Silanol-functional polyolefins

Abstract

Embodiments of the present disclosure relate to a method of making a silanol-functional polyolefin, the method comprising combining starting materials comprising A) a silyl hydride-functionalized polyolefin, optionally B) a solvent, C) a peroxy acid, optionally D) a neutralizing agent, under thermal conditions for effecting synthesis of a silanol moiety, thereby forming a reaction mixture, the reaction mixture produces the silanol functional polyolefin having the silanol moiety under the thermal conditions.

Description

Technical Field

[0001] The embodiments disclosed herein relate to polyolefins, and more specifically to silanol-functionalized polyolefins. Background Technology

[0002] The synthesis of polar polyolefins has long been a challenge, for at least the following reasons. Polar comonomers can be copolymerized with ethylene monomers; however, this is a capital-intensive, high-pressure method, and the resulting polymers have extensive branching and other property / compositional limitations. Radical grafting can be performed on high-density polyethylene or linear low-density polyethylene polymers, but the range of graftable monomers is limited, and typically only mixtures with non-uniform grafting points and lengths (e.g., single, low, and multiple grafts) are obtained. Furthermore, solution-phase polyolefin synthesis in commercial reactors is not tolerant of polar monomers due to their incompatibility with the catalyst.

[0003] In another approach, silane (-SiH) functional groups can be incorporated “in-reactor” and are compatible with conventional catalysts, but are nonpolar and require additional reactions to produce polar functionality. The simplest reaction to produce polar functionality from -SiH is through oxidation or hydrolysis to produce SiOH (silanol). However, silanols are difficult to synthesize in a controlled manner without further condensation into Si-O-Si. Transition metal compounds (e.g., Pd, Ru, Ir, Cr, and Rh) can also be used, but these compounds are expensive and require separation from the final reaction products, which also presents problems. Additionally, several silane hydrolysis methods using stoichiometric oxidants such as diethylene oxide and potassium permanganate have been reported. Unfortunately, diethylene oxide is unstable and unsuitable for the temperatures required for polyolefin functionalization, and potassium permanganate is expensive, highly discolored, and difficult to remove from the final product. Therefore, it is desirable to develop alternative, ideal in-reactor methods for synthesizing polar polyolefins that do not suffer from these drawbacks. Summary of the Invention

[0004] This disclosure provides various embodiments, including addressing the aforementioned disadvantages by providing a method for preparing a silanol-functionalized polyolefin, the method comprising, under thermal conditions for achieving the synthesis of the silanol moiety, forming a reaction mixture comprising: A) a silylhydride-functionalized polyolefin, optionally B) a solvent, C) a peroxy acid, and optionally D) a neutralizing agent, thereby forming a reaction mixture under thermal conditions to produce a silanol-functionalized polyolefin having a silanol moiety. As disclosed herein, the silylhydride-functionalized polyolefin may comprise a silylhydride moiety of Formula I:

[0005] ,

[0006] (For example, comprising the silylhydride portion of Formula I), wherein each R is independently selected from the group consisting of an alkyl group of 1 to 4 carbon atoms and an aryl group of 6 to 10 carbon atoms. As disclosed herein, each R may be a methyl group (e.g., each R is a methyl group). Furthermore, as disclosed herein, silylhydride-functionalized polyolefins may comprise 0.10 wt% to 10 wt% of the silylhydride portion of Formula I based on the total weight of the silylhydride-functionalized polyolefin (e.g., the silylhydride-functionalized polyolefin comprises 0.10 wt% to 10 wt% of the silylhydride portion of Formula I based on the total weight of the silylhydride-functionalized polyolefin). In a specific embodiment, the silylhydride-functionalized polyolefin may be selected from the group consisting of silylhydride-functionalized polyethylene and silylhydride-functionalized polypropylene (e.g., the silylhydride-functionalized polyolefin is selected from the group consisting of silylhydride-functionalized polyethylene and silylhydride-functionalized polypropylene). In one embodiment, the silylhydride-functionalized polyolefin may be a branched silylhydride-functionalized polyolefin (e.g., the silylhydride-functionalized polyolefin is a branched silylhydride-functionalized polyolefin).

[0007] As disclosed herein, the thermal conditions for achieving the synthesis of the silanol moiety may include melting and blending the reaction mixture at a temperature of 100°C to 180°C for a duration of 30 seconds to 60 minutes (e.g., the thermal conditions for achieving the synthesis of the silanol moiety include melting and blending the reaction mixture at a temperature of 100°C to 180°C for a duration of 30 seconds to 60 minutes). As disclosed herein, the method can be performed in the absence of a solvent (e.g., in the absence of a solvent). As disclosed herein, the thermal conditions for achieving the synthesis of the silanol moiety include dissolving the silanol-functionalized polyolefin in a solvent of the reaction mixture (B). As disclosed herein, the thermal conditions for achieving the synthesis of the silanol moiety include heating the reaction mixture at a temperature of 60°C to 120°C for a duration of one minute to 60 minutes. As disclosed herein, the method of this disclosure further includes separating the silanol-functionalized polyolefin from the reaction mixture.

[0008] As disclosed herein, peroxyacid is used in the method of this disclosure in an amount of 1 to 3 molar equivalents based on the silicon-bonded hydrogen content of the silane-functionalized polyolefin A). As disclosed herein, peracetic acid may be selected from (e.g., selected from) the group consisting of peracetic acid, m-chloroperoxybenzoic acid, peroxybenzoic acid, and combinations thereof. As disclosed herein, neutralizing agent D) may be present in (e.g., present in) the reaction mixture. As disclosed herein, this disclosure provides a silanol-functionalized polyolefin formed by the method disclosed herein. Detailed Implementation

[0009] The following detailed description provides a method for synthesizing polar polyolefins (e.g., in-reactor methods), etc. As discussed herein, typical commercial in-reactor solution-phase polyolefin synthesis is intolerant of polar monomers due to incompatibility with the catalyst, and therefore cannot produce polar polyolefins. Furthermore, while silane (-SiH) functional groups can be incorporated “in-reactor” and are compatible with conventional catalysts, they are nonpolar and require additional reactions to generate polar functionality. The simplest reaction for generating polar functionality from silanes to produce polyolefins is through the oxidation or hydrolysis of silanes to form silanols (-SiOH). However, the controlled synthesis of silanols without further condensation of Si-OH to Si-O-Si is unacceptable. Moreover, while transition metal compounds (e.g., Pd, Ru, Ir, Cr, and Rh) can be used in these methods, these transition metal compounds are expensive and need to be separated from the final reaction products. In addition, silane hydrolysis methods using stoichiometric oxidants such as diethylene oxide are unstable and unsuitable for the temperatures required for polyolefin functionalization, while those using potassium permanganate are too costly and produce highly colored and difficult-to-remove byproducts.

[0010] To address the shortcomings discussed herein, embodiments of this disclosure provide a method for preparing silanol-functionalized polyolefins, the method comprising forming a reaction mixture under thermal conditions comprising a combination of starting materials including: A) a silyl hydride-functionalized polyolefin, optionally B) a solvent, C) a peroxy acid, and optionally D) a neutralizing agent, thereby producing a silanol-functionalized polyolefin having a silanol moiety under thermal conditions.

[0011] As used herein, “optionally” means “with or without”. For example, “optionally solvent” means with or without a solvent.

[0012] 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.

[0013] As used herein, the terms "an," "a," and "the" used after open-ended terms such as "comprising" mean "at least one (kind)." In any aspect or embodiment of this disclosure described herein, the term "about" may be removed from phrases referring to numerical values ​​to give another aspect or embodiment of this disclosure. In the foregoing aspects or embodiments employing the term "about," the meaning of "about" may be interpreted according to the context in which it is used.

