Olefin-based polymer and peroxide compositions with excellent cure response

Abstract

A process for forming a crosslinked composition, the process comprising a composition comprising at least the following components a) and b): a) an olefin-based polymer having a total unsaturation value of ≧0.20 / 1000C; b) at least one peroxide selected from at least one of the following: i) a peroxide containing at least one peroxy group containing an oxyl radical unit of radical I; ii) a peroxide containing at least one peroxy group containing an oxyl radical unit of radical II; iii) a peroxide containing at least one peroxy group containing an oxyl radical unit of radical III; iv) a peroxide containing at least one peroxy group containing an oxyl radical unit of radical IV, or v) applying heat, and optionally radiation, to a composition comprising any combination of i) to iv) and at least one peroxide selected from the group consisting of: wherein radical I, radical II, radical III, or radical IV are each as described herein. [Case 1] JPEG2024526140000069.jpg40170

Description

[Background technology]

[0001] The global photovoltaic market is growing very rapidly. This growth is driven by the increasing efficiency and decreasing cost of PV power generation relative to conventional grid power sources, as well as government incentives for increasing the use of photovoltaic power sources. PV encapsulant films are a key component of PV modules. Currently, films formed from ethylene vinyl acetate (EVA) are widely used as encapsulant materials for solar cells due to EVA's excellent transparency and cure response. EVA typically cures at a faster rate than conventional non-polar olefin-based polymers. However, more recent high-efficiency PERC (Passivated Emitter and Rear Cell) bifacial modules exhibit a high risk of potential I-induced degradation (PID) when using conventional EVA as an encapsulant film. Such olefin-based polymer compositions offer improved anti-PID performance but typically have a reduced peroxide cure response compared to EVA. A Moving Die Rheometer (MDR) is used to characterize the cure response, generating MH (maximum torque applied) and T90 values ​​(time to achieve 90% of (MH-ML), where ML is the minimum torque applied).

[0002] Alternative peroxides with increased decomposition rates have been used to shorten the cure time (reducing T90) of olefin-based polymers. While such peroxides improve cure speed as indicated by a reduced T90 value, they also reduce the degree of cure as indicated by a reduced MH value. There is a need for new olefin-based polymer compositions that provide improved cure speed while maintaining or increasing the degree of cure in the composition.

[0003] European Patent Application No. EP2958151(A1) states that the viscosity is 0.860 to 0.920 g / cm3 It has a density of 0.1 to 100 g / 10 min and an MFR (Melt Flow Rate) of 0.1 to 100 g / 10 min. * The present invention discloses an encapsulant resin composition containing ethylene / alpha-olefin (α-olefin) satisfying the relationship V≧10, where N is the number of branches derived from the comonomer, and V is the total number of vinyl and vinylidene units, both expressed per 1000 carbon atoms. Examples of organic peroxides include t-butylperoxyisopropyl carbonate, t-butylperoxy-2-ethylhexyl carbonate, t-butylperoxyacetate, t-butylperoxybenzoate, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, 1,1-di-(t-butylperoxy)-3,3,5-trimethyl- Examples of peroxides include 2,5-dimethyl-hexyl-2,5-diperoxybenzoate, t-butyl hydroperoxide, p-menthane hydroperoxide, benzoyl peroxide, p-chlorobenzoyl peroxide, t-butyl peroxyisobutyrate, hydroxyheptyl peroxide, and dicyclohexanone peroxide (see paragraph

[0058] ). See also Japanese Patent No. JP2012009688(A) (machine translation), in which the total amount of vinyl, vinylidene, cis-vinylene, trans-vinylene, and trisubstituted vinylene in an ethylene / α-olefin copolymer is 0.22 (per 1000°C) or more.

[0004] PCT International Publication No. WO2020 / 135680(A1) discloses a curable composition for an encapsulant film, the curable composition comprising a compound represented by formula A 1 L 1 L 2 A 2 or a telechelic polyolefin of formula A 1 L 1and curing components including a crosslinking agent, a crosslinking coagent, and a silane coupling agent. The crosslinking agent may include one or more organic peroxides, including, but not limited to, alkyl peroxides, aryl peroxides, ester peroxides, peroxycarbonates, diacyl peroxides, ketal peroxides, cyclic peroxides, dialkyl peroxides, ester peroxides, peroxydicarbonates, or combinations thereof. Examples of peroxides include di-tert-butyl peroxide, dicumyl peroxide, di-(3,3,5-trimethylhexanoyl) peroxide, t-butyl peroxypivalate, t-butyl peroxyneodecanoate, di-(sec-butyl)peroxydicarbonate, t-amyl peroxyneodecanoate, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butyl-cumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)-hexane, 1,3-bis(tert-butyl-peroxyl-isopropyl)benzene, or combinations thereof. An exemplary crosslinking agent is dicumyl peroxide, commercially available from Arkema under the trade name LUPEROX, from Akzo Nobel under the trade name TRIGONOX, and from Vanderbilt Chemicals under the trade name VAROX DBPH-50. See paragraph

[0241] . See also PCT International Publication Nos. WO2020 / 135708(A1), WO2020 / 140058, WO2020 / 140061, and WO2020 / 140067.

[0005] European Patent Application No. EP2637217(A1) discloses an encapsulating material for solar cells, which contains an ethylene / α-olefin copolymer that satisfies the following requirements (a1) to (a4): (a1) the content of structural units derived from ethylene is 80 to 90 mol % and the content of structural units derived from α-olefins (C3 to C20) is 10 to 20 mol %, (a2) the MFR is 2 g / 10 min or more and less than 10 g / 10 min, and (a3) ​​the MFR is 0.865 to 0.884 g / cm 3and (a4) a Shore A hardness of 60 to 85. The encapsulating material also contains a peroxide and a silane coupling agent. Preferred peroxides include dilauroyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, dibenzoyl peroxide, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleate, 1,1-di-(t-amylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di-(t-amylperoxy)cyclohexane, t-amylperoxyisononanoate, and t-amylperoxy-n tert-octoate, 1,1-di-(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di-(t-butylperoxy)cyclohexane, t-butylperoxyisopropyl carbonate, t-butylperoxy-2-ethylhexyl carbonate, 2,5-dimethyl-2,5-di-(benzoylperoxy)hexane, t-amylperoxybenzoate, t-butylperoxyacetate, t-butylperoxyisononanoate, 2,2-di(t-butylperoxy)butane, t-butylperoxybenzoate, etc. Preferred peroxides are dilauroyl peroxide, t-butylperoxyisopropyl carbonate, t-butylperoxyacetate, t-butylperoxyisononanoate, t-butylperoxy-2-ethylhexyl carbonate, t-butylperoxybenzoate, etc. (See paragraph

[0098] ).

[0006] European Patent Application No. EP2747150(A1) discloses an encapsulant for solar cells, which contains an ethylene / α-olefin copolymer and a specific peroxyketal having a half-life temperature of 1 hour in the range of 100°C to 135°C. The peroxyketal is contained in an amount of 0.1 to less than 0.8 parts by weight per 100 parts by weight of the ethylene / α-olefin copolymer. The ethylene / α-olefin copolymer satisfies the following characteristics: a1) a Shore A hardness of 60 to 85 (ASTM D2240), and a2) a MFR of 2 to 50 g / 10 min (190°C, 2.16 kg, ASTM D1238). See Abstract.

[0007] K. Thaworn et al., "Effects of Organic Peroxides on the Curing Behavior of EVA Encapsulant Resin," Open Journal of Polymer Chemistry, 2012, 2, 77-85, discloses the curing of poly(ethylene-co-vinyl acetate) (EVA) with three different organic peroxides: dialkyl peroxide, peroxyester peroxide, and peroxyketal peroxide. Dynamic cure measurements obtained by torque rheometry showed that dialkyl peroxide was not suitable because it has a long half-life temperature and its by-products can discolor the final product. Peroxyester peroxides were good for curing at temperatures ranging from 150°C to 160°C, with final cure occurring within 5 to 8 minutes. Peroxyketal peroxides performed better, but this reduced the optimal cure time to 3 minutes. The thermal decomposition mechanism of organic peroxides was used to explain how the generated free radicals affect the curing behavior. See Abstract.

[0008] PCT International Publication No. WO 2011 / 033232 (Abstract) discloses a composition containing: a) a copolymer made of ethylene and ethylene monomers and having polar functional groups; and b) at least one organic peroxide solution selected from tert-butyl 2-ethylperhexanoate, tert-amyl 2-ethylperhexanoate, and dilauroyl peroxide. The amount of the peroxide solution by weight ranged from 5% to 30% of the total weight of the composition. The crosslinked composition is disclosed to be useful as a photovoltaic cell encapsulant (see Abstract). See also U.S. Patent Application Publication No. 2012 / 0273718.

[0009] Additional polymers and / or peroxides are disclosed in the following documents: U.S. Patent No. 8,581,094, PCT International Publication No. WO2019 / 136823 (Abstract), Chinese Patent No. 106833406A (Machine Translation), Chinese Patent No. 108517188A (Machine Translation), J. Kruzelak et al., Vulcanization of Rubber Compounds with Peroxide Curing Systems, Rubber Chemistry and Technology, 90(1), 60-88, 2017, J. Meijer et al., Organic Peroxides in Radical Synthesis Reactions, Acros Organics, Review 6.

[0010] However, as noted above, there remains a need for new olefin-based polymer compositions and related crosslinking processes for improved cure performance. This need has been met by the following invention. Summary of the Invention

[0011] In a first aspect, there is provided a process for forming a crosslinked composition, the process comprising a composition comprising at least the following components a) and b): a) an olefin-based polymer containing a total unsaturation value of ≥ 0.20 / 1000C; b) at least one peroxide selected from at least one of the following: i) a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical I, or ii) a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical II, or iii) a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical III, or iv) a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical IV, or v) applying heat, and optionally radiation, to a composition comprising any combination of i) to iv) and at least one peroxide selected from wherein radical I, radical II, radical III, or radical IV is respectively represented as follows:

[0012] [ka] (radical I), wherein R1, R2, and R3 are each independently selected from H, CH3, CH2-alkyl, or aryl, each of R1, R2, and R3 may be the same as or different from one or both of the other two, and at least one of R1, R2, or R3 is CH2-alkyl;

[0013] [ka] (Radical II), wherein R1, R2, and R3 are each independently selected from H, CH3, CH2-alkyl, or aryl, each of R1, R2, and R3 may be the same as or different from one or both of the other two, and at least one of R1, R2, or R3 is CH2-alkyl;

[0014] [ka] (radical III), wherein R1 is CH2-alkyl;

[0015] [ka] (Radical IV), wherein R1 and R2 are selected from the following y) or z): y) R1 and R2 are each independently CH3 or CH2-alkyl, where R1 and R2 may be the same or different, and at least one of R1 or R2 is CH2-alkyl; or z) R1 and R2 are joined together to form an aliphatic ring, the ring containing at least one -CH2- structure (R1-C(O·)(O·)-R2) adjacent to a quaternary carbon.

[0016] In a second embodiment, the composition comprises at least the following components a) and b): a) an olefin-based polymer containing a total unsaturation value of ≥ 0.20 / 1000C; b) at least one peroxide selected from at least one of the following: i) a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical I, or ii) a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical II, or iii) a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical III, or iv) a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical IV, or v) any combination of i) to iv), and at least one peroxide selected from the group consisting of: wherein radical I, radical II, radical III, or radical IV is respectively represented as follows:

[0017] [ka] (radical I), wherein R1, R2, and R3 are each independently selected from H, CH3, CH2-alkyl, or aryl, each of R1, R2, and R3 may be the same as or different from one or both of the other two, and at least one of R1, R2, or R3 is CH2-alkyl;

[0018] [ka] (Radical II), wherein R1, R2, and R3 are each independently selected from H, CH3, CH2-alkyl, or aryl, each of R1, R2, and R3 may be the same as or different from one or both of the other two, and at least one of R1, R2, or R3 is CH2-alkyl;

[0019] [ka] (radical III), wherein R1 is CH2-alkyl;

[0020] [ka] (Radical IV), wherein R1 and R2 are selected from the following y) or z): y) R1 and R2 are each independently CH3 or CH2-alkyl, where R1 and R2 may be the same or different, and at least one of R1 or R2 is CH2-alkyl; or z) R1 and R2 are joined together to form an aliphatic ring, the ring containing at least one -CH2- structure (R1-C(O·)(O·)-R2) adjacent to a quaternary carbon. DETAILED DESCRIPTION OF THE INVENTION

[0021] Olefin-based polymer compositions have been discovered that have good cure rates without sacrificing the level of cure. As described above, in a first aspect, a process for forming such a crosslinked composition is provided. In a second aspect, a composition is provided. Each process may comprise a combination of two or more embodiments described herein. Each composition may comprise a combination of two or more embodiments described herein. Each component a and b may comprise a combination of two or more embodiments described herein. The following embodiments apply to both the first and second aspects, unless otherwise specified.

[0022] In one embodiment, or a combination of two or more embodiments, each described herein, component b is a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical I.

[0023] In one embodiment, or a combination of two or more embodiments, each described herein, component b is a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical II.

[0024] In one embodiment, or a combination of two or more embodiments, each described herein, component b is a peroxide containing at least one peroxy group comprising an oxyl radical unit selected from radical III.

[0025] In one embodiment, or a combination of two or more embodiments, each described herein, component b is a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical IV.

