Siloxane-modified and silane-modified polymers via direct insertion of silyl vinyl groups into metal-carbon bonds

Abstract

Processes and related compositions for forming siloxane-modified olefin polymers, silane-modified olefin polymers, or silanes, each process as described herein. Each process forms a Si-C bond through the insertion of silyl vinyl into a metal-carbon bond. The silyl vinyl double bond is directly inserted into the metal-carbon bond to form a new, for example, alkyl-Si bond.

Description

[Technical Field]

[0001] Silicone / polyolefin (Si-POE) blends and grafted copolymers are widely used across many application areas, where the silicone properties impart modified surface characteristics (reduced coefficient of friction, or COF) or moisture-curing functionality to the material. Silicones are blended with various ethylene-based polymers to impart improved tactile properties. Silicone-modified low-density polyethylene (LDPE) materials, formed by direct copolymerization of ethylene and silicon monomers under high pressure, are used in wire and cable applications. Silicone functionality is also added to linear low-density polyethylene (LLDPE) materials by reactive extrusion using peroxide grafting of silane monomers, such as vinyltriethoxysilane. While many examples of these physical blends and reactive extrusion grafting techniques are implemented today, these materials have limitations in their final properties, which are related to the nature of the material blend. True Si-POE hybrid materials are hypothesized to offer several advantages, including enhanced surface modification, improved adhesion, alternative crosslinking mechanisms, and the potential benefit of imparting controllable crystallinity to silicone products. In particular, there is a need for efficient and economical processes to produce Si-modified polymers, including random copolymers and block copolymers, using olefin-based polymers and silicone sources.

[0002] International Publication No. WO 2012 / 103080 discloses a process for preparing a polyolefin-polysiloxane block copolymer, the process comprising contacting a polyolefin-aluminum compound with an acyclic polysiloxane or a cyclic siloxane monomer under coupling effective conditions in a manner that provides a polyolefin-polysiloxane block copolymer. Such block copolymers include polyolefin blocks directly covalently bonded to polysiloxane blocks, the polyolefin blocks comprising the polyolefin moiety of the polyolefin-aluminum compound and the polysiloxane blocks comprising 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] U.S. Patent Application Publication No. 2022 / 0073658 discloses a telechelic polyolefin of formula (I), A 1 L 1 L 2 A[[ID=十一]] 2 and a process for its preparation. This reference discloses a process for preparing a telechelic polyolefin, the process comprising: 1) combining starting materials comprising (A) a monomer component, (B) a chain transfer agent component, and (C) a catalyst component comprising a pre-catalyst to form a solution and polymerizing greater than 10 mol% to less than or equal to 99 mol% of the (A) monomer component in the solution; 2) heating the solution; and 3) recovering a product comprising the telechelic polyolefin. The (B) chain transfer agent component comprises an organoaluminum compound of the formula Al(CH2CH(Y 2 )A 2 )3, wherein Y 2 is independently, for each occurrence, hydrogen or a C1-C 30 hydrocarbyl group and A 2However, each instance independently contains a sterically hindered double bond in the hydrocarbyl group. See claim 12. Telechelic polyolefins can be chemically modified 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] JJEisch et al., Stereospecific Reductive Alkylation of Acetylenes by Successive Hydralumination and Carbodemetalation, J.Org.Chem., 1976, 41, 2214-2215, discloses stereospecific cis-hydralumination of acetylene and alkylation of the resulting vinyl alanate complex. See page 2214. Direct hydralumination of monosubstituted or disubstituted acetylene is disclosed as providing convenient and direct pathways to stereoregular disubstituted and trisubstituted olefins, respectively. The drawbacks are as follows: (1) the slow rate of hydralumination of certain disubstituted acetylenes, (2) the formation of positional isomer mixtures when R is not equal to R', and (3) contamination of RHC=CR'Al(i-C4H9)2 by small amounts of RC=C-A1R2' formed from metallization of terminal alkynes by aluminum alkyl. Trimethylsilyl derivatives of monosubstituted acetylenes can also be hyraluminated. See page 2214.

[0005] PRJones et al., Silaethylene Intermediates from alpha-Lithiosilanes.2. Reactions with Chlorosilanes and 1,3-Butadiene, 1977, J.Am.Chem.Soc., 99(26), 8447-8451, discloses the formation of silaethylene intermediates by the elimination of lithium chloride from alpha-lithiochlorosilanes under suitable experimental conditions. The reaction of tert-butyllithium with vinyldimethylchlorosilane at low temperatures in a hydrocarbon solvent is disclosed to yield high yields of cis and trans-1,1,3,3-tetramethyl-2,4-dineopentyl-1,3-disilacyclobutane. When the reaction is carried out in the presence of 1,3-butadiene, obvious [2+2] and [2+4] cycloadducts are produced by the reaction of the silaethylene intermediate with butadiene. Among these is 1,1-dimethyl-2-neopentyl-3-vinylsilacyclo-butane, a compound that cannot be formed by adding alpha-lithiochlorosilane to butadiene followed by ring closure. See abstract for details.

[0006] PR.Jones et al., alpha-Lithiosilanes.4. Silaethylene Cycloadditions with Conjugated Dienes, J.Am.Chem.Soc.1980, 102, 4970-4973, discloses the reaction of vinyldimethylchlorosilane 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 produce cycloadditions of silaethylene intermediates in hydrocarbon solvents. The presence of tetrahydrofuran in the reaction mixture inhibits the formation of cycloadditions and is favorable for the formation of 1,3-disilacyclobutane. No cycloaddition is obtained with 2,5-dimethylfuran. This reference discloses that the exclusion of lithium chloride, which yields the silaethylene intermediate, occurs in a hydrocarbon solvent, while in THF or in the presence of a strong Lewis base, an addition reaction yielding alpha-lithiosilane occurs, yielding products that lead to their coupling reaction. See the abstract.

[0007] N. Petzetakis et al., "Synthesis of Well Defined Polyethylene-Polydimethylsiloxane-Polyethylene Triblock Copolymers by Diimide-Based Hydrogenation of Polybutadiene Blocks," Macromolecules, 2014, 47, 4151-4159, discloses a synthesis route for well-defined polyethylene-b-polydimethylsiloxane-b-polyethylene (EDE) triblock copolymers. Poly(1,4-butadiene)-b-polydimethylsiloxane-b-poly(1,4-butadiene) (BDB) copolymer precursors were synthesized by anionic polymerization followed by diimide-based hydrogenation. Under standard hydrogenation conditions, the siloxane bond is cleaved, leading to significant degradation of the PDMS block. This reference discloses reaction conditions that avoid PDMS degradation using optimal hydrogenation conditions. See abstract.

[0008] U.S. Patent No. 3,691,257 discloses the synthesis of polyolefin siloxane block copolymers using living anionic polymerization (see abstract). These processes typically require the use of butadiene or isoprene, which is then hydrogenated to obtain the polyolefin equivalent. Monomers for anionic polymerization are very limited, typically styrene or butadiene. Therefore, a typical method for producing "polyolefin-like" block copolymers is to produce polybutadiene segments and then remove unsaturation by hydrogenation. Anionic polymerization is less efficient and more costly for the production of these block copolymers. Anionic polymerization generally requires lower temperatures and longer reaction times, resulting in lower efficiency.

[0009] As described above, there is still a need for an efficient and economical process for producing Si-modified polymers, including random copolymers and block copolymers, using olefin-based polymers and silicone sources. This need has been met as described herein. [Overview of the Initiative]

[0010] A process for forming a composition containing a siloxane-modified olefin polymer, wherein A) shown below is reacted with B) to form C) shown below, A)M[(CR 1 R 2 -CR 3 R 4 ) n -CH3]x(wherein M is a metal selected from Zn or Al, x is 2 or 3, when x=2 M is Zn, when x=3 M is Al, and each n independently ≥ 1; for each respective value of n, R 1 , R 2 , R 3 , R 4 Each of them is independently H or hydrocarbyl; R 1 For each consecutive repeating unit, it may or may not be the same, R2 For each consecutive repeating unit, it may or may not be the same, R 3 For each consecutive repeating unit, it may or may not be the same, R 4 (This may or may not be the same for each consecutive repeating unit.) B) Polysiloxane containing at least one silyl vinyl group, C) i, ii, iii, iv, v, vi, vii, viii, ix or x: i)

[0011] [ka] (In the formula, each n is defined above, R 1 , R 2 , R 3 , R 4 Each of the units is defined above, and each of R and R' is independently hydrocarbyl or heterohydrocarbyl, x=1 or 2, where x=1 is Zn, and x=2 is Al, and the asterisk ( * (This represents the remainder of the complex.) ii)

[0012] [ka] (In the formula, each n is defined above, R 1 , R 2 , R 3 , R 4 Each unit is defined above, where R is hydrocarbyl or heterohydrocarbyl, x=1 or 2, where if x=1, M is Zn, where if x=2, M is Al, and each asterisk ( * (These terms independently represent the respective remnants of the complex.) iii)

[0013] [ka] (In the formula, each n is defined above, R 1 , R 2 , R 3 , R 4 Each of the units is defined above, and each of R and R' is independently hydrocarbyl or heterohydrocarbyl, x=0 or 1, and when x=0 ([(CR 1 R 2 -CR 3 R 4 ) n -CH3) If the part does not exist, M is Zn, and if x=1, M is Al, and each asterisk ( * (These terms independently represent the respective remnants of the complex.) iv)

[0014] [ka] (In the formula, each n is defined above, R 1 , R 2 , R 3 , R 4 Each of the units is defined above, and each R'' is independently a hydrocarbyl or heterohydrocarbyl, x=0 or 1, and when x=0 ([(CR 1 R 2 -CR 3 R 4 ) n -CH3) If the part does not exist, M is Zn, and if x=1, M is Al, and each asterisk ( * (These terms independently represent the respective remnants of the complex.) v)

