Siloxane-modified and silane-modified polymers formed via direct insertion of silylvinyl groups into metal-carbon bonds

Abstract

The present invention provides methods of forming siloxane-modified olefin-based polymers, silane-modified olefin-based polymers, or silanes, each as described herein, and related compositions. Each method forms a Si-C bond by inserting a silylvinyl group into a metal carbon bond. Silylvinyl double bonds are inserted directly into the metal-carbon bonds to form, for example, new alkyl-Si linkages.

Description

Background Technology

[0001] Silicone / polyolefin (Si-POE) blends and graft copolymers are widely used in many applications, where the characteristics of silicon impart modified surface properties (reduced coefficient of friction or COF) or moisture-curing functionality to the material. Silicones are blended into a variety of ethylene-based polymers to impart improved tactile properties. Silicone-modified low-density polyethylene (LDPE) materials, formed by direct copolymerization of ethylene with silicon monomers in high-pressure processes, are used in wire and cable applications. Silicone functional groups are also added to linear low-density polyethylene (LLDPE) materials via reactive extrusion, using peroxide grafting of silane monomers such as, for example, vinyltriethoxysilane. Although many examples of these physical blends and reactive extrusion grafting techniques are practiced today, these materials are limited in terms of the final properties related to the blend properties of the material. It is assumed that true Si-POE hybrids offer several advantages, including enhanced surface modification, improved adhesion, alternative crosslinking mechanisms, and the potential benefit of imparting controllable crystallinity to silicone products. Specifically, there is a need for an efficient and economical method to prepare Si-modified polymers (including random copolymers and block copolymers) using olefin-based polymers and silicone sources.

[0002] International publication WO 2012 / 103080 discloses a method for preparing polyolefin-polysiloxane block copolymers, comprising contacting a polyolefin-aluminum compound with an acyclic polysiloxane or cyclic siloxane monomer under effective coupling conditions, in such a manner as to obtain the polyolefin-polysiloxane block copolymer. Such block copolymers comprise polyolefin blocks directly covalently bonded to polysiloxane blocks, wherein the polyolefin blocks comprise the polyolefin-aluminum compound's polyolefin moiety, and the polysiloxane blocks comprise at least a portion of the acyclic polysiloxane. See claim 1. The coupling reaction involves chain scission of the polysiloxane or cyclic polysiloxane and is a relatively slow reaction.

[0003] The United States published formula (I), namely A, in document 2022 / 0073658. 1 L 1 L 2 A 2 Telechelic polyolefin and its preparation method are disclosed in this reference. The method includes: 1) combining raw materials comprising (A) a monomer component, (B) a chain transfer agent component, and (C) a catalyst component comprising a main catalyst to form a solution, and polymerizing (A) a monomer component in the solution at a concentration greater than 10 mol% to less than or equal to 99 mol%; 2) heating the solution; and 3) recovering the product containing the telechelic polyolefin. The (B) chain transfer agent component comprises Al(CH2CH(Y) 2A 2 )3 organoaluminum compounds, in which Y 2 Each time it appears, it is independently hydrogen or C1 to C2. 30 hydrocarbon group; and A 2 Each occurrence is independently a hydrocarbon group containing a hindered double bond. See claim 12. The telechelic polyolefin can be chemically modified, such as by grafting (e.g., by using maleic anhydride (MAH), silane, glycidyl methacrylate or other grafting agents), halogenation, amination, sulfonation or other chemical modifications. See paragraph

[0497] .

[0004] JJ Eisch et al., Stereospecific Reductive Alkylation of Acetylenes by Successive Hydralumination and Carbodemetalation, J. Org. Chem., 1976, 41, 2214-2215, disclose the stereospecific cis-hydralumination of acetylene and the alkylation of the resulting vinylalane aluminate complex. See page 2214. Direct hydralumination of monosubstituted or disubstituted acetylenes is disclosed, providing a convenient and direct route to prepare stereodisubstituted and trisubstituted alkenes, respectively. The disadvantages are as follows: (1) the hydralumination rate of some disubstituted acetylenes is slow; (2) a mixture of positional isomers is produced when R is not equivalent to R'; and (3) RHC=CR'Al(i-C4H9)2 is contaminated by a small amount of RC=C-A1R2' formed by the metallization of terminal alkynes by alkylaluminum. Trimethylsilyl derivatives of monosubstituted acetylene can also be hydroaluminized. See page 2214.

[0005] PR Jones et al., Silaethylene Intermediates from alpha-Lithiosilanes. 2. Reactions with Chlorosilanes and 1,3-Butadiene, 1977, J. Am. Chem. Soc., 99(26), 8447-8451, disclose the formation of silane intermediates by eliminating lithium chloride from alpha-lithium chlorosilanes under appropriate experimental conditions. The reaction of tert-butyllithium with vinyldimethylchlorosilane in a hydrocarbon solvent at low temperature is disclosed to produce cis- and trans-1,1,3,3-tetramethyl-2,4-dineoptyl-1,3-disilcyclobutane in high yields. When this reaction is carried out in the presence of 1,3-butadiene, distinct [2+2] and [2+4] cycloadditions are generated by the reaction of the silane intermediate with butadiene. One of them is 1,1-dimethyl-2-neopentyl-3-vinylsilcyclobutane, which is a compound that cannot be formed by adding α-lithium chlorosilane to butadiene and then cyclizing it. See abstract.

[0006] PR Jones et al., alpha-Lithiosilanes. 4. Silaethylene Cycloadditions with Conjugated Dienes, J. Am. Chem. Soc. 1980, 102, 4970-4973, disclose the reaction of vinyldimethyl-chlorosilanes with tert-butyllithium in the presence of several conjugated dienes. The following dienes: 1,3-butadiene; 2,3-dimethyl-1,3-butadiene; cyclopentadiene; and anthracene; generate cycloadditions of silylene intermediates in hydrocarbon solvents. The presence of tetrahydrofuran in the reaction mixture inhibits the formation of cycloadditions and favors the formation of 1,3-disilacyclobutane. No cycloadditions of 2,5-dimethylfuran were obtained. This reference discloses lithium chloride elimination in hydrocarbon solvents to give silylene intermediates, while addition reactions in THF or in the presence of strong Lewis bases yield α-lithium silanes, and products resulting from their coupling reactions. See abstract.

[0007] N. Petzetakis et al., in their paper "Synthesis of Well Defined Polyethylene-Polydimethylsiloxane-Polyethylene Triblock Copolymers by Diimide-Based Hydrogenation of Polybutadiene Blocks," Macromolecules, 2014, 47, 4151-4159, disclosed a route for synthesizing well-defined polyethylene-b-polydimethylsiloxane-b-polyethylene (EDE) triblock copolymers. The precursors for poly(1,4-butadiene)-b-polydimethylsiloxane-b-poly(1,4-butadiene) (BDB) copolymers were synthesized via anionic polymerization followed by diimide-based hydrogenation. Under standard hydrogenation conditions, the siloxane bonds underwent breakage, leading to significant degradation of the PDMS blocks. This reference discloses the reaction conditions for avoiding PDMS degradation using optimal hydrogenation conditions. See abstract.

[0008] US Patent 3,691,257 discloses the synthesis of polyolefin-siloxane block copolymers using living anionic polymerization (see abstract). These methods typically employ butadiene or isoprene, which must then be hydrogenated to obtain the polyolefin equivalent. The monomers available for anionic polymerization are very limited, typically styrene or butadiene. Therefore, a typical approach to preparing “polyolefin-like” block copolymers is to prepare polybutadiene segments and then remove the unsaturation through hydrogenation. Anionic polymerization is less efficient and more expensive for the production of these block copolymers. Anionic polymerization is generally inefficient and requires lower temperatures and longer reaction times.

[0009] As discussed above, there remains a need for an efficient and economical method to produce Si-modified polymers (including random copolymers and block copolymers) from olefin-based polymers and silicone sources. As discussed in this paper, this need has been met. Summary of the Invention

[0010] A method for forming a composition comprising a siloxane-modified olefin-based polymer, the method comprising reacting A) and B) respectively as shown below to form C) as shown below:

[0011] A)M[(CR 1 R 2 -CR 3 R 4 ) n-CH3]x, where M is a metal selected from Zn or Al; x is 2 or 3, and if x=2, then M is Zn, and if x=3, then M is Al; each n is independently ≥1; and for each corresponding value of n, R 1 R 2 R 3 R 4 Each of them is independently an H or hydrocarbon group; and R 1 For each consecutive repeating unit, it can be the same or it can be different; R 2 For each consecutive repeating unit, it can be the same or it can be different; R 3 For each consecutive repeating unit, it can be the same or it can be different; R 4 Each consecutive repeating unit can be the same or can be different;

[0012] B) A polysiloxane containing at least one silyl vinyl group;

[0013] C) Form one or more polysiloxane-M-polymer complexes, each independently selected from i, ii, iii, iv, v, vi, vii, viii, ix, or x:

[0014] i) where each n is as defined above, and R 1 R 2 R 3 R 4 Each of the corresponding units is as defined above; and each of R and R' is independently a hydrocarbon group or a heterohydrocarbon group; x = 1 or 2, and if x = 1, then M is Zn, and if x = 2, then M is Al; and an asterisk (*) indicates the remainder of the complex;

[0015] ii) where each n is as defined above, and R 1 R 2 R 3 R 4 Each corresponding unit is as defined above; and R" is a hydrocarbon group or a heterohydrocarbon group; x = 1 or 2, and if x = 1, then M is Zn, and if x = 2, then M is Al; and each asterisk (*) independently represents the corresponding remainder of the complex;

[0016] iii) where each n is as defined above, and R 1 R 2 R 3 R 4Each corresponding unit is as defined above; and each of R and R' is independently a hydrocarbon group or a heterohydrocarbon group; x = 0 or 1, and if x = 0 (the [(CR 1 R 2 -CR 3 R 4 If the [n-CH3]) portion does not exist, then M is Zn, and if x=1, then M is Al; and each asterisk (*) independently represents the corresponding remainder of the complex;

[0017] iv) where each n is as defined above, and R 1 R 2 R 3 R 4 Each corresponding unit is as defined above; and each R” is independently a hydrocarbon group or a heterohydrocarbon group; x = 0 or 1, and if x = 0 (the [(CR)] 1 R 2 -CR 3 R 4 If the [n-CH3]) portion does not exist, then M is Zn, and if x=1, then M is Al; and each asterisk (*) independently represents the corresponding remainder of the complex;

[0018] v) where each n is as defined above, and R 1 R 2 R 3 R 4 Each corresponding unit is as defined above; and each of R, R', and R" is independently a hydrocarbon group or a heterohydrocarbon group; x = 0 or 1, and if x = 0 (the [(CR 1 R 2 -CR 3 R 4 If the [n-CH3]) portion does not exist, then M is Zn, and if x=1, then M is Al; and each asterisk (*) independently represents the corresponding remainder of the complex;

[0019] vi) where each n is as defined above, and R 1 R 2 R 3 R 4 Each of the corresponding units is as defined above; and each of R and R' is independently a hydrocarbon group or a heterohydrocarbon group; and M is Al; and each asterisk (*) independently represents the corresponding remainder of the complex;

[0020] vii) where each n is as defined above, and R1 R 2 R 3 R 4 Each corresponding unit is as defined above; and each R" is independently a hydrocarbon group or a heterohydrocarbon group; and M is Al; and each asterisk (*) independently represents the corresponding remainder of the complex;

[0021] viii) where each n is as defined above, and R 1 R 2 R 3 R 4 Each of the corresponding units is as defined above; and each of R, R' and R" is independently a hydrocarbon group or a heterohydrocarbon group; and M is Al; and each asterisk (*) independently represents the corresponding remainder of the complex;

[0022] ix) where each n is as defined above, and

[0023] R 1 R 2 R 3 R 4 Each corresponding unit is as defined above; and each of R, R', and R" is independently a hydrocarbon group or a heterohydrocarbon group; and M is Al; and each asterisk (*) independently represents the corresponding remainder of the complex; or

[0024] x) any combination of them;

[0025] Hydrolyze one or more polysiloxane-M polymer complexes (C) to form the siloxane-modified olefin-based polymer.

