Functionalized propylene-based elastomeric compositions and methods of making the same

Abstract

Disclosed is a composition comprising C2-C 12 A polyalphaolefin and a functionalized propylene-based elastomer comprising about 4 to about 25 weight percent of a polyalphaolefin derived from one or more C2 or C4 to C 12 The present invention relates to a propylene-based elastomer having a functionalized propylene-based elastomer and ...

Description

[0001] Inventors: Sun Yingying, Li Liang, Zhang Shanshan, Zhao Bin, Gong Zhenyu, Ni Yiping, Qian Qingyun and Bao Peite

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS

[0003] This application claims priority to USSN 62 / 950,772 filed on December 19, 2019 and EP application No. 20164145.3 filed on March 19, 2020.

[0004] field

[0005] The present invention relates to a C2-C 12 Compositions of polyalphaolefins and functionalized propylene-based elastomers. Background of the Invention

[0007] Polypropylene is conventionally used to produce fibers and spunbond nonwovens for a wide range of products such as disposable hygiene products, including diapers, sanitary napkins, training pants, adult incontinence products, medical gowns, baby wipes, wet wipes, cleaning cloths, etc. Common polypropylene nonwoven fabrics can mimic the appearance, texture, and strength of woven fabrics. Together with other materials, they provide a spectrum of products with a variety of properties, and are also used alone or as components of clothing, home furnishings, health care, engineering, industry, and consumer products.

[0008] However, polypropylene and other polyalphaolefins are generally hydrophobic. Various end uses require fabrics to have hydrophilic properties. Polyalphaolefin fabrics can be imparted with hydrophilic properties by post-reactor processes, such as by grafting of polyalphaolefins with polar moieties. Such processes significantly increase the cost and complexity of the process. In addition, polyalphaolefin fabrics generally do not have the flexibility and softness levels suitable for more desired applications. There is a need in the art for polyalphaolefin fabrics such as spunbond or other fabrics with hydrophilic properties and other tactile attributes. SUMMARY OF THE INVENTION

[0010] This Summary is provided to introduce some concepts that are further described in the Detailed Description below. This Summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to be used as an aid in limiting the scope of the claimed subject matter.

[0011] It was discovered that propylene-based elastomers can be functionalized to impart polar functionality and hydrophilicity by exposing the material to oxygen for a sufficient period of time at a temperature greater than the melting temperature of the elastomer. It was also discovered that such functionalization does not substantially affect the rheological properties of the material, and that the functionalized propylene-based elastomer forms a melt blended composition with a polyalphaolefin having improved properties.

[0012] In one or more embodiments, the composition comprises C2-C12 A polyalphaolefin and a functionalized propylene-based elastomer comprising from about 4 to about 25 weight percent of a polyalphaolefin derived from one or more C2 or C4-C 12 α-olefin units; greater than about 90% triad tacticity; less than about 75 J / g heat of fusion; and a plurality of oxygen-containing functional groups selected from carboxylic acids, anhydrides, ketones, carbonates, esters, ethers, lactones and combinations thereof.

[0013] In other embodiments, the method comprises contacting a first propylene-based elastomer with an oxygen-containing gas at a temperature of about 200° C. or greater for a period of time sufficient to form a functionalized propylene-based elastomer comprising about 4 to about 25 weight percent of a propylene-based elastomer derived from one or more C2 or C4-C 12 α-olefin units; greater than about 90% triad stereoregularity; less than about 75 J / g heat of fusion; and greater than about 0.1% by weight oxygen-containing functional groups selected from carboxylic acids, anhydrides, ketones, carbonates, esters, ethers, lactones, and combinations thereof; and melt mixing the functionalized propylene-based elastomer with one or more C2-C 12 polyalphaolefin to form a blend composition.

[0014] In one or more embodiments, the method further comprises mixing the first propylene-based elastomer with the polyalphaolefin prior to said contacting of the first propylene-based elastomer with the oxygen-containing gas at a temperature of greater than or equal to about 200° C. for a period of time sufficient to form the functionalized propylene-based elastomer, or melt mixing the first propylene-based elastomer with the polyalphaolefin simultaneously with said contacting.

[0015] BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Embodiments according to the present application are described with reference to the following drawings. The same numerals are used throughout the drawings to refer to the same features and components.

[0017] Figure 1 is a plurality of superimposed FTIR spectra showing functionalization of a propylene-based elastomer by heating in the presence of oxygen to form a functionalized propylene-based elastomer according to an embodiment of the present disclosure;

[0018] Figure 2 is a plurality of superimposed FTIR spectra showing functionalization of another propylene-based elastomer by heating in the presence of oxygen to form a functionalized propylene-based elastomer according to an embodiment of the present disclosure;

[0019] Figure 3is a plurality of FTIR spectra taken over time showing functionalization of a propylene-based elastomer according to an embodiment of the present disclosure; and

[0020] Figure 4 is a graph showing the formation of oxygen-containing functional groups over time in a functionalized propylene-based elastomer according to an embodiment of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0022] Provided herein are blends comprising a polyalphaolefin and a grafted or otherwise functionalized propylene-based elastomer (f-PBE), as well as methods of forming the blends and articles comprising the blends.

[0023] First, it should be noted that in the development of any such actual implementation, in order to achieve the developer's specific goals, many implementation-specific decisions must be made, such as compliance with system-related and business-related constraints, which will vary from time to time with the implementation. In addition, it will be appreciated that such development efforts may be complex and time-consuming, but are routine tasks for those of ordinary skill in the art who benefit from the present disclosure. In addition, the compositions used / disclosed herein may also include some components other than those cited. In the overview and in this detailed description, each numerical value should be understood to be modified once by the term "about" (unless it has been explicitly so modified), and then again to be understood to be not so modified, unless otherwise indicated in the context.

[0024] Furthermore, in the Summary and in this Detailed Description, it should be understood that physical ranges listed or described as useful, suitable, etc. are intended to be considered to have described any and every value (including the endpoints) within the range. For example, "a range of 1-10" should be understood to indicate every possible number along the continuum between about 1 and about 10. Therefore, even if specific data points within the range are explicitly identified, or even if there are no data points within the range, or only a few specific data points are referred to, it should be understood that the inventors appreciate and understand that any and all data points within the range are considered to have been specified, and the inventors have an understanding of the entire range and all points within the range.

[0025] For the purposes of this document, "olefins" or "alkene" are linear, branched or cyclic compounds of carbon and hydrogen with at least one carbon-carbon double bond. For the purposes of this specification and the appended claims, when a polymer or copolymer is referred to as including an olefin, the olefin present in such a polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have a "propylene" content of 90% to 95% by weight, it is understood that the monomer units in the copolymer are derived from propylene in the polymerization reaction, and the derived units are present at 90% to 95% by weight based on the weight of the copolymer. Unless otherwise indicated, a "polymer" has two or more identical or different monomer units. A "homopolymer" is a polymer with the same monomer units. A "copolymer" is a polymer with two or more monomer units that are different from each other. A "terpolymer" is a polymer with three monomer units that are different from each other. "Different" used to refer to monomer units means that the monomer units differ from each other by at least one atom or are isomerically different. Therefore, as used herein, the definition of copolymers includes terpolymers, etc.

[0026] For the purposes of this disclosure, ethylene ("C2") shall be considered an alpha-olefin (α-olefin). Thus, a polyalphaolefin refers to a polymer comprising a plurality of alpha-olefin residues, each having two or more carbon atoms, preferably each olefin residue having from 2 carbon atoms (ethylene) up to 12 carbon atoms (dodecene).

[0027] As used herein, Mn is the number average molecular weight, Mw is the weight average molecular weight, and Mz is the z-average molecular weight, unless otherwise indicated, all percentages refer to weight percentages, wt% is weight percentage, and mol% is mole percentage. Molecular weight distribution (MWD), also known as polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise indicated, all molecular weight units (e.g., Mw, Mn, Mz) are g / mol. Unless otherwise indicated, all melting points (Tm) are determined by DSC secondary melt.

[0028] The following abbreviations may be used herein: dme is 1,2-dimethoxyethane, Me is methyl, Ph is phenyl, Et is ethyl, Pr is propyl, iPr is isopropyl, n-Pr is n-propyl, Bu is butyl, cPr is cyclopropyl, iBu is isobutyl, tBu is tert-butyl, p-tBu is p-tert-butyl, nBu is n-butyl, sBu is sec-butyl, TMS is trimethylsilyl, TIBAL is triisobutylaluminum, TNOAL is tri(n-octyl)aluminum, MAO is methylaluminoxane, p-Me is p-methyl, Ph is phenyl, Bn is benzyl (i.e., CH2Ph), THF is tetrahydrofuran, RT is room temperature (and is 23°C unless otherwise indicated), tol is toluene, EtOAc is ethyl acetate, Cy is cyclohexyl, Cp is cyclopentadienyl, Cp is cyclohexyl, * is pentamethylcyclopentadienyl, and Ind is indenyl, PP refers to polypropylene, iPP refers to isotactic polypropylene, CD refers to cyclodiene monomer, HMS-iPP refers to metallocene isotactic polypropylene, which is substantially linear, and the like.

[0029] The term "blend" as used herein refers to a mixture of two or more polymers, which is homogeneous or heterogeneous. The term "elastomer" shall refer to any polymer that exhibits a degree of elasticity, wherein elasticity is the ability of a material that has been deformed by a force (e.g., by stretching) to return at least partially to its original dimensions once the force has been removed. A "propylene-based elastomer" is a polymer or copolymer having elastomeric properties that further includes at least 50 mol% of propylene-derived units. The term melt blended composition refers to a mixture or blend of two or more components formed under conditions where at least one component is in a liquid or semi-liquid state (e.g., heated at a temperature greater than the melting point of the material).

[0030] A mixture or blend refers to a combination of two or more components that forms a homogeneous "solution" or a dispersion in which one of the materials is dispersed as a discontinuous phase in another material that forms a continuous phase. Unless otherwise indicated, the terms "mixture" and "blend" are used interchangeably herein.

[0031] As used herein, the term "monomer" or "comonomer" can refer to the monomer used to form a polymer (i.e., the unreacted compound in its form prior to polymerization), and can also refer to the monomer after it has been incorporated into a polymer (also referred to herein as a "[monomer]-derived unit"), which, by virtue of the polymerization reaction, typically has fewer hydrogen atoms than it did prior to the polymerization reaction.

[0032] Unless otherwise indicated, melt flow rate ("MFR") is determined by ASTM method D1238, Condition L (230°C, 2.16 kg).

