Ibleed~ that is, the liquid ", , . , .. . . . .
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ingredient tends to disassociate ~rom the solid component.
It would be desirable to have a liquid or low melting point solid in a solid form, to fa-cilitate handling, measuring and storing, and which can be added directly to the processes which require the liquid or low melting point solid in-gredient. It would also be desirable to have a high activity, homogenous product in a non-powdered form. Finally, a product that would fullymelt into a formulation, such as a rubber formula-tion, during processing, eliminating the undis-persèd solid particles, would be very desirable.
The present invention relates to either a liquid compound or a low melting point solid compound, referred to herein as "active ingre-dientsl', uniformly mixed with a binder, to provide a solid composite of high activity and longer shelf life, and also relates to the method of their preparation. The composites provide a temporary form ~or liquid or low melting point solid ingredients; the composites may be incor-porated into a variety of industrial and/or com-mercial processes in the same way that the active ingredient would be used. The composites may be added to processes which tolerate the addition of the binder. Composites may be made of a variety of active ingredients, such as: organic peroxides;
modified melamine resins; cyanurates; aldehyde-amine reaction products; phenylamines; methacry-lates and organo-phosphites. As used herein "composite" means a solid mixture o~ an active ingredient and a binder. The "activity" of a par-ticular composite, that is, the percentage of active ingredient in the composite, will depend upon the type of active ingredient. The active 2~3~ b~

ingredient i.s "composi-ted" by being combined with a binder, which contains a wax, and a thermo-plastic polymer. Depending upon the type of active ingredient in -the composite, the binder may also contain a compatibilizing agent such as a fatty acid or an ethylene vinyl acetate copolymer resin or both. Optional minor components, such as wet-ting agents, stabilizers, plasticizers, homoge-nizing agents and mineral oils may also be added.
In accordance with the present invention, there is thus provided a solid homoge-neous composite comprising:
a) at least one active ingredient selected from the group consisting of organic peroxides, modified melamine resins, cyanurates, phenylamines, methacrylates, organo-phosphites and aldehyde-amine reaction products; and b) a binder comprising a wax and a thermoplastic polymer;
wherein the binder an the active ingredient are added together while both are in a liquid phase.
The composite is prepared by blending the active ingredient with the binder while bot~
are in a liquid phase, then cooling the mixture and forming or shaping ~he composite, using con~ntional ~orming procedures.
THE_ACTIVE INGREDIENT
According to the present invention, a variety of li~uid and low melting point solid active ingredients are "composited" to produce composites that are easier and safer to handle, easier to measure, have an increased shelf life, and a high activity, that is, a high percentage, in some composites up to 90%, of the active ingre-dient. The maximum percentage of active ingredien-t depends on the type of active ingredient. When . :
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more than the maximum percent of the ac~ive ingredient is present in the composite (and thus, less than minimum binder is present) the composite becomes oily, ~rosted and/or tacky. This condition is often described as surface bloom. Where the active ingredient is present in the preferred amou~t, the composite has a high activity without a surface bloom. Where the acti~e ingredient is present in an amount between the pre~erred amount and the maximum amount, the composite contains some sur~ace bloom but may be satis~actory for some uses. Whlle as little as about 1% actlve in-gredient may be present in the composite, the economic interests dictate that the composite have a higher activity, usually at least 30%.
For organic peroxide, a high activity means the composite will have about 70~ to about 80% or~anic peroxide. For cyànurates, modified melamine resins, oxgano-phosphites, and aldehyde-amine reaction products, a high activity means thecomposite will have about 50% to about 80% active ingredient. For phenylamine based antidegradants and methacrylates, a high activity means the com-posite will have about 60% to about ~0% act:i~e ingredient~
Co~posites may be made o~ a variety of oryanic peroxides~ for example, dialkyl peroxides, including dicumyl peroxide, 2,5-dimethyl-2,5-di-(t-butylperoxy)hexane, a,a'-di(t-butylperoxy)di-isopropylbenzene, 2,5-dimethyl-2,5-di-(t-butyl peroxy)hexyne-3 and butyl-4,~bis(t-butylperoxy) valerate. A suitable dicumyl peroxide is sold by Hercules, Inc. under the trademark DICUP R, or by Akzo Chemicals Inc. under the trademark PERKADOX
BC. A suitable 2,5-dimethyl-2,5-di-(t-butyl-peroxy)hexane is sold by Akzo Chemicals IncO under 2 ~

