Air-curable ethylene / alpha-olefin interpolymer compositions

Abstract

and ii) a total unsaturation level of ≥ 0.20 / 1000C; b) at least one Tempo compound of Structure I); and c) at least one peroxide, wherein the molar ratio of NO· from component b to peroxide (OO) linkages from component c is 0.30 to 0.90, and component b is present in an amount of 0.20 to 0.90 phr, based on 100 parts of component a, and wherein Structure I is selected from Structure IA, Structure IB, or Structure IC, each as described herein. Also disclosed are processes for forming crosslinked compositions from the above and related compositions.

Description

[Technical Field]

[0001] Vulcanized EPDM is the current material for weatherstrip profiles. It is highly filled with carbon black and oil and cured with a complex sulfur curative system. Recently, the automotive industry has been demanding lightweight materials (especially for electric vehicles), low conductivity materials, and materials with lower VOCs / odor. Typical vulcanized EPDM cannot meet all of these needs.

[0002] For various applications such as footwear and PV films, peroxide curing of olefin-based elastomer (polyolefin elastomer (POE)) compositions is typically completed in the absence of oxygen. When POE is cured via peroxide in the presence of oxygen, carbon radicals react with the oxygen, and these products decompose into polar functional groups such as carboxylic acids, carbonyls, and esters. These polar species create an unacceptable tacky surface, especially when the cured surface is the outermost layer of the final product. To reduce surface tack, peroxide curing processes require more expensive and complex equipment (e.g., salt baths) to remove oxygen from the crosslinking environment. A need exists for new compositions that are air-curable and provide a tack-free surface. Furthermore, such compositions should meet most or all of the requirements for lightweight materials for automotive applications.

[0003] U.S. Patent Application Publication No. 2020 / 0263018 discloses a composition comprising: A) an ethylene / alpha-olefin / diene interpolymer; B) a peroxide containing at least one peroxide linkage; and C) a bis-TEMPO compound having structure (I) described therein. The ratio of the molar amount of nitroxide groups in component C to the molar amount of peroxide linkages in component B is 0.100:1.000 to 2.000:1.000. See Abstract.

[0004] WO 2020 / 140067 discloses a curable composition comprising A) a polyolefin component and B) a curing component comprising a crosslinker. 1 L 1 wherein L 1 is a polyolefin, and A 1 is a vinyl group, formula CH2=C(Y 1 )-, a vinylidene group of formula Y 1 Vinylene group of CH=CH-, vinyl group and formula Y 1 A mixture of vinyl groups with CH=CH- vinyl groups and the formula CH2=C(Y 1 )- with vinylidene groups, the formula CH2=C(Y 1 )- and the vinylidene group of formula Y 1 Mixtures of vinylene groups with CH=CH- and vinyl groups with the formula CH2=C(Y 1 )- and the vinylidene group of formula Y 1 and a mixture of CH═CH— and vinylene groups; Y 1 is independently at each occurrence a C1 to C30 hydrocarbyl group. See claim 1. The curing component may also contain scorch inhibitors / retarders, such as hindered phenols, semi-hindered phenols; TEMPO; TEMPO derivatives; 1,1-diphenylethylene; 2,4-diphenyl-4-methyl-1-pentene; and allyl-containing compounds described in U.S. Patent No. 6,277,925 (B1). See paragraph

[0247] . See also WO 2020 / 140061, WO 2020 / 135681, WO 2020 / 135708, WO 2020 / 135680, WO 2020 / 139993, and WO 2020 / 140058.

[0005] U.S. Patent No. 8,581,094 discloses an electronic device module comprising A) at least one electronic device and B) a polymeric material in intimate contact with at least one surface of the electronic device. The polymeric material comprises the following components (1) and, optionally, (2) and (3): (1) a polyolefin copolymer having at least one of: (a) a density less than about 0.90 g / cc; (b) a 2% secant modulus less than about 150 megaPascals (mPa); (c) a melting point less than about 95°C; (d) an alpha-olefin content of at least about 15% by weight and less than about 50% by weight, based on the weight of the polymer; (e) a Tg less than about -35°C; and (f) an SCBDI of at least about 50; and (2) optionally a free radical initiator (e.g., a peroxide or an azo compound) or a photoinitiator (e.g., benzophenone), and (3) optionally a coagent. See Abstract. Typically, the polyolefin copolymer is an ethylene / alpha-olefin copolymer. Optionally, the polymeric material can further comprise a vinyl silane and / or a scorch inhibitor, and the copolymer can be uncrosslinked or crosslinked. See Abstract. Scorch inhibitors include 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, also known as nitroxyl 2, or NR 1, or 4-oxypiperidol, or tanol, or tempol, or tmpn, or 4-hydroxy-TEMPO (see column 11, lines 30-54).

[0006] J. Kruzelak, et al., Vulcanization of Rubber Compounds with Peroxide Curing Systems, Rubber Chemistry and Technology, 90(1), 60-88, 2017, discloses the characterization of organic peroxides as curing agents and their decomposition mechanisms. This reference also discloses the classification and characterization of coagents used in peroxide crosslinking with respect to the properties of the prepared materials, as well as the interaction and reaction mechanisms between peroxides, coagents, and the rubber matrix. See Abstract. This reference also discloses the use of scorch retarders, such as 2,6-di-tert-butyl-4-methylphenol (BHT), 2,4-diphenyl-4-methyl-1-pentene (methyl styrene dimer), dime (MSD), 1,1-diphenylethylene (DPE), (2,2,6,6-tetramethyl-piperidin-1-yl)oxyl (TEMPO), bis-(2,2,6,6-tetramethyl-4-piperidinyl)sebacate (bis-TEMPO), or acrylate-functionalized TEMPO, 4-acryloyloxy-2,2,6,6-tetramethyl-piperidine-N-oxyl (AOTEMPO). See page 83.

[0007] However, as discussed above, there remains a need for new compositions that are air-curable and provide a tack-free surface. Furthermore, such compositions should meet all or most of the requirements for lightweight materials for automotive applications. These needs have been met by the following inventions. Summary of the Invention

[0008] In a first aspect, the following components a) to c) are included: a) at least one ethylene / alpha-olefin interpolymer comprising the following properties: i) a density of 0.855 to 0.900 g / cc and ii) a total unsaturation level of ≥ 0.20 / 1000 C; b) at least one Tempo compound of structure I); c) at least one peroxide; the molar ratio of NO· from at least one Tempo compound (component b) to peroxide (OO) bonds from at least one peroxide (component c) is 0.30 to 0.90; Component b is present in an amount of 0.20 to 0.90 phr based on 100 parts of component a; A composition wherein Structure I is selected from Structure IA, Structure IB, or Structure IC, each described herein.

[0009] In a second aspect, there is provided a process for forming a crosslinked composition, the process comprising a composition comprising the following components a) to c): a) at least one ethylene / alpha-olefin interpolymer comprising the following properties: i) a density of 0.855 to 0.900 g / cc and ii) a total unsaturation level of ≥ 0.20 / 1000 C; b) at least one Tempo compound of structure I); c) at least one peroxide; the molar ratio of NO· from at least one Tempo compound (component b) to peroxide (OO) bonds from at least one peroxide (component c) is 0.30 to 0.90; Component b is present in an amount of 0.20 to 0.90 phr based on 100 parts of component a; A process comprising heat treating a composition, wherein Structure I is selected from Structure IA, Structure IB, or Structure IC, each of which is described herein.

[0010] In a third aspect, there is provided a process for forming a crosslinked composition, the process comprising at least the following steps A and B: A) The following components a) to c), namely: a) at least one ethylene / alpha-olefin interpolymer comprising the following properties: i) a density of 0.855 to 0.900 g / cc and ii) a total unsaturation level of ≥ 0.20 / 1000 C; b) at least one Tempo compound of structure I); c) extruding a composition comprising at least one peroxide to form a pre-crosslinked composition; B) heat treating the pre-crosslinked composition in air at a temperature of ≥ 150°C to form a crosslinked composition; The process wherein Structure I is selected from Structure IA, Structure IB, or Structure IC, each described herein. [Brief explanation of the drawings]

[0011] [Figure 1] FTIR-ATR profiles of the surfaces of the inventive and comparative compositions after air curing are plotted. From top to bottom, the profiles are as follows: CS1, CS3, CS7, CS9, and IE1. DETAILED DESCRIPTION OF THE INVENTION

[0012] Compositions have been discovered that contain high polymer content, extrude well, and cure efficiently in air. It has been discovered that such compositions can be air cured without producing a sticky surface.

[0013] As discussed above, a first aspect provides a composition comprising components a) to c) as discussed herein. A second aspect provides a process for forming a crosslinked composition, the process comprising heat-treating a composition comprising the following components a) to c) as discussed herein. A third aspect provides a process for forming a crosslinked composition, the process comprising at least steps A and B as discussed herein. Each composition may comprise a combination of two or more embodiments as described herein. Each process may comprise a combination of two or more embodiments as described herein. Each component a, b, and c may comprise a combination of two or more embodiments as described herein. Unless otherwise specified, the following embodiments apply to the first, second, and third aspects.

[0014] As used herein with respect to Structure IA, Structure IB, or Structure IC (see component b), R=R 1 , R2=R 2 , R3=R 3 and the like. Also, with respect to the number of carbon atoms in a chemical substituent of Structure IA, Structure IB, or Structure IC, a notation such as "C1-C18" (where "1-18" represents a sequential number from 1 to 18) refers to "1 to 18 carbon atoms" that may be present in the substituent. An "alkyl" group can be linear, branched, cyclic, or any combination thereof. An "alkylene" group can be linear, branched, cyclic, or any combination thereof.

[0015] In one embodiment, or a combination of two or more embodiments, each described herein, the ethylene / alpha-olefin interpolymer has the formula A, as described herein. 1 L 1 L 2 A 2 or a telechelic ethylene / alpha-olefin interpolymer of formula A 1 L 1and further comprising an unsaturated ethylene / alpha-olefin interpolymer of formula A 1 L 1 The unsaturated ethylene / alpha-olefin interpolymers are selected from the group consisting of:

[0016] In one embodiment, or a combination of two or more embodiments, each described herein, the ethylene / alpha-olefin interpolymer is an ethylene / alpha-olefin copolymer.

[0017] In one embodiment, or a combination of two or more embodiments, each described herein, component a further comprises a second ethylene / alpha-olefin interpolymer having a density of 0.855 to 0.900 g / cc and a total unsaturation of ≥ 0.20 / 1000 C, wherein the second interpolymer is different from the ethylene / alpha-olefin interpolymer.

[0018] In one embodiment, or a combination of two or more embodiments, each described herein, the second ethylene / alpha-olefin interpolymer has the formula A, as described herein. 1 L 1 L 2 A 2 or a telechelic ethylene / alpha-olefin interpolymer of formula A 1 L 1 and further comprising an unsaturated ethylene / alpha-olefin interpolymer of formula A 1 L 1 The unsaturated ethylene / alpha-olefin interpolymers are selected from the group consisting of:

[0019] In one embodiment, or a combination of two or more embodiments, each described herein, the second ethylene / alpha-olefin interpolymer is an ethylene / alpha-olefin copolymer.

[0020] In one embodiment, or a combination of two or more embodiments, each described herein, the ratio of the density of the ethylene / alpha-olefin to the density of the second ethylene / alpha-olefin is ≧0.80, or ≧0.85, or ≧0.90, or ≧0.92, or ≧0.94, or ≧0.96, or ≧0.98, or ≧1.0, and / or ≦1.25, or ≦1.20, or ≦1.18, or ≦1.16, or ≦1.14, or ≦1.12, or ≦1.11.

[0021] In one embodiment, or a combination of two or more embodiments, each described herein, the weight ratio of the ethylene / alpha-olefin to the second ethylene / alpha-olefin is ≧0.50, or ≧1.0, or ≧2.0, or ≧3.0, or ≧3.5, or ≧4.0, or ≧4.5, or ≧5.0, or ≧5.5, and / or ≦20, or ≦15, or ≦10, or ≦9.0, or ≦8.0, or ≦7.5, or ≦7.0, or ≦6.5, or ≦6.0.

[0022] In one embodiment, or a combination of two or more embodiments, each described herein, the composition comprises, based on the weight of the composition, ≦10.0 wt.%, or ≦5.0 wt.%, or ≦2.0 wt.%, or ≦1.0 wt.%, or ≦0.5 wt.%, or ≦0.1 wt.% of a filler (e.g., carbon black), including, but not limited to, carbon black, talc, glass fiber, carbon fiber, calcium carbon, magnesium hydroxide, ATH (Aluminum Trihydrate), TiO, or any combination thereof.

[0023] In one embodiment, or a combination of two or more embodiments, each described herein, the composition comprises ≧90.0 wt.%, or ≧94.0 wt.%, or ≧96.0 wt.%, or ≧97.0 wt.%, or ≧97.5 wt.%, or ≧98.0 wt.%, or ≧98.5 wt.%, or ≧99.0 wt.%, or ≧99.5 wt.%, and / or ≦100.0 wt.%, or ≦99.9 wt.%, or ≦99.8 wt.%, or ≦99.7 wt.% of the sum of components a, b, and c, based on the weight of the composition.