[0015] [ka] (In the formula, each n is defined above, R 1 , R 2 , R 3 , R 4Each of the units is defined above, and each of R, R' and R'' is independently a hydrocarbyl or heterohydrocarbyl, x=0 or 1, and when x=0 ([(CR 1 R 2 -CR 3 R 4 ) n -CH3) If the part does not exist, M is Zn, and if x=1, M is Al, and each asterisk ( * (These terms independently represent the respective remnants of the complex.) vi)

[0016] [ka] (In the formula, each n is defined above, R 1 , R 2 , R 3 , R 4 Each of the units is defined above, where R and R' are independently hydrocarbyl or heterohydrocarbyl, M is Al, and each asterisk ( * (These terms independently represent the respective remnants of the complex.) vii)

[0017] [ka] (In the formula, each n is defined above, R 1 , R 2 , R 3 , R 4 Each of the units is defined above, and each R'' is independently hydrocarbyl or heterohydrocarbyl, M is Al, and each asterisk ( * (These terms independently represent the respective remnants of the complex.) viii)

[0018] [ka] (In the formula, each n is defined above, R1 , R 2 , R 3 , R 4 Each unit of is defined above, each of R, R', and R'' is independently a hydrocarbyl or heterohydrocarbyl, M is Al, and each asterisk ( * ) represents the respective remainder of the complex), ix)

[0019] [Chemical formula] (where each n is defined above, ) R 1 , R 2 , R 3 , R 4 Each unit of is defined above, each of R, R', and R'' is independently a hydrocarbyl or heterohydrocarbyl, M is Al, and each asterisk ( * ) represents the respective remainder of the complex), or x) one or more polysiloxane-M-polymer complexes independently selected from any combination of these, to form hydrolyzing one or more polysiloxane-M polymer complexes (C) to form a siloxane-modified olefinic polymer, a process comprising. [[ID=X]] [[ID=X]]

[0020] [[ID=X]] A process for forming a composition comprising a silane-modified olefinic polymer, which comprises reacting each of D) shown below with E) to form F) shown below, 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, when x = 2, M is Zn, when x = 3, M is Al, each p is independently ≧1, and for each respective p value, R 5 , R 6 , R7 , R 8 Each of which is independently H or hydrocarbyl, and R 5 may be the same or different for each successive repeating unit, and R 6 may be the same or different for each successive repeating unit, and R 7 may be the same or different for each successive repeating unit, and R 8 may be the same or different for each successive repeating unit), E) a silane containing at least one silylvinyl group, F) ic, iic, iiic, or ivc: ic)

[0021]

Chemical formula

[0022]

Chemical formula

[0023] [ka] (In the formula, each p is defined above, R 5 , R 6 , R 7 , R 8 Each of the units is defined above, R A , R B and R C Each of these is independently H, hydrocarbyl, or heterohydrocarbyl, and M is Al), or ivc) Forming one or more silane-M-polymer complexes independently selected from any combination thereof, A process comprising hydrolyzing one or more silane-M polymer complexes (F) to form a silane-modified olefin polymer.

[0024] A process for forming a silane-containing composition, wherein each of the following G) is reacted with H) to form the following I), G)M[R 9 ] x (In the formula, M is a metal selected from Zn or Al, x is 2 or 3, when x=2, M is Zn, when x=3, M is Al, and each R 9 (It is hydrocarbil independently.) H) Silane containing at least one silyl vinyl group, I) id, iid, iiid, or ivd: id)

[0025] [ka] (In the formula, each R9 This is defined above, R D , R E and R F Each of these is independently H, hydrocarbyl, or heterohydrocarbyl, and x=1 or 2, where if x=1, M is Zn, and if x=2, M is Al. iid)

[0026] [ka] (In the formula, each R 9 This is defined above, R D , R E and R F Each of them is independently H, hydrocarbyl, or heterohydrocarbyl, and x=0 or 1, and if x=0 ((R 9 (If the part does not exist, M is Zn, and if x=1, M is Al), iiid)

[0027] [ka] (In the formula, each R 9 This is defined above, R D , R E and R F Each of them is, Independently, H is hydrocarbyl or heterohydrocarbyl, and M is Al), or ivd) To form one or more silane-M-molecular complexes independently selected from any combination thereof, A process comprising hydrolyzing one or more silane-M-molecular complexes (I) to form a silane.

[0028] A composition comprising a siloxane-modified olefin polymer, wherein the siloxane-modified olefin polymer is T1)~T4): T1)

[0029] [ka] (In the formula, m≧2, x≧1, n≧1, and each n Regarding the values, R 1 , R 2 , R 3 , R 4 Each of them is independently H or hydrocarbyl, and R 1 For each consecutive repeating unit, it may or may not be the same, R 2 For each consecutive repeating unit, it may or may not be the same, R 3 For each consecutive repeating unit, it may or may not be the same, R 4 R and R' may be the same or different for each consecutive repeating unit, and each of R and R' is independently hydrocarbyl, and each asterisk ( * ) represents each remaining part of the chain independently. T2)

[0030] [ka] (In the formula, m≧2, x≧1, y≧1, each n is independently ≧1, and for each n value, R 1 , R 2 , R 3 , R 4 Each of them is independently H or hydrocarbyl, and R 1 For each consecutive repeating unit, it may or may not be the same, R 2 For each consecutive repeating unit, it may or may not be the same, R 3 For each consecutive repeating unit, it may or may not be the same, R 4 R and R' may be the same or different for each consecutive repeating unit, and each of R and R' is independently hydrocarbyl, and each asterisk ( * ) represents each remaining part of the chain independently. T3)

[0031] [ka] (In the formula, m≧2, x≧1, y≧1, n≧1, and for each n value, R 1 , R 2 , R 3 , R 4 Each of them is independently H or hydrocarbyl, and R 1 For each consecutive repeating unit, it may or may not be the same, R 2 For each consecutive repeating unit, it may or may not be the same, R 3 For each consecutive repeating unit, it may or may not be the same, R 4 R, R', and R'' may be the same or different for each consecutive repeating unit, and each of them is independently hydrocarbyl, and each asterisk ( * A composition comprising at least one chain having at least one structure selected from T4) (where T4 independently represents the remainder of each chain), or any combination thereof. [Brief explanation of the drawing]

[0032] [Figure 1] This is the GC / MS peak spectrum from the hydrolysis reaction product in Example 1. [Figure 2] This is the GC / MS peak spectrum from the hydrolysis reaction product in Example 2. [Figure 3] This is an overlay of GPC profiles from a reaction product containing DMS-V05 (bottom), polyethylene (top), and PE-PDMS block copolymer (middle). See Example 3. [Figure 4] This is the 29Si NMR profile of the reaction product from Example 3. [Figure 5] This is the 13C NMR profile of the reaction product from Example 3. [Figure 6]This is an overlay of GPC profiles from the reaction product containing VMS-T11 (bottom), polyethylene (top), and PE-PDMS block copolymer (middle). See Example 4. [Figure 7] This is the GC / MS peak spectrum from the hydrolysis reaction product in Example 5. [Modes for carrying out the invention]

[0033] A novel chemical method is provided relating to a novel reaction pathway for forming Si-C bonds via the insertion of silyl vinyl into metal-C bonds, such as Al-C bonds. This chemical method can be used with olefin polymers. In general, the processes provided herein are more efficient and / or economical than polymerization in the art discussed herein.

[0034] As described above, the silyl vinyl double bond is directly inserted into the metal-carbon bond to form a new alkyl-silicon bond, using aluminum alkyl as an example, as illustrated in Scheme 1. These processes can be used to form polyolefin-polydimethylsiloxane block copolymers, as shown in Scheme 2.

[0035] [ka]

[0036] These processes provide an inexpensive route for producing PO-PDMS block copolymers and PO-g-PDMS copolymers, as well as more complex comb-like structures, as shown in Scheme 3.

[0037] [ka]

[0038] A process for forming a Si-C bond is provided, comprising inserting a silyl vinyl group into a metal-carbon bond, wherein the metal is Zn or Al, and furthermore, Al. As described above, a process for forming a composition comprising a siloxane-modified olefin polymer, a composition comprising a silane-modified olefin polymer, or a composition comprising a silane is also provided. A composition comprising a siloxane-modified olefin polymer is also provided, the siloxane-modified olefin polymer comprising at least one structure selected from T1) to T4) as described herein, respectively. See segments a1 and / or a2 and b (see P below), respectively, as described herein. In one embodiment, or a combination of two or more embodiments as described herein, with respect to segment b, each of R''' and R'''' is independently H or an alkyl group, and furthermore, an alkyl group.

[0039] In one embodiment, or in a combination of two or more embodiments described herein, M is Al.

[0040] In one embodiment, or in a combination of two or more embodiments described herein, the process is a solution process.

[0041] In one embodiment, or in a combination of two or more embodiments described herein, the process further includes isolating a "composition comprising a siloxane-modified olefin polymer." See the following example of isolation method (item B).

[0042] In one embodiment, or in a combination of two or more embodiments described herein, the composition further comprises an olefin polymer. In one embodiment, or in a combination of two or more embodiments described herein, the olefin polymer is an ethylene polymer.

[0043] In one embodiment, or in a combination of two or more embodiments described herein, the siloxane-modified olefin polymer comprises at least one chain comprising at least one structure selected from T5) to T8) as described herein (see G3 below).

[0044] In one embodiment, or in combination of two or more embodiments described herein, the composition comprises, based on the weight of the composition, ≥15% by weight, or ≥20% by weight, or ≥30% by weight, or ≥40% by weight, or ≥50% by weight, or ≥55% by weight, and / or ≤100% by weight, or ≤95% by weight, or ≤90% by weight, or ≤85% by weight, or ≤80% by weight, or ≤75% by weight, or ≤70% by weight, or ≤65% by weight, or ≤60% by weight, or ≤60% by weight, of a siloxane-modified olefin polymer.

[0045] In one embodiment, or in combination of two or more embodiments described herein, the composition comprises, based on the weight of the composition, a total of siloxane-modified polymers and olefin-based polymers in an amount of ≥80.0% by weight, or ≥85.0% by weight, or ≥90.0% by weight, or ≥92.0% by weight, or ≥94.0% by weight, or ≥96.0% by weight, or ≥98.0% by weight, or ≥99.0% by weight, or ≥99.2% by weight, or ≥99.4% by weight and / or ≤100.0% by weight, or ≤99.9% by weight, or ≤99.8% by weight, or ≤99.7% by weight, or ≤99.6% by weight.

