copolymer of ethylene and (meth)acrylate-functionalized polysiloxane

Abstract

The various embodiments described herein relate to a polymer composition comprising a reaction product of copolymerization of ethylene and a (meth)acrylate-functionalized polysiloxane, polyethylene, and optionally one or more units derived from a ternary comonomer. Articles made from the polymer composition and methods for preparing the polymer composition are also described.

Description

Technical Field

[0001] The embodiments disclosed herein generally relate to ethylene copolymers, and more specifically to copolymers of ethylene and (meth)acrylate-functionalized polysiloxanes. Background Technology

[0002] Conventional low-density polyethylene (LDPE) exhibits good processability, but when used in applications such as membranes, slip additives are typically required to impart a low coefficient of friction (COF). However, such additives can migrate and leach out over time. Therefore, LDPE compositions can be grafted with such additives to prevent migration and leaching from the surface; one possible additive is polysiloxane. However, during the formation of siloxane-grafted LDPE polymers, achieving a high level of adhesion between the siloxane and LDPE is challenging, resulting in poor processability, poor optical properties, and inconsistent COF behavior due to a lack of homogeneity between the remaining unattached polysiloxane and polyethylene. To avoid these drawbacks, such compositions require special purification after the grafting event to remove unreacted polysiloxane, making this method inefficient and expensive.

[0003] Therefore, there is a need for LDPE compositions with higher levels of attached siloxanes and improved homogeneity. Summary of the Invention

[0004] This disclosure addresses these needs by providing ethylene-based polymer compositions formed by high-pressure (greater than or equal to 100 MPa) free radical polymerization of an ethylene monomer and a (meth)acrylate-functionalized polydimethylsiloxane, thereby yielding a (PDMS-co-LDPE) polymer composition based on low-density polyethylene. This composition exhibits less unattached (free) PDMS for the same weight percentage (wt%) of introduced siloxane and for introduced siloxanes of similar molecular weight, compared to grafting methods. This, in turn, results in improved processability and optical properties compared to grafted analogs. It should be noted that grafted analogs can be further purified from unreacted siloxanes, but this would require additional steps and equipment, and the polymers of the various embodiments described herein may not require any such subsequent purification.

[0005] According to at least one embodiment of the present disclosure, the polymer composition comprises a reaction product of copolymerization of ethylene and (meth)acrylate-functionalized polysiloxane, polyethylene, and optionally one or more units derived from a terpolymer monomer.

[0006] According to another embodiment, the polymer composition comprises the polymer composition described in the foregoing embodiments, wherein the polymer composition is a copolymer of a copolymer of ethylene and a (meth)acrylate-functionalized polysiloxane and a low-density polyethylene.

[0007] According to another embodiment, the polymer composition comprises the polymer composition according to any one of the foregoing embodiments, which includes one or more of the following structures:

[0008]

[0009] Where R is methyl or hydrogen, R 1 As a bridging group connecting the functional group ((meth)acrylate) and the siloxane, R 2 The terminal group is selected from the group consisting of alkyl, substituted alkyl, aryl, alkenyl, H and OH, x is an integer from 10 to 1000, and y is an integer from 1 to 20.

[0010] According to another embodiment, the polymer composition comprises the polymer composition according to any one of the foregoing embodiments, wherein the (meth)acrylate-functionalized polysiloxane has one or more of the following structural formulas:

[0011]

[0012] Where R is methyl or hydrogen, R 1 For bridge foundation, R 2 The terminal group is selected from alkyl, aryl, alkenyl, H or OH, x is an integer from 10 to 1000, and y is an integer from 1 to 20.

[0013] According to another embodiment, the polymer composition comprises the polymer composition according to any one of the foregoing embodiments, wherein each bridging group is selected from the group consisting of substituted and unsubstituted C2-C 20 Alkylene linkers, wherein one or more carbon atoms may be substituted with oxygen, silicon, substituted or unsubstituted aryl groups, or their derivatives and combinations thereof.

[0014] According to another embodiment, the polymer composition comprises the polymer composition according to any one of the foregoing embodiments, wherein the polymer composition has a MWD of 3 to 50.

[0015] According to another embodiment, the polymer composition comprises the polymer composition according to any one of the preceding embodiments, wherein a ternary comonomer is present and selected from the group consisting of: olefins, unsaturated esters, unsaturated acids, monoesters or diesters of maleic acid, functionalized olefins, and combinations thereof.

[0016] According to another embodiment, the polymer blend comprises the polymer composition according to any one of the foregoing embodiments, and one or more additional polymers.

[0017] According to another embodiment, the polymer blend comprises the polymer blend described in the foregoing embodiments, wherein the additional polymer includes low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ultra-low-density polyethylene (ULDPE), very low-density polyethylene (VLDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), copolymers containing (meth)acrylates, copolymers containing (meth)acrylic acid, monoesters or diesters of maleic acid, copolymers containing vinyl acetate, copolymers containing trialkoxyvinylsilane, or grafted polyethylene.

[0018] According to another embodiment, the article comprises a polymer composition according to any one of the foregoing embodiments, the polymer composition including the polymer composition described in the foregoing embodiments.

[0019] According to another embodiment, the article includes the article described in the foregoing embodiment, wherein the article is a membrane.

[0020] According to another embodiment, the method includes reacting ethylene monomer and (meth)acrylate-functionalized polysiloxane in a polymerization reactor under free radical polymerization conditions and at a pressure greater than or equal to 100 MPa to produce a copolymer comprising low-density polyethylene and functionalized polydimethylsiloxane, as well as polyethylene.

[0021] According to another embodiment, the method includes the method described in the foregoing embodiments, wherein the copolymer comprises one or more of the following structures:

[0022]

[0023] Where R is methyl or hydrogen, R 1 As a bridging group connecting the functional group ((meth)acrylate) and the siloxane, R 2 The terminal group is selected from the group consisting of alkyl, substituted alkyl, aryl, alkenyl, H and OH, x is an integer from 10 to 1000, and y is an integer from 1 to 20.

[0024] According to another embodiment, the method includes the method according to any one of the foregoing embodiments, wherein the (meth)acrylate-functionalized polysiloxane has one or more of the following structural formulas:

[0025]

[0026]

[0027] Where R is methyl or hydrogen, R 1 For bridge foundation, R 2 The terminal group is selected from alkyl, aryl, alkenyl, H or OH, x is an integer from 10 to 1000, and y is an integer from 1 to 20.

[0028] According to another embodiment, the method includes the method according to any one of the foregoing embodiments, wherein each bridge base is selected from the group consisting of: substituted and unsubstituted C2-C. 20 Alkylene linkers, wherein one or more carbon atoms may be substituted with oxygen, silicon, substituted or unsubstituted aryl groups, or their derivatives and combinations thereof.

