Air curable ethylene / alpha-olefin interpolymer composition

Abstract

A composition comprising the following components a) to c): a) at least one ethylene / alpha-olefin interpolymer comprising the following properties: i) a density from 0.855 g / cc to 0.900 g / cc and ii) a total unsaturation > = 0.20 / 1000 C, b) at least one Tempo compound of structure I); and c) at least one peroxide; and wherein the molar ratio of NO. From component b to peroxide (O-O) bonds from component c is from 0.30 to 0.90; and wherein component b is present in an amount of from 0.20 phr 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. In addition, methods of forming cross-linked compositions from the above compositions and related compositions.

Description

Background Art

[0001] Vulcanized EPDM is an existing material for weather strip profiles. Vulcanized EPDM is highly filled with carbon black and oil and is cured by a complex sulfur curative system. Today, the automotive industry requires lightweight materials (especially for electric vehicles), materials with lower electrical conductivity, and materials with lower VOC / odor. Typical vulcanized EPDM does not meet all of these needs.

[0002] For various applications, such as footwear and PV films, peroxide cure of olefin-based elastomer (polyolefin elastomer (POE)) compositions is typically accomplished in the absence of oxygen. When POE is cured via peroxide in the presence of oxygen, carbon radicals react with oxygen, and these products degrade into polar functional groups, such as carboxylic acids, carbonyls, and esters. These polar species form a sticky surface, which is unacceptable, especially when the cured surface is the outermost layer of the final product. In order to reduce surface tack, the peroxide cure method requires more expensive and complex equipment (e.g., salt baths) to remove oxygen from the crosslinking environment. New compositions that can be air-cured and provide a non-sticky surface are needed. In addition, such compositions should meet most or all requirements for lightweight materials for automotive applications.

[0003] US Patent Publication No. 2020 / 0263018 discloses a composition comprising: A) an ethylene / α-olefin / diene interpolymer; B) a peroxide comprising at least one peroxide bond; and C) a bis-TEMPO compound having structure I as described therein. The ratio of the molar amount of nitrooxy groups of component C to the molar amount of peroxide bonds of component B is from 0.100:1.000 to 2.000:1.000. See Abstract.

[0004] International publication WO2020 / 140067 discloses a curable composition comprising the following: A) a polyolefin component and B) a curing component comprising a crosslinking agent. The polyolefin component comprises a 1 L 1 unsaturated polyolefin, and wherein L 1 is a polyolefin, and A 1 Selected from vinyl, formula CH2=C(Y 1 )-vinylene, formula Y 1 CH=CH-vinylene, vinyl and formula Y 1 A mixture of CH=CH-vinylene, vinyl and CH2=C(Y 1 )-vinylene mixture, formula CH2=C(Y 1 )-vinylene and formula Y 1 A mixture of vinylene with CH=CH-, and vinyl, CH2=C(Y 1)-vinylene and formula Y 1 A mixture of vinylene groups in which CH=CH-; and Y 1 is independently a C1 to C30 hydrocarbyl group at each occurrence. See claim 1. The curing component may also contain a scorch inhibitor / retardant 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 US 6277925B1. See paragraph

[0247] . See also WO2020 / 140061, WO2020 / 135681, WO2020 / 135708, WO2020 / 135680, WO2020 / 139993 and WO2020 / 140058.

[0005] U.S. Patent 8,581,094 discloses an electronic device module comprising: A) at least one electronic device, and B) a polymer material in intimate contact with at least one surface of the electronic device. The polymer material comprises the following components (1) and optionally (2) and (3): (1) a polyolefin copolymer having at least one of the following: (a) a density of less than about 0.90 g / cc, (b) a 2% tangent modulus of less than about 150 megapascals (mPa), (c) a melting point of less than about 95°C, (d) an α-olefin content of at least about 15 wt% and less than about 50 wt% based on the weight of the polymer, (e) a Tg of less than about -35°C, and (f) a SCBDI of at least about 50, (2) an optional free radical initiator (e.g., a peroxide or a nitrogen-containing compound) or a photoinitiator (e.g., benzophenone), and (3) an optional coagent. See Abstract. Typically, the polyolefin copolymer is an ethylene / α-olefin copolymer. Optionally, the polymeric material may also include a vinyl silane and / or a scorch inhibitor, and the copolymer may be uncrosslinked or crosslinked. See Abstract. Scorch inhibitors include 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl, also known as nitroxyl 2, or NR 1, or 4-oxypiperidinol, 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, Vol. 90, No. 1: 60-88, 2017 discloses the characterization of organic peroxides as curing agents and their decomposition mechanisms. The reference also discloses the classification and characterization of auxiliary agents used in peroxide crosslinking and the interaction and reaction mechanism between peroxides, auxiliary agents and rubber matrix in relation to the properties of the prepared materials. See Abstract. The reference discloses scorch retarders such as 2,6-di-tert-butyl-4-methylphenol (BHT); 2,4-diphenyl-4-methyl-1-pentene (methylstyrene dimer, MSD); 1,1-diphenylethylene (DPE); (2,2,6,6-tetramethyl-piperidin-1-yl)oxy (TEMPO); bis-(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (bis-TEMPO); or acrylate functionalized TEMPO; 4-acryloyloxy-2,2,6,6-tetramethyl-piperidin-N-oxy (AOTEMPO). See page 83.

[0007] However, as mentioned above, there is still a need for a new composition that is air curable and provides a tack-free surface. In addition, such compositions should meet all or most of the requirements for lightweight materials for automotive applications. These needs have been met by the following invention. Summary of the invention

[0008] In a first aspect, a composition comprising the following components a) to c):

[0009] a) at least one ethylene / α-olefin interpolymer, said interpolymer comprising the following properties: i) a density from 0.855 g / cc to 0.900 g / cc and ii) a total unsaturation of ≥ 0.20 / 1000C,

[0010] b) at least one Tempo compound of structure I); and

[0011] c) at least one peroxide;

[0012] and wherein the molar ratio of NO· from the at least one Tempo compound (component b) to the peroxy (OO) bonds from the at least one peroxide (component c) is from 0.30 to 0.90;

[0013] and wherein component b is present in an amount of 0.20 phr to 0.90 phr based on 100 parts of component a; and

[0014] wherein Structure I is selected from Structure IA, Structure IB or Structure IC, each as described herein.

[0015] In a second aspect, a method of forming a crosslinked composition comprises heat treating a composition comprising the following components a) to c):

[0016] a) at least one ethylene / α-olefin interpolymer, said interpolymer comprising the following properties: i) a density from 0.855 g / cc to 0.900 g / cc and ii) a total unsaturation of ≥ 0.20 / 1000C,

[0017] b) at least one Tempo compound of structure I); and

[0018] c) at least one peroxide;

[0019] and wherein the molar ratio of NO· from the at least one Tempo compound (component b) to the peroxy (OO) bonds from the at least one peroxide (component c) is from 0.30 to 0.90;

[0020] and wherein component b is present in an amount of 0.20 phr to 0.90 phr based on 100 parts of component a; and

[0021] wherein Structure I is selected from Structure IA, Structure IB or Structure IC, each as described herein.

[0022] In a third aspect, a method of forming a cross-linked composition, the method comprising at least the following steps A and B:

[0023] A) extruding a composition comprising the following components a) to c) to form a pre-crosslinked composition:

[0024] a) at least one ethylene / α-olefin interpolymer, said interpolymer comprising the following properties: i)

[0025] Density 0.855 g / cc to 0.900 g / cc and ii) total unsaturation ≥ 0.20 / 1000C,

[0026] b) at least one Tempo compound of structure I); and

[0027] c) at least one peroxide;

[0028] B) heat treating the pre-crosslinked composition in air at a temperature of ≥ 150° C. to form a crosslinked composition; and

[0029] wherein Structure I is selected from Structure IA, Structure IB or Structure IC, each as described herein. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 FTIR-ATR curves of the surfaces of the inventive and comparative compositions after air curing are depicted. The curves from top to bottom are as follows: CS1, CS3, CS7, CS9 and IE1. DETAILED DESCRIPTION

[0031] Compositions have been found that contain high levels of polymer and extrude well and cure efficiently in air. It has been found that these compositions can be air cured without producing a tacky surface.

[0032] As described above, in the first aspect, a composition is provided, the composition comprising components a) to c as discussed herein. In the second aspect, a method for forming a crosslinked composition, the method comprising heat treating a composition comprising the following components a) to c) as discussed herein. In the third aspect, a method for forming a crosslinked composition is provided, the method comprising at least the following steps A and B as discussed herein. Each composition may comprise a combination of two or more embodiments as described herein. Each method 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 indicated, the following embodiments apply to the first aspect, the second aspect and the third aspect.

[0033] Note that as used herein, with respect to Structure IA, Structure IB or Structure IC (see component b), R1 = R 1 , R2=R 2 , R3=R 3 etc. In addition, with respect to the number of carbon atoms in a chemical substituent of Structure IA, Structure IB, or Structure IC, notation such as "C1-C18" (where "1 to 18" represents a consecutive number from 1 to 18) refers to "1 to 18 carbon atoms" that may be present in the substituent. An "alkyl" group can be straight chain, branched, cyclic, or any combination thereof. An alkylene group can be straight chain, branched, cyclic, or any combination thereof.

[0034] In one embodiment or a combination of two or more embodiments each as described herein, the ethylene / α-olefin interpolymer is selected from the group consisting of Formula A as described herein 1 L 1 L 2 A 2 A telechelic ethylene / α-olefin interpolymer of formula A as described herein 1 L 1 unsaturated ethylene / α-olefin interpolymers and further selected from the group consisting of formula A as described herein 1 L 1 Unsaturated ethylene / α-olefin interpolymer.

[0035] In one embodiment or a combination of two or more embodiments individually described herein, the ethylene / α-olefin interpolymer is an ethylene / α-olefin copolymer.

[0036] In one embodiment or a combination of two or more embodiments each described herein, component a further comprises a second ethylene / α-olefin interpolymer having a density from 0.855 g / cc to 0.900 g / cc and a total unsaturation ≥ 0.20 / 1000C, and the second interpolymer is different from the ethylene / α-olefin interpolymer.

[0037] In one embodiment or a combination of two or more embodiments each as described herein, the second ethylene / α-olefin interpolymer is selected from Formula A as described herein 1 L 1 L 2 A 2 A telechelic ethylene / α-olefin interpolymer of formula A as described herein 1 L 1 unsaturated ethylene / α-olefin interpolymers and further selected from the group consisting of formula A as described herein 1 L 1 Unsaturated ethylene / α-olefin interpolymers.

[0038] In one embodiment or a combination of two or more embodiments individually described herein, the second ethylene / α-olefin interpolymer is an ethylene / α-olefin copolymer.

[0039] In one embodiment or a combination of two or more embodiments each described herein, the ratio of the density of the ethylene / α-olefin to the density of the second ethylene / α-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.