[0024] In one embodiment, or a combination of two or more embodiments, each described herein, with respect to the second aspect, the heat treatment is carried out in air. In one embodiment, or a combination of two or more embodiments, each described herein, with respect to the second aspect, the heat treatment is carried out at a temperature of ≧150°C, ≧155°C, or ≧160°C, or ≧165°C, or ≧170°C, or ≧175°C, or ≧180°C, or ≧185°C, or ≧190°C, or ≧195°C, or ≧200°C, and / or ≦240°C, or ≦235°C, or ≦230°C, or ≦225°C, or ≦220°C, or ≦215°C, or ≦210°C, or ≦205°C.

[0025] In one embodiment, or a combination of two or more embodiments, each described herein, with respect to the second or third aspect, the composition is extruded at an average barrel temperature of ≥ 60°C, or ≥ 65°C, or ≥ 70°C, or ≥ 75°C, ≥ 80°C, ≥ 85°C, or ≥ 90°C, or ≥ 95°C, or ≥ 100°C, or ≥ 105°C, or ≥ 110°C, and / or at a temperature of ≤ 150°C, or ≤ 145°C, or ≤ 135°C, or ≤ 130°C, or ≤ 125°C, or ≤ 120°C, or ≤ 115°C.

[0026] In one embodiment, or a combination of two or more embodiments, each described herein, with respect to the third aspect, for Step B, the pre-crosslinked composition is heat treated at a temperature of ≧150°C, or ≧155°C, or ≧160°C, or ≧165°C, or ≧170°C, or ≧175°C, or ≧180°C, or ≧185°C, or ≧190°C, or ≧195°C, or ≧200°C, and / or at a temperature of ≦240°C, or ≦235°C, or ≦230°C, or ≦225°C, or ≦220°C, or ≦215°C, or ≦210°C, or ≦205°C.

[0027] In one embodiment, or a combination of two or more embodiments, each described herein, the molar ratio of NO· from component b to peroxide (OO) bonds from component c is ≧0.30, or ≧0.31, or ≧0.33, or ≧0.34, and / or ≦0.90, or ≦0.88, or ≦0.85, or ≦0.82, or ≦0.80, or ≦0.78, or ≦0.75, or ≦0.72, or ≦0.70, or ≦0.68, or ≦0.65, or ≦0.62, or ≦0.60, or ≦0.58.

[0028] In one embodiment, or a combination of two or more embodiments, each described herein, for the composition, component b is present in an amount based on 100 parts of component a of ≥ 0.20, or ≥ 0.22, or ≥ 0.25, or ≥ 0.28, or ≥ 0.30, or ≥ 0.32, or ≥ 0.35, or ≥ 0.38, or ≥ 0.40, or ≥ 0.42, or ≥ 0.45 phr, and / or ≤ 0.90, or ≤ 0.88, or ≤ 0.85, or ≤ 0.82, or ≤ 0.80, or ≤ 0.78, or ≤ 0.75 phr.

[0029] Also provided are crosslinked compositions formed from one or more of the compositions or from one or more of the processes described herein. Also provided are articles comprising at least one component formed from one or more of the compositions described herein.

[0030] Ethylene / alpha-olefin interpolymer (component a) Ethylene / alpha-olefin interpolymers comprise, in polymerized form, ethylene and an alpha-olefin. The alpha-olefins include, but are not limited to, C3 to C20 alpha-olefins, further C3 to C10 alpha-olefins, and further C3 to C8 alpha-olefins, such as propylene, 1-butene, 1-hexene, and 1-octene. The distribution of the monomer units, particularly the alpha-olefins, can be random, block, uniform, heterogeneous, etc. Preferably, the interpolymer is a random interpolymer (i.e., comprises a random distribution of its monomer components).

[0031] In one embodiment, the ethylene / alpha-olefin interpolymer has the formula: 1 L 1 L 2 A 2 Telechelic ethylene / alpha-olefin interpolymers of formula A 1 L 1 is an unsaturated ethylene / alpha-olefin interpolymer of

[0032] Telechelic ethylene / alpha-olefin interpolymers, such as A 1 L 1 L 2 A 2 (Formula I), and unsaturated ethylene / alpha-olefin interpolymers, such as A 1 L 1 (Formula II) are each described below. See also WO 2020 / 140058 and WO 2020 / 140067 (each incorporated herein by reference).

[0033] Formula I:A 1 L 1 L 2 A 2 is a telechelic ethylene / alpha-olefin interpolymer of the formula: L 1 are ethylene / alpha-olefin interpolymers and also ethylene / alpha-olefin copolymers, and L 1 (divalent) is A 1 and L 2 Note that the bond is

[0034] A 1 is the following: a) vinyl group, b) group of the formula CH2=C(Y 1 )-, c) a vinylidene group of formula Y 1 a vinylene group of CH=CH-; d) a vinyl group and a vinyl group of formula Y 1 e) a mixture of vinyl groups with the formula CH2=C(Y 1 )- with vinylidene groups, f) compounds of the formula CH2=C(Y 1 )- and the vinylidene group of formula Y 1 and g) mixtures of vinyl groups with the formula CH2=C(Y 1 )- and the vinylidene group of formula Y 1 CH═CH— and a mixture of vinylene groups; Y 1 are independently generated for each occurrence, C1 to C 30 is a hydrocarbyl group, L 2 is C1~C 32 is a hydrocarbylene group, A 2 is a hydrocarbyl group containing a hindered double bond.

[0035] Formula II:A 1 L 1 an unsaturated ethylene / alpha-olefin interpolymer of the formula: L 1are ethylene / alpha-olefin interpolymers, and also ethylene / alpha-olefin copolymers, (L 1 (monovalent) is A 1 (note that it is bound to A 1 is a group having the formula: a) a vinyl group, b) a group having the formula CH2=C(Y 1 )-, c) a vinylidene group of formula Y 1 a vinylene group of CH=CH-; d) a vinyl group and a vinyl group of formula Y 1 e) a mixture of vinyl groups with the formula CH2=C(Y 1 )- with vinylidene groups, f) compounds of the formula CH2=C(Y 1 )- and the vinylidene group of formula Y 1 and g) mixtures of vinyl groups with the formula CH2=C(Y 1 )- and the vinylidene group of formula Y 1 and a mixture of CH═CH— and vinylene groups; Y1 is independently selected from the group consisting of C1 to C 30 It is a hydrocarbyl group.

[0036] For Formula I and Formula II, L 1are independently described above at each occurrence, and may result in part from the polymerization (e.g., coordination polymerization) of unsaturated monomers (and comonomers). Examples of suitable monomers (and comonomers) include ethylene and alpha-olefins having 3 to 30 carbon atoms, and also 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 3,5,5-trimethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 5-ethyl-1-nonene, 1-octadecene, and 1-eicosene; conjugated dienes or non-conjugated dienes. Dienes such as butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,5-heptadiene, 1,6-heptadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 1,9-decadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, and 5,9 -dimethyl-1,4,8-decatriene, 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, 3,7-dimethyl-1,7-octadiene, and mixed isomers of dihydromyrcene and dihydroocimene; norbornene and alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes, for example, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, dicyclopentadiene, 5-methylene-2-norbornene, 5-propenyl-2-norbornene, and norbornadiene; and aromatic vinyl compounds such as styrene, mono- or polyalkylstyrenes (including styrene, o-methylstyrene, t-methylstyrene, m-methylstyrene, p-methylstyrene, o-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, and p-ethylstyrene).Preferred monomers include ethylene and alpha-olefins of 3 to 30 carbon atoms, and also 3 to 20 carbon atoms.

[0037] Tempo compound (ingredient b) Tempo compounds have structure IA, structure IB, or structure IC, each of which is described herein. Tempo compounds include, but are not limited to, bis-(2,2,6,6-tetramethyl-1-piperidinyloxy-4-yl) sebacate.

[0038] peroxide As used herein, a peroxide contains at least one oxygen-oxygen bond (OO). Peroxides include, but are not limited to, dialkyl, diaryl, and dialkaryl peroxides having the same or different respective alkyl, aryl, alkaryl, or aralkyl moieties, and further, dialkyl, diaryl, dialkaryl, or diaralkyl peroxides having the same respective alkyl, aryl, alkaryl, or aralkyl moieties.

[0039] Examples of organic peroxides include dicumyl peroxide ("dicumyl peroxide, DCP"), tert-butyl peroxybenzoate, di-tert-amyl peroxide ("DTAP"), bis(t-butyl-peroxyisopropyl)benzene ("BIPB"), isopropylcumyl t-butyl peroxide, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane ("LUPEROX"). 101"), 2,5-bis(t-butylperoxy)-2,5-dimethylhexane-3, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, isopropyl cumyl cumyl peroxide, butyl 4,4-di(tert-butylperoxy)valerate, di(isopropyl cumyl) peroxide, 1,1-di-(tert-butylperoxy)cyclohexane ("LUPEROX 331"), 1,1-di-(tert-amylperoxy)cyclohexane ("LUPEROX 531"), tert-butyl peroxyacetate ("tert-butylperoxyacetate, TBPA"), tert-amyl peroxyacetate ("tert-amyl peroxyacetate, TAPA"), tert-butylperoxy-2-ethylhexyl carbonate ("tert-butylperoxy-2-ethylhexyl carbonate, TBEC"), and mixtures of two or more thereof.

[0040] The peroxide may be a cyclic peroxide. Examples of cyclic peroxides include those derived from acetone, methyl amyl ketone, methyl heptyl ketone, methyl hexyl ketone, methyl propyl ketone, methyl butyl ketone, diethyl ketone, methyl ethyl ketone, methyl octyl ketone, methyl nonyl ketone, methyl decyl ketone, methyl undecyl ketone, and combinations thereof. The cyclic peroxides can be used alone or in combination with each other. Some cyclic peroxides, such as 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane, are commercially available, for example, under the trade name TRIGONOX.

[0041] additives The compositions of the present invention may contain one or more additives, including, but not limited to, crosslinking aids, foaming agents, antioxidants, UV stabilizers, colorants, and processing aids (e.g., zinc stearate).

[0042] Crosslinking coagents include, but are not limited to, triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), triallyl trimellitate (TATM), trimethylolpropane triacylate (TMPTA), trimethylolpropane trimethylacrylate (TMPTMA), 1,6-hexanediol diacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, tris-(2-hydroxyethyl) isocyanurate triacrylate, trivinyl cyclohexane (TVCH), or combinations thereof. Additional crosslinking coagents include alkenyl-functional monocyclic organosiloxanes (e.g., monocyclic organosiloxanes of the formula [R1,R2SiO2 / 2]n, where the subscript n is an integer greater than or equal to 3, and each R1 is independently (C2-C4)alkenyl or HC=C(R1a)-C(=O)-O-, as disclosed in WO 2019 / 000311 and WO 2019 / 000654, the entireties of which are incorporated herein by reference). (CH)-, where R is H or methyl, subscript m is an integer from 1 to 4, and each R is independently H, (C-C) alkyl, phenyl, or R, such as, but not limited to, 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 2,4,6-trimethyl-2,4,6-trivinyl-cyclotrisiloxane, or a combination thereof.

[0043] In one embodiment, the additive is present in an amount of ≧0.10, or ≧0.20, or ≧0.30, or ≧0.35 phr based on 100 parts of component a, and / or ≦5.0, or ≦4.0, or ≦3.0, or ≦2.0, or ≦1.0 wt. %, or ≦0.50 phr based on 100 parts of component a.

[0044] definition Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percentages are by weight and all test methods are current as of the filing date of this disclosure.

[0045] As used herein, the term "composition" includes a mixture of materials, including the composition and reaction and decomposition products formed from the materials of the composition. Any reaction or decomposition products are typically present in trace or residual amounts.

[0046] As used herein, the term "polymer" refers to a polymeric compound prepared by polymerizing monomers of the same or different types. Thus, the generic term polymer includes the term homopolymer (used to refer to a polymer prepared from only one type of monomer, with the understanding that trace amounts of impurities may be incorporated into the polymer structure) and the term interpolymer, as defined below. Trace amounts of impurities, such as catalyst residues, may be incorporated into and / or within the polymer. Typically, polymers are stabilized with very small amounts ("ppm (parts per million)" amounts) of one or more stabilizers.

[0047] As used herein, the term "interpolymer" refers to a polymer prepared by the polymerization of at least two different types of monomers. Thus, the term interpolymer includes the term copolymer (used to refer to a polymer prepared from two different types of monomers) and polymers prepared from three or more different types of monomers.

[0048] As used herein, the term "olefin-based polymer" refers to a polymer that, in polymerized form, comprises 50 weight percent or a majority weight percent (based on the weight of the polymer) of an olefin, such as ethylene or propylene, and may optionally contain one or more comonomers.

[0049] As used herein, the term "propylene-based polymer" refers to a polymer that, in polymerized form, comprises a majority weight percent propylene (based on the weight of the polymer) and may optionally include one or more comonomers.

[0050] As used herein, the term "ethylene-based polymer" refers to a polymer that, in polymerized form, contains at least 50 weight percent or majority weight percent ethylene (based on the weight of the polymer), and may optionally contain one or more comonomers.

[0051] As used herein, the term "ethylene / alpha-olefin interpolymer" refers to an interpolymer that comprises, in polymerized form, 50 weight percent or a majority weight percent (based on the weight of the interpolymer) ethylene and an alpha-olefin.

[0052] As used herein, the term "ethylene / alpha-olefin copolymer" refers to a copolymer that, in polymerized form, contains 50 weight percent or a majority weight percent of ethylene (based on the weight of the copolymer) and an alpha-olefin as the only two monomer types.