[0033] As used herein, "catalyst system" means a combination of one or more catalysts with one or more activators and optionally one or more support compositions. An "activator" is any compound or component, or combination of compounds or components, that is capable of enhancing the ability of one or more catalysts to polymerize monomers into polymers.

[0034] Functional groups refer to the replacement of hydrogen or carbon atoms along or pendant to the polymer backbone with a structural moiety containing one or more heteroatoms. Functional groups include halogens (e.g., Br, Cl, F, or I), --NR*2, --OR*, --SeR*, --TeR*, --PR*2, --AsR*2, --SbR*2, --SR*, --BR*2, --SiR*, --SiR*3, --GeR*, --GeR*3, --SnR*, --SnR*3, --PbR*3, where R* is hydrogen, alkyl, or another functional group. For the purposes of this article, oxygen-containing functional groups include carboxylic acids (and their salts), anhydrides, ketones, carbonates (-O-CO-O-), esters, ethers, lactones, and combinations thereof.

[0035] As is commonly understood in the art, accurate quantification of the weight percent of oxygen imparted to a functionalized elastomer is difficult to obtain and is impossible to obtain when combined with another oxygen-containing polymer. For the purposes of this article, the FTIR method is used. As is known, FTIR does not provide absolute concentrations in complex systems such as polymers. Instead, the peak height and / or corresponding peak area of ​​a representative absorption peak (one or more) in an infrared spectrum are given. In such a complex system as disclosed herein, the polymer material may contain any number of possible oxidation products, such as ketones, lactones, esters, etc., and a single representative absorption must be selected. Therefore, the analytical method commonly used to calibrate the FTIR results for more defined and less complex systems cannot be used. This is similar to other such methods including NMR, titration, etc. It should be understood that the absolute calibration or correlation between IR peak area / height and substance concentration has a limited precision and accuracy commonly understood in the art. However, such a method does allow accurate qualitative comparison of oxygen functionalization between examples prepared, processed and analyzed in the same manner.

[0036] For purposes herein, a quantitative method originally developed to calculate maleic acid concentration on grafted elastomeric polymers similar to those used herein has been modified to determine the weight percent oxygen concentration, and therefore the amount of functionalization referred to in the present disclosure. For purposes herein, a calibration curve is established that is related to the ratio of the peak height of the carbonyl absorption divided by the peak height of the absorption indicating the amount of polymer present. This ratio is determined using a propylene-based elastomer with a known maleic acid concentration. This correlation (response factor) is then compared to a sample of a functionalized propylene-based elastomer according to the present disclosure to determine the theoretical maleic acid concentration, which is then converted to the weight percent of oxygen present, based on the relative molecular weights of maleic acid and oxygen.

[0037] The method for determining the concentration of maleic acid grafted onto similar polymers is related to the ratio of the absorbance representing the carbonyl moiety to the known value of the maleic acid grafted onto the polymer. The maleic acid method first determines the concentration of maleic acid grafted onto the polymer at ~1,710 cm -1 and ~1,780cm -1 The carbonyl absorption peak area (representing the carbonyl structure) is divided by the carbonyl absorption peak area at 4,352 cm -1 The ratio of the peak areas of peaks 1710 and 1780 (near IR, representing the CH stretch and therefore the amount of polymer present in the sample). A calibration is established based on (ratio = (peak 1710 + peak 1780) / peak 4352) relative to the weight percent of maleic acid (MA wt%) determined by other means. In the present disclosure, the carbonyl absorbances used in the calibration are similar to those observed in maleic acid grafted polymers. For the purposes of this article, the calibration table is prepared as follows: Maleic acid grafted polymers with known maleic acid concentrations are used at ~1,710 cm -1 and ~1,780cm -1 The maximum peak height of the carbonyl species in the region is then divided by 2,723 cm -1 The peak height of the absorption (=CH stretch) at 1 / 400 nm is used to normalize the amount of functionalization to the amount of polymer present. The ratio obtained is then correlated with the maleic acid concentration in the known maleic acid grafted polymer. This calibration is then used for the samples of the present invention to determine the theoretical maleic acid concentration, which is then corrected to obtain the oxygen concentration (i.e., wt% oxygen functionalization is equal to the theoretical wt% maleic acid as determined by the corrected calibration curve, multiplied by the molecular weight of oxygen (16 g / mol) and divided by the molecular weight of maleic acid (mw 116 g / mol).

[0038] For the purposes of this document, an oxygen-containing gas is defined as any gas that contains diatomic oxygen, namely O2. Thus, for the purposes of this document, air is an oxygen-containing gas but carbon dioxide CO2 is not an oxygen-containing gas.

[0039] In one or more embodiments, the composition comprises a blend (i.e., a melt blend) of a polyalphaolefin and a functionalized propylene-based elastomer comprising from about 4 to about 25 weight percent of a polyalphaolefin derived from one or more C2 or C4-C 12 α-olefin units; greater than about 90% triad tacticity; less than about 75 J / g heat of fusion; and a plurality of oxygen-containing functional groups selected from carboxylic acids, anhydrides, ketones, carbonates, esters, ethers, lactones and combinations thereof.

[0040] In one or more embodiments, the functionalized propylene-based elastomer comprises from about 0.01 wt% to about 10 wt% oxygen, preferably from about 0.1 wt% to 5 wt% oxygen, based on the total amount of functionalized propylene-based elastomer present. In one or more embodiments, the functionalized propylene-based elastomer comprises an MFR greater than or equal to about 20, when measured according to ASTM D-1238 (Condition L, i.e., 2.16 kg weight at 230°C). In some embodiments, the functionalized propylene-based elastomer comprises ethylene, preferably the functionalized propylene-based elastomer comprises greater than or equal to about 10 wt% ethylene, based on the total amount of functionalized propylene-based elastomer present.

[0041] In one or more embodiments, the melt blended composition has a static water contact angle of less than 90°, preferably less than 85°, preferably less than 82°, when measured according to ASTM D7490 or its equivalent.

[0042] In one or more embodiments, the functionalized propylene-based elastomer is the reaction product of an oxygen-containing gas (typically air) and a first propylene-based elastomer comprising from about 4 to about 25 weight percent of a C2 or C4-C6-derived elastomer when the first propylene-based elastomer is contacted with oxygen at a temperature greater than about 200° C. and less than or equal to about 260° C. for a period of time greater than about 1 minute, preferably from about 2 minutes to about 20 minutes. 12 The alpha-olefin units have a triad tacticity greater than about 90% and a heat of fusion less than about 75 J / g.

[0043] For the purpose of this article, C2-C 12Polyalphaolefin refers to a polyalphaolefin formed by one or more alpha-olefin monomers, each monomer having from 2 carbon atoms to 12 carbon atoms, i.e., ethylene to dodecene. In an embodiment, the polyalphaolefin comprises greater than about 50 mol% of propylene. In some embodiments, the polyalphaolefin also comprises ethylene, butene, pentene, hexene, 4-methyl-1-pentene, octene, decene, or a combination thereof. In one or more embodiments, the polyalphaolefin is isotactic polypropylene (iPP), and in some embodiments, the iPP preferably has an MFR greater than about 30, when measured according to ASTM D-1238 (condition L, i.e., 2.16 kg weight at 230°C).

[0044] In one or more embodiments, the composition comprises from about 10 wt% to about 40 wt% of the functionalized propylene-based elastomer, with in other embodiments the composition comprises from about 70 wt% to about 90 wt% of the functionalized propylene-based elastomer, based on the total amount of functionalized propylene-based elastomer and polyalphaolefin present.

[0045] In one or more embodiments, the method includes contacting a first propylene-based elastomer with an oxygen-containing gas at a temperature of about 200° C. or greater for a period of time sufficient to form a functionalized propylene-based elastomer comprising about 4 to about 25 weight percent of a propylene-based elastomer derived from one or more C2 or C4-C 12 units of alpha-olefins; greater than about 90% triad tacticity; less than about 75 J / g heat of fusion; and greater than about 0.01 wt. % oxygen-containing functional groups, preferably greater than about 0.1 wt. % oxygen-containing functional groups, the oxygen-containing functional groups being selected from carboxylic acids, anhydrides, ketones, carbonates, esters, ethers, lactones, and combinations thereof; and melt mixing the functionalized propylene-based elastomer with one or more polyalphaolefins to form a blended composition according to one or more embodiments disclosed herein.

[0046] In some embodiments of the process, the first propylene-based elastomer is contacted with an oxygen-containing gas at a temperature of greater than or equal to about 200° C., preferably greater than or equal to about 230° C. to about 260° C., for a period of time greater than about 5 minutes. In one or more embodiments, the oxygen-containing gas is air. In embodiments, the first propylene-based elastomer is contacted with the oxygen-containing gas at a temperature of greater than or equal to about 200° C. in the absence of an antioxidant and / or an antioxidant package.

[0047] In one or more embodiments, the first propylene-based elastomer is mixed with the polyalphaolefin prior to reacting or otherwise contacting the first propylene-based elastomer with the oxygen-containing gas at a temperature of greater than or equal to about 200°C for a period of time sufficient to form the functionalized propylene-based elastomer, or the first propylene-based elastomer is melt mixed with the polyalphaolefin while reacting or otherwise contacting. In other embodiments of the process, the first propylene-based elastomer and the polyalphaolefin are blended together prior to melt mixing and fed into an extruder, wherein the contacting of the first propylene-based elastomer with the oxygen-containing gas at a temperature of greater than or equal to about 200°C for a period of time sufficient to form the functionalized propylene-based elastomer is performed.

[0048] In one or more embodiments of the present invention, the article comprises a blend composition according to one or more embodiments disclosed herein. Thus, in one or more embodiments, the article comprises a polyalphaolefin and a functionalized propylene-based elastomer comprising about 4 to about 25 weight percent of a polyolefin derived from one or more C2 or C4-C 12 α-olefin units; greater than about 90% triad tacticity; less than about 75 J / g heat of fusion; and a plurality of oxygen-containing functional groups selected from carboxylic acids, anhydrides, ketones, carbonates, esters, ethers, lactones and combinations thereof.

[0049] In one or more embodiments, the article has a static water contact angle of less than 90°, preferably less than 85°, preferably less than 82°, when measured according to ASTM D7490 or its equivalent. In some embodiments, the article is a nonwoven fabric, a diaper, or a film.

[0050] In some embodiments, the functionalized propylene-based elastomer comprises from about 4 wt% to about 10 wt% ethylene, preferably from about 4 wt% to about 5 wt%, based on the total amount of propylene-based elastomer present. In one or more embodiments, the functionalized propylene-based elastomer has an Mn greater than 50,000 and an Mw / Mn greater than 2, when measured by GPC. In one or more embodiments, the functionalized propylene-based elastomer also comprises an elastic modulus greater than about 5 MPa and / or a yield stress greater than about 5 MPa and / or a strain at break of less than about 10 mm / mm and / or a stress at break greater than about 5 MPa, when measured according to ASTM D638 or its equivalent.