[0029] These and other implementations are described in more detail in the following description and figures. Attached Figure Description

[0030] Figure 1A This is an exemplary differential scanning calorimetry (DSC) second heating profile of LDPE-co-PDMS according to one or more embodiments shown and described herein;

[0031] Figure 1B These are exemplary DSC cooling profiles of LDPE-co-PDMS according to one or more embodiments shown and described herein;

[0032] Figure 2 The molecular weight distribution is obtained from gel permeation chromatography (GPC) analysis of exemplary LDPE-co-PDMS according to one or more embodiments shown and described herein;

[0033] Figure 3A It is the Fourier transform infrared (FTIR) spectrum of LDPE-g-PDMS;

[0034] Figure 3B yes Figure 3A The FTIR spectrum starts from approximately 1850 cm⁻¹ -1 Approximately 1600cm -1 Close-up;

[0035] Figure 3C These are exemplary FTIR spectra of LDPE-co-PDMS according to one or more embodiments shown and described herein; and

[0036] Figure 3D yes Figure 3C The FTIR spectrum starts from approximately 1850 cm⁻¹ -1 Approximately 1600cm -1 A close-up shot. Detailed Implementation

[0037] Specific embodiments of this application will now be described. However, this disclosure may be implemented in various forms and should not be construed as limiting it to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art.

[0038] definition

[0039] Any reference to the periodic table is as in the version published by CRC Press, Inc. in 1990-1991. A group of elements in the table is referred to using a new notation for numbering the groups.

[0040] The numerical ranges disclosed herein include all values ​​from the upper limit to the lower limit, and include both the upper and lower limits. For a range containing definite values ​​(e.g., 1 or 2, or 3 to 5, or 6 or 7), any subrange between any two definite values ​​is included (e.g., the range 1-7 above includes subranges of 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6; etc.).

[0041] Unless otherwise stated, implied by the context or customary in the art, all parts and percentages are by weight, and all test methods are current methods as of the date of this disclosure.

[0042] The term "composition" refers to a mixture of materials comprising the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0043] 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 they are specifically disclosed. Conversely, the term “consisting 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 stated or listed. Unless otherwise stated, the term “or” refers to members listed individually and in any combination. Use of the singular includes use of the plural, and vice versa.

[0044] As used in this article, "pendant functional group" refers to a functional group located on the polymer backbone except at the end.

[0045] The term "polymer" refers to a polymeric compound prepared by polymerizing monomers of the same or different types, wherein the monomers provide, in polymeric form, multiple and / or repeating "units" constituting the polymer. Therefore, the general term polymer encompasses the term "homopolymer," which is commonly used to refer to polymers prepared from only one type of monomer, and the term "copolymer," which refers to polymers prepared from two or more different monomers. It should be noted that although polymers are often referred to as being "made" "from" one or more specified monomers, "based on" a specified monomer or monomer type, "containing" a specified monomer content, etc., in this context, the term "monomer" should be understood to refer to the polymer residue of the specified monomer.

[0046] As used herein, the term "blend" or "polymer blend" refers to a mixture of two or more polymers. Blends may be miscible or immiscible (not phase-separated at the molecular level). Blends may or may not be phase-separated. Blends can be achieved by physically mixing two or more polymers at a macroscopic level (e.g., melt blending of resins or compounding) or a microscopic level (e.g., simultaneous formation within the same reactor).

[0047] As used herein, the term "terminal olefinic group" refers to a double bond between two carbon atoms in a polymer chain, wherein one of the carbon atoms in the double bond is a =CH2 group. The terminal double bond is located at the end of the polymer chain and / or at a branched end of the polymer chain. The term "internal olefinic group," as used herein, refers to a 1,2-disubstituted carbon-carbon double bond with the carbon atom in a trans configuration (not a cis configuration). Terminal and internal olefinic groups are measured by infrared spectroscopy ("IR").

[0048] "Polyethylene" or "ethylene-based polymer" should mean a polymer comprising more than 50 mol% of units derived from ethylene monomers. This includes polyethylene homopolymers or copolymers (meaning units derived from two or more comonomers). Common forms of polyethylene known in the art include low-density polyethylene (LDPE); linear low-density polyethylene (LLDPE); ultra-low-density polyethylene (ULDPE); very low-density polyethylene (VLDPE); medium-density polyethylene (MDPE); and high-density polyethylene (HDPE).

[0049] The term "LDPE" can also be referred to as "high-pressure ethylene polymer" or "highly branched polyethylene" and is defined as meaning a polymer partially or fully homopolymerized or copolymerized in an autoclave or tubular reactor at pressures above 14,500 psi (100 MPa) using a free radical initiator (such as a peroxide) (see, for example, US 4,599,392, which is incorporated herein by reference). LDPE resins typically have densities ranging from 0.916 g / cm³ to 0.935 g / cm³.

[0050] The term "LLDPE" includes resins prepared using Ziegler-Natta catalyst systems, as well as resins prepared using mono-site catalysts, including but not limited to bismetallocene catalysts (sometimes referred to as "m-LLDPE") and geometry-restricted catalysts; and resins prepared using post-metallocene and molecular catalysts. LLDPE comprises linear, substantially linear, or heterogeneous polyethylene copolymers or homopolymers. Compared to LDPE, LLDPE comprises fewer long-chain branched components and consists of substantially linear ethylene polymers, further defined in U.S. Patents 5,272,236, 5,278,272, 5,582,923, and 5,733,155; homogeneous branched linear ethylene polymer compositions, such as those in U.S. Patent No. 3,645,992; multiphase branched ethylene polymers, such as those prepared according to the process disclosed in U.S. Patent No. 4,076,698; and / or blends thereof (such as those disclosed in U.S. 3,914,342 or U.S. 5,854,045). LLDPE resins can be prepared via gas-phase, solution-phase, or slurry polymerization, or any combination thereof, using any type of reactor or reactor configuration known in the art.

[0051] The term "MDPE" refers to polyethylene with a density of 0.926 to 0.945 g / cc. MDPE is typically prepared using chromium or Ziegler-Natta catalysts or using single-point catalysts (including, but not limited to, bis-ceramic catalysts and catalysts with defined geometries).

[0052] The term "HDPE" refers to polyethylene with a density greater than about 0.945 g / cc, which is typically prepared using Ziegler-Natta catalysts, chromium catalysts, or single-point catalysts (including, but not limited to, bis-ceramic catalysts and confined geometry catalysts).

[0053] The term "ULDPE" refers to polyethylene with a density of 0.880 to 0.909 g / cc, typically prepared using Ziegler-Natta catalysts and unit-point catalysts (including, but not limited to, bismetallocene catalysts and geometry-restricted catalysts, post-metallocene, and molecular catalysts). As used herein, the term "propylene-based polymer" refers to polymers in polymeric form comprising more than 50% by weight units derived from propylene monomers. This includes propylene homopolymers, random copolymers of polypropylene, impact copolymers of polypropylene, propylene / α-olefin interpolymers, and propylene / α-olefin copolymers. These polypropylene materials are well known in the art.

[0054] As used herein, the term "siloxane" includes polysiloxanes and low molecular weight siloxanes. In embodiments, the siloxane is a polydimethylsiloxane (PDMS) having the various end groups described below.