[0046] In one embodiment, or in a combination of two or more embodiments described herein, the siloxane-modified olefin polymer is a siloxane-modified ethylene polymer.

[0047] Also provided are crosslinked compositions formed from any one embodiment or a combination of two or more embodiments described herein; or from any one embodiment or a combination of two or more embodiments described herein.

[0048] Also provided are articles comprising at least one component formed from a composition of any one embodiment or a combination of two or more embodiments described herein, or from a process of any one embodiment or a combination of two or more embodiments described herein.

[0049] additives The composition may contain one or more additives. Examples of additives include, but are not limited to, crosslinking agents, curing catalysts, fillers, pigments, UV stabilizers, antioxidants, processing aids, solvents, and furthermore, crosslinking agents, curing catalysts, UV stabilizers, and antioxidants. In one embodiment, the additive is present in an amount of ≥0.01% by weight, or ≥0.02% by weight, or ≥0.05% by weight, or ≥0.10% by weight, or ≥0.20% by weight, or ≥0.30% by weight, or ≥0.40% by weight, or ≥0.50% by weight and / or ≤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, based on the weight of the composition.

[0050] definition Unless otherwise stated, implied by the context, or customary in the art, all parts and percentages are based on weight, and all test methods are current as of the filing date of this disclosure.

[0051] As used herein, the term “composition” includes materials or mixtures of materials comprising the composition, as well as reaction and decomposition products formed from the materials of the composition. Any reaction or decomposition products are typically present in trace or residual amounts.

[0052] As used herein, the term “polymer” refers to a polymer compound (containing polymer chains or structures) prepared by polymerizing multiple monomers, whether of the same or different types. Thus, the general term polymer includes the terms 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 interpolymer, as defined below. Trace amounts of impurities, such as catalyst residues, may be incorporated into and / or within the polymer. Typically, polymers are stabilized with one or more stabilizers (e.g., antioxidants) in very small amounts ("ppm").

[0053] As used herein, the term “interpolymer” refers to a polymer prepared by the polymerization of at least two different types of monomers. Thus, the term interpolymer includes the term copolymer (used to refer to a polymer prepared from two different types of monomers) and polymers prepared from three or more different types of monomers.

[0054] As used herein, the term “olefinic polymer” means a polymer that, in its polymeric form, contains 50% by weight or more than half by weight percent of an olefin such as ethylene or propylene (based on the weight of the polymer), and may optionally contain one or more comonomers.

[0055] As used herein, the term “ethylene-based polymer” means a polymer in its polymerized form that contains 50% by weight or more than half by weight of ethylene (based on the weight of the polymer) and may optionally contain one or more comonomers.

[0056] As used herein, the term "ethylene / alpha-olefin interpolymer" refers to an interpolymer comprising, in its polymerized form, 50% by weight or a majority by weight of ethylene and an alpha-olefin (based on the weight of the interpolymer). As used herein, the term "ethylene / alpha-olefin copolymer" refers to a copolymer comprising, in its polymerized form, 50% by weight or a majority by weight of ethylene and an alpha-olefin as only two monomer types (based on the weight of the copolymer).

[0057] As used herein, the term “propylene polymer” means a polymer that, in its polymerized form, contains a majority by weight percent of propylene (based on the weight of the polymer) and may optionally contain one or more comonomers.

[0058] As used herein, the term “propylene / alpha-olefin interpolymer” refers to an interpolymer in which, in its polymerized form, a majority by weight percent of propylene and an alpha-olefin (based on the weight of the interpolymer). As used herein, the term “propylene / alpha-olefin copolymer” refers to a copolymer in which, in its polymerized form, a majority by weight percent of propylene and an alpha-olefin are the only two types of monomers (based on the weight of the copolymer).

[0059] As used herein, the term “propylene / ethylene interpolymer” refers to an interpolymer in which, in its polymerized form, it comprises a majority by weight percent of propylene and ethylene (based on the weight of the interpolymer). As used herein, the term “propylene / ethylene copolymer” refers to a copolymer in which, in its polymerized form, it comprises a majority by weight percent of propylene and ethylene as only two monomer types (based on the weight of the copolymer).

[0060] As used herein, the term "major weight percent" with respect to a polymer (or interpolymer or copolymer) refers to the amount of the monomer present in the polymer in the greatest amount.

[0061] As used herein, the term "crosslinked composition" is understood by those skilled in the art and refers to a composition that includes a crosslinked polymer having a network structure resulting from the formation of chemical bonds between polymer chains.

[0062] The term "heteroatom" refers to an atom other than hydrogen or carbon (e.g., Si, O, N, or P, typically Si or O). The term "heteroatom group" refers to a heteroatom or a chemical group containing one or more heteroatoms.

[0063] As used herein, the terms "hydrocarbon", "hydrocarbyl", and similar terms each refer to a compound or chemical group containing only carbon atoms and hydrogen atoms. [[ID=十三]]

[0064] As used herein, the terms "heterohydrocarbon", "heterohydrocarbyl group", and similar terms each refer to a compound or chemical group containing carbon, hydrogen, and one or more heteroatom groups (e.g., Si, O, N, or P), etc.

[0065] As used herein, the term "siloxane or siloxane group" and similar terms refer to a chemical group or moiety containing a "-Si-O-Si-" (siloxane) bond.

[0066] As used herein, the term "polysiloxane" and similar terms refer to a molecule containing one or more "-Si-O-Si-" (siloxane) bonds. Typically, a polysiloxane contains ≧2 siloxane bonds.

[0067] As used herein, the term "polysiloxane containing at least one silylvinyl group" refers to a polysiloxane containing at least one -Si-CH=CH2 moiety. For example, refer to the following structures s1) to s18).

[0068] As used herein, the term "siloxane-modified olefinic polymer" refers to an olefinic polymer containing at least one "-Si-O-Si-" (siloxane) bond.

[0069] As used herein, the term "silane" refers to a "RSi(R D )(R E )(R F )" molecule, wherein each of R, R D , R E , R F is independently H, hydrocarbyl or heterohydrocarbyl.

[0070] As used herein, the term "silane-modified olefinic polymer" refers to an olefinic polymer containing at least one -Si(R A )(R B )(R C )(silane) bond, wherein each of R A , R B , R C is independently H, hydrocarbyl or heterohydrocarbyl, and the olefinic polymer does not contain a "-Si-O-Si-" (siloxane) bond.

[0071] As used herein, the term "silylvinyl group" refers to a chemical group or moiety containing -Si-CH=CH2.

[0072] As used herein, the term "silane containing at least one silylvinyl group" refers to a silane containing at least one -Si-CH=CH2 moiety.

[0073] 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, where M is Zn or Al.

[0074] As used herein, the term "silane-M-polymer complex" refers to a metal complex comprising at least one olefinic polymer segment and at least one silane segment, where M is Zn or Al.

[0075] As used herein, the term "silane-M-molecular complex" refers to a metal complex comprising at least one hydrocarbyl segment and at least one silane segment, where M is Zn or Al.

[0076] As used herein, the term “hydrolyze” and similar terms refer to a chemical reaction in which a polysiloxane-M-polymer complex, a silane-M-polymer complex, or a silane-M-molecular complex reacts with water or alcohol to cleave “M-(polymer)2,” “M-polymer,” “M-(molecular)2,” “M-molecular,” or “M” from the respective complex to produce a metal complex containing at least one -OH or at least one -OR moiety (wherein R is an alkyl group), where M is Zn or Al.

[0077] As used herein, the term "catalytic system" refers to a catalytic composition comprising a procatalyst and optionally a cocatalyst.

[0078] For example, the term “repeating unit” as used herein with respect to metal complex A, or complexes i through ix, is CR 4 R 3 -CR 2 R 1 ) refers to the unit, and in the formula, R 1 , R 2 , R 3 , R 4 Each of these is defined herein (see, for example, A below).

[0079] For example, the term “repeating unit” as used herein with respect to metal complex D, or complex ic to iiic, is CR 5 R 6 -CR 7 R 8 ) refers to the unit, and in the formula, R 5 , R 6 , R 7 , R 8 Each of these is defined herein (see, for example, U below).

[0080] For example, the term “repeating unit” as used herein with respect to polymer structures T1, T2 and T3 is (CR 4 R 3 -CR 2 R 1 ) refers to the unit, and in the formula, R 1 , R 2 , R 3 , R 4 Each of these is defined herein (see, for example, F3 below).

[0081] As used herein, the term “solution process” refers to a chemical reaction process in which both the starting materials and the final product are soluble in one or more solvents used in the process.

[0082] The terms “comprising,” “including,” and “having,” and their derivatives, are not intended to exclude the existence of any additional components, processes, or procedures, whether or not they are specifically disclosed. To avoid any doubt, all compositions claimed through the use of the term “comprising” may, unless otherwise stated, include, for example, any additional additives, adjuvants, or compounds, whether polymeric or otherwise. In contrast, the term “essentially consisting of” excludes any other components, processes, or procedures from any subsequent enumeration, except those not essential to operability. The term “consisting of” excludes any components, processes, or procedures not specifically described or enumerated.