the trademark TRIGONOX 101, or by Atochem under the trademark LUPERSOL 101. A suitable a,a'-di(t-butylperoxy)diisopropylbenzene is sold by Hercules, Inc. under the trademark VULCUP R, or by Akzo under the trademark PERKADOX 14S. A suitable 2,5-dimethyl-2,5-di-(t-butylperoxy) hexyne-3 is sold by Atochem under the trademark LUPERSOL 130 or by Akzo under the trademark TRIGONOX 145. A
suitable m-butyl-4,4-bis(t-butylperoxy) valerate is sold by Akzo under the trademark TRIGONOX 17, or by Atochem under the trademark LUPEROX 230.
The compositization of organic peroxides according to this invention preserves the shelf life of the peroxides, and thus is particularly beneficial because peroxides are unstable and over time, present an explosive hazard. In addition, many organic peroxides are semi-solids at op-erating temperature and thus are difficult to handle and measure because of their tendency to stick to containers and to reagglomerate. The organic peroxide composites of the present invention overcome these problems.
A composite may be made containing a modified melamine resin, (also known as modified melamine ~ormaldehyde resin) such as hexamethoxy-methylmelamine. A suitable hexamethoxymethylmela-mine is available from American Cyanamid under the trademark CYREZ 963 or from Monsanto Company under the trademark RESIMEN~ 3520. ~examethoxymethyl-melamine is a methylene donor and is widely usedparticularly in the tire industry, as an adhesion promoter.
Composites may be made from cyanurates, such as triallyl cyanurate, which is a low melting point solid and triallyl isocyanurate, which is a liquid at room temperature. A suitable triallyl 2~8~

cyanurate is sold by Akzo under -the trademark PERKALINK 300, or by American Cyanamid under the trademark TRIALLYLCYANUR~TE. A suitable triallyl isocyanurate is sold by Akzo under the trademark PERKA~.INK 301. Cyanurates are used in various in-dustrial applications as reactive monomers Erom free radical polymerization. In the rubber industry cyanurates are used as co-agents, in the non-sulfur, (peroxide) curing of rubber.
Composites may be made of phenylamine based antidegradants such as: phenylenediamines, such as N-phenyl-N'-2-octyl-p-phenylenediamine, which is a liquid at room temperature; alkylated diphenylamines; and the reaction products of diphenylamines, such as the reaction product of diphenylamine and acetone, commercially available as BLE-25 from Uniroyal. The BLE-25 formulation is proprietary; it is characterized by a viscosity of 25-50 poise at 86F, and specific gravity of 1.08 to 1.10. A suitable N-phenyl-N'-2-octyl-p-phenylenediamine is sold by UOP Inc. under the trademark UOP 688. The phenylamine based anti-degradants serve as antidegradants in rubber compositions.
Composites may be made of methacrylates, such as trimethylolpropane trimethacrylate and trimethylolpropane triacrylate. A suitable trimethylolpropane trimethacrylate is sold by Sartomer Corporation under the trademark SARTOMER
RESIN 350. A suitable trimethylolpropane tri-acrylate is also sold by Sartomer Corporation under the trademark SARTOMER RESIN 351. Methacry-lates often serve as a co-agent in the pero~ide curing of rubber.
A composite according to the present invention may also be made of organo-phosphites, 2 ~