[0026] In one embodiment, or a combination of two or more embodiments, each described herein, component b is selected from the following structures r1) to r132), each of which is described below (see V] below):

[0027] In one embodiment, or a combination of two or more embodiments, each described herein, the peroxide is present in an amount of ≧0.10 wt.%, or ≧0.20 wt.%, or ≧0.30 wt.%, or ≧0.40 wt.%, or ≧0.50 wt.%, or ≧0.52 wt.%, or ≧0.54 wt.%, and / or ≦2.00 wt.%, or ≦1.80 wt.%, or ≦1.60 wt.%, or ≦1.40 wt.%, or ≦1.20 wt.%, or ≦1.00 wt.%, based on the weight of the composition.

[0028] In one embodiment, or a combination of two or more embodiments, each described herein, the composition comprises ≧50.0 wt.%, or ≧60.0 wt.%, or ≧70.0 wt.%, or ≧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.%, and / or ≦100.0 wt.%, or ≦99.9 wt.%, or ≦99.8 wt.%, or ≦99.7 wt.%, or ≦99.6 wt.% of the sum of component a and component b, based on the weight of the composition.

[0029] In one embodiment, or a combination of two or more embodiments, each described herein, the weight ratio of component a to component b is ≧50, or ≧60, or ≧70, or ≧80, or ≧90, or ≧100, and / or ≦200, or ≦190, or ≦180, or ≦170, or ≦160, or ≦150, or ≦145, or ≦140, or ≦135, or ≦130.

[0030] In one embodiment, or a combination of two or more embodiments, each described herein, component a has a viscosity of ≧0.22 / 1000C, or ≧0.24 / 1000C, or ≧0.26 / 1000C, or ≧0.28 / 1000C, or ≧0.30 / 1000C, or ≧0.35 / 1000C, or ≧0.40 / 1000C, or ≧0.45 / 1000C, or ≧0.50 / 1000C, or ≧0.55 / 1000C, or ≧0.60 / 10 00C, or ≧0.65 / 1000C, and / or ≦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.

[0031] In one embodiment, or a combination of two or more embodiments, each described herein, component a is an ethylene-based polymer.

[0032] In one embodiment, or a combination of two or more embodiments, each described herein, component a is a compound of formula A 1 L 1 L 2 A 2 Telechelic polyolefins of formula A 1 L 1 unsaturated polyolefins, ethylene / alpha-olefin / non-conjugated polyene copolymers, or ethylene / alpha-olefin copolymers.

[0033] In one embodiment, or a combination of two or more embodiments, each described herein, component a has a viscosity of ≧0.854, or ≧0.856, or ≧0.858, or ≧0.860, or ≧0.862, or ≧0.864, or ≧0.866, or ≧0.868, or ≧0.870 g / cc, and / or ≦0.960, or ≦0.955, or ≦0.950, or ≦0.945, or ≦0.940, or ≦0.935, or ≦0.930, or ≦0.925, or ≦0.920, or ≦0.915, or ≦0.910, or ≦0.905, or ≦0.900, or ≦0.895, or ≦0.890, or ≦0.885, or ≦0.880, or ≦0.878, or ≦0.876, or ≦0.875, or ≦0.874g / cc (1cc=1cm 3 ) density.

[0034] In one embodiment, or a combination of two or more embodiments, each described herein, component a has a molecular weight distribution MWD (Molecular Weight Distribution) (= Mw / Mn) of ≧1.80, or ≧1.90, or ≧2.00, or ≧2.10, or ≧2.15, or ≧2.20, or ≧2.25, or ≧2.30, or ≧2.35, or ≧2.40, and / or ≦5.00, or ≦4.80, or ≦4.60, or ≦4.40, or ≦4.20, or ≦4.00, or ≦3.80, or ≦3.60, or ≦3.40, or ≦3.20, or ≦3.0.

[0035] In one embodiment, or a combination of two or more embodiments, each described herein, the composition has a percent change in T90 (Δ), as described herein, of ≧−80%, or ≧−70%, or ≧−65%, or ≧−60%, or ≧−55%, or ≧−50%, or ≧−45%, or ≧−40%, and / or ≦−10%, or ≦−15%, or ≦−20%, or ≦−25%, or ≦−30%.

[0036] In one embodiment, or a combination of two or more embodiments, each described herein, the composition has a percent change in MH (Δ), as described herein, of ≧−40%, or ≧−35%, or ≧−30%, or ≧−25%, or ≧−20%, or ≧−15%, or ≧−10%, or ≧−5.0%, or ≧0%, or ≧2.0%, or ≧4.0%, or ≧6.0%, or ≧8.0%, and / or ≦400%, or ≦350%, or ≦300%, or ≦250%, or ≦200%, or ≦150%, or ≦100%, or ≦90%, or ≦80%, or ≦70%, or ≦60%, or ≦50%, or ≦40%, or ≦30%, or ≦20%, or ≦10%.

[0037] Crosslinked compositions formed from the process of one or more embodiments described herein or from the composition of one or more embodiments described herein are also provided.

[0038] Also provided are articles comprising at least one component formed from the composition of one or more embodiments described herein.

[0039] olefin polymer Olefin-based polymers include, but are not limited to, elastomers and other olefin-based polymers. Elastomers are polymers that have viscoelastic (i.e., both viscous and elastic) properties. Olefin-based polymers include, but are not limited to, ethylene / alpha-olefin / non-conjugated polyene copolymers, represented by formula A 1 L 1 L 2 A 2 Telechelic polyolefins of formula A 1 L 1 Unsaturated polyolefin, ethylene / alpha-olefin copolymer.

[0040] The ethylene / alpha-olefin / non-conjugated polyene copolymers described herein comprise, in polymerized form, ethylene, an alpha-olefin, and a non-conjugated polyene. The alpha-olefin may be either an aliphatic or aromatic compound. Alpha-olefins include, but are not limited to, C3 to C20 alpha-olefins, further C3 to C10 alpha-olefins, and further C3 to C8 alpha-olefins. In one embodiment, the copolymer is an ethylene / propylene / non-conjugated diene copolymer, further EPDM. Suitable examples of non-conjugated polyenes include C4 to C40 non-conjugated dienes. Non-conjugated dienes include, but are not limited to, 5-ethylidene-2-norbornene (ENB), 5-vinyl-2-norbornene (VNB), dicyclopentadiene, 1,4-hexadiene, or 7-methyl-1,6-octadiene, and further ENB, VNB, dicyclopentadiene, or 1,4-hexadiene, and further ENB or VNB, and further ENB.

[0041] Ethylene / alpha-olefin copolymers comprise, in polymerized form, ethylene and an alpha-olefin, including, but not limited to, C3 to C20 alpha-olefins, further C3 to C10 alpha-olefins, further C3 to C8 alpha-olefins, such as propylene, 1-butene, 1-hexene, and 1-octene.

[0042] Telechelic polyolefins, such as A 1 L 1 L 2 A 2 (Formula I) and unsaturated polyolefins, such as A 1 L 1 (Formula II) are described below, respectively. See also PCT International Publication Nos. 2020 / 140058 and 2020 / 140067 (each of which is incorporated herein by reference).

[0043] Formula I:A 1 L 1 L 2 A2 A telechelic polyolefin of the formula: L 1 is a polyolefin, preferably an ethylene-based polymer, further preferably an ethylene / alpha-olefin copolymer, further preferably an ethylene / alpha-olefin copolymer, and L 1 (divalent) is A 1 and L 2 Note that the .times. ...

[0044] A 1 is as follows: a) vinyl group, b) group of the formula CH2=C(Y 1 )-, c) a vinylidene group of formula Y 1 a vinylene group of CH═CH—; d) a vinyl group and a group of formula Y 1 e) a mixture of vinyl groups and vinylene groups of the formula CH═C(Y 1 )- and a mixture of vinylidene groups of the formula CH2=C(Y 1 )- and a vinylidene group of formula Y 1 and g) a mixture of vinyl groups and vinylene groups of the formula CH2=C(Y 1 )- and a vinylidene group of formula Y 1 vinylene groups of CH═CH—; and mixtures thereof; Y 1 In each occurrence, independently, C1 to C 30 is a hydrocarbyl group, L 2 is C1~C 32 is a hydrocarbylene group, A 2 is a hydrocarbyl group containing a hindered double bond.

[0045] Formula II:A 1 L 1 An unsaturated polyolefin of L 1 is a polyolefin, preferably an ethylene-based polymer, further preferably an ethylene / alpha-olefin copolymer, further preferably an ethylene / alpha-olefin copolymer, and L1 (monovalent) is A 1 Note that the .times. ...

[0046] A 1 is a group consisting of: g) a vinyl group, b) a group of the formula CH2=C(Y 1 )-, c) a vinylidene group of formula Y 1 a vinylene group of CH═CH—; d) a vinyl group and a group of formula Y 1 e) a mixture of vinyl groups and vinylene groups of the formula CH═C(Y 1 )- and a mixture of vinylidene groups of the formula CH2=C(Y 1 )- and a vinylidene group of formula Y 1 and g) a mixture of vinyl groups and vinylene groups of the formula CH2=C(Y 1 )- and a vinylidene group of formula Y 1 and a mixture of CH═CH— vinylene groups, and Y1, in each occurrence, is independently selected from the group consisting of C1 to C 30 It is a hydrocarbyl group.

[0047] With respect to Formula I and Formula II, L 1are, independently at each occurrence, polyolefins, which, as noted above, may result in part from the polymerization (e.g., coordination polymerization) of unsaturated monomers (and comonomers). Examples of suitable monomers (and comonomers) include ethylene and alpha-olefins having 3 to 30 carbon atoms, and also 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 3,5,5-trimethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 5-ethyl-1-nonene, 1-octadecene, and 1-eicosene, as well as conjugated or non-conjugated dienes. Dienes, such as butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,5-heptadiene, 1,6-heptadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 1,9-decadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 5,9-di Methyl-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, together with norbornene and alkenyl, alkylidene, cycloalkenyl, and cycloalkylidene norbornenes, such as 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, dicyclopentadiene, 5-methylene-2-norbornene, 5-propenyl-2-norbornene, Examples of suitable vinyl styrene compounds include, but are not limited to, norbornene, 5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene, and norbornadiene, and aromatic vinyl compounds such as styrene, mono- or polyalkylstyrenes (including styrene, o-methylstyrene, t-methylstyrene, m-methylstyrene, p-methylstyrene, o-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, and p-ethylstyrene).

[0048] peroxide As used herein, a peroxide contains at least one oxygen-oxygen bond (OO). Useful peroxides include, but are not limited to, peroxycarbonates, such as, for example, tert-amylperoxy-2-ethylhexyl carbonate (TAEC), and peroxyketals, such as, for example, 1,1-di(tert-amylperoxy)cyclohexane. See also structures r1) through r132) below.

[0049] additives The composition of the present invention may contain one or more additives, such as one or more alkoxysilane coupling agents, such as vinyltrimethoxysilane (VTMS) or 3-(trimethoxysilyl)propylmethacrylate (VMMS), or a combination of alkoxysilane coupling agents, tetraethoxysilane TEOS (or pre-hydrolyzed products), crosslinking coagents, such as triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), triallyl trimellitate (TATM), trimethylolpropane triacylate (TMPTA), trimethylolpropane trimethyl acrylate ... Acrylate (TMPTMA), 1,6-hexanediol diacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, trivinylcyclohexane (TVCH), or a combination thereof.Additional crosslinking coagents include alkenyl-functional monocyclic organosiloxanes (e.g., monocyclic organosiloxanes of the formula [R,RSiO], where the subscript n is an integer greater than or equal to 3 and each R is independently (C-C) alkenyl, or HC=C( R1a)-C(=O)-O-(CH2)m-, where R1a is H or methyl, the subscript m is an integer from 1 to 4, and each R2 is independently H, (C1-C4)alkyl, phenyl, or R1, such as 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 2,4,6-trimethyl-2,4,6-trivinyl-cyclotrisiloxane, or a combination thereof.

[0050] Additional additives include UV absorbers and / or stabilizers such as TINUVIN 770, one or more antioxidants, processing aids such as fluoropolymers, polydimethylsiloxane (PDMS), ultra-high molecular weight PDMS, ion scavengers, anti-PID agents, other siloxanes, fumed silica, nano-Al2O3, nanoclays, and one or more other fillers. In one embodiment, the additive is present in an amount of ≥ 0.20 wt%, or ≥ 0.40 wt%, or ≥ 0.60 wt%, or ≥ 0.80 wt%, and / or ≤ 5.0 wt%, or ≤ 4.0 wt%, or ≤ 3.0 wt%, or ≤ 2.0 wt%, or ≤ 1.5 wt%, or ≤ 1.0 wt%, based on the weight of the composition.

[0051] definition Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percentages are by weight and all test methods are current as of the filing date of this disclosure.

[0052] As used herein, the term "composition" includes a mixture of materials, including the composition and reaction and decomposition products formed from the materials of the composition. Any reaction or decomposition products are typically present in trace or residual amounts.

[0053] As used herein, the term "polymer" refers to a polymeric compound prepared by polymerizing monomers of the same or different types. The generic term polymer includes the term homopolymer (used to refer to a polymer prepared from only one type of monomer, with the understanding that trace amounts of impurities may be incorporated into the polymer structure) and the term copolymer, as defined herein below. Trace amounts of impurities, such as catalyst residues, may be incorporated into and / or within the polymer. Typically, polymers are stabilized with very small amounts ("ppm" amounts) of one or more stabilizers.