[0026] A method is provided for forming a composition comprising a silane-modified olefin-based polymer, the method comprising reacting D) and E) respectively as shown below to form F) as shown below:

[0027] D)M[(CR 5 R 6 -CR 7 R 8 ) p -CH3] x Where M is a metal selected from Zn or Al; x is 2 or 3, and if x=2, then M is Zn, and if x=3, then M is Al; each p is independently ≥1; and for each corresponding p value, R 5 R 6 R 7 R 8 Each of them is independently an H or hydrocarbon group; and R5 Each consecutive repeating unit can be the same or can be different; R 6 Each consecutive repeating unit can be the same or can be different; R 7 Each consecutive repeating unit can be the same or can be different; R 8 Each consecutive repeating unit can be the same or can be different;

[0028] E) Silanes containing at least one silyl vinyl group;

[0029] F) Form one or more silane-M-polymer complexes, each independently selected from ic, iic, iiic or ivc:

[0030] ic) Each p is as defined above; and R 5 R 6 R 7 R 8 Each corresponding unit is as defined above; and R A R B and R C Each of them is independently H, a hydrocarbon group, or a heterohydrocarbon group; x = 1 or 2, and if x = 1, then M is Zn, and if x = 2, then M is Al;

[0031] iic) Each p is as defined above; and R 5 R 6 R 7 R 8 Each corresponding unit is as defined above; and R A R B and R C Each of them is independently H, a hydrocarbon group, or a heterohydrocarbon group; x = 0 or 1, and if x = 0 (the [(CR 5 R 6 -CR 7 R 8 ) p If the -CH3]) part does not exist, then M is Zn, and if x=1, then M is Al;

[0032] iiic) Each p is as defined above; and

[0033] R 5 R 6 R 7 R 8 Each corresponding unit is as defined above; and R A R B and R CEach of them is independently H, a hydrocarbon group, or a heterohydrocarbon group; M is Al; or

[0034] ivc) any combination of them;

[0035] Hydrolyze one or more silane-M polymer complexes (F) to form the silane-modified olefin-based polymer.

[0036] A method is provided for forming a composition comprising silane, the method comprising reacting G) as shown below with H) to form I) as shown below:

[0037] G)M[R 9 ] x Where M is a metal selected from Zn or Al; x is 2 or 3, and if x=2, then M is Zn, and if x=3, then M is Al; each R 9 Independently a hydrocarbon group;

[0038] H) Silanes containing at least one silyl vinyl group,

[0039] I) Forming one or more silane-M-molecule complexes, each independently selected from id, iid, iiid, or ivd:

[0040] id) , where each R 9 As defined above; and R D R E and R F Each of them is independently H, a hydrocarbon group, or a heterohydrocarbon group; x = 1 or 2, and when x = 1, then M is Zn, and when x = 2, then M is Al;

[0041] iid) , where each R 9 As defined above; and R D R E and R F Each of them is independently H, a hydrocarbon group, or a heterohydrocarbon group; x = 0 or 1, and when x = 0 ((R 9 If the part does not exist, then M is Zn, and when x=1, then M is Al;

[0042] iiid) , where each R 9 As defined above; and R D R E and R F Each of them

[0043] Independently H, hydrocarbon group, or heterohydrocarbon group; M is Al; or

[0044] ivd) any combination of them;

[0045] Hydrolyze one or more silane-M-molecule complexes (I) to form silanes.

[0046] A composition comprising a siloxane-modified olefin-based polymer, wherein the siloxane-modified olefin-based polymer comprises at least one chain, the at least one chain comprising at least one structure selected from T1) to T4):

[0047] T1) Where m≥2; x≥1; n≥1; and for each value of n, R 1 R 2 R 3 R 4 Each of them is independently an H or hydrocarbon group; and R 1 For each consecutive repeating unit, it can be the same or it can be different; R 2 For each consecutive repeating unit, it can be the same or it can be different; R 3 For each consecutive repeating unit, it can be the same or it can be different; R 4 Each consecutive repeating unit can be the same or can be different; and each of R and R' is independently a hydrocarbon group; and each asterisk (*) independently represents the corresponding remainder of the chain;

[0048] T2) Where m≥2; x≥1; y≥1; each n independently ≥1; and for each corresponding value of n, R 1 R 2 R 3 R 4 Each of them is independently an H or hydrocarbon group; and R 1 For each consecutive repeating unit, it can be the same or it can be different; R 2 For each consecutive repeating unit, it can be the same or it can be different; R 3 For each consecutive repeating unit, it can be the same or it can be different; R 4 Each consecutive repeating unit can be the same or can be different; and each of R, R' and R" is independently a hydrocarbon group; and each asterisk (*) independently represents the corresponding remainder of the chain;

[0049] T3) Where m≥2; x≥1; y≥1; n≥1; and for each value of n, R 1 R 2 R 3 R 4 Each of them is independently an H or hydrocarbon group; and R 1 For each consecutive repeating unit, it can be the same or it can be different; R2 For each consecutive repeating unit, it can be the same or it can be different; R 3 For each consecutive repeating unit, it can be the same or it can be different; R 4 Each consecutive repeating unit can be the same or can be different; and each of R, R' and R" is independently a hydrocarbon group; and each asterisk (*) independently represents the corresponding remainder of the chain; or T4) any combination thereof. Attached Figure Description

[0050] Figure 1 These are GC / MS peak spectra from the hydrolysis reaction products in Example 1. Figure 2 These are GC / MS peak spectra from the hydrolysis reaction products in Example 2.

[0051] Figure 3 This is a superimposed graph of GPC curves from DMS-V05 (lower part), polyethylene (upper part), and the reaction product containing PE-PDMS block copolymer (middle part). See Example 3.

[0052] Figure 4 It is the reaction product of Example 3. 29 Si NMR spectrum. Figure 5 It is the reaction product of Example 3. 13 C10 NMR spectrum.

[0053] Figure 6 This is a superimposed graph of GPC curves from VMS-T11 (lower part), polyethylene (upper part), and the reaction product containing PE-PDMS block copolymer (middle part). See Example 4.

[0054] Figure 7 These are GC / MS peak spectra from the hydrolysis reaction products in Example 5. Detailed Implementation

[0055] A novel chemical approach is provided regarding the formation of Si-C bonds through a new reaction pathway involving the insertion of silyl vinyl groups into metal-C bonds (e.g., Al-C bonds). This chemical approach can be used for olefin-based polymers. In general, the method presented herein is more efficient and / or more economical than the polymerization techniques discussed in this paper.

[0056] As discussed above, silyl vinyl double bonds are directly inserted into metal-carbon bonds to form new alkyl-silicon bonds, as shown in Scheme 1, using alkylaluminum as an example. These methods can be used to form polyolefin-polydimethylsiloxane block copolymers as shown in Scheme 2.

[0057]

[0058]

[0059] These methods provide low-cost pathways to produce PO-PDMS block copolymers and PO-g-PDMS copolymers, as well as more complex comb-like structures, as shown in Scheme 3.

[0060]

[0061] A method for forming Si-C bonds is provided, the method comprising inserting a silyl vinyl group into a metal carbon bond, wherein the metal is Zn or Al, and further, Al. As discussed above, methods for forming compositions comprising siloxane-modified olefin-based polymers, compositions comprising silane-modified olefin-based polymers, or compositions comprising silanes are provided. A composition comprising a siloxane-modified olefin-based polymer is also provided, wherein the siloxane-modified olefin-based polymer comprises at least one structure selected from T1) to T4) as described herein. Segments a1 and / or a2 and b, each as described herein (see below P]). In one embodiment or a combination of two or more embodiments described herein, for segment b, each of R'” and R”” is independently H or an alkyl group, and further, an alkyl group.

[0062] In one or more of the embodiments described herein, M stands for Al.

[0063] In one or a combination of two or more embodiments described herein, the method is a solution method.

[0064] In one or a combination of two or more embodiments described herein, the method further includes separating “compositions comprising siloxane-modified olefin-based polymers”. See the following example of a separation method (Item B).

[0065] In one embodiment or a combination of two or more embodiments described herein, the composition further comprises an olefin-based polymer. In one embodiment or a combination of two or more embodiments described herein, the olefin-based polymer is an ethylene-based polymer.

[0066] In one or a combination of two or more embodiments described herein, the siloxane-modified olefin-based polymer comprises at least one chain containing at least one structure selected from T5 to T8 as described herein (see G3 below).

[0067] In one embodiment or a combination of two or more embodiments described herein, the composition comprises, based on weight, ≥15% or ≥20% or ≥30% or ≥40% or ≥50% or ≥55% of the composition. and / or ≤100 wt% or ≤95 wt% or ≤90 wt% or ≤85 wt% or ≤80 wt% or ≤75 wt% or ≤70 wt% or ≤65 wt% or ≤60 wt% of siloxane-modified olefin-based polymers.

[0068] In one embodiment or a combination of two or more embodiments described herein, the composition comprises, based on weight, ≥80.0% or ≥85.0% or ≥90.0% or ≥92.0% or ≥94.0% or ≥96.0% or ≥98.0% or ≥99.0% or ≥99.2% or ≥99.4% and / or The sum of siloxane-modified polymers and olefin-based polymers in amounts of ≤100.0% by weight or ≤99.9% by weight, ≤99.8% by weight or ≤99.7% by weight or ≤99.6% by weight.