[0014] 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 such components, steps, or procedures are specifically disclosed. For the avoidance of any doubt, unless otherwise stated, all compositions claimed using the term “comprising” may include any additional additives, auxiliaries, or compounds, whether in polymeric or other forms. In contrast, the term “consistently composed of” excludes any other components, steps, or procedures from any subsequently listed scope, except those that are not essential for operability. The term “consisting of” excludes any components, steps, or procedures not specifically described or listed.

[0015] Preferably, "about" means 90% to 100% of the index value, 100% to 110% of the numerical value, or 90% to 110% of the numerical value. In any aspect or embodiment of this disclosure described herein, the open-ended terms "comprising / comprises," etc. (which are synonymous with "comprising," "having," and "characterized in") may be replaced by corresponding partially closed phrases such as "consisting essentially of / consists essentially of," or corresponding closed phrases such as "consisting of / consists of," to give another aspect or embodiment of this disclosure. Partially closed phrases such as "consisting essentially of," etc., limit the scope of the claims to the materials or steps listed therein and do not substantially affect the basic and novel features of the disclosure protected by the claims. The term "characterizable" is open-ended and means distinguishable.

[0016] As used herein, the term "composition" includes a mixture of materials constituting the composition, as well as reaction products and decomposition products formed from the materials of the composition. Any reaction product or decomposition product is typically present in trace or residual amounts.

[0017] As used herein, the term "polymer" refers to a polymer compound 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 in very low amounts ("ppm").

[0018] As used herein, the term "interpolymer" refers to a polymer prepared by polymerization of at least two different types of monomers. The term "interpolymer" therefore includes the term "copolymer" (used to refer to a polymer prepared from two different types of monomers) and polymers prepared from more than two different types of monomers (e.g., terpolymers).

[0019] 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.

[0020] As used herein, the term "propylene-based polymer" refers to a polymer that contains 50% by weight or most of a weight percentage of propylene (by weight of the polymer) in polymeric form and optionally may contain one or more comonomers.

[0021] As used herein, the term "ethylene-based polymer" refers to 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.

[0022] As used herein, the term "ethylene / α-olefin interpolymer" refers to a random interpolymer comprising 50% by weight or most of the weight percentage of ethylene (based on the weight of the interpolymer) and α-olefin in polymeric form.

[0023] As used herein, the term "ethylene / α-olefin copolymer" refers to a random copolymer in polymeric form comprising 50% by weight or most of the weight of ethylene (based on the weight of the copolymer) and α-olefin as the only two monomer types.

[0024] As used herein, the term "propylene / α-olefin interpolymer" refers to a random interpolymer comprising 50% by weight or most of the weight percentage of propylene (based on the weight of the interpolymer) and α-olefin in polymeric form.

[0025] As used herein, the term "propylene / α-olefin copolymer" refers to a random copolymer in polymeric form comprising 50% by weight or most of the weight percentage of propylene (based on the weight of the copolymer) and α-olefin as only two monomer types.

[0026] As used herein, the term "silylhydride-functionalized polyolefin" refers to a random interpolymer comprising 50% by weight or a majority weight percentage of an olefin (based on the weight of the interpolymer) and a silane monomer in polymeric form. As used herein, the interpolymer contains at least one Si-H group, and the phrase "at least one Si-H group" refers to the type of "Si-H" group. It should be understood that interpolymers in the art will contain a variety of these groups. Siylhydride-functionalized polyolefins are formed by copolymerization (e.g., using bis-biphenyl-phenoxy metal complexes) of at least an olefin (e.g., ethylene and / or propylene) and a silane monomer as provided herein. Examples of silane monomers are shown in Formula 1 as described herein.

[0027] As used herein, the term "ethylene / silane interpolymer" refers to a random interpolymer comprising 50% by weight or a majority weight percentage of ethylene (based on the weight of the interpolymer) and silane monomers in polymeric form. As used herein, the interpolymer contains at least one Si-H group, and the phrase "at least one Si-H group" is as discussed above. Ethylene / silane interpolymers are formed by copolymerization of at least ethylene and silane monomers.

[0028] As used herein, the term "ethylene / α-silylhydride functionalized polyolefin" refers to a random interpolymer comprising 50% by weight or a majority by weight of ethylene (based on the weight of the interpolymer), α-olefin, and silane monomers in polymeric form. As used herein, these interpolymers contain at least one Si-H group, as discussed above. Ethylene / silane interpolymers are formed by copolymerization of at least ethylene, α-olefin, and silane monomers.

[0029] As used herein, the term "ethylene / α-olefin / silane terpolymer" refers to a random terpolymer in polymeric form comprising 50% by weight or a majority by weight of ethylene (based on the weight of the terpolymer), α-olefin, and silane monomers as the only three monomer types. As used herein, the terpolymer contains at least one Si-H group, as discussed above. Ethylene / silane terpolymers are formed through copolymerization of ethylene, α-olefin, and silane monomers.

[0030] In this application, when referring to the aforementioned list of elements (e.g., ingredients), the phrases “mixtures of them,” “combinations of them,” etc., mean any two or more of the listed elements, including all of them. Unless otherwise stated, the term “or” used in the list of members refers to members listed individually and in any combination, and supports additional embodiments that list any single member (e.g., in an embodiment listing the phrase “10% or more,” “or” supports another embodiment listing “10%” and yet another embodiment listing “more than 10%”). The term “multiple” means two or more, where each plurality is independently selected unless otherwise stated. The terms “first,” “second,” etc., are used as a convenient way to distinguish two or more elements or limiting features (e.g., first chair and second chair) and do not imply quantity or order unless specifically indicated. The symbols “<” and ">” represent less than or equal to and greater than or equal to, respectively.

[0031] As used herein, the term "alkyl group" means a saturated straight-chain or branched (where possible) hydrocarbon group having the provided number of carbon atoms, which is unsubstituted or compounded by at least one R s Substitution. Therefore, for example, alkyl groups with 1 to 4 carbon atoms can include, but are not limited to, methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2-butyl; 2-methylpropyl; and 1,1-dimethylethyl. Examples of substituted alkyl groups with 1 to 4 carbon atoms can include, but are not limited to, the alkyl groups provided herein, wherein at least one hydrogen atom is replaced by an R s Replace, where each R s It is a halogen atom that exists independently.

[0032] As used herein, the term "aryl group" refers to an unsubstituted or substituted (with at least one R) ring carbon atom having 6 to 10 ring carbon atoms. s The substituted aryl group (e.g., an aryl group with 6 to 10 carbon atoms) comprises a mono- or di-aromatic hydrocarbon group, wherein the mono- or di-group comprises one or two rings, wherein one ring and two rings are aromatic, and the two rings may be fused with or not fused with the one ring. Examples of substituted aryl groups with 6 to 10 carbon atoms may include, but are not limited to, the aryl groups provided herein, wherein at least one hydrogen atom is replaced by an R s Replace, where each R s It is a halogen atom that exists independently.

[0033] As used herein, the term "silylhydride-functionalized polyolefin" is used to describe polyolefin copolymers formed using α-olefin monomers and α-silyl monomers or b) polyolefin terpolymers formed using α-olefin monomers, olefin comonomers, and α-silyl monomers. As used herein, the term "α-olefin monomer" may include ethylene (CH2=CH2), propylene (CH2=CH2-CH3), or combinations thereof. As used herein, the term "olefin comonomer" may include vinyl acetate, 1-butene, 2-butene, isobutene, styrene, acrylic acid, methyl acrylate, vinyl chloride, 1-hexene, 1-octene, and dienes (such as butadiene and isoprene). Other olefin comonomers may also be used. Furthermore, as discussed herein, the silylhydride-functionalized polyolefins of this disclosure can be formed as block copolymers / terpolymers or random copolymers / terpolymers.

[0034] As discussed herein, the methods disclosed herein are used to prepare silanol-functionalized polyolefins, including the use of a combination of starting materials comprising the following under thermal conditions for achieving the synthesis of the silanol moiety:

[0035] A) Silicylhydride-functionalized polyolefins

[0036] Optionally B) Solvent,

[0037] C) Peroxyacids,

[0038] Optionally, use (D) a neutralizing agent.