[0054] As used herein, the term "interpolymer" refers to a polymer prepared by polymerization of at least two different types of monomers. Thus, the term interpolymer includes the term copolymer (used to refer to a polymer prepared from two different types of monomers) and polymers prepared from more than two different types of monomers.

[0055] As used herein, the term "olefin-based polymer" refers to a polymer that contains 50% or a majority weight percent (based on the weight of the polymer) of an olefin in polymerized form, such as, for example, ethylene or propylene, and may optionally contain one or more comonomers. As used herein, olefin-based polymers include ethylene / alpha-olefin / non-conjugated polyene copolymers, Formula A 1 L 1 L 2 A 2 Telechelic polyolefins of formula A 1 L 1 unsaturated polyolefins, and ethylene / alpha-olefin copolymers.

[0056] As used herein, the term "polyolefin" refers to a polymer that, in polymerized form, comprises 50% or a majority weight percent (based on the weight of the polymer) of an olefin, such as ethylene or propylene, and may optionally contain one or more comonomers.

[0057] As used herein, the term "propylene-based polymer" refers to a polymer that, in polymerized form, contains a majority weight percent propylene (based on the weight of the polymer) and may optionally contain one or more comonomers.

[0058] As used herein, the term "ethylene-based polymer" refers to a polymer that, in polymerized form, contains at least 50 weight percent or majority weight percent ethylene (based on the weight of the polymer), and may optionally contain one or more comonomers.

[0059] As used herein, the term "ethylene / alpha-olefin copolymer" refers to a copolymer that, in polymerized form, comprises 50 weight percent or a majority weight percent (based on the weight of the copolymer) of ethylene and an alpha-olefin. Preferably, the ethylene / alpha-olefin copolymer is a random copolymer (i.e., composed of randomly distributed monomer components).

[0060] As used herein, the term "ethylene / alpha-olefin copolymer" refers to a copolymer that, in polymerized form, comprises 50 weight percent or a majority weight percent (based on the weight of the copolymer) of ethylene and an alpha-olefin as the only two monomer types. Preferably, the ethylene / alpha-olefin copolymer is a random copolymer (i.e., composed of its monomer constituents randomly distributed).

[0061] As used herein, the term "ethylene / alpha-olefin / non-conjugated polyene copolymer" refers to a copolymer comprising, in polymerized form, ethylene, an alpha-olefin, and a non-conjugated polyene. In one embodiment, the "ethylene / alpha-olefin / non-conjugated polyene copolymer" comprises, in polymerized form, 50% or a majority weight percent ethylene (based on the weight of the interpolymer). As used herein, the term "ethylene / alpha-olefin / non-conjugated diene copolymer" refers to a random copolymer comprising, in polymerized form, ethylene, an alpha-olefin, and a non-conjugated diene. In one embodiment, the "ethylene / alpha-olefin / non-conjugated diene copolymer" comprises, in polymerized form, 50% or a majority weight percent ethylene (based on the weight of the copolymer). It should be noted that the terms "ethylene / alpha-olefin / non-conjugated polyene terpolymer" and "ethylene / alpha-olefin / non-conjugated diene terpolymer" are similarly defined; however, for each, the terpolymer comprises, in polymerized form, ethylene, an alpha-olefin, and a polyene (or diene) as the only three monomer types.

[0062] As used herein, with respect to a polymer (or interpolymer or terpolymer or copolymer), the phrase "major weight percent" refers to the amount of monomer that is present in the greatest amount in the polymer.

[0063] As used herein, the term "crosslinked composition" refers to a composition having a network structure due to the formation of chemical bonds between polymer chains. The degree of formation of this network structure is indicated by an increase in the difference between "MH-ML" compared to the non-crosslinked composition. Crosslinked compositions typically have a gel content of ≥ 50 wt%, further ≥ 60 wt%, further ≥ 70 wt%, and even ≥ 80 wt%, based on the weight of the crosslinked composition. See Gel Test below.

[0064] The phrases "applying heat," "heat treated," "heat treatment," and similar phrases used herein in connection with compositions comprising olefin-based polymers refer to heating the composition as discussed herein. Heat may be applied by electrical means (e.g., heating coils). It should be noted that the temperature at which heat treatment is performed refers to the temperature of the composition (e.g., the cure temperature of the composition).

[0065] As used herein in connection with compositions comprising the above-described olefin-based polymers, the phrases "applying radiation," "radiation treating," "radiation treatment," and similar terms refer to exposing the composition to radiation (e.g., high-energy electron beam or UV).

[0066] The phrases "heat treating," "thermal treatment," and similar terms, as used herein with respect to compositions comprising olefin-based polymers, refer to raising the temperature of the composition by application of heat, radiation, or other means (e.g., chemical reaction), and preferably heat, as discussed herein. Note that the temperature at which the heat treatment is carried out refers to the temperature of the composition (e.g., the curing temperature of the composition).

[0067] The terms "comprising," "including," "having," and their derivatives are not intended to exclude the presence of any additional component, step, or procedure, whether specifically disclosed or not. For the avoidance of doubt, all compositions claimed through the use of the term "comprising" may include any additional additives, adjuvants, or compounds, whether polymeric or otherwise, unless specifically stated to the contrary. In contrast, the term "consisting essentially of" excludes that which is not essential to operability and excludes any other component, step, or procedure from the scope of any subsequent recitation. The term "consisting of" excludes any component, step, or procedure not specifically defined or listed.

[0068] List of some processes and compositions A] A process for forming a crosslinked composition, the process comprising a composition comprising at least the following components a) and b): a) an olefin-based polymer containing a total unsaturation value of ≥ 0.20 / 1000C; b) at least one peroxide selected from at least one of the following: i) a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical I, or ii) a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical II, or iii) a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical III, or iv) a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical IV, or v) applying heat, and optionally radiation, to a composition comprising any combination of i) to iv) and at least one peroxide selected from wherein radical I, radical II, radical III, or radical IV is respectively represented as follows:

[0069] [ka] (radical I), wherein R1, R2, and R3 are each independently selected from H, CH3, CH2-alkyl, or aryl, each of R1, R2, and R3 may be the same as or different from one or both of the other two, and at least one of R1, R2, or R3 is CH2-alkyl;

[0070] [ka] (Radical II), wherein R1, R2, and R3 are each independently selected from H, CH3, CH2-alkyl, or aryl, each of R1, R2, and R3 may be the same as or different from one or both of the other two, and at least one of R1, R2, or R3 is CH2-alkyl;

[0071] [ka] (radical III), wherein R1 is CH2-alkyl;

[0072] [ka] (Radical IV), wherein R1 and R2 are selected from the following y) or z): y) R1 and R2 are each independently CH3 or CH2-alkyl, where R1 and R2 may be the same or different, and at least one of R1 or R2 is CH2-alkyl; or z) R1 and R2 are joined together to form an aliphatic ring, the ring containing at least one -CH2- structure (R1-C(O·)(O·)-R2) adjacent to a quaternary carbon.

[0073] As used herein, with respect to peroxides it should be noted that R1 = R1, R2 = R2, R3 = R3, etc. It is understood that two oxyl radicals (e.g., R0·) combine together to form a peroxy group (O-O) in peroxides (component b).

[0074] The phrase "peroxy group comprising an oxyl radical unit selected from radical I," and similar phrases disclosed herein, refers, in part, to a peroxy group formed from the radical in question and forming an -OO- bond with another oxyl radical.

[0075] The alkyl group (Alkyl) may be linear or branched. The aryl group (Ar) may or may not contain one or more alkyl substitutions. The aliphatic ring may or may not contain one or more alkyl substitutions.

[0076] B] The process described in A] above, wherein for radical IV, R1 and R2 are each independently CH3 or CH2-alkyl, R1 and R2 may be the same or different, and at least one of R1 or R2 is CH2-alkyl.

[0077] C] The process described in A] above, wherein for radical IV, R1 and R2 are bonded together to form an aliphatic ring, and the ring contains at least one -CH2- structure (R1-C(O·)(O·)-R2) adjacent to the quaternary carbon.

[0078] D] The process described in A] or C] above, wherein for radical IV, the ring structure contains 5 to 15 carbon atoms, further 5 to 9 carbon atoms.

[0079] E] The process described in A] above, wherein component b is a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical I. For example, see the following structures r1) to r68), r76) to r78).

[0080] F] The process described in A) above, wherein component b is a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical II. For example, see the following structures r13) to r28), r31), r32), r34) to r44), r123), and r129) to r132).

[0081] G] Component b is The process described in A) above, which comprises at least one peroxy group containing an oxyl radical unit selected from radical III. For example, see the following structures r46), r51) to r68), and r124) to r128).

[0082] H] The process according to any one of A] to D] above, wherein component b is a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical IV. For example, see structures r69) to r93) below.

[0083] I] The process according to any one of A] to D] above, wherein component b is a peroxide containing multiple peroxy groups formed from at least two oxyl radical units independently selected from radical IV to form a cyclic structure. Furthermore, each radical unit is identical. For example, see r94) to r99) below.

[0084] J] The process of any one of A] to D] or I] above, wherein component b is a peroxide containing multiple peroxy groups formed from at least three oxyl radical units independently selected from radical IV to form a cyclic structure. Furthermore, each radical unit is identical. See, for example, r96) to r99) below.

[0085] K] The process according to any one of A] to D] above, wherein component b is a peroxide containing at least two peroxy groups formed from at least two oxyl radical units independently selected from radical IV to form a non-cyclic structure. Furthermore, each radical unit is identical. For example, see r100) to r122) below.

[0086] L] The process of any one of A] to D] or K] above, wherein component b is a peroxide containing at least three peroxy groups formed from at least three oxyl radical units independently selected from radical IV to form a non-cyclic structure. Furthermore, each radical unit is identical. See, for example, r100) to r110), r121), and r122) below.

[0087] M] The process described in A] above, wherein component b is a peroxide containing at least one peroxy group formed from an oxyl radical unit selected from radical I and an oxyl radical unit selected from radical II. For example, see the following structures r13) to r28), r31), r32), r34) to r44).

[0088] N] The process according to A] above, wherein component b is a peroxide containing at least one peroxy group formed from an oxyl radical unit selected from radical I and an oxyl radical unit selected from radical III. For example, see the following structures r46), r51) to r68).

[0089] O] The process described in A] above, wherein component b is a peroxide containing at least one peroxy group formed from an oxyl radical unit selected from radical I and an oxyl radical unit selected from radical IV. For example, see the following structures r70) to r73), r75) to r79), r81) to r88), r90), and r93).

[0090] P] The process of any one of A]-O] (through A]-O]) above, wherein the peroxide is present in an amount of ≧0.10 wt%, or ≧0.20 wt%, or ≧0.30 wt%, or ≧0.40 wt%, or ≧0.50 wt%, or ≧0.52 wt%, or ≧0.54 wt%, and / or ≦2.00 wt%, or ≦1.80 wt%, or ≦1.60 wt%, or ≦1.40 wt%, or ≦1.20 wt%, or ≦1.00 wt%, based on the weight of the composition.

[0091] Q] The process of any one of A] to P] above, wherein the composition comprises ≧50.0 wt%, or ≧60.0 wt%, or ≧70.0 wt%, or ≧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%, and / or ≦100.0 wt%, or ≦99.9 wt%, or ≦99.8 wt%, or ≦99.7 wt%, or ≦99.6 wt%, of the sum of components a and b, based on the weight of the composition.

[0092] R] component a is ≧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 ≦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.

[0093] S] The process described in any one of A] to R] above, wherein component a is an ethylene-based polymer.

[0094] T] component a has a viscosity of ≧0.854, or ≧0.856, or ≧0.858, or ≧0.860, or ≧0.862, or ≧0.864, or ≧0.866, or ≧0.868, or ≧0.870 g / cc, and / or ≦0.960, or ≦0.955, or ≦0.950, or ≦0.945, or ≦0.940, or ≦0.935, or ≦0.930, or ≦0.925, or ≦0.920, or ≦0.915, or ≦0.910, or ≦0.905, or ≦0.900, or ≦0.895, or ≦0.890, or ≦0.885, or ≦0.880, or ≦0.875 g / cc (1 cc = 1 cm 3 The process according to any one of A] to S] above, wherein the density is

[0095] U] The process of any one of A]-T] above, wherein component a has a melt index (I2) of ≧0.1, or ≧0.2, or ≧0.5, or ≧1.0, or ≧2.0, or ≧5.0, or ≧8.0, or ≧10, or ≧15, or ≧20, or ≧25 dg / min, and / or ≦2000, or ≦1000, or ≦500, or ≦200, or ≦100, or ≦50, or ≦40, or ≦35, or ≦30 dg / min.

[0096] V] Component b has the following structure: r1) to r132),

[0097] [ka]

[0098] [ka]

[0099] [ka]

[0100] [ka]

[0101] [ka]

[0102] [ka]

[0103] [ka]

[0104] [ka] The process according to any one of A] or P] to U] above, wherein the process is selected from the following:

[0105] W] component a is a compound of formula A 1 L 1 L 2 A 2 Telechelic polyolefins of formula A 1 L 1 The process according to any one of A] to V] above, wherein the copolymer is selected from the group consisting of unsaturated polyolefins, ethylene / alpha-olefin / non-conjugated polyene copolymers, and ethylene / alpha-olefin copolymers.