[0083] Enumeration of the characteristics of several processes and compositions A) A process for forming a composition containing a siloxane-modified olefin polymer, wherein each of the following A) is reacted with B) to form the following C), A)M[(CR 1 R 2 -CR 3 R 4 ) n -CH3] x (In the formula, M is a metal selected from Zn or Al, x is 2 or 3, when x=2, M is Zn, when x=3, M is Al, each n is independently ≥1, and for each respective n value, R 1 , R 2 , R 3 , R 4 Each of them is independently H or hydrocarbyl, and R 1 This may or may not be the same for each consecutive repeating unit (or R 1 Each instance is independently selected from H or hydrocarbyl), R 2 This may or may not be the same for each consecutive repeating unit (or R 2 Each instance is independently selected from H or hydrocarbyl), R 3may be the same or different for each successive repeating unit (or R 3 is independently selected from H or hydrocarbyl each time it appears), R 4 may be the same or different for each successive repeating unit (or R 4 is independently selected from H or hydrocarbyl each time it appears)), B) a polysiloxane containing at least one silyl vinyl group, C) i, ii, iii, iv, v, vi, vii, viii, ix or x: i)

[0084]

Chemical formula

[0086] Enumeration of the characteristics of several processes and compositions A) A process for forming a composition containing a siloxane-modified olefin polymer, wherein each of the following A) is reacted with B) to form the following C), A)M[(CR 1 R 2 -CR 3 R 4 ) n -CH3]x(wherein M is a metal selected from Zn or Al, x is 2 or 3, when x=2 M is Zn, when x=3 M is Al, each n is independently ≥1, and for each respective n value, R 1 , R 2 , R 3 , R 4 Each of them is independently H or hydrocarbyl, and R 1 This may or may not be the same for each consecutive repeating unit (or R 1 Each instance is independently selected from H or hydrocarbyl), R 2 This may or may not be the same for each consecutive repeating unit (or R 2 Each instance is independently selected from H or hydrocarbyl), R 3 This may or may not be the same for each consecutive repeating unit (or R 3 Each instance is independently selected from H or hydrocarbyl), R 4 This may or may not be the same for each consecutive repeating unit (or R 4 Each instance, it is independently selected from H or hydrocarbyl. B) Polysiloxane containing at least one silyl vinyl group, C) i, ii, iii, iv, v, vi, vii, viii, ix or x: i)

[0087] [ka] (In the formula, each n is defined above, R 1 , R 2 , R 3 , R 4 Each of the units is defined above, and each of R and R' is independently hydrocarbyl or heterohydrocarbyl, and further hydrocarbyl, and x=1 or 2, when x=1 M is Zn, when x=2 M is Al, and asterisk ( * (This represents the remainder of the complex.) ii)

[0088] [ka] (In the formula, each n is defined above, R 1 , R 2 , R 3 , R 4 Each unit is defined above, R'' is hydrocarbyl or heterohydrocarbyl, and also hydrocarbyl, x=1 or 2, if x=1, M is Zn, if x=2, M is Al, and each asterisk ( * (These terms independently represent the respective remnants of the complex.) iii)

[0089] [ka] (In the formula, each n is defined above, R 1 , R 2 , R 3 , R 4 Each of the units is defined above, and each of R and R' is independently hydrocarbyl or heterohydrocarbyl, and further hydrocarbyl, where x=0 or 1, and when x=0 ([(CR 1 R 2 -CR 3 R 4 ) n-CH3) If the part does not exist, M is Zn, and if x=1, M is Al, and each asterisk ( * (These terms independently represent the respective remnants of the complex.) iv)

[0090] [ka] (In the formula, each n is defined above, R 1 , R 2 , R 3 , R 4 Each of the units is defined above, and each R'' is independently hydrocarbyl or heterohydrocarbyl, and further hydrocarbyl, where x=0 or 1, and when x=0 ([(CR 1 R 2 -CR 3 R 4 ) n -CH3) If the part does not exist, M is Zn, and if x=1, M is Al, and each asterisk ( * (These terms independently represent the respective remnants of the complex.) v)

[0091] [ka] (In the formula, each n is defined above, R 1 , R 2 , R 3 , R 4 Each of the units is defined above, and each of R, R' and R'' is independently hydrocarbyl or heterohydrocarbyl, and further hydrocarbyl, and x=0 or 1, and when x=0 ([(CR 1 R 2 -CR 3 R 4 If the )-CH3]) part does not exist, M is Zn, and if x=1, M is Al, and each asterisk ( * (These terms independently represent the respective remnants of the complex.) vi)

[0092] [ka] (In the formula, each n is defined above, R 1 , R 2 , R 3 , R 4 Each of the units is defined above, where R and R' are independently hydrocarbyl or heterohydrocarbyl, and furthermore hydrocarbyl, and M is Al, and each asterisk( * (These terms independently represent the respective remnants of the complex.) vii)

[0093] [ka] (In the formula, each n is defined above, R 1 , R 2 , R 3 , R 4 Each of the units is defined above, and each R'' is independently hydrocarbyl or heterohydrocarbyl, and further hydrocarbyl, and M is Al, and each asterisk ( * ) independently represent the remainder of each complex, viii)

[0094] [ka] (In the formula, each n is defined above, R 1 , R 2 , R 3 , R 4 Each of the units is defined above, and each of R, R' and R'' is independently hydrocarbyl or heterohydrocarbyl, and further hydrocarbyl, and M is Al, and each asterisk ( * (These terms independently represent the respective remnants of the complex.) ix)

[0095] [ka] (In the formula, each n is defined above, R 1 , R 2 , R 3 , R 4 Each of the units is defined above, and each of R, R' and R'' is independently hydrocarbyl or heterohydrocarbyl, and further hydrocarbyl, and M is Al, and each asterisk ( * ) represents the respective remainders of the complex independently, or x) Forming one or more polysiloxane-M-polymer complexes independently selected from any combination of these, A process comprising hydrolyzing one or more polysiloxane-M polymer complexes (C) to form a siloxane-modified olefin polymer. In further embodiments, each polysiloxane-M polymer complex is independently selected from i, ii, iii, iv, v, vi, vii, viiii, or ix. B) The process according to A) above, further comprising isolating a "composition comprising a siloxane-modified olefin polymer." Isolation methods are known in the art and include, but are not limited to, filtration, distillation, and extraction.

[0096] 2-Diyl(methane)(hafniumdimethyl)). P] The siloxane-modified olefin polymer comprises the following polymer segments a1 and / or a2, and b, as follows: a1)-O-Si(R)(R')-CH2-CH2-(CR 1 R 2 -CR 3 R 4 ) n -CH3, (wherein n is defined herein (see, for example, A), each of R and R' is defined herein (see, for example, A), R 1 , R 2 , R 3 , R 4Each of these is defined herein (see, for example, A), a2)-O-Si(R”)-CH2-CH2-((CR 1 R 2 -CR 3 R 4 ) n -CH3)-, (wherein n is defined herein (see, for example, A), R'' is defined herein (see, for example, A), R 1 , R 2 , R 3 , R 4 Each of these is defined herein (see, for example, A), b)-O-SiR'''(R'''')) m -, (wherein m≧1, and for each value of m, R''' and R'''' are independently H or hydrocarbyl, and furthermore hydrocarbyl) the process described in any one of A]~O] above. Q] The process described in P] above, wherein for 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. The process described in P] or Q] above, wherein, for segment b, each of R'" and R'''' is independently H or an alkyl group. The process according to any one of P] to R] above, wherein, with respect to 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. T] For segment b, the process described in any one of the above P]~S], where R'''=R''''. U] A process for forming a composition containing a silane-modified olefin polymer, wherein each of the following D) is reacted with E) to form the following F), D)M[(CR5 R 6 -CR 7 R 8 ) p -CH3]x, (wherein M is a metal selected from Zn or Al, x is 2 or 3, when x=2 M is Zn, when x=3 M is Al, each p is independently ≥1, and for each respective p value R 5 , R 6 , R 7 , R 8 Each of them is independently H or hydrocarbyl, and R 5 This may or may not be the same for each consecutive repeating unit (or R 5 (In each occurrence, it is selected independently from H or hydrocarbyl), R 6 This may or may not be the same for each consecutive repeating unit (or R 6 Each instance is independently selected from H or hydrocarbyl), R 7 This may or may not be the same for each consecutive repeating unit (or R 7 Each instance is independently selected from H or hydrocarbyl), R 8 This may or may not be the same for each consecutive repeating unit (or R 8 Each instance, it is independently selected from H or hydrocarbyl. E) Silane containing at least one silyl vinyl group, F)ic, iic, iiic, or ivc: I C)

[0097] [ka] (In the formula, each p is defined above, R 5 , R 6 , R 7 , R 8 Each of the units is defined above, R A , R B and R CEach of these is independently H, hydrocarbyl, or heterohydrocarbyl, and further H or hydrocarbyl, where x=1 or 2, where if x=1, M is Zn, and if x=2, M is Al), iic)

[0098] [ka] (In the formula, each p is defined above, R 5 , R 6 , R 7 , R 8 Each of the units is defined above, R A , R B and R C Each of them is independently H, hydrocarbyl or heterohydrocarbyl, and further H or hydrocarbyl, and x=0 or 1, and when x=0 ([(CR 5 R 6 -CR 7 R 8 ) p (If the -CH3]) part does not exist, M is Zn, and if x=1, M is Al. iiic)

[0099] [ka] (In the formula, each p is defined above, R 5 , R 6 , R 7 , R 8 Each of the units is defined above, R A , R B and R C Each of these is independently H, hydrocarbyl, or heterohydrocarbyl, further H or hydrocarbyl, and M is Al), or ivc) Forming one or more silane-M-polymer complexes independently selected from any combination thereof, A process comprising hydrolyzing one or more silane-M polymer complexes (F) to form a silane-modified olefin polymer. In further embodiments, each silane-M polymer complex is independently selected from ic, iic, or iiic. V) The process of U) above, further comprising isolating the "composition comprising a silane-modified olefin polymer." See the example of the isolation method described above (item B)). The process described in U] or V] above, wherein the W] process is a solution process. X] Independently, for each ic~iiic, each p is independently ≥2, or ≥5, or ≥50, or ≥20, or ≥50, or ≥100, or ≥500 and / or ≤20000, and does not have to be the same for each consecutive repeating unit (or R 5 (In each occurrence, it is independently selected from H or hydrocarbyl), R 6 This may or may not be the same for each consecutive repeating unit (or R 6 Each instance is independently selected from H or hydrocarbyl), R 7 This may or may not be the same for each consecutive repeating unit (or R 7 Each instance is independently selected from H or hydrocarbyl), R 8 This may or may not be the same for each consecutive repeating unit (or R 8 (Each instance, it is independently selected from H or hydrocarbyl), E) Silane containing at least one silyl vinyl group, F)ic, iic, iiic, or ivc: I C)

