Patent Description:
Sulfur vulcanization is completed under atmosphere, meaning the process is simpler and uses simpler equipment. However, the C-S and S-S bonds formed during sulfur vulcanization are weaker than the C-C bonds formed during peroxide vulcanization, and the resulting sulfur-vulcanized EPDM compositions have reduced compression set values and longevity compared to the peroxide-vulcanized EPDM compositions.

Peroxide vulcanization is typically completed in the absence of oxygen. When EPDM is vulcanized via peroxide under atmosphere, carbon radicals react with oxygen followed by degradation to polar functionalities, e.g., carboxylic acids, carbonyl, esters, etc. These polar species create a tacky surface. Surface tackiness is an issue particularly when de-molding of final products is completed at high temperatures. To reduce surface tackiness, peroxide vulcanization uses more expensive and complicated equipment to remove oxygen from the vulcanization environment.

There is a need for new EPDM compositions which are air curable and provide improved mechanical properties and longevity.

<CIT> disclosed a peroxide vulcanization process using nitroxides such as <NUM>-hydroxy-TEMPO as a scorch retardant. <CIT> disclosed compositions containing a nitroxide and a crosslinking promotor having at least one double bond as scorch retardants for crosslinking processes.

<CIT> disclosed a formulation containing a rubber component, peroxide, a nitroxide, and trimethylolpropane trimethacrylate or trimethylol-propane triacrylate for use as a battery sealing material.

<CIT> disclosed a formulation containing a rubber component, peroxide, and bis-TEMPO components as scorch retardants.

However, as discussed above, there is a need for new EPDM compositions which are air curable and provide improved mechanical properties and longevity.

The invention provides a composition comprising (A) an ethylene/alpha-olefin/diene interpolymer; (B) a peroxide comprising at least one -<NUM>-O- peroxide bond; and (C) a bis-TEMPO compound having the Structure I:
<CHM>
wherein R<NUM>, R<NUM>, R<NUM> and R<NUM> are each independently selected from the group consisting of H and C<NUM>-C<NUM> alkyl groups; X is selected from the group consisting of S, O, N, P, Se, a carbonyl group (C=O), a carboxyl group (O-C=O), an amide group (N-C=O), an azo group (N=N), an imino group (C=N), a carbamate group (N-C=O), a peroxy group (O-O), a phosphono group (-(O)<NUM>P=O), a phosphate group (O=P-(O)<NUM>), a sulfonyl group ((O=)<NUM>S), a sulfinyl group (O=S), a sulfonate ester group ((O=)<NUM>S-O), a sulfonate ester group (O=S-O), and combinations thereof; Y is selected from the group consisting of a substitute or unsubstituted aliphatic alkyl group , a substituted or unsubstituted aromatic alkyl group , a heterocyclic group, a siloxane group, an ethylene glycol group, an imide group, and combinations thereof; and n is greater than <NUM>, and wherein the ratio of the molar amount of nitroxide (NO·) groups of component (C) to the molar amount of the peroxide bonds of component (B) is from <NUM>:<NUM> to <NUM>:<NUM>.

<FIG> depicts the IR spectra of Comparative Samples <NUM>-<NUM> and Inventive Example <NUM>.

"Alkyl" refers to a saturated linear, cyclic, or branched hydrocarbon group. Nonlimiting examples of suitable alkyl groups include, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl (or <NUM>-methylpropyl), etc. In one embodiment, the alkyls have <NUM> to <NUM> carbon atoms. "Substituted alkyl," refers to an alkyl in which one or more hydrogen atom bound to any carbon of the alkyl is replaced by another group such as a halogen, aryl, substituted aryl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, halogen, haloalkyl, hydroxy, amino, phosphide, alkoxy, amino, thio, nitro, and combinations thereof. Suitable substituted alkyls include, for example, benzyl, trifluoromethyl and the like. "Heteroalkyl" refers to an alkyl as described above in which one or more carbon atoms to any carbon of the alkyl is replaced by a heteroatom selected from the group consisting of N, O, P, B, S, Si, Sb, Al, Sn, As, Se and Ge. This same list of heteroatoms is useful throughout this specification. The bond between the carbon atom and the heteroatom may be saturated or unsaturated. Thus, an alkyl substituted with a heterocycloalkyl, substituted heterocycloalkyl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl, thio, or seleno is within the scope of the term heteroalkyl. Suitable heteroalkyls include cyano, benzoyl, <NUM>-pyridyl, <NUM>-furyl and the like.

The term "composition," as used herein, includes the material(s), which comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition. Any reaction product or decomposition product is typically present in trace or residual amounts.

A "heteroatom" is an atom other than carbon or hydrogen. The heteroatom can be a non-carbon atom from Groups IV, V, VI and VII of the Periodic Table. Nonlimiting examples of heteroatoms include: F, N, O, P, B, S, and Si.

The term "polymer," as used herein, refers to a compound prepared by polymerizing monomers, whether of the same or a different type. The generic term polymer thus embraces the term homopolymer (employed to refer to polymers prepared from only one type of monomer, with the understanding that trace amounts of impurities can be incorporated into the polymer structure) and the term interpolymer as defined hereinafter. Trace amounts of impurities, such as catalyst residues, can be incorporated into and/or within the polymer.

The term "interpolymer," as used herein, refers to polymers prepared by the polymerization of at least two different types of monomers. The term interpolymer thus includes the term copolymer (employed to refer to polymers prepared from two different types of monomers) and polymers prepared from more than two different types of monomers.

The term "ethylene/α-olefin/diene interpolymer," as used herein, refers to a polymer that comprises, in polymerized form, ethylene, an α-olefin, and a diene. In one embodiment, the "ethylene/α-olefin/diene interpolymer" comprises a majority weight percent of ethylene (based on the weight of the interpolymer).

The "molar amount of nitroxide groups" is calculated by the equation:
molar amount of nitroxide groups in peroxide = gt * molet/g * (number of nitroxide groups) wherein gt is the amount of bis-TEMPO compound in grams, molet/g is the moles of bis-TEMPO compound in one gram, and the number of nitroxide groups is the number of nitroxide groups in one bis-TEMPO molecule.

The "molar amount of the peroxide bonds" is calculated by the equation:
molar amount of peroxide bonds = gp * molep/g * (number of peroxide bonds) wherein gp is the amount of peroxide in grams, molep/g is the moles of peroxide per gram, and the number of peroxide bonds is the number of -<NUM>-O- bonds in one peroxide molecule.

The terms "comprising," "including," "having," and their derivatives, are not intended to exclude the presence of any additional component, step or procedure, whether or not the same is specifically disclosed. In order to avoid any doubt, all compositions claimed through use of the term "comprising" may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless stated to the contrary. In contrast, the term, "consisting essentially of " excludes from the scope of any succeeding recitation any other component, step or procedure, excepting those that are not essential to operability. The term "consisting of" excludes any component, step or procedure not specifically delineated or listed. The term "or," unless stated otherwise, refers to the listed members individually as well as in any combination. Use of the singular includes use of the plural and vice versa.

The numerical ranges disclosed herein include all values from, and including, the lower and upper value. For ranged containing explicit values (e.g., <NUM> or <NUM>; or <NUM> to <NUM>; or <NUM>; or <NUM>), any subrange between any two explicit values is included (e.g., <NUM> to <NUM>; <NUM> to <NUM>; <NUM> to <NUM>; <NUM> to <NUM>; <NUM> to <NUM>; etc.).