[0106] X] The process according to any one of A] to W] above, wherein the composition is heat treated at a temperature of ≥ 80°C, or ≥ 90°C, or ≥ 100°C, or ≥ 110°C, or ≥ 120°C, or ≥ 130°C, or ≥ 140°C, and / or at a temperature of ≤ 200°C, or ≤ 190°C, or ≤ 180°C, or ≤ 170°C, or ≤ 160°C, or ≤ 155°C, and further heat treated.

[0107] Y] A crosslinked composition formed by the process described in any one of A] to X] above.

[0108] A2] The composition comprises at least the following components a) and b): a) an olefin-based polymer containing a total unsaturation value of ≥ 0.20 / 1000C; b) at least one peroxide selected from at least one of the following: i) a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical I, or ii) a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical II, or iii) a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical III, or iv) a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical IV, or and at least one peroxide selected from any combination of i) to iv), wherein radical I, radical II, radical III, or radical IV is each described above (see (A)).

[0109] B2] The composition described in A2] above, wherein for radical IV, R1 and R2 are each independently CH3 or CH2-alkyl, R1 and R2 may be the same or different, and at least one of R1 or R2 is CH2-alkyl.

[0110] C2] The composition described in A2] above, wherein for radical IV, R1 and R2 are bonded together to form an aliphatic ring, and the ring contains at least one -CH2- structure (R1-C(O·)(O·)-R2) adjacent to a quaternary carbon.

[0111] D2] The composition according to A2] or C2] above, wherein for radical IV, the ring structure contains 5 to 15 carbon atoms, further 5 to 9 carbon atoms.

[0112] E2] The composition according to A2] above, wherein component b is a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical I. See, for example, structures r1) to r68), r76) to r78) above.

[0113] F2] component b is The composition according to A2) above, comprising at least one peroxy group comprising an oxyl radical unit selected from radical II. See, for example, structures r13) to r28), r31), r32), r34) to r44), r123), and r129) to r132) above.

[0114] G2] The composition according to A2] above, wherein component b is a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical III. See, for example, structures r46), r51) to r68), and r124) to r128) above.

[0115] H2] The composition according to any one of A2] to D2] above, wherein component b is a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical IV. See, for example, structures r69) to r93) above.

[0116] I2] The composition according to any one of A2] to D2] above, wherein component b is a peroxide containing multiple peroxy groups formed from at least two oxyl radical units independently selected from radical IV to form a cyclic structure. Furthermore, each radical unit is identical. See, for example, r94) to r99) above.

[0117] J2] The composition according to any one of A2], D2], or I2] above, wherein component b is a peroxide containing multiple peroxy groups formed from at least three oxyl radical units independently selected from radical IV to form a cyclic structure. Furthermore, each radical unit is identical. See, for example, r96) to r99) above.

[0118] K2] The composition according to any one of A2] to D2] above, wherein component b is a peroxide containing at least two peroxy groups formed from at least two oxyl radical units independently selected from radical IV to form a non-cyclic structure. Furthermore, each radical unit is identical. For example, see r100) to r122) above.

[0119] L2] The composition according to any one of A2] to D2] or K2] above, wherein component b is a peroxide containing at least three peroxy groups formed from at least three oxyl radical units independently selected from radical IV to form a non-cyclic structure. Furthermore, each radical unit is identical. See, for example, r100) to r110), r121), and r122) above.

[0120] M2] The composition according to A2] above, wherein component b is a peroxide containing at least one peroxy group formed from an oxyl radical unit selected from radical I and an oxyl radical unit selected from radical II. See, for example, the above structures r13) to r28), r31), r32), and r34) to r44).

[0121] N2] The composition according to A2] above, wherein component b is a peroxide containing at least one peroxy group formed from an oxyl radical unit selected from radical I and an oxyl radical unit selected from radical III. See, for example, structures r46), r51) to r68) above.

[0122] O2] The composition according to A2] above, wherein component b is a peroxide containing at least one peroxy group formed from an oxyl radical unit selected from radical I and an oxyl radical unit selected from radical IV. See, for example, structures r70) to r73), r75) to r79), r81) to r88), r90), and r93) above.

[0123] P2] The component b is selected from the following structures r1) to r132), as described above, respectively (see composition (V) of A2] above).

[0124] Q2] A composition according to any one of A2] to P2] above, wherein the peroxide is present in an amount of ≧0.10 wt%, or ≧0.20 wt%, or ≧0.30 wt%, or ≧0.40 wt%, or ≧0.50 wt%, or ≧0.52 wt%, or ≧0.54 wt%, and / or ≦2.00 wt%, or ≦1.80 wt%, or ≦1.60 wt%, or ≦1.40 wt%, or ≦1.20 wt%, or ≦1.00 wt%, based on the weight of the composition.

[0125] R2] The composition of any one of A2] to Q2], wherein the composition comprises ≧50.0 wt%, or ≧60.0 wt%, or ≧70.0 wt%, or ≧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%, and / or ≦100.0 wt%, or ≦99.9 wt%, or ≦99.8 wt%, or ≦99.7 wt%, or ≦99.6 wt% of the sum of components a and b, based on the weight of the composition.

[0126] S2] component a is ≧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 ≦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.

[0127] T2] The composition according to any one of the above A2] to S2], wherein component a is an ethylene-based polymer.

[0128] U2] Component a is ≥ 0.854, or ≥ 0.856, or ≥ 0.858, or ≥ 0.860, or ≥ 0.862, or ≥ 0.864, or ≥ 0.866, or ≥ 0.868, or ≥ 0.870 g / cc, and / or ≤ 0.960, or ≤ 0.955, or ≤ 0.950, or ≤ 0.945, or ≤ 0.940, or ≤ 0.935, or ≤ 0.930, or The composition of any one of A2] to T2] above, wherein the composition has a density of ≦0.925, or ≦0.920, or ≦0.915, or ≦0.910, or ≦0.905, or ≦0.900, or ≦0.895, or ≦0.890, or ≦0.885, or ≦0.880, or ≦0.878, or ≦0.876, or ≦0.875, or ≦0.874 g / cc.

[0129] V2] The composition according to any one of A2] to U2] above, wherein component a has a melt index (I2) of ≧0.1, or ≧0.2, or ≧0.5, or ≧1.0, or ≧2.0, or ≧5.0, or ≧8.0, or ≧10, or ≧15, or ≧20, or ≧25 dg / min, and / or ≦2000, or ≦1000, or ≦500, or ≦200, or ≦100, or ≦50, or ≦40, or ≦30 dg / min.

[0130] W2] Component a is represented by the formula A 1 L 1 L 2 A 2 Telechelic polyolefins of formula A 1 L 1 The composition according to any one of A2] to V2] above, wherein the copolymer is selected from the group consisting of unsaturated polyolefins, ethylene / alpha-olefin / non-conjugated polyene copolymers, and ethylene / alpha-olefin copolymers.

[0131] X2] The composition according to any one of the above A2] to W2], wherein the composition is heat-treated at a temperature of ≥ 80°C, or ≥ 90°C, or ≥ 100°C, or ≥ 110°C, or ≥ 120°C, or ≥ 130°C, or ≥ 140°C, and / or at a temperature of ≤ 200°C, or ≤ 190°C, or ≤ 180°C, or ≤ 170°C, or ≤ 160°C, or ≤ 155°C, and further heat-treated.

[0132] Y2] A crosslinked composition formed from the composition described in any one of A2] to X2] above.

[0133] A3] Component a is a compound of formula A 1 L 1 L 2 A 2 wherein L 1 The process of any one of A] to X] above, wherein is an ethylene-based polymer, further an ethylene / alpha-olefin interpolymer, and further an ethylene / alpha-olefin interpolymer.

[0134] B3] Alpha-olefins are C3-C 20 Alpha-olefins, further C3 to C 10 The process described in A3] above, or the composition described in A3] above, wherein the alpha-olefin is further propylene, 1-butene, 1-hexene or 1-octene, further propylene, 1-butene or 1-octene, further 1-butene or 1-octene, further 1-octene.

[0135] C3] Formula A 1 L 1 L 2 A 2 The process of A3] or B3] above, or the composition of A3] or B3] above, wherein the telechelic polyolefin has a melt index (I2) of ≧0.1, or ≧0.2, or ≧0.5, or ≧1.0, or ≧5.0, or ≧10, or ≧15, or ≧20, or ≧25 dg / min, and / or ≦2000, or ≦1000, or ≦500, or ≦200, or ≦100, or ≦50, or ≦45, or ≦40, or ≦35, or ≦30 dg / min.

[0136] D3] Component a is a compound of formula A 1 L 1 wherein L is an unsaturated polyolefin of the formula 1 The process described in any one of A] to X] above, or the composition described in any one of Y] to Y2] above, wherein is an ethylene-based polymer, further an ethylene / alpha-olefin interpolymer, and further an ethylene / alpha-olefin interpolymer.

[0137] E3] Alpha-olefins are C3-C 20 Alpha-olefins, further C3 to C 10 The process described in D3] above, or the composition described in D3] above, wherein the alpha-olefin is further propylene, 1-butene, 1-hexene or 1-octene, further propylene, 1-butene or 1-octene, further 1-butene or 1-octene, further 1-octene.

[0138] F3] Formula A 1 L 1 or ≧0.6, or ≧0.8, or ≧0.9, or ≧1.0, or ≧1.1, or ≧1.2, or ≧1.4, or ≧1.6, or ≧1.8, or ≧2.0, or ≧5.0, or ≧8.0, or ≧10, or ≧12 dg / min, and / or ≦2000, or ≦1000, or ≦500, or ≦200, or ≦100, or ≦50, or ≦45, or ≦35, or ≦30 dg / min.

[0139] G3] The process described in any one of A] to X] above, or the composition described in any one of Y] to Y2] above, wherein component a is an ethylene / alpha-olefin / non-conjugated polyene copolymer, further an ethylene / alpha-olefin / non-conjugated diene copolymer, further an ethylene / alpha-olefin / non-conjugated diene terpolymer.

[0140] H3] The process of G3] above, or the composition of G3] above, wherein the ethylene / alpha-olefin / non-conjugated polyene copolymer has a Mooney Viscosity (ML1+4, 125°C) of ≥ 2.0, or ≥ 5.0, or ≥ 10, or ≥ 12, or ≥ 14, or ≥ 16, or ≥ 18, and / or ≤ 60, or ≤ 55, or ≤ 50, or ≤ 45, or ≤ 40, or ≤ 35, or ≤ 30, or ≤ 25, or ≤ 22 dg / min.

[0141] I3] The process described in any one of A] to X] above, or the composition described in any one of Y] to Y2] above, wherein component a is an ethylene / alpha-olefin interpolymer, further an ethylene / alpha-olefin copolymer.

[0142] J3] Alpha-olefins are C3-C 20 Alpha-olefins, further C3 to C 10 The process described in I3] above, or the composition described in I3] above, wherein the alpha-olefin is further propylene, 1-butene, 1-hexene or 1-octene, further propylene, 1-butene or 1-octene, further 1-butene or 1-octene, further 1-octene.

[0143] K3] The process of I3] or J3] above, or the composition of I3] or J3] above, wherein the ethylene / alpha-olefin copolymer has a melt index (I2) of ≥ 0.1, or ≥ 0.2, or ≥ 0.5, or ≥ 1.0, or ≥ 2.0, or ≥ 4.0 dg / min, and / or ≤ 2000, or ≤ 1000, or ≤ 500, or ≤ 200, or ≤ 100, or ≤ 50, or ≤ 40, or ≤ 35 dg / min.

[0144] L3] The process according to any one of A] to X] or A3] to K3] above, or the composition according to any one of Y] to Y2] or A3] to K3] above, wherein component a has a molecular weight distribution MWD (= Mw / Mn) of ≥ 1.80, or ≥ 1.90, or ≥ 2.00, or ≥ 2.10, or ≥ 2.15, or ≥ 2.20, or ≥ 2.25, or ≥ 2.30, or ≥ 2.35, or ≥ 2.40, and / or ≤ 5.00, or ≤ 4.80, or ≤ 4.60, or ≤ 4.40, or ≤ 4.20, or ≤ 4.00, or ≤ 3.80, or ≤ 3.60, or ≤ 3.40, or ≤ 3.20, or ≤ 3.00.

[0145] M3] The process of any one of A] to X] or A3] to L3] above, or the composition of any one of Y] to Y2] or A3] to L3] above, wherein component a has a number average molecular weight Mn of ≥ 5,000, or ≥ 6,000, or ≥ 8,000, or ≥ 10,000, or ≥ 12,000, or ≥ 14,000, or ≥ 16,000, or ≥ 18,000, or ≥ 20,000 g / mol, and / or ≤ 120,000, or ≤ 100,000, or ≤ 80,000, or ≤ 60,000, or ≤ 55,000, or ≤ 50,000, or ≤ 45,000, or ≤ 4,0000, or ≤ 35,000 g / mol.

[0146] N3] The process of any one of A] to X] or A3] to M3] above, or the composition of any one of Y] to Y2] or A3] to M3] above, wherein component a has a V0.1(190°C) of ≥ 10 Pa s, or ≥ 50 Pa s, or ≥ 100 Pa s, or ≥ 200 Pa s, or ≥ 500 Pa s, or ≥ 800 Pa s, or ≥ 1000 Pa s, or ≥ 1200 Pa s, or ≥ 1400 Pa s, or ≥ 1500 Pa s, and / or ≤ 100,000 Pa s, or ≤ 50,000 Pa s, or ≤ 20,000 Pa s, or ≤ 10,000 Pa s, or ≤ 9,000 Pa s, or ≤ 8,000 Pa s, or ≤ 7,000 Pa s, or ≤ 6,000 Pa s. See the DMS test method in PCT International Publication No. WO2020 / 140067, which is incorporated herein by reference.