[0055] As used in this article, "SiH functional methacrylate converter" refers to 3-(1,1,3,3-tetramethyldisiloxyl)propyl methacrylate:

[0056]

[0057] copolymer of ethylene and functionalized polysiloxane

[0058] The various embodiments described herein provide copolymers of ethylene and functionalized polysiloxanes. In these embodiments, the copolymers are formed by high-pressure free radical polymerization by reacting ethylene monomers with functionalized polysiloxanes (sometimes referred to herein as f-PDMS), or by reacting a mixture of ethylene monomers with functionalized polysiloxanes. In these embodiments, PDMS is attached to the high-pressure ethylene polymer by several covalent bonds generated by the reaction of initial functional groups of the functionalized PDMS with the growth chain of the ethylene polymer, followed by further reaction with the ethylene monomers, and also includes bridges between the polymerized functional groups and the siloxanes.

[0059] In an embodiment, based on the total weight of the LDPE-co-PDMS composition, the LDPE-co-PDMS may contain 0.1 wt% to 50 wt% of PDMS, such as 0.1 wt% to 20 wt%, 0.5 wt% to 20 wt%, 2.0 wt% to 20 wt%, 2.0 wt% to 15 wt%, 2.0 wt% to 12 wt%, 2.0 wt% to 10 wt%, 1.0 wt% to 10 wt%, 5.0 wt% to 10 wt%, or 5.0 wt% to 20 wt%, and also contains LDPE formed during copolymerization but not covalently attached to PDMS.

[0060] In various embodiments, the copolymer comprises one or more of the following structures, but is not limited to:

[0061]

[0062] Where R is methyl or hydrogen, R 1 As a bridging group connecting the functional group ((meth)acrylate) and the siloxane, R 2 R is a terminal group selected from the group consisting of alkyl, substituted alkyl, aryl, alkenyl, H, and OH, where x is an integer from 10 to 1000 and y is an integer from 1 to 20. 1 and R 2 The groups can be the same or different.

[0063] In the implementation scheme, the bridging matrix of LDPE-co-PDMS is selected from substituted or unsubstituted C2-C. 20 An alkylene linker, wherein one or more carbon atoms may be substituted with oxygen and / or silicon, substituted or unsubstituted aryl groups, and their derivatives and combinations. In embodiments, the functional group bound to the bridging group is bound to a high-pressure ethylene polymer via copolymerization with an ethylene monomer. In various embodiments, the functional group is a (meth)acrylate group. In further embodiments, the bridging group is a group described below:

[0064]

[0065] In the above structural formula, the ethylene-based polymer side chain is depicted as polyethylene (PE), but it is anticipated that, in the embodiments, the ethylene-based polymer side chain can be a homopolymer (e.g., LDPE) or a copolymer, such as ethylene (meth)acrylate copolymer, or ethylene (meth)acrylate copolymer, or ethylene vinyltrimethoxysilane copolymer, or ethylene vinyl acetate copolymer.

[0066] The polymer comprises polysiloxane units, which in embodiments are derived from functionalized polydimethylsiloxanes (e.g., f-PDMS). In embodiments, the functionalized polysiloxane is (meth)acrylate-functionalized polymethyldisiloxane (f-PDMS), wherein the (meth)acrylate functional groups are bridged to PDMS.

[0067] In the embodiments, the polymer optionally comprises one or more units derived from a ternary comonomer. The ternary comonomer may be selected from the group consisting of olefins, unsaturated esters, unsaturated acids, functionalized olefins, and combinations thereof.

[0068] Functionalized polysiloxanes

[0069] Polysiloxanes can be any of the different kinds of polymers manufactured as fluids, resins, or elastomers. Polysiloxanes are partially organic compounds, but unlike most polymers, they have a carbon-free backbone composed of alternating silicon and oxygen atoms as shown above. Although each silicon atom is illustrated in the structural formula shown above as being linked to a methyl and / or R group, it is contemplated that each of those positions could individually be alkyl, vinyl, phenyl, hydrogen, hydroxy, acetoxy, alkenoxy, oxime, methoxy, ethoxy, alkoxy, dimethylamino, aminopropyl, hydroxypropyl, mercaptopropyl, chloropropyl, acryloyloxypropyl, methacryloyloxypropyl, epoxypropoxypropyl, or epoxycyclohexylethyl. In embodiments, each position is methyl.

[0070] In some embodiments, x is large enough that the polysiloxane has a viscosity of 100 or greater, 200 or greater, or 500 or greater centiliters (CST). In other embodiments, x is not greater than a value that will produce a polysiloxane with a viscosity not greater than 2.5 million CST. However, the upper limit of the expected viscosity is below 2.5 million CST, for example, 1 million or 600,000 CST.

[0071] Polysiloxanes suitable for various embodiments include those described in U.S. Patent No. 6,239,244, the entire contents of which are incorporated herein by reference. Polysiloxanes are commercially available from many different manufacturers, including but not limited to Dow, Momentive, Wacker, Shin-Etsu, and Evonik.

[0072] In the various embodiments described herein, the polysiloxane is a polydimethylsiloxane (PDMS) comprising one or more functional groups, and is therefore referred to as functionalized PDMS or f-PDMS. In various embodiments, f-PDMS is (meth)acrylate-functionalized PDMS, wherein the (meth)acrylate groups are bonded to the PDMS via bridging groups. The PDMS can be monofunctional, difunctional, or polyfunctional, and one or more functional groups can be attached to the end or side positions of the siloxane. Therefore, in embodiments, f-PDMS comprises one or a combination of the following structures:

[0073]

[0074] Where R is methyl or hydrogen, R 1 For bridge foundation, R 2 The terminal group is selected from alkyl, aryl, alkenyl, H or OH, x is an integer from 10 to 1000, and y is an integer from 1 to 20.

[0075] Methods - Functionalized Polysiloxanes

[0076] In various embodiments, each bridging group in f-PDMS is determined by a method of linking a siloxane backbone to a (meth)acrylate functional group. In embodiments, the siloxane backbone is linked to the (meth)acrylate functional group via direct hydrogenation silanization of an (meth)acrylate alkenyl ester, hydrogenation silanization of mono- or polyvinyl PDMS using a SiH-functionalized (meth)acrylate converter, or equilibrium / condensation with a (meth)acrylate-functionalized alkoxysilane. Other methods for linking the siloxane backbone and the (meth)acrylate functional group are contemplated and may be used, depending on the specific embodiment.

[0077] Method - Copolymers of ethylene and functionalized polysiloxanes

[0078] In various embodiments, LDPE-co-PDMS is formed in the presence of ethylene. In some embodiments, LDPE-co-PDMS is produced via a high-pressure, free-radical polymerization process. Two different types of free-radical-initiated high-pressure polymerization processes are known. In the first process type, a stirred autoclave reactor with one or more reaction zones is used. The autoclave reactor includes several injection points for initiator or monomer feed, or both. In the second process type, a jacketed tube is used as the reactor, having one or more reaction zones. Suitable reactor lengths include, but are not limited to, 100 meters (m) to 3000 meters, or 1000 meters to 2000 meters. The start of the reaction zone in either type of reactor is typically defined by a side injection of the initiator, ethylene, chain transfer agent (or telomer), one or more comonomers, or a combination thereof. The high-pressure process can be carried out in an autoclave reactor or a tubular reactor with one or more reaction zones, or in a combination of an autoclave reactor and a tubular reactor, each each containing one or more reaction zones.