The terpolymers containing ethylene, propylene, and <NUM>-ethylidene-<NUM>-norbomene were analyzed using ASTM D3900 for their respective ethylene contents and ASTM D6047 for their ethylidene-norbomene or dicyclopentadiene contents.

Density is determined in accordance with ASTM D792, Method B. The results are recorded in grams (g) per cubic centimeter (g/cc or g/cm<NUM>).

The rheology ratio (RR) (V0. <NUM>/V100) is determined by examining samples using melt rheology techniques on a Rheometric Scientific, Inc. ARES (Advanced Rheometric Expansion System) dynamic mechanical spectrometer (DMS). The samples are examined at <NUM>, using the dynamic frequency mode, and <NUM> millimeter (mm) diameter parallel plate fixtures with a <NUM> gap. With a strain rate of <NUM>%, and an oscillatory rate that is incrementally increased from <NUM> to <NUM> rad/sec, five data points are taken for each decade of frequency analyzed. Each sample (either pellets or bale) is compression molded into <NUM> inch (<NUM> centimeter (cm)) diameter plaques by ⅛ inch (<NUM>) thick at <NUM>,<NUM> psi (<NUM> megaPascals (MPa)) pressure for one minute at <NUM>. The plaques are quenched and cooled (over a period of <NUM> minute) to room temperature. The "<NUM> plaques" are cut from the center portion of larger plaques. These <NUM> diameter aliquots are then inserted into the ARES, at <NUM>, and allowed to equilibrate for five minutes, prior to initiation of testing. The samples are maintained in a nitrogen environment throughout the analyses to minimize oxidative degradation. Data reduction and manipulation are accomplished by the ARES2/A5:RSI Orchestrator Windows <NUM> based software package. RR measures the ratio of the viscosity versus shear rate curve.

Viscosity refers to the resistance of a fluid which is being deformed by either sheer stress or tensile stress. For purposes of this specification, viscosity is measured at <NUM> using a Brookfield viscometer as measured in accordance with ASTM D <NUM>.

Mooney Viscosity (ML1+<NUM> at <NUM>) was measured in accordance with ASTM <NUM>, with a one minute preheat time and a four minute rotor operation time. The instrument is an Alpha Technologies Mooney Viscometer <NUM>.

The viscosity of each formulated composition is measured using an uncured blanket (see experimental section), so that the viscosity of the uncured composition could be examined. Samples were conditioned for <NUM> hours at room temperature, prior to testing.

Molecular weight is determined using gel permeation chromatography (GPC) on a Waters <NUM> high temperature chromatographic unit equipped with three mixed porosity columns (Polymer Laboratories <NUM>, <NUM>, <NUM>, and <NUM>), operating at a system temperature of <NUM>. The solvent is <NUM>,<NUM>,<NUM>-trichlorobenzene, from which <NUM> percent by weight solutions of the samples are prepared for injection. The flow rate is <NUM>/min and the injection size is <NUM> microliters.

The molecular weight determination is deduced by using narrow molecular weight distribution polystyrene standards (from Polymer Laboratories) in conjunction with their elution volumes. The equivalent polyethylene molecular weights are determined by using appropriate Mark-Houwink coefficients for polyethylene and polystyrene (as described by <NPL>)) to derive the following equation: <MAT> In this equation, a = <NUM> and b = <NUM>.

Number average molecular weight, Mn, of a polymer is expressed as the first moment of a plot of the number of molecules in each molecular weight range against the molecular weight. In effect, this is the total molecular weight of all molecules divided by the number of molecules and is calculated in the usual matter according to the following formula: <MAT> where ni = number of molecules with molecular weight Mi; wi = weight fraction of material having molecular weight Mi; and Σ n i= total number of molecules.

Weight average molecular weight, Mw, is calculated in the usual manner according to the following formula: Mw = Σ wi x Mi, where w; and Mi are the weight fraction and molecular weight, respectively, of the ith fraction eluting from the GPC column.

The ratio of these two averages, the molecular weight distribution (MWD or Mw/Mn), defines the breadth of the molecular weight distribution.

MDR cure properties of each formulation are measured in accordance to ASTM D-<NUM>, using an Alpha Technologies MDR <NUM>. A <NUM> sample is cut from the compression molded sample and put in the MDR. The MDR test is carried out at <NUM> over a period of <NUM> minutes at an oscillation frequency of <NUM> CPM (<NUM>) and an oscillation angle of <NUM> degree (<NUM>% strain). The minimum torque (ML) maximum torque (MH) exerted by the MDR during the testing interval are reported in dNm. The difference between MH and ML is indicative of the extent of crosslinking, with the greater the difference reflecting a greater extent of crosslinking. The time it takes for torque to reach X% of MH (tx) is reported in minutes. The time required for the increase of <NUM> (ts1) or <NUM> (ts2) points from minimum torque is recorded in minutes. The ts1 and ts2 values are indicative of the time required for the crosslinking process to begin. A shorter time indicates crosslinking initiates faster.

The degradation of the hot air vulcanized samples is determined by FTIR-ATR Analysis. Methylene groups (CH<NUM>) signal around <NUM>-<NUM> and are used as the industry standard. Carbonyl groups (C=O) signal around <NUM>-<NUM> and are used to monitor the degradation degree. The height ratio between <NUM>-<NUM> and <NUM>-<NUM> represents the degradation degree: <MAT> wherein D is the degradation degree, H<NUM> is the IR peak height at <NUM>-<NUM> (using <NUM>-<NUM>-<NUM> as a baseline), and H<NUM> is the IR peak height at <NUM>-<NUM> (using <NUM>-<NUM>-<NUM> as a baseline).

Relative degradation degree is calculated according to the formula below: <MAT> wherein RD is the relative degradation degree, D is the degradation degree of the tested specimen, and D<NUM> is the degradation degree of CS1 (control).

The hot air vulcanized samples are tested for surface tackiness using the Finger Test. The Finger Test is a laboratory qualitative test method. Laboratory testers use their fingers to touch the vulcanized sample and provide feedback regarding the surface tackiness of the sample using the following criteria:.

As discussed above, the invention provides a composition comprising (A) an ethylene/alpha-olefin/diene interpolymer; (B) a peroxide comprising at least one -<NUM>-O-peroxide bond; and (C) a bis-TEMPO compound having the Structure I:
<CHM>
wherein R<NUM>, R<NUM>, R<NUM> and R<NUM> are each independently selected from H and C<NUM>-C<NUM> alkyl groups; X is selected from S, O, N, P, Se, a carbonyl group (C=O), a carboxyl group (O-C=O), an amide group (N-C=O), an azo group (N=N), an imino group (C=N), a carbamate group (N-C=O), a peroxy group (O-O), a phosphono group (-(O)<NUM>P=O), a phosphate group (O=P-(O)<NUM>), a sulfonyl group ((O=)<NUM>S), a sulfinyl group (O=S), a sulfonate ester group ((O=)<NUM>S-O), a sulfonate ester group (O=S-O), and combinations thereof; Y is selected from a substituted or unsubstituted aliphatic alkyl group, a substituted or unsubstituted aromatic alkyl group, a heterocyclic group, a siloxane group, an ethylene glycol group, an imide group, and combinations thereof; and n is greater than <NUM>, and wherein the ratio of the molar amount of nitroxide (NO·) groups of component (C) to the molar amount of the peroxide bonds of component (B) is from <NUM>:<NUM> to <NUM>:<NUM>.