such as tri(monononylphenyl)phosphite and tri(dinonylphenyl)phosphite or mixtures thereof. A
suitable mixture is sold under the trademark POLYGARD HR by Uniroyal Chemical Company. The organo-phosphites serve as antidegradants in rubber compositions Composites may also be made of aldehyde-amine reaction products, such as butyraldehyde-aniline reaction products, butyraldehyde-butyl-amine reaction products, formaldehyde-ammonia-ethyl chloride reaction products, and heptal-dehyde-aniline reaction products. A suitable bu-tyraldehyde-butylamine reaction product is sold by R.T. Vanderbilt under the trademark VANAX 833. A
suitable formaldehyde-ammonia-ethyl chloride reaction product is sold by Uniroyal under the trademark TRIMENE BASE. A suitable heptaldehyde-aniline reaction product is sold by Uniroyal under the trademark HEPTEEN BASE. Suitabl~ butyral-dehyde-aniline reaction products are sold by R.T.
Vanderbilt under the trademarks VANAX AT and VANAX
808. The aldehyde-amine reaction products serve as accelerators in rubber formulations.
It should be understood that the active ingredients, particularly cornmercial grades, depending on their source, may contain substantial amounts of a wide variety of impurities. There-fore, such impurities also will be incorporated into the composite.
THE BINDER
As used herein, the term "binder"
includes all additives, except the active ingre-dient, in the composite. The binder has a higher melting point/softening point than the a~tive ingredient, and imparts the solid form to the com-posite. The binder contains at least one wax/ and 2 ~

at least one thermoplastic polymer, for example, a polyolefin, preferably polyethylene, most prefer-ably oxidized polyethylene. Depending on the type of active ingredient, the binder may also contain at least one compatibilizing agent, for example, ethylene vinyl acetate copolymer resin or a fatty acid, or mlxtures thereof. A compatibilizing agent promotes the compatibility between the active ingredient and the binder, which promotes the cohesiveness of the composite. Where the active ingredient and the binder are of sufficiently different polarity so that the composite is not cohesive, a compatibilizing agent may be required.
Optional minor components such as wetting agents, stabilizers, plasticizers, and mineral oils may also be added.
Any wax could be used, including, but not limited to, petroleum derived waxes such as paraffin and microcrystalline wax, and natural waxes such as beeswax and carnauba. Good results have been obtained using paraffin wax or a micro-crystalline wax or mixture of both~ Paraffin is preferred. However, it should be understood that paraffin may contain some microcrystalline wax.
While any paraffln wax may be used, good results have been obtained using a paraffin wax having a melting point in the range of 140 to 145F. Suit-able paraffin is sold by Astor Wax Company available through M.E. Cachat, Cleveland, Ohio, under the trademark ASTAX 140il45 PARAFFIN. The wax helps impark the solid form to the binder.
A thermoplastic polymer, such as poly-ethylene, preferably oxidized polyéthylene, promotes compatibility bekween the active i.ngre-dient and the binder components and helps to impart the necessary hardness to the composite. A

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suitable oxidized polyethylene having a melking point from about 170F to about 250F, a viscosity from about 80 to about 160 cps at 120C, and a hardness of from about 1 to about 5 penetration units at 25CI is sold by Huls of Germany, and is available from M.F. Cachat, Cleveland, Ohio under the trademark VESTOW~X AO 1539.
Depending on the active ingredient, a fatty acid may be added to the binder. The addition of fatty acids improves the compatibility of the active ingredient and the binder, and also lowers the initial melting point of the composite.
Preferably, fatty acid is added where the active ingredient is a modified melamine resin, a cyanurate, or a reaction product of acetone and diphenylamine. Due to the difficulty in separating fatty acids, a fatty acid is a mixture of several different fatty acids. Preferably, a fatty acid having a stearic acid content from about 10% to about 92% stearic acid, and more preferably, a high stearic acid content fatty acid having a stearic acid content of 70% is used. The other fatty acids present in the mixture typically in-clude palmit:lc acid, oleic acid and myrlstic acid.
These Eatty acids may also be llsed alone or in combination although they are not preferred. A
suitable high stearic acid content fatty acid is sold by Witco Industries under the trademark HYSTRENE 701~.
Depending on the type of active ingredient in the composite, an ethylene vinyl acetate copolymer resin may also be added. Prefer-ably, ethylene vinyl acetate copolymer resin is added where the active ingredient is a phenylamine based antidegradant, a cyanurate, a modi-fied mela-mine resin or an organo-phosphite. Ethylene vinyl 2 ~

