Polyolefin elastomer and its use in laminates with improved vibration dampening

Abstract

Embodiments are directed to a polyolefin elastomer comprising a polymerized reaction product of 50 mol% to 99.5 mol% ethylene and 0.5 mol% to 40 mol% cyclic olefin. The polyolefin elastomer comprises a glass transition temperature of -30 °C to 30 °C, as measured according to Differential Scanning Calorimetry and a weight average molecular weight of 50,000 g / mol to 500,000 g / mol, as measured according to conventional Gel Permeation Chromatography. Further embodiments are directed to laminates comprising the polyolefin elastomer.

Description

85662-WO-PCT / DOW 85662 WO 1 POLYOLEFIN ELASTOMER AND ITS USE IN LAMINATES WITH IMPROVED VIBRATION DAMPENING CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application Serial No. 63 / 650,954 filed May 23, 2024, the contents of which are incorporated in their entirety herein. TECHNICAL FIELD

[0002] Embodiments of the present disclosure generally relate to polyolefin elastomers and specifically relate to polyolefin elastomers used in laminates to impart vibration dampening. BACKGROUND

[0003] Laminated glasses, a sandwich configuration of two pieces of glass with a polymeric interlayer therebetween, are widely used in automotive window and architectural glass applications. Conventionally, polyvinylbutyral (PVB) is used as a polymeric interlayer due to its relatively high clarity, impact resistance, and vibration dampening properties.

[0004] PVB is generally formulated with additives, such as plasticizers, low molecular weight compounds that decrease the glass transition temperature (Tg) of the formulation closer to the end-use temperature (e.g., -30 °C to 30 °C). The formulation has optimal performance, such as vibration dampening, at or near the Tgof the formulation. Due to the relatively high Tg of neat PVB polymer (i.e., about 40 °C), a relatively large amount of plasticizer (e.g., 30 wt% to 40 wt%) may be needed to provide a desirable Tg (e.g., -30 °C to 30 °C). A relatively large amount of plasticizer may lead to difficulties in handling and may not be cost effective.

[0005] Accordingly, there is a need for improved polyolefin elastomers that achieve the desired Tgwithout the addition of plasticizers. SUMMARY

[0006] The embodiments of the present disclosure meet this need by utilizing a combination of ethylene, cyclic olefin, whose homopolymer has a relatively high Tg, and optionally C3-C14α-olefin, whose homopolymer has a relatively low Tg. This resulted in a85662-WO-PCT / DOW 85662 WO 2 polyolefin elastomer having a desired Tg(e.g., -30 °C to 30 °C), thereby imparting an improved vibration dampening (e.g., a maximum composite loss factor of greater than or equal to 0.1, as measured according to ASTM E-756 at a temperature range from -20 °C to 70 °C). The resulting polyolefin elastomers also have a weight average molecular weight (Mw) of 50,000 grams per mole (g / mol) to 500,000 g / mol, which yields a relatively higher viscosity polymer that may be desired for handling and pelletization purposes.

[0007] In one embodiment, a polyolefin elastomer comprises: a polymerized reaction product of 50 mol% to 99.5 mol% ethylene; and 0.5 mol% to 40 mol% cyclic olefin, wherein the polyolefin elastomer comprises: a glass transition temperature (Tg) of -30 °C to 30 °C, as measured according to Differential Scanning Calorimetry (DSC); and a weight average molecular weight (Mw) of 50,000 g / mol to 500,000 g / mol, as measured according to conventional Gel Permeation Chromatography (GPC).

[0008] Additional features and advantages will be set forth in the detailed description, which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the embodiments described herein, including the detailed description which follows and the claims.

[0009] It is to be understood that both the foregoing general description and the following detailed description describe various embodiments and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] The following detailed description of specific embodiments of the present disclosure can be best understood when read in conjunction with the following drawings, where like structure is indicated with like reference numerals and in which:

[0011] FIG. 1 schematically illustrates a laminate, according to one or more embodiments described in this disclosure;

[0012] FIG. 2 graphically illustrates composite loss factor versus temperature (°C) for comparative and exemplary laminates, according to one or more embodiments described in this disclosure; and85662-WO-PCT / DOW 85662 WO 3

[0013] FIG. 3 graphically illustrates composite loss factor versus frequency (Hz) at 23 °C for comparative and exemplary laminates, according to one or more embodiments described in this disclosure.

[0014] Reference will now be made in detail to various embodiments, some embodiments of which are illustrated in the accompanying drawings. DETAILED DESCRIPTION

[0015] Specific embodiments of the present application will now be described. The disclosure may be embodied in different forms and should not be construed as limited to the embodiments set forth in this disclosure. 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.

[0016] DEFINITIONS

[0017] Unless stated to the contrary, implicit from the context, or customary in the art, all test methods are current as of the filing date of this disclosure.

[0018] The amount of a component (e.g., ethylene, cyclic olefin, and C3-C14α-olefin) in the reaction product is provided herein in mole percent (mol%), based on the total number of moles of the polyolefin elastomer (i.e., the reaction product), unless otherwise noted.

[0019] The amount of a component (e.g., plasticizer and C3-C14α-olefin) in the laminate interlayer having the reaction product is provided herein in weight percent (wt%), based on the total weight of the laminate interlayer having the reaction product, unless otherwise noted.

[0020] Ranges may be expressed herein as from "about" one particular value, and / or to "about" another particular value. When such a range is expressed, another embodiment includes from the one particular value and / or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms another embodiment. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.

[0021] The term "polymer" refers to a material prepared by reacting (i.e., polymerizing) a set of monomers, wherein the set is a homogenous (i.e., only one type) set85662-WO-PCT / DOW 85662 WO 4 of monomers or a heterogeneous (i.e., more than one type) set of monomers. The generic term polymer as used herein includes the term "homopolymer," which refers to polymers prepared from a homogenous set of monomers, and the term "interpolymer" as defined below.

[0022] The term homopolymer is employed to refer to polymers prepared from only one type of monomer, with the understanding that trace amounts of impurities can be incorporated into the polymer structure. For example, references to an ethylene homopolymer refer to polymer prepared only from ethylene monomers (i.e., polyethylene). References to cyclic olefin homopolymer refer to polymers prepared only from cyclic olefin monomers. References to C3-C14 α-olefin homopolymer refer to polymers prepared only from C3-C14 α-olefin monomers.

[0023] The term "interpolymer" refers to a polymer prepared by the polymerization of at least two different types of monomers. This term includes both "copolymers, " (i.e., polymers prepared from two different types of monomers), and polymers prepared from more than two different types of monomers, (i.e., terpolymers, tetrapolymers, etc.). This term also embraces all forms of interpolymers, such as random, block, homogeneous, heterogeneous, etc.

[0024] An "ethylene-based polymer" is a polymer that contains a majority amount of polymerized ethylene, based on the weight of the polymer, and, optionally, may further contain polymerized units of at least one comonomer. An "ethylene-based interpolymer" is an interpolymer that contains, in polymerized form, a majority amount of ethylene, based on the weight of the interpolymer, and further contains polymerized units of at least one comonomer. An "ethylene homopolymer" is a polymer that comprises repeating units derived from ethylene but does not exclude residual amounts of other components.

[0025] The term "ethylene / alpha-olefin interpolymer," as used herein, refers to a polymer that comprises, in polymerized form, a majority weight percent of ethylene (based on the weight of the interpolymer), and at least one comonomer that is an alpha-olefin. The ethylene / alpha-olefin interpolymer may be a random or block interpolymer. The terms "ethylene / alpha-olefin copolymer" and "ethylene / alpha-olefin multi-block interpolymer" are covered by the term "ethylene / alpha-olefin interpolymer."

[0026] The term "ethylene / alpha-olefin copolymer," as used herein, refers to a copolymer that comprises, in polymerized form, a majority weight percent of ethylene (based85662-WO-PCT / DOW 85662 WO 5 on the weight of the copolymer), and a comonomer that is an alpha-olefin, where ethylene and the alpha-olefin are the only two monomer types. The ethylene / alpha-olefin copolymer does not exclude residual amounts of other components. The ethylene / alpha-olefin copolymer may be a random or block copolymer.