The composition may comprise a combination of two or more embodiments described herein.

The invention also provides a vulcanized, or crosslinked, composition formed from a composition of one or more embodiments described herein.

The invention also provides an article comprising at least one component formed from a composition of one or more embodiments described herein. In a further embodiment, the article is selected from the group consisting of profiles, injection molded parts, gaskets, automotive parts, building and construction materials, shoe components, and tubes.

In one embodiment, the article is an automotive part.

The invention also provides an article comprising at least one component formed from a crosslinked composition of one or more embodiments described herein. In a further embodiment, the article is selected from the group consisting of profiles, injection molded parts, gaskets, automotive parts, building and construction materials, shoe components, and tubes.

An article may comprise a combination of two or more embodiments described herein.

The composition includes an ethylene/alpha-olefin/diene interpolymer. The ethylene/alpha-olefin/diene interpolymer comprises, in polymerized form, a majority amount of ethylene, an alpha-olefin, and a diene.

In an embodiment, the EAODM comprises from <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt% to <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt% ethylene, based on the total weight of the EAODM , as measured according to FTIR analysis.

The alpha-olefin may be either an aliphatic or an aromatic compound. In an embodiment, the alpha-olefin is preferably a C<NUM>-C<NUM> aliphatic compound, or a C<NUM>-C<NUM> aliphatic compound, or a C<NUM>-C<NUM> aliphatic compound. Exemplary C<NUM>-C<NUM> aliphatic alpha-olefins are propylene, <NUM>-butene, <NUM>-hexene and <NUM>-octene. In an embodiment, the alpha-olefin is propylene.

In an embodiment, the EAODM comprises from <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt% to <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt% alpha-olefin, based on the total weight of the EAODM, as measured according to FTIR analysis.

Illustrative dienes include straight chain acyclic dienes, such as <NUM>,<NUM>-hexadiene and <NUM>,<NUM>-heptadiene; branched chain acyclic dienes, such as <NUM>-methyl-<NUM>,<NUM>-hexadiene, <NUM>-methyl-<NUM>,<NUM>-hexadiene, <NUM>-methyl-<NUM>,<NUM>-heptadiene, <NUM>-methyl-<NUM>,<NUM>-octadiene, <NUM>,<NUM>-dimethyl-<NUM>,<NUM>-octadiene, <NUM>,<NUM>-dimethyl-<NUM>,<NUM>-octadiene, <NUM>,<NUM>-dimethyl-<NUM>,<NUM>-octadiene, <NUM>,<NUM>-decadiene, and mixed isomers of dihydromyrcene; single ring alicyclic dienes such as <NUM>,<NUM>-cyclohexadiene, <NUM>,<NUM>-cyclooctadiene and <NUM>,<NUM>-cyclododecadiene; multi-ring alicyclic fused and bridged ring dienes, such as tetrahydroindene, methyl tetrahydroindene; alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes such as <NUM>-methylene-<NUM>-norbomene (MNB), <NUM>-ethylidene-<NUM>-norbornene (ENB), <NUM>-vinyl-<NUM>-norbomene, <NUM>-propenyl-<NUM>-norbomene, <NUM>-isopropylidene-<NUM>-norbornene, <NUM>-(<NUM>-cyclopentenyl)-<NUM>-norbomene, and <NUM>-cyclohexylidene-<NUM>-norbomene. In an embodiment, the diene is selected from ENB, dicyclopentadiene, <NUM>,<NUM>-hexadiene, <NUM>-methyl-<NUM>,<NUM>-octadiene, and preferably, ENB, dicyclopentadiene and <NUM>,<NUM>-hexadiene. In an embodiment, the diene is selected from ENB and dicyclopentadiene. In an embodiment, the diene is ENB.

In an embodiment, the EAODM comprises from greater than <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt% to <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt% diene, based on the total weight of the EAODM, as measured according to FTIR analysis.

In an embodiment, the ethylene/alpha-olefin/diene interpolymer is an ethylene/propylene/diene interpolymer (EPDM). In a further embodiment, the diene is ENB.

In an embodiment, the density of the EAODM is from <NUM>/cc, <NUM>/cc to <NUM>/cc, or <NUM>/cc, or <NUM>/cc, or <NUM>/cc.

In one embodiment, the EAODM has a rheology ratio (V0. <NUM>/V100 at <NUM>) from greater than or equal to <NUM>, or greater than or equal to <NUM>, or greater than or equal to <NUM>, or greater than or equal to <NUM> to <NUM>, or <NUM>, or <NUM>. The rheology ratio (V0. <NUM>/V100 at <NUM>) of the EAODM is that of the neat polymer (no oil, no filler). The interpolymer may be stabilized with "ppm amounts" of one or more antioxidants and/or other stabilizers.

In one embodiment, the EAODM has a viscosity at <NUM> rad/sec, <NUM>, from <NUM>,<NUM> Pa•s, or <NUM>,<NUM> Pa•s, or <NUM>,<NUM> Pa•s to <NUM>,<NUM> Pa•s, or190,<NUM> Pa•s, or <NUM>,<NUM> Pa•s.

In one embodiment, the EAODM comprises from <NUM> weight percent (wt%), or <NUM> wt%, or <NUM> wt% to <NUM> wt%, or <NUM> wt%, or <NUM> wt% diene, based on the weight of the interpolymer.

In one embodiment, the EAODM has a Mooney Viscosity greater than or equal to <NUM>, or greater than or equal to <NUM>, or greater than or equal to <NUM>, or greater than or equal to <NUM>, or greater than or equal to <NUM>, or greater than or equal to <NUM>, or greater than or equal to <NUM> to less than or equal to <NUM>, or less than or equal to <NUM>, or less than or equal to <NUM>, or less than or equal to <NUM>, or less than or equal to <NUM>, or less than or equal to <NUM> (ML <NUM>+<NUM>, <NUM>). Mooney viscosity is that of the neat polymer (no oil, no filler). The polymer may be stabilized with "ppm amounts" of one or more antioxidants and/or other stabilizers.

In one embodiment, the EAODM has a molecular weight distribution (MWD, or Mw/Mn) greater than or equal to <NUM>, or greater than or equal to <NUM>, or greater than or equal to <NUM>, or greater than or equal to <NUM>, or greater than or equal to <NUM>, or greater than or equal to <NUM> to less than or equal to <NUM>, or less than or equal to <NUM>, or less than or equal to <NUM>, or to less than or equal to <NUM>, or to less than or equal to <NUM>.

In one embodiment, the EAODM has a weight average molecular weight (Mw) from <NUM>,<NUM>/mol, or <NUM>,<NUM>/mol to less than or equal to <NUM>,<NUM>/mol, or less than or equal to <NUM>,<NUM>/mol, or less than or equal to <NUM>,<NUM>/mol.

In an embodiment, the EAODM has one, some or all of the following properties:.

In an embodiment, the EAODM has, at least two, or at least three, or all four of properties (i)-(iv).