[0039] As discussed herein, the above-described starting materials are combined to form a reaction mixture, which, under the thermal conditions discussed herein, produces a silanol-functionalized polyolefin having a silanol moiety according to the present disclosure. Each of the starting materials A), C), and optionally B) and / or D) listed above is discussed herein, along with the thermal conditions for achieving the synthesis of the silanol moiety. For the purposes of this disclosure, the preparation of the silanol-functionalized polyolefin according to the present disclosure occurs either without the use of a catalyst or in the presence of a catalyst.

[0040] Silylhydride-functionalized polyolefins

[0041] The silyl hydride functionalized polyolefins disclosed herein can be prepared according to any of the following patents: U.S. Patent Publication 2023 / 0272206, U.S. Patent No. 6,624,254; WO 2012 / 027448; WO 2012 / 027448 and WO1995 / 000526, the entire contents of each of these patents being incorporated herein by reference.

[0042] For the purposes of this disclosure, silylhydride-functionalized polyolefins include at least one of the silylhydride moieties of Formula I:

[0043] ,

[0044] Each R is independently selected from the group consisting of an alkyl group of 1 to 4 carbon atoms and an aryl group of 6 to 10 carbon atoms (both groups as defined herein). For the purposes of this disclosure, preferably, each R is a methyl group. For the purposes of this disclosure, the silylhydride-functionalized polyolefin comprises a silylhydride moiety of Formula I comprising 0.10 wt% to 10 wt% of the total weight of the silylhydride-functionalized polyolefin. This includes all individual values ​​and sub-ranges from 0.10 wt% to 10 wt%; for example, the weight percentage of the silylhydride moiety of Formula I may have a lower limit of 0.10 wt%, 0.20 wt%, 0.40 wt%, or 1.0 wt% to an upper limit of 10 wt%, 8 wt%, 6 wt%, or 4 wt% based on the total weight of the silylhydride-functionalized polyolefin.

[0045] For the purposes of this disclosure, the silylhydride-functionalized polyolefin is selected from the group consisting of silylhydride-functionalized polyethylene and silylhydride-functionalized polypropylene. Furthermore, the silylhydride-functionalized polyolefin may be a branched silylhydride-functionalized polyolefin. For example, the silylhydride-functionalized polyolefin may be branched silylhydride-functionalized polyethylene or branched silylhydride-functionalized polypropylene.

[0046] For the purposes of this disclosure, the silyl hydride portion of Formula I is derived from a silane monomer selected from Formula II:

[0047]

[0048] Wherein A is an alkenyl group of 2 to 12 carbon atoms; B is a hydrocarbon group of 1 to 10 carbon atoms; R is as defined above, H is hydrogen, and x is 0 to 10. For the purposes of this disclosure, x may also be 0 to 8, or 0 to 6, or 0 to 4, or 0 to 2, or 0 or 1, or 0. For the purposes of this disclosure, A may be a C2-C12 alkenyl group, and further a C2-C8 alkenyl group, further a C2-C6 alkenyl group, further a C2-C4 alkenyl group. In one embodiment or a combination of two or more embodiments each described herein, formula II may be selected from the following compounds a) to h):

[0049]

[0050] Some examples of silane monomers of Formula II include hexenylsilane, allylsilane, vinylsilane, octenylsilane, hexenyldimethylsilane, octenyldimethylsilane, vinyldimethylsilane, vinyldiethylsilane, vinyldi(n-butyl)silane, vinylmethyloctadecylsilane, allyldimethylsilane, allyldiethylsilane, allyldi(n-butyl)silane, allylmethyloctadecylsilane, and bishexenylsilane. Mixtures of the above-mentioned alkenylsilanes may also be used. More specific examples of silane monomers of Formula II include the following: 5-hexenyl-dimethylsilane (HDMS), 7-octenyl-dimethylsilane (ODMS), allyl-dimethylsilane (ADMS), 3-butenyl-dimethylsilane, 1-(but-3-en-1-yl)-1,1,3,3-tetramethyldisiloxane (BuMMH), and 1-(hex-5-en-1-yl)-1,1,3,3-tetramethyldisiloxane (HexMMH). Mixtures of the above alkenylsilanes may also be used.

[0051] Additional monomers used to form the silylhydride-functionalized polyolefins of this disclosure may include addition-polymerizable monomers, including olefins or mixtures of olefins and dienes. The most preferred olefin is C1. 2-20 α-olefins and mixtures thereof, most preferably ethylene, propylene, and mixtures thereof with ethylene, propylene, 1-butene, 1-hexene, or 1-octene.

[0052] The method for forming the silylhydride-functionalized polyolefins of this disclosure using monomers of Formula II can be carried out under slurry, solution, bulk, gas-phase, or suspension polymerization conditions or other suitable reaction conditions. Polymerization can be carried out at temperatures from 0°C to 180°C, preferably from 25°C to 170°C, for a sufficient time to produce the desired polymer. Typical reaction times range from one minute to 100 hours, preferably from one hour to 10 hours. Optimal reaction times or reactor residence times will vary depending on the temperature, solvent, and other reaction conditions employed. Polymerization can be carried out at pressures below and above atmospheric pressure, suitably in the range of 1 psig to 800 psig (6.9 kPa–5,515 kPa).

[0053] Suitable catalysts and co-catalysts used herein preferably include those provided in WO 2012 / 027448; WO 2012 / 027448 and WO 1995 / 000526. Examples of such catalysts and co-catalysts are provided in the Examples section of this document. For example, a catalyst may include the following structure:

[0054]

[0055] Where M is a metal from any of Groups 3 to 6 of the periodic table, and the metal M is in an oxidation state of +2, +3, +4, +5, or +6; n is an integer from 0 to 5, where X does not exist when n is 0; each X is independently a neutral, monoanionic, or dianionic monodentate ligand; or two X are combined to form a neutral, monoanionic, or dianionic bidentate ligand; X and n are chosen in such a way that the metal-ligand complex of formula (I) is generally neutral; each Z is independently an O, S, N (Ci-C4g) hydrocarbon group or P (C j -C4Q) hydrocarbon group; L is (Ci -C4Q) hydrocarbon subgroup or (Ci -C4Q) heterohydrocarbon subgroup, wherein

[0056] The (Ci-C4Q) heteroalkyl group has a portion comprising a 1-carbon to 18-carbon atom linker backbone including Z atoms linked in formula (I), and the (Ci-C4Q) heteroalkyl group has a portion comprising a 1-atom to 12-atom linker backbone including Z atoms linked in formula (I), wherein each of the 1 to 18 atoms of the 1-atom to 18-atom linker backbone of the (Cj-C4Q) heteroalkyl group is independently a carbon atom or a heteroatom, wherein each heteroatom is independently O, S, S(O), S(O)2, Si(R)2, or S(O)2. c 2. P(R) P ) or N(R N ), where independently, each R c For unsubstituted (Cj-Cjg) hydrocarbon groups, each R p It is an unsubstituted (Cj-Cjg) hydrocarbon group; and each R N The (Cj-Cjg) hydrocarbon group is unsubstituted or absent; R^ a 、R^ a Each of R^b and R^b is independently a hydrogen atom (C r C 40 ) hydrocarbon group; (C r C 40 ) heterohydrocarbon group; -; Si(R c )3;0(R C ); S(R) C );N(R N )2;P(R P )2 or halogen atom; R 6c R 7c and R 8c At least one of them and R 6d R 7d and R 8d At least one of them is independently a (C2-C4o) hydrocarbon group; Si(R c )3 and R^ c R 7c R8c R 6d R 7d and R 8d Each of the other groups in the group is independently a hydrogen atom; (Cj-C4Q) hydrocarbon group; (C r C4o) heterohydrocarbon group; -; Si(R) c )3;0(R C ); S(R) C );N(R N )2;P(R P )2 or halogen atom, optionally two or more R groups (R^ a To R 8d These monomers can combine to form ring structures, which have 3 to 50 atoms (excluding hydrogen atoms) in the ring. The molar ratio of polymerizable monomers to catalysts can range from 100:1 to 1 × 10⁻⁶. 10 :1, preferably 1000:1 to 1×10 6 :1.