[0051] In one or more embodiments, the functionalized propylene-based elastomer has or exhibits a static water contact angle of less than 90°, preferably less than 88°, preferably less than 85°, when measured according to ASTM D7490 or its equivalent. Thus, in embodiments, the functionalized propylene-based elastomer is hydrophilic, in contrast to the same propylene-based elastomer prior to functionalization, which is hydrophobic, i.e., has a static water contact angle greater than or equal to 90° when measured in the same manner.

[0052] In one or more embodiments, the functionalized propylene-based elastomer comprises an increased amount of carbonyl functionality relative to the amount of carbonyl functionality (if any) present in the first (non-functionalized) propylene-based elastomer, as measured using the same method under substantially the same conditions, such as by the presence of carbonyl functionality at about 1,780 cm in the infrared spectrum of the functionalized propylene-based elastomer. -1 - Approx. 1,690cm -1 The absorption (i.e., centered at about 1,773 cm -1 and 1,719cm -1 carbonyl stretch) relative to about 1,780 cm in the infrared spectrum of the first propylene-based elastomer -1 - Approx. 1,690cm -1 Optionally, other suitable indicators include the absorption increase associated with COC and -OH functional groups.

[0053] In one or more embodiments, the amount of functionalization of the propylene-based elastomer results in a percentage difference in the Mn of the functionalized propylene-based elastomer of less than about 30%, preferably less than about 15%, or less than about 10% of the Mn of the first propylene-based elastomer when measured according to the formula:

[0054] [( 1 Mn-Mn f ) / 1 Mn]*100%;

[0055] in 1 Mn is the Mn of the first propylene-based elastomer (PBE) determined by GPC, and Mn f is the Mn of the functionalized propylene-based elastomer (f-PBE) as determined by GPC.

[0056] Propylene-based elastomers (PBE)

[0057] In certain embodiments of the present invention, the composition comprises a propylene-based elastomer ("PBE") that is at least partially grafted or otherwise functionalized by reaction with oxygen to form a functionalized propylene-based elastomer ("f-PBE"). As noted, suitable PBEs include those comprising propylene and from about 4 to about 25 weight percent of a C4-C5 hydrocarbon selected from ethylene and / or C4-C6 hydrocarbons. 12 Those of one or more comonomers of alpha-olefins. In one or more embodiments, the propylene-based elastomer also comprises a triad tacticity greater than about 90% and a heat of fusion less than about 75 J / g. At least a portion of the PBE is then functionalized to include oxygen-containing functional groups by contacting with oxygen under conditions sufficient to impart or otherwise modify the PBE. Suitable temperatures for contacting the PBE with oxygen to form the functionalized propylene-based elastomer (f-PBE) include temperatures greater than the melting point of the starting PBE material, preferably at temperatures of about 200° C. to about 300° C. or higher, and suitable times at that temperature greater than or equal to about 1 minute, typically greater than or equal to 2 minutes. It should be understood that the suitable reaction time required to form the functionalized propylene-based elastomer (f-PBE) can be reduced by increasing the reaction temperature, by using pure oxygen instead of air, and / or by subjecting the PBE to shear, such as by mixing in an extruder or contacting the molten PBE with oxygen.

[0058] In an embodiment, at least a portion of the functionalized propylene-based elastomer comprises an oxygen-containing functional group that is pendant to or within the polymer backbone. Examples of oxygen-containing functional groups include carboxylic acids, anhydrides, ketones, carbonates, esters, ethers, lactones, and combinations thereof. In one or more embodiments, the alpha-olefin comonomer unit may be derived from ethylene, butene, pentene, hexene, 4-methyl-1-pentene, octene, or decene. The embodiments described below are discussed with reference to ethylene as an alpha-olefin comonomer, but the embodiments are equally applicable to other copolymers containing other alpha-olefin comonomers. In this regard, the copolymer (elastomer) may be referred to as a functionalized propylene-based elastomer, and / or with reference to ethylene as an alpha-olefin, such as a "functionalized propylene-ethylene elastomer".

[0059] In one or more embodiments of the invention, the f-PBE may include at least about 4 wt% ethylene, preferably at least about 5 wt%, at least about 6 wt%, at least about 7 wt%, or at least about 8 wt%, or at least about 9 wt%, or at least about 10 wt%, or at least about 12 wt% ethylene-derived units. In those or other embodiments of the invention, the f-PBE may include up to about 30 wt% ethylene, preferably up to about 25 wt%, or up to about 22 wt%, or up to about 20 wt%, or up to about 19 wt%, or up to about 18 wt%, or up to about 17 wt% ethylene-derived units, wherein the percentages by weight are based on the combined weight of the propylene-derived units and the alpha-olefin-derived units. In other words, the f-PBE may include at least about 70 wt%, or at least about 75 wt%, or at least about 80 wt%, or at least about 81 wt% propylene derived units, or at least about 82 wt% propylene derived units, or at least about 83 wt% propylene derived units; and in these or other embodiments of the invention, the f-PBE may include up to about 95 wt%, or up to about 94 wt%, or up to about 93 wt%, or up to about 92 wt%, or up to about 90 wt%, or up to about 88 wt% propylene derived units, wherein the percentages by weight are based on the total weight of the propylene derived units and the alpha-olefin derived units. In certain embodiments of the invention, the f-PBE may contain from about 5 to about 25 wt% ethylene derived units or from about 9 to about 18 wt% ethylene derived units.

[0060] In embodiments, where the f-PBE is produced by reacting a PBE with oxygen, either alone or in situ with other components, as an at least partial melt blend with a polyalphaolefin. As disclosed herein, the reaction of the PBE with oxygen according to embodiments of the present disclosure does not significantly change the rheological properties and other physical properties of the f-PBE, such as molecular weight and melting point, relative to the rheological properties and other physical properties of the PBE prior to reaction with oxygen according to the present disclosure. In one or more embodiments, the amount of grafting and / or functionalization with oxygen present in or on the functionalized propylene-based elastomer (f-PBE) is limited to an amount that does not significantly affect the rheological properties of the f-PBE relative to the PBE prior to reaction with oxygen at elevated temperatures, except for those related to hydrophobicity and other properties related to oxygen-containing functional groups. Therefore, unless otherwise noted, the rheological and other properties of the f-PBE are identified as being substantially the same, or having the differences noted. As discussed herein, most rheological properties vary little, if at all, between the PBE and the f-PBE. For example, it was found that the Mn of f-PBE changes by less than about 30% of the Mn of PBE, typically less than about 20% of the Mn of PBE, preferably less than about 15% of the Mn of PBE, or within about 10% of the Mn of PBE, or within about 5% of the Mn of PBE, even though the material changes from being hydrophobic (i.e., having a static contact angle greater than or equal to 90°) to being hydrophilic (i.e., having a static contact angle less than 90°).

[0061] The f-PBE of one or more embodiments of the present invention is characterized by a melting point (Tm), which can be determined by differential scanning calorimetry (DSC). For purposes herein, the maximum of the highest temperature peak is considered to be the melting point of the polymer. A "peak" in this context is defined as a change in the overall slope of the DSC curve (heat flow versus temperature) from positive to negative, resulting in a maximum, without a baseline shift, wherein the DSC curve is drawn so that an endothermic reaction would appear as a positive peak.

[0062] In one or more embodiments of the invention, the f-PBE has a Tm of less than about 115°C, or less than about 110°C, or less than about 100°C, or less than about 95°C, or less than about 90°C.

[0063] In one or more embodiments of the invention, the f-PBE can have a Hf of at least about 0.5 J / g, or at least about 1.0 J / g, or at least about 1.5 J / g, or at least about 3.0 J / g, or at least about 4.0 J / g, or at least about 5.0 J / g, or at least about 6.0 J / g, or at least about 7.0 J / g. In these or other embodiments of the invention, the f-PBE has a Hf of less than about 75 J / g, or less than about 70 J / g, or less than about 60 J / g, or less than about 50 J / g, or less than about 45 J / g, or less than about 40 J / g, or less than about 35 J / g, or less than about 30 J / g.

[0064] As used in this specification, the DSC procedure for determining Tm and Hf includes the following. The polymer is pressed at a temperature of about 200°C to about 230°C in a heated press, and the resulting polymer sheet is suspended in air under ambient conditions to cool. A polymer sheet of about 6 to 10 mg is removed with a die. The 6 to 10 mg sample is annealed at room temperature for about 80 to 100 hours. At the end of this stage, the sample is placed in a DSC (Perkin Elmer Pyris One thermal analysis system) and cooled to about -50°C to about -70°C. The sample is heated at 10°C / min to reach a final temperature of about 200°C. The sample is kept at 200°C for 5 minutes and subjected to a second cooling-heating cycle. Events from two cycles are recorded. The thermal output is recorded as the area under the sample melting peak, which usually occurs between about 0°C and about 200°C. It is measured in joules and is a measure of the Hf of the polymer.

[0065] f-PBE can have 13 C NMR measurement of 75% or more, 80% or more, 85% or more, 90% or more, 92% or more, 95% or more, or 97% or more of the three propylene units of the triad tacticity. In one or more embodiments of the present invention, the triad tacticity can be in the range of about 75 to about 99%, or about 80 to about 99%, or about 85 to about 99%, or about 90 to about 99%, or about 90 to about 97%, or about 80 to about 97%. The triad tacticity is determined by the method described in U.S. Patent No. 7,232,871.

[0066] The f-PBE may have a tacticity index ranging from a lower limit of 4 or 6 to an upper limit of 8 or 10 or 12. 13C nuclear magnetic resonance ("NMR") determines the stereoregularity index, denoted herein as "m / r". The stereoregularity index (m / r) is calculated as defined in Cheng, HN (1984) Macromolecules, Vol. 17, p. 1950, which is incorporated herein by reference. The designation "m" or "r" describes the stereochemistry of adjacent pairs of propylene groups, with "m" indicating meso and "r" indicating racemic. An m / r ratio of 1.0 generally describes a syndiotactic polymer, and an m / r ratio of 2.0 generally describes an atactic material. Isotactic materials can theoretically have a ratio approaching infinity, and many byproduct atactic polymers have sufficient isotactic content to result in a ratio greater than 50.

[0067] In one or more embodiments of the invention, the f-PBE may have a % crystallinity of about 0.5% to about 40%, or about 1% to about 30%, or about 5% to about 25%, as determined according to the DSC procedure. The crystallinity may be determined by dividing the Hf of the sample by the Hf of a 100% crystalline polymer (assumed to be 189 Joules / gram for isotactic polypropylene or 350 Joules / gram for polyethylene).