In an embodiment, the EAODM has two properties of (i)-(iv). In an embodiment, the EAODM has properties (i) and (ii), or (i) and (iii), or (i) and (iv), or (ii) and (iii), or (ii) and (iv), or (iii) and (iv).

In an embodiment, the EAODM has three properties of (i)-(iv). In an embodiment, the EAODM has properties (i), (ii) and (iii); or (i), (ii) and (iv); or (i), (iii) and (iv); or (ii), (iii) and (iv).

In an embodiment, the EAODM has all four properties (i)-(iv).

In an embodiment, the EAODM is an EPDM having one, some or all of the following properties:.

In an embodiment, the EPDM has, at least two, or at least three, or all four of properties (i)-(iv).

Nonlimiting examples of commercially available EAODMs include NORDEL IP <NUM>, an ethylene/propylene/ENB terpolymer having a density of <NUM>/cc, an ethylene content of <NUM> wt%, an ENB content of <NUM> wt%, and a Mooney viscosity of <NUM>, available from the Dow Chemical Company, and NORDEL IP <NUM>, an ethylene/propylene/ENB terpolymer having a density of <NUM>/cc, an ethylene content of <NUM> wt%, an ENB content of <NUM> wt%, and a Mooney viscosity of <NUM>, available from the Dow Chemical Company.

In one embodiment, the EAODM is present in the composition in an amount from greater than or equal to <NUM> wt%, or greater than or equal to <NUM> wt%, or greater than or equal to <NUM> wt%, or greater than or equal to <NUM> wt% to <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, based on the total weight of the composition.

In an embodiment, the composition may include a mixture of two or more EAODM as described herein. In an embodiment, the sum total amount of all EAODM in the composition is from greater than or equal to <NUM> wt%, or greater than or equal to <NUM> wt%, or greater than or equal to <NUM> wt%, or greater than or equal to <NUM> wt% to <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, based on the total weight of the composition.

The EAODM, further an EPDM, may comprise a combination of two or more embodiments as described herein.

The composition includes a peroxide comprising at least one peroxide (-O-O-) bond.

Suitable peroxides include, but are not limited to, aromatic dacyl peroxides; aliphatic dacyl peroxides; dibasic acid peroxides; ketene peroxides; alkyl peroxyesters; alkyl hydroperoxides, for example, diacetylperoxide; dibenzoylperoxide; bis-<NUM>,<NUM>-dichlorobenzoyl peroxide; di-tert-butyl peroxide; dicumylperoxode; tert-butyl-perbenzoate; tertbutylcumylperoxide; <NUM>,<NUM>-bis (t-butylperoxy)-<NUM>,<NUM>-dimethylhexane; <NUM>,<NUM>-bis (t-butylperoxy)-<NUM>,<NUM>-dimethylhexyne-<NUM>; <NUM>,<NUM>,<NUM>',<NUM>'-tetra-(t-butylperoxy)-<NUM>,<NUM>-dicyclohexylpropane; <NUM>,<NUM>-bis-(t-butylperoxyisopropyl)-benzene; <NUM>,<NUM>-bis-(t-butylperoxy)-<NUM>,<NUM>,<NUM>-trimethyl-cyclohexane; lauroyl peroxide; succinic acid peroxide; cyclohexanone peroxide; t-butyl peracetate; butyl hydroperoxide; <NUM>,<NUM>-dimethyl-<NUM>,<NUM>-di(t-butylperoxy)hexane; and combinations thereof.

In an embodiment, the peroxide is present in an amount from greater than <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt% to <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, based on the total weight of the composition.

In an embodiment, the peroxide is present in an amount from <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt% to <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, based on the total weight of the composition.

A peroxide may comprise a combination of two or more embodiments as described herein.

The composition includes a bis-TEMPO compound having the Structure I:
<CHM>
wherein R<NUM>, R<NUM>, R<NUM> and R<NUM> are each independently selected from H and C<NUM>-C<NUM> alkyl groups; X is selected from S, O, N, P, Se, a carbonyl group (C=O), a carboxyl group (O-C=O), an amide group (N-C=O), an azo group (N=N), an imino group (C=N), a carbamate group (N-C=O), a peroxy group (O-O), a phosphono group (-(O)<NUM>P=O), a phosphate group (O=P-(O)<NUM>), a sulfonyl group ((O=)<NUM>S), a sulfinyl group (O=S), a sulfonate ester group ((O=)<NUM>S-O), a sulfonate ester group (O=S-O), and combinations thereof; Y is selected from a substituted or unsubstituted aliphatic alkyl group, a substituted or unsubstituted aromatic alkyl group, a heterocyclic group, a siloxane group, an ethylene glycol group, an imide group, and combinations thereof; and n is greater than <NUM>. In an embodiment, each of R<NUM>, R<NUM>, R<NUM> and R<NUM> are the same. In an embodiment, at least one of R<NUM>, R<NUM>, R<NUM> and R<NUM> is different than the others of R<NUM>, R<NUM>, R<NUM> and R<NUM>.

In an embodiment, R<NUM>, R<NUM>, R<NUM> and R<NUM> are the same. In an embodiment, R<NUM>, R<NUM>, R<NUM> and R<NUM> are the same and selected from H and a methyl group. In an embodiment, R<NUM>, R<NUM>, R<NUM> and R<NUM> are each a methyl group.

In an embodiment, X is a carboxyl group.

In an embodiment, Y is a substituted or unsubstituted aliphatic alkyl group or a substituted or unsubstituted aromatic alkyl group having from <NUM>, or <NUM>, or <NUM> to <NUM>, or <NUM>, or <NUM>, or <NUM> carbon atoms.

In an embodiment, Y is an aliphatic C<NUM>-C<NUM> alkyl.

In an embodiment, Y is an aliphatic C<NUM> alkyl.

In an embodiment, n is from <NUM> to <NUM>. In an embodiment, n is <NUM>.

In an embodiment, the bis-TEMPO compound is bis(<NUM>,<NUM>,<NUM>,<NUM>-tetramethyl-<NUM>-piperidinyloxy-<NUM>-yl) sebacate (<NPL>) and has the Structure II:
<CHM>.

In an embodiment, the bis-TEMPO compound is present in an amount from greater than <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt% to <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, or <NUM> wt%, based on the total weight of the composition.

A bis-TEMPO compound may comprise a combination of two or more embodiments as described herein.

In an embodiment, the composition optionally includes one or more additives. Nonlimiting examples of additives include oils, fillers, processing aids, and/or stabilizers.

In one embodiment, the composition includes one or more oils. In an embodiment, the weight ratio of the first composition to the oil is form <NUM>/<NUM> to <NUM>/<NUM>. Oils include, but are not limited to, petroleum oils, such as paraffinic, aromatic and naphthenic oils; polyalkylbenzene oils; organic acid monoesters; and combinations thereof.

In one embodiment, the composition further comprises one or more fillers. Fillers include, but are not limited to, clay, calcium carbonate, talc, carbon black, silica, mineral fillers, and combinations thereof.

In one embodiment, the composition further comprises one or more processing aids. Processing aids include, but are not limited to, aliphatic acids, mineral aliphatic acid salts, polyethylene glycol, and combinations thereof.