[0147] O3] The process of any one of A] to X] or A3] to N3] above, or the composition of any one of Y] to Y2] or A3] to N3] above, wherein component a has a rheology ratio (RR=V0.1 / V100, respectively, at 190°C) of ≥ 1.0, or ≥ 1.5, or ≥ 1.6, or ≥ 1.7, or ≥ 1.8, or ≥ 1.9, or ≥ 2.0, or ≥ 2.1, and / or ≤ 20, or ≤ 15, or ≤ 10, or ≤ 8.0, or ≤ 6.0, or ≤ 5.5, or ≤ 5.2, or ≤ 5.0, or ≤ 4.8, or ≤ 4.6, or ≤ 4.5. See DMS test method above.

[0148] P3] The process of any one of A]-X] or A3]-O3] above, or the composition of any one of Y]-Y2] or A3]-O3] above, wherein component a has a tan delta (0.1 rad / sec, 190°C) of ≥ 3.0, or ≥ 3.5, or ≥ 4.0, or ≥ 4.5, or ≥ 5.0, or ≥ 5.5, or ≥ 6.0, or ≥ 7.0, or ≥ 8.0, or ≥ 9.0, or ≥ 10, and / or ≤ 70, or ≤ 65, or ≤ 60, or ≤ 55. See DMS test method above.

[0149] Q3] The process of any one of A] to X] or A3] to P3] above, or the composition of any one of Y] to Y2] or A3] to P3] above, wherein component a has a % vinyl of ≥ 2.0%, or ≥ 4.0%, or ≥ 6.0%, or ≥ 8.0%, or ≥ 10%, or ≥ 15%, or ≥ 20%, or ≥ 25%, or ≥ 30%, or ≥ 35%, or ≥ 40%, or ≥ 45%, or ≥ 50%, and / or ≤ 90%, or ≤ 85%, or ≤ 80%, or ≤ 75%, or ≤ 70%, or ≤ 65%, where % vinyl = [(vinyl / 1000C) / (total unsaturation / 1000C)] x 100.

[0150] R3] component a is ≧0.02 / 1000C, or ≧0.05 / 1000C, or ≧0.10 / 1000C, or ≧0.20 / 1000C, or ≧0.23 / 1000C, or ≧0.26 / 1000C, or ≧0.28 / 1000C, or ≧0.30 / 1000C, or ≧0.32 / 1000C, or ≧0.34 / 1000C, or ≧0.36 / 1000C; and / or a vinyl content of ≦0.80 / 1000C, or ≦0.75 / 1000C, or ≦0.70 / 1000C, or ≦0.65 / 1000C, or ≦0.62 / 1000C, or ≦0.65 / 1000C.

[0151] S3] Component a is ≧0.08 / 1000C, or ≧0.10 / 1000C, or ≧0.20 / 1000C, or ≧0.30 / 1000C, or ≧0.40 / 1000C, or ≧0.42 / 1000C, or ≧0.44 / 1000C, or ≧0.46 / 1000C, or ≧0.48 / 1000C, or ≧0.50 / 1000C, or ≧0. The process of any one of A] to X] or A3] to R3] above, or the composition of any one of Y] to Y2] or A3] to R3] above, having a combined vinyl and vinylidene content of 52 / 1000C, and / or ≦1.00 / 1000C, or ≦0.95 / 1000C, or ≦0.90 / 1000C, or ≦0.85 / 1000C.

[0152] T3] The process of any one of A] to X] or A3] to S3] above, or the composition of any one of Y] to Y2] or A3] to S3] above, wherein component a has a % vinylidene of ≥ 2.0%, or ≥ 4.0%, or ≥ 6.0%, or ≥ 8.0%, or ≥ 10%, or ≥ 15%, or ≥ 17%, or ≥ 20%, or ≥ 22%, or ≥ 24%, and / or ≤ 60%, or ≤ 58%, or ≤ 56%, or ≤ 54%, or ≤ 52%, or ≤ 50%, or ≤ 48%, or ≤ 46%, or ≤ 44%, where % vinylidene = [(vinylidene / 1000C) / (total unsaturations / 1000C)] x 100.

[0153] U3] The process of any one of A] to X] or A3] to T3] above, or the composition of any one of Y] to Y2] or A3] to T3] above, wherein component a has a vinylidene content of ≧0.02 / 1000C, or ≧0.04 / 1000C, or ≧0.06 / 1000C, or ≧0.08 / 1000C, or ≧0.10 / 1000C, and / or ≦0.38 / 1000C, or ≦0.36 / 1000C, or ≦0.34 / 1000C, or ≦0.32 / 1000C, or ≦0.30 / 1000C, or ≦0.29 / 1000C, or ≦0.25 / 1000C.

[0154] V3] Component a is ≥ 0.20%, or ≥ 0.40%, or ≥ 0.60%, or ≥ 0.80%, or ≥ 1.0%, or ≥ 1.5%, or ≥ 2.0%, or ≥ 3.0%, or ≥ 4.0%, or ≥ 5.0%, or ≥ 6.0%, or ≥ 7.0%, or ≥ 8.0%, or ≥ 9.0%, or ≥ 10%, and / or ≤ 50%, or ≤ 45%, or ≤ 40%, or The process of any one of A] to X] or A3] to U3] above, or the composition of any one of Y] to Y2] or A3] to U3] above, wherein the vinylene % is ≦35%, or ≦30%, or ≦25%, or ≦22%, or ≦20%, or ≦18%, or ≦15%, where vinylene %=[(vinylene / 1000C) / (total unsaturation / 1000C)]×100.

[0155] W3] component a is ≧0.10%, or ≧0.15%, or ≧0.20%, or ≧0.25%, or ≧0.30%, or ≧0.40%, or ≧0.50%, or ≧0.60%, or ≧0.70%, or ≧0.80%, or ≧0.90%, or ≧1.0%, or ≧1.1%, or ≧1.2%, or ≧1.3%, or ≧1.4%, and / or ≦25%, or ≦20%, or ≦10%, or ≦9.0%, or ≦8.0%, or ≦7.0%, or ≦6.0%, or ≦5.8%, or ≦5.6%, where trisubstitution %=[(trisubstitution / 1000C) / (total unsaturation / 1000C)]×100.

[0156] X3] The process of any one of A] to X] or A3] to W3] above, or the composition of any one of Y] to Y2] or A3] to W3] above, wherein the composition comprises ≥ 90.0 wt%, or ≥ 92.0 wt%, or ≥ 94.0 wt%, or ≥ 96.0 wt%, or ≥ 98.0 wt%, or ≥ 98.1 wt%, or ≥ 98.2 wt%, or ≥ 98.3 wt%, or ≥ 98.4 wt%, or ≥ 98.5 wt%, and / or ≤ 100.0 wt%, or ≤ 99.9 wt%, or ≤ 99.8 wt%, or ≤ 99.7 wt%, or ≤ 99.6 wt%, or ≤ 99.5 wt% of component a, based on the weight of the composition.

[0157] Y3] The process according to any one of A] to X] or A3] to X3] above, or the composition according to any one of Y] to Y2] or A3] to X3] above, wherein the weight ratio of component a to component b is ≧50, or ≧60, or ≧70, or ≧80, or ≧90, or ≧100, and / or ≦200, or ≦190, or ≦180, or ≦170, or ≦160, or ≦150, or ≦145, or ≦140, or ≦135, or ≦130.

[0158] Z3] The process described in any one of A] to X] or A3] to Y3] above, or the composition described in any one of Y] to Y2] or A3] to Y3] above, wherein the composition comprises a crosslinking coagent (component c).

[0159] A4] The process of Z3] above, or the composition of Z3] above, wherein component c is present in an amount of ≧0.10 wt%, or ≧0.20 wt%, or ≧0.30 wt%, or ≧0.40 wt%, or ≧0.50 wt%, and / or ≦1.0 wt%, or ≦0.95 wt%, or ≦0.90 wt%, or ≦0.85 wt%, or ≦0.80 wt%, based on the weight of the composition.

[0160] B4] The process of Z3] or A4] above, or the composition of any one of Z3] or A4] above, wherein the weight ratio of component b to component c is ≧0.50, or ≧0.60, or ≧0.70, or ≧0.80, or ≧0.90, or ≧1.0, or ≧1.1, and / or ≦5.0, or ≦4.5, or ≦4.0, or ≦3.5, or ≦3.0, or ≦2.5, or ≦2.0, or ≦1.9, or ≦1.8, or ≦1.7, or ≦1.6.

[0161] C4] The process described in any one of A] to X] or A3] to B4] above, or the composition described in any one of Y] to Y2] or A3] to B4] above, wherein the composition further comprises at least an additive.

[0162] D4] The process described in any one of A] to X] or A3] to C4] above, or the composition described in any one of Y] to Y2] or A3] to C4] above, wherein the composition further comprises a polymer that differs from component a in one or more characteristics, such as comonomer type, comonomer content, Mn, Mw, MWD, V0.1, V100, or RR.

[0163] E4] The process of any one of A] to X] or A3] to D4] above, or the composition of any one of Y] to Y2] or A3] to D4] above, wherein the composition comprises, based on the weight of the composition, ≦10 ppm, or ≦5.0 ppm, or ≦2.0 ppm, or ≦1.0 ppm, or ≦0.5 ppm of a silane coupling agent, and further wherein the composition is free of a silane coupling agent.

[0164] F4] The composition has a percent change (Δ) in T90 of ≧−80%, or ≧−70%, or ≧−65%, or ≧−60%, or ≧−55%, or ≧−50%, or ≧−45%, or ≧−40%, and / or ≦−10%, or ≦−15%, or ≦−20%, or ≦−25%, or ≦−30% (when compared to a comparative composition that is similar to the composition in question except that the comparative composition contains TBEC (tert-butylperoxy-2-ethylhexyl carbonate) as the peroxide), where Δ% in T90=[(T90 比較 -T90 TBEC ) / (T90 TBEC )] × 100, where T90 比較 is the T90 value of the composition, and T90 TBEC The process of any one of A] to X] or A3] to E4] above, or the composition of any one of Y] to Y2] or A3] to E4] above, wherein the value is the T90 of a comparative composition. The T90 value is determined according to the MDR test described below.

[0165] G4] The composition has a percent change (Δ) in MH of ≧−40%, or ≧−35%, or ≧−30%, or ≧−25%, or ≧−20%, or ≧−15%, or ≧−10%, or ≧5.0%, or ≧0%, or ≧2.0%, or ≧4.0%, or ≧6.0%, or ≧8.0%, or ≧10%, or ≧20%, or ≧30%, and / or ≦400%, or ≦350%, or ≦300%, or ≦250%, or ≦200%, or ≦150%, or ≦100%, or ≦90%, or ≦80%, or ≦70%, or ≦60%, or ≦50%, or ≦40% (when compared to a comparative composition that is similar to the composition in question except that the comparative composition contains TBEC as the peroxide), where Δ% in MH=[(MH 比較 -MH TBEC ) / (MH TBEC )] × 100, where MH 比較 is the MH value of the composition, and MH TBECThe process of any one of A] to X] or A3] to F4] above, or the composition of any one of Y] to Y2] or A3] to F4] above, wherein the value is the MH of a comparative composition. The MH value is determined according to the MDR test described below.

[0166] H4] The composition has a percent change (Δ) in MH of ≥ 2.0%, or ≥ 5.0%, or ≥ 10%, or ≥ 20%, or ≥ 30%, or ≥ 40%, or ≥ 50%, or ≥ 60%, or ≥ 80%, or ≥ 100%, and / or ≤ 400%, or ≤ 350%, or ≤ 300%, or ≤ 250%, or ≤ 200% (when compared to a comparative composition that is similar to the composition in question except that the comparative composition contains TBEC as the peroxide), where %Δ% in MH = [(MH 比較 -MH TBEC ) / (MH TBEC )] × 100, where MH 比較 is the MH value of the composition, and MH TBEC The process of any one of A] to X] or A3] to G4] above, or the composition of any one of Y] to Y2] or A3] to G4] above, wherein the value is the MH of a comparative composition. The MH value is determined according to the MDR test described below.

[0167] I4] The process of any one of A] to X] or A3] to H4] above, or the composition of any one of Y] to Y2] or A3] to H4] above, wherein the composition has a [Mn x(Total Unsat / 1000C)] value of ≧4.0, or ≧4.5, or ≧5.0, or ≧5.5, or ≧6.0, or ≧6.5, or ≧7.0, or ≧8.0, or ≧8.5, and / or ≦50, or ≦45, or ≦43, or ≦40, or ≦35, or ≦30, or ≦28, or ≦26, or ≦24, or ≦22 kg / mol.

[0168] J4] The process described in any one of A] to X] or A3] to I4] above, or the composition described in any one of Y] to Y2] or A3] to I4] above, wherein the composition is crosslinked by the application of heat alone.

[0169] K4] The process described in any one of A] to X] or A3] to I4] above, or the composition described in any one of Y] to Y2] or A3] to I4] above, wherein the composition is crosslinked by the application of heat and radiation.