[0068] In one or more embodiments of the present invention, the f-PBE may have a room temperature (which for purposes herein is 25° C.) of about 0.85 g / cm 3 - About 0.92g / cm 3 , or about 0.86 g / cm 3 -About 0.90g / cm 3 , or about 0.86 g / cm 3 - About 0.89g / cm 3 The density of the composite is measured according to ASTM D-792 test method.

[0069] In one or more embodiments of the invention, the f-PBE can have a melt index (MI) (ASTM D-1238, 2.16 kg at 190°C) of less than or equal to about 100 g / 10 min, or less than or equal to about 50 g / 10 min, or less than or equal to about 25 g / 10 min, or less than or equal to about 10 g / 10 min, or less than or equal to about 9.0 g / 10 min, or less than or equal to about 8.0 g / 10 min, or less than or equal to about 7.0 g / 10 min.

[0070] In one or more embodiments of the invention, the f-PBE can have a melt flow rate (MFR) greater than about 0.5 g / 10 min, greater than about 1 g / 10 min, or greater than about 2 g / 10 min, or greater than about 5 g / 10 min, or greater than about 8 g / 10 min, or greater than about 10 g / 10 min, as measured according to ASTM D-1238 (Condition L, i.e., 2.16 kg weight at 230° C.). In the same or other embodiments of the invention, the f-PBE can have an MFR less than about 500 g / 10 min, or less than about 400 g / 10 min, or less than about 300 g / 10 min, or less than about 200 g / 10 min, or less than about 100 g / 10 min, or less than about 75 g / 10 min, or less than about 50 g / 10 min. In certain embodiments of the present invention, the f-PBE may have an MFR of about 1 to about 100 g / 10 min, or about 2 to about 75 g / 10 min, or about 5 to about 50 g / 10 min. Preferably, the f-PBE has an MFR of 1 to 100 g / 10 min, more preferably 20 to 50 g / 10 min.

[0071] In one or more embodiments of the present invention, the f-PBE may be a reactor grade polymer. In other embodiments of the present invention, the f-PBE may be produced from a PBE polymer that has been "visbroken" to increase the MFR after leaving the reactor and then functionalized with oxygen-containing functional groups according to the present disclosure. "Visbreaking" as used herein is a process of reducing the molecular weight of a polymer by subjecting the polymer to chain scission. The visbreaking process also increases the MFR of the polymer and may narrow its molecular weight distribution. However, it should be understood that visbreaking does not refer to the functionalized propylene-based elastomers described.

[0072] In one or more embodiments of the invention, the f-PBE can have a Mooney viscosity [ML (1+4) at 125°C] of less than about 100, or less than about 75, or less than about 50, or less than about 30, as determined in accordance with ASTM D-1646.

[0073] In one or more embodiments of the present invention, the f-PBE may have a g' index value of 0.95 or greater, or at least 0.97, or at least 0.99, where g' is measured with the Mw of the polymer using the intrinsic viscosity of isotactic polypropylene as a baseline. For use herein, the g' index is defined as:

[0074]

[0075] where η b is the intrinsic viscosity of the polymer, and η lis the intrinsic viscosity of a linear polymer having the same viscosity average molecular weight (Mv) as the polymer, where η l =KMv α , K and α are measurements for linear polymers and should be obtained on the same instrument as used for g' index measurements.

[0076] In one or more embodiments of the invention, the f-PBE can have a weight average molecular weight (Mw) of about 50,000 to about 5,000,000 g / mol, or about 75,000 to about 1,000,000 g / mol, or about 100,000 to about 500,000 g / mol, or about 125,000 to about 300,000 g / mol. In the same or other embodiments of the invention, the f-PBE can have a number average molecular weight (Mn) of about 2,500 to about 2,500,000 g / mol, or about 5,000 to about 500,000 g / mol, or about 10,000 to about 250,000 g / mol, or about 25,000 to about 200,000 g / mol. In the same or other embodiments of the invention, the f-PBE can have a Z-average molecular weight (Mz) of about 10,000 to about 7,000,000 g / mole, or about 50,000 to about 1,000,000 g / mole, or about 80,000 to about 700,000 g / mole, or about 100,000 to about 500,000 g / mole. In certain embodiments of the invention, the molecular weight distribution (MWD, equal to Mw / Mn) of the f-PBE can be about 1 to about 40, or about 1 to about 15, or about 1.8 to about 5, or about 1.8 to about 3.

[0077] Techniques for determining molecular weight (Mn, Mw and Mz) and MWD can be found in U.S. Pat. No. 4,540,753 (Cozewis, Ju and Ver Strate) (incorporated herein by reference for purposes of U.S. practice) and references cited therein, and Ver Strate et al. (1988) Macromolecules, Vol. 21, pp. 3360-3371 (incorporated herein by reference for purposes of U.S. practice) and references cited therein. For example, molecular weight can be determined by size exclusion chromatography (SEC) using a Waters 150 gel permeation chromatograph equipped with a differential refractive index detector and calibrated using polystyrene standards.

[0078] Optionally, the f-PBE may also include one or more dienes. The term "diene" is defined as a hydrocarbon compound having two sites of unsaturation, i.e., a compound having two double bonds connecting carbon atoms. Depending on the context, the term "diene" in this patent refers broadly to a diene monomer prior to polymerization (e.g., forming a portion of the polymerization medium), or a diene monomer after polymerization has begun (also referred to as a diene monomer unit or a diene-derived unit). Exemplary dienes suitable for use in the present invention include, but are not limited to, butadiene, pentadiene, hexadiene (e.g., 1,4-hexadiene), heptadiene (e.g., 1,6-heptadiene), octadiene (e.g., 1,7-octadiene), nonadiene (e.g., 1,8-nonadiene), decadiene (e.g., 1,9-decadiene), undecadiene (e.g., 1,10-undecadiene), dodecadiene (e.g., 1,11-dodecadiene), tridecadiene (e.g., 1,12-tridecadiene). Examples of branched acyclic dienes include, but are not limited to, 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, and 3,7-dimethyl-1,7-octadiene. Examples of monocyclic alicyclic dienes include, but are not limited to, 1,4-cyclohexadiene, 1,5-cyclooctadiene, and 1,7-cyclododecadiene. Examples of polycyclic alicyclic fused and bridged cyclodienes include, but are not limited to, tetrahydroindene, norbornadiene, methyltetrahydroindene, dicyclopentadiene, bicyclo(2.2.1)hept-2,5-diene, and alkenyl norbornene, alkylidene norbornene, cycloalkenyl norbornene, and cycloalkylidene norbornene [including, for example, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene, and 5-vinyl-2-norbornene]. Examples of cycloalkenyl substituted olefins include, but are not limited to, vinylcyclohexene, allylcyclohexene, vinylcyclooctene, 4-vinylcyclohexene, allylcyclodecene, vinylcyclododecene, and tetracyclododecadiene.In some embodiments of the present invention, the diene is selected from 5-ethylidene-2-norbornene (ENB), 1,4-hexadiene, 5-methylene-2-norbornene (MNB), 1,6-octadiene, 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, 1,3-cyclopentadiene, 1,4-cyclohexadiene, vinyl norbornene (VNB), dicyclopentadiene (DCPD), and combinations thereof. In one or more embodiments of the present invention, the diene is ENB.

[0079] In some embodiments of the invention, the f-PBE may optionally contain 0.05 to about 6 weight percent diene-derived units. In other embodiments of the invention, the polymer contains about 0.1 to about 5.0 weight percent diene-derived units, or about 0.25 to about 3.0 weight percent diene-derived units, or about 0.5 to about 1.5 weight percent diene-derived units.

[0080] The polymerization of PBE is carried out by reacting the monomers at a temperature of 0°C to 200°C in the presence of a catalyst system for a time period of 1 second to 10 hours, the PBE being the material prior to functionalization with oxygen-containing functional groups. Preferably, homogeneous conditions are used, such as a bulk polymerization process or a continuous solution process using excess monomer as a diluent. A continuous process may use some form of agitation to reduce concentration differences in the reactor and maintain steady state polymerization conditions. Although an internal cooling system may be used, it is preferred to remove the heat of the polymerization reaction by cooling the polymerization feed and allowing the polymerization to heat the polymerization.

[0081] Further description of exemplary processes and catalyst systems suitable for preparing the PBEs described herein can be found in U.S. Pat. No. 6,881,800 and U.S. Pat. No. 10,059,081, which are incorporated herein by reference for purposes of U.S. practice.

[0082] The triad stereoregularity and stereoregularity index of PBE can be controlled by the catalyst (which affects the stereoregularity of the propylene arrangement), the polymerization temperature (which can reduce stereoregularity by increasing the temperature), and by the type and amount of comonomer (which tends to reduce the level of longer propylene-derived sequences).

[0083] Too much comonomer can reduce the crystallinity provided by the crystallization of stereoregular propylene-derived sequences to the point where the material lacks strength; too little and the material can be over-crystalline. 13C nuclear magnetic resonance (NMR) measures the comonomer content and sequence distribution of polymers. Comonomer content of discrete molecular weight ranges can be measured using methods known to those skilled in the art, including Fourier transform infrared spectroscopy (FTIR) in conjunction with samples from GPC, as described in Wheeler and Willis (1993) Applied Spectroscopy, Vol. 47, pp. 1128-1130. For propylene ethylene copolymers containing greater than 75 wt. % propylene, the comonomer content (ethylene content) of such polymers can be measured as follows: a thin uniform film is pressed at a temperature of about 150° C. or higher and mounted on a Perkin Elmer PE 1760 infrared spectrophotometer. The sample is recorded from 600 cm -1 Up to 4,000cm -1 The full spectrum of ethylene can be calculated according to the following equation: Ethylene weight % = 82.585-111.987X + 30.045X 2 , where X is at 1,155cm -1 The peak height at 722cm -1 or 732cm -1 For propylene ethylene copolymers having 75 wt% or less propylene content, the comonomer (ethylene) content can be measured using the procedure described in Wheeler and Willis.

[0084] Reference is made to US Pat. No. 6,525,157, whose test methods are also fully applicable to the various measurements mentioned in this specification, and which contains more details on GPC measurement, determination of ethylene content by NMR, and DSC measurement.