[0057] Another example of a suitable catalyst may include:

[0058]

[0059] R' is independently selected each time it appears from hydrogen, hydrocarbon, silyl, germanyl, cyano, halogen, and combinations thereof, R' has up to 20 non-hydrogen atoms, and optionally two R' groups (when R' is not hydrogen, halogen, or cyano) together form its divalent derivative, which is attached to an adjacent position of the cyclopentadienyl ring to form a fused ring structure, and X is a neutral q having up to 30 non-hydrogen atoms. 4 The bonded diene group forms a π-complex with M, and Y is -0-, -S-, or -NR. * -、-PR * -, M represents titanium or zirconium in the +2 oxidation state, Z * For SiR * 2. CR * 2. SiR * 2SiR * 2. CR * 2CR I 2CR * = CR * CR * 2SιR * 2 or GeR * 2, where each R * Each time it appears, it is independently hydrogen or a member selected from hydrocarbon groups, silyl groups, haloalkyl groups, haloaryl groups, and combinations thereof, wherein the R *It has at most 10 non-hydrogen atoms, and optionally, two R atoms. * Group, or from Z * R * Groups and R from Y * Group (when R) * (When not hydrogen) a ring system is formed. The molar ratio of polymerizable monomer to catalyst can range from 100:1 to 1×10⁻⁶. 10 :1, preferably 1000:1 to 1×10 6 :1.

[0060] The support may optionally be present in the catalyst formulation, particularly in gas-phase or slurry polymerization. Suitable supports include any inert particulate material, but are most preferably metal oxides, preferably alumina, silica, or aluminosilicate materials. Suitable particle sizes are from 1 μm to 1000 μm, preferably from 10 μm to 100 μm. The most desirable support is calcined silica, which can be treated by reacting with silanes or similar reactive compounds to reduce surface hydroxyl groups. Such a support can be included in the catalyst formulation by any suitable method, such as by dispersing the component in a liquid and contacting it with the support, then drying; by spraying or coating the support with such liquid and then removing the liquid; or by co-precipitating the co-catalyst and support material from a liquid medium.

[0061] Polymerization can be carried out with or without an inert diluent or solvent, i.e., in the presence of excess monomer. Examples of suitable diluents or solvents include C. 6-20 Aliphatic, alicyclic, aromatic, and halogenated aliphatic or aromatic hydrocarbons, and mixtures thereof. Preferred diluents include C 6-10 Alkanes, toluene, and mixtures thereof. A particularly desirable diluent for polymerization is isooctane, isononane, or blends thereof, such as Isopar-E, available from Exxon Chemical Company. ™ Use an appropriate amount of solvent to provide a monomer concentration of 5% to 100% by weight. Polymerization can be carried out in the presence of hydrogen.

[0062] Polymerization is advantageously carried out in a continuous polymerization manner, wherein the catalyst component, monomer, and optionally solvent are continuously supplied to the reaction zone and the polymer product is continuously removed therefrom. Within the scope of the term "continuous" as used in this context are those methods in which reactants are added intermittently and products are removed at less regular time intervals so that the overall process is continuous over time.

[0063] For the purposes of this disclosure, the number average molecular weight (Mn) of the silylhydride functionalized polyolefin may be ≥10,000 g / mol, or ≥12,000 g / mol, or ≥14,000 g / mol, or ≥16,000 g / mol, or ≥18,000 g / mol, or ≥20,000 g / mol, or ≥22,000 g / mol, or ≥24,000 g / mol, or ≥26,000 g / mol, or ≥28,000 g / mol, or ≥30,000 g / mol. 1 mol, or ≥32,000 g / mol to ≤100,000 g / mol, or 95,000 g / mol, or 90,000 g / mol, or ≤85,000 g / mol, or ≤80,000 g / mol, or 75,000 g / mol, or ≤70,000 g / mol, or ≤68,000 g / mol, or ≤66,000 g / mol, or ≤64,000 g / mol, or ≤62,000 g / mol, or ≤60,000 g / mol. For the purposes of this disclosure, the weight-average molecular weight (Mw) of the silylhydride-functionalized polyolefin may be ≥20,000 g / mol, or ≥25,000 g / mol, or ≥30,000 g / mol, or ≥35,000 g / mol, or ≥40,000 g / mol, or ≥45,000 g / mol, or ≥50,000 g / mol, or ≥52,000 g / mol, or ≥54,000 g / mol, or ≥56,000 g / mol, or ≥58,000 g / mol, or ≥60,000 g / mol, or ≥62,000 g / mol. 1 to ≤300,000 g / mol, or ≤250,000 g / mol, or ≤200,000 g / mol, or ≤190,000 g / mol, or ≤180,000 g / mol, or ≤170,000 g / mol, or ≤160,000 g / mol, or ≤150,000 g / mol, or ≤148,000 g / mol, or ≤146,000 g / mol, or ≤144,000 g / mol, or ≤142,000 g / mol, or ≤140,000 g / mol, or ≤138,000 g / mol. For the purposes of this disclosure, the molecular weight distribution (MWD = Mw / Mn) of the silylhydride functionalized polyolefin can also be ≥1.5, or ≥1.6, or ≥1.7, or ≥1.8, or ≥1.9 to ≤5.0, or ≤4.5, or ≤4.0, or ≤3.5, or ≤3.0, or ≤2.9, or ≤2.8, or ≤2.7, or 2.6, or 2.5, or ≤2.4, or ≤2.3. The measurement techniques for Mw and Mn are as described in the Examples section of this document.

[0064] For the purposes of this disclosure, the density of the silylhydride-functionalized polyolefin may be ≥0.855 g / cc, or ≥0.856 g / cc, or ≥0.857 g / cc, or ≥0.858 g / cc, or ≥0.859 g / cc, or ≥0.860 g / cc, or ≥0.861 g / cc, or ≥0.862 g / cc, or ≥0.863 g / cc, or ≥0.864 g / cc, or ≥0.865 g / cc, or ≥0.866 g / cc, or ≥0.867 g / cc (1 cc = 1 cm³). 3 Density is specified to be ≤0.950 g / cc, or ≤0.920 g / cc, or ≤0.900 g / cc, or ≤0.890 g / cc, or ≤0.888 g / cc, or ≤0.886 g / cc, or ≤0.884 g / cc, or ≤0.882 g / cc, or ≤0.880 g / cc, or ≤0.878 g / cc, or ≤0.876 g / cc, or ≤0.874 g / cc. The density measurement technique is as described in the Examples section of this document.

[0065] For the purposes of this disclosure, the melt index (I2) of silylhydride functionalized polyolefins can be ≥0.5 dg / min, or ≥1.0 dg / min, or ≥2.0 dg / min, or ≥5.0 dg / min, or ≥10 dg / min to ≤100 dg / min, or ≤50 dg / min, or ≤30 dg / min, or ≤20 dg / min, or ≤15 dg / min. The melt index (I2) measurement technique is as described in the Examples section of this document.