[0100] [ka] (In the formula, each p is defined above, R 5 , R 6 , R 7 , R 8 Each of the units is defined above, RA , R B and R C Each of these is independently H, hydrocarbyl, or heterohydrocarbyl, and further H or hydrocarbyl, where x=1 or 2, where if x=1, M is Zn, and if x=2, M is Al), iic)

[0101] [ka] (In the formula, each p is defined above, R 5 , R 6 , R 7 , R 8 Each of the units is defined above, R A , R B and R C Each of them is independently H, hydrocarbyl or heterohydrocarbyl, and further H or hydrocarbyl, and x=0 or 1, and when x=0 ([(CR 5 R 6 -CR 7 R 8 ) p (If the -CH3]) part does not exist, M is Zn, and if x=1, M is Al. iiic)

[0102] [ka] (In the formula, each p is defined above, R 5 , R 6 , R 7 , R 8 Each of the units is defined above, R A , R B and R C Each of these is independently H, hydrocarbyl, or heterohydrocarbyl, further H or hydrocarbyl, and M is Al), or ivc) Forming one or more silane-M-polymer complexes independently selected from any combination thereof, G)M[R9 ] x (In the formula, M is a metal selected from Zn or Al, x is 2 or 3, when x=2, M is Zn, when x=3, M is Al, and each R 9 (It is hydrocarbil independently.) H) Silane containing at least one silyl vinyl group, I) id, iid, iiid, or ivd: id)

[0103] [ka] (In the formula, each R 9 This is defined above, R D , R E and R F Each of these is independently H, hydrocarbyl, or heterohydrocarbyl, and further H or hydrocarbyl, where x=1 or 2, where if x=1, M is Zn, and if x=2, M is Al), iid)

[0104] [ka] (In the formula, each R 9 This is defined above, R D , R E and R F Each of them is independently H, hydrocarbyl or heterohydrocarbyl, and further H or hydrocarbyl, and x=0 or 1, and when x=0 ((R 9 (If the part does not exist, M is Zn, and if x=1, M is Al), iiid)

[0105] [ka] (In the formula, each R 9 This is defined above, R D , R E and R FEach of these is independently H, hydrocarbyl, or heterohydrocarbyl, further H or hydrocarbyl, and M is Al), or ivd) To form one or more silane-M-molecular complexes independently selected from any combination thereof, A process according to any one of the above U] to W], comprising hydrolyzing one or more silane-M-molecular complexes (I) to form a silane. In further embodiments, each silane-M-molecular complex is independently selected from id, iid, or iiid. J2 The process of I2 above, further comprising isolating the "composition containing silane". See the example of the isolation method described above. (Item B) K2] The process described in I2] or J2] above, wherein the process is a solution process. L2] Independently, for each of id to iiid, R D , R E and R F The process according to any one of the above I2] to K2], wherein each of is independently an alkyl group or a vinyl group. M2] Independently, for each of id to iiid, R D , R E and R F The process according to any one of I2] to L2] above, wherein each of is independently an alkyl group, or a C1-C5 alkyl group, or a C1-C4 (2,6-di(1-methylethyl)phenyl)amide)(2-isopropylphenyl)(α-naphthalene-2-diyl(6-pyridine-2-diyl)methane)hafniumdimethyl]. [H2] Silane-modified olefin polymers include the following polymers: c)Si(R A )(R B )(R C )-CH2-CH2-(CR 5 R 6 -CR 7 R 8 ) p -CH3, (where p is defined above (see, for example, U), R A , RB and R C These are defined above (see, for example, U), and for each p-value, R 5 , R 6 , R 7 , R 8 Each of these is defined above (see, for example, U)) and is a process described in any one of the above U] to G2]. I2] A process for forming a silane-containing composition, wherein each of the following G) is reacted with H) to form the following I), G)M[R 9 ] x (wherein M is a metal selected from Zn or Al, x is 2 or 3, if x=2, M is Zn, if x=3, M is Al, and each R 9 (It is hydrocarbil, independently.) H) Silane containing at least one silyl vinyl group, I) id, iid, iiid, or ivd: id)

[0106] [ka] In the formula, each R 9 This is defined above, R D , R E and R F Each of these is independently H, hydrocarbyl, or heterohydrocarbyl, and further H or hydrocarbyl, where x=1 or 2, where if x=1, M is Zn, and if x=2, M is Al), iid)

[0107] [ka] (In the formula, each R 9 This is defined above, R D , R E and R FEach of them is independently H, hydrocarbyl or heterohydrocarbyl, and further H or hydrocarbyl, and x=0 or 1, and when x=0 ((R 9 (If the part does not exist, M is Zn, and if x=1, M is Al), iiid)

[0108] [ka] (In the formula, each R 9 This is defined above, R D , R E and R F Each of these is independently H, hydrocarbyl, or heterohydrocarbyl, further H or hydrocarbyl, and M is Al), or

[0109] [ka] A process comprising forming one or more silane-M-molecular complexes, each independently selected from s18) and s19) any combination thereof. W2] The process according to any one of A]~T], U2], or V2] above, wherein the "polysiloxane containing at least one silyl vinyl group" contains ≥2, ≥3, ≥4, ≥5, ≥6, ≥8, or ≥10 Si atoms per molecule and / or ≤1000, ≤800, ≤600, ≤400, ≤200, ≤100, or ≤50 Si atoms per molecule. X2] The process according to any one of A]~T] or U2]~V2] above, wherein the polysiloxane containing at least one silyl vinyl group has a density of ≥0.80 g / cc, or ≥0.82 g / cc, or ≥0.85 g / cc. d)Si(R D )(R E )(R F )-CH2-CH2-R 9 , (where R D , RE and R F Each of these is defined above (see, for example, I2), R 9 This is defined above (see, for example, I2). U2] The process described in any one of A] to T2] above, wherein the process is carried out at a temperature of ≥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 ≤200°C, or ≤190°C, or ≤180°C, or ≤170°C, or ≤160°C, or ≤150°C, or ≤145°C, or ≤140°C, or ≤135°C, or ≤130°C, or ≤125°C. Furthermore, the process is carried out under an inert atmosphere (e.g., nitrogen). V2] A polysiloxane containing at least one silyl vinyl group is selected from the group consisting of s1) to s19) below; independently for each of s1) to s6), s10) to s13), s15), s16), s18), each n is independently ≥ 1; independently for each of s2) to s10), s14), s17), s18), each m is independently ≥ 1; and for s18), p ≥ 1, in any one of the above processes A) to T) or U2):

[0110] [ka]

[0111] [ka] s18) and s19) any combination thereof. W2] The process according to any one of A]~T], U2], or V2] above, wherein the "polysiloxane containing at least one silyl vinyl group" contains ≥2, ≥3, ≥4, ≥5, ≥6, ≥8, or ≥10 Si atoms per molecule and / or <1000, ≤800, ≤600, ≤400, ≤200, ≤100, or ≤50 Si atoms per molecule. X2] "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 A process according to any one of the above A]~T] or U2]~V2] having a density of ). Y2] The process according to any one of A]~T] or U2]~W2] above, wherein the polysiloxane comprising at least one silyl vinyl group has a weight percentage of silyl vinyl groups 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 wt%, or ≤35 wt%, or ≤30 wt%, or ≤25 wt%, or ≤20 wt%, or ≤15 wt% based on the weight of the polysiloxane. A3) A composition formed by any one of the processes described in A) to Y2) above. B3) A composition comprising a siloxane-modified olefin polymer formed by any one of the processes described in A]~T] or U2]~Y2] above. [C3] The siloxane-modified olefin polymer comprises the following polymer segments a1 and / or a2 and b as follows: a1)-O-Si(R)(R')-CH2-CH2-(CR 1 R 2 -CR3 R 4 ) n -CH3, (wherein n is defined herein (see, e.g., P), each of R and R' is defined herein (see, e.g., P), R 1 , R 2 , R 3 , R 4 Each of these is defined herein (see, for example, P[)), a2)-O-Si(R”)-CH2-CH2-((CR 1 R 2 -CR 3 R 4 )n-CH3)-, (wherein n is defined herein (see, for example, P), R'' is defined herein (see, for example, P), R 1 , R 2 , R 3 , R 4 Each of these is defined herein (see, for example, P[)), b)-(O-SiR'''(R'''')) m -, (wherein m is defined herein (or see, for example, P), and each of R''' and R'''' is defined herein (or see, for example, P)), the composition according to B3]. D3) A composition comprising a silane-modified olefin polymer formed by any one of the processes described in U] to H2] or U2] above. E3) A composition comprising a silane formed by any one of the processes described in I2] to T2] or U2] above. F3] A composition comprising a siloxane-modified olefin polymer, wherein the siloxane-modified olefin polymer is T1)~T4): T1)

[0112] [ka] (In the formula, m≧2, x≧1, n≧1, and for each value of n, R1 , R 2 , R 3 , R 4 Each of them is independently H or hydrocarbyl, and R 1 This may or may not be the same for each consecutive repeating unit (or R 1 Each instance is independently selected from H or hydrocarbyl), R 2 This may or may not be the same for each consecutive repeating unit (or R 2 Each instance is independently selected from H or hydrocarbyl), R 3 This may or may not be the same for each consecutive repeating unit (or R 3 Each instance is independently selected from H or hydrocarbyl), R 4 This may or may not be the same for each consecutive repeating unit (or R 4 Each instance of R is independently selected from H or hydrocarbyl), and each of R and R' is independently hydrocarbyl, and each asterisk ( * ) represents each remaining part of the chain independently. T2)