[0069] In one embodiment or a combination of two or more embodiments described herein, the siloxane-modified olefin-based polymer is a siloxane-modified ethylene-based polymer based on the weight of the composition.

[0070] A crosslinking composition is also provided, which is formed by a composition of any one of the embodiments described herein or a combination of two or more embodiments; or by a method of any one of the embodiments described herein or a combination of two or more embodiments.

[0071] An article of manufacture is also provided, comprising at least one component formed by a composition of any one of the embodiments described herein or a combination of two or more embodiments; or at least one component formed by a method of any one of the embodiments described herein or a combination of two or more embodiments.

[0072] additive

[0073] The composition may contain one or more additives. Additives include, but are not limited to, crosslinking agents, curing catalysts, fillers, pigments, UV stabilizers, antioxidants, processing aids, solvents, and additional crosslinking agents, curing catalysts, UV stabilizers, and antioxidants. In one embodiment, the additives are present in an amount of ≥0.01% by weight, ≥0.02% by weight, ≥0.05% by weight, ≥0.10% by weight, ≥0.20% by weight, ≥0.30% by weight, ≥0.40% by weight, or ≥0.50% by weight based on the weight of the composition. and / or The amount present is ≤10% by weight or ≤8.0% by weight or ≤6.0% by weight or ≤4.0% by weight or ≤2.0% by weight or ≤1.5% by weight or ≤1.0% by weight or ≤0.80% by weight.

[0074] definition

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

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

[0077] As used herein, the term "polymer" refers to a polymer compound (containing polymer chains or structures) prepared by polymerizing monomers of the same or different types. Therefore, the general term polymer includes the terms homopolymer (used to refer to polymers prepared from only one type of monomer; it should be understood that trace impurities may be incorporated into the polymer structure) and interpolymer as defined below. Trace impurities (such as catalyst residues) may be incorporated into and / or within the polymer. Typically, polymers are stabilized with one or more stabilizers (e.g., antioxidants) in very low amounts ("ppm").

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

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

[0080] As used herein, the term "ethylene-based polymer" means a polymer that contains 50% by weight or most of the weight of ethylene (based on the weight of the polymer) in polymeric form and optionally may contain one or more comonomers.

[0081] As used herein, the term "ethylene / α-olefin interpolymer" refers to an interpolymer comprising 50% by weight or majority by weight of ethylene (based on the weight of the interpolymer) and an α-olefin in polymeric form. As used herein, the term "ethylene / α-olefin copolymer" refers to a copolymer comprising 50% by weight or majority by weight of ethylene (based on the weight of the copolymer) and an α-olefin as the only two monomer types in polymeric form.

[0082] As used herein, the term "propylene-based polymer" refers to a polymer that contains a majority weight percentage of propylene (based on the weight of the polymer) in polymeric form and may optionally contain one or more comonomers.

[0083] As used herein, the term "propylene / α-olefin interpolymer" refers to an interpolymer comprising, in polymeric form, a majority weight percentage of propylene (based on the weight of the interpolymer) and an α-olefin. As used herein, the term "propylene / α-olefin copolymer" refers to a copolymer comprising, in polymeric form, a majority weight percentage of propylene (based on the weight of the copolymer) and an α-olefin as the only two monomer types.

[0084] As used herein, the term "propylene / ethylene interpolymer" refers to an interpolymer comprising a majority weight percentage of propylene (based on the weight of the interpolymer) and ethylene in polymeric form. As used herein, the term "propylene / ethylene copolymer" refers to a copolymer comprising a majority weight percentage of propylene (based on the weight of the copolymer) and ethylene as the only two monomer types in polymeric form.

[0085] As used herein, the phrase “major weight percentage” for polymers (or interpolymers or copolymers) refers to the amount of monomers present in the polymer in the largest quantity.

[0086] As used herein, the term "crosslinked composition" means, as understood by those skilled in the art, a composition comprising a crosslinked polymer, which is a polymer having a network structure due to the formation of chemical bonds between polymer chains.

[0087] The term "heteroatom" refers to an atom other than hydrogen or carbon (e.g., Si, O, N, or P, and typically Si or O). The term "heteroatom group" refers to a heteroatom or a chemical group containing one or more heteroatoms.

[0088] As used herein, the terms “hydrocarbon,” “hydrocarbon group,” and similar terms refer to chemical compounds or chemical groups containing only carbon and hydrogen atoms, respectively.

[0089] As used herein, the terms “heterohydrocarbon,” “heterohydrocarbon group,” and similar terms refer to chemical compounds or chemical groups containing carbon, hydrogen, and one or more heteroatoms (e.g., Si, O, N, or P).

[0090] As used herein, the term "siloxane or siloxane group" and similar terms refer to chemical groups or portions containing "-Si-O-Si-" (siloxane) bonds.

[0091] As used herein, the term "polysiloxane" and similar terms refer to molecules containing one or more "-Si-O-Si-" (siloxane) bonds. Typically, polysiloxanes contain ≥2 siloxane bonds.

[0092] As used herein, the term "polysiloxane comprising at least one silyl vinyl group" refers to a polysiloxane comprising at least one -Si-CH=CH2 moiety. See, for example, structures s1) to s18 below.

[0093] As used herein, the term "siloxane-modified olefin-based polymer" refers to an olefin-based polymer containing at least one "-Si-O-Si-" (siloxane) bond.

[0094] As used herein, the term "silane" refers to "RSi(R... D (R) E (R) F )” molecules, where R, R D R E R F Each of them is independently H, a hydrocarbon group, or a heterohydrocarbon group.

[0095] As used herein, the term "silane-modified olefin-based polymer" refers to a polymer containing at least one -Si(R) group. A (R) B (R) C ) (silane)-linked olefin-based polymers, wherein R A R B R C Each of them is independently H, a hydrocarbon group or a heterohydrocarbon group; and the olefin-based polymers therein do not contain "-Si-O-Si-" (siloxane) bonds.

[0096] As used herein, the term "silyl vinyl group" refers to a chemical group or portion containing -Si-CH=CH2.

[0097] As used herein, the term "silane comprising at least one silyl vinyl group" refers to a silane comprising at least one -Si-CH=CH2 moiety.

[0098] As used herein, the term "polysiloxane-M-polymer complex" refers to a metal complex comprising at least one olefin-based polymer segment and at least one polysiloxane segment. Here, M is Zn or Al.

[0099] As used herein, the term "silane-M-polymer complex" refers to a metal complex comprising at least one olefin-based polymer segment and at least one silane segment. Here, M is Zn or Al.

[0100] As used herein, the term "silane-M-molecular complex" refers to a metal complex comprising at least one hydrocarbon segment and at least one silane segment. Here, M is Zn or Al.

[0101] As used herein, the term "hydrolysis" and similar terms refer to a chemical reaction in which a polysiloxane-M-polymer complex, a silane-M-polymer complex, or a silane-M-molecule complex reacts with water or an alcohol to remove "M-(polymer)2", "M-polymer", "M-(molecule)2", "M-molecule", or "M" from the respective complex, producing a metal complex comprising at least one -OH or at least one -OR moiety, wherein R is an alkyl group. Here, M is Zn or Al.

[0102] As used herein, the term "catalyst system" refers to a catalyst composition comprising a main catalyst and an optional co-catalyst.

[0103] As used herein, the term "repeating unit" in relation to, for example, metal complex A or complexes i to ix refers to (CR... 4 R 3 -CR 2 R 1 ) unit, where R 1 R 2 R 3 R 4 Each of these is as defined herein (see, for example, A below).

[0104] As used herein, the term "repeating unit" in relation to, for example, metal complex D or complex ic to iiic refers to (CR) 5 R 6 -CR 7 R 8 ) unit, where R 5 R 6 R 7 R 8 Each of these is as defined herein (see, for example, U below).

[0105] As used herein, the term "repeating unit" in relation to, for example, polymer structures T1, T2, and T3 refers to (CR)4 R 3 -CR 2 R 1 ) unit, where R 1 R 2 R 3 R 4 Each of these is as defined herein (see, for example, F3 below).

[0106] As used herein, the term "solution method" refers to a chemical reaction method in which both the raw materials and the final product are soluble in one or more solvents used in the method.

[0107] The terms “comprising,” “including,” “having,” and their derivatives are not intended to exclude the presence of any additional components, steps, or procedures, whether or not specifically disclosed. For the avoidance of any doubt, unless stated to the contrary, all compositions claimed using the term “comprising” may include, for example, any additional additives, adjuvants, or compounds, whether polymerized or otherwise. In contrast, the term “consistently comprising” excludes any other components, steps, or procedures from any subsequently listed scope, except those not essential for operability. The term “consisting of” excludes any ingredients, steps, or procedures not specifically described or listed.

[0108] List of some methods and composition characteristics

[0109] A] A method for forming a composition comprising a siloxane-modified olefin-based polymer, the method comprising reacting A) and B) respectively as shown below to form C) as shown below:

[0110] A)M[(CR 1 R 2 -CR 3 R 4 ) n -CH3] x Where M is a metal selected from Zn or Al; x is 2 or 3, and if x=2, then M is Zn, and if x=3, then M is Al; each n is independently ≥1; and for each corresponding value of n, R 1 R 2 R 3 R 4 Each of them is independently an H or hydrocarbon group; and R 1 For each consecutive repeating unit, it can be the same or it can be different (or R) 1 (Each time it appears, it is independently selected from H or hydrocarbon groups); R 2 For each consecutive repeating unit, it can be the same or it can be different (or R) 2(Each time it appears, it is independently selected from H or hydrocarbon groups); R 3 For each consecutive repeating unit, it can be the same or it can be different (or R) 3 (Each time it appears, it is independently selected from H or hydrocarbon groups); R 4 For each consecutive repeating unit, it can be the same or it can be different (or R) 4 (Each time it appears, it is independently selected from H or hydrocarbon groups);

[0111] B) A polysiloxane containing at least one silyl vinyl group;

[0112] C) Form one or more polysiloxane-M-polymer complexes, each independently selected from i, ii, iii, iv, v, vi, vii, viii, ix, or x:

[0113] i) where each n is as defined above, and R 1 R 2 R 3 R 4 Each of the corresponding units is as defined above; and each of R and R' is independently a hydrocarbon group or a heterohydrocarbon group, and further a hydrocarbon group; x = 1 or 2, and if x = 1, then M is Zn, and if x = 2, then M is Al; and an asterisk (*) indicates the remainder of the complex;

[0114] ii) where each n is as defined above, and R 1 R 2 R 3 R 4 Each corresponding unit is as defined above; and R” is independently a hydrocarbon group or a heterohydrocarbon group, and further a hydrocarbon group; x = 1 or 2, and if x = 1, then M is Zn, and if x = 2, then M is Al; and each asterisk (*) independently represents the corresponding remainder of the complex;

[0115] Or listed.