[0079] In various embodiments, chain transfer agents (CTAs) can be used to control polymer properties, including but not limited to the molecular weight and melt index of the resulting polymer. Chain transfer involves the termination of growing polymer chains, thus limiting the final molecular weight of the polymer material. Chain transfer agents are typically hydrogen atom donors, which react with the growing polymer chains and stop the polymerization reaction. For high-pressure free radical polymerization, CTAs can be of many different types, such as saturated hydrocarbons, unsaturated hydrocarbons, aldehydes, ketones, or alcohols. Non-limiting examples of CTAs include propylene, isobutane, n-butane, 1-butene, methyl ethyl ketone, acetone, ethyl acetate, propionaldehyde, products available under the trade name ISOPAR (available from ExxonMobil Chemical Co.), and isopropanol. In embodiments, the amount of CTA used in the method is from 0.01% by weight to 10% by weight of the total reaction mixture.

[0080] In this embodiment, the free radical initiator may include CTA as a solvent or as a blend injected simultaneously with ethylene. For example, CTA may be blended with ethylene, pressurized, and then injected into the reactor.

[0081] In various embodiments, one or more radical initiators are used to generate LDPE-co-PDMS. Radical initiators commonly used to generate ethylene-based polymers such as LDPE are oxygen and peroxides. Non-limiting examples of radical initiators include tert-butyl peroxypentanoate, di-tert-butyl peroxide, tert-butyl peroxyacetate (TPA), tert-butyl peroxyoctanoate (TPO), tert-butyl peroxy-2-hexanoate, and combinations thereof. Other initiators known and used in the art are also contemplated. In embodiments, the initiator is included in conventional amounts, such as 0.005 wt% to 0.2 wt% based on the weight of the polymerizable monomer. In embodiments, the initiator is injected before or within the reaction zone that induces radical polymerization. Termination of catalyst activity can be achieved by a combination of high reactor temperatures for the radical polymerization portion of the reaction, or by feeding the initiator dissolved in a polar solvent such as propanol, water, or a mixture of conventional initiator solvents such as branched or unbranched alkanes into the reactor. In the implementation scheme, a free radical initiator initiates the formation of a polyethylene chain, which is then attacked by the functional group of f-PDMS (e.g., (meth)acrylate group), and the newly formed α-carbonyl free radical is further reacted with the ethylene monomer, thereby enabling the ethylene (monomer or polymer form) to attach to the (meth)acrylate.

[0082] In this embodiment, at least one hydrocarbon solvent may be included in the radical initiator system. The hydrocarbon solvent may be, for example, C5 to C64. 30 Hydrocarbon solvents. Exemplary hydrocarbon solvents include, but are not limited to, mineral solvents, normal paraffinic solvents, isoparaffinic solvents, cyclic solvents, etc. In embodiments, the hydrocarbon solvent is selected from the group consisting of: n-octane, isooctane (2,2,4-trimethylpentane), n-dodecane, isododecane (2,2,4,6,6-pentamethylheptane), and other isoparaffinic solvents. Exemplary hydrocarbon solvents such as isoparaffinic solvents can be, for example, commercially available from ExxonMobil Chemical Company under the trademarks ISPAR C, ISOPAR E, and ISOPAR H. In embodiments, the hydrocarbon solvent constitutes less than 99% by weight of the radical initiator system.

[0083] The implementation scheme may also include a polar cosolvent, such as an alcohol cosolvent (e.g., C1 to C2). 30Alcohols, aldehydes, ketones, or esters. The alcohol functional group in the alcohol cosolvent can be monofunctional or polyfunctional. Suitable alcohol cosolvents may include, for example, but not limited to, isopropanol (2-propanol), allyl alcohol, 1-pentanol, methanol, ethanol, propanol, 1-butanol, 1,4-butanediol, combinations thereof, or mixtures thereof. In some embodiments, the polar cosolvent may be included in an amount less than 40% by weight of the free radical initiator system.

[0084] Other additives include processing aids, plasticizers, stabilizers, UV absorbers, antistatic agents, pigments, dyes, nucleating agents, fillers, slip agents, flame retardants, lubricants, smoke suppressants, viscosity control agents, and anti-caking agents. In embodiments, one or more of the additives are included in an amount less than 50% by weight of the combined weight of the additives, based on the weight of the polymer.

[0085] In one embodiment, the method includes a process loop to further improve conversion efficiency. In such embodiments, the downstream reaction zone or area is maintained at a temperature lower than the temperature at which the ethylene-based polymer will separate from the polysiloxane phase. In another embodiment, the loop may be treated to neutralize residues or byproducts from previous reaction cycles, as such residues or byproducts can inhibit the polymerization of the polysiloxane or the ethylene-based polymer.

[0086] Ethylene, f-PDMS, initiator, and CTA are each added to the reactor at one or more locations to achieve the desired component ratios in the reactor feed and / or reaction zone. As those skilled in the art will recognize, the selection of the feed point for each component in the reactor and / or reaction zone depends on several factors, including, but not limited to, the solubility of the component in pressurized ethylene and / or condensation and / or scaling that may occur in the preheater used to heat the reactor contents prior to the injection of the initiator.

[0087] The ethylene used to produce LDPE-co-PDMS can be purified ethylene obtained by removing polar components from a reaction system configuration in which LDPE-co-PDMS polymers are prepared using only fresh ethylene from a loop recycle stream.

[0088] In one embodiment, propylene is used as a chain transfer agent in a continuous stirred tank reactor for polymerization. Ethylene and propylene are fed to the top of the reactor along the stirring shaft. In another embodiment, tert-butyl peroxyacetate (TPA) and tert-butyl peroxyoctanoate (TPO) are used as initiators injected into the sides of the reactor. In yet another embodiment, f-PDMS is injected separately into the sides of the reactor.

[0089] In this embodiment, the maximum temperature in each reaction zone is 150°C to 360°C, 170°C to 350°C, or 200°C to 325°C. In this embodiment, the polymerization pressure at the reactor inlet is 100 MPa to 360 MPa, 150 MPa to 340 MPa, or 185 MPa to 320 MPa. After polymerization, the reactor contents, including unreacted reactants and LDPE-co-PDMS polymer, are discharged from the reactor outlet.

[0090] The LDPE-co-PDMS polymer can be separated from any remaining reactants using any method known and used in the art. In one embodiment, atomization is used to separate the LDPE-co-PDMS polymer from the remaining reactants, and the LDPE-co-PDMS polymer is collected in powder form.