[0113] [ka] (In the formula, m ≥ 2, Furthermore, m≧3, x≧1, y≧1, each n is independently ≧1, and for each n value, R 1 , R 2 , R 3 , R 4 Each of them is independently H or hydrocarbyl, and R 1 This may or may not be the same for each consecutive repeating unit (or R 1 Each instance is independently selected from H or hydrocarbyl), R 2 This may or may not be the same for each consecutive repeating unit (or R 2 Each instance is independently selected from H or hydrocarbyl), R3 This may or may not be the same for each consecutive repeating unit (or R 3 Each instance is independently selected from H or hydrocarbyl), R 4 This may or may not be the same for each consecutive repeating unit (or R 4 Each instance of R is independently selected from H or hydrocarbil, and each of R, R' and R'' is independently hydrocarbil, and each asterisk ( * ) represents each remaining part of the chain independently. T3)

[0114] [ka] (In the formula, m≧2, and furthermore, m≧3, x≧1, y≧1, n≧1, and for each n value, R 1 , R 2 , R 3 , R 4 Each of them is independently H or hydrocarbyl, and R 1 This may or may not be the same for each consecutive repeating unit (or R 1 Each instance is independently selected from H or hydrocarbyl), R 2 This may or may not be the same for each consecutive repeating unit (or R 2 Each instance is independently selected from H or hydrocarbyl), R 3 This may or may not be the same for each consecutive repeating unit (or R 3 Each instance is independently selected from H or hydrocarbyl), R 4 This may or may not be the same for each consecutive repeating unit (or R 4 Each instance of R is independently selected from H or hydrocarbil, and each of R, R' and R'' is independently hydrocarbil, and each asterisk ( * ) represents each remaining part of the chain independently, or T4) A composition comprising at least one chain containing at least one structure selected from any combination of these. G3) The siloxane-modified olefin polymer comprises at least one chain containing at least one structure selected from T5) to T8), and each asterisk ( * ) independently represents the remaining parts of the chain: T5)

[0115] [ka] (In the equation, m≧2, x≧1, and n≧1.) T6)

[0116] [ka] (In the equation, m≧2, and furthermore, m≧3, x≧1, y≧1, and each n is independently ≧1.) T7)

[0117] [ka] (wherein the formula, m≧2, and furthermore, m≧3, x≧1, y≧1, and n≧1), or T8) Any combination of these, the compositions described in F3 above. H3) A composition according to any one of A3) to C3) above (see F3), wherein the siloxane-modified olefin polymer comprises at least one structure selected from T1) to T4) above. I3) The composition according to H3) above (see G3) wherein the siloxane-modified olefin polymer comprises at least one structure selected from T5) to T8) above. J3] A composition further comprising a siloxane-modified olefin polymer or a polymer different from a silane-modified polymer in one or more characteristics such as monomer type, Mn, Mw, MWD, density, or any combination thereof, according to the process described in any one of A]~H2] or U2]~Y2] above, or according to the composition described in A3]~D3] or F3]~I3] above. K3] A composition further comprising an olefin polymer, according to the process described in any one of A]~H2] or U2]~Y2] or J3] above, or according to the composition described in A3]~D3] or F3]~J3] above. Propylene, 1-butene, or 1-octene; or 1-butene or 1-octene; or 1-octene, etc. I4) A process according to any one of A]~T], U2]~Y2] or J3]~D4] above, wherein the siloxane-modified olefin polymer is a siloxane-modified propylene polymer, or a composition according to any one of A3]~C3] or F3]~D4] above. J4] The process described in I4] above, or the composition described in I4] above, wherein the siloxane-modified propylene polymer is a siloxane-modified polypropylene homopolymer. K4] The process according to I4] above, or the composition according to I4] above, wherein the siloxane-modified propylene polymer is a siloxane-modified propylene / ethylene interpolymer, or more precisely, a siloxane-modified propylene / ethylene copolymer; or a siloxane-modified propylene / alpha-olefin interpolymer, or more precisely, a siloxane-modified propylene / alpha-olefin copolymer. L4] The process described in K4] above, or the composition described in K4] above, wherein the alpha-olefin is a C4-C20 alpha-olefin, or a C4-C10 alpha-olefin, or selected from 1-butene, 1-pentene, 1-hexene or 1-octene, or selected from 1-butene, 1-hexene or 1-octene, or selected from 1-butene or 1-octene, or 1-octene. [M4] Independently, for each of the polysiloxane-M-polymer complexes i to ix, the remainder of the complex * ) or the remainder of each of the complexes ( * A process according to any one of A]~T], U2]~Y2] or J3]~L4] above, or a composition according to any one of A3]~C3] or F3]~L4] above, wherein the above-mentioned process may or may not independently include one or more additional polysiloxane-M-polymer complexes. N4] Remaining part of the complex ( * ) or the remainder of each of the complexes ( * The process described in M4) above, or the composition described in M4) above, wherein the process independently comprises one or more additional polysiloxane-M-polymer complexes. O4] Remaining part of the complex ( * ) or the remainder of each of the complexes ( * The process described in [M4] above, or the composition described in [M4] above, wherein the process described in [M4] above does not include one or more additional polysiloxane-M-polymer complexes. A5) A crosslinked composition formed from any one of the processes described in A] to H2], U2] to Y2], or J3] to O4] above. B5] A crosslinked composition formed from any one of the compositions described in A3] to D3] or F3 to O4] above. C5] An article comprising any one of the compositions described in A3] to O4] above. D5] An article comprising at least one component formed from any one of the compositions described in A3] to A4] above. E5] An article comprising the crosslinking composition described in A5] or B5] above. F5] An article comprising at least one component formed from the crosslinked composition described in A5] or B5] above. G5] An article comprising at least one component formed from any one of the processes described in A] to Y2] or J3] to O4] above.

[0118] Test method Gas chromatography-mass spectrometry (GC / MS) Tandem gas chromatography / low-resolution mass spectrometry using electron impulse 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 microns). The following conditions (programmed method) were used: a) oven equilibrium time of 0.5 minutes, b) oven equilibrium at 50°C at the start of the analysis, then temperature increased to 200°C at 25°C / min and maintained at 200°C for 5 minutes, c) run time of 11 minutes.

[0119] density The density of the polymer is measured by preparing the polymer sample according to ASTM D1928, and then measuring the density according to ASTM D792, Method B, within one hour of pressing the sample.

[0120] Gel permeation chromatography Conventional composition GPC The chromatography system consisted of a PolymerChar (Valencia, Spain) GPC-IR high-temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5). The autosampler oven compartment was set to 160°C and the column compartment to 150°C. The columns used were four Agilent "Mixed A" 30 cm, 20 micron linear mixed-bed columns. The chromatography solvent was 1,2,4-trichlorobenzene containing 200 ppm butylated hydroxytoluene (BHT). The solvent source was spurged with nitrogen. The injection volume was 200 microliters, and the flow rate was 1.0 ml / min.

[0121] Calibration of the GPC column set was performed using 21 narrow molecular weight distribution polystyrene standards with molecular weights ranging from 580 to 8,400,000 g / mol, arranged in six “cocktail” mixtures with at least one-order-of-magnitude intervals between individual molecular weights. The standards were purchased from Agilent Technologies. For molecular weights greater than 1,000,000, polystyrene standards were prepared at “0.025 grams in 50 ml of solvent,” and for molecular weights less than 1,000,000, at “0.05 grams 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 an autosampler dissolution oven at 160°C for 30 minutes and cooled. The peak molecular weights of the polystyrene standards were converted to polyethylene molecular weights using Equation 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)). ポリエチレン =A × (M ポリスチレン ) B (EQ1), where M is the molecular weight, A has a value of 0.424, and B is equal to 1.0. A quintic polynomial was used to fit the respective polyethylene equivalent calibration points.

[0122] The total plate count of the GPC column set was performed using decane introduced into the blank sample via a micropump controlled by PolymerChar's GPC-IR system. The plate count of the chromatography system should be greater than 18,000 for four Agilent "Mixed A" 30 cm² 20 micron linear mixed-bed columns. The sample was prepared semi-automatically using PolymerChar's "Instrument Control" software, with a target weight of 2 mg / mL, and the solvent (containing 200 ppm BHT) was added to a pre-spared nitrogen-filled vial with a septacap via PolymerChar's high-temperature autosampler. The sample was dissolved at 160°C for 2 hours under "low-speed" shaking.

[0123] 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. Using this flow rate marker (FM), the pump flow rate (nominal flow rate) for each sample was linearly corrected by RV matching the RV of each decane peak in the sample (RV(FM sample)) with the RV of the calibrated decane peak in the narrow standard material (RV(FM calibrated)). It was assumed that any temporal change in the decane marker peak corresponds to a linear shift in the flow rate (effective flow rate) over the entire run. After calibrating the system based on the flow rate marker peaks, the effective flow rate (relative to the narrow standard calibration) was calculated using Equation 2. The processing of the flow rate marker peaks was performed via PolymerChar's GPCOne® software. An acceptable flow rate correction is required so that the effective flow rate is within ±0.5% of the nominal flow rate. Effective flow rate = Nominal flow rate * (RV (FM calibrated) / RV (FM sample)) (EQ2) IR5 GPC octene composition calibration

[0124] Calibration of the IR5 detector ratio adjustment involves a narrow short-chain branching (SCB or CH3) distribution and known comonomer content. 13 The process was carried out using at least 10 ethylene-based polymer standards (octene as comonomer) prepared by single-site metallocene catalysts (polyethylene homopolymer and ethylene / octene copolymer) from a single reactor in a solution process (Qiu et al., Anal. Chem. 2009, 81, 8585-8589), as measured by 13C NMR. These standards ranged from homopolymer (0 SCB / 1000 total C) to approximately 40 SCB / 1000 total C, where total C = carbon in the backbone + carbon in the branches. Each standard had a weight-average molecular weight of 36,000 g / mol to 126,000 g / mol as measured by GPC. Each standard had a molecular weight distribution (Mw / Mn) of 2.0 to 2.5. The polymer properties of the SCB standards are shown in Table A.