[0066] Thermal conditions for achieving the synthesis of silanol moieties

[0067] For the purposes of this disclosure, a method for preparing silanol-functionalized polyolefins includes combining A), C), and optionally B) and / or D) to form a reaction mixture that, under thermal conditions, produces a silanol-functionalized polyolefin having a silanol moiety as discussed herein. For embodiments, the thermal conditions include heating the reaction mixture as discussed herein to a temperature close to or above the melt temperature (Tm) of the silylhydride-functionalized polyolefin. For example, forming the reaction mixture by combining A), C), and optionally B) and / or D) while simultaneously providing thermal conditions to produce a silanol-functionalized polyolefin having a silanol moiety can be achieved through melt blending using a variety of different apparatuses. For various embodiments, a variety of different apparatuses are designed to heat, mix, and process the molten reaction mixture to produce a silanol-functionalized polyolefin having a silanol moiety as discussed herein. Examples of such apparatuses include single-screw extruders, twin-screw extruders, internal mixers (e.g., Banbury mixers and Intermix mixers), and kneaders or crank mixers. For each device, heat can be provided in addition to the mixing friction of the container or shell in which the reaction mixture is processed. Thus, for example, a single-screw or twin-screw extruder can have a heated barrel to heat the reaction mixture as needed.

[0068] As disclosed herein, the thermal conditions for achieving the synthesis of the silanol moiety include combining (e.g., melt blending) the reaction mixtures discussed herein at temperatures from 100°C to 180°C for durations from 30 seconds to 60 minutes. This includes all individual values ​​and sub-ranges from 100°C to 180°C; for example, the thermal conditions may have a lower limit of 100°C, 110°C, 120°C, or 130°C to an upper limit of 180°C, 170°C, 160°C, or 150°C. For the duration (e.g., reaction time), this includes all individual values ​​and sub-ranges from 30 seconds to 60 minutes; for example, the duration may have a lower limit of 30 seconds, 60 seconds, 90 seconds, 120 seconds, or 150 seconds to an upper limit of 60 minutes, 45 minutes, 30 minutes, 20 minutes, 10 minutes, or 5 minutes. It may also be any combination of the aforementioned individual values ​​of temperature and duration.

[0069] B) Solvent

[0070] As disclosed herein, the method may optionally use solvent B) to aid in mixing the starting materials A) and C) of the reaction mixture. For example, the silylhydride-functionalized polyolefin A) may be dissolved in solvent B) prior to combining A) the silylhydride-functionalized polyolefin and C) the peracetic acid. Solvents that may be used herein are those that help to fluidize the starting materials A) and C) but do not substantially react with these starting materials. The solvent may be selected based on the solubility of the starting materials A) and C) and the volatility of the solvent. Solubility refers to the solvent's ability to dissolve and / or disperse the starting material (e.g., A). Volatility refers to the solvent's vapor pressure. For example, if the solvent is not volatile enough (vapor pressure too low), it may be difficult to remove the solvent in subsequent processes.

[0071] When present, the solvent is a nonpolar solvent, which can be used to dissolve silylhydride-functionalized polyolefins while helping to control the exothermic nature of the method of the present invention, etc. Examples of suitable nonpolar solvents include C6-C. 20 Aliphatic, alicyclic, aromatic, and halogenated aliphatic or aromatic hydrocarbons, and mixtures thereof. Preferred nonpolar solvents include C6-C... 10 Alkanes, toluene, and mixtures thereof. Particularly desirable nonpolar solvents for the synthesis of silanol moieties are toluene, isooctane, isononane, or blends thereof, such as Isopar-E, available from Exxon Chemical Company. ™ .

[0072] When solvent B) is present, the thermal conditions for achieving the synthesis of the silanol moiety include dissolving the silylhydride-functionalized polyolefin in the solvent of the reaction mixture B). The amount of solvent will depend on various factors, including the type of solvent chosen and the amount and type of other starting materials chosen for the method. For the purposes of this disclosure, the ratio of a suitable solvent to the silylhydride-functionalized polyolefin used to dissolve the silylhydride-functionalized polyolefin in solvent B) can range from 15:1 to 1:1 (mL solvent:g silylhydride-functionalized polyolefin). As disclosed herein, when solvent B) is present in the reaction mixture, the thermal conditions for achieving the synthesis of the silanol moiety include heating the reaction mixture at a temperature of 60°C to 120°C for a duration of one minute to 60 minutes. This includes all individual values ​​and sub-ranges from 60°C to 120°C; for example, thermal conditions can have a lower limit of 60°C, 65°C, 70°C, or 75°C to an upper limit of 120°C, 115°C, 110°C, 105°C, or 100°C. For duration (e.g., reaction time), this includes all individual values ​​and sub-ranges from 1 minute to 60 minutes; for example, duration can have a lower limit of 1 minute, 2 minutes, 3 minutes, 4 minutes, or 5 minutes to an upper limit of 60 minutes, 45 minutes, 30 minutes, 20 minutes, or 10 minutes. It can also be any combination of the above individual values ​​for temperature and duration.

[0073] In one embodiment, the method of this disclosure as discussed herein occurs in the absence of solvent B). Thus, for example, the melt blending of the reaction mixture under the thermal conditions for achieving the synthesis of the silanol moiety as discussed herein can occur in the absence of solvent (e.g., in the absence of solvent).

[0074] C) Peroxyacids

[0075] As disclosed herein, the method for preparing silanol-functionalized polyolefins involves the use of peroxy acids. As used herein, peroxy acids are a class of organic compounds containing peroxide groups (OO) bonded to a carboxylic acid group (-COOH), which makes them oxidizing agents. Without being bound by theory, it is assumed that peroxy acids act as oxidizing agents, thereby forming the silanol (Si-OH) moiety from the Si-H portion of the starting material A) described herein. For the purposes of this disclosure, peroxy acids are selected from the group consisting of peracetic acid, m-chloroperoxybenzoic acid, peroxybenzoic acid, and combinations thereof. In particular, the use of peracetic acid as an oxidizing agent for the oxidation of -SiH to -SiOH is surprising, as peracetic acid is generally considered a milder oxidizing agent, and therefore a slightly lower reaction efficiency is expected. Another surprising result of this disclosure is the small molecular weight change (crosslinking) observed at the high temperatures required for the reaction with peroxy acids. Therefore, the results of this disclosure are surprising because peracetic acid would be efficient for this conversion.

[0076] For the purposes of this disclosure, the amount of peroxy acid used in the method for preparing silanol-functionalized polyolefins includes 1 to 3 molar equivalents of peroxy acid based on the silicon-bonded hydrogen content of the A) silyl hydride-functionalized polyolefin. Other ranges of the amount of peroxy acid used in the method for preparing silanol-functionalized polyolefins may also be included. For example, the amount of peroxy acid used in the method for preparing silanol-functionalized polyolefins may include not only 1 to 3 molar equivalents based on the silicon-bonded hydrogen content of the A) silyl hydride-functionalized polyolefin, but also 1.2 to 2 molar equivalents; 1.2 to 3 molar equivalents; or 2 to 3 molar equivalents of peroxy acid. As used herein, the molar equivalent of peroxy acid based on the silicon-bonded hydrogen content of the silylhydride-functionalized polyolefin is the molar amount of peroxy acid (e.g., 1 to 3 moles of peroxy acid) used in the method of the present invention to react with one mole of the -SiH portion present in the silylhydride-functionalized polyolefin of the present disclosure.

[0077] For the purposes of this disclosure, peroxyacids can be used either purely or as aqueous solutions. When used in aqueous solutions, the peroxyacids are present in an amount of 5% to 50% by weight based on the total weight of the aqueous solution. The discovery that aqueous peracetic acid is a stoichiometric oxidant for the synthesis of -SiOH from -SiH is surprising. For example, the use of aqueous peracetic acid as described herein allows for high conversion rates of -SiH to -SiOH within short reaction times (<20 min) and at the high temperatures required for molten or solution functionalization, wherein such reactions can occur in the presence of nonpolar solvents (such as toluene or other solvents as provided herein) or in the molten state of the polymer. Furthermore, the peroxyacids provided herein are commercially available. Moreover, the peroxyacids of this disclosure are degradable to relatively mild and volatile (e.g., strippable) byproducts such as hydrogen peroxide, acetic acid, and water, making the method of the present invention quite "environmentally friendly." Low / controllable molecular weight growth during functionalization and stable molecular weight of the SiOH polymer during long-term storage are also observed.