[0027] The terms "comprising," "including," "having," and their derivatives, are not intended to exclude the presence of any additional component, step or procedure, whether the same is specifically disclosed. In order to avoid any doubt, all compositions claimed through use of the term "comprising" may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless stated to the contrary. In contrast, the term, "consisting essentially of" excludes from the scope of any succeeding recitation any other component, step or procedure, excepting those that are not essential to operability. The term "consisting of" excludes any component, step or procedure, not specifically delineated or listed.

[0028] EMBODIMENTS

[0029] Polyolefin Elastomer

[0030] Embodiments of the present disclosure are directed to a polyolefin elastomer comprising a polymerized reaction product of 50 mol% to 99.5 mol% ethylene and 0.5 mol% to 40 mol% cyclic olefin. The polyolefin elastomer comprises a glass transition temperature (Tg) of -30 °C to 30 °C, as measured according to Differential Scanning Calorimetry (DSC) and a weight average molecular weight (Mw) of 50,000 g / mol to 500,000 g / mol, as measured according to conventional Gel Permeation Chromatography (GPC). Further embodiments are directed to laminates comprising the polyolefin elastomer.

[0031] Ethylene may impact the Tg of the polyolefin elastomer. A homopolymer of ethylene (i.e., polyethylene) has a Tgof from -125 °C to -110 °C. Replacing ethylene with cyclic olefin may increase the Tgof the polyolefin elastomer. Replacing ethylene with C3- C14 α-olefin may decrease the Tg of the polyolefin elastomer. Ethylene may also impart desired mechanical properties, such as impact resistance, and crystallinity to the polyolefin elastomer.

[0032] A minimum amount of ethylene (e.g., greater than or equal to 50 mol%) may be included in the polyolefin elastomer to achieve a desired Tg (-30 °C to 30 °C) and impart desired mechanical properties and crystallinity. The amount of ethylene may be limited (e.g.,85662-WO-PCT / DOW 85662 WO 6 less than or equal to 99.5 mol%) to ensure a sufficient amount of cyclic olefin and optionally C3-C14 α-olefin is present in the polyolefin elastomer to achieve a desired Tg (e.g., -30 °C to 30 °C). In embodiments, the polyolefin elastomer may comprise 50 mol% to 99.5 mol% ethylene. In embodiments, the polyolefin elastomer may comprise 85 mol% to 93 mol% ethylene. In embodiments, the amount ethylene in the polyolefin elastomer may be greater than or equal to 50 mol%, greater than or equal to 55 mol%, greater than or equal to 60 mol%, greater than or equal to 65 mol%, greater than or equal to 70 mol%, greater than or equal to 75 mol%, or even greater than or equal to 80 mol%. In embodiments, the amount of ethylene in the polyolefin elastomer may be less than or equal to 99.5 mol%, less than or equal to 95 mol%, less than or equal to 90 mol%, less than or equal to 85 mol%, or even less than or equal to 80 mol%. In embodiments, the amount of ethylene in the polyolefin elastomer may be from 50 mol% to 99.5 mol%, from 50 mol% to 95 mol%, from 50 mol% to 90 mol%, from 50 mol% to 85 mol%, from 50 mol% to 80 mol%, from 55 mol% to 99.5 mol%, from 55 mol% to 95 mol%, from 55 mol% to 90 mol%, from 55 mol% to 85 mol%, from 55 mol% to 80 mol%, from 60 mol% to 99.5 mol%, from 60 mol% to 95 mol%, from 60 mol% to 90 mol%, from 60 mol% to 85 mol%, from 60 mol% to 80 mol%, from 65 mol% to 99.5 mol%, from 65 mol% to 95 mol%, from 65 mol% to 90 mol%, from 65 mol% to 85 mol%, from 65 mol% to 80 mol%, from 70 mol% to 99.5 mol%, from 70 mol% to 95 mol%, from 70 mol% to 90 mol%, from 70 mol% to 85 mol%, from 70 mol% to 80 mol%, from 75 mol% to 99.5 mol%, from 75 mol% to 95 mol%, from 75 mol% to 90 mol%, from 75 mol% to 85 mol%, from 75 mol% to 80 mol%, from 80 mol% to 99.5 mol%, from 80 mol% to 95 mol%, from 80 mol% to 90 mol%, or even from 80 mol% to 85 mol%, or any and all sub-ranges formed from any of these endpoints.

[0033] Cyclic olefin, whose homopolymer has a relatively high Tg(e.g., greater than or equal to 150 °C), may, in combination with ethylene and optionally C3-C14α-olefin, whose homopolymer has a relatively low Tg, may help to achieve a desired Tg (e.g., -30 °C to 30 °C).

[0034] In embodiments, a homopolymer of the cyclic olefin may have a Tgfrom 150 °C to 400 °C, from 150 °C to 380 °C, from 150 °C to 360 °C, from 170 °C to 400 °C, from 170 °C to 380 °C, from 170 °C to 360 °C, from 190 °C to 400 °C, from 190 °C to 380 °C, from 190 °C to 360 °C, from 210 °C to 400 °C, from 210 °C to 380 °C, from 210 °C to 360 °C, from 230 °C to 400 °C, from 230 °C to 380 °C, from 230 °C to 360 °C, from 250 °C to85662-WO-PCT / DOW 85662 WO 7 400 °C, from 250 °C to 380 °C, or even from 250 °C to 360 °C, or any and all sub-ranges formed from any of these endpoints, as measured according to DSC.

[0035] In embodiments, the cyclic olefin may comprise norbornene (NB), 5- ethylidene-2-norbornene (ENB), cyclopentene, dicyclopentadiene (DCPD), or a combination thereof.

[0036] The polyolefin elastomer may comprise 0.5 mol% to 40 mol% cyclic olefin to achieve a desired Tg (e.g., -30 °C to 30 °C). In embodiments, the polyolefin elastomer may comprise 10 mol% to 20 mol% cyclic olefin. In embodiments, the amount of cyclic olefin in the polyolefin elastomer may be greater than or equal to 0.5 mol%, greater than or equal to 1 mol%, greater than or equal to 2 mol%, greater than or equal to 5 mol%, greater than or equal to 7 mol%, greater than or equal to 10 mol%, greater than or equal to 12 mol%, or even greater than or equal to 15 mol%. In embodiments, the amount of cyclic olefin in the polyolefin elastomer may be less than or equal to 40 mol%, less than or equal to 35 mol%, less than or equal to 30 mol%, less than or equal to 25 mol%, less than or equal to 20 mol%, or even less than or equal to 15 mol%. In embodiments, the amount of cyclic olefin in the polyolefin elastomer may be from 0.5 mol% to 40 mol%, from 0.5 mol% to 35 mol%, from 0.5 mol% to 30 mol%, from 0.5 mol% to 25 mol%, from 0.5 mol% to 20 mol%, from 0.5 mol% to 15 mol%, from 1 mol% to 40 mol%, from 1 mol% to 35 mol%, from 1 mol% to 30 mol%, from 1 mol% to 25 mol%, from 1 mol% to 20 mol%, from 1 mol% to 15 mol%, from 2 mol% to 40 mol%, from 2 mol% to 35 mol%, from 2 mol% to 30 mol%, from 2 mol% to 25 mol%, from 2 mol% to 20 mol%, from 2 mol% to 15 mol%, from 7 mol% to 40 mol%, from 7 mol% to 35 mol%, from 7 mol% to 30 mol%, from 7 mol% to 25 mol%, from 7 mol% to 20 mol%, from 7 mol% to 15 mol%, from 10 mol% to 40 mol%, from 10 mol% to 35 mol%, from 10 mol% to 30 mol%, from 10 mol% to 25 mol%, from 10 mol% to 20 mol%, from 10 mol% to 15 mol%, from 12 mol% to 40 mol%, from 12 mol% to 35 mol%, from 12 mol% to 30 mol%, from 12 mol% to 25 mol%, from 12 mol% to 20 mol%, from 12 mol% to 15 mol%, from 15 mol% to 40 mol%, from 15 mol% to 35 mol%, from 15 mol% to 30 mol%, from 15 mol% to 25 mol%, or even from 15 mol% to 20 mol%, or any and all sub-ranges formed from any of these endpoints.