In one embodiment, the composition includes one or more stabilizers. Stabilizers include organic molecules that inhibits oxidation, or a collection of such molecules. The stabilizer functions to provide antioxidizing properties to the EAODM composition and/or crosslinked product. Nonlimiting examples of suitable stabilizers are <NUM>,<NUM>,<NUM>-trimethyl-<NUM>,<NUM>-dihydroquinoline, polymerized (e.g., Vulnanox HS/LG or TMQ); Zinc <NUM>-mercaptotolumidazole (e.g., VANOX ZMTI); bis(<NUM>-(<NUM>-methyl-<NUM>-phenylethyl)phenyl)amine (e.g., NAUGARD <NUM>); <NUM>,<NUM>'-methylene-bis(<NUM>-methyl-<NUM>-t-butylphenol) (e.g., VANOX MBPC); <NUM>,<NUM>'-thiobis(<NUM>-t-butyl-<NUM>-methylphenol (<NPL>, commercially LOWINOX TBM-<NUM>); <NUM>,<NUM>'-thiobis(<NUM>-t-butyl-<NUM>-methylphenol (<NPL>, commercially LOWINOX TBP-<NUM>); tris[(<NUM>-tert-butyl-<NUM>-hydroxy-<NUM>,<NUM>-dimethylphenyl)methyl]-<NUM>,<NUM>,<NUM>-triazine-<NUM>,<NUM>,<NUM>-trione (e.g., CYANOX <NUM>); pentaerythritol tetrakis(<NUM>-(<NUM>,<NUM>-bis(<NUM>,<NUM>-dimethylethyl)-<NUM>-hydroxyphenyl)propionate (e.g., IRGANOX <NUM>, <NPL>); <NUM>,<NUM>-bis(<NUM>,<NUM>-dimethylethyl)-<NUM>-hydroxybenzenepropanoic acid <NUM>,<NUM>'- thiodiethanediyl ester (e.g., IRGANOX <NUM>, <NPL>); and distearyl thiodipropionate ("DSTDP"). When present, the stabilizers may be present in an amount from <NUM> phr, or <NUM> phr, or <NUM> phr to <NUM> phr, or <NUM> phr, or <NUM> phr.

In an embodiment, the composition further includes one or more processing aids. Nonlimiting examples of suitable processing aids include aliphatic acid, mineral aliphatic acid salts, polyethylene glycol, and combinations thereof.

The invention provides a composition comprising (A) an ethylene/alpha-olefin/diene interpolymer; (B) a peroxide comprising at least one -<NUM>-O- peroxide bond; and (C) a bis-TEMPO compound having the Structure I:
<CHM>
wherein R<NUM>, R<NUM>, R<NUM> and R<NUM> are each independently selected from H and C<NUM>-C<NUM> alkyl groups; X is selected from S, O, N, P, Se, a carbonyl group (C=O), a carboxyl group (O-C=O), an amide group (N-C=O), an azo group (N=N), an imino group (C=N), a carbamate group (N-C=O), a peroxy group (O-O), a phosphono group (-(O)<NUM>P=O), a phosphate group (O=P-(O)<NUM>), a sulfonyl group ((O=)<NUM>S), a sulfinyl group (O=S), a sulfonate ester group ((O=)<NUM>S-O), a sulfonate ester group (O=S-O), and combinations thereof; Y is selected from a substituted or unsubstituted aliphatic alkyl group, a substituted or unsubstituted aromatic alkyl group, a heterocyclic group, a siloxane group, an ethylene glycol group, an imide group, and combinations thereof; and n is greater than <NUM>, and wherein the ratio of the molar amount of nitroxide (NO·) groups of component (C) to the molar amount of the peroxide bonds of component (B) is from <NUM> to <NUM>.

In an embodiment, the ratio of the molar amount of nitroxide (NO·) groups of component (C) to the molar amount of the peroxide bonds of component (B) is from <NUM>, or <NUM> to <NUM>, or <NUM>, or <NUM>.

The ratio of the molar amount of nitroxide (NO·) groups of component (C) to the molar amount of the peroxide bonds of component (B) is calculated according to the following equation: <MAT> wherein gt is the amount of bis-TEMPO compound in grams, molet/g is the moles of bis-TEMPO compound in one gram, the number of nitroxide groups is the number of nitroxide groups in one bis-TEMPO molecule, gp is the amount of peroxide in grams, molep/g is the moles of peroxide in one gram, and the number of peroxide bonds is the number of peroxide bonds in one peroxide molecule.

In an embodiment, the ratio of the molar amount of nitroxide (NO·) groups of component (C) to the molar amount of the peroxide bonds of component (B) is from <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>.

In an embodiment, the ratio of the molar amount of nitroxide (NO·) groups of component (C) to the molar amount of the peroxide bonds of component (B) is from <NUM>:<NUM> to <NUM>:<NUM>, or from <NUM>:<NUM> to <NUM>:<NUM>, or from <NUM>:<NUM> to <NUM>:<NUM>, or from <NUM>:<NUM> to <NUM>:<NUM>, or from <NUM>:<NUM> to <NUM>:<NUM>, or from <NUM>:<NUM> to <NUM>:<NUM>, or from <NUM>:<NUM> to <NUM>:<NUM>, or from <NUM>:<NUM> to <NUM>:<NUM>, or from <NUM>:<NUM> to <NUM>. <NUM>:<NUM>.

In an embodiment, the composition is prepared by mixing (A) the EAODM, (B) peroxide, and (C) bis-TEMPO compound.

In an embodiment, the invention provides a crosslinked composition comprising the reaction product of a composition comprising (A) an ethylene/alpha-olefin/diene interpolymer; (B) a peroxide comprising at least one -O-O- peroxide bond; and (C) a bis-TEMPO compound having the Structure I:
<CHM>
wherein R<NUM>, R<NUM>, R<NUM> and R<NUM> are each independently selected from H and C<NUM>-C<NUM> alkyl groups; X is selected from S, O, N, P, Se, a carbonyl group (C=O), a carboxyl group (O-C=O), an amide group (N-C=O), an azo group (N=N), an imino group (C=N), a carbamate group (N-C=O), a peroxy group (O-O), a phosphono group (-(O)<NUM>P=O), a phosphate group (O=P-(O)<NUM>), a sulfonyl group ((O=)<NUM>S), a sulfinyl group (O=S), a sulfonate ester group ((O=)<NUM>S-O), a sulfonate ester group (O=S-O), and combinations thereof; Y is selected from a substituted or unsubstituted aliphatic alkyl group, a substituted or unsubstituted aromatic alkyl group, a heterocyclic group, a siloxane group, an ethylene glycol group, an imide group, and combinations thereof; and n is greater than <NUM>, and wherein the ratio of the molar amount of nitroxide (NO·) groups of component (C) to the molar amount of the peroxide bonds of component (B) is from <NUM>:<NUM> to <NUM>:<NUM>.

In an embodiment, the crosslinked EAODM has the structure III:
<CHM>.