[0053] As used herein, with respect to a polymer (eg, an interpolymer or copolymer), the phrase "major weight percent" refers to the amount of monomer that is present in the greatest amount in the polymer.

[0054] The term "heteroatom" refers to an atom other than hydrogen or carbon (e.g., O, S, N, or P). The term "heteroatomic group" refers to a heteroatom or a chemical group that contains one or more heteroatoms.

[0055] As used herein, the terms "hydrocarbon," "hydrocarbyl," and similar terms refer to respective compounds or chemical groups etc. that contain only carbon and hydrogen atoms. A divalent "hydrocarbylene group" is similarly defined.

[0056] As used herein, the terms "heterohydrocarbon," "heterohydrocarbyl," and similar terms refer to a hydrocarbon or hydrocarbyl group, respectively, in which at least one carbon atom has been replaced with a heteroatom group (e.g., O, S, N, or P). A monovalent heterohydrocarbyl group can be bonded to the remainder of the compound of interest through a carbon atom or through a heteroatom. A divalent "heterohydrocarbylene group" is similarly defined; a divalent heterohydrocarbylene group can be bonded to the remainder of the compound of interest through two carbon atoms, two heteroatoms, or a carbon atom and a heteroatom.

[0057] As used herein, the terms "substituted hydrocarbon," "substituted hydrocarbyl group," and similar terms refer to each hydrocarbon or hydrocarbyl group in which one or more hydrogen atoms have been independently replaced with a heteroatom group. A "substituted hydrocarbylene group" is similarly defined.

[0058] As used herein, the terms "substituted heterohydrocarbon," "substituted heterohydrocarbyl group," and similar terms refer to heterohydrocarbon or heterohydrocarbyl groups, respectively, in which one or more hydrogen atoms have been independently replaced with a heteroatom group. A "substituted heterohydrocarbylene group" is similarly defined.

[0059] As used herein, the term "crosslinked composition" refers to a composition having a network structure due to the formation of chemical bonds between polymer chains. The degree of network structure formation is indicated by an increase in the difference between "MH-ML" compared to the uncrosslinked composition. Crosslinked compositions typically have a gel content of ≥ 60 wt%, further ≥ 70 wt%, further ≥ 80 wt%, and even ≥ 90 wt%, based on the weight of the crosslinked composition. The gel content can be measured by refluxing the crosslinked composition in xylene. For example, approximately 0.5 g of the crosslinked composition (Ws) is sealed in a metal mesh (mesh number 120) to form a packed sample, and the packed sample is weighed (Wt1). The packed sample is then transferred to a flask (500 ml) equipped with a condenser and containing 350 ml of xylene. After refluxing for 5 hours, the packed sample is removed from the xylene, placed in a vacuum oven, and heated at 120°C under vacuum conditions for 2 hours. The packed sample is then removed from the oven and weighed (Wt2). Gel content = 1-[(Wt1-Wt2) / Ws] * 100%.

[0060] As used herein, with respect to compositions comprising the ethylene / alpha-olefin interpolymers discussed herein, "heat treating," "heat treated," "heat treatment," and similar terms refer to raising the temperature of the composition by the application of heat. By way of example, heat can be applied by electrical means (e.g., heating coils), and / or by radiation, and / or by hot oil, and / or by mechanical shear. It should be noted that the temperature at which heat treatment is carried out refers to the temperature of the "heating" device, or, if the device contains a closed or semi-closed atmosphere, the temperature of the atmosphere within the device, e.g., an oven or tunnel (e.g., the air temperature within a hot air oven or hot air tunnel).

[0061] As used herein, the term "extruder configuration" refers to the arrangement and number (n > 1) of extruders used in an extrusion process. Typically, two or more extruders are arranged in a series orientation.

[0062] The term "average barrel temperature," as used herein with respect to an extrusion process using one or more extruders, each containing at least one barrel, refers to the average temperature of the sum of the barrel temperatures if more than one barrel is present, or the temperature of that barrel if only one barrel is present.

[0063] The term "Garvey die" as used herein in connection with extrusion processes refers to a particular die shape that conforms to ASTM D2230-17 and allows for observation of the appearance and profile of the extrudate.

[0064] 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 it is specifically disclosed. For the avoidance of doubt, all compositions claimed through the use of the term "comprising" may include any additional additive, adjuvant, or compound, whether polymeric or not, 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, except those that are not essential to operability. The term "consisting of" excludes any component, step, or procedure not specifically defined or listed.

[0065] List of some compositions and processes A] The following components a) to c), namely: a) at least one ethylene / alpha-olefin interpolymer comprising the following properties: i) a density of 0.855 to 0.900 g / cc and ii) a total unsaturation level of ≥ 0.20 / 1000 C; b) at least one Tempo compound of structure I) below; c) at least one peroxide; the molar ratio of NO· from at least one Tempo compound (component b) to peroxide (OO) bonds from at least one peroxide (component c) is 0.30 to 0.90; Component b is present in an amount of 0.20 to 0.90 phr based on 100 parts of component a; Structure I is selected from Structure IA, Structure IB, or Structure IC, each of which is as follows: Structure IA is

[0066] [ka] and wherein n is an integer ≧1; R1, R2, R3, and R4 are each independently selected from H or C1-C18 alkyl; X is CH2, ether (-O-), thioether (-S m -, m≧1), carbonyl (—C(O)—), ester (—OC(O)— or —C(O)—O—), amine (—N(R)—), amide (—N(R)—C(O)— or —C(O)—N(R)—), urethane (—OC(O)—NH— or —NH—C(O)—O—), carbamide (—NH—C(O)—NH—), or imide (—C(O)—N(R)—C(O)—); R' is selected from C1 to C30 alkylene; R" may be present or absent, and when present, R" is selected from C1 to C30 alkylene; Y is CR 4-n (n=1-4), OR 2-n (n=1-2), NR 3-n (n=1-3), SR 2-n (n=1-2), PR3-n (n=1-3), PR 5-n (n=1-5), SiR 4-n (n=1 to 4), selected from a difunctional C-C core, a phenyl core, an ester-substituted phenyl core, an amide-substituted phenyl core, a tris-isocyanurate core, or a melamine core; The difunctional C-C core is selected from the following structures, where each R′ represents a divalent R′ group in structure IA above:

[0067] [ka] The phenyl core is selected from the following structures, where each R′ represents a divalent R′ group in structure IA above:

[0068] [ka] The ester-substituted phenyl core is selected from the following structures, where each R′ represents a divalent R′ group in structure IA above:

[0069] [ka] The amido-substituted phenyl core is selected from the following structures, where each R′ represents a divalent R′ group in structure IA above:

[0070] [ka] The tris-isocyanurate core is as follows, where each R′ represents a divalent R′ group in structure IA above:

[0071] [ka] The melamine core is as follows, where each R′ represents a divalent R′ group in structure IA above:

[0072] [ka] each R group in Structure IA is independently selected from H, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heterohydrocarbyl, or substituted heterohydrocarbyl; Structure IB comprises the following substructures IB):

[0073] [ka] wherein n is an integer ≧1; R1, R2, R3, and R4 are each independently selected from H or C1-C18 alkyl; X is CH2, ether (-O-), thioether (-S m -, m≧1), carbonyl (—C(O)—), ester (—OC(O)— or —C(O)—O—), amine (—N(R)—), amide (—N(R)—C(O)— or —C(O)—N(R)—), urethane (—OC(O)—NH— or —NH—C(O)—O—), carbamide (—NH—C(O)—NH—), or imide (—C(O)—N(R)—C(O)—); R' is selected from C1 to C30 alkylene; R" may be present or absent, and when present, R" is selected from C1 to C30 alkylene; each R group in substructure IB is independently selected from H, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heterohydrocarbyl, or substituted heterohydrocarbyl; Each in substructure IB * (asterisk) represents each chemical terminus of structure IB; The structure IC includes the following substructures IC):

[0074] [ka] wherein n is an integer ≧1; R1, R2, R3, and R4 are each independently selected from H or C1 to C18; X is CH2, ether (-O-), thioether (-S m -, m≧1), carbonyl (—C(O)—), ester (—OC(O)— or —C(O)—O—), amine (—N(R)—), amide (—N(R)—C(O)— or —C(O)—N(R)—), urethane (—OC(O)—NH— or —NH—C(O)—O—), carbamide (—NH—C(O)—NH—), or imide (—C(O)—N(R)—C(O)—); R' is selected from C1 to C30 alkylene; R" may be present or absent, and when present, R" is selected from C1 to C30 alkylene; each R''' group in substructure IC is independently selected from unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heterohydrocarbyl, or substituted heterohydrocarbyl; each R group in substructure IC is independently selected from H, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heterohydrocarbyl, or substituted heterohydrocarbyl; Each sub-structure IC * (asterisk) represents each chemical terminus of structure IC, and when n≧3, each terminus may or may not form a cyclic structure with the other terminus, composition.

[0075] B] The ethylene / alpha-olefin interpolymer has a viscosity of ≥ 0.856, or ≥ 0.858, or ≥ 0.860, or ≥ 0.862, or ≥ 0.864, or ≥ 0.866 g / cc, and / or ≤ 0.898, or ≤ 0.896, or ≤ 0.894, or ≤ 0.892, or ≤ 0.890, or ≤ 0.888, or ≤ 0.886, or ≤ 0.884, or ≤ 0.882, or ≤ 0.880, or ≤ 0.878, or ≤ 0.876, or ≤ 0.874, or ≤ 0.872 g / cc (1 cc = 1 cm 3The composition of A] above, having a density of

[0076] C] the ethylene / alpha-olefin interpolymer has a temperature of ≥ 0.22 / 1000C, or ≥ 0.24 / 1000C, or ≥ 0.26 / 1000C, or ≥ 0.28 / 1000C, or ≥ 0.30 / 1000C, or ≥ 0.35 / 1000C, or ≥ 0.40 / 1000C, or ≥ 0.45 / 1000C, or ≥ 0.50 / 1000C, or ≥ 0.55 / 1000C, or ≥ 0.60 / 1000C, or ≥ 0.65 / 1000C; and / or a total unsaturation level of ≦15.0 / 1000C, or ≦10.0 / 1000C, or ≦5.00 / 1000C, or ≦2.00 / 1000C, or ≦1.80 / 1000C, or ≦1.60 / 1000C, or ≦1.50 / 1000C, or ≦1.40 / 1000C, or ≦1.30 / 1000C, or ≦1.20 / 1000C, or ≦1.10 / 1000C, or ≦1.00 / 1000C.

[0077] D] Any one of the compositions A]-C] above, wherein the ethylene / alpha-olefin interpolymer has a melt index (I2, dg / min) of ≥ 0.1, or ≥ 0.2, or ≥ 0.4, or ≥ 0.6, or ≥ 0.8, or ≥ 1.0, or ≥ 1.2, or ≥ 1.4, or ≥ 1.6, or ≥ 1.8, or ≥ 2.0, and / or ≤ 2000, or ≤ 1000, or ≤ 500, or ≤ 200, or ≤ 100, or ≤ 50, or ≤ 45, or ≤ 40, or ≤ 35, or ≤ 30, or ≤ 25, or ≤ 20.

[0078] E] the ethylene / alpha-olefin interpolymer is of formula A described herein 1 L 1 L 2 A 2 or a telechelic ethylene / alpha-olefin interpolymer of formula A 1 L1 and further comprising an unsaturated ethylene / alpha-olefin interpolymer of formula A 1 L 1 The composition of any one of A] to D] above, wherein the unsaturated ethylene / alpha-olefin interpolymer is selected from the group consisting of:

[0079] F] The composition of any one of A] to E] above, wherein the ethylene / alpha-olefin interpolymer is an ethylene / alpha-olefin copolymer.

[0080] G] The alpha-olefin of the ethylene / alpha-olefin interpolymer is C3-C 20 Alpha-olefins, further C3 to C 10 The composition of any one of A] to F] above, wherein the alpha-olefin is further propylene, 1-butene, 1-hexene, or 1-octene, further propylene, 1-butene, or 1-octene, further 1-butene, or 1-octene, further 1-octene.

[0081] H] Any one of the compositions A] through G] above, wherein the ethylene / alpha-olefin interpolymer is free, in polymerized form, of ENB, and further diene monomers, and further polyene monomers.

[0082] I] Any one of the compositions A] to H] above, wherein component a further comprises a second ethylene / alpha-olefin interpolymer having a density of 0.855 to 0.900 g / cc and a total unsaturation of ≥ 0.20 / 1000C, and this second interpolymer differs from the ethylene / alpha-olefin interpolymer and further differs in one or more characteristics selected from density, total unsaturation, melt index (I2), or any combination thereof.

[0083] J] The composition of I] above, wherein the second ethylene / alpha-olefin interpolymer has a density of ≥ 0.856, or ≥ 0.858, or ≥ 0.860, or ≥ 0.862, or ≥ 0.864, or ≥ 0.866 g / cc, and / or ≤ 0.898, or ≤ 0.896, or ≤ 0.894, or ≤ 0.892, or ≤ 0.890, or ≤ 0.888, or ≤ 0.886, or ≤ 0.884, or ≤ 0.882, or ≤ 0.880, or ≤ 0.878, or ≤ 0.876, or ≤ 0.874, or ≤ 0.872 g / cc, or ≤ 0.870 g / cc.