[0037] In embodiments, the polyolefin elastomer may comprise 75 mol% to 85 mol% ethylene and 12 mol% to 25 mol% cyclic olefin.85662-WO-PCT / DOW 85662 WO 8

[0038] The polyolefin elastomer may optionally comprise C3-C14α-olefin. C3-C14α- olefin, whose homopolymer has a relatively low Tg (e.g., less than or equal to 55 °C), may, in combination with ethylene and cyclic olefin, whose homopolymer has a relatively high Tg, help to achieve a desired Tg(e.g., -30 °C to 30 °C).

[0039] In embodiments, homopolymer of C3-C14α-olefin may have a Tgfrom -70 °C to 55 °C, from -70 °C to 35 °C, from -70 °C to 15 °C, from -70 °C to -5 °C, from -70 °C to - 25 °C, from -70 °C to -45 °C, from -50 °C to 55 °C, from -50 °C to 35 °C, from -50 °C to 15 °C, from -50 °C to -5 °C, from -50 °C to -25 °C, from -50 °C to -45 °C, from -30 °C to 55 °C, from -30 °C to 35 °C, from -30 °C to 15 °C, from -30 °C to -5 °C, from -30 °C to -25 °C, from -10 °C to 55 °C, from -10 °C to 35 °C, from -10 °C to 15 °C, from -10 °C to -5 °C, from 10 °C to 55 °C, from 10 °C to 35 °C, from 10 °C to 15 °C, from 30 °C to 55 °C, or even from 30 °C to 35 °C, or any and all sub-ranges formed from any of these endpoints, as measured according to DSC.

[0040] In embodiments, the C3-C14α-olefin may comprise C3-C14α-olefin, C3-C12α- olefin, C3-C10α-olefin, C3-C8α-olefin, C3-C6α-olefin, C5-C14α-olefin, C5-C12α-olefin, C5- C10 α-olefin, C5-C8 α-olefin, C5-C6 α-olefin, C7-C14 α-olefin, C7-C12 α-olefin, C7-C10 α-olefin, C7-C8 α-olefin, C9-C14 α-olefin, C9-C12 α-olefin, C9-C10 α-olefin, C11-C14 α-olefin, C11-C12 α- olefin, or α-olefin having a range of the number of carbon atoms formed from any of these endpoints. In embodiments, the C3-C14 α-olefin may comprise propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecane, 3- methyl-1-butene, or 4-methyl-1-pentene. In embodiments, the C3-C14α-olefin may comprise octene.

[0041] The polyolefin elastomer may comprise 0.5 mol% to 30 mol% C3-C14 α- olefin to achieve a desired Tg(e.g., -30 °C to 30 °C). In embodiments, the polyolefin elastomer may comprise 0.5 mol% to 2.5 mol% C3-C14α-olefin. In embodiments, the amount of C3-C14 α-olefin in the polyolefin elastomer may be greater than or equal to 0 mol%, greater than or equal to 0.5 mol%, greater than or equal to 1 mol%, or even greater than or equal to 1.5 mol%. In embodiments, the amount of C3-C14α-olefin in the polyolefin elastomer may be less than or equal to 30 mol%, less than or equal to 20 mol%, less than or equal to 10 mol%, less than or equal to 5 mol%, or even less than or equal to 2.5 mol%. In embodiments, the amount of C3-C14α-olefin in the polyolefin elastomer may be from 0 mol% to 30 mol%, from 0 mol% to 20 mol%, from 0 mol% to 10 mol%, from 0 mol% to 585662-WO-PCT / DOW 85662 WO 9 mol%, from 0 mol% to 2.5 mol%, from 0.5 mol% to 30 mol%, from 0.5 mol% to 20 mol%, from 0.5 mol% to 10 mol%, from 0.5 mol% to 5 mol%, from 0.5 mol% to 2.5 mol%, from 1 mol% to 30 mol%, from 1 mol% to 20 mol%, from 1 mol% to 10 mol%, from 1 mol% to 5 mol%, from 1 mol% to 2.5 mol%, from 1.5 mol% to 30 mol%, from 1.5 mol% to 20 mol%, from 1.5 mol% to 10 mol%, from 1.5 mol% to 5 mol%, or even from 0.5 mol% to 2.5 mol%, or any and all sub-ranges formed from any of these endpoints. In embodiments, the polyolefin elastomer may be free or substantially free of C3-C14 α-olefin. "Substantially free of C3-C14α-olefin" means that C3-C14α-olefin is not intentionally added to the polyolefin elastomer. However, the polyolefin elastomer may contain traces of C3-C14 α- olefin as a contaminant or tramp in amounts of less than 0.05 wt%. "Free of C3-C14 α- olefin" means that C3-C14α-olefin is not present in the polyolefin elastomer.

[0042] In embodiments, the polyolefin elastomer may comprise 75 mol% to 85 mol% ethylene; 0.5 mol% to 2.5 mol% C3-C14 α-olefin; and 10 mol% to 20 mol% cyclic olefin.

[0043] As described herein, the ability of a material to dampen vibration will be enhanced at temperatures near the Tgof the material. For vibration dampening material used in, for example, an automobile, the temperature range that the material is subjected to may be relatively large. When a material is laminated between sheets, such as glass, the effective Tg(e.g., maximum composite loss factor temperature) increases. As such, the polyolefin elastomers described herein may have a minimum Tg (e.g., greater than or equal to -30 °C) that is relatively close to the temperature at which the polyolefin elastomer will be used while also accounting for the effect lamination sheets will have on the Tg. At relatively higher Tg(e.g., greater than 30 °C), the polyolefin elastomer may become difficult to handle. As such, the Tg may be limited (e.g., less than or equal to 30 °C).

[0044] Accordingly, in embodiments, the polyolefin elastomer may have a Tgof -30 °C to 30 °C, as measured according to DSC. In embodiments, the polyolefin elastomer may have a Tg of -10 °C to 20 °C, as measured according to DSC. In embodiments, the Tg of the polyolefin elastomer may be greater than or equal to -30 °C, greater than or equal to -25 °C, greater than or equal to -20 °C, greater than or equal to -15 °C, greater than or equal to -10 °C, greater than or equal to -5 °C, greater than or equal to 0 °C, greater than or equal to 5 °C, or even greater than or equal to 10 °C. In embodiments, the Tg of the polyolefin elastomer may be less than or equal to 30 °C, less than or equal to 25 °C, less than or equal to 20 °C, less than or equal to 15 °C, less than or equal to 10 °C, less than or equal to 5 °C, or even85662-WO-PCT / DOW 85662 WO 10 less than or equal to 0 °C. In embodiments, the Tgof the polyolefin elastomer may be from -30 °C to 30 °C, from -30 °C to 25 °C, from -30 °C to 20 °C, from -30 °C to 25 °C, from -30 °C to 20 °C, from -30 °C to 15 °C, from -30 °C to 10 °C, from -30 °C to 5 °C, from -30 °C to 0 °C, from -25 °C to 30 °C, from -25 °C to 25 °C, from -25 °C to 20 °C, from -25 °C to 25 °C, from -25 °C to 20 °C, from -25 °C to 15 °C, from -25 °C to 10 °C, from -25 °C to 5 °C, from -25 °C to 0 °C, from -20 °C to 30 °C, from -20 °C to 25 °C, from -20 °C to 20 °C, from -20 °C to 25 °C, from -20 °C to 20 °C, from -20 °C to 15 °C, from -20 °C to 10 °C, from -20 °C to 5 °C, from -20 °C to 0 °C, from -15 °C to 30 °C, from -15 °C to 25 °C, from -15 °C to 20 °C, from -15 °C to 25 °C, from -15 °C to 20 °C, from -15 °C to 15 °C, from -15 °C to 10 °C, from -15 °C to 5 °C, from -15 °C to 0 °C, from -10 °C to 30 °C, from -10 °C to 25 °C, from -10 °C to 20 °C, from -10 °C to 25 °C, from -10 °C to 20 °C, from -10 °C to 15 °C, from -10 °C to 10 °C, from -10 °C to 5 °C, from -10 °C to 0 °C, from -5 °C to 30 °C, from - 5 °C to 25 °C, from -5 °C to 20 °C, from -5 °C to 25 °C, from -5 °C to 20 °C, from -5 °C to 15 °C, from -5 °C to 10 °C, from -5 °C to 5 °C, from -5 °C to 0 °C, from 0 °C to 30 °C, from 0 °C to 25 °C, from 0 °C to 20 °C, from 0 °C to 25 °C, from 0 °C to 20 °C, from 0 °C to 15 °C, from 0 °C to 10 °C, from 0 °C to 5 °C, from 5 °C to 30 °C, from 5 °C to 25 °C, from 5 °C to 20 °C, from 5 °C to 25 °C, from 5 °C to 20 °C, from 5 °C to 15 °C, from 5 °C to 10 °C, from 10 °C to 30 °C, from 10 °C to 25 °C, from 10 °C to 20 °C, from 10 °C to 25 °C, from 10 °C to 20 °C, or even from 10 °C to 15 °C, or any and all sub-ranges formed from any of these endpoints.