[0091] Although certain specific LDPE-co-PDMS structures are shown in the accompanying drawings and the structures given herein, other structures are contemplated and expected. Additionally, in embodiments, the LDPE-co-PDMS polymer is present in blends comprising one or more of the structures depicted herein. For example, in embodiments, in addition to attaching f-PDMS to LDPE by copolymerizing the double bonds of functional groups with ethylene, the reaction may also produce a certain amount of byproducts, wherein LDPE is attached to PDMS via a chain transfer mechanism through the methyl groups of PDMS. Furthermore, it should be recognized that LDPE-co-PDMS may constitute only a small amount of the reaction product, with the majority of the reaction product being LDPE. In embodiments, LDPE-co-PDMS is present in blends comprising at least one additional polymer. Other polymers may be, for example, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ultra-low-density polyethylene (ULDPE), very low-density polyethylene (VLDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), copolymers containing (meth)acrylates, copolymers containing (meth)acrylic acid, monoesters or diesters of maleic acid, copolymers containing vinyl acetate, copolymers containing trialkoxyvinylsilane, grafted polyethylene, or derivatives or combinations thereof.

[0092] In the implementation scheme, LDPE-co-PDMS can have a strength of 3.0 to 50.0, such as 3.0 to 45.0, 3.0 to 40.0, 3.0 to 35.0, 3.0 to 30.0, 3.0 to 20.0, 3.0 to 15.0, 3.0 to 10.0, 4.0 to 50.0, such as 4.0 to 45.0, 4.0 to 40.0, 4.0 to 35.0, 4.0 to 30.0, 4.0 to 20.0, 4.0 to 15.0, 4.0 to 10.0, and 5.0 to 50.0, such as 5.0 to 45.0, 5.0 to 40.0, 5.0. Polydispersity index (PDI) ranges from 35.0 to 50.0, 5.0 to 30.0, 5.0 to 20.0, 5.0 to 15.0, 5.0 to 10.0, 7.0 to 50.0, such as 7.0 to 45.0, 7.0 to 40.0, 7.0 to 35.0, 7.0 to 30.0, 7.0 to 20.0, 7.0 to 15.0, 7.0 to 10.0, 8.0 to 50.0, such as 8.0 to 45.0, 8.0 to 40.0, 8.0 to 35.0, 8.0 to 30.0, 8.0 to 20.0, 8.0 to 14.0, or 8.0 to 10.0. In the implementation, LDPE-co-PDMS may have a PDI of 3.0 to 14.0, 5.0 to 14.0, or 7.0 to 14.0. In the implementation scheme, LDPE-co-PDMS can have a concentration ranging from 0.15 g / 10 min to 500.00 g / 10 min, such as 0.15 g / 10 min to 100 g / 10 min, 0.15 g / 10 min to 25.00 g / 10 min, 0.15 g / 10 min to 10.00 g / 10 min, 0.3 to 1.7, 0.3 to 2.0, 0.3 to 3.0, 0.3 to 10. Melt index (I2) of 0.5 to 1.7, 0.5 to 2.0, 0.5 to 3.0, 0.5 to 10, 1.0 to 1.7, 1.0 to 2.0, 1.0 to 3.0, 1.0 to 10, 1.3 to 1.7, 1.3 to 2.0, 1.3 to 3.0, 1.3 to 10, 0.50 g / 10 min to 10.00 g / 10 min, or 0.50 g / 10 min to 7.50 g / 10 min. PDI is determined by “conventional GPC” or “3D-GPC”.

[0093] use

[0094] The embodiments of the LDPE-co-PDMS polymer described herein can be used in a variety of thermoplastic manufacturing processes to produce useful articles, including objects comprising one or more film layers, molded articles, extrusions, fibers, and woven or nonwoven fabrics, pipes, cables, and linings. Thermoplastic compositions comprising the LDPE-co-PDMS polymer comprise blends with other natural or synthetic materials, polymers, additives, reinforcing agents, flame retardants, antioxidants, stabilizers, colorants, extenders, crosslinking agents, foaming agents, and plasticizers.

[0095] Suitable applications for LDPE-co-PDMS polymers include articles manufactured using conventional polyolefin processing techniques, elastic films and fibers, soft-touch items, gaskets and profiles, adhesives, footwear, automotive interior parts and profiles, foam articles, impact modifiers, coated fabrics, hoses, pipes, weatherstripping, cover linings, flooring, etc.

[0096] In the embodiments, the membrane containing LDPE-co-PDMS can exhibit a maximum peel force of less than or equal to 5 Newtons (N), such as 0.3N to 5N, 1N to 4.5N, 1N to 4N, 1.5N to 4N, 2.0N to 4.5N, 2.5N to 4.5N, or 3N to 4.5N. In the embodiments, the membrane containing LDPE-co-PDMS can exhibit a static coefficient of friction (COF) of 0.05 to 0.50, or 0.2N to 0.4N, and a dynamic coefficient of friction (COF) of 0.05 to 0.50, or 0.2N to 0.4N.

[0097] Test methods

[0098] The testing methods include the following:

[0099] Melt index (I2)

[0100] Melt index (I2) was measured at 190°C and 2.16 kg according to ASTM D-1238. Values ​​are reported in g / 10 min (or dg / min), corresponding to the number of grams eluted per 10 minutes. Multiple measurements were performed for each sample.

[0101] density

[0102] The samples used for density measurement were prepared according to ASTM D4703 and expressed in grams per cubic centimeter (g / cc or g / cm³). 3 Reports are made in units of ). Measurements were performed using ASTM D792 Method B within one hour of sample pressing.

[0103] DSC crystallinity

[0104] Differential scanning calorimetry (DSC) can be used to measure the crystallinity of a sample over a wide temperature range at a given temperature. For example, a TA Model Q1000DSC (TA Instruments, New Castle, DE) equipped with an RCS (Refrigerated Cooling System) cooling accessory and an autosampler module was used for testing. During testing, a nitrogen purge flow of 50 mL / min was used. The resin was compressed and molded into 3 mm thick × 1 inch circular sheets at 350 °C for 5 minutes in air at 1500 psi pressure. The samples were then removed from the press and placed on a counter to cool to room temperature (approximately 25 °C). 3–10 mg of the cooled material was cut into 6 mm diameter discs, weighed, placed in a lightweight aluminum dish, and rolled up. The thermal properties of the samples were then tested.

[0105] The thermal properties of a sample were determined by varying its temperature to generate a response-temperature curve. First, the sample was rapidly heated to 180°C and held isothermally for 3 minutes to remove any prior thermal history. Next, the sample was cooled to -40°C at a cooling rate of 10°C / min and held at -40°C for 3 minutes. Then, the sample was heated to 150°C at a heating rate of 10°C / min. The cooling curve and the second heating curve were recorded. The determined value is the peak melting temperature (T0). m Peak crystallization temperature (T) c ), heat of fusion (H) f (in J / g), and the percentage of crystallinity of the polyethylene sample calculated using the following Equation 1:

[0106]

[0107] The heat of fusion (H) is reported from the second heating curve. f The peak melting temperature is determined by the cooling profile.

[0108] Gel permeation chromatography (GPC)

[0109] The GPC system consisted of a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5) connected to a Precision Detectors (now Agilent Technologies, Amherst, MA) 2-angle light scattering (LS) detector model 2040 and four capillary solution viscometers (DV). A GPC with the last two independent detectors and at least one of the first detectors is sometimes referred to as a "3D-GPC," while the term "GPC" alone usually refers to a conventional GPC. A 15-degree angle was used for all absolute light scattering measurements. The autosampler chamber operated at 160°C, and the column chamber at 150°C. The columns used were four Agilent "MixedA" 30cm 20µm linear mixed-bed columns. The chromatographic solvent used was 1,2,4-trichlorobenzene containing 200 ppm butylated hydroxytoluene (BHT). The solvent source was purged with nitrogen. The polyethylene sample was gently stirred at 160 °C for four hours. The injection volume was 200 μL. The flow rate through the GPC was set to 1 mL / min.