[0084] K] the second ethylene / alpha-olefin interpolymer has a temperature of ≥ 0.22 / 1000C, or ≥ 0.24 / 1000C, or ≥ 0.26 / 1000C, or ≥ 0.28 / 1000C, or ≥ 0.30 / 1000C, or ≥ 0.35 / 1000C, or ≥ 0.40 / 1000C, or ≥ 0.45 / 1000C, or ≥ 0.50 / 1000C, or ≥ 0.55 / 1000C, or ≥ 0.60 / 1000C, or ≥ 0.65 / 1000C and / or a total unsaturation of ≦15.0 / 1000C, or ≦10.0 / 1000C, or ≦5.00 / 1000C, or ≦2.00 / 1000C, or ≦1.80 / 1000C, or ≦1.60 / 1000C, or ≦1.50 / 1000C, or ≦1.40 / 1000C, or ≦1.30 / 1000C, or ≦1.20 / 1000C, or ≦1.10 / 1000C, or ≦1.00 / 1000C.

[0085] L] Any one of the above compositions I]-K], wherein the second ethylene / alpha-olefin interpolymer has a melt index (I2, g / 10 min or dg / min) of ≥ 0.1, or ≥ 0.2, or ≥ 0.4, or ≥ 0.6, or ≥ 0.8, or ≥ 1.0, and / or ≤ 2000, or ≤ 1000, or ≤ 500, or ≤ 200, or ≤ 100, or ≤ 50, or ≤ 40, or ≤ 30, or ≤ 20, or ≤ 10, or ≤ 5.0, or ≤ 2.0.

[0086] M] the second ethylene / alpha-olefin interpolymer is represented by Formula A 1 L 1 L 2 A 2 or a telechelic ethylene / alpha-olefin interpolymer of formula A 1 L 1 and further comprising an unsaturated ethylene / alpha-olefin interpolymer of formula A 1 L 1 The composition of any one of I] to L] above, wherein the unsaturated ethylene / alpha-olefin interpolymer is selected from the group consisting of:

[0087] N] The composition of any one of I] through M] above, wherein the second ethylene / alpha-olefin interpolymer is an ethylene / alpha-olefin copolymer.

[0088] O] the alpha-olefin of the second ethylene / alpha-olefin interpolymer is C3-C 20 Alpha-olefins, further C3 to C 10 The composition of any one of I] to N] above, wherein the alpha-olefin is further propylene, 1-butene, 1-hexene, or 1-octene, further propylene, 1-butene, or 1-octene, further 1-butene, or 1-octene, further 1-octene.

[0089] P] The composition of any one of I]-O] above, wherein the second ethylene / alpha-olefin interpolymer is free, in polymerized form, of ENB, and further free of diene monomers and polyene monomers.

[0090] Q] the ethylene / alpha-olefin interpolymer and the second ethylene / alpha-olefin interpolymer are each independently represented by Formula A as described herein 1 L 1 L 2 A 2 or a telechelic ethylene / alpha-olefin interpolymer of formula A 1 L 1 and further comprising an unsaturated ethylene / alpha-olefin interpolymer of formula A 1 L 1 The composition of any one of I] to P] above, wherein the unsaturated ethylene / alpha-olefin interpolymer is selected from the group consisting of:

[0091] R] Any one of the above compositions I] to Q], wherein the ratio of the density of the ethylene / alpha-olefin to the density of the second ethylene / alpha-olefin is ≧0.80, or ≧0.85, or ≧0.90, or ≧0.92, or ≧0.94, or ≧0.96, or ≧0.98, or ≧1.0, and / or ≦1.25, or ≦1.20, or ≦1.18, or ≦1.16, or ≦1.14, or ≦1.12, or ≦1.11.

[0092] S] Any one of the above compositions I] to R], wherein the ratio of the total unsaturation of the ethylene / alpha-olefin to the total unsaturation of the second ethylene / alpha-olefin is ≧0.8, or ≧0.9, or ≧1.0, or ≧1.2, or ≧1.4, or ≧1.6, or ≧1.8, ≧2.0, and / or ≦5.0, or ≦4.5, or ≦4.0, or ≦3.8, or ≦3.6, or ≦3.4, or ≦3.2, or ≦3.0, or ≦2.8, or ≦2.6, or ≦2.4, or ≦2.2.

[0093] T] Any one of the above compositions I] to S], wherein the ratio of the melt index (I2) of the ethylene / alpha-olefin to the melt index (I2) of the second ethylene / alpha-olefin is ≧0.8, or ≧6.0, or ≧8.0, or ≧10, or ≧15, or ≧20, or ≧25, or ≧30, and / or ≦100, or ≦80, or ≦60, or ≦50, or ≦45, or ≦40, or ≦35.

[0094] U] Any one of the above compositions I] to T], wherein the weight ratio of ethylene / alpha-olefin to the second ethylene / alpha-olefin is ≧0.50, or ≧1.0, or ≧2.0, or ≧3.0, or ≧3.5, or ≧4.0, or ≧4.5, or ≧5.0, or ≧5.5, and / or ≦20, or ≦15, or ≦10, or ≦9.0, or ≦8.0, or ≦7.5, or ≦7.0, or ≦6.5, or ≦6.0.

[0095] V] Any one of compositions I]-U], wherein component a comprises ≧80.0 wt%, or ≧85.0 wt%, or ≧90.0 wt%, or ≧95.0 wt%, or ≧98.0 wt%, or ≧99.0 wt%, or ≧99.2 wt%, or ≧99.4 wt%, or ≧99.6 wt%, or ≧99.7 wt%, and / or ≦100.0 wt%, or ≦99.9 wt%, or ≦99.8 wt% of the total of the ethylene / alpha-olefin and the second ethylene / alpha-olefin, based on the weight of component a.

[0096] W] Any one of the compositions A]-H], wherein component a comprises ≥80.0 wt%, or ≥85.0 wt%, or ≥90.0 wt%, or ≥95.0 wt%, or ≥98.0 wt%, or ≥99.0 wt%, or ≥99.2 wt%, or ≥99.4 wt%, or ≥99.6 wt%, or ≥99.7 wt%, and / or ≤100.0 wt%, or ≤99.9 wt%, or ≤99.8 wt% ethylene / alpha-olefins, based on the weight of component a.

[0097] A2] A process for forming a crosslinked composition, the process comprising at least the following steps A and B: A) The following components a) to c), namely: a) at least one ethylene / alpha-olefin interpolymer comprising the following properties: i) a density of 0.855 to 0.900 g / cc and ii) a total unsaturation level of ≥ 0.20 / 1000 C; b) at least one Tempo compound of structure I); c) extruding a composition comprising at least one peroxide to form a pre-crosslinked composition; B) heat treating the pre-crosslinked composition in air at a temperature of ≧150° C. to form a crosslinked composition, wherein Structure I is selected from Structure IA, Structure IB, or Structure IC (see A] above), each described herein.

[0098] B2] The process of A2] above, wherein for step A, the composition is extruded at an average barrel temperature of ≧60°C, or ≧65°C, or ≧70°C, or ≧75°C, ≧80°C, ≧85°C, or ≧90°C, or ≧95°C, or ≧100°C, or ≧105°C, or ≧110°C, and / or ≦150°C, ≦145°C, ≦140°C, or ≦135°C, or ≦130°C, or ≦125°C, or ≦120°C, or ≦115°C.

[0099] C2] The process of A2] or B2] above, wherein for step B, the pre-crosslinked composition is heat treated at a temperature of ≧150°C, or ≧155°C, or ≧160°C, or ≧165°C, or ≧170°C, or ≧175°C, or ≧180°C, ≧185°C, or ≧190°C, or ≧195°C, or ≧200°C, and / or at a temperature of ≦240°C, or ≦235°C, or ≦230°C, or ≦225°C, or ≦220°C, or ≦215°C, or ≦210°C, or ≦205°C.

[0100] D2] For step B, the pre-crosslinked composition is heat treated in a continuous high temperature oven or a hot air tunnel.

[0101] E2] Any one of the processes A2]-D2] above, wherein for step A, the composition is extruded in a series extruder configuration with a Garvey die at the end of the last extruder in the extruder configuration.

[0102] F2] The process of any one of A2] to E2] above, wherein for the composition, the molar ratio of NO from component b to peroxide (OO) bonds from component c is 0.30 to 0.90.

[0103] G2] The process of any one of A2] through F2] above, wherein for the composition, component b is present in an amount of 0.20 to 0.90 phr, based on 100 parts of component a.

[0104] H2] A process for forming a crosslinked composition, the process comprising: a composition comprising the following components a) to c): a) at least one ethylene / alpha-olefin interpolymer comprising the following properties: i) a density of 0.855 to 0.900 g / cc and ii) a total unsaturation level of ≥ 0.20 / 1000 C; b) at least one Tempo compound of structure I); c) at least one peroxide; the molar ratio of NO· from at least one Tempo compound (component b) to peroxide (OO) bonds from at least one peroxide (component c) is 0.30 to 0.90; wherein component b is present in an amount of 0.20 to 0.90 phr, based on 100 parts of component a, and structure I is selected from structure IA, structure IB, or structure IC (see A above), each described herein.

[0105] I2] The process of H2] above, wherein the heat treatment is carried out in air.

[0106] J2] The process of H2] or I2] above, wherein the composition is heat treated at a temperature of ≥ 150°C, or ≥ 155°C, or ≥ 160°C, or ≥ 165°C, or ≥ 170°C, or ≥ 175°C, or ≥ 180°C, ≥ 185°C, or ≥ 190°C, or ≥ 195°C, or ≥ 200°C, and / or at a temperature of ≤ 240°C, or ≤ 235°C, or ≤ 230°C, or ≤ 225°C, or ≤ 220°C, or ≤ 215°C, or ≤ 210°C, or ≤ 205°C.

[0107] K2] The process of any one of H2]-J2] above, wherein the composition is extruded before being heat treated.

[0108] L2] The process of K2] above, wherein the composition is extruded at an average barrel temperature of ≥ 60°C, or ≥ 65°C, or ≥ 70°C, or ≥ 75°C, ≥ 80°C, ≥ 85°C, or ≥ 90°C, or ≥ 95°C, or ≥ 100°C, or ≥ 105°C, or ≥ 110°C, or ≤ 150°C, or ≤ 145°C, or ≤ 140°C, or ≤ 135°C, or ≤ 130°C, or ≤ 125°C, or ≤ 120°C, or ≤ 115°C.

[0109] M2] The process of any one of A2] through L2] above, wherein the ethylene / alpha-olefin interpolymer has a density of ≥ 0.856, or ≥ 0.858, or ≥ 0.860, or ≥ 0.862, or ≥ 0.864, or ≥ 0.866 g / cc, and / or ≤ 0.898, or ≤ 0.896, or ≤ 0.894, or ≤ 0.892, or ≤ 0.890, or ≤ 0.888, or ≤ 0.886, or ≤ 0.884, or ≤ 0.882, or ≤ 0.880, or ≤ 0.878, or ≤ 0.876, or ≤ 0.874, or ≤ 0.872 g / cc.

[0110] N2] the ethylene / alpha-olefin interpolymer has a temperature of ≥ 0.22 / 1000C, or ≥ 0.24 / 1000C, or ≥ 0.26 / 1000C, or ≥ 0.28 / 1000C, or ≥ 0.30 / 1000C, or ≥ 0.35 / 1000C, or ≥ 0.40 / 1000C, or ≥ 0.45 / 1000C, or ≥ 0.50 / 1000C, or ≥ 0.55 / 1000C, or ≥ 0.60 / 1000C, or ≥ 0.65 / 1000C, and / or has a total unsaturation of ≦15.0 / 1000C, or ≦10.0 / 1000C, or ≦5.00 / 1000C, or ≦2.00 / 1000C, or ≦1.80 / 1000C, or ≦1.60 / 1000C, or ≦1.50 / 1000C, or ≦1.40 / 1000C, or ≦1.30 / 1000C, or ≦1.20 / 1000C, or ≦1.10 / 1000C, or ≦1.00 / 1000C.

[0111] O2] The process of any one of A2] through N2] above, wherein the ethylene / alpha-olefin interpolymer has a melt index (I2, g / 10 min or dg / min) of ≥ 0.1, or ≥ 0.2, or ≥ 0.4, or ≥ 0.6, or ≥ 0.8, or ≥ 1.0, or ≥ 1.2, or ≥ 1.4, or ≥ 1.6, or ≥ 1.8, or ≥ 2.0, and / or ≤ 2000, or ≤ 1000, or ≤ 500, or ≤ 200, or ≤ 100, or ≤ 50, or ≤ 45, or ≤ 40, or ≤ 35, or ≤ 30, or ≤ 25, or ≤ 20.

[0112] P2] The ethylene / alpha-olefin interpolymer is of formula A described herein 1 L 1 L 2 A 2 or a telechelic ethylene / alpha-olefin interpolymer of formula A 1 L 1and further comprising an unsaturated ethylene / alpha-olefin interpolymer of formula A 1 L 1 The process of any one of A2] to O2] above, wherein the unsaturated ethylene / alpha-olefin interpolymer is selected from the group consisting of:

[0113] Q2] The process of any one of A2] through P2] above, wherein the ethylene / alpha-olefin interpolymer is an ethylene / alpha-olefin copolymer.