[0116] List of some methods and composition characteristics

[0117] A] A method for forming a composition comprising a siloxane-modified olefin-based polymer, the method comprising reacting A) and B) respectively as shown below to form C) as shown below:

[0118] A)M[(CR 1 R 2 -CR ³ R 4 ) n-CH3]x, where M is a metal selected from Zn or Al; x is 2 or 3, and if x=2, then M is Zn, and if x=3, then M is Al; each n is independently ≥1; and for each corresponding value of n, R 1 R 2 R 3 R 4 Each of them is independently an H or hydrocarbon group; and R 1 For each consecutive repeating unit, it can be the same or it can be different (or R) 1 (Each time it appears, it is independently selected from H or hydrocarbon groups); R 2 For each consecutive repeating unit, it can be the same or it can be different (or R) 2 (Each time it appears, it is independently selected from H or hydrocarbon groups); R 3 For each consecutive repeating unit, it can be the same or it can be different (or R) 3 (Each time it appears, it is independently selected from H or hydrocarbon groups); R 4 For each consecutive repeating unit, it can be the same or it can be different (or R) 4 (Each time it appears, it is independently selected from H or hydrocarbon groups);

[0119] B) A polysiloxane containing at least one silyl vinyl group;

[0120] C) Form one or more polysiloxane-M-polymer complexes, each independently selected from i, ii, iii, iv, v, vi, vii, viii, ix, or x:

[0121] i) where each n is as defined above, and R 1 R 2 R 3 R 4 Each of the corresponding units is as defined above; and each of R and R' is independently a hydrocarbon group or a heterohydrocarbon group, and further a hydrocarbon group; x = 1 or 2, and if x = 1, then M is Zn, and if x = 2, then M is Al; and an asterisk (*) indicates the remainder of the complex;

[0122] ii) where each n is as defined above, and R 1 R 2 R 3 R 4 Each corresponding unit is as defined above; and R" is independently a hydrocarbon group or a heterohydrocarbon group, and further a hydrocarbon group; x = 1 or 2, and if x = 1, then M is Zn, and if x = 2, then M is Al; and each asterisk (*) independently represents the corresponding remainder of the complex;

[0123] iii) where each n is as defined above, and R 1 R 2 R 3 R 4 Each corresponding unit is as defined above; and each of R and R' is independently a hydrocarbon group or a heterohydrocarbon group, and further a hydrocarbon group; x = 0 or 1, and if x = 0 (the [(CR 1 R 2 -CR 3 R 4 If the [n-CH3]) portion does not exist, then M is Zn, and if x=1, then M is Al; and each asterisk (*) independently represents the corresponding remainder of the complex;

[0124] iv) where each n is as defined above, and R 1 R 2 R 3 R 4 Each corresponding unit is as defined above; and each R” is independently a hydrocarbon group or a heterohydrocarbon group, and further a hydrocarbon group; x = 0 or 1, and if x = 0 (the [(CR)] 1 R 2 -CR 3 R 4 If the [n-CH3]) portion does not exist, then M is Zn, and if x=1, then M is Al; and each asterisk (*) independently represents the corresponding remainder of the complex;

[0125] v) where each n is as defined above, and R 1 R 2 R 3 R 4 Each of the corresponding units is as defined above; and each of R, R', and R" is independently a hydrocarbon group or a heterohydrocarbon group, and further a hydrocarbon group; x = 0 or 1, and if x = 0 ([(CR 1 R 2 -CR 3 R 4 If the [-CH3]) portion is absent, then M is Zn, and if x=1, then M is Al; and each asterisk (*) independently represents the corresponding remainder of the complex;

[0126] vi) where each n is as defined above, and R 1 R 2 R 3 R 4Each of the corresponding units is as defined above; and each of R and R' is independently a hydrocarbon group or a heterohydrocarbon group, and further a hydrocarbon group; and M is Al; and each asterisk (*) independently represents the corresponding remainder of the complex;

[0127] vii) where each n is as defined above, and R 1 R 2 R 3 R 4 Each corresponding unit is as defined above; and each R” is independently a hydrocarbon group or a heterohydrocarbon group, and further a hydrocarbon group; and M is Al; and each asterisk (*) independently represents the corresponding remainder of the complex;

[0128] viii) where each n is as defined above, and R 1 R 2 R 3 R 4 Each of the corresponding units is as defined above; and each of R, R' and R" is independently a hydrocarbon group or a heterohydrocarbon group, and further a hydrocarbon group; and M is Al; and each asterisk (*) independently represents the corresponding remainder of the complex;

[0129] ix) where each n is as defined above, and R 1 R 2 R 3 R 4 Each corresponding unit is as defined above; and each of R, R', and R" is independently a hydrocarbon group or a heterohydrocarbon group, and further, a hydrocarbon group; and M is Al; and each asterisk (*) independently represents the corresponding remainder of the complex; or

[0130] x) any combination of them;

[0131] Hydrolyzing one or more polysiloxane-M polymer complexes (C) to form the siloxane-modified olefin-based polymer. In another embodiment, each polysiloxane-M polymer complex is independently selected from i, ii, iii, iv, v, vi, vii, viiii, or ix.

[0132] [B] The method described in A] above, wherein the method further includes separating "a composition comprising a siloxane-modified olefin-based polymer". Separation methods are known in the art and include, but are not limited to, filtration, distillation, and extraction.

[0133] 2-Dimethyl)methane]dimethylhafnium].

[0134] P] According to any one of A] to O] above, the siloxane-modified olefin-based polymer comprises the following polymer segments a1 and / or a2 and b:

[0135] a1)-O-Si(R)(R')-CH2-CH2-(CR 1 R 2 -CR 3 R 4 ) n -CH3, where n is as defined herein (e.g., see A]); and each of R and R' is as defined herein (e.g., see A]); and R 1 R 2 R 3 R 4 Each of these is as defined herein (see, for example, A).

[0136] a2)-O-Si(R”)-CH2-CH2-((CR 1 R 2 -CR 3 R 4 ) n -CH3)-, where n is as defined herein (e.g., see A]); and R” is as defined herein (e.g., see A]); and R 1 R 2 R 3 R 4 Each of these is as defined herein (see, for example, A).

[0137] b)-(O-SiR'""R"")) m - where m≥1, and for each value of m, each of R'” and R”” is independently H or hydrocarbon group, and further is hydrocarbon group.

[0138] Q] According to the method described in P] above, for chain segment b, m≥2, or ≥5, or ≥10, or ≥20, or ≥50, or ≥100 and / or ≤20000, or ≤15000, or ≤10000, or ≤5000, or ≤2000, or ≤1000, or ≤500.

[0139] R] according to the method described in P] or Q] above, wherein for segment b, each of R'” and R”” is independently an H or alkyl group.

[0140] S] The method according to any one of P] to R] above, wherein for segment b, each of R'” and R”” is independently an alkyl group, or a C1-C5 alkyl group, or a C1-C4 alkyl group, or a C1-C3 alkyl group, or a C1-C2 alkyl group, or a methyl group.

[0141] T] according to any one of P] to S] above, wherein for chain segment b, R'”=R””.

[0142] U] provides a method for forming a composition comprising a silane-modified olefin-based polymer, the method comprising reacting D) and E) respectively as shown below to form F) as shown below:

[0143] D)M[(CR 5 R 6 -CR 7 R 8 ) p -CH3]x, where M is a metal selected from Zn or Al; x is 2 or 3, and if x=2, then M is Zn, and if x=3, then M is Al; each p is independently ≥1; and for each corresponding p value, R 5 R 6 R 7 R 8 Each of them is independently an H or hydrocarbon group; and R 5 For each consecutive repeating unit, it can be the same or it can be different (or R). 5 (Each time it appears, it is independently selected from H or hydrocarbon groups); R 6 For each consecutive repeating unit, it can be the same or it can be different (or R). 6 (Each time it appears, it is independently selected from H or hydrocarbon groups); R 7 For each consecutive repeating unit, it can be the same or it can be different (or R). 7 (Each time it appears, it is independently selected from H or hydrocarbon groups); R 8 For each consecutive repeating unit, it can be the same or it can be different (or R). 8 (Each time it appears, it is independently selected from H or hydrocarbon groups);

[0144] E) Silanes containing at least one silyl vinyl group;

[0145] F) Form one or more silane-M-polymer complexes, each independently selected from ic, iic, iiic or ivc:

[0146] ic) Each p is as defined above; and R 5 R 6 R 7 R8 Each corresponding unit is as defined above; and R A R B and R C Each of them is independently H, a hydrocarbon group or a heterohydrocarbon group, and further is H or a hydrocarbon group; x = 1 or 2, and if x = 1, then M is Zn, and if x = 2, then M is Al;

[0147] iic) Each p is as defined above; and R 5 R 6 R 7 R 8 Each corresponding unit is as defined above; and R A R B and R C Each of them is independently H, a hydrocarbon group, or a heterohydrocarbon group, and further is H or a hydrocarbon group; x = 0 or 1, and if x = 0 (the [(CR 5 R 6 -CR 7 R 8 ) p If the -CH3]) part does not exist, then M is Zn, and if x=1, then M is Al;

[0148] iiic) Each p is as defined above; and R 5 R 6 R 7 R 8 Each corresponding unit is as defined above; and R A R B and R C Each of them is independently H, a hydrocarbon group, or a heterohydrocarbon group, and further is H or a hydrocarbon group; M is Al; or

[0149] ivc) any combination of them;

[0150] Hydrolyzing one or more silane-M polymer complexes (F) to form the silane-modified olefin-based polymer. In another embodiment, each silane-M polymer complex is independently selected from ic, iic, or iiic.

[0151] V] According to the method described in U] above, the method further includes separating "a composition comprising a silane-modified olefin-based polymer". See the example of the separation method discussed above (Item B].

[0152] W] according to the method described in U] or V] above, wherein the method is a solution method.