[0170] L4] An article comprising at least one component formed from the composition described in any one of Y] to Y2] or A3] to K4] above.

[0171] M4] An article according to L4] above, wherein the article is a film, or a foam, further a film.

[0172] N4] The article of L4] above, wherein the article is a solar cell module, a wire or cable, a footwear part, an automotive part, a window frame, a tire, a tube / hose, or a roofing membrane, further a solar cell module, a wire or cable, a footwear part, an automotive part, further a solar cell module.

[0173] O4] The article of L4] above, wherein the article is an encapsulation film for a solar cell module.

[0174] P4] The article of L4] above, wherein the article is a solar cell module comprising a front transparent surface protective layer, a front crosslinked encapsulating film, a solar cell element, a back crosslinked encapsulating film, and a back transparent surface protective layer.

[0175] Q4] A lamination process for preparing a solar cell module, comprising crosslinking a film formed from the composition described in any one of A2] to X2] or A3] to K4] above.

[0176] R4] A process for forming a crosslinked composition, comprising thermally treating a composition described in any one of A2] to X2] or A3] to K4] above.

[0177] S4] A crosslinked composition formed from the process described in any one of A] to X] or A3] to K4] above.

[0178] Test Method Moving Die Rheometer (MDR) Testing Cure properties were measured using an Alpha Technology Working Die Rheometer (MDR) 2000 according to ASTM D5289, using a 0.5-degree arc on the pellets, which were then stored in bottles at room temperature for 24 hours after immersion. For each composition, approximately 4.5 g of pellets were loaded into the MDR. The MDR was run for 25 minutes at 150°C or 200°C, and a "time vs. torque" profile was generated at each interval. The following data was used for each MDR run: MH (dNm), i.e., the maximum torque exerted by the MDR during the 25-minute test interval (which usually corresponds to the torque exerted at the 25-minute point), ML (dNm), i.e., the minimum torque exerted by the MDR during the 25-minute test interval (which usually corresponds to the torque exerted at the beginning of the test interval), and T90 (the time required to reach 90% of the (MH-ML) value).

[0179] 1 H NMR method Sample preparation: Each sample was prepared in a NORELL 1001-7, 10 mm, NMR tube by adding approximately 130 mg of sample to 3.25 g of 50 / 50 by weight tetrachloroethane-d₂ / perchloroethylene (TCE-d₂ / PCE) containing 0.001 M Cr(AcAc)₃. The sample was purged by bubbling N₂ through the solvent via a pipette inserted into the tube for approximately 5 minutes to prevent oxidation. The tube was then capped and sealed with Teflon tape before being heated to 115°C and vortex mixed to obtain a homogeneous solution.

[0180] Data acquisition parameters and data analysis: Bruker AVANCE 600 MHz spectrometer equipped with a Bruker high-temperature CryoProbe and a sample temperature of 120°C. 1 H NMR was performed. Two experiments were performed to obtain a spectrum for quantifying total polymer protons, a control spectrum, and a double presaturation experiment to suppress the strong peaks associated with the polymer chains and enable a highly sensitive spectrum for quantification of end groups. This control was performed with a ZG pulse, 16 scans, AQ 1.82 s, D1 (relaxation delay) 14 s. A double presaturation experiment was performed with a modified pulse sequence, lc1prf2.zz, 64 scans, AQ 1.82 s, D1 (presaturation time) 2 s, D 13 The relaxation delay was 12 seconds. The unsaturation measurements were performed according to the following method: The areas under the resonances from the polymer chains (i.e., CH, CH2, and CH3 in the polymer) were measured from the spectrum obtained during the first experiment (control spectrum) described above.

[0181] The degree of unsaturation was analyzed using the method of Reference 3 below. Reference 1: Z. Zhou, R. Kuemmerle, JC Stevens, D. Redwine, Y. He, X. Qiu, R. Cong, J. Klosin, N. Montanez, G. Roof, Journal of Magnetic Resonance, 2009, 200, 328.

[0182] Reference 2: Z. Zhou, R. Kummerle, X. Qiu, D. Redwine, R. Cong, A. Taha, D. Baugh, B. Winniford, Journal of Magnetic Resonance: 187 (2007) 225. Reference 3: Z. Zhou, R. Cong, Y. He, M. Paradkar, M. Demirors, M. Cheatham, W. deGroot, Macromolecular Symposia, 2012, 312, 88.

[0183] The peak areas for each type of unsaturation observed (i.e., vinyl, vinylidene, vinylene, trisubstituted, cyclohexene, and ethylidene norbornene endo and exo isomers from EPDM unsaturation) were measured from the spectra obtained during the second (presaturation) experiment described above. In the case of the EPDM spectrum, overlapping peak areas were appropriately compensated for. Both spectra were normalized to the solvent peak area. The moles of each unsaturation were calculated by dividing the area under the unsaturated resonance by the number of protons contributing to that resonance. The moles of carbon in the polymer were calculated by dividing the area under the polymer chain peak (i.e., CH, CH, and CH in the polymer) by 2. The amount of total unsaturation (the sum of the above unsaturations) was then expressed as the relative ratio of moles of total unsaturation to moles of carbon in the polymer, expressed as unsaturations per 1000 carbons (per 1000C). It should be noted that the results for the EPDM sample in TCE-d2 / PCE can be calculated from the spectrum obtained using 1,4-orthodichlorobenzene-d4 / PCE to eliminate the TCE peak interference with the single vinyl proton at approximately 5.9 ppm. The results are the same within <5% relative.

[0184] Mooney viscosity of polymers (oil-free, unfilled) Mooney viscosity (ML1+4 at 125°C) was measured according to ASTM 1646 using a 1 minute warm-up time and a 4 minute rotor run time. The instrument was an Alpha Technology Mooney Viscometer 2000. Samples were approximately 25 grams in size.

[0185] Melt Index The melt index I2 (MI) of ethylene-based polymers is measured according to ASTM D-1238, condition 190°C / 2.16 kg. The melt flow rate MFR of propylene-based polymers is measured according to ASTM D-1238, condition 230°C / 2.16 kg.

[0186] Polymer Density ASTM D4703 was used to prepare polymer plaques for density analysis. ASTM D792, Method B was used to measure the density of each polymer.

[0187] Gel test Lamination: Plaques (9 pieces in one mold) of each composition, measuring 3 cm x 3 cm x 0.5 mm (thickness), were prepared by compression molding at 100°C (2 minutes of preheating and 2 minutes of 10 MPa pressure). Each plaque was cured during lamination on a SHUNHONG SH-X-1000 laminator. Each plaque (3 cm x 3 cm x 0.5 mm) was placed on a 0.15 mm thick PTFE film, which was then placed on a 3 mm thick glass substrate in a 3 cm x 3 cm x 0.5 mm metal frame (9 pieces in one mold), and another 0.15 mm thick PTFE film was placed on top of the plaque. Lamination was performed at 150°C using a two-step process: 1) 4 minutes of preheating (at 150°C) under vacuum without pressure, and 2) 4, 6, 8, 10, or 12 minutes of curing at 150°C with 1 bar pressure. Thus, the total lamination time was 8 (4+4), 10 (4+6), 12 (4+8), 14 (4+10), or 16 (4+12) minutes.

[0188] The cured plaques prepared from the lamination process were cut into 3 mm x 3 mm pieces. Approximately 0.5 g of the sample (Ws) was then sealed in a metal mesh (mesh number 120) to form a filled sample, and the filled sample was weighed (Wt1). The filled sample was placed in a glass bottle (250 mL) containing xylene (100 mL) for 24 hours. The filled sample was then transferred to a flask (500 mL) equipped with a condenser and containing 350 mL of xylene. After refluxing for 5 hours, the filled sample was removed from the xylene, placed in a vacuum oven, and heated at 120°C under vacuum conditions for 2 hours. The filled sample was then removed from the oven and weighed (Wt2). Gel content = (Wt2 - Wt1) / Ws * 100%.

[0189] Gel Permeation Chromatography Ethylene-Based Polymers The chromatographic system consisted of a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph (Gel Permeation Chromatograph) equipped with an internal IR5 infrared detector (IR5). The autosampler oven compartment was set to 160 °C, and the column compartment was set to 150 °C. The columns were four Agilent "Mixed A" 30 cm, 20 micron linear mixed-bed columns. The chromatographic solvent was 1,2,4-trichlorobenzene containing 200 ppm butylated hydroxytoluene (BHT). The solvent source was sparged with nitrogen. The injection volume was 200 microliters, and the flow rate was 1.0 milliliters / minute.

[0190] The GPC column set was calibrated using 21 narrow molecular weight distribution polystyrene standards ranging from 580 to 8,400,000 g / mol. These standards were prepared as six "cocktail" mixtures with at least a 10-fold separation between individual molecular weights. The standards were purchased from Agilent Technologies. The polystyrene standards were prepared at 0.025 grams in 50 milliliters of solvent for molecular weights above 1,000,000 and 0.05 grams in 50 milliliters for molecular weights below 1,000,000. The polystyrene standards were dissolved at 80°C with gentle agitation for 30 minutes. The polystyrene standard peak molecular weights were converted to polyethylene molecular weights using Equation 1 (as described by Williams and Ward, J. Polym. Sci., Polym. Lett., 6, 621 (1968)). M ポリエチレン =A×(M ポリスチレン ) B (Formula 1) where M is the molecular weight, A has a value of 0.4315, and B is equal to 1.0.

[0191] A fifth-order polynomial is used to fit each polyethylene-equivalent calibration point. A small adjustment (approximately 0.375 to 0.445) is made to A to correct for column resolution and band broadening effects, such that a linear homopolymer polyethylene standard is obtained at 120,000 MW.

[0192] A total plate count for the GPC column set is performed using decane (prepared at 0.04 g in 50 milliliters of TCB and dissolved for 20 minutes with gentle agitation). Plate count (Equation 2) and symmetry (Equation 3) are measured with a 200 microliter injection according to the following equations:

[0193]

number

[0194]

number

[0195] Samples are prepared semi-automatically using PolymerChar "Instrument Control" software to target a sample weight of 2 mg / mL, and the solvent (containing 200 ppm BHT) is added via the PolymerChar high-temperature autosampler to a septa-capped vial that has been pre-sparged with nitrogen. The sample is dissolved at 160°C for 2 hours under "slow" shaking.

[0196] Mn (GPC) , Mw (GPC) , and Mz (GPC) is calculated based on the GPC results using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatogram according to Equations 4-6 using PolymerChar GPCOne™ software, a baseline-subtracted IR chromatogram at each equally spaced data collection point (i), and the polyethylene equivalent molecular weight obtained from a narrow standard calibration curve at point (i) from Equation 1. Equations 4-6 are as follows:

[0197]