[0125] [Table 1]

[0126] "IR5 region ratio (or "IR5") of "Baseline subtraction region response of IR5 methyl channel sensor" to "Baseline subtraction region response of IR5 measurement channel sensor" メチルチャネル領域 / IR5 測定チャネル領域 The standard filter and filter wheel (Part Number IR5_FWM01SS, supplied by PolymerChar, was included as part of the GPC-IR instrument) was calculated for each of the "SCB" standards. A linear fit of SCB frequency versus "IR5 region ratio" was constructed in the form of the following equation 3: SCB / 1000 Total C = A0 + [A1 x (IR5 メチルチャネル領域 / IR5 測定チャネル領域 )](Equation 3), where A0 is the intercept of "SCB / 1000 Total C" at zero "IR5 region ratio", and A1 is the slope of "SCB / 1000 Total C" versus "IR5 region ratio", representing the increase in "SCB / 1000 Total C" as a function of "IR5 region ratio". The IR region ratio is equal to the IR5 height ratio for narrow PDI and narrow SCBD standard materials.

[0127] GPC profile overlay can be performed using commercially available software, such as software available with a chromatography system, or Excel software, or by other means known in the art.

[0128] NMR (13C and 29Si) 13 1C NMR and 29Both Si NMR spectra were acquired using a Bruker 600 MHz Avance III HD system equipped with a 10 mm multinuclear helium NMR cryoprobe. Conventional zgig pulse sequencing was used. Polymer samples were prepared by adding approximately 2.6 g of a 50 / 50 mixture of tetrachloroethane-d2 / orthodichlorobenzene containing 0.025 M chromium trisacetylacetonate (relaxant) to 0.2 g of polymer in a 10 mm NMR tube. The sample was dissolved and homogenized by heating the tube and its contents to 150 °C. Data were acquired at a sample temperature of 120 °C using 320 scans per data file and a pulse repetition delay of 7.3 seconds. Further NMR samples and parameters are detailed in Z. Zhou et al., Macromolecules 2023, 56, 234-240 (incorporated herein by reference). The respective peak integrals are shown in Figures 4 and 5.

[0129] experiment The reagents, co-catalysts, and pro-catalysts are shown below.

[0130] Vinyl-terminated polydimethylsiloxane (DMS-V05), MW 800, viscosity 4-8, density 0.93, vinyl weight 7-9, vinyl (equivalent / kg) 2.4-2.9, available from Gelest.

[0131] [ka]

[0132] 1,3-Divinyltetramethyldisiloxane (DVTMDS), MW 186.40 g / mol, available from Sigma-Aldrich.

[0133] Octenyldimethylvinylsilane (ODMVS) is available from Gelest.

[0134] Vinyl methylsiloxane homopolymer (VMS-T11), linear, MW 1000-5000, viscosity 7-15, density 0.96, available from Gelest.

[0135] [ka]

[0136] Triethylaluminum (TEA) is available from Sigma-Aldrich.

[0137] Trioctyl aluminum (TOA) is available from Sigma-Aldrich.

[0138] Diethylzinc (DEZ) is available from Sigma-Aldrich.

[0139] ISOPAR-E solvent is available from ExxonMobil.

[0140] Decane solvent is available from Sigma-Aldrich.

[0141] Co-catalyst 1 is bis(hydrogenated tulowalkyl)methyl,tetrakis(penta-fluorophenyl)borate(1-)amine, available from Boulder Scientific.

[0142] Procatalyst (1): (E)-((2,6-diisopropylphenyl)(2-methyl-3-(octylimino)butan-2-yl)amino)trimethylhafnium:

[0143] [ka]

[0144] Procatalyst (2): (N-((6E)-6-(butylimino-κN)-1-cyclohexen-1-yl)-2,6-bis(1-methyl-ethyl)benzeneaminoto-κN)trimethyl-hafnium:

[0145] [ka]

[0146] Procatalyst (3): [N-(2,6-di(1-methylethyl)phenyl)amide)(2-isopropylphenyl)(α-naphthalene-2-diyl(6-pyridine-2-diyl)methane)]hafniumdimethyl]:

[0147] [ka]

[0148] Study 1 - GC mass spectrum of reaction product (Al) Example 1 The reaction between trioctylaluminum (TOA) and 1,3-divinyltetramethyldisiloxane (DVTMDS) followed Scheme 4 shown below.

[0149] [ka] In a dry box 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 heated to 130°C (heating block temperature). Samples taken at 15 minutes and 1 hour were hydrolyzed (with MeOH) for GC / MS analysis, and the formation of inserted products was monitored. The GC / MS results are shown in Figure 1. The GC / MS results indicated the presence of the following molecular species (A-E). These results confirmed the reaction in Scheme 4 described above.

[0150] [ka] SCB / 1000 Total C as a function of "IR5 region ratio". The IR5 region ratio is equal to the IR5 height ratio for narrow PDI and narrow SCBD standard materials.

[0151] GPC profile overlay can be performed using commercially available software, such as software available with a chromatography system, or Excel software, or by other means known in the art.

[0152] NMR (13C and 29Si) 13 1C NMR and 29 Both Si NMR spectra were collected using a Bruker 600MHz Avance III HD system equipped with a 10mm multinuclear helium NMR cryoprobe. Conventional zgig pulse sequencing was used. Polymer samples were prepared by adding approximately 2.6g of a 50 / 50 mixture of tetrachloroethane-d2 / orthodichlorobenzene containing 0.025M chromium trisacetylacetonate (relaxant) to 0.2g of polymer in a 10mm NMR tube. The sample was dissolved and homogenized by heating the tube and its contents to 150°C. Data were acquired at a sample temperature of 120°C using 320 scans per data file and a pulse repetition delay of 7.3 seconds. Further NMR samples and parameters are detailed in Z. Zhou et al., Macromolecules 2023, 56, 234-240 (incorporated herein by reference). The respective peak integrals are shown in Figures 4 and 5. [Examples]

[0153] The reagents, co-catalysts, and pro-catalysts are shown below.

[0154] Vinyl-terminated polydimethylsiloxane (DMS-V05), MW 800, viscosity 4-8, density 0.93, vinyl weight 7-9, vinyl (equivalent / kg) 2.4-2.9, available from Gelest.

[0155] [ka]

[0156] 1,3-Divinyltetramethyldisiloxane (DVTMDS), MW 186.40 g / mol, available from Sigma-Aldrich.

[0157] Octenyldimethylvinylsilane (ODMVS) is available from Gelest.

[0158] Vinyl methylsiloxane homopolymer (VMS-T11), linear, MW 1000-5000, viscosity 7-15, density 0.96, available from Gelest.

[0159] [ka]

[0160] Triethylaluminum (TEA) is available from Sigma-Aldrich.

[0161] Trioctyl aluminum (TOA) is available from Sigma-Aldrich.

[0162] Diethylzinc (DEZ) is available from Sigma-Aldrich.

[0163] ISOPAR-E solvent is available from ExxonMobil.

[0164] Decane solvent is available from Sigma-Aldrich.

[0165] Co-catalyst 1 is bis(hydrogenated tulowalkyl)methyl,tetrakis(penta-fluorophenyl)borate(1-)amine, available from Boulder Scientific.

[0166] Procatalyst (1): (E)-((2,6-diisopropylphenyl)(2-methyl-3-(octylimino)butan-2-yl)amino)trimethylhafnium:

[0167] [ka]

[0168] Procatalyst (2): (N-((6E)-6-(butylimino-κN)-1-cyclohexen-1-yl)-2,6-bis(l-methyl-ethyl)benzeneamino-κN)trimethyl-hafnium:

[0169] [ka]

[0170] Procatalyst (3): [N-(2,6-di(1-methylethyl)phenyl)amide)(2-isopropylphenyl)(α-naphthalene-2-diyl(6-pyridine-2-diyl)methane)]hafniumdimethyl]:

[0171] [ka]

[0172] Study 1 - GC mass spectrum of reaction product (Al) Example 1 The reaction between trioctylaluminum (TOA) and 1,3-divinyltetramethyldisiloxane (DVTMDS) followed Scheme 4 shown below.

[0173] [ka] In a dry box 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 heated to 130°C (heating block temperature). Samples taken at 15 minutes and 1 hour were hydrolyzed (with MeOH) for GC / MS analysis, and the formation of inserted products was monitored. The GC / MS results are shown in Figure 1. The GC / MS results indicated the presence of the following molecular species (A-E). These results confirmed the reaction in Scheme 4 described above.

[0174] [ka]

[0175] The GC peak with m / z 114 is octane formed from the hydrolysis of TOA. The peak with m / z 171 is a fragment of the starting siloxane after the loss of the methyl group. Samples 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), which correspond to fragments of the product in which octane was added to one or both vinyl groups. Samples taken at 1 hour (see Figure 1) showed growth of product peaks.

[0176] Example 2 The reaction between trioctylaluminum (TOA) and octenyldimethylvinylsilane (ODMVS) is shown in Scheme 5 below.

[0177] [ka]

[0178] Octenyldimethylvinylsilane (ODMVS) (0.536 g, 2.73 mmol) and trioctylaluminum (0.1 g, 0.273 mmol) were dissolved in 5 mL of decane in a vial under a nitrogen atmosphere in a dry box and heated to 130°C. Samples taken at 15 minutes and 1 hour were hydrolyzed (with MeOH) for GC / MS analysis, and the formation of inserted products was monitored. The results are shown in Figure 2. The GC / MS results showed the presence of the following molecular species (A-D). These results confirmed the reaction in Scheme 5 described above.

[0179] [ka]

[0180] Peak A, with an m / z of 114, is octane formed from the hydrolysis of TOA. Peak B, with an m / z of 181, is a fragment of the starting silane after the loss of the methyl radical. New peaks C and D, with m / z values ​​of 293 and 295 respectively, correspond to fragments of the product having octane added to the silyl vinyl group, as shown above.

[0181] Research 2 - Polymer Synthesis - Solution Processes Example 3 The preparation of polyethylene-PDMS linear block polymer is shown in Scheme 6 below.