[0110] The GPC column assembly was calibrated before running the example by running at least twenty narrow molecular weight distribution polystyrene standards. The standards ranged in molecular weight (Mw) from 580 g / mol to 8,400,000 g / mol and were contained in six “cocktail” mixtures. Each standard mixture was separated by at least a decimal place from the individual molecular weights. The standard mixtures were purchased from Agilent Technologies. The polystyrene standards were prepared as follows: 0.025 g in 50 mL of solvent for molecular weights equal to or greater than 1,000,000 g / mol; and 0.05 g in 50 mL of solvent for molecular weights less than 1,000,000 g / mol. The polystyrene standards were dissolved by gently stirring at 80°C for 30 minutes. The narrow standard mixtures were run first, in descending order of molecular weight to minimize degradation. The peak molecular weight of the polystyrene standard was converted to the molecular weight of polyethylene using Equation 2 (as described by Williams and Ward, Journal of Polymer Science, 6, 621 (1968)).

[0111] M 聚乙烯 =A×(M) 聚苯乙烯 ) B (Equation 2)

[0112] Where M is the molecular weight of polyethylene or polystyrene (as labeled), A has a value of 0.43, and B equals 1.0.

[0113] Polynomials between the 3rd and 5th orders were used to fit the corresponding polyethylene equivalent calibration points. Total plate counts of the GPC column assembly were performed using eicosane (prepared in 50 mL of TCB at 0.04 g and dissolved under gentle stirring for 20 min). Plate counts (Equation 3) and symmetry (Equation 4) were measured at 200 μL injections according to the following equations:

[0114]

[0115] Where RV is the retention volume in mL, peak width is in mL, peak value is the maximum height of the peak, and 1 / 2 height is 1 / 2 the height of the peak value.

[0116]

[0117] Where RV is the retention volume in mL and peak width is in mL, peak maximum is the position of the peak, one-tenth height is 1 / 10 of the height of the peak maximum, and a subsequent peak refers to the tail of the peak whose retention volume is later than the peak maximum, while a preceding peak refers to the front of the peak whose retention volume is earlier than the peak maximum. The plate count of the chromatographic system should be greater than 24,000, and the symmetry should be between 0.98 and 1.22.

[0118] 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 then dissolved at 160°C for 2 hours with "low-speed" shaking.

[0119] Based on the GPC results, using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph, according to Equation 5-7, the PolymerChar GPCOne was used. TM The software, baseline-subtracted IR chromatograms at each equidistant data collection point (i), and polyethylene equivalent molecular weight (Mn) obtained from the narrow standard calibration curve at point (i) according to Equation 2 are used to determine the molecular weight. (GPC) Mw (GPC) and Mz (GPC) The calculation.

[0120]

[0121]

[0122]

[0123] To monitor deviations over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by the PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly correct the pump flow rate (nominal flow rate) for each sample by comparing the RV (RV(FM sample)) of the corresponding decane peak within the sample with the RV (RV(FM calibrated)) of the decane peak within the narrow standard calibration. It was then assumed that any variation in the decane marker peak time was linearly correlated with the flow rate (effective flow rate) throughout the run. To facilitate the highest accuracy in 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 first derivative of the quadratic equation was then used to solve for the true peak position. After calibrating the system based on the flow marker peak, the effective flow rate (relative to the narrow standard calibration) was calculated according to Equation 8. (Performed via PolymerChar GPCOne) TM The software processes the flow marker peaks. Acceptable flow rate correction ensures that the effective flow rate is within + / - 2% of the nominal flow rate.

[0124]

[0125] Triple detector GPC (3D-GPC)

[0126] Perform the chromatographic system, operating conditions, column settings, column calibration, and calculation of conventional molecular weight moments and distributions according to the methods described in Gel Permeation Chromatography (GPC).

[0127] To determine the offsets of the viscometer and light scattering detector relative to the IR5 detector, a systematic method for determining the multi-detector offsets was employed in accordance with the method published by Balke, Mourey et al. (Mourey and Balke, Chromatorography Polym., Chapter 12, (1992)) (Balke, Thitiratsakul, Lew, Cheung, and Mourey, Chromatorography Polym., Chapter 13, (1992)), thereby using PolymerChar GPCOne. TM The software optimizes the triple detector logarithm (Mw / Mn>3) from wide homopolymer polyethylene standards. w The results (and intrinsic viscosity) are compared with the narrow standard column calibration results from the narrow standard calibration curve.

[0128] Absolute molecular weight data were obtained in a manner consistent with those published by Zimm (Zimm, BH, *Journal of Chemical Physics*, 16, 1099 (1948)) and Kratochvil (Kratochvil, P., *Classical Light Scattering from Polymer Solutions*, Elsevier, Oxford, NY (1987)). The total injection concentration used to determine the molecular weight was obtained from the mass detector area and the mass detector constant, which was derived from one of suitable linear polyethylene homopolymers or polyethylene standards with known weight-average molecular weights. The calculated molecular weights (using GPCOne) were... TM The light scattering constant and refractive index concentration coefficient dn / dc 0.104 were obtained using one or more of the mentioned polyethylene standards. Generally, the mass detector response (IR5) and light scattering constant (using GPCOne) are also used. TM (The determination) should be made using linear standards with a molecular weight exceeding approximately 50,000 g / mol. Viscometer calibration (using GPCOne) TM The determination can be done using the method described by the manufacturer, or alternatively, by using the published values ​​of a suitable linear standard (such as Standard Reference Material (SRM) 1475a), which are available from the National Institute of Standards and Technology (NIST). The viscometer constant is calculated (using GPCOne). TM The specific viscosity area (DV) of the standard will be used for calibration, and the injection mass is related to its intrinsic viscosity. It is assumed that the chromatographic concentration is low enough to eliminate the effect of the second viral coefficient (the effect of concentration on molecular weight).

[0129] Absolute weight-average molecular weight (Mw) (Abs) (using GPCOne) TM The molecular weight and intrinsic viscosity responses are obtained by dividing the area of ​​the light scattering (LS) integral chromatogram (calculated from the light scattering constant) by the mass recovered from the mass constant and the area of ​​the mass detector (IR5). The molecular weight and intrinsic viscosity responses are at the chromatographic ends where the signal-to-noise ratio decreases (using GPCOne). TM Linear extrapolation. Other corresponding moments Mn (Abs) and Mz (Abs) The calculation is based on equation 9-10 as follows:

[0130]

[0131]

[0132] PDI is calculated as Mw divided by Mn (i.e., Mw / Mn).

[0133] Fourier transform infrared analysis

[0134] Sample films (approximately 250-300 micrometers thick) used for Fourier transform infrared (FTIR) analysis are compressed and molded by pressing approximately 0.5 g of sample particles into a Carver hydraulic press with heated plates set to 190°C.