In an embodiment, the crosslinked composition is formed by thermally treating a composition comprising (A) an ethylene/alpha-olefin/diene interpolymer; (B) a peroxide comprising at least one -<NUM>-O- peroxide bond; and (C) a bis-TEMPO compound having the Structure I:
<CHM>
wherein R<NUM>, R<NUM>, R<NUM> and R<NUM> are each independently selected from H and C<NUM>-C<NUM> alkyl groups; X is selected from S, O, N, P, Se, a carbonyl group (C=O), a carboxyl group (O-C=O), an amide group (N-C=O), an azo group (N=N), an imino group (C=N), a carbamate group (N-C=O), a peroxy group (O-O), a phosphono group (-(O)<NUM>P=O), a phosphate group (O=P-(O)<NUM>), a sulfonyl group ((O=)<NUM>S), a sulfinyl group (O=S), a sulfonate ester group ((O=)<NUM>S-O), a sulfonate ester group (O=S-O), and combinations thereof; Y is selected from a substituted or unsubstituted aliphatic alkyl group, a substituted or unsubstituted aromatic alkyl group, a heterocyclic group, a siloxane group, an ethylene glycol group, an imide group, and combinations thereof; and n is greater than <NUM>, and wherein the ratio of the molar amount of nitroxide (NO·) groups of component (C) to the molar amount of the peroxide bonds of component (B) is from <NUM>:<NUM> to <NUM>:<NUM>.

In an embodiment, the temperature at which the composition is thermally treated to produce the crosslinked composition is from <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM> to <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>.

In an embodiment, the crosslinked composition is a thermally treated composition comprising (A) an ethylene/alpha-olefin/diene interpolymer having a diene content from <NUM> wt%, or <NUM> wt% to <NUM> wt%, or <NUM> wt%; (B) a peroxide comprising at least one -O-O-peroxide bond; and (C) a bis-TEMPO compound having the Structure I:
<CHM>
wherein R<NUM>, R<NUM>, R<NUM> and R<NUM> are each independently selected from H and C<NUM>-C<NUM> alkyl groups; X is selected from S, O, N, P, Se, a carbonyl group (C=O), a carboxyl group (O-C=O), an amide group (N-C=O), an azo group (N=N), an imino group (C=N), a carbamate group (N-C=O), a peroxy group (O-O), a phosphono group (-(O)<NUM>P=O), a phosphate group (O=P-(O)<NUM>), a sulfonyl group ((O=)<NUM>S), a sulfinyl group (O=S), a sulfonate ester group ((O=)<NUM>S-O), a sulfonate ester group (O=S-O), and combinations thereof; Y is selected from a substituted or unsubstituted aliphatic alkyl group, a substituted or unsubstituted aromatic alkyl group, a heterocyclic group, a siloxane group, an ethylene glycol group, an imide group, and combinations thereof; and n is greater than <NUM>, and wherein the ratio of the molar amount of nitroxide (NO·) groups of component (C) to the molar amount of the peroxide bonds of component (B) is from <NUM>:<NUM> to <NUM>:<NUM> (hereinafter "Crosslinked Composition <NUM>").

In an embodiment, the crosslinked composition is a thermally treated composition comprising (A) an ethylene/propylene/diene interpolymer having a diene content from <NUM> wt%, or <NUM> wt% to <NUM> wt%, or <NUM> wt%; (B) a peroxide comprising at least one -O-O- peroxide bond; and (C) a bis-TEMPO compound having the Structure I:
<CHM>
wherein R<NUM>, R<NUM>, R<NUM> and R<NUM> are each independently selected from H and C<NUM>-C<NUM> alkyl groups; X is selected from S, O, N, P, Se, a carbonyl group (C=O), a carboxyl group (O-C=O), an amide group (N-C=O), an azo group (N=N), an imino group (C=N), a carbamate group (N-C=O), a peroxy group (O-O), a phosphono group (-(O)<NUM>P=O), a phosphate group (O=P-(O)<NUM>), a sulfonyl group ((O=)<NUM>S), a sulfinyl group (O=S), a sulfonate ester group ((O=)<NUM>S-O), a sulfonate ester group (O=S-O), and combinations thereof; Y is selected from a substituted or unsubstituted aliphatic alkyl group, a substituted or unsubstituted aromatic alkyl group, a heterocyclic group, a siloxane group, an ethylene glycol group, an imide group, and combinations thereof; and n is greater than <NUM>, and wherein the ratio of the molar amount of nitroxide (NO·) groups of component (C) to the molar amount of the peroxide bonds of component (B) is from <NUM>:<NUM> to <NUM>:<NUM> (hereinafter "Crosslinked Composition <NUM>").

In an embodiment, the crosslinked composition is a thermally treated composition comprising (A) an ethylene/propylene/ENB interpolymer having an ENB content from <NUM> wt%, or <NUM> wt% to <NUM> wt%, or <NUM> wt%; (B) a peroxide comprising at least one -<NUM>-O-peroxide bond; and (C) a bis-TEMPO compound having the Structure I:
<CHM>
wherein R<NUM>, R<NUM>, R<NUM> and R<NUM> are each independently selected from H and C<NUM>-C<NUM> alkyl groups; X is selected from S, O, N, P, Se, a carbonyl group (C=O), a carboxyl group (O-C=O), an amide group (N-C=O), an azo group (N=N), an imino group (C=N), a carbamate group (N-C=O), a peroxy group (O-O), a phosphono group (-(O)<NUM>P=O), a phosphate group (O=P-(O)<NUM>), a sulfonyl group ((O=)<NUM>S), a sulfinyl group (O=S), a sulfonate ester group ((O=)<NUM>S-O), a sulfonate ester group (O=S-O), and combinations thereof; Y is selected from a substituted or unsubstituted aliphatic alkyl group, a substituted or unsubstituted aromatic alkyl group, a heterocyclic group, a siloxane group, an ethylene glycol group, an imide group, and combinations thereof; and n is greater than <NUM>, and wherein the ratio of the molar amount of nitroxide (NO·) groups of component (C) to the molar amount of the peroxide bonds of component (B) is from <NUM>:<NUM> to <NUM>:<NUM> (hereinafter "Crosslinked Composition <NUM>").

In an embodiment, the crosslinked composition is Crosslinked Composition <NUM>, Crosslinked Composition <NUM>, or Crosslinked Composition <NUM> and has an MH from <NUM> dNm, or <NUM> dNm, or <NUM> dNm to <NUM> dNm, or <NUM> dNm, or <NUM> dNm, as measured in accordance with ASTM D-<NUM>.

In an embodiment, the crosslinked composition is Crosslinked Composition <NUM>, Crosslinked Composition <NUM>, or Crosslinked Composition <NUM> and has a ML from. <NUM> dNm, or. <NUM> dNm, or. <NUM> dNm, or. <NUM> dNm, or. <NUM> dNm to. <NUM> dNm, or. <NUM> dNm, or. <NUM> dNm, or. <NUM> dNm, as measured in accordance with ASTM D-<NUM>.

In an embodiment, the crosslinked composition is Crosslinked Composition <NUM>, Crosslinked Composition <NUM>, or Crosslinked Composition <NUM> and has a MH-ML from <NUM> dNm, or <NUM> dNm, or <NUM> dNm, or <NUM> dNm, or <NUM> dNm, or <NUM> dNm, or <NUM> dNm, or <NUM> dNm, or <NUM> dNm to <NUM> dNm, or <NUM> dNm, of <NUM> dNm, or <NUM> dNm, or <NUM> dNm, or <NUM> dNm, or <NUM> dNm, or <NUM> dNm, or <NUM> dNm, or <NUM> dNm, or <NUM> dNm, or <NUM> dNm, as measured in accordance with ASTM D-<NUM>.