number

[0198] To monitor deviations over time, a flow rate marker (decane) is introduced into each sample via a micropump controlled by the PolymerChar GPC-IR system. This flow rate marker (FM) is used to linearly correct the pump flow rate (Flow Rate (Apparent)) for each sample by aligning the RV of each decane peak in the sample (RV (FM Sample)) with that of the decane peak in the narrow standard calibration (RV (FM Calibrated)). Any change in the time of the decane marker peak is then assumed to be related to a linear shift in flow rate (Flow Rate (Effective)) throughout the run. To facilitate the highest accuracy in the RV measurement of the flow rate marker peaks, a least-squares fitting routine is used to fit the peaks in the flow rate marker concentration chromatogram to a quadratic equation. The first derivative of the quadratic equation is then used to solve for the true peak position. After calibrating the system based on the flow marker peaks, the effective flow rate (for a narrow standard calibration) is calculated as per Equation 7: Flow Rate (Effective) = Flow Rate (Apparent) * (RV (FM Calibrated) / RV (FM Sample)) (Equation 7). Processing of the flow marker peaks is performed via PolymerChar GPCOne™ software. An acceptable flow rate correction is one where the effective flow rate is within + / - 0.7% of the apparent flow rate. The present specification includes the following aspects. Section 1: 1. A process for forming a crosslinked composition, said process comprising: a composition comprising at least the following components a) and b): a) an olefin-based polymer containing a total unsaturation value of ≥ 0.20 / 1000C; b) at least one peroxide selected from at least one of the following: i) a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical I, or ii) a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical II, or iii) a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical III, or iv) a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical IV, or v) applying heat, and optionally radiation, to a composition comprising any combination of i) to iv) and at least one peroxide selected from wherein radical I, radical II, radical III, or radical IV is respectively represented by the following: [ka] wherein R1, R2, and R3 are each independently selected from H, CH3, CH2-alkyl, or aryl, each of R1, R2, and R3 may be the same as or different from one or both of the other two, and at least one of R1, R2, or R3 is CH2-alkyl; [ka] wherein R1, R2, and R3 are each independently selected from H, CH3, CH2-alkyl, or aryl, each of R1, R2, and R3 may be the same as or different from one or both of the other two, and at least one of R1, R2, or R3 is CH2-alkyl; [ka] wherein R1 is CH2-alkyl; [ka] wherein R1 and R2 are selected from the following y) or z): y) R1 and R2 are each independently CH3 or CH2-alkyl, where R1 and R2 may be the same or different, and at least one of R1 or R2 is CH2-alkyl; or z) A process in which R1 and R2 are bonded together to form an aliphatic ring, the ring containing at least one -CH2- structure (R1-C(O·)(O·)-R2) adjacent to a quaternary carbon. Section 2: Item 1, the process of item 1, wherein component b is a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical I. Section 3: Item 1, the process according to item 1, wherein component b is a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical II. Section 4: Item 1, the process of item 1, wherein component b is a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical III. Section 5: Item 1, the process of item 1, wherein component b is a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical IV. Item 6: Item 6. The process according to any one of items 1 to 5, wherein component a is an ethylene-based polymer. Section 7: Component a is of formula A 1 L 1 L 2 A 2 Telechelic polyolefins of formula A 1 L 1 Item 7. The process according to any one of items 1 to 6, wherein the unsaturated polyolefin is selected from the group consisting of an ethylene / alpha-olefin / non-conjugated polyene copolymer and an ethylene / alpha-olefin copolymer. Section 8: A crosslinked composition formed by the process of any one of items 1 to 7. Section 9: A composition comprising at least the following components a) and b): a) an olefin-based polymer containing a total unsaturation value of ≥ 0.20 / 1000C; b) at least one peroxide selected from at least one of the following: i) a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical I, or ii) a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical II, or iii) a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical III, or iv) a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical IV, or v) any combination of i) to iv), and at least one peroxide selected from the group consisting of: wherein radical I, radical II, radical III, or radical IV is respectively represented by the following: [ka] wherein R1, R2, and R3 are each independently selected from H, CH3, CH2-alkyl, or aryl, each of R1, R2, and R3 may be the same as or different from one or both of the other two, and at least one of R1, R2, or R3 is CH2-alkyl; [ka] wherein R1, R2, and R3 are each independently selected from H, CH3, CH2-alkyl, or aryl, each of R1, R2, and R3 may be the same as or different from one or both of the other two, and at least one of R1, R2, or R3 is CH2-alkyl; [ka] wherein R1 is CH2-alkyl; [ka] wherein R1 and R2 are selected from the following y) or z): y) R1 and R2 are each independently CH3 or CH2-alkyl, where R1 and R2 may be the same or different, and at least one of R1 or R2 is CH2-alkyl; or z) A composition wherein R1 and R2 are joined together to form an aliphatic ring, said ring containing at least one -CH2- structure (R1-C(O·)(O·)-R2) adjacent to a quaternary carbon. Section 10: Item 10. The composition according to item 9, wherein component b is a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical I. Section 11: Item 10. The composition according to item 9, wherein component b is a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical II. Section 12: Item 10. The composition according to item 9, wherein component b is a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical III. Section 13: Item 10. The composition according to item 9, wherein component b is a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical IV. Section 14: Item 14. The composition according to any one of items 9 to 13, wherein component a is an ethylene-based polymer. Section 15: Component a is represented by the formula A 1 L 1 L 2 A 2 telechelic polyolefin of the formula A 1 L 1 Item 15. The composition according to any one of items 9 to 14, wherein the unsaturated polyolefin is selected from the group consisting of an ethylene / alpha-olefin / non-conjugated polyene copolymer and an ethylene / alpha-olefin copolymer. Section 16: Item 16. The composition according to any one of Items 9 to 15, wherein component a has a molecular weight distribution (MWD) (=Mw / Mn) of 1.80 to 5.00. Section 17: Item 17. The composition according to any one of items 9 to 16, wherein the composition contains 50.0 wt % to 100.0 wt % of the total of component a and component b, based on the weight of the composition. Section 18: The composition has a percent change in T90 (Δ) of -80% to -10% (when compared to a comparative composition similar to the composition except that the comparative composition contains TBEC (tert-butylperoxy-2-ethylhexyl carbonate) as the peroxide), and the Δ% change in T90 = [(T90 比較 -T90 TBEC ) / (T90 TBEC )] × 100, where T90 比較 is the T90 value of the composition, and TBEC Item 18. The composition according to any one of items 9 to 17, wherein the value is T90 of the comparative composition. Section 19: The composition has a percent change (Δ) in MH of -40% to 400% (when compared to a comparative composition similar to the composition except that the comparative composition contains TBEC (tert-butylperoxy-2-ethylhexyl carbonate) as the peroxide), and the Δ% in MH = [(MH 比較 -MH TBEC ) / (MH TBEC )] × 100, where MH 比較 is the MH value of the composition, and TBEC Item 19. The composition according to any one of items 9 to 18, wherein the value is MH of the comparative composition. Section 20: An article comprising at least one component formed from the composition according to any one of items 8 to 19.

[0199] experiment Commercially Available Polymers and Additives Commercially available polymers and additives are listed below: A summary of the olefin-based polymers used in the following studies is listed in Tables 1A-1C.

[0200] NORDEL 3720P EPDM, Mooney viscosity = 20 (ML 1+4 at 125°C), 0.5 wt% ENB, 69.5 wt% ethylene, available from The Dow Chemical Company. NORDEL 3722P EPDM, Mooney viscosity = 18 (ML 1+4 at 125°C), 0.5 wt% ENB, 70.5 wt% ethylene, available from The Dow Chemical Company.

[0201] ENGAGE PV 8669 Polyolefin Elastomer (POE), density = 0.873 g / cc, I² = 14 dg / min, available from The Dow Chemical Company. XUS38661.00 Experimental Polyolefin Elastomer (POE), ethylene / 1-octene copolymer: density = 0.8770-0.8830 g / cc, I² = 14-22 dg / min, available from The Dow Chemical Company. ENGAGE 8407 Polyolefin Elastomer (POE), ethylene / 1-octene copolymer: density = 0.870 g / cc, I² = 30 dg / min, available from The Dow Chemical Company. EVA E282PV (ethylene vinyl acetate copolymer), density = 0.948 g / cc, I2 = 25 dg / min, VA content 28 wt%, available from Hanwha.

[0202] Vinyl D4: 2,4,6,8-tetramethyl-2,4,6,8-tetravinyl-cyclotetrasiloxane (CAS number 2554-06-5, monocyclic organosiloxane), available from The Dow Chemical Company. TAIC (Tri Allyl Iso Cyanurate): triallyl isocyanurate, manufactured by Hunan Farida Technology Co. Ltd. VMMS: 3-(trimethoxy-silyl)propyl methacrylate, manufactured by The Dow Chemical Company. TMPTA (Tri Methylol Propane Tri Acrylate): trimethylolpropane triacrylate [15625-89-5], available from SCRC. TBEC (Tert-Butyl-peroxy-2-Ethylhexyl Carbonate): tert-butyl-peroxy-2-ethylhexyl carbonate [34443-12-4], manufactured by Arkema

[0203] [ka] TAEC (Tert-Amylperoxy-2-Ethylhexyl Carbonate): tert-Amylperoxy-2-ethylhexyl carbonate [70833-40-8], manufactured by Arkema

[0204] [ka] TRIGANOX 301: 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane [24748-23-0], manufactured by Akzo

[0205] [ka] LUPEROX 26: tert-butylperoxy-2-ethylhexanoate, manufactured by Arkema

[0206] [ka] TMCH-90MO: 1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane [6731-36-8], 90%, manufactured by Qiangsheng Chemical Co., Ltd.

[0207] [ka] CH-80MO: 1,1-di-(tert-butylperoxy)cyclohexane [3006-86-8], 80%, manufactured by Qiangsheng Chemical Co., Ltd.

[0208] [ka]

[0209] [Table 1] Note that % of specific unsaturation (pu%) = [(amount)]pu / 1000C) / (amount.total unsaturation / 1000C)] × 100, where pu% = vinyl%, vinylidene%, vinylene%, trisub%, or ENB%. EO = ethylene / octene copolymer

[0210] [Table 2] * CTA = TCHEA (tris-(2-(cyclohex-3-en-1-yl)ethyl)aluminum). ** CTA = TEA (triethylaluminum). EB = ethylene / butene copolymer Note that % of specific unsaturation (pu%) = {[(amount.pu / 1000C) / (amount.totalunsaturation / 1000C)] x 100}, where pu% = vinyl%, vinylidene%, vinylene%, trisub%, or ENB%.

[0211] [Table 3]

[0212] Polymer synthesis of EO1-EO9 and EB1-EB7 Preparation of BPP E (ligand disclosed in PCT International Publication No. WO2018 / 022975(A1))

[0213] [ka]

[0214] Synthesis of 6',6'''-(((diisopropylsilanediyl)bis(methylene))bis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-fluoro-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-ol)dimethyl-zirconium (BPP-E). MeMgBr in diethyl ether (3.00 M, 5.33 mL, 16.0 mmol) was added to a solution of ZrCl4 (0.895 g, 3.84 mmol) in toluene (60 mL) at -30 °C. After stirring for 3 minutes, solid ligand (5.00 g, 3.77 mmol) was added in small portions. The mixture was stirred for 8 hours, and then the solvent was removed under reduced pressure overnight to give a dark residue. Hexane / toluene (10:1, 70 mL) was added to the residue, and the solution was shaken at room temperature for several minutes. The material was then passed through a fritted funnel CELITE plug. The frit was extracted with hexane (2 × 15 mL). The combined extracts were concentrated to dryness under reduced pressure. Pentane (20 mL) was added to the tan solid, and the heterogeneous mixture was placed in a freezer (-35 °C) for 18 hours. The brown pentane layer was removed using a pipette, and the remaining material was dried under vacuum to give BPP-E (4.50 g, 83% yield) as a white powder.

[0215] 1 H NMR(400MHz,C6D6)δ 8.65-8.56(m, 2H), 8.40(dd, J=2.0, 0.7Hz, 2H), 7.66-7.55(m, 8H), 7.45(d, J=1.9Hz, 1H), 7.43(d, J=1.9Hz, 1H), 7.27(d, J=2.5Hz, 2H), 7.10(d, J=3.2Hz, 1H), 7.08(d, J=3.1Hz, 1H), 6.80(ddd, J=9.0, 7.4, 3.2Hz, 2H), 5.21(dd, J=9.1, 4.7Hz, 2H), 4.25(d, J=13.9Hz, 2H), 3.23(d, J=14.0Hz, 2H), 1.64-1.52(m, 4H), 1.48(s, 18H) ), 1.31(s, 24H), 1.27(s, 6H), 0.81(s, 18H), 0.55(t, J=7.3Hz, 12H), 0.31(hept, J=7.5Hz, 2H), -0.84(s, 6H), 19 F NMR (376MHz, C6D6) δ-116.71.

[0216] EO2 (ethylene / octene copolymer) - a representative polymerization EO2 was prepared in a hydraulically charged, one-gallon polymerization reactor operated at steady-state conditions. The catalyst and cocatalyst are listed in Table 2. Solvent, hydrogen, catalyst, and cocatalyst were fed to the reactor according to the process conditions outlined in Tables 3A-3C. The solvent was ISOPAR E, supplied by ExxonMobil Chemical Company. The reactor temperature was measured at or near the reactor exit. The copolymer was isolated and pelletized.

[0217] [Table 4] * The methyl is modified with an n-octyl substituent such that the n-octyl ratio is about 6:1, and 10 to Contains 20% (mol%) of trialkylaluminum species.

[0218] [Table 5]

[0219] [Table 6] * "ppm" amounts based on the weight of the respective catalyst feed solution.

[0220] [Table 7] * "ppm" amount based on weight of cocatalyst feed solution. ** The "ppm" amount of Al based on the weight of the cocatalyst feed solution.

[0221] EO Tele 1 and Mono 2, 3, 4, 5, 6, 7 Synthesis of tris(2-(cyclohex-3-en-1-yl)ethyl)aluminum chain transfer agent ("CTA 1") In a drybox, 4-vinyl-1-cyclohexene (3.2 mL, 24.6 mmol) and tri-isobutylaluminum (2.0 mL, 7.92 mmol) were added to 5 mL of decane in a vial equipped with a stir bar and a vent needle in the cap. The mixture was heated at 120° C. with stirring for 3 hours. 1 A sample was dissolved in benzene-d6 for H NMR analysis, and another aliquot was hydrolyzed with water and analyzed by GC / MS. 1 H NMR showed that all vinyl groups had reacted, leaving an internal double bond. GC / MS showed a distinct peak at m / z 110, consistent with the molecular weight of ethylcyclohexene. Therefore, as shown below, 1 H NMR and GC / MS confirmed the synthesis of tris(2-(cyclohex-3-en-1-yl)ethyl)aluminum (“CTA”) according to non-limiting Scheme 1.

[0222] [ka]

[0223] catalyst Catalyst 1 may be prepared according to the teachings of PCT International Publication No. WO 03 / 40195 and U.S. Pat. No. 6,953,764 B2 and has the following structure:

[0224] [ka]

[0225] Catalyst 2 may be prepared according to the teachings of PCT International Publication No. WO2011 / 102989(A1) and has the following structure:

[0226] [ka]

[0227] Catalyst 3 may be prepared according to the teachings of PCT International Publication No. WO2007 / 136496(A2) and has the following structure:

[0228] [ka]

[0229] Polymerization of EO Tele 1 (see PCT International Publication No. WO2020 / 140058) EO Tele 1(A 1 L 1 L 2 A 2) was prepared by continuous solution polymerization as follows. Polymerization was carried out in a computer-controlled autoclave reactor equipped with an internal stirrer. Purified mixed alkane solvent (ISOPAR E, available from ExxonMobil), monomer, and molecular weight regulator (hydrogen or chain transfer agent) were fed into a 3.8 L reactor jacketed for temperature control. Solvent feed to the reactor was measured by a mass flow controller. A variable-speed diaphragm pump controlled the solvent flow rate and pressure to the reactor. At the pump outlet, a side stream was taken to provide a steep flow to the procatalyst, activator, and chain transfer agent (CTA) (catalyst component solution) injection lines. These streams were measured by mass flow meters and controlled by control valves. The remaining solvent was mixed with monomer and hydrogen and fed to the reactor. The temperature of the solvent / monomer solution was controlled using a heat exchanger before entering the reactor. This stream entered the bottom of the reactor. The catalyst component solutions were metered using pumps and mass flow meters and combined with the catalyst flush solvent into the bottom of the reactor. The reactor was filled with liquid at 500 psig under vigorous stirring. Polymer was removed through an outlet line at the top of the reactor. All outlet lines from the reactor were vapor traced and insulated. The product stream was then heated to 230°C by passing it through a post-reactor heater (PRH), where beta-H removal of the polymer-Al was performed. A small amount of isopropyl alcohol, along with any stabilizers or other additives, was added after the PRH and before devolatilization. The polymer product was recovered by extrusion using a devolatilization extruder. The polymerization process conditions and results before the post-reactor heating (PRH) are listed in Tables 4A and 4B.