acetate copolymer resin acts as a homogeni~er and also increases the viscosity of the heated binder-active ingredient blend, which provides a more defined shape upon forming. Good results have been obtained using an ethylene vinyl acetate copolymer resin having about 18% vinyl acetate, about 82%
ethylene and a softening point of 190F. A
suitable resin is sold by DuPont DeNemours Company under the trademark ELVAX and also sold by Quantum Chemical under the trademark ULTRATHENE.
The percentage of individual binder components will depend upon the type of active in-gredient in the composite. The following binder component percentages represent the percent of total binder composition. When the active ingre-dient is an organic peroxide, the paraffin may be present in the binder from about 20% to about 95%, preferably about 63.3%. The polyethylene is present in the binder from about 5% to about 80%, preferably about 36.7%.
Where the active ingredient is a modified melamine resin, such as hexamethoxy-methylmelamine, the paraffin may be present in the binder ~rom about 1% to 60% of the total bln~er composition, preferably about 30%. ~'he poly-ethylene is present in the binder from about 1% to about.40%, preferably about 20%. In addition, the binder contains either from about 1% to about 40~, of ethylene vinyl acetate copolymer resin or from about 1% to about 50%, fatty acid, or both.
Preferably, the binder contains both fatty acid and ethylene vinyl acetate copolymer resin;
preferably about 40% fatty acid and about 10%
ethylene vinyl acetate copolymer resin.
~ here the active ingredient is a cyanurate, the paraffin is present into the binder , ' , ' ' ~ : ' .
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in an amount from about 1% to about 60% of the total binder cornposition, preferably about 30%.
The polyethylene is present in the binder from about 1% to about 40%, pre~erably about 15%. In addition, the binder contains either -from about 1%
to about 40% of ethylene vinyl acetate copolymer resin or from about 1% to about 50% fatty acid, or both. Preferably, the binder contains both fatty acid and ethylene vinyl acetate copolymer resin;
preferably about 40% fatty acid and about 15%
ethylene vinyl acetate copolymer resin.
Where the active ingredient is a phenyl-amine, such as N-phenyl-N'-2-octyl-p-phenylenedi-amine, the paraffin is present in the binder in an amount from about 5% to about 70% of the total binder composition, preferably about 38%. The polyethylene is present in the binder from about 1% to about 40%, preferably about 12%. Preferably from about 5% to about 70%, preferably about SO9G/
of ethylene vinyl acetate copolymer resin is added.
Where the active ingredient is a liquid high temperature reaction product of acetone and a diphenylamine, such as BL~-25, the paraffln is present in the binder in an amount from about 5%
to about 50% o:E the total binder composition, preferably about 20%. The polyethylene is present in the binder from about 1% to about 60%, prefer-ably about 30%~ In addition, the binder contains either from about 1% to about 60% of ethylene vinyl acetate copolymer resin or from about 1~ to about 50% fatty acid, or both~ Preferably, the binder contains both fatty acid and ethylene vinyl acetate copolymer resin; preferably about 20%
fatty acid and about 30% ethylene vinyl acetate copolymer resin.

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Where the active ingredient is a methacrylate the paraffin is present in the binder in an amount from about 20% to about 99% of the total binder composition, preferably about 63.3~.
The oxidized polyethylene is present in the binder from about 1% to about 80%, preferably about 36.7%.
Where the active ingredient is an organo-phosphite, the paraffin is present in the binder in an amount from about 5% to about 50% of the total binder composition, preferably about 20%. The oxidized polyethylene is present in the binder from about 1% to about 60~, preferably about 40%. Preferably, ethylene vinyl acetate co-polymer resin is also present in the binder from about 1% to about 60%, more preferably about 40~.
Where the active ingredient is an aldehyde-amine reaction product, the paraffin is present in the binder in an amount from about 5%
to about 95%, preferably about 50.6%. The oxidized polyethylene is present in the binder from about 1~ to about 60%, preferably about 29.4%. Prefer-ably, ethylene vinyl acetate copolymer is also present ln the binder from about 1% to about 50%, more preferably about 20%.
Additional components such as stabilizers, plasticizers, wetting agents and mineral oils may be added, in minor amounts, to the binder. Stabilize.rs, such as hydroquinone, may be added to the binder in an amount from about 0.1% to about 10%, to prevent the oxidation or hydrolysis of the active ingredient in the com-posite. Plasticizers, such as phthalate plasti-cizers, preferably diisodecylphthalate or dioctyl-phthalate may be added to the binder in an amount from about 1% to about 20% to decrease the melting :, ' - ~ ' " -, , . ' .~