[0045] The polyolefin elastomer may comprise a Mwof 50,000 g / mol to 500,000 g / mol, as measured according to GPC to impart a relatively higher viscosity polymer that may be desired for handling and palletization purposes. The Mw of the polyolefin elastomer may also improve the maximum composite loss factor achieved by a laminate including the polyolefin elastomer, when compared to similar compositions. In embodiments, the polyolefin elastomer may comprise a Mw of 200,000 g / mol to 350,000 g / mol. In embodiments, the Mw of the polyolefin elastomer may be greater than or equal to 50,000 g / mol; greater than or equal to 75,000 g / mol; greater than or equal to 100,000 g / mol; greater than or equal to 125,000 g / mol; greater than or equal to 150,000 g / mol; greater than or equal to 175,000 g / mol; or even greater than or equal to 200,000 g / mol. In embodiments, the Mw of the polyolefin elastomer may be less than or equal to 500,0000 g / mol, less than or equal to 450,000 g / mol, less than or equal to 400,000 g / mol; less than or equal to 375,000 g / mol;85662-WO-PCT / DOW 85662 WO 11 less than or equal to 350,000 g / mol; less than or equal to 325,000 g / mol, or even less than or equal to 300,000 g / mol. In embodiments, the Mw of the polyolefin elastomer may be from 50,000 g / mol to 500,000 g / mol; from 50,000 g / mol to 450,000 g / mol; from 50,000 g / mol to 400,000 g / mol; from 50,000 g / mol to 375,000 g / mol; from 50,000 g / mol to 350,000 g / mol; from 50,000 g / mol to 325,000 g / mol; from 50,000 g / mol to 300,000 g / mol; from 75,000 g / mol to 500,000 g / mol; from 75,000 g / mol to 450,000 g / mol; from 75,000 g / mol to 400,000 g / mol; from 75,000 g / mol to 375,000 g / mol; from 75,000 g / mol to 350,000 g / mol; from 75,000 g / mol to 325,000 g / mol; from 75,000 g / mol to 300,000 g / mol; from 100,000 g / mol to 500,000 g / mol; from 100,000 g / mol to 450,000 g / mol; from 100,000 g / mol to 400,000 g / mol; from 100,000 g / mol to 375,000 g / mol; from 100,000 g / mol to 350,000 g / mol; from 100,000 g / mol to 325,000 g / mol; from 100,000 g / mol to 300,000 g / mol; from 125,000 g / mol to 500,000 g / mol; from 125,000 g / mol to 450,000 g / mol; from 125,000 g / mol to 400,000 g / mol; from 125,000 g / mol to 375,000 g / mol; from 125,000 g / mol to 350,000 g / mol; from 125,000 g / mol to 325,000 g / mol; from 125,000 g / mol to 300,000 g / mol; from 150,000 g / mol to 500,000 g / mol; from 150,000 g / mol to 450,000 g / mol; from 150,000 g / mol to 400,000 g / mol; from 150,000 g / mol to 375,000 g / mol; from 150,000 g / mol to 350,000 g / mol; from 150,000 g / mol to 325,000 g / mol; from 150,000 g / mol to 300,000 g / mol; from 175,000 g / mol to 500,000 g / mol; from 175,000 g / mol to 450,000 g / mol; from 175,000 g / mol to 400,000 g / mol; from 175,000 g / mol to 375,000 g / mol; from 175,000 g / mol to 350,000 g / mol; from 175,000 g / mol to 325,000 g / mol; from 175,000 g / mol to 300,000 g / mol; from 200,000 g / mol to 500,000 g / mol; from 200,000 g / mol to 450,000 g / mol; from 200,000 g / mol to 400,000 g / mol; from 200,000 g / mol to 375,000 g / mol; from 200,000 g / mol to 350,000 g / mol; from 200,000 g / mol to 325,000 g / mol; or even from 200,000 g / mol to 300,000 g / mol; or any and all sub-ranges formed from any of these endpoints.

[0046] In certain applications, such as automotive window and architectural glass applications, it may be desirable for the for the polyolefin elastomer to have a relatively high optical clarity (e.g., a haze less than or equal to 5%, as measured according to ASTM D1003). The polyolefin elastomer may have a limited crystallinity (e.g., less than or equal to 25%) and / or melting temperature (Tm) (e.g., less than or equal to 100 °C) to achieve a desired optical clarity. While not wishing to be bound by theory, it is believed that relatively low crystallinity would result in relatively low haze. While also not wishing to be bound by theory, a relatively higher Tg may result in a relatively higher haze. While also not wishing85662-WO-PCT / DOW 85662 WO 12 to be bound by theory, addition of the cyclic olefin may increase haze. The desire for relatively high optical clarity may be balanced against handling difficulties, both of which may result from the crystallinity, Tg, and / or Tm of the polyolefin elastomer.

[0047] In embodiments, the polyolefin elastomer may comprise a crystallinity of 0% to 25%, as measured according to DSC. In embodiments, the polyolefin elastomer may comprise a crystallinity greater than or equal to 0%, greater than or equal to 1%, greater than or equal to 3%, or even greater than or equal to 5%, as measured according to DSC. In embodiments, the polyolefin elastomer may comprise a crystallinity less than or equal to 25%, less than or equal to 20%, less than or equal to 15%, less than or equal to 10%, less than or equal to 5%, less than or equal to 3%, or even less than or equal to 1%, as measured according to DSC. In embodiments, the polyolefin elastomer may comprise a crystallinity from 0% to 25%, from 0% to 20%, from 0% to 15%, from 0% to 10%, from 0% to 5%, from 0% to 3%, from 0% to 1%, from 1% to 25%, from 1% to 20%, from 1% to 15%, from 1% to 10%, from 1% to 5%, from 1% to 3%, from 3% to 25%, from 3% to 20%, from 3% to 15%, from 3% to 10%, from 3% to 5%, from 5% to 25%, from 5% to 20%, from 5% to 15%, or even from 5% to 10%, or any and all sub-ranges formed from any of these endpoints, as measured according to DSC. Crystallinity may be measured via dynamic mechanical analysis (DMA). References to crystallinity herein refer to crystallinity measured according to DSC.

[0048] In embodiments, the polyolefin elastomer may have a Tm less than or equal to 100 °C, less than or equal to 75 °C, or even less than or equal to 50 °C. In embodiments, the polyolefin elastomer may not have a Tm.

[0049] In embodiments, the polyolefin elastomer may comprise a polydispersity index (PDI) of from 1.5 to 20.0, from 1.5 to 15.0, from 1.5 to 10.0, from 1.5 to 7.0, from 1.5 to 5.0, from 1.5 to 4.5, from 1.5 to 4.0, from 1.5 to 3.5, from 1.5 to 3.0, from 2.0 to 20.0, from 2.0 to 15.0, from 2.0 to 10.0, from 2.0 to 7.0, from 2.0 to 5.0, from 2.0 to 4.5, from 2.0 to 4.0, from 2.0 to 3.5, from 2.0 to 3.0, from 2.5 to 20.0, from 2.5 to 15.0, from 2.5 to 10.0, from 2.5 to 7.0, from 2.5 to 5.0, from 2.5 to 4.5, from 2.5 to 4.0, from 2.5 to 3.5, or even from 2.5 to 3.0,, or any and all sub-ranges formed from any of these endpoints.