[0153] X] According to any one of U] to W] above, wherein independently for each of ic-iiic, each p independently ≥2, or ≥5, or ≥50, or ≥20, or ≥50, or ≥100, or ≥500 and / or ≤20000, each consecutive repeating unit can be different (or R) 5 (Each time it appears, it is independently selected from H or hydrocarbon groups); R 6 For each consecutive repeating unit, it can be the same or it can be different (or R). 6 (Each time it appears, it is independently selected from H or hydrocarbon groups); R 7 For each consecutive repeating unit, it can be the same or it can be different (or R). 7 (Each time it appears, it is independently selected from H or hydrocarbon groups); R 8 For each consecutive repeating unit, it can be the same or it can be different (or R). 8 (Each time it appears, it is independently selected from H or hydrocarbon groups);

[0154] E) Silanes containing at least one silyl vinyl group;

[0155] F) Form one or more silane-M-polymer complexes, each independently selected from ic, iic, iiic or ivc:

[0156] ic) Each p is as defined above; and R 5 R 6 R 7 R 8 Each corresponding unit is as defined above; and R A R B and R C Each of them is independently H, a hydrocarbon group or a heterohydrocarbon group, and further is H or a hydrocarbon group; x = 1 or 2, and if x = 1, then M is Zn, and if x = 2, then M is Al;

[0157] iic) Each p is as defined above; and R 5 R 6 R 7 R 8 Each corresponding unit is as defined above; and R A R B and R C Each of them is independently H, a hydrocarbon group, or a heterohydrocarbon group, and further is H or a hydrocarbon group; x = 0 or 1, and if x = 0 (the [(CR 5 R 6 -CR 7 R 8 ) pIf the -CH3]) part does not exist, then M is Zn, and if x=1, then M is Al;

[0158] iiic) Each p is as defined above; and R 5 R 6 R 7 R 8 Each corresponding unit is as defined above; and R A R B and R C Each of them is independently H, a hydrocarbon group, or a heterohydrocarbon group, and further is H or a hydrocarbon group; M is Al; or

[0159] ivc) any combination of them

[0160] G)M[R 9 ] x Where M is a metal selected from Zn or Al; x is 2 or 3, and if x=2, then M is Zn, and if x=3, then M is Al; each R 9 Independently a hydrocarbon group;

[0161] H) Silanes containing at least one silyl vinyl group,

[0162] I) Forming one or more silane-M-molecule complexes, each independently selected from id, iid, iiid, or ivd:

[0163] id) , where each R 9 As defined above; and R D R E and R F Each of them is independently H, a hydrocarbon group or a heterohydrocarbon group, and further is H or a hydrocarbon group; x = 1 or 2, and when x = 1, then M is Zn, and when x = 2, then M is Al;

[0164] iid) , where each R 9 As defined above; and R D R E and R F Each of them is independently H, a hydrocarbon group, or a heterohydrocarbon group, and further is H or a hydrocarbon group; x = 0 or 1, and when x = 0 ((R 9 If the part does not exist, then M is Zn, and when x=1, then M is Al;

[0165] iiid) , where each R 9 As defined above; and R D RE and R F Each of them is independently H, a hydrocarbon group, or a heterohydrocarbon group, and further is H or a hydrocarbon group; M is Al; or

[0166] ivd) any combination of them;

[0167] Hydrolysis of one or more silane-M-molecular complexes (I) is performed to form a silane. In another embodiment, each silane-M-molecular complex is independently selected from id, iid, or iiid.

[0168] J2] According to the method described in I2 above, the method further includes separating the "composition containing silane". See the example of the separation method discussed above. (Item)

[0169] K2] According to the method described above I2] or J2], wherein the method is a solution method.

[0170] L2] According to any one of I2] to K2] above, wherein independently for each of id-iiid, R D R E and R F Each of them is independently an alkyl group or a vinyl group.

[0171] M2] According to any one of I2] to L2] above, wherein independently for each of id-iiid, R D R E and R F Each of them is independently an alkyl group, or a C1-C5 alkyl group, or a C1-C4 (2,6-bis(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphth-2-diyl(6-pyridin-2-diyl)methane)]dimethylhafnium].

[0172] H2] According to any one of U] to G2] above, the silane-modified olefin-based polymer comprises the following polymer c:

[0173] c)Si(R A (R) B (R) C )-CH2-CH2-(CR 5 R 6 -CR 7 R 8 ) p -CH3, where p is as defined above (see, for example, U); and R A R B and R CEach of them is as defined above (see, for example, U); and for each p value, R 5 R 6 R 7 R 8 Each of them is as defined above (see, for example, U).

[0174] [I2] A method for forming a composition comprising silane, the method comprising reacting G) as shown below with H) to form I) as shown below:

[0175] G)M[R 9 ] x Where M is a metal selected from Zn or Al; x is 2 or 3, and if x=2, then M is Zn, and if x=3, then M is Al; each R 9 Independently a hydrocarbon group;

[0176] H) Silanes containing at least one silyl vinyl group,

[0177] I) Forming one or more silane-M-molecule complexes, each independently selected from id, iid, iiid, or ivd:

[0178] id) , where each R 9 As defined above; and R D R E and R F Each of them is independently H, a hydrocarbon group or a heterohydrocarbon group, and further is H or a hydrocarbon group; x = 1 or 2, and when x = 1, then M is Zn, and when x = 2, then M is Al;

[0179] iid) , where each R 9 As defined above; and R D R E and R F Each of them is independently H, a hydrocarbon group, or a heterohydrocarbon group, and further is H or a hydrocarbon group; x = 0 or 1, and when x = 0 ((R 9 If the part does not exist, then M is Zn, and when x=1, then M is Al;

[0180] iiid) , where each R 9 As defined above; and R D R E and R F Each of them is independently H, a hydrocarbon group, or a heterohydrocarbon group, and further is H or a hydrocarbon group; M is Al; or

[0181]

[0182] s18) and s19) any combination thereof.

[0183] W2] According to any one of A] to T], U2] or V2] above, the "polysiloxane containing at least one silyl vinyl group" contains ≥2, or ≥3, or ≥4, or ≥5, or ≥6, or ≥8, or ≥10 Si atoms per molecule. and / or Each molecule contains ≤1000, or ≤800, or ≤600, or ≤400, or ≤200, or ≤100, or ≤50 Si atoms.

[0184] X2] According to any one of A] to T] or U2] to V2] above, the density of the "polysiloxane containing at least one silyl vinyl group" is ≥0.80 g / cc, or ≥0.82 g / cc, or ≥0.85 g / cc.

[0185] d)Si(R D (R) E (R) F )-CH2-CH2-R 9 , where R D R E and R F Each of them is as defined above (see, for example, I2), and R 9 As defined above (for example, see I2).

[0186] U2] The method according to any one of A] to T2] above, wherein the method is performed at ≥50°C, or ≥60°C, or ≥70°C, or ≥80°C, or ≥85°C, or ≥90°C, or ≥95°C, or ≥100°C, or ≥105°C, or ≥110°C. and / or The method shall operate at temperatures ≤200°C, ≤190°C, ≤180°C, ≤170°C, ≤160°C, ≤150°C, ≤145°C, ≤140°C, ≤135°C, ≤130°C, or ≤125°C. Furthermore, the method shall operate under an inert atmosphere (e.g., nitrogen).

[0187] V2] According to any one of A] to T] or U2] above, the polysiloxane containing at least one silyl vinyl group is selected from the group consisting of s1) to s19); and independently for each of s1)-s6), s10)-s13), s15), s16), s18), each n is independently ≥1; and independently for each of s2)-s10), s14), s17), s18), each m is independently ≥1; and for s18), p ≥1:

[0188]

[0189]

[0190] s18) and s19) any combination thereof.

[0191] W2] According to any one of A] to T], U2] or V2] above, the "polysiloxane containing at least one silyl vinyl group" contains ≥2, or ≥3, or ≥4, or ≥5, or ≥6, or ≥8, or ≥10 Si atoms per molecule. and / or Each molecule contains <1000, or ≤800, or ≤600, or ≤400, or ≤200, or ≤100, or ≤50 Si atoms.

[0192] X2] According to any one of A] to T] or U2] to V2] above, the density of the "polysiloxane containing at least one silyl vinyl group" is ≥0.80 g / cc, or ≥0.82 g / cc, or ≥0.85 g / cc, or ≥0.87 g / cc, or ≥0.90 g / cc, or ≥0.91 g / cc, or ≥0.92 g / cc and / or ≤1.0 g / cc, or ≤0.99 g / cc, or ≤0.98 g / cc, or ≤0.97 g / cc (1 cc = 1 cm³). 3 ).

[0193] Y2] According to any one of A] to T] or U2] to W2] above, wherein, based on the weight of the polysiloxane, the polysiloxane containing at least one silyl vinyl group has a silyl vinyl group weight percentage of ≥0.50 wt%, or ≥0.70 wt%, or ≥1.0 wt%, or ≥1.2 wt%, or ≥1.5 wt%, or ≥1.7 wt%, or ≥2.0 wt%. and / or ≤40% by weight, or ≤35% by weight, or ≤30% by weight, or ≤25% by weight, or ≤20% by weight, or ≤15% by weight.

[0194] A3] A composition formed by any one of A] to Y2] above.

[0195] B3] A composition comprising a siloxane-modified olefin-based polymer formed by any one of the methods described in A] to T] or U2] to Y2] above.

[0196] C3] The composition according to B3], wherein the siloxane-modified olefin-based polymer comprises the following polymer segments a1 and / or a2 and b as follows:

[0197] a1)-O-Si(R)(R')-CH2-CH2-(CR 1 R 2 -CR 3 R 4 ) n -CH3, where n is as defined herein (e.g., see P]); and each of R and R' is as defined herein (e.g., see P]); and R 1 R 2 R 3 R 4 Each of these is as defined herein (e.g., see P]);

[0198] a2)-O-Si(R")-CH2-CH2-((CR 1 R 2 -CR 3 R 4 )n-CH3)-, where n is as defined herein (e.g., see P]; and R” is as defined herein (e.g., see P]; and R 1 R 2 R 3 R 4 Each of these is as defined herein (e.g., see P]);

[0199] b)-(O-SiR'""R"")) m - where m is as defined herein (e.g., see P]); each of R'” and R”” is as defined herein (e.g., see P]).

[0200] [D3] A composition comprising a silane-modified olefin-based polymer formed by any one of the methods described above, from [U] to [H2] or [U2].

[0201] E3] A composition comprising a silane formed by any one of the methods described above [I2] to [T2] or [U2].