[0085] Catalysts can also control stereoregularity in combination with comonomers and polymerization temperature. The PBE described herein can be prepared using one or more catalyst systems, which are then reacted with oxygen at elevated temperatures according to the embodiments disclosed herein. As used herein, a "catalyst system" comprises at least a transition metal compound (also referred to as a catalyst precursor) and an activator. In the solution upstream of the polymerization reactor or in the polymerization reactor of the disclosed process, the transition metal compound (catalyst precursor) and the activator are contacted to produce the catalytically active component (catalyst) of the catalyst system. Any given transition metal compound or catalyst precursor can produce a catalytically active component (catalyst) with a variety of activators, providing a wide range of catalysts that can be configured in the process of the present invention. A suitable catalyst system can include at least one transition metal compound and at least one activator. However, the catalyst system can also include more than one transition metal compound and one or more activators. Such a catalyst system can optionally include an impurity scavenger.

[0086] The catalyst system for preparing PBE can include a metallocene compound, such as a bridged bis-indenyl metallocene. The activator for preparing PBE can include a cationic component and an anionic component (which together form an activator compound) as well as an aluminoxane and an alkyl aluminum. In addition, a combination of two different activators can be used with the same or different (one or more) metallocenes. In addition, in addition to the transition metal compounds and activators described above, the catalyst system suitable for use in the present invention may also contain additional activators (co-activators) and / or scavengers. Co-activators are compounds that are capable of reacting with transition metal complexes so that when used with activators, active catalysts are formed. Scavengers can be used to "scavenge" the reaction of any poisons that would otherwise react with the catalyst and deactivate it. Further description of the catalyst system for preparing PBE can be found in U.S. Pat. No. 10,059,081.

[0087] In one or more embodiments of the present invention, at least a portion of the propylene-based elastomer is functionalized (i.e., grafted with oxygen-containing functional groups) by reacting the PBE with an oxygen-containing gas at a temperature greater than the melting point of the PBE to form a functionalized propylene-based elastomer comprising oxygen-containing functional groups; preferably, the oxygen-containing functional groups are selected from carboxylic acids, anhydrides, ketones, carbonates, esters, ethers, lactones, and combinations thereof, and may be located pendant to the carbon-carbon backbone of the elastomer, such as pendant carboxylic acids, anhydrides, esters, ketones, carbonates, alcohols, ethers, lactones, etc., and / or at the ends of the polymer chains, and / or within the elastomer backbone forming a continuous molecular chain of the polymer (e.g., esters and ethers), and / or between polymer chains forming ethers, anhydrides, and / or ester linkages between pendant groups of two or more polymer chains. As used herein, the term "functionalized" or "grafted" means that oxygen is covalently bonded to the polymer chain and / or within the polymer backbone of the PBE.

[0088] In addition to oxygen-containing functional groups, prior to reacting the PBE according to embodiments disclosed herein with oxygen, the PBE can first be grafted with one or more grafting monomers, which can include at least one ethylenically unsaturated carboxylic acid or acid derivative, such as anhydrides, esters, salts, amides, imides, acrylates, and the like. Illustrative monomers include, but are not limited to, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, 4-methylcyclohexene-1,2-dicarboxylic anhydride, bicyclo(2.2.2)octene-2,3-dicarboxylic anhydride, 1,2,3,4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic anhydride, 2-oxa-1,3-diketospiro(4.4)nonene, bicyclo(2.2.1)heptene-2,3-dicarboxylic anhydride, maleopimaric acid, tetrahydrophthalic anhydride, norbornene-2,3-dicarboxylic anhydride, nadic anhydride, methylnadic anhydride, himic anhydride, methyl himic anhydride, and 5-methylbicyclo(2.2.1)heptene-2,3-dicarboxylic anhydride. Other suitable grafting monomers include methyl acrylate and higher alkyl acrylates, methyl methacrylate and higher alkyl methacrylates, acrylic acid, methacrylic acid, hydroxymethyl methacrylate, hydroxyethyl methacrylate and higher hydroxyalkyl methacrylates and glycidyl methacrylate.

[0089] In one or more embodiments of the present invention, the functionalized propylene-based elastomer comprises from about 0.01 wt% to about 10 wt% oxygen, based on the total amount of functionalized propylene-based elastomer present, more preferably from about 0.1 wt% to about 5 wt%, more preferably from about 0.5 wt% to about 3 wt%; in other embodiments of the present invention, from about 0.5 wt% to about 5 wt%, more preferably from about 1 wt% to about 3 wt%. In a preferred embodiment, the functionalized propylene-based elastomer comprises from about 0.5 wt% to about 3 wt% oxygen, preferably from about 0.7 wt% to about 1.5 wt% oxygen, which is present as oxygen-containing functional groups selected from carboxylic acids, anhydrides, ketones, carbonates, esters, ethers, lactones, and combinations thereof.

[0090] Suitable propylene-based elastomers include Vistamaxx elastomers (ExxonMobil).Such polymers are known to blend well with other polyolefins, but are known not to form cohesive compositions when blended with non-polyolefins due to the lack of polar groups in the backbone molecular chain or on pendant groups.

[0091] Applicants have discovered that functionalized propylene-based elastomers (f-PBEs) can be successfully blended with non-polyolefin materials by functionalizing the propylene-based elastomer with a polar material. This is in contrast to known methods, which include reaction and post-treatment with grafting agents such as maleic anhydride and the like, which significantly increase the cost and complexity of such methods. Applicants have discovered that according to embodiments disclosed herein, the reaction of propylene-based elastomers with oxygen at elevated temperatures results in an effective means of increasing the polarity of the propylene-based elastomer, thereby enhancing properties relative to blends with other polymers and other properties disclosed herein.

[0092] In one or more embodiments, the propylene-based elastomer is reacted with oxygen (diatomic oxygen) at an elevated temperature to produce a functionalized propylene-based elastomer. It has been found that the amount of functionalization can also be controlled by appropriate selection of temperature, reaction time, polymer composition, etc. to produce f-PGE. Polarity can be improved after the adjusted oxidation treatment because polar oxygen-containing functional groups, mainly those containing carbonyl groups, are formed in the elastomer backbone and / or in the side groups. As a result, an improved interaction is obtained between the previously non-polar / non-reactive backbone and the polar material, which results in improved performance of blends with polar polymers or other materials (e.g., fillers, other polymers, organic or inorganic modifiers, etc.).

[0093] In one or more embodiments, the functionalized propylene-based elastomer comprises ethylene. In at least one embodiment, the functionalized propylene-based elastomer is prepared from a propylene-based elastomer, and the propylene-based elastomer is composed of propylene and ethylene or is substantially composed of propylene and ethylene. It has been found that the propylene-ethylene elastomer with a relatively low ethylene concentration is oxidized (functionalized) to a greater extent in a given time period and / or is oxidized (functionalized) to a greater extent at a lower temperature than the propylene-ethylene elastomer with a relatively high ethylene concentration. Therefore, the propylene-ethylene elastomer with an appropriate amount of ethylene can be selected for subsequent functionalization according to the embodiments disclosed herein to adjust the functionalization amount required for producing a specific blend or producing a material with a specific property such as hydrophilicity or stability in a blend with a polar material.

[0094] Likewise, the temperature at which the propylene-based elastomer is functionalized can also be controlled to adjust the polarity of the resulting functionalized propylene-based elastomer. In one or more embodiments, the propylene-based elastomer, preferably a propylene-ethylene elastomer, is contacted with oxygen at a temperature greater than the melting point of the elastomer to form the functionalized propylene-based elastomer. In one or more embodiments, the propylene-based elastomer, preferably a propylene-ethylene elastomer, is contacted with oxygen (as a gas) at a temperature greater than or equal to about 200°C, preferably greater than or equal to about 230°C, or greater than or equal to about 250°C, or greater than or equal to about 270°C, or greater than or equal to about 280°C. In one or more embodiments, the propylene-based elastomer, preferably a propylene-ethylene elastomer, is contacted with oxygen at a specified temperature greater than the melting point of the elastomer for a period of time greater than or equal to about 1 minute (also referred to herein as a residence time) to form the functionalized propylene-based elastomer. In one or more embodiments, the residence time at the specified temperature is greater than or equal to about 2 minutes, or greater than or equal to about 5 minutes, or greater than or equal to about 7 minutes, or greater than or equal to about 10 minutes, and less than or equal to about 60 minutes, or less than or equal to about 30 minutes, or less than or equal to about 25 minutes, or less than or equal to about 20 minutes.

[0095] In one or more embodiments, the presence of oxygen-containing functional groups on or within the elastomer chain is observed by the presence of an increased amount of carbonyl functional groups relative to the amount of carbonyl functional groups present in the first propylene-based elastomer, if any, as measured using the same method under substantially the same conditions, such as by the presence of about 1,780 cm-1 in the infrared spectrum of the functionalized propylene-based elastomer. -1 - Approx. 1,690cm -1 The absorption relative to the first propylene-based elastomer is about 1,780 cm in the infrared spectrum. -1 - Approx. 1,690cm -1 The residence time necessary to produce the desired functionalized propylene-based elastomer for a particular temperature or temperature range can therefore be determined, at least in part, by monitoring the infrared spectrum of the material during heating in air or another oxygen-containing gas. However, it should be noted that applicants have also discovered that the amount of shear present during the mixing and contacting of the propylene-based elastomer with oxygen to form the functionalized propylene-based elastomer increases the rate of functionalization, thereby reducing the necessary residence time indicated by static infrared analysis.

[0096] In addition to the indicated approx. 1,780cm -1 - Approx. 1,690cm -1 In addition to the carbonyl stretch absorption, other absorptions in the infrared spectrum attributed to carboxylic acids, anhydrides, ketones, carbonates, esters, ethers and / or lactones may also be monitored to indicate the desired level of functionalization.

[0097] In one or more embodiments, the functionalized propylene-based elastomer comprises ethylene and is therefore prepared from a corresponding propylene-based elastomer comprising ethylene, which in some embodiments is a propylene-ethylene elastomer. In one or more such embodiments, ethylene is present in the functionalized propylene-based elastomer at greater than about 4 wt%, or greater than about 5 wt%, or greater than about 6 wt%, or greater than about 7 wt%, or greater than about 8 wt%, and less than or equal to about 10 wt%, or less than or equal to about 9 wt%, based on the total amount of functionalized propylene-based elastomer present. Thus, the functionalized propylene-ethylene elastomer is produced by contacting a corresponding propylene-ethylene elastomer having a corresponding ethylene amount, i.e., about 4 wt%-10 wt%, preferably about 4 wt%-about 5 wt%, based on the total amount of propylene-ethylene elastomer present.