[0135] High-temperature liquid chromatography (HTLC)

[0136] High-temperature liquid chromatography (HTLC) was used for the separation and characterization of Si-PE hybrids. Free PDMS was quantified using an external standard calibration method. Sample solutions of ~2.0 mg / mL were prepared in anhydrous decane. The samples were dissolved at 130 °C for ~1 hour using a laboratory-heated shaker. The sample solutions were then transferred to a PolymerChar autosampler. Before injection, the sample solutions were reheated and shaken at 130 °C for 1 hour using the heated shaker in the PolymerChar. HTLC was performed using a PolymerChar high-temperature 2DLC / GPC instrument. The LC pump was an Agilent 1260 HPLC system with a flow rate set to 1.0 mL / min. The injection loop contained 20 μL of solution. A Thermo-Fisher hypercarb column (4.6 mm inner diameter (id) × 100 mm length (l.), 5 μm particle size and...) was used. Separation was performed using pore size. The detector was an Agilent HT-ELSD detector (model G7826A), with the atomizer temperature set to 160°C, the evaporator temperature to 120°C, and the N2 flow rate to 0.2 SLM. A gradient between decane and ODCB was applied in the separation according to Table 1. Data were collected using PolymerChar software version 1.1 and reduced using Agilent SEC software Cirrus 3.3.

[0137] Table 1 :

[0138]

[0139] Nuclear magnetic resonance (NMR)

[0140] Samples were prepared as follows: 0.1 g to 0.2 g of sample was added to 3.25 g (by weight) of 50 / 50 tetrachloroethane-d2 / perchloroethylene containing 0.001 M Cr(AcAc)3 in a Norell 1001-7 10 mm NMR tube. The sample was purged by bubbling N2 through the solvent for approximately 5 minutes via a pipette inserted into the tube to prevent oxidation. The tube was capped and sealed with Teflon tape. The sample was heated and vortexed at 115–135 °C to ensure homogeneity. The NMR was performed on a Bruker AVANCE 600 MHz spectrometer equipped with a Bruker 10 mm CryoProbe and a sample temperature of 120 °C. 1 ¹H NMR. Spectra were acquired using ZG pulses, 16 scans, AQ 1.8s, D1 14s. The polymer integral from approximately 0.6 ppm to 2.6 ppm was set to an arbitrary value. This value was divided by 2 to obtain the total number of moles of the polymer (CH₂s). The total number of moles of CH₂s was multiplied by 14 g / mol to obtain the polymer weight. The PDMS integral from approximately -0.3 ppm to 0.6 ppm was divided by 6 to obtain the number of moles of PDMS units. Multiplied by 74.1 g / mol of PDMS units to obtain the PDMS weight. The weight-percentage of PDMS was calculated using both weights.

[0141] Peel strength

[0142] Peel strength was measured by placing the C layer of the membrane in contact with a commercially available pouch wrapping film ("Salvaslip EVAX normal" from The Procter & Gamble Company, Cincinnati, OH). Samples were conditioned in an oven at 40°C for 20 hours under 2 kg weight, followed by 4 hours at room temperature without weight. Peel strength was measured at 300 mm / min, a clamping distance of 25 mm, and a measurement distance of 100 mm at 90° on a 25 x 175 mm probe with a 10 N sensor (cell).

[0143] Coefficient of friction (COF)

[0144] According to ISO-8295, the COF of the inner side relative to the outer side is measured, with layer C placed as the inner side and layer A placed as the outer side.

[0145] Example

[0146] The following examples illustrate the features of this disclosure, but are not intended to limit the scope of this disclosure.

[0147] Example 1

[0148] The f-PDMS used for copolymerization is a 1:2:1 mixture of the following three siloxanes:

[0149] methacrylate-functionalized PDMS MW = 15kJ

[0150] F-PDMS

[0151]

[0152]

[0153]

[0154] Polymerization was carried out in a 300 mL continuous stirred tank reactor (CSTR) heated to 220 °C using four electric heating bands. The stirrer speed was 1800 rpm. The reactor pressure was maintained at approximately 193 MPa. Propylene was used as a chain transfer agent. Ethylene and propylene were fed along the stirring shaft to the top of the reactor at a flow rate of 5440-5470 g / h ethylene at the ratios reported in Table 1 below. TPA and TPO were used as initiators at a mass ratio of 0.61:1. The initiators were diluted in ISOPAR E (available from ExxonMobil Chemical Co.) and injected into the reactor side at a pressure of 193 MPa at a ratio of 30-33 ppm TPA and 50-54 ppm TPO to ethylene. f-PDMS was diluted to 30 wt% in ethyl acetate (available from Sigma-Aldrich) and injected separately into the reactor side at the flow rates reported in Table 1 below.

[0155] The reactor residence time is approximately 1.5 minutes. All unreacted reactants and polymer are discharged through a single outlet located at the bottom of the reactor. The LDPE-co-PDMS polymer is then separated from the remaining reactants by atomization, reducing the pressure of the feed stream to approximately 0.1 MPa while simultaneously cooling it to ambient temperature. The LDPE-co-PDMS polymer is then collected in powder form.

[0156] LDPE grafted with 10% by weight PDMS (“LDPE-g-PDMS”, starting PDMS 15K Mn) was also obtained. LDPE-g-PDMS was prepared according to the method described in U.S. Patent No. 8,691,923, the entire contents of which are incorporated herein by reference.

[0157] The amount of attached and unattached PDMS in sample 3 was estimated by ¹H NMR, showing 7.77 wt% PDMS in the resin. For samples 1 and 2, the wt% PDMS was determined based on the addition flow rate during copolymerization (Table 2). For comparative purposes, LDPE-g-PDMS was also analyzed by NMMR, showing a total of 7.47 wt% PDMS in the resin.

[0158] The amount of unbound (free) f-PDMS in LDPE-co-PDMS resin was estimated using HTLC analysis. The average of two replicates for Sample 3 was 3.0 wt% unbound PDMS in the resin, corresponding to a 61.4% conversion of added f-PDMS to LDPE-co-PDMS. For LDPE-g-PDMS resin, HTLC showed 6.8 wt% unbound PDMS, corresponding to only 9% conversion of added unfunctionalized PDMS to LDPE-g-PDMS.

[0159] The process conditions for preparing LDPE-co-PDMS polymers are reported in Table 2.

[0160] Table 2 :

[0161]

[0162] Example 2

[0163] DSC analysis of LDPE-co-PDMS in sample 3 was performed, and the results are provided. Figure 1A and 1B middle. Figure 1A and 1B The data shown indicates a melting temperature of 107.7℃. Figure 1A And the heat of fusion is 136.1 J / g. Figure 1B The density of sample 3, measured according to ASTM methods, is 0.9256 g / cm³. 3 .

[0164] Sample 3 was analyzed using both conventional GPC and 3D-GPC. Table 3 reports the molecular weight characteristics of the samples. The molecular weight distribution was plotted on [date missing]. Figure 2 middle.