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point of the composite. Wetting ayents, such as amine derivatives of fatty acids, may be added in an amount from 1% to about 50% to promote compati-bility of the active in~redient in the composite.
Mineral oils, such as paraffinic oils and naph-thenic oils, may be added to the binder to decrease the melting point of the composite. A
suitable paraffinic oil is sold by Sun Oil under the trademark SUNPAR 2280. A suitable naph-thenic oil is sold by Ergon under the trademark ~YPRENE V
2000. The mineral oil is added in an amount suffi~
cient to adjust the melting point of the composite to the desired melting point.
THE COMPOSITE
The composite of the active ingredient and the binder is prepared by combining the active ingredient with the binder so that at some point in the mixing procedure, the binder and the active ingredient are both in a liquid phase, and are then blended while both are in a liquid phase. As used herein, "liquid phase" lncludes high vis-cosity paste-like phases. This may be accomplished by mixing the liquid active ingredie~t (or if active ingredient is a semi-solid, heating the active ingre~ient beyond its meltlng point) with a molten binder. Alternatively, the active ingre-dient may be mixed with a solid binder an~ the temperature of the mixture raised above the melting points of the active ingredient and the binder ingredients. Then, once both the active ingredient and binder are in a liquid phase, they are thoroughly blended to provide a homogenous mixture, at a temperature which will keep both the binder and active ingredient in a liquid phase.
After a thorough blending, the homogenous mixture is cooled just above the melting point of the ' '~ .

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composite. The mixture is then fed through conventional forming processes so -that the finished composite may be in the form of pellets, pastilles, flakes, prills, powder or slabs, depending upon the desired form. A suitable method of forming the composites into pastilles, or half sphere shape, is by using a rotary head for forming drops onto a cooled stainless steel con-veyor. This equipment is available from Sandvik Process Systems Inc.
It should be noted that as the percent of active ingredient in the composite is in-creased, (and the percentage of binder is cor-respondingly decreased) the tolerances of the binder and its components become narrower. That is, as the percentage of active ingredient in-creases, the percentage range of each binder component that will provide a satisfactory com-posite becomes narrower. Similarly, the type of the binder components needed to provide a satis-factory composite also become restricted. Where the percentage of active ingredient is very high, the preferred optional ingredients may ~ecome necessary ingredients; that is, they become necessary to mai.ntain the form of the composite.
When there is less binder in the composite, i-t becomes more di-Eficult to obtain a solid composite and more dif~icult to form or shape the composite.
These results affect not only the finished product, but also affect the operating speed of the composite forming equipment and the stability of the composite during storage and transpor-tation. Alsor decreasing the binder percentage in the composite reduces the compatibility between the active ingredient and the binder.