[0098] In order to functionalize the propylene-based elastomer, the propylene-based elastomer is contacted with oxygen at an elevated temperature in the absence of any antioxidant or antioxidant package. However, it should be understood that once a functionalized propylene-based elastomer is produced, any suitable antioxidant or antioxidant package and / or any other component can be included with the functionalized propylene-based elastomer or a composition comprising the functionalized propylene-based elastomer. For example, in one embodiment, a functionalized propylene-based elastomer is produced and then combined with one or more antioxidants in a subsequent process. In an alternative embodiment, a suitable propylene-based elastomer is contacted with oxygen for a suitable time period at a suitable temperature in an extruder, for example, to produce a functionalized propylene-based elastomer, and then one or more antioxidants and / or any other components are incorporated into the composition in the same extruder or in the same extrusion or mixing process.

[0099] The blends described above can be produced by mixing the elastomer of the invention with one or more polymers (as described above), by connecting reactors together in series to make reactor blends, or by using more than one catalyst in the same reactor to produce multiple polymer species. The polymers can be mixed together before being placed in the extruder or can be mixed in the extruder while the PGE is contacted with oxygen at elevated temperatures to form f-PGE.

[0100] The blend can be formed using conventional equipment and methods, such as by dry blending the individual components and then melt mixing in a mixer, or by mixing the components together directly in a mixer, such as a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single or twin screw extruder, which can include a compounding extruder and a side arm extruder used directly downstream of the polymerization process, which can include powders or pellets of the blended resin at the extruder hopper. In addition, additives can be added to the blend, to one or more components of the blend, (at any point along the formation process), and / or to the product formed from the blend (e.g., desired pellets, masterbatch, film, and / or article). Such additives are well known in the art and may include, for example: fillers; antioxidants (e.g., hindered phenols such as IRGANOX 1010 or IRGANOX 1076 available from Ciba-Geigy); phosphites (e.g., IRGAFOS 168 available from Ciba-Geigy); anti-stick additives; tackifiers such as polybutene, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metals and glycerol stearate; and hydrogenated rosin; UV stabilizers; heat stabilizers; anti-blocking agents; release agents; antistatic agents; pigments; colorants; dyes; waxes; silica; fillers; talc, etc.

[0101] In embodiments, the functionalized propylene-based elastomer may be formed within or added to other components to form a melt blended composition. In embodiments, the functionalized propylene-based elastomer is adjusted to have a polarity sufficient to prepare a stable melt blended composition comprising an intimate mixture of the functionalized propylene-based elastomer and the polyalphaolefin.

[0102] Functionalized propylene-based elastomers and blends (melt blended compositions) containing functionalized propylene-based elastomers also show improved surface properties. For example, functionalization of the propylene-based elastomer converts the material from a hydrophobic material (having a static water contact angle greater than 90° when measured according to ASTM D7490) to a hydrophilic material (having a static water contact angle less than 90°, preferably less than 88°, preferably less than 85° when measured according to ASTM D7490 or its equivalent). Likewise, the melt blended composition containing the functionalized propylene-based elastomer becomes hydrophilic, indicating the presence of the functionalized propylene-based elastomer on the surface of the material.

[0103] Depending on the intended purpose, various additives can be incorporated into the polymer blends described herein. For example, when using the blend to form fibers and weave or knit fabrics, such additives can include but are not limited to stabilizers, antioxidants, fillers, colorants, nucleators, dispersants, mold release agents, slip agents, flame retardants, plasticizers, pigments, vulcanization or curing agents, vulcanization or curing accelerators, curing delay agents, processing aids, tackifying resins, etc. Other additives can include fillers and / or reinforcing materials, such as carbon black, clay, talcum, calcium carbonate, mica, silicon oxide, silicates, their combinations, etc. Primary and secondary antioxidants include, for example, hindered phenols, hindered amines, and phosphates. Nucleators include, for example, sodium salts, such as sodium stearate, sodium ionomers, and plasticizers such as poly (ether esters). In addition, in order to improve crystallization rate, other nucleators such as Ziegler-Natta olefin products or other highly crystalline polymers can also be used. Other additives such as dispersants (such as Acrowax C) can also be included. Slip agents include, for example, oleamide and erucamide.Catalyst deactivators such as calcium stearate, hydrotalcite, and calcium oxide, and / or other acid neutralizers known in the art are also commonly used.

[0104] In addition, in some exemplary embodiments, the f-PBE and any additives can be incorporated into the polyalphaolefin blend directly or as part of a masterbatch, i.e., the f-PBE and / or an additive package containing several additives added at once in a predetermined ratio can be included. In one or more embodiments herein, the composition of the present invention also comprises a masterbatch. The masterbatch can be added in any suitable amount to achieve the desired result. For example, a masterbatch containing one or more additional additives or components can be used in an amount ranging from about 0.1 to about 10 weight percent, or about 0.25 to about 7.5 weight percent, or about 0.5 to about 5 weight percent, or about 1 to about 5 weight percent, or about 2 to about 4 weight percent, based on the total weight of the polymer blend and the masterbatch.

[0105] In any embodiment, the polyalphaolefin functionalized propylene-based elastomer (PA-f-PBE) blend can be formed into continuous filaments, yarns, and conventional woven or knitted textiles. Conventional fiber operations, including continuous filaments and a large number of continuous filaments, can be used as a means of producing the fibers of the blends of the present invention. Typically, the polyalphaolefin functionalized propylene-based elastomer blend is dried to less than 0.004% by weight moisture before use, and the molten blend is extruded at 280°C-285°C through a single filament or multifilament hole die (spinneret) with a diameter of 0.05mm to 1mm (e.g., 0.3-0.8mm), typically through a manifold, static mixer, metering pump, and / or spinning assembly. The spinneret typically has 50-250 holes. From the spinneret, the filaments typically pass through a quench chamber, a spinning finish applicator, a winder, etc. The filaments are typically 1 to 10 deniers, and multifilament yarns are typically 40 to 2,000 deniers. In certain embodiments, the fiber may have a thickness of about 1 to about 10 denier, or about 2 to about 8 denier, or about 4 to about 6 denier. The spinning speed may be 500 m / min to 9,000 m / min, but is typically 1,000 m / min to 4,000 m / min. The monofilaments or yarns may be woven or knitted into fabrics or textiles using conventional weaving and knitting equipment and techniques.

[0106] In one or more embodiments, the present invention relates to melt-spun (e.g., meltblown or spunbond) fibers and nonwoven compositions (e.g., fabrics) comprising the above-mentioned polymer blends. As used herein, "melt-spun nonwoven compositions" refer to compositions having at least one melt-spun layer, and the entire composition is not required to be melt-spun or nonwoven. In some embodiments, the nonwoven composition additionally comprises one or more layers on one or both sides of the nonwoven layer (one or more) comprising the PA-f-PBE blend. As used herein, "nonwoven" refers to a textile material prepared by a method other than weaving. In nonwoven fabrics, the fibers are directly processed into a planar sheet-like fabric structure and then chemically bonded, thermally bonded, or mechanically interlocked (or both) to achieve a bonded fabric.

[0107] In some embodiments, the method also includes forming a nonwoven composition from fibers. In other embodiments, a nonwoven composition formed by a polyalphaolefin functionalized propylene-based elastomer blend is used as a face layer, and the process may also include forming one or more nonwoven elastic layers and arranging the face layer comprising the polyalphaolefin functionalized propylene-based elastomer blend on the elastic layer. Optionally, two or more face layers may be arranged on one or more elastic layers on opposite sides so that the elastic layer is sandwiched between the face layers. In one or more embodiments, one or more elastic layers may include a polyalphaolefin functionalized propylene-based elastomer with the composition and properties described above. In certain embodiments, the nonwoven composition comprising the polyalphaolefin functionalized propylene-based elastomer blend may be described as extensible. As used herein, "extensible" means any fiber or nonwoven composition that yields or deforms (i.e. stretches) when a force is applied. Although many extensible materials are also elastic, the term extensible also includes those materials that remain extended or deformed after the force is removed. When an extensible top layer is used in combination with an elastic core layer, desirable aesthetic properties can be produced because the extensible layer permanently deforms when the attached elastic layer stretches and retracts. This results in a wrinkled or textured outer surface with a soft feel, which is particularly suitable for articles where the top layer contacts the wearer's skin.

[0108] Can form fiber and nonwoven composition of the present invention by any method known in the art.For example, can produce nonwoven composition by meltblowing or spunbond process.In certain embodiments herein, produce one or more layers of nonwoven composition of the present invention by spunbond process.When composition also comprises one or more elastic layers, can produce elastic layer by meltblowing process, by spunbond or spunlace (spunlace) process or by any other applicable nonwoven process.

[0109] As used herein, "meltblown fibers" and "meltblown compositions" (or "meltblown fabrics") refer to fibers formed by extruding a molten thermoplastic material through a plurality of fine, usually circular die capillaries as molten strands or filaments into a high-speed, usually hot gas stream at a certain processing temperature, the gas stream attenuating the filaments of the molten thermoplastic material to reduce their diameter, which may be a microfiber diameter. Thereafter, the meltblown fibers are carried by the high-speed gas stream and deposited on a collecting surface to form a web or nonwoven fabric of randomly dispersed meltblown fibers. Such processes are generally described, for example, in U.S. Patent Nos. 3,849,241 and 6,268,203. Meltblown fibers are continuous or discontinuous microfibers and, depending on the resin, may be less than about 10 microns or, in certain high-yield processes such as those described herein, meltblown fibers may have a diameter greater than 10 microns, for example, about 10 to about 30 microns, or about 10 to about 15 microns. The term meltblown as used herein is meant to include melt-blowing processes.

[0110] Commercial meltblowing processes use extrusion systems with a relatively high output of more than 0.3 grams per hole per minute ("ghm"), or more than 0.4 ghm, or more than 0.5 ghm, or more than 0.6 ghm, or more than 0.7 ghm. Commercial meltblowing processes, preferably high pressure meltblowing processes available from Biax-Fiberfilm Corporation, can be used to produce the nonwoven compositions of the present invention, or in a test or pilot scale process. In one or more embodiments of the present invention, an extrusion system having a production rate of about 0.01 to about 3.0 ghm, or about 0.1 to about 2.0 ghm, or about 0.3 to about 1.0 ghm is used to form the fibers for forming the nonwoven compositions.

[0111] In common spunbond process, polymer is supplied to heated extruder to melt and homogenize polymer. Extruder supplies molten polymer to spinneret, where polymer is fiberized by one or more rows of fine openings arranged in spinneret, thereby forming filament curtain. Fibrils are usually quenched with air at low temperature, pulled (usually pneumatically) and deposited on moving pad, belt or "forming line" to form nonwoven composition. For example, see U.S. Patent No. 4,340,563, 3,692,618, 3,802,817, 3,338,992, 3,341,394, 3,502,763 and U.S. Patent No. 3,542,615. As used herein, term spunbond means including spunlace process, wherein high-speed water jet is used to entangle filaments to form a net (referred to as "hydraulic entanglement").