[0202] [F3] A composition comprising a siloxane-modified olefin-based polymer, wherein the siloxane-modified olefin-based polymer comprises at least one chain, the at least one chain comprising at least one structure selected from T1) to T4):

[0203] T1) Where m≥2; x≥1; n≥1; and for each value of n, R 1 R 2 R 3 R 4 Each of them is independently an H or hydrocarbon group; and R1 For each consecutive repeating unit, it can be the same or it can be different (or R) 1 (Each time it appears, it is independently selected from H or hydrocarbon groups); R 2 For each consecutive repeating unit, it can be the same or it can be different (or R) 2 (Each time it appears, it is independently selected from H or hydrocarbon groups); R 3 For each consecutive repeating unit, it can be the same or it can be different (or R) 3 (Each time it appears, it is independently selected from H or hydrocarbon groups); R 4 For each consecutive repeating unit, it can be the same or it can be different (or R) 4 Each time it appears, it is independently selected from H or a hydrocarbon group); and each of R and R' is independently a hydrocarbon group; and each asterisk (*) independently represents the corresponding remainder of the chain;

[0204] T2) where m≥2 and

[0205] Furthermore, m ≥ 3; x ≥ 1; y ≥ 1; each n independently ≥ 1; and for each corresponding value of n, R 1 R 2 R 3 R 4 Each of them is independently an H or hydrocarbon group; and R 1 For each consecutive repeating unit, it can be the same or it can be different (or R) 1 (Each time it appears, it is independently selected from H or hydrocarbon groups); R 2 For each consecutive repeating unit, it can be the same or it can be different (or R) 2 (Each time it appears, it is independently selected from H or hydrocarbon groups); R 3 For each consecutive repeating unit, it can be the same or it can be different (or R) 3 (Each time it appears, it is independently selected from H or hydrocarbon groups); R 4 For each consecutive repeating unit, it can be the same or it can be different (or R) 4 Each time it appears, it is independently selected from H or a hydrocarbon group); and each of R, R' and R" is independently a hydrocarbon group; and each asterisk (*) independently represents the corresponding remainder of the chain;

[0206] T3) Where m≥2 and further m≥3; x≥1; y≥1; n≥1; and for each value of n, R 1 R 2 R 3 R 4 Each of them is independently an H or hydrocarbon group; and R 1 For each consecutive repeating unit, it can be the same or it can be different (or R) 1(Each time it appears, it is independently selected from H or hydrocarbon groups); R 2 For each consecutive repeating unit, it can be the same or it can be different (or R) 2 (Each time it appears, it is independently selected from H or hydrocarbon groups); R 3 For each consecutive repeating unit, it can be the same or it can be different (or R) 3 (Each time it appears, it is independently selected from H or hydrocarbon groups); R 4 For each consecutive repeating unit, it can be the same or it can be different (or R) 4 Each time it appears, it is independently selected from H or a hydrocarbon group); and each of R, R', and R" is independently a hydrocarbon group; and each asterisk (*) independently represents the corresponding remainder of the chain; or

[0207] T4) any combination of them.

[0208] G3] According to the composition described in F3 above, wherein the siloxane-modified olefin-based polymer comprises at least one chain, the at least one chain comprising at least one structure selected from T5) to T8), and wherein each asterisk (*) independently represents the corresponding remaining portion of the chain:

[0209] T5) Where m≥2; x≥1; n≥1;

[0210] T6) Where m≥2 and further m≥3; x≥1; y≥1; each n independently≥1;

[0211] T7) Where m≥2 and further m≥3; x≥1; y≥1; n≥1; or

[0212] T8) any combination of them.

[0213] H3] The composition according to any one of A3] to C3] above, wherein the siloxane-modified olefin-based polymer comprises at least one structure selected from T1) to T4) as described above (see F3]).

[0214] I3] According to the composition described above in H3], the siloxane-modified olefin-based polymer comprises at least one structure selected from T5) to T8) as described above (see G3)

[0215] J3] The method according to any one of A] to H2] or U2] to Y2] above, or the composition according to A3] to D3] or F3] to I3] above, wherein the composition further comprises a polymer that is different from the siloxane-modified olefin-based polymer or the silane-modified polymer in one or more aspects, such as monomer type, Mn, Mw, MWD, density or any combination thereof.

[0216] K3] according to any one of the methods described above A] to H2] or U2] to Y2] or J3], or according to the compositions described above A3] to D3] or F3] to J3], wherein the compositions further comprise olefin-based polymers.

[0217] Propylene, 1-butene or 1-octene; or 1-butene or 1-octene; or 1-octene.

[0218] I4] The method according to any one of A] to T], U2] to Y2] or J3 to D4] above, or the composition according to any one of A3] to C3] or F3] to D4] above, wherein the siloxane-modified olefin-based polymer is a siloxane-modified propylene-based polymer.

[0219] J4] The method or composition according to I4 above, wherein the siloxane-modified propylene-based polymer is a siloxane-modified polypropylene homopolymer.

[0220] [K4] According to the method described in [I4] above or the composition described in [I4] above, wherein the siloxane-modified propylene-based polymer is a siloxane-modified propylene / ethylene interpolymer, and further is a siloxane-modified propylene / ethylene copolymer; or a siloxane-modified propylene / α-olefin interpolymer, and further is a siloxane-modified propylene / α-olefin copolymer.

[0221] L4] According to the method described in K4 above or the composition described in K4 above, wherein the α-olefin is a C4-C20 α-olefin; or a C4-C10 α-olefin; or selected from 1-butene, 1-pentene, 1-hexene or 1-octene; or 1-butene, 1-hexene or 1-octene; or 1-butene or 1-octene; or 1-octene.

[0222] M4] according to any one of the methods of A] to T], U2] to Y2] or J3] to L4] above, or according to any one of the compositions of A3] to C3] or F3] to L4] above, wherein independently for each of the polysiloxane-M-polymer complexes i to ix, the remainder (*) of the complex or the corresponding remainder (*) of the complex may independently contain or may independently not contain one or more other polysiloxane-M-polymer complexes.

[0223] [N4] According to the method described in [M4] above or the composition described in [M4] above, wherein the remainder (*) of the composite or the corresponding remainder (*) of the composite independently comprises one or more additional polysiloxane-M-polymer composites.

[0224] O4] According to the method of M4 above or the composition of M4 above, the remainder (*) of the composite or the corresponding remainder (*) of the composite does not contain one or more additional polysiloxane-M-polymer composites.

[0225] A5] A crosslinking composition formed by a method according to any one of A] to H2], U2] to Y2] or J3] to O4] above.

[0226] B5] A crosslinking composition formed from a composition according to any one of A3] to D3] or F3 to O4] above.

[0227] C5] An article comprising the composition according to any one of A3] to O4] above.

[0228] [D5] An article comprising at least one component formed of a composition according to any one of [A3] to [O4] above.

[0229] E5] An article comprising a crosslinking composition according to A5 or B5 above.

[0230] F5] An article comprising at least one component formed of a crosslinking composition according to A5 or B5 above.

[0231] G5] An article comprising at least one component formed by the method according to any one of A] to Y2] or J3] to O4] above.

[0232] Test methods

[0233] Gas chromatography-mass spectrometry (GC / MS)

[0234] Tandem gas chromatography / low-resolution mass spectrometry using electron collisional ionization (EI) was performed at 70 eV on an Agilent Technologies 6890N series gas chromatograph equipped with an Agilent Technologies 5975 inert XL mass selective detector and an Agilent Technologies capillary column (HP1MS, 15 m × 0.25 mm, 0.25 μm). The following conditions (programmed method) were used: a) oven equilibration time of 0.5 min; b) oven equilibration at 50 °C at the start of analysis, followed by temperature ramping to 200 °C at 25 °C / min and holding at 200 °C for 5 min; c) run time of 11 min.

[0235] density

[0236] The density of the polymer was measured by preparing a polymer sample according to ASTM D 1928 and then measuring the density within one hour of sample pressing according to ASTM D792 Method B.

[0237] Gel permeation chromatography

[0238] Composition of conventional GPC

[0239] The chromatographic system consisted of a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5). The autosampler oven chamber was set to 160°C, and the column chamber to 150°C. Four Agilent "Mixed A" 30 cm, 20 μm linear mixed-bed columns were used. The chromatographic solvent was 1,2,4-trichlorobenzene containing 200 ppm of butylated hydroxytoluene (BHT). The solvent source was nitrogen injection. The injection volume was 200 μL, and the flow rate was 1.0 mL / min.

[0240] The calibration of the GPC column was performed using 21 narrow molecular weight distribution polystyrene standards ranging from 580 g / mol to 8,400,000 g / mol, arranged in six “mixture” solutions with at least ten-fold intervals between individual molecular weights. The standards were purchased from Agilent Technologies. For molecular weights equal to or greater than 1,000,000, polystyrene standards were prepared using “0.025 g in 50 mL of solvent”, and for molecular weights less than 1,000,000, polystyrene standards were prepared using “0.05 g in 50 mL of solvent”. The polystyrene standards were pre-dissolved at 80°C with gentle stirring for 30 minutes, then cooled, and the “room temperature solution” was transferred to a 160°C autosampler dissolution oven for cooling for 30 minutes. The peak molecular weights of the polystyrene standards were converted to polyethylene molecular weights using Equation 1 (e.g., Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)). , where M is the molecular weight, A has a value of 0.424 and B equals 1.0. A fifth-order polynomial is used to fit the calibration point for the corresponding polyethylene equivalent.

[0241] Total plate counts were performed on the GPC column array using decane, which was introduced into the blank sample via a micropump controlled by a PolymerChar GPC-IR system. For four Agilent "Mixed Type A" 30 cm, 20 μm linear mixed-bed columns, the plate count of the chromatographic system should be greater than 18,000. Samples were prepared semi-automatically using PolymerChar "InstrumentControl" software, with a target sample weight of 2 mg / mL, and the solvent (containing 200 ppm BHT) was added to a pre-bubbled, septum-capped vial using a PolymerChar high-temperature autosampler. The sample was dissolved at 160°C for 2 hours with "low-speed" shaking.

[0242] To monitor deviations over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by a PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly correct the pump flow rate (nominal flow rate) for each sample by comparing the RV (RV(FM sample)) of the corresponding decane peak within the sample with the RV (RV(FM calibrated)) of the decane peak within the narrow standard calibration. It was then assumed that any variation in the decane marker peak time was linearly related to the flow rate (effective flow rate) throughout the run. After calibration based on the flow marker peak, the effective flow rate (relative to the narrow standard calibration) was calculated according to Equation 2. (via PolymerChar GPCOne)™ The software processes the flow marker peaks. Acceptable flow rate correction ensures that the effective flow rate is within + / - 0.5% of the nominal flow rate.

[0243] IR5 GPC Octene Composition Calibration

[0244] Calibration for quantitative dispensing of the IR5 detector was performed using at least ten ethylene-based polymer standards (octene as a comonomer), which were characterized by narrow short-chain branching (SCB or CH3) distribution and known comonomer content (e.g., by means of...). 13 The standards (measured by C NMR, Qiu et al., Anal. Chem. 2009, 81, 8585−8589) were prepared from a single reactor using a single-point metallocene catalyst in a solution process (polyethylene homopolymer and ethylene / octene copolymer). These standards range from homopolymers (0 SCB / 1000 total C) to approximately 40 SCB / 1000 total C, where total C = carbon in the main chain + carbon in the branches. Each standard has a weight-average molecular weight of 36,000 g / mol to 126,000 g / mol as measured by GPC. Each standard has a molecular weight distribution (Mw / Mn) of 2.0 to 2.5. The polymer properties of the SCB standards are shown in Table A.