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While the ~ollowing examples of composites contain one active ingredient, more than one active ingredient may be added to a composite. It ~hould be understood that composites having two or more active ingredients are within the scope of this invention.
The Organic Peroxide Composite Organic peroxides, such as dialkyl peroxides may be present in the composite from about 30% to about 80%, preferably about 70%. The binder is present from about 20~ to about 70~, preferably about 30%. Dialkyl peroxide composites may ~e prepared as follows.
Example 1:
A dicumyl peroxide (DCP) composite was prepared by measuring 136 kilograms of a recrys-tallized grade DCP, from Akzo Inc. which is 96-100% pure and has a melting point of about 100F.
The DCP was then placed in a vat with a hot water jacketing. The water temperature within the jacketing was controlled to yield a DCP tempera-ture of -from 150-160F. The binder was prepared separatel~ by mel-ting together 36.7% oE the total binder weiyht, or 21.~ kllograms oF o~idized poly-ethylene ~VESTOWAX AO 1539) having a melting point of 225F an~ 63.3%, or 36.9 kilograms of ~STAX
140/145 paraffin. The polyethylene and para-EEin were thoroughly blended together in a heated blend tank at 195F. Then the DCP was added to the liquid binder. The DCP-binder mixture was then thoroughly blended. (The addition of the DCP to the binder decreased the temperature of the mix-ture roughly to 170F.) When a homogenous mixture was achieved, it was then fed in portions through a pelletizer, while the remainder was mildly agitated in the tank. The pelletizer, a Sandvik 2 ~ 6 process system, dispensed the DCP binder mixture in droplets Gnto a cold stainless steel conveyer belt. As a result, composite pellets in a "half-sphere" shape were produced.
Example lA:
A dicumyl peroxide ~DCP) composite was also prepared by first preparing the binder. The binder was prepared by melting together 36.7% of the total binder weight, or 21.4 kilograms, of oxidized polyethylene (VESTOWAX AO 1539) having a melting point of 225F and 63.3%, or 36.9 kilo-grams of ASTAX 140/145 paraffin. The polyethylene and paraffin were thoroughly blended together in a heated blend tank at 195F. Then 136 kilograms of a recrystallized grade DCP, from Akzo Chemical Inc. which is 96-100~ pure and has a melting point of about 100F, was added to molten binder. The DCP-binder mixture was then thoroughly blended.
(The addition of the DCP to the binder decreases the temperature of the mixture roughly to 170F.) When a homogenous mixture was achieved, it was then fed in portions through a pelletizer, while the remainder was mildly agitated in the tank. The pelletizer, a ~a~dvik process system, dispensed the DCP-binder mixture in droplets onto a cold stainless steel conveyer belt. As a result, composite peLlets in a "half-sphere'l shape were produced.
Example 2:
An a,a'-di(t-butylperoxy)diisopropyl-benzene composite was prepared by first preparing the binder which was made by placing 36.7% of the total binder weight, or 5.5 grams of oxidized polyethylene (VESTOWAX AO 1539) having a melting point of 225F and 63.3% or 9.5 grams of ASTAX
140/145 paraffin in an aluminum dish. The dish was ,.

then heated on a hot plate to melt the binder components. When temperature reached 250F and the binder components were completely melted, the binder was thoroughly stirred. The binder was then cooled to just above 225F and then 70% or 35 grams of a,a'-di~t-butylperoxy)diisopropylbenzene was added. The a,a'-di(t-butylperoxy)diisopropyl-benzene-binder mixture was maintained at between 150-200F and thoroughly blended. When a homogenous mixture was achieved, production methods for forming the composite were simulated by dispensing droplets from a stirring rod onto a chilled metal surface, such as aluminum. As a result, composite pellets in a "half-sphere" shape were produced.
Example 3:
A 2,5-dimethyl-2,5-di-(t-butylperoxy)-hexane(DBPH) composite was prepared as in Example 2. The binder was prepared by mixing together 36.7% of the total bindex weight or 9.2 grams oxidized polyethylene, (VESTOWAX AO 1539) and 63.3% or 15.8 grams of ASTAX 1~0/l~S parafEin having a 1~0-~5F meltin~ point. An equal weight, 25 grams, of DBPH, (I,UPERSOI, 101) was add0d to the binder mixture whlle agitating the mixture. The composite was prepared as in Example 2.
The Modified Melamine Resin Composite The modified melamine resin, such as hexamethoxymethylmelamine, may be present in the composite in an amount of from about 1~ to about 80%, preferably about 30% to about 70%, most preferably about 50%. the binder is pxesent from abut 20% to about 99%, pxeferably about 70% to about 30%, most preferably about 50%. A hexa-methoxymethylmelamine composite was prepared as follow~.