[0040] In one embodiment or a combination of two or more embodiments each described herein, the weight ratio of ethylene / α-olefin to the second ethylene / α-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.

[0041] In one embodiment or a combination of two or more embodiments described herein, 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 filler (e.g., carbon black) by weight of the composition; and further the composition does not comprise filler. Fillers include, but are not limited to, carbon black, talc, glass fiber, carbon fiber, calcium carbon, magnesium hydroxide, ATH (aluminum trihydrate), TiO2, or any combination thereof.

[0042] In one embodiment or a combination of two or more embodiments each as 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.

[0043] In one embodiment or a combination of two or more embodiments each as 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 as described herein, with respect to the second aspect, the heat treatment is carried out at ≥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 The reaction is carried out 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.

[0044] In one embodiment or a combination of two or more embodiments each as described herein, with respect to the second or third aspect, at ≥60°C, or ≥65°C, or ≥70°C, or ≥75°C, or ≥80°C, or ≥85°C, or ≥90°C, or ≥95°C, or ≥100°C, or ≥105°C, or ≥110°C and / or The composition is extruded at an average barrel temperature of ≤150°C, or ≤145°C, or ≤135°C, or ≤130°C, or ≤125°C, or ≤120°C, or ≤115°C.

[0045] In one embodiment or a combination of two or more embodiments each as described herein, with respect to the third aspect, for step B, 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 The pre-crosslinked composition is heat treated 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.

[0046] In one embodiment or a combination of two or more embodiments each as described herein, for the composition, the molar ratio of NO· from component b to peroxy (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.

[0047] In one embodiment or a combination of two or more embodiments each as described herein, for the composition, based on 100 parts of component a, component b is ≥0.20 phr, or ≥0.22 phr, or ≥0.25 phr, or ≥0.28 phr, or ≥0.30 phr, or ≥0.32 phr, or ≥0.35 phr, or ≥0.38 phr, or ≥0.40 phr, or ≥0.42 phr, or ≥0.45 phr. and / or The amount of ≤0.90 phr, or ≤0.88 phr, or ≤0.85 phr, or ≤0.82 phr, or ≤0.80 phr, or ≤0.78 phr, or ≤0.75 phr is present.

[0048] A cross-linked composition is also provided, which is formed from the composition of one or more embodiments as described herein or formed from the method of one or more embodiments as described herein. An article is also provided, which comprises at least one component formed from the composition of one or more embodiments as described herein.

[0049] Ethylene / α-olefin interpolymer (component a)

[0050] Ethylene / α-olefin interpolymers include ethylene and α-olefins in polymerized form. α-olefins include, but are not limited to, C3-C20 α-olefins, further C3-C10 α-olefins, further C3-C8 α-olefins, such as propylene, 1-butene, 1-hexene and 1-octene. The distribution of monomer units, especially α-olefins, can be random, block, uniform, non-uniform, etc. Preferably, the interpolymer is a random interpolymer (i.e., comprising a random distribution of its monomer components).

[0051] In one embodiment, the ethylene / α-olefin interpolymer is of Formula A 1 L 1 L 2 A 2 A telechelic ethylene / α-olefin interpolymer of formula A 1 L 1 Unsaturated ethylene / α-olefin interpolymers.

[0052] Telechelic ethylene / α-olefin interpolymers (e.g. A 1 L 1 L 2 A 2 (those of Formula I)) and unsaturated ethylene / α-olefin interpolymers (e.g. A 1 L 1 (those of Formula II)) are each described below. See also, for example, WO 2020 / 140058 and WO 2020 / 140067, each of which is incorporated herein by reference.

[0053] Formula I:A 1 L 1 L 2 A 2 A telechelic ethylene / α-olefin interpolymer of claim 1, wherein:

[0054] L 1 is an ethylene / α-olefin interpolymer, and further an ethylene / α-olefin copolymer; it should be noted that L 1 (Bivalent) and A 1 and L 2 Bonding.

[0055] A 1 Selected from the group consisting of:

[0056] a) vinyl, b) formula CH2=C(Y 1 )-vinylene, c) formula Y 1 CH=CH-vinylene, d) vinyl and formula Y 1 A mixture of vinylene with CH=CH-, e) vinyl and CH2=C(Y 1 )-vinylene mixture, f) formula CH2=C(Y 1)-vinylene and formula Y 1 CH=CH-, and g) vinyl, CH2=C(Y 1 )-vinylene and formula Y 1 A mixture of vinylene groups in which CH=CH-.

[0057] Y 1 C1 to C independently at each occurrence 30 Hydrocarbyl groups;

[0058] L 2 It is C1 to C 32 an alkylene group; and

[0059] A 2 is a hydrocarbyl group containing a hindered double bond.

[0060] Formula II:A 1 L 1 An unsaturated ethylene / α-olefin interpolymer of

[0061] L 1 is an ethylene / α-olefin interpolymer, and further an ethylene / α-olefin copolymer; it should be noted that L 1 (Unitary) Bonded to A 1 ;

[0062] A 1 Selected from the group consisting of: a) a vinyl group, b) a group of formula CH2=C(Y 1 )-vinylene group, c) formula Y 1 CH=CH-vinylene group, d) vinyl group and formula Y 1 mixture of vinylene groups of the formula CH=CH-, e) vinyl groups and CH2=C(Y 1 )-vinylene groups, f) formula CH2=C(Y 1 )-vinylene group and formula Y 1 CH=CH-, and g) vinyl groups, CH2=C(Y 1 )-vinylene group, and formula Y 1 CH=CH-; and Y1 is independently C1 to C 30 Hydrocarbyl group.

[0063] For Formula I and Formula II, L 1In each occurrence, it is independently an ethylene / α-olefin interpolymer as described above, and may be produced in part by polymerization (e.g., coordination polymerization) of unsaturated monomers (and comonomers). Examples of suitable monomers (and comonomers) include, but are not limited to, ethylene and α-olefins of 3 to 30 carbon atoms, further 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 or non-conjugated dienes, for example 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-ethyl-8-methyl- l,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 norbornene, alkylidene norbornene, cycloalkenyl norbornene and cycloalkylidene norbornene, such as 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, dicyclopentadiene, 5-methylene The monomers include ethylene and α-olefins of 3 to 30 carbon atoms, further 3 to 20 carbon atoms.

[0064] Tempo compound (component b)

[0065] Tempo compounds have Structure IA, Structure IB, or Structure IC, each as described herein.Tempo compounds include, but are not limited to, bis-(2,2,6,6-tetramethyl-1-piperidinyloxy-4-yl) sebacate.

[0066] peroxide

[0067] As used herein, peroxides contain at least one oxygen-oxygen bond (OO). Peroxides include, but are not limited to, dialkyl, diaryl, dialkylaryl, or diaralkyl peroxides having the same or different corresponding alkyl, aryl, alkaryl, or aralkyl moieties, and further each dialkyl, diaryl, dialkylaryl, or diaralkyl peroxide having the same corresponding alkyl, aryl, alkaryl, or aralkyl moieties.

[0068] Examples of organic peroxides include dicumyl peroxide ("DCP"). tert-Butyl peroxybenzoate; di-tert-amyl peroxide ("DTAP"); bis(tert-butylperoxyisopropyl)benzene ("BIPB"); isopropyl cumyl tert-butyl peroxide; tert-butyl cumyl peroxide; di-tert-butyl peroxide; 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane ("LUPEROX 101"); 2,5-bis(tert-butylperoxy)-2,5-dimethylhexyne-3; 1,1-bis(tert-butylperoxy)3,3,5-trimethylcyclohexane; isopropyl cumyl cumyl peroxide; butyl 4,4-di(tert-butylperoxy)valerate; di(isopropylcumyl) peroxide; 1,1-di-(tert-butylperoxy)cyclohexane ("LUPEROX 331"); 1,1-di-(tert-amylperoxy)cyclohexane ("LUPEROX 531"); tert-butyl peroxyacetate ("TBPA"); tert-amyl peroxyacetate ("TAPA"); tert-butylperoxy-2-ethylhexyl carbonate ("TBEC"); and mixtures of two or more thereof.

[0069] Peroxide can be a cyclic peroxide. The example of cyclic peroxide comprises the cyclic peroxide 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 their combination or the like. Cyclic peroxide can be used alone or in combination with each other. Many cyclic peroxides can be commercially available for example under the trade name TRIGONOX such as 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxynonane.

[0070] additive

[0071] The composition of the present invention may contain one or more additives. The additives include, but are not limited to, crosslinking aids, foaming agents, antioxidants, UV stabilizers, colorants, and processing aids (eg, zinc stearate).

[0072] Crosslinking aids include, but are not limited to, triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), triallyl trimellitate (TATM), trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), 1,6-hexanediol diacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, trivinylcyclohexane (TVCH), or a combination thereof. Additional adjuvants include alkenyl functional monocyclic organosiloxanes, such as those disclosed in WO 2019 / 000311 and WO 2019 / 000654, which are incorporated herein by reference in their entirety (e.g., monocyclic organosiloxanes of the formula [R1, R2SiO2 / 2]n, wherein subscript n is an integer greater than or equal to 3; each R1 is independently (C2-C4)alkenyl or H2C=C(R1a)-C(=O)-O-(CH2)m-, wherein R1a is H or methyl, and subscript m is an integer from 1 to 4; and each R2 is independently H, (C1-C4)alkyl, phenyl, or R1; for example, 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 2,4,6-trimethyl-2,4,6-trivinyl-cyclotrisiloxane, or a combination thereof).

[0073] In one embodiment, the additive is ≥0.10 phr, or ≥0.20 phr, or ≥0.30 phr, or ≥0.35 phr based on 100 parts of component a. and / or The amount is present in an amount of ≤5.0 phr, or ≤4.0 phr, or ≤3.0 phr, or ≤2.0 phr, or ≤1.0 weight %, or ≤0.50 phr based on 100 parts of component a.

[0074] definition

[0075] Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percentages are based on weight and all test methods are current as of the filing date of this disclosure.

[0076] As used herein, the term "composition" includes mixtures of materials including the composition as well as reaction products and decomposition products formed from the composition materials. Any reaction products or decomposition products are typically present in trace or residual amounts.

[0077] The term "polymer" as used herein refers to a polymer compound prepared by polymerizing monomers of the same or different types. Thus, the generic term polymer includes the term homopolymer (used to refer to polymers prepared from only one type of monomer, it being understood that trace impurities may be incorporated into the polymer structure) and the term interpolymer as defined below. Trace impurities (such as catalyst residues) may be incorporated into and / or within the polymer. Typically, the polymer is stabilized with very low amounts ("ppm" amounts) of one or more stabilizers.

[0078] As used herein, the term "interpolymer" refers to polymers prepared by the polymerization of at least two different types of monomers. The term interpolymer thus includes the term copolymer (used to refer to polymers prepared from two different types of monomers) and polymers prepared from more than two different types of monomers.

[0079] As used herein, the term "olefin-based polymer" refers to polymers that contain, in polymerized form, 50 wt% or a majority weight percent of an olefin such as ethylene or propylene (based on the weight of the polymer), and optionally may contain one or more comonomers.