[0245]

[0246] For each of the “SCB” standards, calculate the “IR5 area ratio” (or “IR5 area ratio”) of the “area response of the IR5 methyl channel sensor minus the baseline” to the “area response of the IR5 measurement channel sensor minus the baseline”. 甲基通道面积 / IR5 测量通道面积 (e.g., standard filters and filter wheels supplied via PolymerChar: part number IR5_FWM01SS includes parts as part of a GPC-IR instrument). The linear fit between the SCB frequency and the "IR5 area ratio" is constructed in the form of the following Equation 3: Where A0 is the intercept of SCB / 1000 total C at zero "IR5 area ratio", and A1 is the slope of "SCB / 1000 total C" versus "IR5 area ratio" and represents the increase of SCB / 1000 total C as a function of "IR5 area ratio". For narrow PDI and narrow SCBD standard materials, the IR5 area ratio is equal to the IR5 height ratio.

[0247] The superposition of GPC curves can be performed using commercially available software, such as software available for the chromatography system or Excel software; or by other methods known in the art.

[0248] NMR (13C and 29Si)

[0249] 13 C NMR and 29 Si NMR spectra were collected individually using a Bruker 600MHz Avance III HD system equipped with a 10mm multinuclear, helium NMR cryopreservation probe. A standard zgig pulse sequence was used. Polymer samples were prepared by adding approximately 2.6g of a 50 / 50 mixture of tetrachloroethane-d2 / o-dichlorobenzene containing 0.025M chromium triacetylacetonate (relaxant) to 0.2g of the polymer in a 10mm NMR tube. The samples were dissolved and homogenized by heating the tube and its contents to 150°C. Data were acquired using 320 scans per data file at a 7.3-second pulse repetition delay and a sample temperature of 120°C. More NMR samples and parameters are detailed in Z. Zhou et al., Macromolecules 2023, 56, 234–240, which is incorporated herein by reference. Corresponding peak integrals are shown below. Figure 4 and Figure 5 As shown.

[0250] experiment

[0251] The reagents, co-catalysts, and main catalysts are shown below.

[0252] Vinyl-terminated polydimethylsiloxane (DMS-V05), with a MW of 800, a viscosity of 4-8, a density of 0.93, a vinyl weight percentage of 7-9, and a vinyl content (eq / kg) of 2.4-2.9, is available from Gelest.

[0253]

[0254] 1,3-Divinyltetramethyldisiloxane (DVTMDS), with a molecular weight of 186.40 g / mol, is available from Sigma-Aldrich.

[0255] Octenyl dimethyl vinyl silane (ODMVS) is available from Gelest.

[0256] Vinylmethylsiloxane homopolymer (VMS-T11), linear, with a MW of 1000-5000, a viscosity of 7-15, and a density of 0.96, is available from Gelest.

[0257]

[0258] Triethylaluminum (TEA) is available from Sigma-Aldrich.

[0259] Trioctyl aluminum (TOA) is available from Sigma-Aldrich.

[0260] Diethylzinc (DEZ) is available from Sigma-Aldrich.

[0261] ISOPAR-E solvent is available from ExxonMobil.

[0262] Decane solvent is available from Sigma-Aldrich.

[0263] Co-catalyst 1 (Co-Cat 1) is bis(hydrogenated tallow alkyl)methyltetra(pentafluorophenyl)boronic acid (1-)amine, which is available from Boulder Scientific.

[0264] Main catalyst (1): (E)-((2,6-diisopropylphenyl)(2-methyl-3-(octylimino)butane-2-yl)amino)trimethylhafnium:

[0265] .

[0266] Main catalyst (2): (N-((6E)-6-(butylimino-κN)-l-cyclohexen-l-yl)-2,6-bis(1-methyl-ethyl)anilino-κN)trimethylhafnium

[0267] .

[0268] Main catalyst (3): [N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphth-2-diyl(6-pyridin-2-diyl)methane)]dimethylhafnium]:

[0269] .

[0270] Study of GC mass spectrometry of reaction product (Al)

[0271] Example 1

[0272] The reaction of trioctyl aluminum (TOA) with 1,3-divinyltetramethyldisiloxane (DVTMDS) follows Scheme 4 as shown below.

[0273]

[0274] In a drying oven under a nitrogen atmosphere, 1,3-divinyltetramethyldisiloxane (0.254 g, 1.364 mmol) and trioctylaluminum (0.1 g, 0.273 mmol) were dissolved in 5 mL of decane in a vial, and the solution was heated to 130 °C (temperature of the heating block). Samples were taken at 15 minutes and 1 hour and hydrolyzed (with MeOH) for GC / MS analysis to monitor the formation of the insertion product. GC / MS results are shown in [the table / image / image]. Figure 1 As shown in the figure. GC / MS results indicate the presence of the following molecular species (A to E). These results confirm the reaction of Scheme 4 above.

[0275]

[0276] SCB / 1000 total C is used as a function of "IR5 area ratio". For narrow PDI and narrow SCBD standard materials, the IR5 area ratio is equal to the IR5 height ratio.

[0277] The superposition of GPC curves can be performed using commercially available software, such as software available for the chromatography system or Excel software; or by other methods known in the art.

[0278] NMR (13C and 29Si)

[0279] 13 C NMR and 29 Si NMR spectra were collected individually using a Bruker 600MHz Avance III HD system equipped with a 10mm multinuclear, helium NMR cryopreservation probe. A standard zgig pulse sequence was used. Polymer samples were prepared by adding approximately 2.6g of a 50 / 50 mixture of tetrachloroethane-d2 / o-dichlorobenzene containing 0.025M chromium triacetylacetonate (relaxant) to 0.2g of the polymer in a 10mm NMR tube. The samples were dissolved and homogenized by heating the tube and its contents to 150°C. Data were acquired using 320 scans per data file at a 7.3-second pulse repetition delay and a sample temperature of 120°C. More NMR samples and parameters are detailed in Z. Zhou et al., Macromolecules 2023, 56, 234–240, which is incorporated herein by reference. Corresponding peak integrals are shown below. Figure 4 and Figure 5 As shown.

[0280] experiment

[0281] The reagents, co-catalysts, and main catalysts are shown below.

[0282] Vinyl-terminated polydimethylsiloxane (DMS-V05), with a MW of 800, a viscosity of 4-8, a density of 0.93, a vinyl weight percentage of 7-9, and a vinyl content (eq / kg) of 2.4-2.9, is available from Gelest.

[0283]

[0284] 1,3-Divinyltetramethyldisiloxane (DVTMDS), with a molecular weight of 186.40 g / mol, is available from Sigma-Aldrich.

[0285] Octenyl dimethyl vinyl silane (ODMVS) is available from Gelest.

[0286] Vinylmethylsiloxane homopolymer (VMS-T11), linear, with a MW of 1000-5000, a viscosity of 7-15, and a density of 0.96, is available from Gelest.

[0287]

[0288] Triethylaluminum (TEA) is available from Sigma-Aldrich.

[0289] Trioctyl aluminum (TOA) is available from Sigma-Aldrich.

[0290] Diethylzinc (DEZ) is available from Sigma-Aldrich.

[0291] ISOPAR-E solvent is available from ExxonMobil.

[0292] Decane solvent is available from Sigma-Aldrich.

[0293] Co-catalyst 1 (Co-Cat 1) is bis(hydrogenated tallow alkyl)methyltetra(pentafluorophenyl)boronic acid (1-)amine, which is available from Boulder Scientific.

[0294] Main catalyst (1): (E)-((2,6-diisopropylphenyl)(2-methyl-3-(octylimino)butane-2-yl)amino)trimethylhafnium:

[0295]

[0296] Main catalyst (2): (N-((6E)-6-(butylimino-κN)-l-cyclohexen-l-yl)-2,6-bis(l-methyl-ethyl)anilino-κN)trimethylhafnium

[0297] .

[0298] Main catalyst (3): [N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphth-2-diyl(6-pyridin-2-diyl)methane)]dimethylhafnium]:

[0299]

[0300] Study of GC mass spectrometry of reaction product (Al)

[0301] Example 1

[0302] The reaction of trioctyl aluminum (TOA) with 1,3-divinyltetramethyldisiloxane (DVTMDS) follows Scheme 4 as shown below.

[0303]

[0304] In a drying oven under a nitrogen atmosphere, 1,3-divinyltetramethyldisiloxane (0.254 g, 1.364 mmol) and trioctylaluminum (0.1 g, 0.273 mmol) were dissolved in 5 mL of decane in a vial, and the solution was heated to 130 °C (temperature of the heating block). Samples were taken at 15 minutes and 1 hour and hydrolyzed (with MeOH) for GC / MS analysis to monitor the formation of the insertion product. GC / MS results are shown in [the table / image / image]. Figure 1 As shown in the figure. GC / MS results indicate the presence of the following molecular species (A to E). These results confirm the reaction of Scheme 4 above.

[0305]

[0306] The GC peak at m / z 114 is octane formed by the hydrolysis of TOA. The peak at m / z 171 is a fragment of the initial siloxane after the loss of a methyl group. The sample taken at 15 minutes showed three new product peaks, C, D, and E, with m / z values ​​of 285, 397, and 399, respectively. Figure 1 These product peaks are consistent with fragments of products formed by the addition of octane to one or two vinyl groups. Samples taken at 1 hour (see...) Figure 1 This shows the growth of the product peak.

[0307] Example 2

[0308] The reaction of trioctylaluminum (TOA) with octenyldimethylvinylsilane (ODMVS) is shown in Scheme 5 below.

[0309]

[0310] In a drying oven under a nitrogen atmosphere, octenyl dimethyl vinyl silane (ODMVS) (0.536 g, 2.73 mmol) and trioctyl aluminum (0.1 g, 0.273 mmol) were dissolved in 5 mL of decane in a vial and heated to 130 °C. Samples collected at 15 min and 1 h were hydrolyzed (with MeOH) and analyzed by GC / MS to monitor the formation of insertion products. Results are shown below. Figure 2 The GC / MS results indicate the presence of the following molecular species (A through D). These results confirm the reaction in Scheme 5 above.

[0311]

[0312] Peak A at m / z 114 is octane formed by the hydrolysis of TOA. Peak B at m / z 181 is a fragment of the starting silane after the loss of a methyl group. The new peaks C and D at m / z 293 and 295, respectively, are consistent with the fragments of the product of octane added to a silyl vinyl group as shown above.

[0313] Study 2 - Polymer Synthesis - Solution Method

[0314] Example 3

[0315] The preparation of the polyethylene-PDMS linear block polymer is shown in Scheme 6 below.