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Example 4:
The composite was prepared as in Example 2. The binder was prepared by mixing together 20%
of the total binder weight or 5 grams, oxidized polyethylene (VESTOWAX AO 1539), 30% or 7.5 grams, of ASTAX 140/145 paraffin having a 140 145F
melting point, 40% or 10 grams stearic acid (HYSTRENE 7018) and 10% or 2.5 grams EVA copolymer (ELVAX). An equal weight, 25 grams of hexamethoxy-methylmelamine, (CYREZ 963~ was added to thebinder mixture while agitating the mixture. The composite was prepared as in Example 2.
The Cyanurate Composite The cyanurate may be present in the composite in an amount from about 1% to about 80%, preferably 30% to about 70~, most preferably about 50~. The binder is present from about 20% to about 99~, preferably about 70~ to about 30%, most preferably about 50%. A triallyl cyanurate (TAC) composite was prepared as follows.
Example 5:
The composite was prepared as in Example 2. The binder was prepared by mixing together 155k of the total binder weight or 3.75 grams o~ an ethylene vinyl acetate copoly~er resin, (ELVAX), 15~ or 3.75 grams oxidized polyethylene, (VESTOWAX
AO 1539), 40~ or 10 grams high stearic acid con-tent fatty acid (HYSTERENE 7018) and 30% or 7~5 grams ASI~AX 140/145 paraffin having a 140~145F
melting point. An equal weight, 25 grams of TAC, ~PERK~LINK 300) was added to the binder mixture while agitating the mi~ture. The composite was prepared as in Example 2.
The Phenylamine Composite Phenylamines, particularly phenylamine based antidegradants, may be present in the ' ; ' 2 ~ v~

composite in an amount from about 30% to about 80%, preferably about 60%. The binder is present from about 20% to about 70%, preferably about 30%
to about 50%, preferably about 40%. Phenylamine composites may be prepared as follows.
Example 6-A composite of N-phenyl-NI-2-octyl-p-phenylenediamine was prepared as in Example 2. The binder was prepared by mixing together 50% of the - 10 total binder weight or 10 grams of an ethylene vinyl acetate copolymer resin, (ELVAX) 12% or 2.4 grams oxidized polyethylene (VESTOWAX AO 1539) and 38% or 7.6 grams ASTAX 140/145 paraffin having a 140-145F melting point. Then 30 grams of N-phenyl N'-2-octyl-p-phenylenediamine, (UOP 688) was added to the binder mixture while agitating the mixture. The composite was prepared as in Example 2.
Example 7:
A composite of a high temperature reaction product of acetone and diphenylamine, commercially available as BLE-25 from Uniroyal Chemical Company, was prepared as in Example 2.
The binder was prepared by mixing together 30% of the total binder weight or 7.5 yrams o~ an eth-ylene vinyl acetate copolymer resin, (ELVAX~ 30%
or 7.5 grams oxidized polyethylene, (VESTOW~X AO
1539) 20% or 5 grams ASTAX 140/145 paraffin having a 140-145F melting point, and 20% or 5 grams of a high stearic acid content fatty acid An equal weight, 25 grams, of BLE-25 was added to the binder mixture while agitating the mixture. The composite was prepared as in Example 2.
The Methacrylate Composite The methacrylate is present in the composite in an amount from about 30% to about 2 ~ c~ ~

80%, preferably about 60%. The binder is present from about 20% to about 70%, preferably about 30%
to about 50%, most preferably about 40%. A
composite of trimethylolpropane trimethacrylate may be made as follows.
Example 8:
The composite was prepared as in Example 2. The binder was prepared by mixing 36.7% of the total binder weight or 7.3 grams oxidized poly-ethylene (VESTOWAX AO 1539) and 63.3% or 12.7grams ASTAX 140il45 paraffin~ Then 30 grams of trimethylolpropane trimethacrylate, (SARTOMER
RESIN 350) was added to the binder mixture while agitating the mixture. The composite was prepared as in Example 2.
Organo-phosphite Composite The organo-phosphite is present in the composite in an amount from about 30% to about 80%, preferably about 50%. The binder is present from about 20% to about 70~, most preferably about 50%. ~ composite of tri(mixed monononylphenyl and dinonylphenyl)phosphite may be made as follows.
Example 9:
A composite was prepared as in Example 2. The binder was prepared by mixing 40% o~ the total binder weight or 10 grams oxidized poly-ethylene, (VESTOWAX AO 1539) 20% or 5 grams ASTAX
140/145 paraffin, and 40~ or 10 grams ethylene vinyl acetate copolymer resin (ELV~X). An equal weight, 25 grams, of POLYGARD HR a tri(mixed monononylphenyl and dinonylphenyl)phosphite, was added to the binder mixture while agitating the mixture. The composite was prepared as in Example 2.