[0078] The peroxyacid aqueous solution may also contain other compounds to adjust the pH of the aqueous solution, wherein such compounds may include acids such as acetic acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, and hydrochloric acid, as well as other inorganic acids. For the purposes of this disclosure, the pKa of the peroxyacid in the aqueous solution can be in the range of 4 to 10.

[0079] D) Neutralizing agent

[0080] As disclosed herein, the method may optionally use a neutralizing agent D) in the reaction mixture. It is not desirable to be bound by theory and to assume that the peroxyacids provided herein contain residual inorganic acids (e.g., in commercially available peracetic acid, pH < 1). A neutralizing agent may be added to prevent or minimize undesirable condensation. For example, a mildly alkaline neutralizing agent in an amount sufficient to provide pH 3 to 4 for C) peracetic acid, where condensation is relatively slow, may be added. The starting material D) neutralizing agent may be added together with other starting materials A) and C), or the starting material containing C) peroxyacid may be combined with the neutralizing agent D) prior to combination with starting material A). Suitable neutralizing agents include sodium carbonate, sodium bicarbonate, calcium carbonate (CaO3), and potassium carbonate, all of which are commercially available, for example, from Sigma-Aldrich, Inc.

[0081] additive

[0082] The silanol-functionalized polyolefins disclosed herein may also contain one or more additives. Additives include, but are not limited to: UV stabilizers, antioxidants, fillers, scorch inhibitors, tackifiers, waxes, compatibilizers, tackifiers, plasticizers (e.g., oils), blocking agents, antiblocking agents, antistatic agents, release agents, anti-stick additives, colorants, dyes, pigments, and combinations thereof.

[0083] Separation of silanol-functionalized polyolefins from the reaction mixture

[0084] As disclosed herein, the method further includes the separation of silanol-functionalized polyolefins from the reaction mixture. The separation of silanol-functionalized polyolefins from the reaction mixture, with or without solvent B, can be achieved by a variety of techniques, including precipitation in a suitable polar solvent, cooling the silanol-functionalized polyolefin below its glass transition temperature, salting out (e.g., in the presence of solvent B), or spray drying (e.g., in the presence of solvent B). Examples of suitable polar solvents for separating silanol-functionalized polyolefins from the reaction mixture include polar aprotic solvents such as acetone and acetonitrile, as well as other solvents known in the art. Other polar solvents such as alcohols are not preferred because they may produce alkoxysilane byproducts. Once separated, the silanol-functionalized polyolefin can be washed once or multiple times with a polar aprotic solvent and then dried (e.g., at elevated temperatures of 30°C–50°C under dry nitrogen).

[0085] Example

[0086] The embodiments of the invention (IE) and the comparative examples (CE) were obtained using the following materials and methods. Table 1 provides the materials used in the IE and CE.

[0087] General process

[0088] Table 1A provides the polymer substrates, each of which is a -SiH-containing polyolefin. For each IE and CE, the corresponding polymer substrate was melt-blended in a twin-screw extruder (Thermo Fisher Scientific Process 11 twin-screw extruder) to a temperature equal to or higher than the melt temperature of the polymer substrate as discussed herein (Tables 1A and 2A / 2B), or dissolved in a solvent at the temperatures provided in Tables 1A and 3A / 3B and as discussed herein. The peracids provided in the table below were introduced in equimolar to three-molar excesses relative to the molar number of silane groups (-SiH).

[0089]

[0090] Polymer Synthesis and Properties

[0091] Polymers 1-5 (Table 1A) were each prepared in a one-gallon polymerization reactor filled with liquid and operated under steady-state conditions. Detailed synthesis information is provided below. The solvent was ISOPAR-E supplied by ExxonMobil Chemical Company. 5-Hexenyldimethylsilane (HDMS) supplied by Gelest was used as the ternary comonomer and purified via AZ-300 alumina supplied by UOP Honeywell prior to use. HDMS was fed into the reactor as a 22% by weight solution of ISOPAR-E. The reactor temperature was measured at or near the reactor outlet. The polymers were separated and granulated. Polymerization conditions are listed in Tables 1C-1E, and catalysts are shown in Table 1B. Polymer properties of each ethylene / octene / silane polymer (SiH-POE) and ethylene / octene interpolymer (polyolefin elastomer, POE) are shown in Tables 2A and 2B.

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100] Test methods for POLY 1-POLY 5

[0101] Gel permeation chromatography

[0102] The chromatographic system consisted of a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph equipped with an internal IR5 infrared detector. The autosampler oven chamber was set to 160°C and the column chamber to 150°C. The columns were four Agilent "Mixed A" 30 cm 20 μm linear mixed-bed columns. The chromatographic solvent was 1,2,4-trichlorobenzene containing 200 ppm butylated hydroxytoluene (BHT). The solvent source was nitrogen injection. The injection volume used was 200 μL, and the flow rate was 1.0 mL / min.

[0103] The GPC column assembly was calibrated using 21 polystyrene standards with narrow molecular weight distributions, ranging from 580 to 8,400,000, arranged in a six-cocktail mixture, with individual molecular weights spaced at least ten times apart. The standards were purchased from Agilent Technologies. For molecular weights equal to or greater than 1,000,000, 0.025 g of polystyrene standard was prepared in 50 mL of solvent; for molecular weights less than 1,000,000, 0.05 g of polystyrene standard was prepared in 50 mL of solvent. The polystyrene standards were dissolved at 80°C by gentle stirring for 30 minutes. The peak molecular weights of the polystyrene standards were converted to polyethylene molecular weights using Equation 1 (as described in Williams and Ward, J. Polym.Sci., Polym.Let., 6, 621 (1968)).

[0104]

[0105] Where M is the molecular weight, A has a value of 0.4315, and B equals 1.0.

[0106] A fifth-order polynomial was used to fit the calibration point for the corresponding polyethylene equivalent. A small adjustment was made to A (from approximately 0.375 to 0.445) to correct for column resolution and band broadening effects.

[0107] Linear homopolymer polyethylene standards were obtained at 120,000 Mw. Total plate counts were performed on the GPC column assembly using decane (“prepared as 0.04 g in 50 mL TCB”, dissolved under slow stirring for 20 min). Plate counts (Equation 2) and symmetry (Equation 3) were measured at 200 μL injections according to the following equations:

[0108]

[0109] Where RV is the retention volume in milliliters, peak width is in milliliters, peak maximum is the maximum height of the peak, and ½ height is half the height of the peak maximum; and

[0110]

[0111] Where RV is the retention volume in milliliters, and peak width is in milliliters. The peak maximum is the position of the highest peak value, and one-tenth of the peak height is 1 / 10 of the peak maximum height. A "tail peak" refers to the peak tail whose retention volume is later than the peak maximum, and a "front peak" refers to the peak front whose retention volume is earlier than the peak maximum. The plate count of the chromatographic system should be greater than 18,000, and the symmetry should be between 0.98 and 1.22.

[0112] Samples were prepared semi-automatically using PolymerChar "Instrument Control" software, with a target sample weight of 2 mg / ml. Solvent (containing 200 ppm BHT) was added to a pre-bubbled, diaphragm-capped vial using a PolymerChar high-temperature autosampler. The sample was dissolved at 160°C for two hours with "low-speed" oscillation.