[0114] R2] The alpha-olefin of the ethylene / alpha-olefin interpolymer is C3-C 20 Alpha-olefins, further C3 to C 10 The process of any one of A2] to Q2] above, wherein the alpha-olefin is further propylene, 1-butene, 1-hexene, or 1-octene, further propylene, 1-butene, or 1-octene, further 1-butene, or 1-octene, further 1-octene.

[0115] S2] The process of any one of A2]-R2] above, wherein the alpha-olefin of the ethylene / alpha-olefin interpolymer is free, in polymerized form, from ENB, and further from diene monomers, and further from polyene monomers.

[0116] T2] The process of any one of A2] to S2] above, wherein component a further comprises a second ethylene / alpha-olefin interpolymer having a density of 0.855 to 0.900 g / cc and a total unsaturation of ≧0.20 / 1000C, wherein this second interpolymer differs from the ethylene / alpha-olefin interpolymer and further differs in one or more characteristics selected from density, total unsaturation, melt index (I2), or any combination thereof.

[0117] U2] The process of T2] above, wherein the second ethylene / alpha-olefin interpolymer has a density of ≥ 0.856, or ≥ 0.858, or ≥ 0.860, or ≥ 0.862, or ≥ 0.864, or ≥ 0.866 g / cc, and / or ≤ 0.898, or ≤ 0.896, or ≤ 0.894, or ≤ 0.892, or ≤ 0.890, or ≤ 0.888, or ≤ 0.886, or ≤ 0.884, or ≤ 0.882, or ≤ 0.880, or ≤ 0.878, or ≤ 0.876, or ≤ 0.874, or ≤ 0.872 g / cc, or ≤ 0.871 g / cc.

[0118] V2] the second ethylene / alpha-olefin interpolymer has a temperature of ≥ 0.22 / 1000C, or ≥ 0.24 / 1000C, or ≥ 0.26 / 1000C, or ≥ 0.28 / 1000C, or ≥ 0.30 / 1000C, or ≥ 0.35 / 1000C, or ≥ 0.40 / 1000C, or ≥ 0.45 / 1000C, or ≥ 0.50 / 1000C, or ≥ 0.55 / 1000C, or ≥ 0.60 / 1000C, or ≥ 0.65 / 1000C; and / or having a total unsaturation of ≦15.0 / 1000C, or ≦10.0 / 1000C, or ≦5.00 / 1000C, or ≦2.00 / 1000C, or ≦1.80 / 1000C, or ≦1.60 / 1000C, or ≦1.50 / 1000C, or ≦1.40 / 1000C, or ≦1.30 / 1000C, or ≦1.20 / 1000C, or ≦1.10 / 1000C, or ≦1.00 / 1000C.

[0119] W2] The process of any one of T2] through V2] above, wherein the second ethylene / alpha-olefin interpolymer has a melt index (I2, g / 10 min or dg / min) of ≥ 0.1, or ≥ 0.2, or ≥ 0.4, or ≥ 0.6, or ≥ 0.8, or ≥ 1.0, and / or ≤ 2000, or ≤ 1000, or ≤ 500, or ≤ 200, or ≤ 100, or ≤ 50, or ≤ 40, or ≤ 30, or ≤ 20, or ≤ 10, or ≤ 5.0, or ≤ 2.0.

[0120] X2] the second ethylene / alpha-olefin interpolymer has Formula A 1 L 1 L 2 A 2 or a telechelic ethylene / alpha-olefin interpolymer of formula A 1 L 1 and further comprising an unsaturated ethylene / alpha-olefin interpolymer of formula A 1 L 1 The process of any one of T2] to W2] above, wherein the unsaturated ethylene / alpha-olefin interpolymer is selected from the group consisting of:

[0121] Y2] The process of any one of T2] through X2] above, wherein the second ethylene / alpha-olefin interpolymer is an ethylene / alpha-olefin copolymer.

[0122] Z2] the alpha-olefin of the second ethylene / alpha-olefin interpolymer is C3-C 20 Alpha-olefins, further C3 to C 10 The process of any one of T2] to Y2] above, wherein the alpha-olefin is propylene, 1-butene, 1-hexene, or 1-octene, further propylene, 1-butene, or 1-octene, further 1-butene, or 1-octene, further 1-octene.

[0123] A3] The process of any one of T2] through Z2] above, wherein the second ethylene / alpha-olefin interpolymer is free, in polymerized form, of ENB, and further diene monomers, and further polyene monomers.

[0124] B3] the ethylene / alpha-olefin interpolymer and the second ethylene / alpha-olefin interpolymer each independently have the formula A described herein 1 L 1 L 2 A 2 or a telechelic ethylene / alpha-olefin interpolymer of formula A 1 L 1 and further comprising an unsaturated ethylene / alpha-olefin interpolymer of formula A 1 L 1 The process of any one of T2] to A3] above, wherein the unsaturated ethylene / alpha-olefin interpolymer is selected from the group consisting of:

[0125] C3] The process of any one of T2] through B3] above, wherein the ratio of the density of the ethylene / alpha-olefin to the density of the second ethylene / alpha-olefin is ≥ 0.80, or ≥ 0.85, or ≥ 0.90, or ≥ 0.92, or ≥ 0.94, or ≥ 0.96, or ≥ 0.98, or ≥ 1.0, and / or ≤ 1.25, or ≤ 1.20, or ≤ 1.18, or ≤ 1.16, or ≤ 1.14, or ≤ 1.12, or ≤ 1.11.

[0126] D3] The process of any one of T2] - C3] above, wherein the ratio of the total unsaturation of the ethylene / alpha-olefin to the total unsaturation of the second ethylene / alpha-olefin is ≥ 0.8, or ≥ 0.9, or ≥ 1.0, or ≥ 1.2, or ≥ 1.4, or ≥ 1.6, or ≥ 1.8, or ≥ 2.0, and / or ≤ 5.0, or ≤ 4.5, or ≤ 4.0, or ≤ 3.8, or ≤ 3.6, or ≤ 3.4, or ≤ 3.2, or ≤ 3.0, or ≤ 2.8, or ≤ 2.6, or ≤ 2.4, or ≤ 2.2.

[0127] E3] The process of any one of T2] through D3] above, wherein the ratio of the melt index (I2) of the ethylene / alpha-olefin to the melt index (I2) of the second ethylene / alpha-olefin is ≧0.8, or ≧6.0, or ≧8.0, or ≧10, or ≧15, or ≧20, or ≧25, or ≧30, and / or ≦100, or ≦80, or ≦60, or ≦50, or ≦45, or ≦40, or ≦35.

[0128] F3] The process of any one of T2] - E3] above, wherein the weight ratio of the ethylene / alpha-olefin to the second ethylene / alpha-olefin is ≧0.50, or ≧1.0, or ≧2.0, or ≧3.0, or ≧3.5, or ≧4.0, or ≧4.5, or ≧5.0, or ≧5.5, and / or ≦20, or ≦15, or ≦10, or ≦9.0, or ≦8.0, or ≦7.5, or ≦7.0, or ≦6.5, or ≦6.0.

[0129] G3] The process of any one of T2]-F3], wherein component a comprises ≥ 80.0 wt%, or ≥ 85.0 wt%, or ≥ 90.0 wt%, or ≥ 95.0 wt%, or ≥ 98.0 wt%, or ≥ 99.0 wt%, or ≥ 99.2 wt%, or ≥ 99.4 wt%, or ≥ 99.6 wt%, or ≥ 99.7 wt%, and / or ≤ 100.0 wt%, or ≤ 99.9 wt%, or ≤ 99.8 wt%, of the sum of the ethylene / alpha-olefin and the second ethylene / alpha-olefin, based on the weight of component a.

[0130] H3] The process of any one of A2]-S2], wherein component a comprises ≥ 80.0 wt%, or ≥ 85.0 wt%, or ≥ 90.0 wt%, or ≥ 95.0 wt%, or ≥ 98.0 wt%, or ≥ 99.0 wt%, or ≥ 99.2 wt%, or ≥ 99.4 wt%, or ≥ 99.6 wt%, or ≥ 99.7 wt%, and / or ≤ 100.0 wt%, or ≤ 99.9 wt%, or ≤ 99.8 wt%, ethylene / alpha-olefins, based on the weight of component a.

[0131] A4] The composition of any one of A] through W] above, or the process of any one of A2] through H3] above, wherein the ethylene / alpha-olefin of component a has a number average molecular weight Mn of ≥ 5,000, or ≥ 6,000, or ≥ 8,000, or ≥ 10,000, or ≥ 12,000, or ≥ 14,000, or ≥ 16,000, or ≥ 18,000, or ≥ 20,000 g / mol, and / or ≤ 120,000, or ≤ 100,000, or ≤ 80,000, or ≤ 70,000, or ≤ 65,000, or ≤ 60,000, or ≤ 58,000, or ≤ 56,000, or ≤ 54,000 g / mol.

[0132] B4] The composition of any one of A] through W] or A4] above, or the process of any one of A2] through H3] or A4] above, wherein the ethylene / alpha-olefin of component a has a weight average molecular weight Mn of ≥ 20,000, or ≥ 25,000, or ≥ 30,000, or ≥ 35,000, or ≥ 40,000, or ≥ 45,000 g / mol, and / or ≤ 150,000, or ≤ 145,000, or ≤ 140,000, or ≤ 135,000, or ≤ 130,000, or ≤ 125,000, or ≤ 120,000, or ≤ 115,000 g / mol.

[0133] C4] The composition of any one of A] to W], A4], or B4] above, or the process of any one of A2] to H3], A4], or B4] above, wherein the ethylene / alpha-olefin of component a has a molecular weight distribution MWD (= Mw / Mn) of ≧1.80, or ≧1.85, or ≧1.90, or ≧1.95, or ≧2.00, or ≧2.05, or ≧2.10, and / or ≦5.00, or ≦4.50, or ≦4.00, or ≦3.50, or ≦3.20, or ≦3.00, or ≦2.90, or ≦2.80, or ≦2.70, or ≦2.60, or ≦2.50, or ≦2.45, or ≦2.40, or ≦2.35.

[0134] D4] The composition of any one of I] to W] or A4] to C4] above, or the process of any one of T2] to H3] or A4] to C4] above, wherein the ratio of Mn of the ethylene / alpha-olefin to Mn of the second ethylene / alpha-olefin interpolymer is ≧0.10, or ≧0.20, or ≧0.25, or ≧0.30, or ≧0.35, and / or ≦0.60, or ≦0.55, or ≦0.50, or ≦0.45, or ≦0.40.

[0135] E4] The composition of any one of I]-W] or A4]-D4] above, or the process of any one of T2]-H3] or A4]-D4] above, wherein the ratio of the Mw of the ethylene / alpha-olefin to the Mw of the second ethylene / alpha-olefin interpolymer is ≥ 0.20, or ≥ 0.25, or ≥ 0.30, or ≥ 0.35, or ≥ 0.40, and / or ≤ 0.70, or ≤ 0.65, or ≤ 0.60, or ≤ 0.55, or ≤ 0.50, or ≤ 0.45.

[0136] F4] The composition of any one of I]-W] or A4]-E4] above, or the process of any one of T2]-H3] or A4]-E4] above, wherein the ratio of the MWD of the ethylene / alpha-olefin to the MWD of the second ethylene / alpha-olefin interpolymer is ≧0.90, or ≧0.95, or ≧1.00, or ≧1.05, and / or ≦1.25, or ≦1.20, or ≦1.15, or ≦1.10.

[0137] G4] Any one of the compositions A] to W] or A4] to F4] above, or any one of the processes A2] to H3] or A4] to F4] above, wherein for structure I of component b, R1, R2, R3, and R4 are the same.

[0138] H4] Any one of the compositions A] to W] or A4] to F4] above, or any one of the processes A2] to H3] or A4] to F4] above, wherein for structure I of component b, at least one of R1, R2, R3, and R4 is different from the others of R1, R2, R3, and R4.

[0139] I4] For structure I of component b, any one of the compositions A] to W] or A4] to F4] above, or any one of the processes A2] to H3] or A4] to F4] above, wherein each of R1, R2, R3, and R4 is independently selected from H or C1-C5 alkyl, further H or C1-C4 alkyl, further H or C1-C3 alkyl, further H or C1-C2 alkyl, further H or methyl.

[0140] J4] For structure I of component b, any one of the compositions A] to W] or A4] to F4] above, or any one of the processes A2] to H3] or A4] to F4] above, wherein each of R1, R2, R3, and R4 is independently selected from C1 to C6 alkyl, further C1 to C5 alkyl, further C1 to C4 alkyl, further C1 to C3 alkyl, further C1 to C2 alkyl, and further methyl.

[0141] K4] The composition of any one of A] to W] or A4] to J4] above, or the process of any one of A2] to H3] or A4] to J4] above, wherein for structure I of component b, X is selected from CH2, ether (-O-), carbonyl (-C(O)-), ester (-O-C(O)- or -C(O)-O-), amine (-N(R)-), or amide (-N(R)-C(O)- or -C(O)-N(R)-), and further CH2, ether (-O-) or ester (-O-C(O)- or -C(O)-O-, and further ester (-O-C(O)- or -C(O)-O-).

[0142] L4] Any one of the compositions A] to W] or A4] to K4] above, or any one of the processes A2] to H3] or A4] to K4] above, wherein for structure I of component b, R' is selected from C1 to C6 alkylene, further C1 to C5 alkylene, further C1 to C4 alkylene, further C1 to C3 alkylene, further C1 to C2 alkylene.