,: .. . . .

2 ~

The Aldehyde-Amine Reaction Product Composite The aldehyde-amine reaction product composite is present in the composite in an amount from about 1% to about 80~ preferably 30% to about 70~, most preferably about 50%. The binder is present from about 30~ to about 70~ preferably about 50~-. A composite of the reaction product or butyraldehyde and aniline may be prepared as follows.
Example 10:
-A butyraldehyde-aniline composite was prepared as in Example 2. The binder was prepared by mixing together 20~ of the total binder weight or 5 grams of ethylene vinyl acetate copolymer resin, (ELVAX) 29.4% or 7.3 grams oxidized poly-ethylene (VESTOWAX AO 1539) and 50.6~ or 12.7 grams ASTAX 140/145 paraffin and mixed as in Example 2. An equal weight, 25 grams of VANAX 808/
a butyraldehyde aniline reaction product was added, and the composite was prepared as in Example 2.
While Examples 2-10 were done on a laboratory scale, the same formulations ca~ be adapted to a commercial scale with approp.riate modi~ications similar to Examples 1 and lA.
While the inven-tion has been described with a certain degree o-f particulari-ty, various adaptations and modifications can be made without departing from the scope of the invention as defined in the appended claims.

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Claims

1. A solid homogeneous composite comprising:
a) at least one active ingredient selected from the group consisting of organic per-oxides, modified melamine resins, cyanurates, phenylamines, methacrylates, organo-phosphites and aldehyde-amine reaction products; and b) a binder comprising a wax and a thermoplastic polymer;
wherein said binder and said active ingredient are added together while both are in a liquid phase.

2. The composite of claim 1 wherein the active ingredient comprises an organic peroxide.

3. The composite of claim 2 wherein the active ingredient is selected from:
dicumyl peroxide, a,a'-di(t-butylperoxy)diisopropyl-benzene, 2,5-dimethyl-2,5-di-(t-butylperoxy)-hexane, 2,5-dimethyl-2,5-di-(t-butylperoxy)-hexyne-3; and m-butyl-4,4-bis-(t-butylperoxy) valerate.

4. The composite of claim 2 wherein the active ingredient comprises a,a'-di(t-butyl-peroxy)diisopropylbenzene.

5. The composite of claim 2 wherein the active ingredient comprises dicumyl peroxide.

6. The composite of claim 1 comprising about 5% to about 90% of the active ingredient and from about 10% to about 95% of the binder.

7. The composite of claim 1 wherein the wax is selected from the group consisting of paraffin wax, microcrystalline wax and beeswax.

8. The composite of claim 1 wherein the thermoplastic polymer is selected from the group consisting of polyethylene and oxidized poly-ethylene.

9. The composite of claim 2 wherein the binder comprises from about 5% to about 80% oxi-dized polyethylene and from about 20% to about 95%
paraffin.

10. The composite of claim 2 wherein the binder comprises about 36.7% oxidized polyethylene and about 63.3% paraffin.

11. The composite of claim 2 comprising from about 30% to about 80% organic peroxide.

12. The composite of claim 4 or 5 comprising about 70% active ingredient and about 30% binder, wherein said binder comprises about 36.7% oxidized polyethylene and about 63.3% paraffin.

13. The composite of claim 1 wherein the active ingredient comprises a cyanurate.

14. The composite of claim 13 comprising from about 30% to about 70% active ingredient and from about 30% to about 70% binder.

15. The composite of claim 14 wherein the binder comprises from about 1% to about 60%
paraffin, from about 1% to about 40% polyethylene and from about 1% to about 40% of a compatibi-lizing agent selected from ethylene vinyl acetate copolymer resin, fatty acid and mixtures thereof.