[0113] Based on the GPC results, using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph, according to Equations 4-6, the PolymerChar GPCOne was used. ™ The software calculates the Mn content based on the baseline-subtracted IR chromatograms at each equidistant data collection point (i) and the polyethylene equivalent molecular weight obtained from the narrow standard calibration curve at point (i) according to Equation 1. (GPC) Mw (GPC) and Mz (GPC) The calculation is as follows: Equation 4-6 is as follows:

[0114]

[0115] 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 time of the decane marker peak was related to a linear variation in the flow rate (effective flow rate) over the entire run. To facilitate the highest accuracy in the RV measurement of the flow marker peak, a least-squares fitting procedure was used to fit the peak value of the flow marker concentration chromatogram to a quadratic equation. The true peak position was then solved using the first derivative of the quadratic equation. After calibration based on the flow marker peak system, the effective flow rate (relative to the narrow standard calibration) was calculated according to Equation 7:

[0116] Flow rate (effective) = Flow rate (nominal) * (RV (FM calibrated) / RV (FM sample)) (Equation 7).

[0117] via PolymerChar GPCOne ™ The software processes the flow marker peaks. Acceptable flow rate correction ensures that the effective flow rate is within + / - 0.7% of the nominal flow rate.

[0118] Melt index

[0119] The melt index I2 of each polymer is determined according to ASTM D-1238 at 190°C / 2.16 kg (melt index I2). 10 Measured at 190℃ / 10.0kg. According to I 10 Calculate I by the ratio of I2 10 / I2. The melt flow rate (MFR) of each polymer was measured according to ASTM D-1238 at 230°C / 2.16 kg.

[0120] density

[0121] Polymer plates were prepared using ASTM D4703 for density analysis. The density of each polymer was measured using ASTM D792, Method B.

[0122] NMR characterization of ternary copolymers

[0123] for 13 For the C10 NMR experiment, the sample was dissolved in tetrachloroethane-d2 (with or without 0.025M Cr(acac)3) in a 10 mm NMR tube. The concentration was approximately 300 mg / 2.8 mL. Each tube was then heated in a heating block set to 110 °C. The sample tubes were repeatedly vortexed and heated to obtain a homogeneous fluid flow. Data were acquired on a BRUKER AVANCE 600 MHz spectrometer equipped with a 10 mm C / H DUAL cryogenic probe. 13 C10 NMR spectroscopy. The following acquisition parameters were used: 60-second relaxation delay, 12.0 µs 90° pulse, 256 scans. The spectrum was centered at 100 ppm and had a spectral width of 250 ppm. All measurements were performed at 110 °C without sample rotation. For the solvent resonance peaks, 13 The C NMR spectrum was at 74.5 ppm. For samples containing Cr, data were acquired with a 7-second relaxation delay and 1024 scans.

[0124] Differential scanning calorimetry (DSC)

[0125] Differential scanning calorimetry (DSC) was used to measure T in each polymer sample. m T c T gCrystallinity. Each sample (0.5 g) was compressed into a film at 5000 psi and 190 °C for two minutes. Approximately 5 mg to 8 mg of film sample was weighed and placed in a DSC pan. The lid was screwed on the pan to ensure a closed atmosphere. Unless otherwise specified, the sample pan was placed in the DSC unit and heated to 180 °C (230 °C for PP) at a rate of 10 °C / min. The sample was held at this temperature for three minutes. Then, for PE, the sample was cooled to -90 °C (for PP, to -60 °C) at a rate of 10 °C / min and held isothermally at this temperature for three minutes. The sample was then heated at a rate of 10 °C / min until completely melted (second heating). Unless otherwise specified, the melting point (T) of each polymer is not specified. m ) and glass transition temperature (T g The crystallization temperature (T) is determined by the second heating curve. c The value (T) is determined by the first cooling curve. Record T. m and T c The corresponding peak temperature. The heat of fusion (H₂) can be determined by the second heating curve. f Divide the theoretical heat of fusion of 292 J / g for PE (165 J / g for PP) and multiply this by 100 to calculate the crystallinity percentage (e.g., Crystallinity % = (Hf / 292 J / g) × 100 (for PE)). In DSC measurements, it is common to observe multiple T values. m Peak, and here recorded as T as polymer m The highest temperature peak.

[0126] Experimental Procedure

[0127] IE 1-IE 10: Oxidative Reactive Extrusion

[0128] Oxidative reactive extrusion of IE 1–IE 10 was carried out in an 11 mm diameter Thermo Fisher Scientific Process 11 twin-screw extruder (TSE) kept in a chemical fume hood. This is a compact, parallel-rotating TSE with a clamshell barrel. The extruder is 44 L / D in length, comprising a 40 L / D barrel and a 4 L / D extension. The barrel has six multi-functional barrel ports for reagent injection or vacuum, and eight independent heating zones along the barrel. The polymer substrate was ground to a particle size of less than 2 mm prior to use to facilitate its feeding. IE 1–IE 10 each used Poly 1 as the substrate and mCPBA as the oxidant, wherein the polymer powder and mCPBA were dry-blended. The polymer substrate was fed into the extruder at a rate of 180 g / h using a MovaColor MCBALANCE single-screw metering feeder. A residence time of 2.5 min was used. Typically, the extruder is run for about 5 minutes to reach equilibrium, and then about 10g-20g of sample is collected for analysis.

[0129] The functionalized polymer was purified by precipitating it from hot toluene into methanol. The purified functionalized polymer was characterized by proton NMR spectroscopy as discussed herein.

[0130] IE11-IE18: Solvent Oxidation

[0131] Solvent oxidation of IE11–IE18 was performed as follows. The polymer substrate was dissolved in toluene (Table 4A) in a three-necked round-bottom flask equipped with a top-mounted stirrer and reflux condenser under a dry nitrogen atmosphere. The solution was heated to the temperature provided in Table 4A. An oxidant as provided in Table 4A was added, and the mixture was vigorously stirred for the time shown in Table 4A. During the reaction, aliquots precipitated in methanol and briefly dried in an aluminum pan at 120 °C were analyzed by NMR and ATRFT-IR, as discussed herein, to provide the conversion of -SiH to Si-OH. Analysis was performed until -SiH remained constant. The hot polymer solution was then precipitated in acetone at atmospheric pressure and room temperature (23 °C). The resulting precipitated polymer was blended in acetone, filtered, resuspended in acetone, filtered again, and dried under nitrogen purging at an elevated temperature (50 °C).

[0132] Test feature results

[0133] Tables 3A / 3B and 4A / 4B provide the test results for IE 1–IE 18. Mn and Mw were determined as described herein.

[0134]

[0135]

[0136]

[0137]

[0138] Data Analysis

[0139] As shown above, IE 1-IE 10 demonstrate that oxidation of mCPBA in the TSE provides extremely high conversion rates of the -SiH moiety to the -SiOH moiety in the polymer substrate. This is achieved with stoichiometric ratios of oxidant to -SiH ranging from only 1:1 to 3:1. The reaction temperature for the conversion is also reasonable, ranging from 100°C to 180°C, especially when the reaction is carried out at atmospheric pressure.

[0140] Solvent oxidation processes in IE 11-IE 18 indicate that mCPBA and PAA are effective oxidants in solution, while CE1 shows that tBHP is not an effective oxidant.

[0141] Measurement information from IE and CE

[0142] GPC

[0143] The chromatographic system consisted of a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph equipped with an internal IR5 infrared detector. The autosampler oven chamber was set to 160°C and the column chamber to 150°C. The columns were four Agilent "Mixed A" 30 cm 20 μm linear mixed-bed columns. The chromatographic solvent was 1,2,4-trichlorobenzene containing 200 ppm butylated hydroxytoluene (BHT). The solvent source was nitrogen injection. The injection volume used was 200 μL, and the flow rate was 1.0 mL / min.

[0144] The GPC column assembly was calibrated using 21 polystyrene standards with narrow molecular weight distributions, ranging from 580 to 8,400,000, arranged in a six-cocktail mixture, with individual molecular weights spaced at least tenfold apart. The standards were purchased from Agilent Technologies. For molecular weights equal to or greater than 1,000,000, 0.025 g of polystyrene standard was prepared in 50 mL of solvent; for molecular weights less than 1,000,000, 0.05 g of polystyrene standard was prepared in 50 mL of solvent. The polystyrene standards were dissolved by gentle stirring at 80°C for 30 minutes. The peak molecular weights of the polystyrene standards were converted to polyethylene molecular weights using Equation 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)).