[0112] The fibers produced in the spunbond process typically have diameters in the range of about 10 to about 50 microns, depending on the process conditions and the desired end use of the fabric produced from such fibers. For example, increasing the polymer molecular weight or decreasing the processing temperature results in larger diameter fibers. Changes in quench air temperature and pneumatic draw pressure also have an effect on fiber diameter.

[0113] Nonwoven compositions described herein can be monolayer or can be multilayer laminate.One application is to make laminate (or "composite") by meltblown ("M") and spunbond ("S") nonwoven compositions, which combines the strength from the spunbond component and the benefit of the better barrier properties of the meltblown component.Common laminates or composites have three or more layers, meltblown layers (one or more) sandwiched between two or more spunbond layers, or "SMS" nonwoven composites.Other combined examples are SSMMSS, SMMS and SMMSS composites.Meltblown or spunbond nonwovens of the present invention can also be made of composite materials with other synthetic or natural materials to produce useful products.

[0114] The nonwoven products described above can be used in many articles, such as sanitary products, including but not limited to diapers, feminine care products and adult incontinence products. The nonwoven products can also be used in medical products, such as sterile wraps, isolation gowns, operating room gowns, surgical gowns, surgical drapes, first aid dressings and other disposable items.

[0115] Having described various aspects of the compositions herein, additional specific embodiments of the invention include those listed in the following paragraphs:

[0116] A1. A composition comprising:

[0117] i) C2-C 12 Polyalphaolefins; and

[0118] ii) a functionalized propylene-based elastomer comprising from about 4 to about 25 weight percent of a propylene-based elastomer derived from one or more C2 or C4-C 12 Units of alpha-olefins;

[0119] A triad tacticity of greater than about 90%;

[0120] A heat of fusion of less than about 75 J / g; and

[0121] The plurality of oxygen-containing functional groups are selected from carboxylic acids, anhydrides, ketones, carbonates, esters, ethers, lactones and combinations thereof.

[0122] A2. A composition according to embodiment A1, wherein the functionalized propylene-based elastomer comprises from about 0.01 wt% to about 10 wt% oxygen, preferably from about 0.1 wt% to 5 wt% oxygen, based on the total amount of functionalized propylene-based elastomer present.

[0123] A3. The composition according to embodiment A1 or A2, wherein the functionalized propylene-based elastomer comprises an MFR greater than or equal to about 20 when measured according to ASTM D-1238 (Condition L, ie, 230° C. with 2.16 kg weight).

[0124] A4. The composition according to any of Embodiments A1 to A3, wherein the functionalized propylene-based elastomer comprises ethylene.

[0125] A5. The composition according to embodiment A4, wherein the functionalized propylene-based elastomer comprises greater than or equal to about 10 weight percent ethylene, based on the total amount of functionalized propylene-based elastomer present.

[0126] A6. The composition according to any one of embodiments A1 to A5, having a static water contact angle of less than 90°, preferably less than 85°, preferably less than 82°, when measured according to ASTM D7490 or its equivalent.

[0127] A7. The composition according to any one of embodiments A1 to A6, wherein the functionalized propylene-based elastomer is the reaction product of:

[0128] i) a gas containing diatomic oxygen; and

[0129] ii) a first propylene-based elastomer comprising from about 4 to about 25 weight percent of a propylene-based elastomer derived from one or more C2 or C4-C 12 alpha-olefin units and having a triad tacticity greater than about 90% and a heat of fusion less than about 75 J / g,

[0130] The contacting is performed at a temperature greater than about 200° C. and less than or equal to about 260° C. for a period of time greater than about 1 minute, preferably about 2 minutes to about 20 minutes.

[0131] A8. The composition according to embodiment A7, wherein the percentage difference in Mn of the functionalized propylene-based elastomer is less than about 30%, preferably less than about 15%, or less than about 10% of the Mn of the first propylene-based elastomer when determined according to the formula:

[0132] [( 1 Mn-Mn f ) / 1 Mn]*100%;

[0133] in 1 Mn is the Mn of the first propylene-based elastomer as determined by GPC, and Mn f is the Mn of the functionalized propylene-based elastomer as determined by GPC.

[0134] A9. The composition of any of Embodiments A1 to A8, wherein the functionalized propylene-based elastomer comprises an increased amount of carbonyl functional groups relative to the amount of carbonyl functional groups present in the first propylene-based elastomer, if any, as measured by a carbonyl functional group at about 1,780 cm-1 in an infrared spectrum of the functionalized propylene-based elastomer when measured using the same method under substantially the same conditions. -1 - Approx. 1,690cm -1 The absorption relative to the first propylene-based elastomer is about 1,780 cm in the infrared spectrum. -1 - Approx. 1,690cm -1 The increase in absorption was measured.

[0135] A10. A composition according to any one of embodiments A1 to A9, wherein C2-C 12 The polyalphaolefin comprises greater than about 50 mol% propylene, preferably isotactic polypropylene homopolymer.

[0136] A11. The composition according to embodiment A10, wherein the polyalphaolefin further comprises ethylene, butene, pentene, hexene, 4-methyl-1-pentene, octene, decene, or a combination thereof.

[0137] A12. The composition according to any one of embodiments A1 to A11, wherein the polyalphaolefin is isotactic polypropylene having an MFR greater than about 30 when measured according to ASTM D-1238 (Condition L, ie, 230° C. at 2.16 kg weight).

[0138] A13. The composition according to any of Embodiments A1 to A12, comprising from about 10 wt% to about 40 wt% of the functionalized propylene-based elastomer, based on the total amount of the functionalized propylene-based elastomer and the polyalphaolefin present.

[0139] A14. The composition according to any of Embodiments A1 to A12, comprising from about 70 wt% to about 90 wt% of the functionalized propylene-based elastomer, based on the total amount of the functionalized propylene-based elastomer and the polyalphaolefin present.

[0140] A15. The composition according to any of Embodiments A1 to A14, wherein the functionalized propylene-based elastomer comprises ethylene, and the ethylene is present at about 4 wt% to about 10 wt%, based on the total amount of functionalized propylene-based elastomer present.

[0141] A16. The composition of any of Embodiments A1 to A15, wherein the functionalized propylene-based elastomer has an Mn greater than 50,000 and an Mw / Mn greater than 2 when measured by GPC.

[0142] A17. The composition according to any of embodiments A1 to A16, wherein the functionalized propylene-based elastomer has an elastic modulus greater than about 5 MPa when measured according to ASTM D638 or its equivalent.

[0143] A18. The composition according to any of embodiments A1 to A17, wherein the functionalized propylene-based elastomer has a strain at break of less than about 10 mm / mm when measured according to ASTM D638 or its equivalent.

[0144] A19. The composition according to any of embodiments A1 to A18, wherein the functionalized propylene-based elastomer has a yield stress greater than about 5 MPa when measured according to ASTM D638 or its equivalent.

[0145] A20. The composition according to any of embodiments A1 to A19, wherein the functionalized propylene-based elastomer has a stress at break greater than about 5 MPa when measured according to ASTM D638 or its equivalent.

[0146] A21. Methods, comprising:

[0147] contacting a first propylene-based elastomer with an oxygen-containing gas at a temperature of about 200° C. or greater for a period of time sufficient to form a functionalized propylene-based elastomer comprising about 4 to about 25 weight percent of a propylene-based elastomer derived from one or more C2 or C4-C 12 Units of alpha-olefins;

[0148] A triad tacticity of greater than about 90%;

[0149] A heat of fusion of less than about 75 J / g; and

[0150] greater than about 0.1 weight percent of oxygen-containing functional groups selected from the group consisting of carboxylic acids, anhydrides, ketones, carbonates, esters, ethers, lactones, and combinations thereof; and

[0151] Melt mixing a functionalized propylene-based elastomer with one or more C2-C 12 A polyalphaolefin to form a blend composition according to any one of Embodiments A1 to A20.

[0152] A22. Methods, comprising:

[0153] contacting a first propylene-based elastomer with an oxygen-containing gas at a temperature of about 200° C. or greater for a period of time sufficient to form a functionalized propylene-based elastomer comprising about 4 to about 25 weight percent of a propylene-based elastomer derived from one or more C2 or C4-C 12 Units of alpha-olefins;

[0154] A triad tacticity of greater than about 90%;

[0155] A heat of fusion of less than about 75 J / g; and

[0156] greater than about 0.1 weight percent of oxygen-containing functional groups selected from the group consisting of carboxylic acids, anhydrides, ketones, carbonates, esters, ethers, lactones, and combinations thereof; and

[0157] Melt mixing a functionalized propylene-based elastomer with one or more C2-C 12 polyalphaolefin to form a blend composition.

[0158] A23. The method according to any of embodiments A21 or A22, wherein the first propylene-based elastomer is contacted with the oxygen-containing gas at a temperature of about 230°C to about 260°C for a period of time greater than about 5 minutes.

[0159] A24. The method according to any one of embodiments A21 to A23, wherein the oxygen-containing gas is air.

[0160] A25. The method of any of Embodiments A21 to A24, wherein the first propylene-based elastomer is contacted with the oxygen-containing gas at a temperature greater than or equal to about 200°C in the absence of an antioxidant and / or antioxidant package.

[0161] A26. The method of any of Embodiments A21 to A25, wherein the first propylene-based elastomer comprises greater than about 10 weight percent ethylene, based on the total amount of the first propylene-based elastomer present.

[0162] A27. The method according to any of embodiments A21 to A26, wherein the blend composition comprises from about 10 wt% to about 40 wt% of the functionalized propylene-based elastomer, based on the total amount of the functionalized propylene-based elastomer and the polyalphaolefin present.

[0163] A28. The method of any of Embodiments A21 to A27, wherein the blend composition comprises from about 70 wt% to about 90 wt% of the functionalized propylene-based elastomer, based on the total amount of the functionalized propylene-based elastomer and the polyalphaolefin present.

[0164] A29. A method according to any one of embodiments A21 to A28, wherein the first propylene-based elastomer is mixed with the polyalphaolefin prior to or simultaneously with the contacting of the first propylene-based elastomer with the oxygen-containing gas at a temperature greater than or equal to about 200°C for a period of time sufficient to form the functionalized propylene-based elastomer.

[0165] A30. A method according to any one of embodiments A21 to A29, wherein the first propylene-based elastomer and the polyalphaolefin are blended together and fed into an extruder prior to the melt mixing, wherein the contacting of the first propylene-based elastomer with the oxygen-containing gas is carried out at a temperature greater than or equal to about 200° C. for a period of time sufficient to form the functionalized propylene-based elastomer.