[0143] M4] Any one of the compositions A] to W] or A4] to L4] above, or any one of the processes A2] to H3] or A4] to L4] above, wherein for structure I of component b, R" is selected from C1 to C6 alkylene, further C1 to C5 alkylene, further C1 to C4 alkylene, further C1 to C3 alkylene, further C1 to C2 alkylene, and further methylene.

[0144] N4] Any one of the compositions A] to W] or A4] to L4] above, or any one of the processes A2] to H3] or A4] to L4] above, wherein for structure I of component b, R" is absent.

[0145] O4] Any one of the compositions A] to W] or A4] to N4] above, or any one of the processes A2] to H3] or A4] to N4] above, wherein for structure I of component b, n is greater than or equal to 2.

[0146] P4] The composition of any one of A] to W] or A4] to O4] above, or the process of any one of A2] to H3] or A4] to O4] above, wherein Structure I (component b) is selected from Structure IA.

[0147] Q4] The composition of any one of P4] above, or the process of any one of P2] above, wherein for structure IA, n is 2 to 4, further 2 or 3, further 2.

[0148] R4] For structure IA, Y is CR 4-n (wherein n=1 to 4), OR 2-n (in the formula, n=1~2), NR 3-n wherein n=1-3, a bifunctional C-C core as described herein, a phenyl core as described herein, an ester-substituted phenyl core as described herein, an amide-substituted phenyl core as described herein, and further comprising CR 4-n (wherein n=1 to 4), OR 2-n (in the formula, n=1~2), NR 3-nwherein n=1-3, a difunctional C-C core as described herein, or a phenyl core as described herein, and further comprising CR 4-n (wherein n=1 to 4), OR 2-n wherein n=1-2, or a difunctional C-C core as described herein, and further comprising CR 4-n wherein n=1-4, or a difunctional C-C core as described herein, further selected from a difunctional C-C core as described herein.

[0149] S4] a bifunctional C-C core,

[0150] [ka] wherein each R' represents a divalent R' group in structure IA above, and further wherein each R in the C-C core is H.

[0151] T4] The composition of any one of P4]-S4] above, or the process of any one of P4]-S4] above, wherein for structure IA, each R is independently selected from H, unsubstituted hydrocarbyl, or substituted hydrocarbyl, and further H or unsubstituted hydrocarbyl, and further H or alkyl, and further H or C1-C5 alkyl.

[0152] U4] Structure IA may be the following structure IA1:

[0153] [ka] The composition of any one of P4] to T4] above, or the process of any one of P4] to T4] above,

[0154] V4] The composition of any one of A] to W] or A4] to O4] above, or the process of any one of A2] to H3] or A4] to O4] above, wherein structure I (component b) is selected from structure IB, including substructure IB.

[0155] W4] The composition of V4] above or the process of V4] above, wherein for substructure IB, n≧10, or n≧20, or n≧50, or n≧100.

[0156] X4] The composition of V4] or W4] above or the process of V4] or W4] above, wherein for substructure IB, each R group is independently selected from H, unsubstituted hydrocarbyl, or substituted hydrocarbyl, and further H or unsubstituted hydrocarbyl, and further H or alkyl, and further H or C1-C5 alkyl.

[0157] Y4] The composition of any one of A]-W] or A4]-O4] above, or the process of any one of A2]-H3] or A4]-O4] above, wherein structure I (component b) is selected from structure IC, including substructure IC.

[0158] Z4] The composition of Y4] above, or the process of Y4] above, wherein for substructure IC, n≧10, or n≧20, or n≧50, or n≧100.

[0159] A5] For substructure IC, the composition of Y4] or Z4] above or the process of Y4] or Z4] above, wherein each R group is independently selected from H, unsubstituted hydrocarbyl, or substituted hydrocarbyl, and further H or unsubstituted hydrocarbyl, and further H or alkyl, and further H or C1-C5 alkyl.

[0160] B5] For substructure IC, the composition of any one of Y4]-A5] above, or the process of any one of Y4]-A5] above, wherein each R''' group is independently selected from unsubstituted hydrocarbyl, or substituted hydrocarbyl, and further unsubstituted hydrocarbyl, and further alkyl, and further C1-C5 alkyl.

[0161] C5] For substructure IC, n≧3, and each terminal * The composition of any one of Y4] to B5] above, or the process of any one of Y4] to B5] above, wherein the (asterisk) forms a cyclic structure with the other end.

[0162] D5] The composition of any one of A] to W] or A4] to C5] above, or the process of any one of A2] to H3] or A4] to C5] above, wherein the molar ratio of NO from at least one Tempo compound (component b) to (OO) bonds from at least one peroxide (component c) is ≧0.31, or ≧0.33, or ≧0.34, and / or ≦0.88, or ≦0.85, or ≦0.82, or ≦0.80, or ≦0.78, or ≦0.75, or ≦0.72, or ≦0.70, or ≦0.68, or ≦0.65, or ≦0.62, or ≦0.60, or ≦0.58.

[0163] E5] The composition of any one of A] through W] or A4] through D5] above, or the process of any one of A2] through H3] or A4] through D5] above, wherein component b is present in an amount of ≥ 0.22, or ≥ 0.25, or ≥ 0.28, or ≥ 0.30, or ≥ 0.32, or ≥ 0.35, or ≥ 0.38, or ≥ 0.40, or ≥ 0.42, or ≥ 0.45 phr, and / or ≤ 0.88, or ≤ 0.85, or ≤ 0.82, or ≤ 0.80, or ≤ 0.78, or ≤ 0.75 phr, based on 100 parts of component a.

[0164] F5] The composition of any one of A] through W] or A4] through E5] above, or the process of any one of A2] through H3] or A4] through E5] above, wherein component c is present in an amount of ≥ 0.40, or ≥ 0.45, or ≥ 0.50, or ≥ 0.55, or ≥ 0.60, or ≥ 0.62, or ≥ 0.65, or ≥ 0.68, or ≥ 0.70, or ≥ 0.72, or ≥ 0.74 phr, and / or ≤ 0.88, or ≤ 0.85, or ≤ 0.82, or ≤ 0.80, or ≤ 0.78 phr, based on 100 parts of component a.

[0165] G5] The composition of any one of A] to W] or A4] to F5] above, or the process of any one of A2] to H3] or A4] to F5] above, wherein the composition comprises ≥ 90.0 wt%, or ≥ 92.0 wt%, or ≥ 94.0 wt%, or ≥ 96.0 wt%, or ≥ 98.0 wt%, or ≥ 98.1 wt%, or ≥ 98.2 wt%, and / or ≤ 100.0 wt%, or ≤ 99.8 wt%, or ≤ 99.5 wt%, or ≤ 99.2 wt%, or ≤ 99.0 wt%, or ≤ 98.8 wt% of component a, based on the weight of the composition.

[0166] H5] The composition of any one of A] to W] or A4] to G5] above, or the process of any one of A2] to H3] or A4] to G5] above, wherein the composition further comprises a crosslinking coagent (component d).

[0167] I5] The composition of H5] or the process of H5] above, wherein component d is present in an amount, based on 100 parts of component a, of ≥ 0.05, or ≥ 0.10, or ≥ 0.15, or ≥ 0.20, or ≥ 0.22, or ≥ 0.25, or ≥ 0.28, or ≥ 0.30, or ≥ 0.32, or ≥ 0.35 phr, and / or ≤ 0.75, or ≤ 0.70, or ≤ 0.65, or ≤ 0.60, or ≤ 0.55, or ≤ 0.50, or ≤ 0.48, or ≤ 0.45, or ≤ 0.42, or ≤ 0.40 phr.

[0168] J5] The composition of any one of A] to W] or A4] to I5] above, or the process of any one of A2] to H3] or [A4] to I5] above, wherein the weight ratio of component c to component b is ≧0.50, or ≧0.60, or ≧0.70, or ≧0.80, or ≧0.85, or ≧0.90, or ≧0.95, or ≧1.0, and / or ≦5.0, or ≦4.5, or ≦4.0, or ≦3.8, or ≦3.5, or ≦3.2, or ≦3.0, or ≦2.8, or ≦2.5, or ≦2.2, or ≦2.0, or ≦1.9, or ≦1.8, or ≦1.7.

[0169] K5] The composition of any one of H5]-J5] above, or the process of any one of H5]-J5] above, wherein the weight ratio of components c to d is ≧0.50, or ≧0.60, or ≧0.80, or ≧1.0, or ≧1.2, or ≧1.4, or ≧1.6, or ≧1.8, or ≧2.0, and / or ≦4.0, or ≦3.5, or ≦3.0, or ≦2.8, or ≦2.6, or ≦2.4, or ≦2.2.

[0170] L5] The composition of any one of A] through W] or A4] through K5] above, or the process of any one of A2] through H3] or A4] through K5] above, wherein the composition comprises ≦10.0 wt %, or ≦5.0 wt %, or ≦2.0 wt %, or ≦1.0 wt %, or ≦0.5 wt %, or ≦0.1 wt %, of a filler, based on the weight of the composition, and further wherein the composition does not comprise a filler.

[0171] M5] The composition of any one of A] through W] or A4] through L5] above, or the process of any one of A2] through H3] or A4] through L5] above, wherein the composition comprises ≥ 90.0 wt%, or ≥ 94.0 wt%, or ≥ 96.0 wt%, or ≥ 97.0 wt%, or ≥ 97.5 wt%, or ≥ 98.0 wt%, or ≥ 98.5 wt%, or ≥ 99.0 wt%, or ≥ 99.5 wt%, and / or ≤ 100.0 wt%, or ≤ 99.9 wt%, or ≤ 99.8 wt%, or ≤ 99.7 wt% of the sum of components a, b, and c, based on the weight of the composition.

[0172] N5] The composition of any one of A] to W] or A4] to M5] above, or the process of any one of A2] to H3] or A4] to M5] above, wherein the composition comprises one Tempo compound for component b.

[0173] O5] The composition of any one of A] to W] or A4] to N5] above, or the process of any one of A2] to H3] or A4] to N5] above, wherein the composition comprises one peroxide for component c.

[0174] P5] The composition of any one of A]-W] or A4]-O5] above, or the process of any one of A2]-H3] or A4]-O5] above, wherein the composition further comprises a polymer that differs from the ethylene / alpha-olefin interpolymer of component a in one or more characteristics, such as comonomer type, comonomer content, density, melt index (I2), total unsaturation, Mn, Mw, MWD, or any combination thereof, and further comonomer type, comonomer content, density, melt index (I2), total unsaturation, or any combination thereof.

[0175] Q5] The composition of any one of A] through W] or A4] through P5] above, or the process of any one of A2] through H3] or A4] through P5] above, wherein the composition has a (MH-ML) value of MH ≥ 4.0, or ≥ 4.1, or ≥ 4.2 dNm, and / or ≤ 10, or ≤ 8.0, or ≤ 6.0 dNm. See Test Methods section.

[0176] R5] The composition of any one of A] to W] or A4] to Q5] above, or the process of any one of A2] to H3] or A4] to Q5] above, wherein the ethylene / alpha-olefin interpolymer (further copolymer) of component a is a random interpolymer (further random copolymer).

[0177] S5] The composition of any one of I] to W] or A4] to R5] above, or the process of any one of T2] to H3] or A4] to R5] above, wherein the second ethylene / alpha-olefin interpolymer (further copolymer) is a random interpolymer (further random copolymer).

[0178] T5] A crosslinked composition formed from any one of the compositions A] to W] or A4] to S5] above by further heat treating the composition, or a crosslinked composition formed by any one of the processes A2] to H3] or A4] to S5] above.

[0179] U5] The crosslinked composition of T5] above, wherein the crosslinked composition has an H1714 value of ≦0.010, or ≦0.005, or ≦0.002, or ≦0.001, the H1714 value being determined by the FTIR-ATR method described herein.

[0180] V5] The crosslinked composition of T5] or U5] above, wherein the crosslinked composition has a D value of ≦0.025, or ≦0.020, or ≦0.015, or ≦0.010, the D value being determined by the FTIR-ATR method described herein.

[0181] W5] Any one of the crosslinked compositions T5] to V5] above, wherein the crosslinked composition has an RD value of ≦8%, or ≦6%, or ≦4%, or ≦2%, wherein the RD value is determined by the FTIR-ATR method described herein.

[0182] X5] The crosslinked composition of any one of T5] to W5] above, having a fingertip test rating of 3 as determined by the fingertip test described herein.

[0183] Y5] An article comprising at least one component formed from the composition of any one of A] to W] or A4] to S5] above, or formed by the process of any one of A2] to H3] or A4] to S5] above.

[0184] Z5] An article comprising at least one component formed from any one of the crosslinked compositions T5] to X5] above.

[0185] A6] Automobile parts or building materials, footwear parts, or PV films, and also articles of Y5] or Z5] above that are automobile parts.

[0186] B6] The article described in Y5] or Z5] above, wherein the article is a profile.