[0145] Where M is the molecular weight, A has a value of 0.4315, and B equals 1.0.

[0146] A fifth-order polynomial was used to fit the calibration point for the corresponding polyethylene equivalent. A small adjustment to A (from approximately 0.375 to 0.445) was made to correct for column resolution and band broadening effects, resulting in a linear homopolymer polyethylene standard at 120,000 Mw. Total plate counts were performed on the GPC column assembly using decane (“prepared as 0.04 g in 50 mL TCB”, dissolved under slow stirring for 20 min). Plate counts (Equation 2) and symmetry (Equation 3) were measured at 200 μL injections according to the following equations:

[0147] Where RV is the retention volume in milliliters, peak width in milliliters, peak maximum value is the peak maximum height, and ½ height is half the peak maximum height; and

[0148] Where RV is the retention volume in milliliters, and peak width is in milliliters, peak value is the position of the maximum peak value, one-tenth height is 1 / 10 of the height of the peak value, and a subsequent peak refers to the tail of a peak whose retention volume is later than the peak value, while a preceding peak refers to the front of a peak whose retention volume is earlier than the peak value. The plate count of the chromatographic system should be greater than 18,000, and the symmetry should be between 0.98 and 1.22.

[0149] Samples were prepared semi-automatically using PolymerChar "Instrument Control" software, with a target sample weight of 2 mg / ml. Solvent (containing 200 ppm BHT) was added to a pre-bubbled, diaphragm-capped vial using a PolymerChar high-temperature autosampler. The sample was dissolved at 160°C for two hours with "low-speed" oscillation.

[0150] Based on the GPC results, using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph, according to Equations 4-6, the PolymerChar GPCOne was used. ™ The software calculates the Mn content based on the baseline-subtracted IR chromatograms at each equidistant data collection point (i) and the polyethylene equivalent molecular weight obtained from the narrow standard calibration curve at point (i) according to Equation 1. (GPC) Mw (GPC) and Mz (GPC) The calculation is as follows: Equation 4-6 is as follows:

[0151]

[0152] 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 time of the decane marker peak was related to a linear variation in the flow rate (effective flow rate) over the entire run. To facilitate the highest accuracy in the RV measurement of the flow marker peak, a least-squares fitting procedure was used to fit the peak values ​​of the flow marker concentration chromatogram to a quadratic equation. The true peak position was then solved using the first derivative of the quadratic equation. After calibration based on the flow marker peak system, the effective flow rate (relative to the narrow standard calibration) was calculated according to Equation 7: Effective Flow Rate = Nominal Flow Rate * (RV(FM calibrated) / RV(FM sample)) (EQ7). (via PolymerChar GPCOne) ™ The software processes the flow marker peaks. Acceptable flow rate correction ensures that the effective flow rate is within + / - 0.7% of the nominal flow rate.

[0153] NMR

[0154] via Varian 500MHz NMR1 H and 29 The extruded polymer was analyzed by Si NMR. Using 10-15 mg of polymer dissolved in 550 μL TCE-d2, the polymer was prepared by D1 = 10 s, 16-32 scans, and other standard methods. 1 ¹H NMR samples were prepared using 100 mg polymer and 500 μL TCE-d2 with 4 mM Cr(acac)3, with D1 = 5 s, 256 scans, and QA-RINEPT method. 29 Si NMR sample. The conversion rate of SiH was determined as follows: by... 1 1H NMR was used to determine the change in the integral of the SiH resonance at 3.95 ppm after extrusion compared to the unextruded sample, and the result was normalized to the integral of the aliphatic resonance. All spectra were collected on a Varian 500 MHz spectrometer with a cryogenic probe cooled by liquid N2.

[0155] FTIR-ATR

[0156] Infrared spectra were collected on a Perkin Elmer Frontier Fourier Transform Infrared Spectrometer (FT-IR) equipped with an Attenuated Total Reflectance (ATR) attachment (single-shot diamond / ZnSe). The sample was cut with scissors to expose a clean inner surface, then placed in the attachment and held at a force of approximately 0.4 at the peak absorbance, and 4–16 scans were collected depending on the spectral quality. Spectra were collected in at least triplicate to ensure representative sampling of the entire sample.

[0157] SiH conversion rate is the molar percentage of SiH bonds in the polymer source that become Si-C bonds due to oxidation. SiH conversion rate is expressed as a percentage of the Si-C bonds formed by oxidation reactions. -1 The peak at 942 cm⁻¹ was normalized and the peak at 942 cm⁻¹ was normalized -1 The baseline at that location was set to 0 to determine this, and then 887cm was used. -1 The conversion rate is determined by the Si-H peak at the 887 cm⁻¹ position. %SiH conversion rate = 100 * (887 cm⁻¹ after oxidation reaction) -1 (absorbance at 887 cm⁻¹) / (absorbance at 887 cm⁻¹ before -1 (Absorbance at that location).

Claims

1. A method for preparing silanol-functionalized polyolefins, the method comprising: The starting material combination will include the following items under the thermal conditions used to achieve the synthesis of the silanol moiety: A) Silicylhydride-functionalized polyolefins Optionally B) Solvent, C) Peroxyacids, Optionally, D) neutralizing agent; This forms a reaction mixture that, under the thermal conditions, produces a polyolefin having the silanol moiety and the silanol functionality.

2. The method of claim 1, wherein the silylhydride-functionalized polyolefin comprises the silylhydride portion of formula I: -SiR2H(I), Each R is independently selected from the group consisting of an alkyl group of 1 to 4 carbon atoms and an aryl group of 6 to 10 carbon atoms.

3. The method according to claim 2, wherein each R is a methyl group.

4. The method according to any one of claims 2 to 3, wherein the silylhydride functionalized polyolefin comprises 0.10 to 10% by weight of the silylhydride portion of Formula I based on the total weight of the silylhydride functionalized polyolefin.

5. The method according to any one of claims 1 to 4, wherein the silylhydride-functionalized polyolefin is selected from the group consisting of silylhydride-functionalized polyethylene and silylhydride-functionalized polypropylene.

6. The method according to any one of claims 1 to 5, wherein the silylhydride-functionalized polyolefin is a branched silylhydride-functionalized polyolefin.

7. The method according to any one of claims 1 to 6, wherein the thermal conditions for achieving the synthesis of the silanol moiety include melting and blending the reaction mixture at a temperature of 100°C to 180°C for a duration of 30 seconds to 60 minutes.

8. The method of claim 7, wherein the method is performed in the presence of a solvent.

9. The method according to any one of claims 1 to 6, wherein the thermal conditions for achieving the synthesis of the silanol moiety comprise dissolving the silylhydride-functionalized polyolefin in the solvent of the reaction mixture in B).

10. The method of claim 9, wherein the thermal conditions for achieving the synthesis of the silanol moiety comprise heating the reaction mixture at a temperature of 60°C to 120°C for a duration of one minute to 60 minutes.

11. The method according to any one of claims 1 to 10, the method further comprising separating the silanol-functionalized polyolefin from the reaction mixture.

12. The method according to any one of claims 1 to 11, wherein the hydrogen content of the silicon bonds of the silylhydride functionalized polyolefin described in A) is used, and the peroxy acid is used in an amount of 1 molar equivalent to 3 molar equivalents of peroxy acid.

13. The method according to any one of claims 1 to 12, wherein the peroxy acid is selected from the group consisting of peracetic acid, m-chloroperoxybenzoic acid, peroxybenzoic acid, and combinations thereof.

14. The method according to any one of claims 1 to 13, wherein the neutralizing agent in claim D) is present in the reaction mixture.

15. A silanol-functionalized polyolefin, said silanol-functionalized polyolefin being formed by any one of claims 1 to 14.

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