[0182] [ka]

[0183] In a dry box (nitrogen atmosphere), ISOPAR-E solvent (10 mL), Co-Cat 1 (1.8 micromoles), and TEA (0.22 mmol) were added to a 40 mL vial equipped with a stirring bar. The vial was capped with a septum-lined lid and placed in a heating block. The vial was connected to the C2 (ethylene) line and used to slowly purge the vial through a needle. After the vial temperature reached 100°C (indicated by the temperature of the heating block), Pro Catalyst 1 [(E)-((2,6-diisopropylphenyl)(2-methyl-3-(octylimino)butan-2-yl)amino)trimethylhafnium], 1.5 micromoles in 0.2 mL of ISOPAR-E] was injected into the vial, the purge needle was removed, and the total pressure was maintained at 12 psig (determined by a pressure gauge on the ethylene line). The reaction was maintained for 20 minutes. After this time, the ethylene line was removed, a portion of the solution was taken and precipitated in MeOH to obtain pure polyethylene. DMS-V05 (1 ml) was added to the remaining solution in the vial, and the resulting solution was heated at 130°C for 30 minutes, followed by precipitation of the reaction product in MeOH. Both the polyethylene and the reaction product were filtered and dried under vacuum. Each sample was analyzed by GPC. The GPC overlay on the composition is shown in Figure 3.

[0184] In Figure 3, with respect to the y-axis of "dW / dLogM", at LogM = 3.00, the upper narrow profile is the profile of polyethylene (PE), the next lower profile is the profile of PE-PDMS and reaction products containing PE, and the lower broad profile is the profile of DMS-V05.

[0185] 29 The Si NMR profile is shown in Figure 4, and the 13C NMR profile is shown in Figure 5. 29Based on Si NMR, approximately 40% of the double bonds in the "Si-C=C" moiety were converted to Si-P (where P is the polyethylene polymer) based on the Si-CH2-P / Si-CH=CH2 ratio (comparing the Si peak intensity in the Si NMR profile). Based on 13C NMR, approximately 47% of the double bonds in the "Si-C=C" moiety were converted to Si-P (comparing the carbon peak intensity in the 13C NMR profile) based on the Si-CH2-P / Si-CH=CH2 ratio. These NMR results each indicate that the reaction proceeded as described in Scheme 6 above.

[0186] Example 4 The synthesis of polyethylene-PDMS comb-shaped block polymers is shown in Scheme 7.

[0187] [ka]

[0188] For Example 4, the same procedure as in Example 3 (containing the same amount of each component) was followed, except that VMS-T11 (1 ML) was used instead of DMS-V05. Each sample was analyzed by GPC. The compositional GPC overlay is shown in Figure 6.

[0189] In Figure 6, with respect to the y-axis of "dW / dLogM", at LogM = 3.00, the upper narrow profile is the profile of polyethylene (PE), the next lower "bimodal" profile is the profile of PE-PDMS and reaction products containing PE, and the lower broad profile is the profile of VMS-T11.

[0190] As described above, in the two polymerizations of Examples 3 and 4, the GPC curves of the block copolymers were superimposed for each reaction using the starting siloxane and polyethylene samples (taken before the addition of siloxane). It is clear that the block copolymers have a higher MW fraction compared to the base polyethylene, particularly in Example 4 where a bimodal MWD is shown, indicating that several block copolymers were formed.

[0191] Study 3 - GC mass spectrum of reaction product (Zn) Example 5 Reaction of diethylzinc (DEZ) with 1,3-divinyltetramethyldisiloxane (DVTMDS) - see Scheme 8.

[0192] [ka]

[0193] In a dry box 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 minutes. The resulting sample was hydrolyzed (with MeOH) for GC / MS analysis. The GC / MS results, according to Scheme 8, showed the presence of an insertion product (m / z=201) as shown below. The corresponding FC / MS peak S spectrum is shown in Figure 7.

[0194] [ka]

Claims

1. A process for forming a composition containing a siloxane-modified olefin polymer, wherein A) shown below is reacted with B) to form C) shown below, A) M[(CR １ R ２ -CR ３ R ４ )( ｎ -CH ３ ｘ (where M is a metal selected from Zn or Al, x is 2 or 3, when x = 2, M is Zn, when x = 3, M is Al, each n is independently ≥ 1; for each respective n value, R １ , R ２ , R ３ , R ４ each is independently H or hydrocarbyl, R １ may or may not be the same for each successive repeating unit, R ２ may or may not be the same for each successive repeating unit, R ３ may or may not be the same for each successive repeating unit, R ４ may or may not be the same for each successive repeating unit),​ B) Polysiloxane containing at least one silyl vinyl group, C) i, ii, iii, iv, v, vi, vii, viii, ix or x: i) 【Chemistry 1】 (In the formula, each n is defined above, R １ , R ２ , R ３ , R ４ Each of the units is defined above, and each of R and R' is independently hydrocarbyl or heterohydrocarbyl, x = 1 or 2, when x = 1, M is Zn, when x = 2, M is Al, and the asterisk ( ＊ ) represents the remainder of the complex. ii) 【Chemistry 2】 (In the formula, each n is defined above, R １ , R ２ , R ３ , R ４ Each unit is defined above, where R'' is hydrocarbyl or heterohydrocarbyl, x = 1 or 2, where if x = 1, M is Zn, where if x = 2, M is Al, and each asterisk ( ＊ (These terms independently represent the respective remnants of the complex.) iii) 【Transformation 3】 (In the formula, each n is defined above, R １ , R ２ , R ３ , R ４ Each of the units is defined above, and each of R and R' is independently a hydrocarbyl or heterohydrocarbyl, x = 0 or 1, and when x = 0 ([(CR １ R ２ -CR ３ R ４ ) - CH ３ ]) If the part does not exist, M is Zn and x = 1, then M is Al and each asterisk ( ＊ (These terms independently represent the respective remnants of the complex.) iv) 【Chemistry 4】 (In the formula, each n is defined above, R １ , R ２ , R ３ , R ４ Each of the units is defined above, and each R'' is independently hydrocarbyl or heterohydrocarbyl, x = 0 or 1, and when x = 0 ([(CR １ R ２ -CR ３ R ４ ) ｎ -CH ３ ]) If the part does not exist, M is Zn, and if x = 1, M is Al, and each asterisk ( ＊ (These terms independently represent the respective remnants of the complex.) v) 【Transformation 5】 (In the formula, each n is defined above, R １ , R ２ , R ３ , R ４ Each of the units is defined above, and each of R, R' and R'' is independently a hydrocarbyl or heterohydrocarbyl, x = 0 or 1, and when x = 0 ([(CR １ R ２ -CR ３ R ４ ) ｎ -CH ３ ]) If the part does not exist, M is Zn, and if x = 1, M is Al, and each asterisk ( ＊ (These terms independently represent the respective remnants of the complex.) vi) 【Transformation 6】 (In the formula, each n is defined above, R １ , R ２ , R ３ , R ４ Each of the units is defined above, where R and R' are independently hydrocarbyl or heterohydrocarbyl, M is Al, and each asterisk ( ＊ (These terms independently represent the respective remnants of the complex.) vii) 【Transformation 7】 (In the formula, each n is defined above, R １ , R ２ , R ３ , R ４ Each of the units is defined above, each R'' is independently hydrocarbyl or heterohydrocarbyl, M is Al, and each asterisk ( ＊ (These terms independently represent the respective remnants of the complex.) viiii) 【Transformation 8】 (In the formula, each n is defined above, R １ , R ２ , R ３ , R ４ Each of the units is defined above, and each of R, R' and R'' is independently hydrocarbyl or heterohydrocarbyl, M is Al, and each asterisk ( ＊ (These terms independently represent the respective remnants of the complex.) ix) 【Chemistry 9】 (In the formula, each n is defined above, R １ , R ２ , R ３ , R ４ Each of the units is defined above, and each of R, R' and R'' is independently hydrocarbyl or heterohydrocarbyl, M is Al, and each asterisk ( ＊ (where ) independently represents the respective remainder of the complex) one or more polysiloxane-M-polymer complexes independently selected from, or x) Forming any combination of these, A process comprising hydrolyzing one or more polysiloxane-M polymer complexes (C) to form the siloxane-modified olefin polymer.

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

3. Independently, for each n value from i to ix, R １ , R ２ , R ３ , R ４ The process according to claim 1 or 2, wherein each of is independently H or an alkyl group.

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

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

6. The siloxane-modified olefin polymer comprises the following polymer segments a1 and / or a2, and b, as follows: a1) -O-Si(R)(R')-CH ２ -CH ２ -(CR １ R ２ -CR ３ R ４ ) ｎ -CH ３ , (where n is defined herein, each of R and R' is defined herein, and each of R １ , R ２ , R ３ , R ４ is defined herein). a2) -O-Si(R")-CH ２ -CH ２ -((CR １ R ２ -CR ３ R ４ ) ｎ -CH ３ )-(where n is defined herein, R" is defined herein, and each of R １ , R ２ , R ３ , R ４ is defined herein). b) -O-SiR''' (R''')) ｍ -, (wherein m ≥ 1, and for each value of m, each of R''' and R'''' is independently H or hydrocarbyl), the process according to any one of claims 1 to 5.

7. The process according to claim 6, wherein, with respect to segment b, each of R''' and R'''' is independently H or an alkyl group.

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

9. The process according to any one of claims 1 to 8, further comprising isolating "the composition comprising the siloxane-modified olefin polymer".

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

11. The process according to claim 10, wherein the olefin polymer is an ethylene polymer.

12. A composition formed by the process described in any one of claims 1 to 11.

13. The composition according to claim 12, wherein the composition further comprises an olefin polymer.

14. The composition according to claim 13, wherein the olefin polymer is an ethylene polymer.

15. The siloxane-modified olefin polymer comprises at least one chain containing at least one structure selected from T5) to T8), and each asterisk ( ＊ ) independently represent the remainder of each of the aforementioned chains: T5) 【Chemistry 10】 (In the equation, m ≥ 2, x ≥ 1, and n ≥ 1.) T6) 【Chemistry 11】 (In the equation, m ≥ 2, x ≥ 1, y ≥ 1, and each n is independently ≥ 1.) T7) 【Chemistry 12】 (wherein m≧2, x≧1, y≧1, n≧1), or T8) any combination thereof, the composition of any one of claims 12 to 14.

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

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