[0316]

[0317] In a drying oven (nitrogen atmosphere), 10 ml of ISOPAR-E solvent, 1.8 μmol of Co-Cat 1, and 0.22 mmol of TEA were added to a 40 ml vial equipped with a stir bar. The vial was capped with a diaphragm-lined cap and placed in a heating block. The vial was connected to the C2 (ethylene) line and slowly purged through a needle using this line. Once the vial reached 100 °C (as indicated by the temperature of the heating block), the main catalyst 1 [(E)-((2,6-diisopropylphenyl)(2-methyl-3-(octylimino)butane-2-yl)amino)trimethylhafnium], 1.5 μmol in 0.2 ml of ISOPAR-E] was injected into the vial, and the purging needle was removed to maintain the total pressure at 12 psig (as determined by the pressure gauge on the ethylene line). The reaction was maintained for 20 minutes. Afterward, the ethylene line was removed, and a portion of the solution was removed and allowed to precipitate in MeOH to obtain pure polyethylene. Add 1 mL of DMS-V05 to the remaining solution in the vial and heat the resulting solution at 130 °C for 30 min, then precipitate the reaction product in MeOH. Filter both the polyethylene and the reaction product and dry them under vacuum. Analyze each product by GPC. The compositional GPC overlay plot is shown in... Figure 3As shown in the image.

[0318] exist Figure 3 In the diagram, regarding the "dW / dLogM" y-axis, when Log M = 3.00, the narrower upper curve represents polyethylene (PE), the next lower curve represents the reaction products containing PE-PDMS and PE, and the wider lower curve represents DMS-V05.

[0319] 29 Si NMR spectrum in Figure 4 The 13C NMR spectrum is shown in Figure 5 As shown in the image. Based on 29 Si NMR, based on the Si-CH2-P / Si-CH=CH2 ratio, shows that approximately 40% of the double bonds in the "Si-C=C" region are converted to Si-P (where P is a polyethylene polymer) (compare the Si peak intensity in the Si NMR spectrum). Based on 13C NMR, based on the Si-CH2-P / Si-CH=CH2 ratio, approximately 47% of the double bonds in the "Si-C=C" region are converted to Si-P (compare the carbon peak intensity in the 13C NMR spectrum). These NMR results each indicate that the reaction proceeded as described in Scheme 6 above.

[0320] Example 4

[0321] The synthesis of the polyethylene-PDMS comb-shaped block polymer is shown in Scheme 7.

[0322]

[0323] For Example 4, the same procedure as in Example 3 was followed, including the same amount of each component, except that VMS-T11 (1 mL) was used instead of DMS-V05. Each product was analyzed by GPC. The composition GPC overlay plot is shown in... Figure 6 As shown in the image.

[0324] exist Figure 6 In the diagram, regarding the "dW / dLogM" y-axis, when Log M=3.00, the narrower upper curve is the curve for polyethylene (PE), the next lower "bimodal" curve is the curve for the reaction products containing PE-PDMS and PE, and the wider lower curve is the curve for VMS-T11.

[0325] As discussed above, in the two polymerizations of Examples 3 and 4, for each reaction, the GPC curves of the block copolymers were superimposed on the starting siloxane and polyethylene samples (obtained before the addition of the siloxane). Clearly, the block copolymers exhibited higher MW fractions compared to the base polyethylene, especially in Example 4, which showed bimodal MWD, indicating the formation of some block copolymers.

[0326] GC-mass spectrometry of the 3-reaction product (Zn) was studied.

[0327] Example 5

[0328] The reaction of diethylzinc (DEZ) with 1,3-divinyltetramethyldisiloxane (DVTMDS) - see Scheme 8.

[0329]

[0330] In a drying oven under a nitrogen atmosphere, 1,3-divinyltetramethyldisiloxane (0.543 g, 2.9 mmol) and trioctylaluminum (0.3 mL, 2.9 mmol) were dissolved in 5 mL of decane in a vial and heated at 150 °C for 20 min. The resulting sample was hydrolyzed (with MeOH) and analyzed by GC / MS. The GC / MS results indicated the presence of the insertion product (m / z = 201) according to Scheme 8, as shown below. The corresponding GC / MS peak chromatogram is shown below. Figure 7 As shown.

[0331]

Claims

1. A method for forming a composition comprising a siloxane-modified olefin-based polymer, the method comprising reacting A) and B) respectively as shown below to form C) as shown below: A)M[(CR 1 R 2 -CR 3 R 4 ) n -CH3] x Where M is a metal selected from Zn or Al; x is 2 or 3, and if x=2, then M is Zn, and if x=3, then M is Al; each n is independently ≥1; and for each corresponding value of n, R 1 R 2 R 3 R 4 Each of them is independently H or a hydrocarbon group; and R¹ can be the same or different for each consecutive repeating unit; R 2 For each consecutive repeating unit, it can be the same or it can be different; R 3 For each consecutive repeating unit, it can be the same or it can be different; R 4 Each consecutive repeating unit can be the same or can be different; B) A polysiloxane, wherein the polysiloxane comprises at least one silyl vinyl group; C) Form one or more polysiloxane-M-polymer complexes, each independently selected from i, ii, iii, iv, v, vi, vii, viii, ix, or x: i) where each n is as defined above, and R 1 R 2 R 3 R 4 Each of the corresponding units is as defined above; and each of R and R' is independently a hydrocarbon group or a heterohydrocarbon group; x = 1 or 2, and if x = 1, then M is Zn, and if x = 2, then M is Al; and an asterisk (*) indicates the remainder of the complex; ii) where each n is as defined above, and R 1 R 2 R 3 R 4 Each corresponding unit is as defined above; and R” is a hydrocarbon group or a heterohydrocarbon group; x = 1 or 2, and if x = 1, then M is Zn, and if x = 2, then M is Al; and each asterisk (*) independently represents the corresponding remainder of the complex; iii) where each n is as defined above, and R 1 R 2 R 3 R 4 Each corresponding unit is as defined above; and each of R and R' is independently a hydrocarbon group or a heterohydrocarbon group; x = 0 or 1, and if x = 0 ([(CR 1 R 2 -CR 3 R 4 If the [n-CH3]) portion does not exist, then M is Zn, and if x=1, then M is Al; and each asterisk (*) independently represents the corresponding remainder of the complex; iv) where each n is as defined above, and R 1 R 2 R 3 R 4 Each corresponding unit is as defined above; and each R” is independently a hydrocarbon group or a heterohydrocarbon group; x = 0 or 1, and if x = 0 (the [(CR)] 1 R 2 -CR 3 R 4 If the [n-CH3]) portion does not exist, then M is Zn, and if x=1, then M is Al; and each asterisk (*) independently represents the corresponding remainder of the complex; v) where each n is as defined above, and R 1 R 2 R 3 R 4 Each corresponding unit is as defined above; and each of R, R', and R" is independently a hydrocarbon group or a heterohydrocarbon group; x = 0 or 1, and if x = 0 (the [(CR 1 R 2 -CR 3 R 4 If the [n-CH3]) portion does not exist, then M is Zn, and if x=1, then M is Al; and each asterisk (*) independently represents the corresponding remainder of the complex; vi) where each n is as defined above, and R 1 R 2 R 3 R 4 Each of the corresponding units is as defined above; and each of R and R' is independently a hydrocarbon group or a heterohydrocarbon group; and M is Al; and each asterisk (*) independently represents the corresponding remainder of the complex; vii) where each n is as defined above, and R 1 R 2 R 3 R 4 Each corresponding unit is as defined above; and each R” is independently a hydrocarbon group or a heterohydrocarbon group; and M is Al; and each asterisk (*) independently represents the corresponding remainder of the complex; viii) where each n is as defined above, and R 1 R 2 R 3 R 4 Each of the corresponding units is as defined above; and each of R, R' and R" is independently a hydrocarbon group or a heterohydrocarbon group; and M is Al; and each asterisk (*) independently represents the corresponding remainder of the complex; ix) where each n is as defined above, and R 1 R 2 R 3 R 4 Each of the corresponding units is as defined above; and each of R, R' and R" is independently a hydrocarbon group or a heterohydrocarbon group; and M is Al; and each asterisk (*) independently represents the corresponding remainder of the complex; or x) any combination of them; Hydrolyze one or more polysiloxane-M polymer complexes (C) to form the siloxane-modified olefin-based polymer.

2. The method according to claim 1, wherein each of R and R' is independently an alkyl group or a vinyl group with respect to i, iii, v, vi, viiii, ix.

3. The method according to claim 1 or claim 2, wherein independently for i-ix, for each corresponding value of n, R 1 R 2 R 3 R 4 Each of them is independently an H or alkyl group.

4. The method according to any one of claims 1 to 3, wherein each R” is independently an alkyl group or a vinyl group for each of ii, iv, v, vii, viiii, ix.

5. The method according to any one of claims 1 to 4, wherein M is Al.

6. The method according to any one of claims 1 to 5, wherein the siloxane-modified olefin-based polymer comprises the following polymer segments a1 and / or a2 and b: a1)-O-Si(R)(R')-CH2-CH2-(CR 1 R 2 -CR 3 R 4 ) n -CH3, where n is as defined herein; and each of R and R' is as defined herein; and R 1 R 2 R 3 R 4 Each of these is as defined in this document; a2)-O-Si(R”)-CH2-CH2-((CR 1 R 2 -CR 3 R 4 ) n -CH3)-, where n is as defined herein; and R” is as defined herein; and R 1 R 2 R 3 R 4 Each of these is as defined in this document; b)-(O-SiR'""R"")) m - where m≥1, and for each value of m, each of R'” and R”” is independently H or a hydrocarbon group.

7. The method according to claim 6, wherein for segment b, each of R'” and R”” is independently an H or alkyl group.

8. The method according to any one of claims 1 to 7, wherein the method is a solution method.

9. The method according to any one of claims 1 to 8, wherein the method further comprises separating "the composition comprising the siloxane-modified olefin-based polymer".

10. The method according to any one of claims 1 to 9, wherein the composition further comprises an olefin-based polymer.

11. The method of claim 10, wherein the olefin-based polymer is an ethylene-based polymer.

12. A composition formed by the method according to any one of claims 1 to 11.

13. The composition of claim 12, wherein the composition further comprises an olefin-based polymer.

14. The composition of claim 13, wherein the olefin-based polymer is an ethylene-based polymer.

15. The composition according to any one of claims 12 to 14, wherein the siloxane-modified olefin-based polymer comprises at least one chain, the at least one chain comprising at least one structure selected from T5 to T8, and wherein each asterisk (*) independently represents the corresponding remaining portion of the chain: T5) Where m≥2; x≥1; n≥1; T6) Where m≥2; x≥1; y≥1; each n independently ≥1; T7) Where m≥2; x≥1; y≥1; n≥1; or T8) any combination of them.

16. The composition according to any one of claims 12 to 15, wherein, based on the weight of the composition, the composition comprises 15% to 95% by weight of the siloxane-modified olefin-based polymer.

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