[0080] 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, optionally, may contain one or more comonomers.

[0081] As used herein, the term "ethylene-based polymer" refers to a polymer that, in polymerized form, contains 50 weight percent or majority weight percent ethylene (based on the weight of the polymer), and optionally may contain one or more comonomers.

[0082] As used herein, the term "ethylene / α-olefin interpolymer" refers to an interpolymer that, in polymerized form, comprises 50 weight percent or majority weight percent ethylene (based on the weight of the interpolymer) and an α-olefin.

[0083] As used herein, the term "ethylene / α-olefin copolymer" refers to a copolymer that contains, in polymerized form, 50 weight percent or majority weight percent ethylene (based on the weight of the copolymer) and α-olefin as the only two monomer types.

[0084]

[0043] The phrase "majority weight percent" as used herein with respect to a polymer (eg, an interpolymer or a copolymer) refers to the amount of monomer present in the largest amount in the polymer.

[0085] The term "heteroatom" refers to an atom other than hydrogen or carbon (eg, O, S, N, or P). The term "heteroatom group" refers to a heteroatom or a chemical group containing one or more heteroatoms.

[0086] As used herein, the terms "hydrocarbon," "hydrocarbyl," and similar terms refer to corresponding compounds or chemical groups, etc., containing only carbon atoms and hydrogen atoms. A divalent "hydrocarbylene group" is defined in a similar manner.

[0087] As used herein, the terms "heterohydrocarbon", "heteroalkyl" and similar terms refer to corresponding hydrocarbon or alkyl groups, etc., in which at least one carbon atom is replaced by a heteroatom group (e.g., O, S, N or P). A monovalent heteroalkyl group can be bonded to the rest of the compound of interest via a carbon atom or via a heteroatom. A divalent "heteroalkylene group" is defined in a similar manner; and a divalent heteroalkylene group can be bonded to the rest of the compound of interest via two carbon atoms or two heteroatoms or a carbon atom and a heteroatom.

[0088] As used herein, the terms "substituted hydrocarbon", "substituted hydrocarbyl group" and similar terms refer to corresponding hydrocarbon or hydrocarbyl groups, etc., in which one or more hydrogen atoms are independently replaced by heteroatom groups. "Substituted hydrocarbylene groups" are defined in a similar manner.

[0089] As used herein, the term "substituted heterohydrocarbon", "substituted heterohydrocarbonyl group" and similar terms refer to the corresponding heterohydrocarbon or heterohydrocarbonyl group, etc., in which one or more hydrogen atoms are independently replaced by a heteroatom group. "Substituted heterohydrocarbonylene group" is defined in a similar manner.

[0090] 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. Relative to a non-crosslinked composition, the degree of formation of the network structure is represented by the increase in the "MH-ML" difference discussed herein. Based on the weight of the crosslinked composition, the crosslinked composition generally has a gel content of ≥60 wt%, further ≥70 wt%, further ≥80 wt%, and further ≥90 wt%. The gel content can be determined by refluxing the crosslinked composition in xylene. For example, about 0.5 g of the crosslinked composition (Ws) is sealed in a metal mesh (mesh number is 120) to form a filled sample, and the filled sample is weighed (Wt1). The filled sample is then transferred to a flask (500 mL) equipped with a condenser and containing 350 mL of xylene. After refluxing for five hours, the filled sample is taken out of the xylene, placed in a vacuum oven and heated at 120 ° C for two hours under vacuum conditions. After this time, the filled sample is taken out from the oven and weighed (Wt2). Gel content = 1 - [(Wt1 - Wt2) / Ws] * 100%.

[0091] As used herein, the terms "heat-treated", "thermally treating", "thermal treatment" and similar phrases with respect to compositions comprising ethylene / α-olefin interpolymers as described herein refer to increasing the temperature of the composition by applying heat. As an example, heat can be applied by an electrical device (e.g., a heating coil) and / or by radiation and / or by hot oil and / or by mechanical shearing. Note that the temperature at which the heat treatment is performed refers to the temperature of the device "applying heat" or, if the device contains a closed atmosphere or semi-closed atmosphere, the temperature of the atmosphere within the device, such as the atmosphere within an oven or tunnel (e.g., the air temperature in a hot air oven or hot air tunnel).

[0092] 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.

[0093] As used herein, with respect to an extrusion process using one or more extruders, each of which comprises at least one barrel, the term "average barrel temperature" refers to the average temperature of the sum of the barrel temperatures if there are two or more barrels, or the temperature of only one barrel if there is only one barrel.

[0094] As used herein, the term "Garvey die" with respect to an extrusion process refers to a die of a specific geometry that complies with ASTM D2230-17 and that allows observation of the appearance and profile of the extrudate.

[0095] The terms "comprising," "including," "having," and derivatives thereof are not intended to exclude the presence of any additional components, steps, or procedures, whether or not the components, steps, or procedures are specifically disclosed. For the avoidance of any doubt, all compositions claimed through use of the term "comprising" may include any additional additives, adjuvants, or compounds, whether polymeric or otherwise, unless stated to the contrary. In contrast, the term "consisting essentially of excludes from the scope of any subsequently recited component, step, or procedure, except those that are not essential to operability. The term "consisting of excludes any component, step, or procedure not specifically recited or listed.

[0096] List of some compositions and methods

[0097] A] A composition comprising the following components a) to c):

[0098] a) at least one ethylene / α-olefin interpolymer, said interpolymer comprising the following properties: i)

[0099] Density 0.855 g / cc to 0.900 g / cc and ii) total unsaturation ≥ 0.20 / 1000C,

[0100] b) at least one Tempo compound of the following structure I); and

[0101] c) at least one peroxide;

[0102] and wherein the molar ratio of NO· from the at least one Tempo compound (component b) to the peroxy (OO) bonds from the at least one peroxide (component c) is from 0.30 to 0.90;

[0103] and wherein component b is present in an amount of 0.20 phr to 0.90 phr based on 100 parts of component a; and

[0104] Wherein Structure I is selected from Structure IA, Structure IB or Structure IC, each of which is as follows:

[0105] Structure IA is Where n is an integer ≥ 1;

[0106] R1, R2, R3 and R4 are each independently selected from H or C1-C18 alkyl;

[0107] X is selected from CH2, ether (-O-), thioether (-S m -, wherein 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)-), polyurethane (-OC(O)-NH- or -NH-C(O)-O-), carbodiamide (-NH-C(O)-NH-) or imide (-C(O)-N(R)-C(O)-);

[0108] R' is selected from C1-C30 alkylene;

[0109] R" may or may not be present, and if present, R" is selected from C1-C30 alkylene;

[0110] Y is selected from CR 4-n (where n = 1 to 4), OR 2-n (where n = 1 to 2), NR 3-n (where n = 1 to 3), SR 2-n (where n = 1 to 2), PR 3-n (where n = 1 to 3), PR 5-n (where n = 1 to 5), SiR 4-n(wherein n=1 to 4), a difunctional CC core, a phenyl core, an ester-substituted phenyl core, an amide-substituted phenyl core, a triisocyanurate core or a melamine core; and

[0111] The bifunctional CC core is selected from the following structures, wherein each R' represents a divalent R' group in the above structure IA:

[0112]

[0113] Wherein the phenyl core is selected from the following structures, wherein each R' represents a divalent R' group in the above structure IA:

[0114]

[0115] The phenyl core substituted with an ester is selected from the following structures, wherein each R' represents the divalent R' group in the above structure IA:

[0116]

[0117] The phenyl core substituted with amide is selected from the following structures, wherein each R' represents the divalent R' group in the above structure IA:

[0118]

[0119] The triisocyanurate core is as follows, wherein each R' represents the divalent R' group in the above structure IA;

[0120]

[0121] The melamine core is as follows, wherein each R' represents the divalent R' group in the above structure IA;

[0122] and

[0123] wherein each R group in structure IA is independently selected from H, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heterohydrocarbyl, or substituted heterohydrocarbyl;

[0124] The structure IB includes the following substructures IB):

[0125]

[0126] Where n is an integer ≥ 1;

[0127] R1, R2, R3 and R4 are each independently selected from H or C1-C18 alkyl;

[0128] X is selected from CH2, ether (-O-), thioether (-S m-, wherein 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)-), polyurethane (-OC(O)-NH- or -NH-C(O)-O-), carbodiamide (-NH-C(O)-NH-) or imide (-C(O)-N(R)-C(O)-);

[0129] R' is selected from C1-C30 alkylene;

[0130] R" may or may not be present, and if present, R" is selected from C1-C30 alkylene;

[0131] Each R group in substructure IB is independently selected from H, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heterohydrocarbyl, or substituted heterohydrocarbyl;

[0132] Each * (asterisk) in substructure IB indicates the corresponding chemical terminus of structure IB;

[0133] The structure IC includes the following sub-structure ICs):

[0134]

[0135] Where n is an integer ≥ 1;

[0136] R1, R2, R3 and R4 are each independently selected from H or C1-C18;

[0137] X is selected from CH2, ether (-O-), thioether (-S m -, wherein 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)-), polyurethane (-OC(O)-NH- or -NH-C(O)-O-), carbodiamide (-NH-C(O)-NH-) or imide (-C(O)-N(R)-C(O)-);

[0138] R' is selected from C1-C30 alkylene;

[0139] R" may or may not be present, and if present, R" is selected from C1-C30 alkylene;

[0140] Each R'' group in substructure IC is independently selected from unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heterohydrocarbyl, or substituted heterohydrocarbyl;

[0141] Each R group in substructure IC is independently selected from H, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heterohydrocarbyl, or substituted heterohydrocarbyl;

[0142] Each * (asterisk) in substructure IC represents the corresponding chemical terminus of structure IC; and if n≥3, each terminus may or may not form a ring structure with the other terminus.

[0143] B] A composition according to A] above, wherein the ethylene / α-olefin interpolymer has

[0144] ≥0.856g / cc, or ≥0.858g / cc, or ≥0.860g / cc, or ≥0.862g / cc, or

[0145] ≥0.864g / cc, or ≥0.866g / cc and / or ≤0.898g / cc, or ≤0.896g / cc, or

[0146] ≤0.894g / cc, or ≤0.892g / cc, or ≤0.890g / cc, or ≤0.888g / cc, or

[0147] ≤0.886g / cc, or ≤0.884g / cc, or ≤0.882g / cc, or ≤0.880g / cc, or

[0148] Density (1cc = 1cm) ≤ 0.878 g / cc, or ≤ 0.876 g / cc, or ≤ 0.874 g / cc, or ≤ 0.872 g / cc 3 ).

[0149] C] A composition according to A] or B] above, wherein the ethylene / α-olefin interpolymer has

[0150] ≥0.22 / 1000C, or ≥0.24 / 1000C, or ≥0.26 / 1000C, or ≥0.28 / 1000C,

[0151] 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 Total unsaturation ≤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.