[0050] Laminates

[0051] The polyolefin elastomers described herein may be used in laminates. Referring now to FIG. 1, a laminate 100 may include a first glass substrate 102, a second85662-WO-PCT / DOW 85662 WO 13 glass substrate 104, and an interlayer 106 disposed between the first glass substrate 102 and the second glass substrate 104. The interlayer 106 may comprise the polyolefin elastomer described herein.

[0052] The interlayer 106 may be free or substantially free of plasticizer. "Substantially free of plasticizer" means that plasticizer is not intentionally added to the interlayer 106. However, the interlayer 106 may contain traces of plasticizer as a contaminant or tramp in amounts of less than 0.05 wt%. "Free of plasticizer" means that plasticizer is not present in the interlayer 106.

[0053] The interlayer 106 may comprise silanes as adhesion modifiers, such as those disclosed in U.S. Patent Nos. 8,445,776; 8,513,357; and 11,673,381, which are incorporated by reference in their entireties. The interlayer 106 may also comprise other additives including, for example, an antioxidant, an ultraviolet ray absorber, a photostabilizer, an antiblocking agent, a colorant such as a pigment and / or a dye, a heat shielding material (e.g., infrared ray absorber), or mixtures thereof.

[0054] Examples of the antioxidant may include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.

[0055] Examples of the phenol-based antioxidant may include acrylate-based compounds, such as 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate and 2,4-di-t-amyl-6-(1-(3,5-di-t-amyl-2-hydroxyphenyl)ethyl)phenyl acrylate; alkyl-substituted phenol-based compounds, such as 2,6-di-t-butyl-4-methylphenol, 2,6-di-t- butyl-4-ethylphenol, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,2′- methylene-bis(4-methyl-6-t-butylphenol), 4,4′-butylidene-bis(4-methyl-6-t-butylphenol), 4,4′-butylidene-bis(6-t-butyl-m-cresol), 4,4′-thiobis(3-methyl-6-t-butylphenol), bis(3- cyclohexyl-2-hydroxy-5-methylphenyl)methane, 3,9-bis(2-(3-(3-t-butyl-4-hydroxy-5- methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,1,3- trix(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4- hydroxybenzyl)benzene, tetrakis(methylene-3-(3′,5′-di-t-butyl-4′- hydroxyphenyl)propionate)methane and triethylene glycolbis(3-(3-t-butyl-4-hydroxy-5- methylphenyl)propionate); triazine group-containing phenol-based compounds, such as 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-t-butylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 6-(4-hydroxy-3,5-di-t-butylanilino)-2,4-bis-octylthio-1,3,5-triazine, 6-(4-hydroxy-3,5-85662-WO-PCT / DOW 85662 WO 14 dimethylanilino)-2,4-bis-octylthio-1,3,5-triazine, 6-(4-hydroxy-3-methyl-5-t-butylanilino)- 2,4-bis-octylthio-1,3,5-triazine and 2-octylthio-4,6-bis-(3,5-di-t-butyl-4-oxyanilino)-1,3,5- triazine.

[0056] Examples of the phosphorus-based antioxidant may include monophosphite- based compounds, such as triphenyl phosphite, diphenylisodecyl phosphite, phenyldiisodecyl phosphite, tris(nonylphenyl) phosphite, tris(dinonylphenyl) phosphite, tris(2-t-butyl-4- methylphenyl) phosphite, tris(2,4-di-t-butyl) phosphite, tris(cyclohexylphenyl) phosphite, 2,2-methylenebis(4,6-di-t-butylphenyl)octylphosphite, 9,10-dihydro-9-oxa-10- phosphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa- 10-phosphaphenanthrene-10-oxide and 10-decyloxy-9,10-dihydro-9-oxa-10- phosphaphenanthrene; diphosphite-based compounds, such as 4,4′-butylidene-bis(3-methyl- 6-t-butylphenyl-di-tridecylphosphite), 4,4′-isopropylidene-bis(phenyl-di-alkyl(C12-C15) phosphite), 4,4′-isopropylidene-bis(diphenylmonoalkyl(C12-C15)phosphite), 1,1,3-tris(2- methyl-4-di-tridecylphosphite-5-t-butylphenyl)butane and tetrakis(2,4-di-t-butylphenyl)- 4,4′-biphenylene phosphite.

[0057] Examples of the sulfur-based antioxidant may include dilauryl 3,3′- thiodipropionate, distearyl 3,3-thiodipropionate, lauryl stearyl 3,3′-thiodipropionate, pentaerythritol-tetrakis-(3-lauryl-thiopropionate), and 3,9-bis(2-dodecylthioethyl)-2,4,8,10- tetraoxaspiro[5.5]undecane.

[0058] Examples of the ultraviolet ray absorber may include benzotriazole-based ultraviolet ray absorbers, such as 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy- 3,5-bis(1,1′-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3,5-di-t-butyl-2- hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5- chlorobenzotriazole, 2-(3,5-di-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole and 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-5′-t- octylphenyl)triazole; hindered amine-based ultraviolet ray absorbers, such as 2,2,6,6- tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n- butylmalonate and 4-(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy)-1-(2-(3-(3,5-di-t- butyl-4-hydroxyphenyl)propionyloxy)ethyl)-2,2,6,6-tetramethylpiperidine; benzoate-based ultraviolet ray absorbers, such as 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate.85662-WO-PCT / DOW 85662 WO 15

[0059] Examples of the photostabilizer may include hindered amine-based materials, such as "ADEKA STAB LA-57" (a trade name) manufactured by Adeka Corporation, and "TINUVIN 622" (a trade name) manufactured by Ciba Specialty Chemicals Inc.

[0060] Suitable heat-shielding fine particles are disclosed, for example, in U.S. Patent No. 10,538,063, which is incorporated by reference in its entirety. Specific examples of the heat-shielding fine particle may include a metal-doped indium oxide, such as tin-doped indium oxide (ITO), a metal-doped tin oxide, such as antimony-doped tin oxide (ATO), a metal-doped zinc oxide, such as aluminum-doped zinc oxide (AZO), a metal element composite tungsten oxide represented by a general formula: MmWOn (wherein M represents a metal element; m is about 0.01 or more and about 1.0 or less; and n is about 2.2 or more and about 3.0 or less), zinc antimonate (ZnSb2O5), and lanthanum hexaboride (LaB6).

[0061] Examples of the heat shielding compound include phthalocyanine compounds, naphthalocyanine compounds, and the like. From the viewpoint of further improving the heat shielding properties, it is preferred that the heat shielding compound contains a metal. Examples of the metal include Na, K, Li, Cu, Zn, Fe, Co, Ni, Ru, Rh, Pd, Pt, Mn, Sn, V, Ca, and Al.

[0062] Colored interlayers may be formed as generally known in the art. For example, one or more pigments may be added to one or more of the ionomer resin compositions as generally disclosed in U.S. Patent Application No. 2008 / 0302461, which is incorporated by reference herein in its entirety. Blends of one or more inorganic particles with one or more dyes may also be used.

[0063] In embodiments, it may be desirable to form a translucent interlayer to produce laminates, for example, having the aesthetic qualities of etched or sandblasted glass, such as disclosed in U.S. Patent No. 7,261,943, which is incorporated by reference in its entirety, or having a translucent white appearance, such as disclosed in U.S. Patent Application No. 2013 / 0225746, which is incorporated by reference in its entirety.

[0064] Decorative glass laminates bearing an image may also be prepared as described, for example, in U.S. Patent No. 7,232,213, which is incorporated by reference in its entirety.85662-WO-PCT / DOW 85662 WO 16

[0065] The interlayer 106 may have a thickness of from 0.5 mm to 1 mm, from 0.75 mm to 1 mm, or even from 0.5 mm to 0.75 mm, or any and all sub-ranges formed from any of these endpoints.

[0066] In embodiments, the interlayer 106 may comprise multiple sub-interlayers, each sub-interlayer having the same or varying materials and / or thickness.