[0187] Test Method Moving Die Rheometer (MDR) Analysis The MDR cure characteristics (Gum—see Experimental Section) of each composition were measured according to ASTM D-5289 using an Alpha Technologies MDR 2000. Approximately 4.5 g of sample was placed in the MDR sample holder. MDR testing was conducted at 180°C for 15 minutes at an oscillation frequency of 100 CPM (1.67 Hz) and an oscillation angle of 0.5 degrees (7% strain). The minimum torque (ML) and maximum torque (MH) exerted by the MDR during the test interval were reported in dNm. The difference between MH and ML indicates the degree of crosslinking; a larger difference indicates a greater degree of crosslinking. The time taken for the torque to reach X% (e.g., 90%) of the MH value or a TX value (e.g., T90) was reported in minutes. The time required for the torque value to increase by one dNm value above the ML value from the start of the test is designated "TS1" and recorded in minutes. The TS1 value indicates the time required to initiate the crosslinking process. A shorter time indicates a faster onset of crosslinking. One sample per composition was tested.

[0188] FTIR-ATR analysis (crosslinked composition) The degradation of each hot air crosslinked composition was determined by FTIR-ATR analysis (Nicolet 5700 from Thermo Electron Corporation). The methylene group (CH) is detected at approximately 1465 cm -1 The carbonyl group (C=O) emits a signal around 1714 cm -1 It emits a signal in the surrounding area and is used to monitor the deterioration level. -1 and 1465cm -1 The height ratio between H1714 and H1465 represents the degradation degree as follows: D = H1714 / H1465, where D is the degradation degree, and in the absorption mode spectrum, H1714 is at 1714 cm -1 is the IR peak height at (1845-1570 cm as the baseline) -1 (Use), H1465 is 1465cm -1 is the IR peak height at 1540-1389 cm (baseline) -1(The formula is used). The relative degradation is calculated according to the following formula: RD = (D / D), where RD is the relative degradation, D is the degradation of the tested specimen, and D is the degradation of the control sample with peroxide but without the Tempo compound. A small sample of the hot air cured compression molded composition was used for each analysis (see Experimental Section). The FTIR analysis used a penetration depth of about 1 micron, and the outer surface of the compression molded sample was exposed to IR radiation (an area with a diameter of about 2 mm). One sample per composition was investigated.

[0189] Fingertip test (surface adhesiveness) The hot-air crosslinked compositions were tested for surface tack using a fingertip test. The fingertip test is a qualitative laboratory test method. Laboratory personnel use their finger to touch the top surface of the crosslinked sample and provide feedback on the sample's surface tack using the following criteria shown in Table A below. One sample per composition was tested.

[0190] [Table 1]

[0191] 1 H NMR method Sample preparation: Each sample was prepared by adding approximately 130 mg of sample to 3.25 g of 50 / 50 by weight tetrachloroethane-d₂ / perchloroethylene (TCE-d₂ / PCE) containing 0.001 M Cr(AcAc)₃ in a NORELL 1001-7, 10 mm, NMR tube. The sample was purged by bubbling N₂ through the solvent via a pipette inserted into the tube for approximately 5 minutes to prevent oxidation. The tube was then capped and sealed with Teflon tape before being heated to 115°C and vortex mixed to obtain a homogeneous solution.

[0192] Data acquisition parameters and data analysis: Bruker AVANCE 600 MHz spectrometer equipped with a Bruker high-temperature CryoProbe, sample temperature 120°C. 1H NMR was performed.

[0193] Two experiments were performed to obtain spectra for quantifying total polymer protons, and a control spectrum. A double pre-saturation experiment was performed to suppress the strong peaks associated with the polymer chains and enable highly sensitive spectra for quantification of end groups. This control was performed with a ZG pulse, 16 scans, AQ 1.82 seconds, and D1 (relaxation delay) 14 seconds. The double pre-saturation experiment was performed with a modified pulse sequence, lc1prf2.zz, 64 scans, AQ 1.82 seconds, D1 (pre-saturation time) 2 seconds, and D 13 The relaxation delay was 12 seconds. The unsaturation measurements were performed according to the following method: The areas under the resonances from the polymer chains (i.e., CH, CH2, and CH3 in the polymer) were measured from the spectrum obtained during the first experiment (control spectrum) described above.

[0194] The degree of unsaturation was analyzed using the method of Reference 3 below. Reference 1: Z. Zhou, R. Kuemmerle, JC Stevens, D. Redwine, Y. He, X. Qiu, R. Cong, J. Klosin, N. Montanez, G. Roof, Journal of Magnetic Resonance, 2009, 200, 328. Reference 2: Z. Zhou, R. Kummerle, X. Qiu, D. Redwine, R. Cong, A. Taha, D. Baugh, B. Winniford, Journal of Magnetic Resonance:187(2007)225. Reference 3: Z. Zhou, R. Cong, Y. He, M. Paradkar, M. Demirors, M. Cheatham, W. deGroot, Macromolecular Symposia, 2012, 312, 88.

[0195] The peak area for each type of unsaturation observed (i.e., vinyl, vinylidene, vinylene, and trisubstituted) was measured from the spectrum acquired during the second (presaturation) experiment. Both spectra were normalized to the solvent peak area. The moles of unsaturation for each were calculated by dividing the area under the unsaturated resonance by the number of protons contributing to that resonance. The moles of carbon in the polymer were calculated by dividing the area under the peak of the polymer chain (i.e., CH, CH, and CH in the polymer) by 2. The amount of total unsaturation (the sum of the above unsaturations) was then expressed as the relative ratio of moles of total unsaturation to moles of carbon in the polymer, expressed as unsaturations per 1000 carbons (per 1000C). Results are consistent within a 5% error.

[0196] Melt Index The melt index I2 (or MI) of an ethylene-based polymer or blend (as used herein) is measured according to ASTM D-1238, condition 190°C / 2.16 kg. The melt flow rate MFR of a propylene-based polymer is measured according to ASTM D-1238, condition 230°C / 2.16 kg.

[0197] Polymer Density ASTM D4703 is used to prepare polymer plaques for density analysis. ASTM D792, Method B is used to measure the density of each polymer.

[0198] Gel Permeation Chromatography - Ethylene-Based Polymers The chromatography system consisted of a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph equipped with an internal infrared detector (IR5). The autosampler oven compartment was set to 160°C, and the column compartment was set to 150°C. The columns were four Agilent "MixedA" 30 cm, 20 micron linear mixed-bed columns. The chromatography solvent was 1,2,4-trichlorobenzene containing 200 ppm butylated hydroxytoluene (BHT). The solvent source was nitrogen sparged. The injection volume was 200 microliters, and the flow rate was 1.0 milliliters / minute.

[0199] Calibration of the GPC column set was performed using 21 narrow molecular weight distribution polystyrene standards with molecular weights ranging from 580 to 8,400,000 g / mol, arranged in six "cocktail" mixtures with at least 10 degrees of separation between individual molecular weights. The standards were purchased from Agilent Technologies. The polystyrene standards were prepared in 0.025 grams in 50 milliliters of solvent for molecular weights of 1,000,000 or greater, and in 0.05 grams in 50 milliliters for molecular weights less than 1,000,000. The polystyrene standards were dissolved at 80°C with gentle agitation for 30 minutes. The peak molecular weights of the polystyrene standards were converted to polyethylene molecular weights using Equation 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)): M ポリエチレン =A×(M ポリスチレン ) B (Equation 1), where M is the molecular weight, A has a value of 0.4315, and B is equal to 1.0.

[0200] A fifth-order polynomial is used to fit each polyethylene-equivalent calibration point. A small adjustment (approximately 0.375 to 0.445) is made to A to correct for column resolution and band broadening effects, such that a linear homopolymer polyethylene standard is obtained at 120,000 MW. A total plate count of the GPC column set is performed using decane (prepared at 0.04 g in 50 milliliters of TCB and dissolved with gentle stirring for 20 minutes). The plate count (Equation 2) and symmetry (Equation 3) are calculated using the following equations for a 200 microliter injection: Plate count 5.54 × [(RV ピーク最大値 ) / (peak width at half height)] 2 (Equation 2) where RV is the retention volume in milliliters, Peak Width is in milliliters, Peak Max is the maximum height of the peak, and ½ Height is half the height of the Peak Max, and

[0201]

number

[0202] Samples are prepared semi-automatically using PolymerChar "Instrument Control" software to target sample weight at 2 mg / ml and add solvent (containing 200 ppm BHT) via the PolymerChar high-temperature autosampler to a septa-capped vial pre-sparged with nitrogen. Samples are dissolved at 160°C for 2 hours under "slow" shaking.

[0203] Mn(GPC) , Mw (GPC) , and Mz (GPC) is calculated based on GPC results using PolymerChar GPCOne™ software, a baseline-subtracted IR chromatograph at each equally spaced data collection point (i), and the polyethylene equivalent molecular weight obtained from a narrow standard calibration curve at point (i) from Equation 1, using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph according to Equations 4-6. Equations 4-6 are as follows:

[0204]

number

[0205] To monitor deviations over time, a flow rate marker (decane) is introduced into each sample via a micropump controlled by the PolymerChar GPC-IR system. This flow rate marker (FM) is used to linearly correct the pump flow rate (Flow Rate (Apparent)) for each sample by aligning the RV of the respective decane peak in the sample (RV(FM Sample)) with the RV of the decane peak in the narrow standard calibration (RV(FM Calibrated)). Any change in the time of the decane marker peak is then assumed to be related to a linear shift in flow rate (Flow Rate (Effective)) throughout the run. To facilitate the highest accuracy in the RV measurement of the flow rate marker peak, a least-squares fitting routine is used to fit the peaks in the flow rate marker concentration chromatogram to a quadratic equation. The first derivative of the quadratic equation is then used to solve for the true peak position. After calibrating the system based on the flow rate marker peak, the effective flow rate (relative to the narrow standard calibration) is calculated as in Equation 7: Flow rate (effective) = Flow rate (apparent) * (RV(FM calibrated) / RV(FM sample)) (Equation 7). Processing of flow marker peaks is performed via PolymerChar GPCOne™ software. An acceptable flow correction is one where the effective flow rate is within + / - 0.7% of the apparent flow rate.

[0206] experiment Commercially Available Polymers and Additives The commercial and experimental polymers and additives are listed in Table 1 below.

[0207] [Table 2]

[0208] Commercial and experimental polymers 1 The 1 H NMR and GPC characterization results are listed below in Tables 2A and 2B, respectively.

[0209] [Table 3] Note that % of a particular unsaturation (pu%) = [(pu / 1000C) / (total unsaturation / 1000C)] x 100, where pu% = vinyl%, vinylidene%, vinylene%, or trisubstituted%. * EO = Ethylene / octene copolymer.

[0210] [Table 4]

[0211] Polymer Synthesis, EO Mono 3 and EO Mono 5 catalyst CAT2 can be prepared according to the teachings of WO 2011 / 102989(A1) and has the following structure:

[0212] [ka]

[0213] Polymerization of EO Mono 3 and EO Mono 5 EO Mono 3 (A 1 L 1 ) and EO Mono 5 (A 1 L 1 Continuous solution polymerizations of 1, 2, and 3 were carried out in computer-controlled autoclave reactors equipped with internal stirrers. Purified mixed alkane solvent (ISOPAR E, available from ExxonMobil), monomer, and molecular weight regulator (hydrogen or chain transfer agent) were fed into a 3.8 L reactor jacketed for temperature control. Solvent feed to the reactor was measured by a mass flow controller. A variable-speed diaphragm pump controlled the solvent flow rate and pressure to the reactor. At the pump outlet, a side stream was taken to provide a steep flow to the procatalyst, activator, and chain transfer agent (CTA) (catalyst component solution) injection lines. These flows were measured by mass flow meters and controlled by control valves. The remaining solvent was mixed with the monomer and hydrogen and fed to the reactor. The temperature of the solvent / monomer solution was controlled using a heat exchanger before entering the reactor. This stream entered the bottom of the reactor. The catalyst component solutions were metered using pumps and mass flow meters and combined with the catalyst flush solvent into the bottom of the reactor. The reactor was filled with liquid at 500 psig under vigorous stirring. Polymer was removed through an outlet line at the top of the reactor. All outlet lines from the reactor were vapor traced and insulated. The product stream was then heated to 230°C by passing it through a post-reactor heater (PRH), where beta-H removal of the polymer-Al was performed. A small amount of isopropyl alcohol, along with any stabilizers or other additives, was added after the PRH and before devolatilization. The polymer product was recovered by extrusion using a devolatilizing extruder. The polymerization process conditions and results before the post-reactor heating (PRH) are listed in Tables 3A and 3B.

[0214] The abbreviations in the table are explained as follows: "Co." stands for comonomer, and "sccm" stands for standard cm 3 / min(standard cm3 / min), "T" refers to temperature, "Cat" refers to Procatalyst, "CAT2" refers to Procatalyst as shown above, "CoCAT-1" refers to Cocatalyst as defined in Table 3B (footnote), "CTA" refers to chain transfer agent, "Poly Rate" refers to polymer production rate, "Conv" refers to percent ethylene conversion in the reactor, "Eff." refers to efficiency (kg polymer / mg catalyst metal), "TEA" refers to triethylaluminum, and "C2" refers to ethylene.

[0215] [Table 5] * "ppm" amounts based on the weight of each feed solution.

[0216] [Table 6] The CTA for EO Mono 3 and EO Mono 5 was TEA. ** CoCAT-1 is a methyldi(C) of tetrakis(pentafluorophenyl)borate prepared by the reaction of a long-chain trialkylamine (ARMEEN M2HT, available from Akzo-Nobel, Inc.), HCl, and Li[B(CF)] substantially as disclosed in U.S. Pat. No. 5,919,983, Example 2 (no further purification was performed). 14~18 It is a mixture of alkyl)ammonium salts (Boulder Scientific). *** "ppm" amounts based on the weight of each feed solution.