[0152] D] A composition according to any one of A]-C] (A] to C] above, wherein the ethylene / α-olefin interpolymer has ≥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 Melt index (I2, dg / min) of ≤2000, or ≤1000, or ≤500, or ≤200, or ≤100, or ≤50, or ≤45, or ≤40, or ≤35, or ≤30, or ≤25, or ≤20.

[0153] E] A composition according to any one of A] to D] above, wherein the ethylene / α-olefin interpolymer is selected from the group consisting of formula A as described herein 1 L 1 L 2 A 2 A telechelic ethylene / α-olefin interpolymer of formula A as described herein 1 L 1 unsaturated ethylene / α-olefin interpolymers and further selected from the group consisting of formula A as described herein 1 L 1 Unsaturated ethylene / α-olefin interpolymers.

[0154] F] A composition according to any one of A] to E] above, wherein the ethylene / α-olefin interpolymer is an ethylene / α-olefin copolymer.

[0155] G] A composition according to any one of A] to F] above, wherein the α-olefin of the ethylene / α-olefin interpolymer is C3-C 20 α-olefins, further C3-C 10 α-olefin, and 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.

[0156] H] A composition according to any one of A] to G] above, wherein the ethylene / α-olefin interpolymer does not comprise ENB in ​​polymerized form, and further a diene monomer, and further a polyene monomer.

[0157] I] A composition according to A] to H] above, wherein component a further comprises a second ethylene / α-olefin interpolymer having a density of 0.855 g / cc to 0.900 g / cc and a total unsaturation of ≥ 0.20 / 1000C, and the second interpolymer is different from the ethylene / α-olefin interpolymer and further differs in one or more characteristics selected from density, total unsaturation, melt index (I2), or any combination thereof.

[0158] J] A composition according to I] above, wherein the second ethylene / α-olefin interpolymer has a molecular weight of ≥0.856 g / cc, or ≥0.858 g / cc, or ≥0.860 g / cc, or ≥0.862 g / cc, or ≥0.864 g / cc, or ≥0.866 g / cc. and / or Density of ≤ 0.898 g / cc, or ≤ 0.896 g / cc, or ≤ 0.894 g / cc, or ≤ 0.892 g / cc, or ≤ 0.890 g / cc, or ≤ 0.888 g / cc, or ≤ 0.886 g / cc, or ≤ 0.884 g / cc, or ≤ 0.882 g / cc, or ≤ 0.880 g / cc, or ≤ 0.878 g / cc, or ≤ 0.876 g / cc, or ≤ 0.874 g / cc, or ≤ 0.872 g / cc, or ≤ 0.870 g / cc.

[0159] K] A composition according to I] or J] above, wherein the second ethylene / α-olefin interpolymer has ≥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 Total unsaturation ≤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.

[0160] L] A composition according to any one of I] to K] above, wherein the second ethylene / α-olefin interpolymer has a molecular weight of ≥0.1, or ≥0.2, or ≥0.4, or ≥0.6, or ≥0.8, or ≥1.0 and / or Melt index (I2, g / 10 min or dg / min) of ≤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.

[0161] M] A composition according to any one of I] to L] above, wherein the second ethylene / α-olefin interpolymer is selected from the group consisting of formula A as described herein 1 L1 L 2 A 2 A telechelic ethylene / α-olefin interpolymer of formula A as described herein 1 L 1 unsaturated ethylene / α-olefin interpolymers and further selected from the group consisting of formula A as described herein 1 L 1 Unsaturated ethylene / α-olefin interpolymers.

[0162] N] A composition according to any one of I] to M] above, wherein the second ethylene / α-olefin interpolymer is an ethylene / α-olefin copolymer.

[0163] O] A composition according to any one of I] to N] above, wherein the α-olefin of the second ethylene / α-olefin interpolymer is C3-C 20 α-olefins, further C3-C 10 α-olefin, and 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.

[0164] P] A composition according to any one of I] to O] above, wherein the second ethylene / α-olefin interpolymer does not comprise ENB in ​​polymerized form, and further a diene monomer, and a polyene monomer.

[0165] Q] A composition according to any one of I] to P] above, wherein the ethylene / α-olefin interpolymer and the second ethylene / α-olefin interpolymer are each independently selected from Formula A as described herein. 1 L 1 L 2 A 2 A telechelic ethylene / α-olefin interpolymer of formula A as described herein 1 L 1 unsaturated ethylene / α-olefin interpolymers and further selected from the group consisting of formula A as described herein 1 L 1 Unsaturated ethylene / α-olefin interpolymers.

[0166] R] A composition according to any one of I] to Q] above, wherein the ratio of the density of the ethylene / α-olefin to the density of the second ethylene / α-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.

[0167] S] A composition according to any one of I] to R] above, wherein the ratio of the total unsaturation of the ethylene / α-olefin to the total unsaturation of the second ethylene / α-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.

[0168] T] A composition according to any one of I] to S] above, wherein the ratio of the melt index (I2) of the ethylene / α-olefin to the melt index (I2) of the second ethylene / α-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.

[0169] U] A composition according to any one of I] to T] above, wherein the weight ratio of the ethylene / α-olefin to the second ethylene / α-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.

[0170] V] A composition according to any one of I] to U] above, 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% based on the weight of component a. and / or ≤ 100.0 wt%, or ≤ 99.9 wt%, or ≤ 99.8 wt% of the sum of the ethylene / α-olefin and the second ethylene / α-olefin.

[0171] W] A composition according to any one of A] to H] above, wherein based on the weight of component a, 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 ethylene / α-olefin.

[0172] A2] A method for forming a cross-linked composition, the method comprising at least the following steps A and B:

[0173] A) extruding a composition comprising the following components a) to c) to form a pre-crosslinked composition:

[0174] a) at least one ethylene / α-olefin interpolymer, said interpolymer comprising the following properties: i) a density from 0.855 g / cc to 0.900 g / cc and ii) a total unsaturation of ≥ 0.20 / 1000C,

[0175] b) at least one Tempo compound of structure I); and

[0176] c) at least one peroxide;

[0177] B) thermally treating the pre-crosslinked composition in air at a temperature ≥ 150°C to form a crosslinked composition; and wherein Structure I is selected from Structure IA, Structure IB or Structure IC, each as described herein (see A] above).

[0178] B2] The method according to A2] above, wherein for step A, at ≥60°C, or ≥65°C, or ≥70°C, or ≥75°C, or ≥80°C, or ≥85°C, or ≥90°C, or ≥95°C, or ≥100°C, or ≥105°C, or ≥110°C and / or The composition is extruded at an average barrel temperature of ≤150°C, or ≤145°C, or ≤140°C, or ≤135°C, or ≤130°C, or ≤125°C, or ≤120°C, or ≤115°C.

[0179] C2] The method according to A2] or B2] above, wherein for step B, at ≥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 The pre-crosslinked composition is heat treated 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.

[0180] D2] The method according to any one of A2] to C2] above, wherein for step B, the pre-crosslinked composition is heat treated in a continuous hot oven or a hot air tunnel.

[0181] E2] The method according to any one of A2] to D2] above, wherein for step A, the composition is extruded in a series of extruder configurations comprising a Garvey die at the end of the last extruder in the extruder configuration.

[0182] F2] The method according to any one of A2] to E2] above, wherein, for the composition, the molar ratio of NO from component b to peroxy (OO) bonds from component c is 0.30 to 0.90.

[0183] G2] The method according to any one of A2] to F2] above, wherein, for the composition, component b is present in an amount of 0.20 phr to 0.90 phr based on 100 parts of component a.

[0184] H2] A method for forming a crosslinked composition, the method comprising heat treating a composition comprising the following components a) to c):

[0185] a) at least one ethylene / α-olefin interpolymer, said interpolymer comprising the following properties: i) a density from 0.855 g / cc to 0.900 g / cc and ii) a total unsaturation of ≥ 0.20 / 1000C,

[0186] b) at least one Tempo compound of structure I); and

[0187] c) at least one peroxide;

[0188] and wherein the molar ratio of NO· from the at least one Tempo compound (component b) to the peroxy (OO) bonds from the at least one peroxide (component c) is from 0.30 to 0.90;

[0189] and wherein component b is present in an amount of 0.20 phr 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 (see A] above).

[0190] I2] The method according to H2] above, wherein the heat treatment is carried out in air.

[0191] J2] The method according to H2] or I2] above, wherein the temperature is ≥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 The composition is heat treated 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.

[0192] K2] A method according to any one of the above H2] to J2], wherein the composition is extruded before heat treatment.

[0193] L2] The method according to K2] above, wherein the composition is extruded at an average barrel temperature of ≥60°C, or ≥65°C, or ≥70°C, or ≥75°C, or ≥80°C, or ≥85°C, or ≥90°C, or ≥95°C, or ≥100°C, or ≥105°C, or ≥110°C≤150°C, or ≤145°C, or ≤140°C, or ≤135°C, or ≤130°C, or ≤125°C, or ≤120°C, or ≤115°C.

[0194] M2] The method according to any one of A2] to L2] above, wherein the ethylene / α-olefin interpolymer has ≥0.856 g / cc, or ≥0.858 g / cc, or ≥0.860 g / cc, or ≥0.862 g / cc, or ≥0.864 g / cc, or ≥0.866 g / cc and / or Density of ≤ 0.898 g / cc, or ≤ 0.896 g / cc, or ≤ 0.894 g / cc, or ≤ 0.892 g / cc, or ≤ 0.890 g / cc, or ≤ 0.888 g / cc, or ≤ 0.886 g / cc, or ≤ 0.884 g / cc, or ≤ 0.882 g / cc, or ≤ 0.880 g / cc, or ≤ 0.878 g / cc, or ≤ 0.876 g / cc, or ≤ 0.874 g / cc, or ≤ 0.872 g / cc.

[0195] N2] The method according to any one of A2] to M2] above, wherein the ethylene / α-olefin interpolymer has ≥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 Total unsaturation ≤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.

[0196] O2] The method according to any one of A2] to N2] above, wherein the ethylene / α-olefin interpolymer has ≥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 Melt index (I2, g / 10 min or dg / min) of ≤2000, or ≤1000, or ≤500, or ≤200, or ≤100, or ≤50, or ≤45, or ≤40, or ≤35, or ≤30, or ≤25, or ≤20.

[0197] P2] A process according to any one of A2] to O2] above, wherein the ethylene / α-olefin interpolymer is selected from the group consisting of formula A as described herein 1 L 1 L 2 A 2 A telechelic ethylene / α-olefin interpolymer of formula A as described herein 1 L 1 unsaturated ethylene / α-olefin interpolymers and further selected from the group consisting of formula A as described herein 1 L 1 Unsaturated ethylene / α-olefin interpolymers.

[0198] Q2] The method according to any one of A2] to P2] above, wherein the ethylene / α-olefin interpolymer is an ethylene / α-olefin copolymer.