[0067] The glass substrates 102,104 included in the laminate are not necessarily limited. For example, the glass substrate may be inorganic or organic in nature. Inorganic glass includes not only window glass, plate glass, silicate glass, sheet glass, low iron glass, tempered glass, tempered CeO-free glass, and float glass, but also to include colored glass, specialty glass (such as those include ingredients to control, e.g., solar heating), coated glass (such as those sputtered with metals (e.g., silver or indium tin oxide) for solar control purposes), E-glass, Toroglass, Solex® glass (PPG Industries, Pittsburgh, Pa.). Such specialty glasses are disclosed in, e.g., U.S. Pat. Nos. 4,615,989; 5,173,212; 5,264,286; 6,150,028; 6,340,646; 6,461,736; and 6,468,934, which are incorporated by reference in their entireties. The type of glass to be selected for a particular laminate may depend on the intended use.

[0068] Organic glass may include, but is not limited to, polycarbonates, acrylics, polyacrylates, cyclic polyolefins (e.g., ethylene norbornene polymers), polystyrenes (preferably metallocene-catalyzed polystyrenes), polyamides, polyesters, fluoropolymers, and combinations of two or more thereof.

[0069] Each of the glass substrate 102, 104 may have a thickness of from 1 mm to 12 mm, from 1 mm to 10 mm, from 1 mm to 8 mm, from 1 mm to 6 mm, from 3 mm to 12 mm, from 3 mm to 10 mm, from 3 mm to 8 mm, from 3 mm to 6 mm, from 5 mm to 12 mm, from 5 mm to 10 mm, from 5 mm to 8 mm, from 5 mm to 6 mm, from 7 mm to 12 mm, from 7 mm to 10 mm, from 7 mm to 8 mm, from 9 mm to 12 mm, or even from 9 mm to 10 mm, or any and all sub-ranges formed from any of these points.

[0070] The laminate 100 may have a concave or convex structure (not shown).

[0071] The polyolefin elastomers described herein have a desired Tg (e.g., -30 °C to 30 °C), thereby imparting an improved vibration dampening to the resulting laminate. In embodiments, the laminate may comprise a maximum composite loss factor (CLF) of greater than or equal to 0.1, as measured according to ASTM E-756 at a temperature range from -20 °C to 70 °C. In embodiments, the maximum CLF of the laminate may be greater than or85662-WO-PCT / DOW 85662 WO 17 equal to 0.1, greater than or equal to 0.15, greater than or equal to 0.2, greater than or equal to 0.25, or even greater than or equal to 0.3. The maximum CLF may not be affected by the Tg of the polyolefin elastomer.

[0072] In embodiments, laminate may comprise a maximum CLF temperature (i.e., the temperature at which the maximum CLF occurs) that correlates with the Tgof the polyolefin elastomer. For example in embodiments, the maximum CLF temperature of the laminate may be greater than or equal 10 °C, greater than or equal 15 °C, or even greater than or equal 20 °C than the Tgof the polyolefin elastomer. The Tgof the polyolefin elastomer may be such that the maximum CLF temperature occurs within a temperature range at which the laminate will be used. In embodiments, the maximum CLF temperature of the laminate may be from -10 °C to 60 °C, from -10 °C to 50 °C, from -10 °C to 40 °C, from -10 °C to 30 °C, from 0 °C to 60 °C, from 0 °C to 50 °C, from 0 °C to 40 °C, from 0 °C to 30 °C, from 10 °C to 60 °C, from 10 °C to 50 °C, from 10 °C to 40 °C, from 10 °C to 30 °C, from 20 °C to 60 °C, from 20 °C to 50 °C, from 20 °C to 40 °C, from 20 °C to 30 °C, from 30 °C to 60 °C, from 30 °C to 50 °C, or even from 30 °C to 40 °C, or any and all sub-ranges formed from any of these endpoints.

[0073] The laminates described herein may be used as part of an automotive window or in architectural glass applications. For example, the laminates may suitable be used as part of an automobile for a windshield, a sunroof, a side window, or a back window. As other examples, the laminates may be suitable used as part of a building member for a window, a wall, a roof, a sunroof, a sound insulating wall, a display window, a balcony, a handrail wall, or a partition glass member of a conference room.

[0074] TEST METHODS

[0075] Gel Permeation Chromatography (GPC)

[0076] The chromatographic system consisted of a Polymer Char GPC-IR (Valencia, Spain) high temperature GPC chromatograph, equipped with an internal IR5 infrared detector (IR5). The autosampler oven compartment was set at 160 °C, and the column compartment was set at 150 °C. The columns were one Agilent PLgel MIXED 7.5 x 50 mm, 20 micrometer (µm) linear mixed-bed guard column and four Agilent PLgel MIXED-A 7.5 x 300 mm, 20 µm linear mixed-bed columns. The chromatographic solvent was 1,2,4-trichlorobenzene, which contained 300 ppm of butylated hydroxytoluene (BHT) and was nitrogen sparged. The85662-WO-PCT / DOW 85662 WO 18 injection volume used was 200 microliters (µL), and the flow rate was 1.0 millimeters per minute (mm / minute).

[0077] Calibration of the GPC column set was performed using Agilent EasiCal Polystyrene standards (EasiCal PS-1 and EasiCal PS-2). Each EasiCal system consisted of two different spatulas supporting a mixture of 5 polymer standards (approximately 5 mg) to obtain 20 molecular weights points ranging from approximately 580 g / mol to 6,570,000 g / mol. Individual spatulas were added to septa-capped vials, sealed, and loaded into the Polymer Char autosampler. Polymer Char Instrument Control Software was utilized to add 8 milliliters (mL) of solvent to each vial and the standards were dissolved for 15 minutes at 160 °C under high-speed shaking prior to injection to the chromatography system. A third order polynomial was used to fit the nominal polystyrene standard peak molecular weights to obtain molecular weight equivalent calibration points at each chromatographic slice. The polystyrene standard peak molecular weights were converted to polyethylene molecular weights using Equation 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)).:where M is the molecular weight, A has a value of 0.41 and B is equal to 1.0.

[0078] The total plate count of the GPC column set was performed with decane (3% decane by volume in 1,2,4-trichlorobenzene introduced via micropump). The plate count for the chromatographic system should be greater than 18,000 for the 4 Agilent "Mixed A" 30 cm 20-micron linear mixed-bed columns.

[0079] Samples were prepared in a semi-automatic manner with the Polymer Char Instrument Control Software, wherein the samples were weight-targeted at 2 mg / mL, and the solvent was added to a septa-capped sealed vial via the Polymer Char high temperature autosampler. The samples were dissolved for two hours at 160 °C under high-speed shaking.

[0080] The calculations of Mn(GPC), Mw(GPC),and Mz(GPC)were based on GPC results using the internal IR5 detector (measurement channel) of the Polymer Char GPC-IR chromatograph according to Equations 2-4. Using Polymer Char GPCOne™ software, the baseline-subtracted IR chromatogram at each equally-spaced data collection point (i) was converted to the polyethylene equivalent molecular weight, obtained from the narrow85662-WO-PCT / DOW 85662 WO 19 standard calibration curve, for the equivalent chromatographic data point (i). Equations 2-4 are as follows: 2) 3) 4)

[0081] In order to monitor the deviations over time, a flowrate marker (3% v / v decane in solvent) was introduced into each sample via a micropump controlled with the Polymer Char GPC-IR system. This flowrate marker (FM) was used to linearly correct the pump flowrate (Flowrate(nominal)) for each sample by RV alignment of the respective decane peak within the sample (RV(FM Sample)) to that of the decane peak within the narrow standards calibration (RV(FM Calibrated)). Any changes in the time of the decane marker peak were then assumed to be related to a linear-shift in flowrate (Flowrate(effective)) for the entire run. After calibrating the system based on a flow marker peak, the effective flowrate (with respect to the narrow standards calibration) was calculated as Equation 5. Processing of the flow marker peak was done via the Polymer Char GPCOne™ Software. Acceptable flowrate correction is such that the effective flowrate should be within + / -0.7% of the nominal flowrate. Flowrate(effective)= Flowrate(nominal)* (RV(FM Calibrated) / RV(FM Sample)) (EQ 5)

[0082] Haze

[0083] The haze was measured according to ASTM D1003 and the values are reported in percentages (%).

[0084] Polydispersity Index (PDI)

[0085] PDI was calculated as a ratio weight average molecular weight to number average molecular weight (i.e., Mw / Mn), as measured according to GPC.