In an embodiment, the crosslinked composition is Crosslinked Composition <NUM>, Crosslinked Composition <NUM>, or Crosslinked Composition <NUM> and has a ts1 from <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , as measured in accordance with ASTM D-<NUM>.

In an embodiment, the crosslinked composition is Crosslinked Composition <NUM>, Crosslinked Composition <NUM>, or Crosslinked Composition <NUM> and has a ts2 from <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , as measured in accordance with ASTM D-<NUM>.

In an embodiment, the crosslinked composition is Crosslinked Composition <NUM>, Crosslinked Composition <NUM>, or Crosslinked Composition <NUM> and has a t<NUM> from <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , or <NUM>. , as measured in accordance with ASTM D-<NUM>.

In an embodiment, the crosslinked composition is hot air vulcanized to form an article.

In an embodiment, Crosslinked Composition <NUM> is hot air vulcanized to form Article <NUM>.

In an embodiment, the hot air vulcanized crosslinked article is Article <NUM>, Article <NUM> or Article <NUM> and has a H<NUM> from less than <NUM>, or less than <NUM>, or less than <NUM>, or less than <NUM>, or less than <NUM>, or less than <NUM> to <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or greater than <NUM>.

In an embodiment, the hot air vulcanized crosslinked article is Article <NUM>, Article <NUM> or Article <NUM> and has a H<NUM> from <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM> to <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>.

In an embodiment, the hot air vulcanized crosslinked article is Article <NUM>, Article <NUM> or Article <NUM> and has a degradation degree from greater than <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM> to <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>, or <NUM>.

In an embodiment, the hot air vulcanized crosslinked article has a relative degradation of less than <NUM>%, or less than or equal to <NUM>%, or less than or equal to <NUM>%, or less than or equal to <NUM>%, or less than or equal to <NUM>%, or less than or equal to <NUM>%, or less than or equal to <NUM>%, or greater than <NUM>%, or <NUM>%.

In an embodiment, the hot air vulcanized crosslinked article is Article <NUM>, Article <NUM> or Article <NUM> and has a relative degradation of less than <NUM>%, or less than or equal to <NUM>%, or less than or equal to <NUM>%, or less than or equal to <NUM>%, or less than or equal to <NUM>%, or less than or equal to <NUM>%, or less than or equal to <NUM>%, or greater than <NUM>%, or <NUM>%.

In an embodiment, the crosslinked composition is Crosslinked Composition <NUM>, Crosslinked Composition <NUM>, or Crosslinked Composition <NUM> and comprises one, some or all of the following properties:.

In an embodiment, the crosslinked composition is Crosslinked Composition <NUM>, Crosslinked Composition <NUM>, or Crosslinked Composition <NUM> and comprises at least two, at least three, at least four, at least five, or all six of properties (i)-(vi).

In an embodiment, the crosslinked composition is Crosslinked Composition <NUM>, Crosslinked Composition <NUM>, or Crosslinked Composition <NUM> and comprises two properties of (i)-(vi). In an embodiment, the crosslinked composition is Crosslinked Composition <NUM>, Crosslinked Composition <NUM>, or Crosslinked Composition <NUM> and comprises properties (i) and (ii), or (i) and (iii), or (i) and (iv), or (i) and (v), or (i) and (vi), or (ii) and (iii), or (ii) and (iv), or (ii) and (v), or (ii) and (vi), or (iii) and (iv), or (iii) and (v), or (iii) and (vi), or (iv) and (v), or (iv) and (vi), or (v) and (vi).

In an embodiment, the crosslinked composition is Crosslinked Composition <NUM>, Crosslinked Composition <NUM>, or Crosslinked Composition <NUM> and comprises at least property (iii). In an embodiment, the crosslinked composition is Crosslinked Composition <NUM>, Crosslinked Composition <NUM>, or Crosslinked Composition <NUM> and comprises properties (iii) and at least one properties (i), (ii), (iv), (v) and (vi), preferably at least one of (i) and (ii).

In an embodiment, the crosslinked composition is hot air vulcanized to form Article <NUM>, Article <NUM>, or Article <NUM> and comprises one, some or all of the following properties:.

In an embodiment, the hot air vulcanized crosslinked article is Article <NUM>, Article <NUM>, or Article <NUM> and comprises at least two, or at least three, or all four of properties (i)-(iv).

In an embodiment, the hot air vulcanized crosslinked article is Article <NUM>, Article <NUM>, or Article <NUM> and comprises two of properties (i)-(iv). In an embodiment, the hot air vulcanized crosslinked article is Article <NUM>, Article <NUM>, or Article <NUM> and comprises properties (i) and (ii), or (i) and (iii), or (i) and (iv), or (ii) and (iii), or (ii) and (iv), or (iii) and (iv). In an embodiment, the hot air vulcanized crosslinked article is Article <NUM>, Article <NUM>, or Article <NUM> and comprises properties (iii) and (iv).

In an embodiment, the hot air vulcanized crosslinked article is Article <NUM>, Article <NUM>, or Article <NUM> and comprises three of properties (i)-(iv). In an embodiment, the hot air vulcanized crosslinked article is Article <NUM>, Article <NUM>, or Article <NUM> and comprises properties (i), (ii) and (iii); or (i), (ii) and (iv); or (i), (iii) and (iv); or (ii), (iii) and (iv).

In an embodiment, the hot air vulcanized crosslinked article is Article <NUM>, Article <NUM>, or Article <NUM> and comprises all four of properties (i)-(iv).

In an embodiment, the composition is Crosslinked Composition <NUM>, Crosslinked Composition <NUM>, or Crosslinked Composition <NUM> and comprises one, some or all of the following properties:.

and the composition is hot air vulcanized into a crosslinked article having one some or all of the following properties:.

In an embodiment, the crosslinked composition is Crosslinked Composition <NUM>, Crosslinked Composition <NUM>, or Crosslinked Composition <NUM> and comprises at least two, at least three, at least four, at least five, or all six of properties (i)-(vi) and the hot air vulcanized crosslinked article comprises at least one, at least two, at least three, or all four of properties (vii)-(x).

In an embodiment, the crosslinked composition is Crosslinked Composition <NUM>, Crosslinked Composition <NUM>, or Crosslinked Composition <NUM> and comprises at least one of properties (i)-(vi) and the hot air vulcanized crosslinked article comprises at least one of properties (vii)-(x). In an embodiment, the crosslinked composition is Crosslinked Composition <NUM>, Crosslinked Composition <NUM>, or Crosslinked Composition <NUM> and comprises at least property (iii) and the hot air vulcanized crosslinked article comprises at least property (ix) or (x). In an embodiment, the crosslinked composition is Crosslinked Composition <NUM>, Crosslinked Composition <NUM>, or Crosslinked Composition <NUM> and comprises at least property (iii) and the hot air vulcanized crosslinked article comprises at least property (x).