[0165] Table 3 :

[0166]

[0167] Example 3

[0168] Sample 3, prepared as described above, was further analyzed using IR spectroscopy. The IR spectrum of the LDPE-g-PDMS copolymer was also obtained. The spectrum of LDPE-g-PDMS is shown in... Figure 3A and 3B The spectrum of LDPE-co-PDMS is given in [the text], and the spectrum of LDPE-co-PDMS is [the text]. Figure 3C and 3D The text is incomplete and contains numerous errors. A proper translation is not possible without the full context. Figure 3B Shown from Figure 3A From approximately 1850cm -1 Approximately 1650cm -1 Other details, and Figure 3D Shown from Figure 3C From approximately 1850cm -1 Approximately 1600cm -1 Further details. Peaks corresponding to LDPE and PDMS are shown in both sets of IR spectra. In both sets of IR spectra, 1742 cm⁻¹... -1 The peak at 1730 cm⁻¹ corresponds to ethyl acetate, which was used as a solvent to add PDMS and functionalized PDMS. However, the peak at 1730 cm⁻¹ is only present in the IR spectrum of PDMS-co-LDPE. -1 The peak at that location corresponds to the ester functional group of the copolymerized methacrylate functional group.

[0169] Example 4

[0170] To evaluate the mechanical properties of PDMS-co-LDPE in membrane applications, three membranes, each with an A / B / C structure, were prepared by extrusion. For each of Comparative Sample B, Comparative Sample C, and Sample 4, the substrates A and B were 70% DOWLEX by weight. TM 2042EC and 30% by weight LDPE 310E. DOWLEX TM2042EC is a linear low-density polyethylene (LLDPE) with a melt index (MI) of 1 g / 10 min and a density of 0.930 g / cc, available from The Dow Chemical Company (Midland, MI). LDPE 310E is an LDPE with an MI of 0.75 g / 10 min and a density of 0.923 g / cc, also available from Dow Chemical Company (Midland, MI). For Comparative Sample B, functional layer C is 100% LDPE 310E. For Comparative Sample C, functional layer C is Comparative Sample A (without f-PDMS, see Table 1), i.e., LDPE with an MI of 2 g / 10 min and a density of 0.920 g / cc. For Sample 4, functional layer C is PDMS-co-LDPE, formed from 15000K functionalized PDMS copolymerized with ethylene as described above at 10% by weight of PDMS. All attempts to prepare membranes from LDPE-g-PDMS have failed due to low processability.

[0171] Peel strength and coefficient of friction were measured, and the results are given in Table 4.

[0172] Table 4 :

[0173]

[0174] As the results in Table 4 show, LDPE-co-PDMS exhibited lower maximum and average peel forces, as well as lower static and dynamic coefficients of friction, compared to LDPE alone, both of which were commercially available and produced under the same facilities / reactors and conditions as Sample 4. Low COF is important for membranes, where lower COF may be crucial for easy transport of the membrane across surfaces or across other membranes. This may also be important for membrane stacking. Low COF can be achieved by adding additives to the membrane, but these additives often migrate, causing COF to change over time. However, because COF control agents (e.g., PDMS) are part of the polymer, this migration cannot occur and COF is expected to remain stable over time.

[0175] It is obvious that modifications and variations are possible without departing from the scope of this disclosure as defined in the appended claims. More specifically, although some aspects of this disclosure are identified herein as preferred or particularly advantageous, this disclosure is not necessarily limited to these aspects.

Claims

1. A polymer composition comprising a reaction product of polyethylene and a copolymer of ethylene with a (meth)acrylate-functionalized polysiloxane and optionally one or more terpolymer monomers, wherein the polymer composition is a copolymer comprising low-density polyethylene and a reaction product of a copolymer of ethylene with a (meth)acrylate-functionalized polysiloxane.

2. The polymer composition of claim 1, wherein the copolymer comprising the reaction product of low-density polyethylene and ethylene with (meth)acrylate-functionalized polysiloxane comprises 0.1% to 50% by weight of polydimethylsiloxane (PDMS).

3. The polymer composition according to claim 1 or 2, comprising one or more of the following structures: as well as Where R is methyl or hydrogen, R1 is a bridging group connecting the functional group ((meth)acrylate) and the siloxane, R2 is a terminal group selected from the group consisting of alkyl, substituted alkyl, aryl, alkenyl, H and OH, x is an integer from 10 to 1000, and y is an integer from 1 to 20.

4. The polymer composition according to claim 1, wherein the (meth)acrylate-functionalized polysiloxane has one or more of the following structural formulas: Where R is methyl or hydrogen, R1 is a bridging group, R2 is a terminal group selected from alkyl, aryl, alkenyl, H or OH, x is an integer from 10 to 1000, and y is an integer from 1 to 20.

5. The polymer composition of claim 3, wherein each bridging group is selected from the group consisting of substituted and unsubstituted C2-C... 20 Alkylene linkers, wherein one or more carbon atoms are substituted with oxygen, silicon, substituted or unsubstituted aryl groups, or combinations thereof.

6. The polymer composition according to claim 1, wherein the polymer composition has a MWD of 3 to 50.

7. The polymer composition of claim 1, wherein the ternary comonomer is present and selected from the group consisting of olefins, unsaturated esters, unsaturated acids, functionalized olefins, and combinations thereof.

8. A blend comprising the polymer composition according to claim 1 and one or more other polymers.

9. The blend of claim 8, wherein the additional polymer comprises low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ultra-low-density polyethylene (ULDPE), very low-density polyethylene (VLDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), copolymers containing (meth)acrylates, copolymers containing (meth)acrylic acid, monoesters or diesters of maleic acid, copolymers containing vinyl acetate, copolymers containing trialkoxyvinylsilane, grafted polyethylene, or combinations thereof.

10. An article comprising the polymer composition according to claim 1.

11. The article of claim 10, wherein the article is a membrane.

12. A method, the method comprising: In a polymerization reactor, ethylene monomers and (meth)acrylate-functionalized polysiloxanes are reacted under free radical polymerization conditions and at a pressure greater than or equal to 100 MPa to produce copolymers comprising low-density polyethylene and functionalized polydimethylsiloxanes, as well as polyethylene.

13. The method of claim 12, wherein the copolymer comprises one or more of the following structures: Where R is methyl or hydrogen, R1 is a bridging group connecting the functional group ((meth)acrylate) and the siloxane, R2 is a terminal group selected from the group consisting of alkyl, substituted alkyl, aryl, alkenyl, H and OH, x is an integer from 10 to 1000, and y is an integer from 1 to 20.

14. The method of claim 12, wherein the (meth)acrylate-functionalized polysiloxane has one or more of the following structural formulas: Where R is methyl or hydrogen, R1 is a bridging group, R2 is a terminal group selected from alkyl, aryl, alkenyl, H or OH, x is an integer from 10 to 1000, and y is an integer from 1 to 20.

15. The method of claim 12, wherein each bridge base is selected from the group consisting of substituted and unsubstituted C2-C. 20 Alkylene linkers, wherein one or more carbon atoms are substituted with oxygen, silicon, substituted or unsubstituted aryl groups, or combinations thereof.

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