[0199] R2] The method according to any one of A2] to Q2] above, wherein the α-olefin of the ethylene / α-olefin interpolymer is C3-C 20 α-olefins, further C3-C 10 α-olefin, and 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.

[0200] S2] The process according to any one of A2] to R2] above, wherein the α-olefin of the ethylene / α-olefin interpolymer does not comprise ENB in ​​polymerized form, and further a diene monomer, and further a polyene monomer.

[0201] T2] The method according to any one of A2] to S2] above, wherein component a further comprises a second ethylene / α-olefin interpolymer having a density of 0.855 g / cc to 0.900 g / cc and a total unsaturation of ≥0.20 / 1000C, and the second interpolymer is different from the ethylene / α-olefin interpolymer and further differs in one or more characteristics selected from density, total unsaturation, melt index (I2) or any combination thereof.

[0202] U2] The method according to T2] above, wherein the second ethylene / α-olefin interpolymer has ≥0.856 g / cc, or ≥0.858 g / cc, or ≥0.860 g / cc, or ≥0.862 g / cc, or ≥0.864 g / cc, or ≥0.866 g / cc and / or Density of ≤0.898 g / cc, or ≤0.896 g / cc, or ≤0.894 g / cc, or ≤0.892 g / cc, or ≤0.890 g / cc, or ≤0.888 g / cc, or ≤0.886 g / cc, or ≤0.884 g / cc, or ≤0.882 g / cc, or ≤0.880 g / cc, or ≤0.878 g / cc, or ≤0.876 g / cc, or ≤0.874 g / cc, or ≤0.872 g / cc, or ≤0.871 g / cc.

[0203] V2] According to the method of T2] or U2] above, wherein the second ethylene / α-olefin interpolymer has ≥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 Total unsaturation ≤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.

[0204] W2] The method according to any one of T2] to V2] above, wherein the second ethylene / α-olefin interpolymer has a molecular weight of ≥0.1, or ≥0.2, or ≥0.4, or ≥0.6, or ≥0.8, or ≥1.0 and / or Melt index (I2, g / 10 min or dg / min) of ≤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.

[0205] X2] The method according to any one of the above T2] to W2], wherein the second ethylene / α-olefin interpolymer is selected from the formula A as described herein1 L 1 L 2 A 2 A telechelic ethylene / α-olefin interpolymer of formula A as described herein 1 L 1 unsaturated ethylene / α-olefin interpolymers and further selected from the group consisting of formula A as described herein 1 L 1 Unsaturated ethylene / α-olefin interpolymer.

[0206] Y2] The method according to any one of T2] to X2] above, wherein the second ethylene / α-olefin interpolymer is an ethylene / α-olefin copolymer.

[0207] Z2] The method according to any one of the above T2]-Y2], wherein the α-olefin of the second ethylene / α-olefin interpolymer is C3-C 20 α-olefins, further C3-C 10 α-olefin, and 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.

[0208] A3] The method according to any one of T2] to Z2] above, wherein the second ethylene / α-olefin interpolymer does not contain ENB in ​​polymerized form, and further a diene monomer, and further a polyene monomer.

[0209] B3] The method according to any one of the above T2]-A3], wherein the ethylene / α-olefin interpolymer and the second ethylene / α-olefin interpolymer are each independently selected from formula A as described herein 1 L 1 L 2 A 2 A telechelic ethylene / α-olefin interpolymer of formula A as described herein 1 L 1 unsaturated ethylene / α-olefin interpolymers and further selected from the group consisting of formula A as described herein 1 L 1 Unsaturated ethylene / α-olefin interpolymer.

[0210] C3] The method according to any one of T2] to B3] above, wherein the ratio of the density of the ethylene / α-olefin to the density of the second ethylene / α-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.

[0211] D3] The method according to any one of T2] to C3] above, wherein the ratio of the total unsaturation of the ethylene / α-olefin to the total unsaturation of the second ethylene / α-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.

[0212] E3] The method according to any one of T2] to D3] above, wherein the ratio of the melt index (I2) of the ethylene / α-olefin to the melt index (I2) of the second ethylene / α-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.

[0213] F3] The method according to any one of T2] to E3] above, wherein the weight ratio of the ethylene / α-olefin to the second ethylene / α-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.

[0214] G3] The method according to any one of T2] to F3] above, wherein based on the weight of component a, 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 / α-olefin and the second ethylene / α-olefin.

[0215] H3] The method according to any one of A2] to S2] above, wherein based on the weight of component a, 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 ethylene / α-olefin.

[0216] A4] A composition according to any one of A] to W] above or a method according to any one of A2] to H3] above, wherein the ethylene / α-olefin of component a has ≥5,000 g / mol, or ≥6,000 g / mol, or ≥8,000 g / mol, or ≥10,000 g / mol, or ≥12,000 g / mol, or ≥14,000 g / mol, or ≥16,000 g / mol, or ≥18,000 g / mol, or ≥20,000 g / mol and / or A number average molecular weight Mn of ≤120,000 g / mol, or ≤100,000 g / mol, or ≤80,000 g / mol, or ≤70,000 g / mol, or ≤65,000 g / mol, or ≤60,000 g / mol, or ≤58,000 g / mol, or ≤56,000 g / mol, or ≤54,000 g / mol.

[0217] B4] A composition according to any one of A]-W] or A4] above or a method according to any one of A2]-H3] or A4] above, wherein the ethylene / α-olefin of component a has ≥20,000 g / mol, or ≥25,000 g / mol, or ≥30,000 g / mol, or ≥35,000 g / mol, or ≥40,000 g / mol, or ≥45,000 g / mol and / or A weight average molecular weight Mw of ≤150,000 g / mol, or ≤145,000 g / mol, or ≤140,000 g / mol, or ≤135,000 g / mol, or ≤130,000 g / mol, or ≤125,000 g / mol, or ≤120,000 g / mol, or ≤115,000 g / mol.

[0218] C4] A composition according to any one of A]-W], A4] or B4] above or a method according to any one of A2]-H3], A4] or B4] above, wherein the ethylene / α-olefin of component a has a ratio of ≥1.80, or ≥1.85, or ≥1.90, or ≥1.95, or ≥2.00, or ≥2.05, or ≥2.10 and / or Molecular weight distribution MWD (=Mw / Mn) of ≤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.

[0219] D4] A composition according to any one of I]-W] or A4]-C4] above or a method according to any one of T2]-H3] or A4]-C4] above, wherein the ratio of the Mn of the ethylene / α-olefin to the Mn of the second ethylene / α-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.

[0220] E4] A composition according to any one of I]-W] or A4]-D4] above or a method according to any one of T2]-H3] or A4]-D4] above, wherein the ratio of the Mw of the ethylene / α-olefin to the Mw of the second ethylene / α-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.

[0221] F4] A composition according to any one of I]-W] or A4]-E4] above or a method according to any one of T2]-H3] or A4]-E4] above, wherein the ratio of the MWD of the ethylene / α-olefin to the MWD of the second ethylene / α-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.

[0222] G4] A composition according to any one of A]-W] or A4]-F4] above or a method according to any one of A2]-H3] or A4]-F4] above, wherein, for structure I of component b, each of R1, R2, R3 and R4 is the same.

[0223] H4] A composition according to any one of A]-W] or A4]-F4] above or a method according to any one of A2]-H3] or A4]-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.

[0224] I4] A composition according to any one of A]-W] or A4]-F4] above or a method according to any one of A2]-H3] or A4]-F4] above, wherein, for structure I of component b, 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.

[0225] J4] A composition according to any one of A]-W] or A4]-F4] above or a method according to any one of A2]-H3] or A4]-F4] above, wherein, for structure I of component b, each of R1, R2, R3 and R4 is independently selected from C1-C6 alkyl, further C1-C5 alkyl, further C1-C4 alkyl, further C1-C3 alkyl, further C1-C2 alkyl, further methyl.

[0226] K4] A composition according to any one of A]-W] or A4]-J4] above or a method according to any one of A2]-H3] or A4]-J4] above, wherein, for structure I of component b, X is selected from CH2, ether (-O-), carbonyl (-C(O)-), ester (-OC(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 (-OC(O)- or -C(O)-O-), and further ester (-OC(O)- or -C(O)-O-).

[0227] L4] A composition according to any one of A]-W] or A4]-K4] above or a method according to any one of A2]-H3] or A4]-K4] above, wherein, for structure I of component b, R' is selected from C1-C6 alkylene, further C1-C5 alkylene, further C1-C4 alkylene, further C1-C3 alkylene, further C1-C2 alkylene.

[0228] M4] A composition according to any one of A]-W] or A4]-L4] above or a method according to any one of A2]-H3] or A4]-L4] above, wherein, for structure I of component b, R" is selected from C1-C6 alkylene, further C1-C5 alkylene, further C1-C4 alkylene, further C1-C3 alkylene, further C1-C2 alkylene, and further methylene.

[0229] N4] A composition according to any one of A]-W] or A4]-L4] above, or a method according to any one of A2]-H3] or A4]-L4] above, wherein, for structure I of component b, R" is absent.

[0230] O4] A composition according to any one of A]-W] or A4]-N4] above or a method according to any one of A2]-H3] or A4]-N4] above, wherein, for structure I of component b, n≥2.

[0231] P4] A composition according to any one of A]-W] or A4]-O4] above, or a method according to any one of A2]-H3] or A4]-O4] above, wherein structure I (component b) is selected from structure IA.

[0232] Q4] A composition according to any one of P4] above or a method according to any one of P2] above, wherein, for structure IA, n is 2 to 4, further 2 or 3, further 2.

[0233] R4] A composition according to O4] or P4] above or a method according to O4] or P4] above, wherein, for structure IA, Y is selected from CR 4-n (where n = 1 to 4), OR 2-n (where n = 1 to 2), NR 3-n (wherein n=1 to 3), a bifunctional CC 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 selected from CR 4-n (where n = 1 to 4), OR 2-n (where n = 1 to 2), NR 3-n (wherein n=1 to 3), a bifunctional CC core as described herein, or a phenyl core as described herein, and further selected from CR 4-n (where n = 1 to 4), OR 2-n (wherein n=1 to 2) or a bifunctional CC core as described herein, and further selected from CR 4-n (wherein n=1 to 4) or a bifunctional CC core as described herein, and further selected from a bifunctional CC core as described herein.

[0234] S4] A composition according to R4] above or a method according to R4] above, wherein the bifunctional CC core is selected from wherein each R′ represents a divalent R′ group in structure IA above; and further each R of the CC core is H.

[0235] T4] A composition according to any one of P4]-S4] above or a method according to any one of P4]-S4] above, wherein, for structure IA, each R is independently selected from H, unsubstituted hydrocarbon group or substituted hydrocarbon group, and further H or unsubstituted hydrocarbon group, and further H or alkyl group, and further H or C1-C5 alkyl group.