[0230] The abbreviations in the table are explained as follows: "Co." stands for comonomer; "sccm" stands for standard cm 3 / min. "T" refers to temperature. "Cat" refers to procatalyst. "CAT1" refers to procatalyst (CAT1). "CoCAT-1" refers to cocatalyst as defined in Table 2. "CTA" refers to chain transfer agent. "Poly Rate" refers to polymer production rate. "Conv" refers to ethylene conversion in the reactor, and "Eff" refers to efficiency (kg polymer / mg catalyst metal).

[0231] [Table 8] * "ppm" amounts based on the weight of each feed solution.

[0232] [Table 9] * "ppm" amounts based on the weight of each feed solution.

[0233] Polymerization of EO Mono 2 (see PCT International Publication No. WO2020 / 140067), EO Mono 3, 4, 5, 6, and 7 EO Mono 2, 3, 4, 5, 6, 7 (A 1 L 1 Continuous solution polymerization of EO Tele 1 was carried out in a manner similar to that of EO Tele 1 (see above). The polymerization conditions and results before post-reactor heating (PHR) are listed in Tables 5A and 5B. Here, "TEA" stands for triethylaluminum, "CAT2" stands for procatalyst (CAT2), "CAT3" stands for procatalyst (CAT3), "CoCAT-3" refers to the cocatalyst defined in Table 2, and "Armeen" refers to Armeen™ M2HT. For other abbreviations, see "EO Tele 1 Polymerization" above.

[0234] [Table 10] * "ppm" amounts based on the weight of each feed solution.

[0235] [Table 11] The CTA for EO Mono 2 to EO Mono 7 was TEA. * "ppm" amounts based on the weight of each feed solution.

[0236] Preparation of the composition - soaking For each composition, polymer pellets were mixed with curing additives (peroxide, optional coagent, and optional silane coupling agent) in a 250 mL fluoride HDPE bottle. The immersion process was performed by shaking and allowed to soak for 5 hours at 50°C until no residue was visually visible on the bottle. The compositions and curing properties are shown in Tables 6-19.

[0237] result For compositions containing highly unsaturated olefinic polymers, replacing TBEC with alternative carbonate peroxides such as TAEC, ketal peroxides such as 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane and 1,1-di(tert-butylperoxy)cyclohexane, or combinations thereof, reduced T90 but generally increased MH values ​​compared to compositions containing olefinic polymers with low unsaturation (<0.20 / 1000C). Note that inventive compositions I-1 through I-6, I-41, I-42, I-45, I-46, I-50, and I-51 had exceptional cure responses with significant decreases in T90 and increases in MH. These properties are relative to comparable compositions similar to the respective inventive compositions, except for the comparative compositions containing TBEC (tert-butylperoxy 2-ethylhexyl carbonate).

[0238] [Table 12]

[0239] [Table 13] A) Δ% in MH = [(MH 比較 -MH TBEC / (MH TBEC )] × 100, where MH 比較 is the MH value of the composition, and MH TBEC Values ​​are MH of the comparative composition. B) Δ% at T90 = [(T90 比較 -T90 TBEC ) / (T90 TBEC )] × 100, where T90 比較 is the T90 value of the composition, and T90 TBEC Values ​​are T90 of the comparative composition.

[0240] [Table 14]

[0241] [Table 15] A) Δ% in MH = [(MH 比較 -MH TBEC / (MH TBEC )] × 100, where MH 比較 is the MH value of the composition, and MH TBEC Values ​​are MH of the comparative composition.

[0242] B) Δ% at T90 = [(T90 comparison - T90 TBEC ) / (T90 TBEC )] × 100, where T90 比較 is the T90 value of the composition, and T90 TBEC Values ​​are T90 of the comparative composition.

[0243] [Table 16]

[0244] [Table 17] A) Δ% in MH = [(MH 比較 -MH TBEC / (MH TBEC )] × 100, where MH 比較 is the MH value of the composition, and MH TBEC Values ​​are MH of the comparative composition.

[0245] B) Δ% at T90 = [(T90 比較 -T90 TBEC ) / (T90 TBEC )] × 100, where T90 比較 is the T90 value of the composition, and T90 TBEC Values ​​are T90 of the comparative composition.

[0246] [Table 18]

[0247] [Table 19]

[0248] [Table 20]

[0249] [Table 21]

[0250] [Table 22]

[0251] [Table 23]

[0252] [Table 24]

[0253] Table 25

Claims

1. 1. A process for forming a crosslinked composition, said process comprising: a composition comprising at least the following components a) and b): a) an olefin-based polymer comprising a total unsaturation level of ≥ 0.20 / 1000C; b) at least one peroxide selected from at least one of the following: ii) a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical II, or iii) a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical III, or v) applying heat, and optionally radiation, to a composition comprising a combination of ii) and iii), and at least one peroxide selected from wherein radical II or radical III is respectively shown below: 【Chemistry 2】 In the formula, R １ , R ２ and R ３ are each independently H, CH ３ , C.H. ２ - selected from alkyl or aryl, R １ , R ２ , and R ３ may be the same as or different from one or both of the other two, and R １ , R ２ , or R ３ At least one of ２ - alkyl, 【Transformation 3】 In the formula, R １ But CH ２ - alkyl, the process.

2. 2. The process of claim 1, wherein component b is a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical II.

3. 2. The process of claim 1, wherein component b is a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical III.

4. The process of any one of claims 1 to 3, wherein component a is an ethylene-based polymer.

5. Component a is represented by the following formula I:A １ L １ L ２ A ２ a telechelic polyolefin of the following formula II:A １ L １ 5. The process of claim 1, wherein the copolymer is selected from the group consisting of unsaturated polyolefins of formula (I), ethylene / alpha-olefin / non-conjugated polyene copolymers, or ethylene / alpha-olefin copolymers. Formula I: A 1 L 1 L 2 A 2 During the ceremony, A 1 is selected from the group consisting of a) a vinyl group, b) a vinylidene group of the formula CH 2 ═C(Y 1 )—, c) a vinylene group of the formula Y 1 CH═CH—, d) a combination of a vinyl group and a vinylene group of the formula Y 1 CH═CH—, e) a combination of a vinyl group and a vinylidene group of the formula CH 2 ═C(Y 1 )—, f) a combination of a vinylidene group of the formula CH 2 ═C(Y 1 )— and a vinylene group of the formula Y 1 CH═CH—, and g) a combination of a vinyl group, a vinylidene group of the formula CH 2 ═C(Y 1 )— and a vinylene group of the formula Y 1 CH═CH—, and Y 1 is independently a C 1 to C 30 hydrocarbyl group; L 1 is a polyolefin, and L 1 (divalent) is bonded to A 1 and L 2 ; L 2 is a C 1 -C 32 hydrocarbylene group; A 2 is a hydrocarbyl group containing a hindered double bond. Formula II: A 1 L 1 During the ceremony, A 1 is selected from the group consisting of a) a vinyl group, b) a vinylidene group of the formula CH 2 ═C(Y 1 )—, c) a vinylene group of the formula Y 1 CH═CH—, d) a combination of a vinyl group and a vinylene group of the formula Y 1 CH═CH—, e) a combination of a vinyl group and a vinylidene group of the formula CH 2 ═C(Y 1 )—, f) a combination of a vinylidene group of the formula CH 2 ═C(Y 1 )— and a vinylene group of the formula Y 1 CH═CH—, and g) a combination of a vinyl group, a vinylidene group of the formula CH 2 ═C(Y 1 )— and a vinylene group of the formula Y 1 CH═CH—, and Y 1 is independently a C 1 to C 30 hydrocarbyl group; L 1 is a polyolefin, and L 1 (monovalent) is bonded to A 1 .

6. A composition comprising at least the following components a) and b): a) an olefin-based polymer comprising a total unsaturation level of ≥ 0.20 / 1000C; b) at least one peroxide selected from at least one of the following: ii) a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical II, or iii) a peroxide containing at least one peroxy group containing an oxyl radical unit selected from radical III, or v) a combination of ii) and iii), and at least one peroxide selected from wherein radical II or radical III is respectively shown below: 【Chemistry 2】 In the formula, R １ , R ２ and R ３ are each independently H, CH ３ , C.H. ２ - selected from alkyl or aryl, R １ , R ２ , and R ３ may be the same as or different from one or both of the other two, and R １ , R ２ , or R ３ At least one of ２ - alkyl, 【Transformation 3】 In the formula, R １ But CH ２ -alkyl.

7. The composition of claim 6 wherein component a is an ethylene-based polymer.

8. Component a is represented by the following formula I:A １ L １ L ２ A ２ a telechelic polyolefin of the following formula II:A １ L １ 8. The composition according to claim 6, wherein the unsaturated polyolefin is selected from the group consisting of an ethylene / alpha-olefin / non-conjugated polyene copolymer and an ethylene / alpha-olefin copolymer. Formula I: A 1 L 1 L 2 A 2 During the ceremony, A 1 is selected from the group consisting of a) a vinyl group, b) a vinylidene group of the formula CH 2 ═C(Y 1 )—, c) a vinylene group of the formula Y 1 CH═CH—, d) a combination of a vinyl group and a vinylene group of the formula Y 1 CH═CH—, e) a combination of a vinyl group and a vinylidene group of the formula CH 2 ═C(Y 1 )—, f) a combination of a vinylidene group of the formula CH 2 ═C(Y 1 )— and a vinylene group of the formula Y 1 CH═CH—, and g) a combination of a vinyl group, a vinylidene group of the formula CH 2 ═C(Y 1 )— and a vinylene group of the formula Y 1 CH═CH—, and Y 1 is independently a C 1 to C 30 hydrocarbyl group; L 1 is a polyolefin, and L 1 (divalent) is bonded to A 1 and L 2 ; L 2 is a C 1 -C 32 hydrocarbylene group; A 2 is a hydrocarbyl group containing a hindered double bond. Formula II: A 1 L 1 During the ceremony, A 1 is selected from the group consisting of a) a vinyl group, b) a vinylidene group of the formula CH 2 ═C(Y 1 )—, c) a vinylene group of the formula Y 1 CH═CH—, d) a combination of a vinyl group and a vinylene group of the formula Y 1 CH═CH—, e) a combination of a vinyl group and a vinylidene group of the formula CH 2 ═C(Y 1 )—, f) a combination of a vinylidene group of the formula CH 2 ═C(Y 1 )— and a vinylene group of the formula Y 1 CH═CH—, and g) a combination of a vinyl group, a vinylidene group of the formula CH 2 ═C(Y 1 )— and a vinylene group of the formula Y 1 CH═CH—, and Y 1 is independently a C 1 to C 30 hydrocarbyl group; L 1 is a polyolefin, and L 1 (monovalent) is bonded to A 1 .

9. The composition according to any one of claims 6 to 8, wherein component a has a molecular weight distribution MWD (= Mw / Mn) of 1.80 to 5.

00.

10. The composition according to any one of claims 6 to 9, wherein the composition comprises 50.0% by weight to 100.0% by weight of the total of component a and component b, based on the weight of the composition.

11. the composition has a percent change (Δ) at T90 of −80% to −10% (when compared to a comparative composition that is similar to the composition except that the comparative composition contains TBEC (tert-butylperoxy-2-ethylhexyl carbonate) as the peroxide); T90 is the time to achieve 90% of (MH-ML), where MH is the maximum torque value applied by a moving die rheometer (MDR) to measure cure characteristics, and ML is the minimum torque value applied by the MDR; Δ% at T90 = [(T90 比較 -T90 ＴＢＥＣ ) / (T90 ＴＢＥＣ ) × 100, where T90 比較 is the T90 value of the composition, and the T90 ＴＢＥＣ The value is the T90 of the comparative composition. The composition according to any one of claims 6 to 10.

12. the composition has a percent change in MH (Δ) of from −40% to 400% (when compared to a comparative composition that is similar to the composition except that the comparative composition contains TBEC (tert-butylperoxy-2-ethylhexyl carbonate) as the peroxide); MH is the maximum torque value applied by a moving die rheometer (MDR) to measure cure characteristics; Δ% in the MH=[(MH 比較 -MH ＴＢＥＣ ) / (MH ＴＢＥＣ ) × 100, where MH 比較 is the MH value of the composition, and the MH ＴＢＥＣ The value is the MH of the comparative composition. The composition according to any one of claims 6 to 11.

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