Applicant surprisingly discovered that an EAODM composition composed of (A) an EAODM, (B) a peroxide having at least one -<NUM>-O- peroxide bond, and (C) a bis-TEMPO compound having the Structure I as disclosed herein, wherein the ratio of the molar amount of nitroxide (NO•) groups of component (C) to the molar amount of the peroxide bonds of component (B) is from <NUM> to <NUM>, exhibits good crosslinking and low degradation. Specifically, Applicant discovered that a composition comprising, based on the total weight of the composition, (A) from <NUM> wt% to <NUM> wt% ethylene/propylene/diene interpolymer, (B) from <NUM> wt% to <NUM> wt% peroxide containing at least one -<NUM>-O- peroxide bond, and (C) from <NUM> wt% to <NUM> wt% of a bis-TEMPO compound having the Structure I as disclosed herein, wherein the ratio of the molar amount of nitroxide (NO·) groups of component (C) to the molar amount of the peroxide bonds of component (B) is from <NUM> to <NUM> exhibits a relative degradation less than <NUM>%, or less than <NUM>%, or less than <NUM>%, or less than <NUM>%, or less than <NUM>%.

In an embodiment, the article is selected from profiles, injection molded parts, gaskets, automotive parts, building and construction materials, shoe components, and tubes.

In an embodiment, the article is an automotive part.

The Haake mixer is preheated and equilibrated at <NUM>. The EPDM, peroxide and bis-TEMPO compound (and any other additives) are added as set forth in Tables 1A and 1B, below. Mixing is started with <NUM> rotations per minute (rpm) at <NUM> for <NUM> minutes to afford the final blend. The blend is removed from the mixer and cold pressed into a sheet. The sheet is further fabricated to a <NUM> thickness using the roll mill at <NUM>.

The ratio of the molar amount of nitroxide (NO·) groups of component (C) to the molar amount of the peroxide bonds of component (B) is calculated according to the equation <MAT> wherein gt is the amount of bis-TEMPO compound in grams, molet/g is the moles of bis-TEMPO compound in one gram, the number of nitroxide groups is the number of nitroxide groups in one bis-TEMPO molecule, gp is the amount of peroxide in grams, molep/g is the moles of peroxide in one gram, and the number of peroxide bonds is the number of peroxide bonds in one peroxide molecule.

For example, with respect to IE1, the amount of bis-TEMPO compound used is <NUM>, <NUM> mole of bis-TEMPO compound is <NUM>, the number of nitroxide groups in a single bis-TEMPO molecule is <NUM>, the amount of peroxide used is <NUM>, <NUM> mole of peroxide is <NUM>, and the number of peroxide bonds in a single peroxide molecule is <NUM>. The ratio is calculated as follows: <MAT>.

Each sample sheet (<NUM>) is placed into a steel mold (<NUM> x <NUM> x <NUM>). The hydraulic press is preheated to <NUM>. The steel mold is transferred into the press, degassed (<NUM> MPa) six times at <NUM>, and hot pressed with <NUM> MPa pressure at <NUM> for <NUM> minute. The steel mold is then cold pressed (water cooling - circulating with the press) with <NUM> MPa for <NUM> minutes. The resulting test specimen is a compression molded sheet having dimensions <NUM> x <NUM> x <NUM>.

The MDR cure properties of each formulation set forth in Table <NUM> are measured in accordance with ASTM D-<NUM> and recorded in Table <NUM> below.

A hot convection oven is preheated and equilibrated at <NUM> or <NUM> under ambient atmosphere. Compression molded samples are transferred into the oven and kept at <NUM> or <NUM> for <NUM> minutes with hot air convection for vulcanization. The vulcanized specimens are then removed and cooled to room temperature.

Degradation of the hot air vulcanized samples is determined by FTIR-ATR analysis as described above, and the tackiness of the surface of the samples is determined by the finger test. The results are reported in Tables 3A and 3B, below, and <FIG>.

Comparative Sample <NUM> does not include a bis-TEMPO compound. CS1 is the control sample having a formulation of only ethylene/alpha-olefin/diene interpolymer, peroxide and additives. As shown in Table <NUM>, CS1 has a very tacky surface and significant degradation (<NUM> degradation). Comparing CS1 to CS2-CS8 shows that addition of the C1-C7 compounds alone, without regard for the ratio of the molar amount of nitroxide groups in the C1-C7 compounds to the molar amount of the peroxide bonds in component B, does not necessarily improve surface tackiness or degradation of hot air vulcanized samples. Rather, as shown by IE1-IE4, it is only when the ratio of the molar amount of nitroxide groups in the component C to the molar amount of the peroxide bonds in component B is from <NUM> to <NUM> that improvement in surface tackiness and degradation is observed.

As shown by IE1-IE4, using a bis-TEMPO compound having the Structure I (as defined herein) in combination with a peroxide such that the ratio of the molar amount of nitroxide (NO·) groups of component (C) to the molar amount of the peroxide bonds of component (B) is from <NUM> to <NUM> results in a stable and non-tacky sample. For example, CS8 and CS9 each use a bis-TEMPO compound/peroxide combination in which the ratio of the molar amount of nitroxide (NO·) groups of component (C) to the molar amount of the peroxide bonds of component (B) is outside <NUM>:<NUM> and each of CS8 and CS9 has a tacky surface (finger test rating of <NUM> or <NUM>) and relative degradation of greater than or equal to <NUM>%. In contrast, IE1-IE4 each have a finger test rating of <NUM>. Moreover, each of IE1-IE4 has a relative degradation of less than <NUM>%, and, in fact, each has a relative degradation of less than or equal to <NUM>%.

As shown in Table <NUM>, CS1-CS7 and IE1 each retain sufficient crosslinking, regardless of the presence of a bis-TEMPO compound or the ratio of the molar amount of nitroxide (NO·) groups of component (C) to the molar amount of the peroxide bonds of component (B). However, and importantly, the inventive examples show an excellent balance of crosslinking density and surface stability during hot air vulcanization. This is shown by IE1 which has a surface tackiness rating of <NUM>, a relative degradation of less than or equal to <NUM>% (i.e., <NUM>%), and an MH-ML of greater than <NUM> dNm (i.e., <NUM> dNm).

Claim 1:
A composition comprising:
(A) an ethylene/alpha-olefin/diene interpolymer;
(B) a peroxide comprising at least one -O-O- peroxide bond;
(C) a bis-TEMPO compound having the Structure I
<CHM>
wherein R<NUM>, R<NUM>, R<NUM> and R<NUM> are each independently selected from the group consisting of H and C<NUM>-C<NUM> alkyl groups;
X is selected from the group consisting of S, O, N, P, Se, a carbonyl group (C=O), a carboxyl group (O-C=O), an amide group (N-C=O), an azo group (N=N), an imino group (C=N), a carbamate group (N-C=O), a peroxy group (O-O), a phosphono group (-(O)<NUM>P=O), a phosphate group (O=P-(O)<NUM>), a sulfonyl group ((O=)<NUM>S), a sulfinyl group (O=S), a sulfonate ester group ((O=)<NUM>S-O), a sulfonate ester group (O=S-O), and combinations thereof;
Y is selected from the group consisting of a substituted or unsubstituted aliphatic alkyl group, a substituted or unsubstituted aromatic alkyl group, a heterocyclic group, a siloxane group, an ethylene glycol group, an imide group, and combinations thereof; and
n is greater than <NUM>, and
wherein the ratio of the molar amount of nitroxide (NO') groups of component (C) to the molar amount of the peroxide bonds of component (B) is from <NUM>:<NUM> to <NUM>:<NUM>.