[0217] Preparation of the composition and its evaluation Brabender mixing and compression molding, and heat treatment in a convection oven The compositions are shown in Tables 4A and 4B below. For each listed composition, the base polymer (pellets) was first immersed in a solution of peroxide LUPEROX 101 and auxiliary agent TAIC in a fluorinated bottle (manufactured by Shanghai Heqi Glassware Co., Ltd.), the bottle was placed on a roller (Model NO: 88881004, DESC: Thermo Scientific bottle / tube roller) equilibrated at 40°C, and the bottle and contents were rotated (360° along the horizontal axis of the bottle, 70 rpm) for 24 hours to form immersed polymer pellets.

[0218] The soaked pellets (whole mixture, unfiltered, 37 grams) were added to a Brabender mixer (50 mL cavity mixing chamber) set at a temperature of 105°C with a rotor speed of 40 rpm. The soaked pellets were mixed and heated uniformly for approximately 2 minutes to form a polymer melt. The Tempo compound was then weighed and gradually added to the mixing chamber. Mixing was then continued for an additional 6 minutes, with the melt temperature being approximately 110°C. The final gum (pre-crosslinked, gel content <5% by weight) was formed. A sample of the final gum was analyzed by MDR, and the results are shown in Tables 4A and 4B below.

[0219] The gum from the Brabender mix was compression molded into plaques in a 1.0 mm thick mold. The gum (14 grams) was preheated at 110°C for 3 minutes, then degassed (compressed and released at 5 MPa six times), and subsequently pressed at 10 MPa and 110°C for an additional 2 minutes. After the mold temperature was reduced to room temperature, a plaque (15 cm x 7 cm x 1 mm, pre-crosslinked) was removed from the mold. The resulting plaque (pre-crosslinked, gel content ≦5 wt%) was further cut into the shape and size required for oven curing (1 / 3 the mass of the plaque used for heat treatment in a hot air convection oven).

[0220] A hot air convection oven was preheated and equilibrated to 200°C under ambient atmosphere. As discussed above, the compression molded composition was transferred to the oven and maintained at 200°C for 10 minutes using hot air convection for crosslinking. The crosslinked composition was then removed and cooled to room temperature. The crosslinked composition was analyzed by the fingertip test and FTIR-ATR, respectively, as discussed above, to evaluate surface tack and surface degradation. The results are shown in Tables 4A and 4B below. The FTIR-ATR profile is shown in Figure 1.

[0221] result The results of MDR, FTIR-ATR, and fingertip testing are shown in Tables 4A and 4B. As can be seen from Table 4B, the compositions of the present invention (IE1 and IE2) have sufficient crosslinking ("MH-ML" values ​​of 5.06 and 4.20), low degradation (D values ​​of 0.010 and 0, RD values ​​of 2% and 0), and a tack-free crosslinked surface (a rating of 3 for each). These compositions cure well in air and, due to their low filler loading, are lighter in weight and less conductive than highly filled EPDM vulcanizates.

[0222] Comparative composition CS3, with a "molar ratio of nitrogen oxide NO· to ​​peroxide bonds" of 0.19, produced a sticky crosslinked surface (a rating of 2) and higher D (0.102) and RD (24%) values ​​compared to the compositions of the present invention. CS1 and CS4 in Table 4B were control compositions without Tempo compound. As shown in Table 4B, they each had a high D rating and a very sticky surface (a rating of 1 for each). With the addition of Tempo compound, the degree of surface degradation decreased compared to the respective control compositions, as evidenced by the decreased D values ​​and higher fingertip test ratings for some of the compositions. It should also be noted that for comparative compositions CS5-CS9, higher levels of peroxide and coagent (TAIC) were required for sufficient crosslinking. However, the same or higher amounts of Tempo compound in these compositions did not result in a sticky surface. For the comparative composition CS9, much more Tempo compound (1.6 phr) was used, but the surface was still tacky, despite the relatively low degradation (D) based on H1714 of 0.020. As can be seen in Figure 1, -1 Another peak at 1737 cm was observed for CS9. This peak may be due to other polar functional groups generated on the surface, possibly due to migration issues. -1 These polar functional groups in may also increase surface tack.

[0223] As can be seen from Table 4A, a high ratio of nitrogen oxide NO· to ​​peroxide bonds (CS10) resulted in very low MH and "MH-ML" values ​​(i.e., insufficient cure). High Tempo compound dosages (CS11) and low Tempo compound dosages (CS12) also resulted in low MH and "MH-ML" values. Each of these three examples exhibited a slightly tacky surface. CS10 and CS11 each exhibited a peak at 1737 cm in the FTIR-ATR spectrum. -1 This also contributes to the surface tackiness to some extent.

[0224] [Table 7]

[0225] [Table 8] * moles of NO· from Tempo compound = {[weight of bis-Tempo compound / (MW=510.7)] * 2. * moles of peroxide bound from LUPEROX 101 = {[weight of LUPEROX 101 / (MW=290.4)]} * 2}. ** For CS9, another peak at 1737 cm-1 (other polar functional groups) appeared in the FTIR-ATR spectrum, which also contributed to the surface stickiness, and the degradation degree D1 and relative degradation degree RD1 based on H1737 were calculated: D1 = 0.092 and RD1 = 18%. The density equation for a blend (e.g., an 85 / 15 blend) is: a and w b are the weight fractions of each of the blend components, and p a and p b Note that σ is the density of each of the blend components.

[0226]

number

Claims

1. The following components a) to c): a) at least one ethylene / alpha-olefin interpolymer comprising the following properties: i) a density of 0.855 to 0.900 g / cc and ii) a total unsaturation level of ≥ 0.20 / 1000 C; b) at least one Tempo compound of structure I) below; c) at least one peroxide; the molar ratio of NO. from said at least one Tempo compound (component b) to peroxide (O—O) bonds from said at least one peroxide (component c) is 0.30 to 0.90; component b is present in an amount of 0.20 to 0.90 phr based on 100 parts of component a; Structure I is selected from Structure IA, Structure IB, or Structure IC, each of which is as follows: Structure IA is 【Chemical 1】 and wherein n is an integer ≧1; R1, R2, R3, and R4 are each independently selected from H or C1-C18 alkyl; X is CH ２ , ether (—O—), thioether (—S ｍ -, m≧1), carbonyl (-C(O)-), ester (-O-C(O)- or -C(O)-O-), amine (-N(R)-), amide (-N(R)-C(O)- or -C(O)-N(R)-), urethane (-O-C(O)-NH or -NH-C(O)-O-), carbamide (-NH-C(O)-NH-), or imide (-C(O)-N(R)-C(O)-); R' is selected from C1 to C30 alkylene; R" may be present or absent, and when present, R" is selected from C1 to C30 alkylene; Y is CR ４－ｎ (n=1-4), OR ２－ｎ (n=1-2), NR ３－ｎ (n=1-3), SR ２－ｎ (n=1-2), PR ３－ｎ (n=1-3), PR ５－ｎ (n=1-5), SiR ４－ｎ (n=1-4), selected from a difunctional C-C core, a phenyl core, an ester-substituted phenyl core, an amide-substituted phenyl core, a tris-isocyanurate core, or a melamine core; The difunctional C-C core is selected from the following structures, where each R′ represents the divalent R′ group in structure IA above: 【Chemistry 2】 The phenyl core is selected from the following structures, where each R′ represents the divalent R′ group in structure IA above: 【Chemistry 3】 The ester-substituted phenyl core is selected from the following structures, where each R′ represents the divalent R′ group in structure IA above: 【Chemistry 4】 The amido-substituted phenyl core is selected from the following structures, where each R′ represents the divalent R′ group in structure IA above: 【Chemistry 5】 The tris-isocyanurate core is as follows, where each R′ represents the divalent R′ group in structure IA above: 【Chemistry 6】 The melamine core is as follows, where each R′ represents the divalent R′ group in Structure IA above: 【Chemistry 7】 Each R group in Structure IA is independently selected from H, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heterohydrocarbyl, or substituted heterohydrocarbyl; Structure IB comprises the following substructure IB): 【Chemistry 8】 wherein n is an integer ≧1; R1, R2, R3, and R4 are each independently selected from H or C1-C18 alkyl; X is CH ２ , ether (—O—), thioether (—S ｍ -, m≧1), carbonyl (-C(O)-), ester (-O-C(O)- or -C(O)-O-), amine (-N(R)-), amide (-N(R)-C(O)- or -C(O)-N(R)-), urethane (-O-C(O)-NH or -NH-C(O)-O-), carbamide (-NH-C(O)-NH-), or imide (-C(O)-N(R)-C(O)-); R' is selected from C1 to C30 alkylene; R" may be present or absent, and when present, R" is selected from C1 to C30 alkylene; each R group in substructure IB is independently selected from H, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heterohydrocarbyl, or substituted heterohydrocarbyl; Each in substructure IB ＊ (asterisk) represents each chemical terminus of structure IB; The structure IC includes the following sub-structure ICs: 【Chemistry 9】 wherein n is an integer ≧1; R1, R2, R3, and R4 are each independently selected from H or C1-C18; X is CH ２ , ether (—O—), thioether (—S ｍ -, m≧1), carbonyl (-C(O)-), ester (-O-C(O)- or -C(O)-O-), amine (-N(R)-), amide (-N(R)-C(O)- or -C(O)-N(R)-), urethane (-O-C(O)-NH or -NH-C(O)-O-), carbamide (-NH-C(O)-NH-), or imide (-C(O)-N(R)-C(O)-); R' is selected from C1 to C30 alkylene; R" may be present or absent, and when present, R" is selected from C1 to C30 alkylene; each R''' group in substructure IC is independently selected from unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heterohydrocarbyl, or substituted heterohydrocarbyl; each R group in substructure IC is independently selected from H, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heterohydrocarbyl, or substituted heterohydrocarbyl; Each in the sub-structure IC ＊ (asterisk) represents each chemical terminus of structure IC, and when n≧3, each terminus may or may not form a cyclic structure with the other terminus.

2. The ethylene / alpha-olefin interpolymer has the formula A １ L １ 10. The composition of claim 1, wherein the unsaturated ethylene / alpha-olefin interpolymer is

3. The composition of claim 1 or 2, wherein the ethylene / alpha-olefin interpolymer is an ethylene / alpha-olefin copolymer.

4. 4. The composition of any one of claims 1 to 3, wherein component a further comprises a second ethylene / alpha-olefin interpolymer having a density of 0.855 to 0.900 g / cc and a total unsaturation of ≥ 0.20 / 1000 C, the second interpolymer being different from the first ethylene / alpha-olefin interpolymer.

5. The second ethylene / alpha-olefin interpolymer has the formula A １ L １ 5. The composition of claim 4, which is an unsaturated ethylene / alpha-olefin interpolymer of the formula:

6. The composition of claim 4 or 5, wherein the second ethylene / alpha-olefin interpolymer is an ethylene / alpha-olefin copolymer.

7. The composition of any one of claims 4 to 6, wherein the ratio of the density of the ethylene / alpha-olefin to the density of the second ethylene / alpha-olefin is from 0.80 to 1.

25.

8. The composition of any one of claims 4 to 7, wherein the weight ratio of the ethylene / alpha-olefin to the second ethylene / alpha-olefin is from 0.50 to 20.

9. The composition of any one of claims 1 to 8, wherein the composition comprises ≦10.0 wt.% of a filler, based on the weight of the composition.

10. The composition of any one of claims 1 to 9, wherein the composition comprises 90.0% to 100.0% by weight of the total of components a, b, and c, based on the weight of the composition.

11. A crosslinked composition formed from the composition of any one of claims 1 to 10.

12. An article comprising at least one component formed from the composition of any one of claims 1-11.

13. A process for forming a crosslinked composition comprising heat treating the composition of any one of claims 1 to 10.

14. 14. The process of claim 13, wherein the heat treatment is carried out in air.

15. 15. The process according to claim 13 or 14, wherein the heat treatment is carried out at a temperature of ≥ 150°C.

16. A process for forming a crosslinked composition, comprising at least the following steps A and B: A) The following components a) to c): a) at least one ethylene / alpha-olefin interpolymer comprising the following properties: i) a density of 0.855 to 0.900 g / cc and ii) a total unsaturation level of ≥ 0.20 / 1000 C; b) at least one Tempo compound of Structure I, wherein Structure I is selected from Structure IA, Structure IB, or Structure IC, each of which is described herein; and c) extruding a composition comprising at least one peroxide to form a pre-crosslinked composition; B) heat treating the pre-crosslinked composition in air at a temperature of ≥ 150°C to form the crosslinked composition; The process includes:

17. 17. The process of claim 16, wherein for step A, the composition is extruded at an average barrel temperature of from 60°C to 150°C.

18. 18. The process according to claim 16 or 17, wherein for step B, the pre-crosslinked composition is heat treated at a temperature of from 150°C to 240°C.

19. 19. The process of any one of claims 16 to 18, wherein the molar ratio of NO. from component b to peroxide (O-O) bonds from component c is from 0.30 to 0.

90.

20. 20. The process of any one of claims 16 to 19, wherein for the composition, component b is present in an amount of 0.20 to 0.90 phr, based on 100 parts of component a.

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