[0086] Differential Scanning Calorimetry (DSC)

[0087] Melting temperature (Tm) and glass transition temperature (Tg) were measured using DSC (Discovery Series DSC, TA Instruments, Inc.) using a heat-cool-heat temperature profile. Samples of 3 mg to 6 mg were loaded in open hermetic aluminum pans and85662-WO-PCT / DOW 85662 WO 20 temperature equilibration was achieved at 200 °C. After being held at this temperature for 3 min, the samples were cooled to -90 °C at 10 °C / min and then held at -90 °C for 4 minutes. The samples were then heated back up to 200 °C at 10 °C / min. Traces of the second heat cycle were analyzed individually using TA Trios software.

[0088] Oberst Bar Testing

[0089] Composite loss factor (CLF) is a measure of vibrational damping derived from the behavior of a test bar (i.e., Oberst bar) undergoing oscillatory flexure. Glass laminate samples were tested for their CLF according to ASTM E-756 at a temperature range from - 20 °C to 70 °C. CLF curves are shown herein for mode 1, which was from 100 Hz to 200 Hz across the temperatures tested. As used herein, "maximum composite loss factor temperature" and "maximum CLF temperature" refer to the temperature at which the maximum CLF occurs.

[0090] Center Impedance Method Testing

[0091] Glass laminate samples were tested using the center impedance method. Testing was performed in accordance with JIS G 0602-1993 for center-supporting, steady exciting methods and ISO 16940:2008. A metal mounting quill was superglued to the center of the bar. The quill was then screwed onto an impedance head attached to a mechanical vibration exciter unit. The vibration device with attached bar was used to test samples at 23 °C. The bar was excited using white noise and the frequency response function was captured from 0 Hz to 8000 Hz. For these samples, this allowed measurement of the CLF of modes 1- 3. CLF was calculated using the 3 dB down technique for each mode. Damping at frequencies of 400 Hz, 800 Hz, 1600 Hz, 3200 Hz, 4000 Hz and 6400 Hz was calculated using linear interpolation between the two nearest vibrational modes.

[0092] EXAMPLES

[0093] Commercial Polymers

[0094] ENGAGE™ 8180 is a polyolefin elastomer available from The Dow Chemical Company, Midland, MI. ENGAGE™ 8180 has a density of 0.863 g / cm3, a melt index (I2) of 0.5 g / 10 min as measured according to ASTM D1238 at 190 °C and a loading of 2.16 kg, and a glass transition temperature (Tg) of -55 °C.

[0095] Automotive PBV is a 0.76 mm thick PVB available from Jiangsu Daruihengte Technology & Science Co., Ltd., Jiangsu, CN, containing about 40% plasticizer, such as85662-WO-PCT / DOW 85662 WO 21 triethyleneglycol di-(2-ethyl hexanoate) (3GO) or tetraethylene glycol di-n-heptanoate (TEGH), dibutyl sebacate (DBS), dihexyl adipate (DHA), dioctyl adipate (DOA), hexyl cyclohexyl adipate, or mixtures of heptyl and nonyl adipates.

[0096] Architectural PVB is a 20 mil thick BUTACITE®PVB available from Dupont Company, Willmington, DE, containing about 26% triethylene glycol di-2-ethylheoxate plasticizer.

[0097] Polymer Synthesis Procedure – 2 L Batch Reactor

[0098] The batch reactor polymerizations were conducted in a 2-L Parr™ batch reactor. The reactor was heated by an electrical heating mantle and cooled by an internal serpentine cooling coil containing cooling water. Both the reactor and the heating / cooling system were controlled and monitored by a Camile™ TG process computer. The bottom of the reactor was fitted with a dump valve, which emptied the reactor contents into a stainless- steel dump pot, the dump pot having been prefilled with a catalyst kill solution (typically 10 mL of an IRGAFOS® / IRGANOX® / toluene mixture). The dump pot was vented to a 30- gallon blow-down tank, with both the pot and the tank purged with nitrogen. All solvents used for polymerization or catalyst makeup were run through solvent purification columns to remove any impurities that may affect polymerization. The 1-octene and Isopar™ E were passed through two columns: the first containing activated A2 alumina, the second containing activated Q5 reactant. The ethylene was passed through two columns: the first containing A204 alumina and 4Å mol sieves, the second containing Q5 reactant. The N2 used for transfers was passed through a single column containing A204 alumna, 4Å mol sieves and Q5. The 5-ethylidene-2-norbornene was purified via passage through activated alumina. The norbornene was prepared as a 50 wt% solution in Isopar™ E and filtered through activated alumina prior to use.

[0099] The reactor was loaded first from the shot tank containing Isopar™ E solvent, 1-octene, cyclic comonomer, and modified methylaluminoxane (50 μL, MMAO-3) depending on the desired reactor loading. The shot tank was filled to the load set points by use of a lab scale to which the shot tank was mounted. After liquid feed addition, the reactor was heated up to the polymerization temperature set point. Ethylene was added to the reactor at reaction temperature to maintain the reaction pressure set point. Ethylene addition amounts were monitored by a micro-motion flow meter.85662-WO-PCT / DOW 85662 WO 22

[0100] In an inert glove box, the catalyst and Armeen™ M2HT (activator) were mixed with the appropriate amount of purified toluene to achieve a solution of the desired molarity. The catalyst / activator solution was drawn into a syringe and pressure transferred into the catalyst shot tank. This was followed by three rinses of toluene, 5 mL each. Immediately after the addition of the catalyst the run timer began. The inventive examples in this disclosure were produced using Catalyst A, the structure of which shown below.

[0101] If ethylene was used, it was then added by the Camile to maintain the reaction at the pressure set point in the reactor. The Isopar™ E, 1-octene, cyclic comonomer, hydrogen, Catalyst A, Armeen™ M2HT, and MMAO-3 were added to the reactor according to the process conditions outlined in Table 1.

[0102] These polymerizations were run for 10 minutes, then the agitator was stopped and the bottom dump valve was opened to empty reactor contents into the dump pot. The dump pot contents were poured into trays placed in a lab hood where the solvent was evaporated off overnight. The trays containing the remaining polymer were then transferred to a vacuum oven, where they were heated at 140 °C under vacuum to remove any remaining solvent. After the trays cooled to ambient temperature, the polymers were weighed for yield / efficiencies, and submitted for characterization. Table 185662-WO-PCT / DOW 85662 WO 23 -3

[0103] Polymer Compositions and Properties

[0104] The compositions (in mol%) and properties of Example Polymers E1-E7 and Comparative Polymer C1 are provided in Tables 2 and 3.

[0105] The Tgof 1-octene homopolymer (i.e., polyoctene) is -63 °C.

[0106] The Tgof norbornene homopolymer (i.e., polynorbornene) is 380 °C.

[0107] The Tg of 5-ethylidene-2-norbornene homopolymer is 178 °C.

[0108] Example Polymers E2, E3, E6, and E7 did not have a melting temperature (i.e., "N / A"). Table 2 2Table 385662-WO-PCT / DOW 85662 WO 24

[0109] Example Polymers E1-E5, polyolefin elastomers comprising ethylene, C3-C14α-olefin (1-octene), and cyclic olefin (norbornene or 5-ethylidene-2-norbornene), had a Tg of -7.8 °C, 11.4 °C, 17.6 °C, -1.1 °C, and -3.2 °C, respectively. As exemplified by Example Polymers E1-E5, utilizing a combination of ethylene, cyclic olefin, whose homopolymer has a relatively high Tg, and C3-C14α-olefin, whose homopolymer has a relatively low Tg,,results in a polyolefin elastomer having a desired Tg (e.g., -30 °C to 30 °C).

[0110] Example Polymers E6 and E7, polyolefin elastomers comprising ethylene and cyclic olefin (norbornene) , had a Tgof 2.9 °C and 29.4 °C, respectively. As exemplified by Example Polymers E6 and E7, utilizing ethylene and cyclic olefin, whose homopolymer has a relatively high Tg, results in a polyolefin elastomer having a desired Tg (e.g., -30 °C to 30 °C).