[0236] U4] A composition according to any one of P4] to T4] above or a method according to any one of P4] to T4] above, wherein structure IA is the following structure IA1:

[0237]

[0238] V4] A composition according to any one of A]-W] or A4]-O4] above or a method according to any one of A2]-H3] or A4]-O4] above, wherein structure I (component b) is selected from structure IB including substructure IB.

[0239] W4] A composition according to V4] above or a method according to V4] above, wherein for substructure IB, n≥10, or n≥20, or n≥50, or n≥100.

[0240] X4] A composition according to V4] or W4] above or a method according to V4] or W4] above, wherein, for substructure IB, each R group is independently selected from H, unsubstituted hydrocarbon group or substituted hydrocarbon group, and further H or unsubstituted hydrocarbon group, and further H or alkyl group, and further H or C1-C5 alkyl group.

[0241] Y4] A composition according to any one of A]-W] or A4]-O4] above, or a method according to any one of A2]-H3] or A4]-O4] above, wherein structure I (component b) is selected from structure IC including substructure IC.

[0242] Z4] A composition according to Y4] above or a method according to Y4] above, wherein for substructure IC, n≥10, or n≥20, or n≥50, or n≥100.

[0243] A5] A composition according to Y4] or Z4] above or a method according to Y4] or Z4] above, wherein, for substructure IC, each R group is independently selected from H, unsubstituted hydrocarbon or substituted hydrocarbon, and further H or unsubstituted hydrocarbon, and further H or alkyl, and further H or C1-C5 alkyl.

[0244] B5] A composition according to any one of Y4]-A5] above or a method according to any one of Y4]-A5] above, wherein, for substructure IC, each R"' group is independently selected from unsubstituted hydrocarbon groups or substituted hydrocarbon groups, and further unsubstituted hydrocarbon groups, and further alkyl groups, and further C1-C5 alkyl groups.

[0245] C5] A composition according to any one of Y4] to B5] above or a method according to any one of Y4] to B5] above, wherein for substructure IC, n≥3 and each end * (asterisk) forms a ring structure with the other end.

[0246] D5] A composition according to any one of A]-W] or A4]-C5] above, or a method according to any one of A2]-H3] or A4]-C5] above, wherein the molar ratio of NO from at least one Tempo compound (component b) to peroxy (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.

[0247] E5] A composition according to any one of A]-W] or A4]-D5] above, or a method according to any one of A2]-H3] or A4]-D5] above, wherein based on 100 parts of component a, component b is ≥0.22 phr, or ≥0.25 phr, ≥0.28 phr, or ≥0.30 phr, or ≥0.32 phr, or ≥0.35 phr, ≥0.38 phr, or ≥0.40 phr, or ≥0.42 phr or ≥0.45 phr. and / or The amount of ≤0.88 phr, or ≤0.85 phr, or ≤0.82 phr, or ≤0.80 phr, or ≤0.78 phr, or ≤0.75 phr is present.

[0248] F5] A composition according to any one of A]-W] or A4]-E5] above, or a method according to any one of A2]-H3] or A4]-E5] above, wherein based on 100 parts of component a, component c is ≥0.40 phr, or ≥0.45 phr, ≥0.50 phr, or ≥0.55 phr, or ≥0.60 phr, or ≥0.62 phr, ≥0.65 phr, or ≥0.68 phr, or ≥0.70 phr, or ≥0.72 phr or ≥0.74 phr. and / or The amount of ≤0.88 phr, or ≤0.85 phr, or ≤0.82 phr, or ≤0.80 phr, or ≤0.78 phr is present.

[0249] G5] A composition according to any one of A]-W] or A4]-F5] above, or a method according to any one of A2]-H3] or A4]-F5] above, wherein based on the weight of the composition, 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.

[0250] H5] A composition according to any one of A]-W] or A4]-G5] above, or a method according to any one of A2]-H3] or A4]-G5] above, wherein the composition further comprises a crosslinking aid (component d).

[0251] I5] The composition according to H5] above or the method according to H5] above, wherein based on 100 parts of component a, component d is ≥0.05phr, or ≥0.10phr, or ≥0.15phr, or ≥0.20phr, or ≥0.22phr, or ≥0.25phr, or ≥0.28phr, or ≥0.30phr, or ≥0.32phr, or ≥0.35phr. and / or The invention also provides an amount of ≤0.75 phr, or ≤0.70 phr, or ≤0.65 phr, or ≤0.60 phr, or ≤0.55 phr, or ≤0.50 phr, or ≤0.48 phr, or ≤0.45 phr, or ≤0.42 phr, or ≤0.40 phr.

[0252] J5] A composition according to any one of A]-W] or A4]-I5] above, or a method according to any one of A2]-H3] or A4]-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.

[0253] K5] A composition according to any one of H5]-J5] above or a method according to any one of H5]-J5] above, wherein the weight ratio of component c to component 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.

[0254] L5] A composition according to any one of A]-W] or A4]-K5] above or a method according to any one of A2]-H3] or A4]-K5] above, wherein based on the weight of the composition, the composition contains ≤10.0 wt%, or ≤5.0 wt%, or ≤2.0 wt%, or ≤1.0 wt%, or ≤0.5 wt%, or ≤0.1 wt% of filler; and further the composition does not contain filler.

[0255] M5] A composition according to any one of A]-W] or A4]-L5] above, or a method according to any one of A2]-H3] or A4]-L5] above, wherein based on the weight of the composition, 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.

[0256] N5] A composition according to any one of A]-W] or A4]-M5] above, or a method according to any one of A2]-H3] or A4]-M5] above, wherein the composition comprises a Tempo compound as component b.

[0257] O5] A composition according to any one of A]-W] or A4]-N5] above or a method according to any one of A2]-H3] or A4]-N5] above, wherein the composition comprises a peroxide as component c.

[0258] P5] A composition according to any one of A]-W] or A4]-O5] above or a method according to any one of A2]-H3] or A4]-O5] above, wherein the composition further comprises a polymer that is different from the ethylene / α-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 in comonomer type, comonomer content, density, melt index (I2), total unsaturation or any combination thereof.

[0259] Q5] A composition according to any one of A]-W] or A4]-P5] above, or a method according to any one of A2]-H3] or A4]-P5] above, wherein the composition has ≥4.0 dNm, or ≥4.1 dNm, or ≥4.2 dNm and / or MH value (MH-ML) of ≤10dNm, or ≤8.0dNm, or ≤6.0dNm. See the "Test Method" section.

[0260] R5] A composition according to any one of A]-W] or A4]-Q5] above or a method according to any one of A2]-H3] or A4]-Q5] above, wherein the ethylene / α-olefin interpolymer (further copolymer) of component a is a random interpolymer (further random copolymer).

[0261] S5] A composition according to any one of I]-W] or A4]-R5] above or a method according to any one of T2]-H3] or A4]-R5] above, wherein the second ethylene / α-olefin interpolymer (further copolymer) is a random interpolymer (further random copolymer).

[0262] T5] A cross-linked composition, which is formed from a composition according to any one of A]-W] or A4]-S5] above, and is further formed by heat treating these compositions; or the cross-linked composition is formed by a method according to any one of A2]-H3] or A4]-S5] above.

[0263] U5] A cross-linked composition according to T5] above, wherein the cross-linked composition has an H1714 value of ≤0.010, or ≤0.005, or ≤0.002, or ≤0.001, wherein the H1714 value is determined by the FTIR-ATR method described herein.

[0264] V5] A cross-linked composition according to T5] or U5] above, wherein the cross-linked composition has a D value of ≤0.025, or ≤0.020, or ≤0.015, or ≤0.010, wherein the D value is determined by the FTIR-ATR method described herein.

[0265] W5] The cross-linked composition according to any one of T5] to V5] above, wherein the cross-linked 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.

[0266] X5] A cross-linked composition according to any one of T5] to W5] above, wherein the cross-linked composition has a finger test rating of 3 as determined by the finger test described herein.

[0267] Y5] An article comprising at least one component formed from a composition according to any one of A]-W] or A4]-S5] above or formed by a method according to any one of A2]-H3] or A4]-S5] above.

[0268] Z5] An article comprising at least one component formed from the cross-linked composition according to any one of T5] to X5] above.

[0269] A6] The article according to Y5] or Z5] above, wherein the article is an automobile part or a building material, a footwear component or a PV film, and further is an automobile part.

[0270] B6] The product according to Y5] or Z5] above, wherein the product is a profile.

[0271] Test Method

[0272] Moving Die Rheometer (MDR) Analysis

[0273] According to ASTM D-5289, the MDR curing properties of each composition (glue-see experimental section) were measured using Alpha Technologies MDR 2000. About "4.5g" samples were placed in the MDR sample holder. The MDR test was performed at an oscillation frequency of 100CPM (1.67Hz) and an oscillation angle of 0.5 degrees (7% strain) at 180°C for a period of 15 minutes. During the test interval, the minimum torque (ML) and maximum torque (MH) applied by the MDR were reported in dNm. The difference between MH and ML indicates the degree of crosslinking, wherein the greater the difference reflects the greater the degree of crosslinking. The time taken for the torque to reach X% (e.g., 90%) of the MH value or the TX value (e.g., T90) is reported in minutes. From the start of the test, the time required for the torque value to increase by a "dNm" value higher than the ML value is expressed as "TS1" and recorded in minutes. The TS1 value indicates the time required to start the crosslinking process. The shorter the time, the faster the crosslinking is initiated. One sample is tested for each composition.

[0274] FTIR-ATR analysis (cross-linked composition)

[0275] The degradation of each hot air crosslinking composition was determined by FTIR-ATR analysis (Nicolet 5700 from Thermo Electron Corporation). The methylene (CH2) signal is approximately 1465 cm -1 , and is used as an industrial standard. The carbonyl (C=O) signal is approximately 1714 cm -1 , and used to monitor degradation. 1714cm -1 and 1465cm -1 The height ratio between the two is as follows: D = H1714 / H1465, where D is the degradation degree and H1714 is at 1714cm -1 IR peak height at 1845-1570cm -1 as the baseline), and H1465 is at 1465cm -1 IR peak height at 1540-1389 cm -1 As a baseline). The relative degradation was calculated according to the following formula: RD = (D / D0), where RD is the relative degradation, D is the degradation of the test sample, and D0 is the degradation of the control sample containing peroxide but not Tempo compound. For each analysis, a small sample of the hot air cured compression molded composition was used (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 (area of ​​about 2 mm in diameter). One sample was examined for each composition.

[0276] Finger test (surface stickiness)

[0277] The surface tack of the hot air crosslinked compositions was tested using the finger test. The finger test is a laboratory qualitative test method. The laboratory personnel touches the upper surface of the crosslinked sample with a finger and provides feedback on the surface tack of the sample using the following criteria shown in Table A below. One sample was tested for each composition.

[0278] Table A: Finger Test Levels

[0279] Viscosity Grade describe 3 Non-sticky surface 2 The surface is a little sticky 1 The surface is very sticky, like tape

[0280] 1 H NMR methods

[0281] 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) with 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 five minutes to prevent oxidation. The tube was capped and sealed with TEFLON tape, then heated and vortexed at 115°C to obtain a homogenous solution.