[0111] Glass Laminate Formulation and Assembly

[0112] A batch reactor sample of a polymer composition was cut into small strips. About 4.5 g of the strips were compression molded in a 0.9 mm x 25.5 cm x 15 cm mold at 175 °C in a Carver press for 2 minutes and cooled in lower platens for 2 minutes. The polymer plaque was removed from the mold and the edges trimmed. A glass laminate was made by placing polymer plaque in between two borosilicate glass plates (2.5 cm x 20 cm x 3 mm). The excess polymer interlayer was trimmed until flush with the glass plates. Glass laminates were sealed in a silicone vacuum bag and heated in the oven at 140 °C or 150 °C 1 hour. Samples including a polymer plaque having a relatively higher Tg (i.e., greater than 15 °C) samples needed relatively higher temperatures (i.e., 150 °C) to successfully laminate.

[0113] Laminate Properties

[0114] Properties of Example Laminates EL1-EL7 and Comparative Laminates CL1- CL3 including Example Polymers E1-E7, Comparative Polymer C1, Architectural PVB, and Automotive PVB are provided in Table 4. Table 485662-WO-PCT / DOW 85662 WO 25Table 4 cont. e

[0115] Referring to Table 4 and FIG.2, Example Laminate EL1 including a polyolefin elastomer having a Tg of 7.8 °C had a maximum CLF of 0.31 at 15.7 °C. Example Laminate EL2 including a polyolefin elastomer having a Tgof 11.4 °C had a maximum CLF of 0.33 at 33 °C. Example Laminate EL3 including a polyolefin elastomer having a Tgof 17.6 °C had a maximum CLF of 0.31 at 38.9 °C. Example Laminate EL4 including a polyolefin elastomer having a Tg of -1.1 °C had a maximum CLF of 0.33 at 23.0 °C. Example Laminate EL6 including a polyolefin elastomer having a Tgof 2.9 °C had a maximum CLF of 0.34 at 21.4 °C. Example Laminate EL7 including a polyolefin elastomer having a Tg of 24.9 °C had a maximum CLF of 0.39 at 52.7 °C. Comparative Laminate CL1 including a polyolefin elastomer having a Tgof -55 °C had a maximum CLF of 0.08 at -18.5 °C As exemplified by Example Laminates EL1-EL7 and Comparative Laminate CL1, polyolefin elastomers having a desired Tg (e.g., -30 °C to 30 °C), impart an improved vibration dampening (e.g., a maximum CLF of greater than or equal to 0.1, as measured according to ASTM E-756 at a temperature range from -20 °C to 70 °C) to a laminate including the polyolefin elastomer.

[0116] Referring back to Table 4 and FIG. 2, Example Laminates EL1-EL7 and Comparative Laminates CL1 and CL3 further exemplify correlations and properties of interest.

[0117] For example, the maximum CLF may not be affected by the Tg of the polymer included in the laminate.85662-WO-PCT / DOW 85662 WO 26

[0118] As another example, Example Laminate EL4 including a polyolefin elastomer having a Mw of 248,018 g / mol, had a slightly higher maximum CLF of 0.33 as compared to Example Laminate EL1 including a polyolefin elastomer having a Mw of 224,636 g / mol. Example Laminate EL2 including a polyolefin elastomer having a Mwof 234,754 g / mol, had a slightly higher maximum CLF of 0.33 as compared to Example Laminate EL3 including a polyolefin elastomer having a Mw of 228,105 g / mol. As exemplified, a laminate including a polyolefin elastomer with a relatively Mw may have a relatively higher maximum CLF.

[0119] As a further example, Example Laminates EL1-EL7 had maximum CLF temperatures range from 15.7 °C to 52.7 °C, which is equal to the Tg of the polymer included in the laminate plus about 20 °C. As exemplified, there may be a correlation between the Tg of the polymer included in the laminate and the maximum CLF temperature.

[0120] As an even further example, Comparative Laminate CL1 had negligible CLF values above 0 °C. Example Laminates EL1, EL4, and EL6 had a maximum CLF temperature relatively close to room temperature (i.e., 23 °C). Comparative Laminates CL2 and CL3 had a maximum CLF temperature at 45.2 °C and 22.0 °C, respectively, exemplifying the conventional use of plasticizers to adjust the Tg of PVB such that PVB laminates may have sufficient vibration dampening around room temperature.

[0121] Referring back to Table 4 and now to FIG. 3, the relationship between the maximum CLF and the vibrational frequency of the glass laminates at room temperature (i.e., 23 °C) is shown. Because the impedance testing was completed at room temperature, laminates with a maximum CLF temperature around room temperature (e.g., 15.7 °C to 30 °C) would have been expected to provide sufficient impedance CLF values across the frequency range (i.e., 400 Hz to 6500 Hz). This was exemplified by Example Laminates EL1 and EL6 including a polyolefin elastomer having a maximum CLF temperature of 15.7 °C and 21.4 °C, respectively, which had the highest impedance CLF values across the frequency range.

[0122] While particular embodiments of the present disclosure have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the disclosure. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this disclosure.

Claims

85662-WO-PCT / DOW 85662 WO 27 CLAIMS 1. A polyolefin elastomer comprising: a polymerized reaction product of: 50 mol% to 99.5 mol% ethylene; and 0.5 mol% to 40 mol% cyclic olefin, wherein the polyolefin elastomer comprises: a glass transition temperature (Tg) of -30 °C to 30 °C, as measured according to Differential Scanning Calorimetry (DSC); and a weight average molecular weight (Mw) of 50,000 g / mol to 500,000 g / mol, as measured according to conventional Gel Permeation Chromatography (GPC).

2. The polyolefin elastomer of claim 1, wherein a homopolymer of the cyclic olefin comprises a Tg greater than or equal to 150 °C, as measured according to DSC.

3. The polyolefin elastomer of any preceding claim, wherein the polyolefin elastomer comprises a crystallinity of 0% to 25%, as measured according to DSC.

4. The polyolefin elastomer of any preceding claim, wherein the cyclic olefin comprises norbornene, 5-ethylidene-2-norbornene, cyclopentene, dicyclopentadiene, or a combination thereof.

5. The polyolefin elastomer of any preceding claim, wherein the polyolefin elastomer further comprises 0.5 mol% to 30 mol% C3-C14 α-olefin.

6. The polyolefin elastomer of claim 5, wherein a homopolymer of the C3-C14α-olefin comprises a Tg less than or equal to 55 °C, as measured according to DSC.

7. The polyolefin elastomer of claim 5 or claim 6, wherein the C3-C14α-olefin comprises propylene, butene, hexene, octene, or a combination thereof.

8. The polyolefin elastomer of any preceding claim, wherein the Mwof the polyolefin elastomer is from 200,000 g / mol to 300,000 g / mol, as measured according to GPC.85662-WO-PCT / DOW 85662 WO 28 9. The polyolefin elastomer of any preceding claim, wherein the Tg of the polyolefin elastomer is from -10 °C to 20 °C, as measured according to DSC.

10. The polyolefin elastomer of any preceding claim, wherein the polyolefin elastomer comprises a melting temperature (Tm) of less than or equal to 100 °C, as measured according to DSC.

11. The polyolefin elastomer of any preceding claim, wherein the polyolefin elastomer comprises a polydispersity index (PDI) of 1.5 to 20.

0.

12. The polyolefin elastomer of any of claims 1 to 4 and 8 to 11, wherein the polyolefin comprises: the polymerized reaction product of: 75 mol% to 85 mol% ethylene; and 12 mol% to 25 mol% cyclic olefin.

13. The polyolefin elastomer of any of claims 5 to 12, wherein the polyolefin elastomer comprises: the polymerized reaction product of: 75 mol% to 85 mol% ethylene; 10 mol% to 20 mol% cyclic olefin; and 0.5 mol% to 2.5 mol% C3-C14 α-olefin.

14. A laminate comprising: a first glass substrate; a second glass substrate opposite the first glass substrate; and an interlayer disposed between the first glass substrate and the second glass substrate, the interlayer comprising the polyolefin elastomer of any preceding claim.

15. The laminate of claim 14, wherein the interlayer is free or substantially free of plasticizer.85662-WO-PCT / DOW 85662 WO 29 16. The laminate of claims 14 or 15, wherein the laminate comprises a maximum composite loss factor (CLF) of greater than or equal to 0.1, as measured according to ASTM E-756 at a temperature range from -20 °C to 70 °C.

17. The laminate of any of claims 14 to 16, wherein the laminate comprises a haze of less than or equal to 5%, as measured according to ASTM D1003.

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