[0282] Data acquisition parameters and data analysis: performed on a Bruker AVANCE 600 MHz spectrometer equipped with a Bruker high temperature CryoProbe and a sample temperature of 120 °C. 1 H NMR. Two experiments were performed to obtain spectra, a control spectrum for quantification of total polymer protons, and a double presaturation experiment that suppressed strong peaks associated with the polymer backbone and achieved high sensitivity of the spectrum for quantification of end groups. The control was run with ZG pulse, 16 scans, AQ 1.82 s, D1 (relaxation delay) 14 s. The double presaturation experiment used a modified pulse sequence, lc1prf2.zz, 64 scans, AQ 1.82 s, D1 (presaturation time) 2 s, D 13 (relaxation delay) 12 s. Unsaturation measurements were performed according to the following method. The area under the resonance of the polymer chain (ie CH, CH2 and CH3 in the polymer) was measured from the spectrum obtained during the first experiment (control spectrum), as described above.

[0283] The degree of unsaturation was analyzed by the method of reference 3 mentioned below.

[0284] Reference 1: Z. Zhou, R. Kuemmerle, JC Stevens, D. Redwine, Y. He, X. Qiu, R. Cong, J. Klosin, N. G. Roof, Journal of Magnetic Resonance, 2009, 200, 328.

[0285] Reference 2: Z. Zhou, R. Kümmerle, 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.

[0286] The peak area of ​​each type of observed unsaturated group (i.e., vinyl, vinylidene, vinylene and trisubstituted) is measured from the spectrum obtained during the above-mentioned second (presaturation) experiment. Both spectra are normalized to the solvent peak area. The moles of each unsaturation are calculated by dividing the area under the unsaturated resonance by the number of protons that contribute to the resonance. The moles of carbon in the polymer are calculated by dividing the area under the polymer chain (i.e., CH, CH2 and CH3 in the polymer) peak by two. The amount of total unsaturation (the sum of the above unsaturations) is then expressed as the relative ratio of the moles of total unsaturation in the polymer to the moles of carbon, expressed as the number of unsaturations per 1000 carbons (per 1000C). The results are identical within relative <5%.

[0287] Melt Index

[0288] The melt index I2 (or MI) of ethylene-based polymers or blends (as used herein) is measured according to ASTM D-1238 at 190°C / 2.16 kg. The melt flow rate MFR of propylene-based polymers is measured according to ASTM D-1238 at 230°C / 2.16 kg.

[0289] Polymer density

[0290] ASTM D4703 was used to prepare polymer plaques for density analysis. ASTM D792, Method B was used to measure the density of each polymer.

[0291] Gel Permeation Chromatography - Ethylene-Based Polymers

[0292] The chromatographic system consists of a PolymerChar GPC-IR (Valencia, Spain) high temperature GPC chromatograph equipped with an internal infrared detector (IR5). The autosampler oven is set to 160°C and the column chamber is set to 150°C. The columns are four AGILENT "Mixed A" 30cm 20 micron linear mixed bed columns. The chromatographic solvent is 1,2,4-trichlorobenzene containing 200ppm of butylated hydroxytoluene (BHT). The solvent source is nitrogen bubbled. The injection volume is 200 microliters and the flow rate is 1.0 ml / min.

[0293] Calibration of the GPC column set was performed with 21 narrow molecular weight distribution polystyrene standards, ranging in molecular weight from 580 g / mol to 8,400,000 g / mol, and arranged in six "cocktail" mixtures with at least ten times intervals between individual molecular weights. These standards were purchased from Agilent Technologies. For molecular weights equal to or greater than 1,000,000, "0.025 grams" of polystyrene standards were prepared in 50 milliliters of solvent, and for molecular weights less than 1,000,000, "0.05 grams" of polystyrene standards were prepared in 50 milliliters of solvent. The polystyrene standards were dissolved at 80° C. for 30 minutes with gentle stirring. The polystyrene standard peak molecular weight was converted to polyethylene molecular weight using Equation 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)):

[0294] M 聚乙烯 =A×(M 聚苯乙烯 ) B (Equation 1), where M is the molecular weight, A has a value of 0.4315 and B equals 1.0.

[0295] A fifth order polynomial was used to fit the calibration points for the corresponding polyethylene equivalents. A small adjustment (approximately 0.375 to 0.445) was made to A to correct for column resolution and band broadening effects so that a linear homopolymer polyethylene standard was obtained at 120,000 Mw. Total plate counts for the GPC column set were performed with decane ("prepared as 0.04 g in 50 ml TCB" and dissolved for 20 minutes with slow stirring). Plate counts (Equation 2) and symmetry (Equation 3) were measured with a 200 microliter injection according to the following equations: Plate count = 5.54*[(RV 最大峰值 ) / (peak width at 1 / 2 height)] 2(Equation 2), where RV is the retention volume in milliliters, peak width is in milliliters, maximum peak is the maximum height of the peak, and 1 / 2 height is 1 / 2 the height of the maximum peak; and

[0296] Where RV is the retention volume in milliliters, and peak width is in milliliters, peak maximum is the maximum peak position, tenth height is 1 / 10 the height of the peak maximum, and where post-peak refers to the tail of the peak at a later retention volume than the peak maximum, and where pre-peak refers to the front of the peak at an earlier retention volume than the peak maximum. The plate count of the chromatographic system should be greater than 18,000, and the symmetry should be between 0.98 and 1.22.

[0297] The samples were prepared semi-automatically using the PolymerChar "Instrument Control" software, where the target weight of the sample was set to "2 mg / ml" and the solvent (containing 200 ppm BHT) was added to a septum-capped vial previously sparged with nitrogen via the PolymerChar high temperature autosampler. The samples were dissolved at 160°C for two hours under "slow" shaking.

[0298] Based on the GPC results, using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR spectrometer, according to Equation 4-Equation 6, the PolymerChar GPCOne TM The software was used to calculate the Mn value of the baseline-subtracted IR chromatogram at each equidistant data collection point (i) and the polyethylene equivalent molecular weight obtained from the narrow standard calibration curve at point (i) according to Equation 1. (GPC) 、Mw (GPC) and Mz (GPC) Calculation of. Equation 4-6 is as follows:

[0299] and

[0300]

[0301] To monitor the deviation over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by a PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly correct the pump flow rate (flow rate (nominal)) of each sample by comparing the RV of the corresponding decane peak in the sample (RV (FM sample)) with the RV of the alkane peak in the narrow standard calibration (RV (FM calibrated)). It was then assumed that any change in the decane marker peak time was related to a linear change in the flow rate (flow rate (effective)) throughout the run. In order to facilitate the highest accuracy of the RV measurement of the flow marker peak, a least squares fitting procedure was used to fit the peak of the flow marker concentration chromatogram to a quadratic equation. The first derivative of the quadratic equation was then used to solve for the true peak position. After calibrating the system based on the flow marker peak, the effective flow rate (relative to the narrow standard calibration) was calculated according to Formula 7: Flow rate (effective) = flow rate (nominal) * (RV (FM calibrated) / RV (FM sample)) (Formula 7). Processing of mobile marker peaks via PolymerChar GPCOne TM Software Complete. Acceptable flow rate correction is such that the effective flow rate is within + / - 0.7% of the nominal flow rate.

[0302] experiment

[0303] Commercially available polymers and additives

[0304] Commercially available and experimental polymers and additives are listed in Table 1 below.

[0305] Table 1: Commercial polymers, experimental polymers and additives

[0306]

[0307] Commercially available polymers and experimental polymers 1 The H NMR and GPC characterization results are listed below in Tables 2A and 2B, respectively.

[0308] Table 2A: 1 H NMR results

[0309]

[0310]

[0311] It should be noted that the % of specific unsaturation (pu%) = [(ambient specific unsaturation / 1000C) / (ambient total unsaturation / 1000C)] x 100; where pu% = vinyl %, vinylidene %, vinylene % or trisubstituted %.

[0312] *EO = ethylene / octene copolymer.

[0313] Table 2B: GPC results

[0314] Mn(g / mol) Mw(g / mol) MWD(Mw / Mn) ENGAGE 8407 23100 49338 2.14 ENGAGE 8100 47700 105400 2.21 EO Mono 3 21332 49277 2.31 EO Mono 5 53722 114965 2.14

[0315] Polymer Synthesis - EOMono3 and EOMono5

[0316] catalyst

[0317] CAT 2 can be prepared according to the teaching of WO 2011 / 102989 A1 and has the following structure:

[0318]

[0319] Polymerization of EOMono 3 and EO Mono 5

[0320] EO Mono 3(A 1 L 1 ) and EO Mono 5(A 1 L 1 ) are each carried out in a computer-controlled autoclave reactor equipped with an internal agitator. Purified mixed alkane solvent (ISOPAR E available from ExxonMobil), monomer and molecular weight regulator (hydrogen or chain transfer agent) are supplied to a "3.8L" reactor equipped with a jacket for temperature control. The solvent fed to the reactor is measured by a mass flow controller. A variable speed diaphragm pump controls the solvent flow rate and pressure to the reactor. At the discharge port of the pump, a side stream is used to provide a flushing flow for the main catalyst, activator and chain transfer agent (CTA) (catalyst component solution) injection pipeline. These flows are measured by a mass flow meter and controlled by a control valve. The remaining solvent is combined with monomer and hydrogen and fed into the reactor. The temperature of the solvent / monomer solution is controlled by using a heat exchanger before entering the reactor. This liquid flow enters the bottom of the reactor. The catalyst component solution is metered using a pump and a mass flow meter, and is combined with a catalyst flushing solvent and introduced into the bottom of the reactor. Under vigorous stirring, the reactor is filled with liquid at "500psig". The polymer is removed through the outlet pipeline at the top of the reactor. All outlet lines from the reactor were steam traced and insulated. The product stream was then heated at 230°C by passing through a post-reactor heater (PRH) where β-H elimination of polymer-based-Al occurred. After the PRH and before devolatilization, a small amount of isopropanol was added along with any stabilizers or other additives. The polymer product was recovered by extrusion using a devolatilization extruder. The polymerization process conditions and results before post-reactor heating (PRH) are listed in Tables 3A and 3B.

[0321] The abbreviations in the table are explained as follows: "Co." means comonomer; "sccm" means standard cubic centimeters per minute; "T" means temperature; "Cat" means the main catalyst; "CAT 2" means the main catalyst (CAT 2) as shown above; "CoCAT-1" means the cocatalyst defined in Table 3B (footnote); "CTA" means chain transfer agent; "Polymerization Rate" means the polymer production rate; "Conv" means the percent ethylene conversion in the reactor; "Eff." means efficiency, kg polymer / mg catalyst metal; "TEA" means triethylaluminum, and "C2" means ethylene.

[0322] Table 3A: Polymerization conditions

[0323]

[0324] * "ppm" amounts are based on the weight of the corresponding feed solution.

[0325] Table 3B: Polymerization conditions

[0326]

[0327] *The CTA of EO Mono 3 and EO Mono 5 is TEA.

[0328] **CoCAT-1 is the methyl di(C) 14-18 A mixture of trialkyl) ammonium salts prepared by reaction of a long chain trialkylamine (ARMEEN M2HT, available from Akzo Nobel), HCl and Li[B(C6F5)4], essentially as disclosed in Example 2 of USP 5,919,983 (without further purification) (Boulder Scientific).

[0329] ***"ppm" amounts are based on the weight of the corresponding feed solution.

[0330] Preparation of compositions and evaluation of compositions

[0331] Brabender mixing and compression molding as well as heat treatment in a convection oven

[0332] The compositions are shown in Table 4A and Table 4B below. For each composition listed, the base polymer (pellets) was first soaked in a fluorinated bottle (from Shanghai Heqi Glassware Co., Ltd.) with a solution of peroxide LUPEROX 101 and auxiliary agent TAIC, and the bottle was placed on a roller (Model: 88881004, DESC: bottle / tube roller from Thermo SCIENTIFIC) balanced at 40°C, and the bottle and contents were rotated (360 degrees along the horizontal axis of the bottle, 70 rpm) for 24 hours to form soaked polymer pellets.

[0333] The soaked pellets (entire mixture, no filtration, 37 grams) were loaded into a Brabender mixer (50 mL cavity - mixing chamber) with a temperature setting of 105°C and a rotor speed of 40 rpm. The soaked pellets were mixed and heated evenly for about two minutes to form a polymer melt. The Tempo compound was then weighed and gradually added to the mixing chamber. Mixing was then continued for another six minutes, and the temperature of the melt was about 110°C. The final glue was formed (pre-crosslinked, gel content <5 wt%). Samples of the final glue were analyzed by MDR, and the results are shown in Table 4A and Table 4B below.

[0334] The glue from the Brabender mix was compression molded into a sheet in a "1.0 mm thick" mold. The glue (14 g) was preheated at 110° C. for three minutes, then degassed (compression and release at 5 MPa repeated six times), and then pressed at a pressure of 10 MPa and 110° C. for another two minutes. After the mold temperature had dropped to room temperature, the sheet (15 cm×7 cm×1 mm, pre-crosslinked) was removed from the mold. The obtained sheet (pre-crosslinked, gel content ≤5% by weight) was further cut into the shape and size required for oven curing (1 / 3 of the mass of the sheet was used for heat treatment in a hot air convection oven).

[0335] The hot air convection oven was preheated and equilibrated at 200°C under ambient atmosphere. The compression molded composition was transferred to an oven with hot air convection as described above and held at 200°C for 10 minutes to effect crosslinking. The crosslinked composition was then removed and cooled to room temperature. The crosslinked composition was analyzed by the finger test and FTIR-ATR as discussed above to evaluate surface tack and surface degradation. The results are shown in Table 4A and Table 4B below. The FTIR-ATR curves are shown in Table 4A and Table 4B. Figure 1 Shown in.

[0336] result

[0337] The MDR, FTIR-ATR and finger test results are shown in Table 4A and Table 4B. As shown in Table 4B, the compositions of the present invention (IE1 and IE2) have adequate 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 non-sticky crosslinked surfaces (rating of 3 for each). These compositions cure well in air and, due to their lack of high filler loading, are lightweight and less conductive than highly filled EPDM vulcanizates.

[0338] Comparative composition CS3, which has a "molar ratio of nitroxide NO· to ​​peroxide bonds" of 0.19, produces a sticky cross-linked surface (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 are control compositions that do not include the Tempo compound. As shown in Table 4B, they each have a high degree of degradation D and a very sticky surface (each rated 1). As can be seen by the reduction in D values ​​and by the higher finger test ratings of some of the compositions, the degree of surface degradation is reduced by the addition of the Tempo compound relative to the corresponding control composition. It is also noted that for comparative compositions CS5 to CS9, higher levels of peroxide and adjuvant (TAIC) are required for adequate crosslinking. However, in these compositions, the same or higher amounts of Tempo compound did not produce a non-sticky surface. For comparative composition CS9, more Tempo compound (1.6 phr) was used, but the surface was still sticky, although the degree of degradation (D) based on H1714 was relatively small at 0.020. As Figure 1 As shown, for CS9 at 1737cm -1 Another peak was observed at 1737 cm. This peak can be attributed to other polar functional groups generated on the surface, probably due to migration issues. -1 Polar functional groups at the sites can also increase surface adhesion.

[0339] As shown in Table 4A, a high ratio of nitroxide NO· to ​​peroxide bonds (CS10) results in very low MH and "MH-ML" values ​​(i.e., poor cure). High Tempo compound loading (CS11) and low Tempo compound loading (CS12) also result in low MH and "MH-ML" values. Each of these three examples exhibits a slightly tacky surface. In the FTIR-ATR spectra, CS10 and CS11 each have a peak at 1737 cm -1 There is a peak at (other polar functional groups), which also contributes to the surface adhesion to a certain extent.

[0340] Table 4A: Comparative compositions and properties (first and second aspects)

[0341]

[0342]

[0343]

[0344] *The number of moles of NO· from Tempo compound = {[weight of bis-Tempo compound / (MW = 510.7)] * 2}; *The number of moles of peroxy bonds from LUPEROX 101 = {[weight of LUPEROX 101 / (MW = 290.4)] * 2}.

[0345] **CS9, another peak at 1737 cm-1 (other polar functional group) appears in the FTIR-ATR spectrum, which also contributes to the surface stickiness, and the degradation degree D1 and the relative degradation degree RD1 based on H1737 are calculated: D1=0.092 and RD1=18%.

[0346] It should be noted that the density equation for a blend (e.g., an 85 / 15 blend) is as follows, where w a and w b are the corresponding weight fractions of the blend components, and p a and p b are the corresponding densities of the blend components:

[0347] Note that the formula for determining the "total unsaturation / 1000C" of a blend (e.g., an 85 / 15 blend) is as follows, where w a and w b is the weight fraction of each blend component.

[0348] Unsat a and Unsat b is the "total unsaturation / 1000C" of each blend component: Unsat = W a Unsat a +W b Unsat b .

Claims

1. A composition comprising the following components a) to c): a) at least one ethylene / α-olefin interpolymer, said interpolymer comprising the following properties: i) a density from 0.855 g / cc to 0.900 g / cc and ii) a total unsaturation of ≥ 0.20 / 1000C, b) at least one Tempo compound of the following structure I); and c) at least one peroxide; and wherein the molar ratio of NO· from the at least one Tempo compound (component b) to the peroxy (OO) bonds from the at least one peroxide (component c) is from 0.30 to 0.90; and wherein component b is present in an amount of 0.20 phr 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 of which is as follows: Structure IA is Where n is an integer ≥ 1; R1, R2, R3 and R4 are each independently selected from H or C1-C18 alkyl; X is selected from CH2, ether (-O-), thioether (-S m -, wherein 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)-), polyurethane (-OC(O)-NH- or -NH-C(O)-O-), carbodiamide (-NH-C(O)-NH-) or imide (-C(O)-N(R)-C(O)-); R' is selected from C1-C30 alkylene; R" may or may not be present, and if present, R" is selected from C1-C30 alkylene; Y is selected from CR 4-n (where n = 1 to 4), OR 2-n (where n = 1 to 2), NR 3-n (where n = 1 to 3), SR 2-n (where n = 1 to 2), PR 3-n (where n = 1 to 3), PR 5-n (where n = 1 to 5), SiR 4-n (wherein n=1 to 4), a difunctional CC core, a phenyl core, an ester-substituted phenyl core, an amide-substituted phenyl core, a triisocyanurate core or a melamine core; and The bifunctional CC core is selected from the following structures, wherein each R' represents a divalent R' group in the above structure IA: Or R′-C≡CR′; Wherein the phenyl core is selected from the following structures, wherein each R' represents a divalent R' group in the above structure IA: The phenyl core substituted with an ester is selected from the following structures, wherein each R' represents the divalent R' group in the above structure IA: The phenyl core substituted with amide is selected from the following structures, wherein each R' represents the divalent R' group in the above structure IA: The triisocyanurate core is as follows, wherein each R' represents the divalent R' group in the above structure IA; The melamine core is as follows, wherein each R' represents the divalent R' group in the above structure IA; and wherein each R group in structure IA is independently selected from H, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heterohydrocarbyl, or substituted heterohydrocarbyl; The structure IB includes the following substructures IB): Where n is an integer ≥ 1; R1, R2, R3 and R4 are each independently selected from H or C1-C18 alkyl; X is selected from CH2, ether (-O-), thioether (-S m -, wherein 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)-), polyurethane (-OC(O)-NH- or -NH-C(O)-O-), carbodiamide (-NH-C(O)-NH-) or imide (-C(O)-N(R)-C(O)-); R' is selected from C1-C30 alkylene; R" may or may not be present, and if present, R" is selected from C1-C30 alkylene; Each R group in substructure IB is independently selected from H, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heterohydrocarbyl, or substituted heterohydrocarbyl; Each * (asterisk) in substructure IB indicates the corresponding chemical terminus of structure IB; The structure IC includes the following sub-structure ICs): Where n is an integer ≥ 1; R1, R2, R3 and R4 are each independently selected from H or C1-C18; X is selected from CH2, ether (-O-), thioether (-S m -, wherein 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)-), polyurethane (-OC(O)-NH- or -NH-C(O)-O-), carbodiamide (-NH-C(O)-NH-) or imide (-C(O)-N(R)-C(O)-); R' is selected from C1-C30 alkylene; R" may or may not be present, and if present, R" is selected from C1-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 * (asterisk) in substructure IC represents the corresponding chemical terminus of structure IC; and if n≥3, each terminus may or may not form a ring structure with the other terminus.

2. The composition of claim 1, wherein the ethylene / α-olefin interpolymer is of formula A 1 L 1 Unsaturated ethylene / α-olefin interpolymers.

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

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

5. The composition of claim 4, wherein the second ethylene / α-olefin interpolymer is of formula A 1 L 1 Unsaturated ethylene / α-olefin interpolymers.

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

7. The composition of any one of claims 4 to 6, wherein the ratio of the density of the first ethylene / α-olefin to the density of the second ethylene / α-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 first ethylene / α-olefin to the second ethylene / α-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% filler, based on the weight of the composition.

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

11. A cross-linked composition, the cross-linked composition being formed from the composition according to any one of claims 1 to 10.

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

13. A method of forming a cross-linked composition, the method comprising heat treating the composition according to any one of claims 1 to 10. The method according to claim 13 , wherein the heat treatment is performed in air.

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

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

17. The method according to claim 16, wherein: For step A, the composition is extruded at an average barrel temperature of 60°C to 150°C.

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

19. The method according to any one of claims 16 to 18, wherein the molar ratio of NO· from component b to peroxy (OO) bonds from component c is from 0.30 to 0.

90.

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

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