[0166] A31. The method according to any of embodiments A21 to A30, wherein the polyalphaolefin further comprises ethylene, butene, pentene, hexene, 4-methyl-1-pentene, octene, decene, or a combination thereof.

[0167] A32. The method according to any one of embodiments A21 to A31, wherein the polyalphaolefin is isotactic polypropylene, preferably isotactic polypropylene having an MFR greater than about 30 when measured according to ASTM D-1238 (Condition L, i.e., 2.16 kg weight at 230°C).

[0168] A33. The method according to any one of embodiments A21 to A32, wherein the blend composition has a static water contact angle of less than 90°, preferably less than 85°, preferably less than 82°, when measured according to ASTM D7490 or its equivalent.

[0169] A34. An article comprising a composition according to any one of embodiments A1 to A20.

[0170] A35. Products, including:

[0171] i) C2-C 12 Polyalphaolefins; and

[0172] ii) a functionalized propylene-based elastomer comprising from about 4 to about 25 weight percent of a propylene-based elastomer derived from one or more C2 or C4-C 12 Units of alpha-olefins;

[0173] A triad tacticity of greater than about 90%;

[0174] A heat of fusion of less than about 75 J / g; and

[0175] The plurality of oxygen-containing functional groups are selected from carboxylic acids, anhydrides, ketones, carbonates, esters, ethers, lactones and combinations thereof.

[0176] A36. An article according to embodiment A34 or A35, having a static water contact angle of less than 90°, preferably less than 85°, preferably less than 82°, when measured according to ASTM D7490 or its equivalent.

[0177] A37. The article according to any one of embodiments A34 to A36, wherein the article comprises a nonwoven fabric, a diaper or a film. Example

[0178] The following examples are used to further illustrate the various embodiments disclosed herein.

[0179] The amount of functionalization present in the propylene-based functionalized elastomer (expressed as weight % oxygen) was determined using a calibration curve obtained by relating the ratio of absorbances representing the carbonyl moiety to the known value of maleic acid grafted onto the polymer. For purposes herein, maleic acid grafted propylene-based elastomers with known amounts of maleic acid incorporation were analyzed as thin films by FTIR to determine the relative molecular mass at ~1,710 cm-1 and ~1,780cm -1 The ratio of the peak height of the carbonyl absorption peak at 2,723 cm-1 (representing the carbonyl structure) is divided by 2,723 cm-1. -1 The peak area at the peak height of the absorption at (=CH stretch) is used to normalize the amount of carbonyl functionalization to the amount of polymer present. This ratio is then correlated to the known concentration of maleic acid present in the maleic acid grafted propylene-based elastomer. A sample of the functionalized propylene-based elastomer is then analyzed by FTIR and the above ratio determined. The ratio is then used to determine the theoretical amount of maleic acid grafting. This theoretical amount of maleic acid grafting is then converted into a weight percent oxygen functionalization based on the ratio of the molecular weights of maleic acid to oxygen. Therefore, the oxygen functionalization weight percent is equal to the theoretical weight percent maleic acid determined by the corrected calibration curve, multiplied by the molar ratio of the number of moles of oxygen (mw 16 g / mol) divided by the number of moles of maleic acid (mw 116 g / mol).

[0180] Using this method, functionalization of propylene-based elastomers at 200° C. results in a theoretical maleic acid concentration range of about 4-8 wt % maleic acid at a maximum concentration over a 20 minute period. This range of conversions corresponds to functionalized propylene-based elastomers having about 0.5 wt % to about 1.2 wt % oxygen.

[0181] For the purposes of this article, molecular weights were determined using the following GPC 4D procedure. Molecular weight averages and distributions (M) were determined by using a high temperature gel permeation chromatography (Polymer Char GPC-IR) equipped with an infrared detector IR5 based on a multi-channel bandpass filter, an 18-angle light scattering detector and a viscometer. w 、M n 、M w / M n etc.), comonomer content (C2, C3, C6, etc.) and branching index (g' vis). Three Agilent PLgel 10 μm mixed-B LS columns are used to provide polymer separation. Aldrich reagent grade 1,2,4-trichlorobenzene (TCB) with 300ppm antioxidant butylated hydroxytoluene (BHT) is used as mobile phase. The TCB mixture is filtered through a 0.1 μm Teflon filter and degassed with an online degasser before entering the GPC instrument. The nominal flow rate is 1.0 ml / min, and the nominal injection volume is 200 μL. The entire system including transfer lines, columns and detectors is accommodated in an oven maintained at 145°C. The polymer sample is weighed and sealed in a standard bottle with 80 μL flow markers (heptane) added thereto. After the bottle is loaded in the autosampler, the polymer is automatically dissolved in the instrument with 8ml of added TCB solvent. Shake continuously for about 1 hour for PE samples or for 2 hours for PP samples at 160°C to dissolve the polymer. The TCB density used for concentration calculations is 1.463 g / ml at about 23°C and 1.284 g / ml at 145°C. The sample solution concentration is 0.2-2.0 mg / ml, with lower concentrations used for higher molecular weight samples. The concentration (c) at each point in the chromatogram is calculated using the following equation from the IR5 broadband signal intensity (I) minus the baseline: c=βI, where β is the mass constant. The mass recovery is calculated from the ratio of the integrated area of ​​the concentration chromatography in the elution volume to the injected mass (which is equal to the predetermined concentration multiplied by the injection loop volume). The conventional molecular weight (IR MW) is determined by combining a universal calibration relationship with a column calibration (which is performed using a series of monodisperse polystyrene (PS) standards ranging from 700 to 10 M gm / mole). The MW at each elution volume is calculated using the following equation:

[0182]

[0183] The variables with the subscript "PS" represent polystyrene, while those without the subscript represent the test sample. In this method, α PS =0.67 and K PS=0.000175, while α and K for other materials are disclosed and calculated in the literature (Sun, T. et al. (2001) Macromolecules, Vol. 34, p. 6812), except that for the purpose of the present invention and the appended claims, for linear ethylene polymers α=0.695 and K=0.000579, for linear propylene polymers α=0.705 and K=0.0002288, for linear butene polymers α=0.695 and K=0.000181, for ethylene-butene copolymers α is 0.695 and K α is 0.000579*(1-0.0087*w2b+0.000018*(w2b)^2) (where w2b is the bulk weight percentage of butene comonomer), for ethylene-hexene copolymers α is 0.695 and K is 0.000579*(1-0.0075*w2b) (where w2b is the bulk weight percentage of hexene comonomer), and for ethylene-octene copolymers α is 0.695 and K is 0.000579*(1-0.0077*w2b) (where w2b is the bulk weight percentage of octene comonomer). Unless otherwise indicated, concentrations are in g / cm 3 The molecular weight is expressed in units of g / mole, and the intrinsic viscosity (and hence K in the Mark-Houwink equation) is expressed in units of dL / g.

[0184] The comonomer composition is determined by the ratio of the IR5 detector intensities corresponding to the CH2 and CH3 channels (calibrated with a series of PE and PP homo / copolymer standards with predetermined nominal values ​​by NMR or FTIP). In particular, this provides methyl groups / 1000 total carbons (CH3 / 1000TC) as a function of molecular weight. The short chain branching (SCB) content (SCB / 1000TC) per 1000TC as a function of molecular weight is then calculated by applying a chain end correction to the CH3 / 1000TC function, assuming that each chain is linear and terminated by a methyl group at each end. The weight % comonomer is then obtained from the following expression, where f is 0.3, 0.4, 0.6, 0.8, etc. for comonomers such as C3, C4, C6, C8, etc.:

[0185] w2=f*SCB / 1000TC.

[0186] The bulk composition of the polymer from GPC-IR and GPC-4D analysis was obtained by considering the entire signal of the CH3 and CH2 channels between the integration limits of the concentration chromatogram. First, the following ratio was obtained:

[0187]

[0188] The same calibration of the ratio of CH3 and CH2 signals (as mentioned previously in obtaining CH3 / 1000TC as a function of molecular weight) was then applied to obtain the bulk CH3 / 1000TC. The bulk methyl chain ends / 1000TC (bulk CH3 ends / 1000TC) was obtained by weighting the average chain end correction over the molecular weight range.

[0189] Then in the same manner as above

[0190] w2b=f*body CH3 / 1000TC

[0191]

[0192] And the body SCB / 1000TC is transformed into body w2.

[0193] The LS detector was an 18-angle Wyatt Technology High Temperature DAWN HELEOSII. The LS molecular weight (M) at each point in the chromatogram was determined by analyzing the output of the LS using the Zimm model for static light scattering (Light Scattering from Polymer Solutions, Huglin, MB ed.; Academic Press, 1972):

[0194]

[0195] Here, ΔR(θ) is the excess Rayleigh scattering intensity measured at the scattering angle θ, c is the polymer concentration determined from IR5 analysis, A2 is the second virial coefficient, P(θ) is the shape factor of the monodisperse random coils, and Ko is the optical constant of the system:

[0196]

[0197] Where NA is Avogadro's constant, and (dn / dc) is the refractive index increment of the system. The refractive index of TCB at 145°C and λ=665nm is n=1.500. For the analysis of polyethylene homopolymers, ethylene-hexene copolymers and ethylene-octene copolymers, dn / dc=0.1048 ml / mg and A2=0.0015; for the analysis of ethylene-butene copolymers, dn / dc=0.1048*(1-0.00126*w2) ml / mg and A2=0.0015, where w2 is the weight percent of butene comonomer.

[0198] A high temperature Agilent (or Viscotek Corporation) viscometer (which has four capillaries arranged in a Wheatstone bridge configuration, and two pressure sensors) is used to determine the specific viscosity. One sensor measures the total pressure drop across the detector, and another sensor placed between the two sides of the bridge measures the pressure difference. The specific viscosity ηs of the solution flowing through the viscometer is calculated from their output. The intrinsic viscosity [η] at each point in the chromatogram is calculated by the equation [η] = ηs / c, where c is the concentration and is determined by the IR5 broadband channel output. The viscosity MW at each point is calculated as

[0199] where α ps is 0.67 and K ps It is 0.000175.

[0200] Tensile properties were obtained according to standard laboratory procedures according to ASTM D638.

[0201] Rheological data were obtained under nitrogen atmosphere using a dynamic mechanical spectrometer obtained from the Advanced Rheometrics Expansion System (ARES).

[0202] Propylene-based elastomers generally do not form compatible blends with more polar materials. The propylene-based elastomers sold under the name of propylene-based elastomers are prepared to form compatible blends with non-polyolefin materials. As shown by these examples, the functionalized propylene-based elastomers are prepared by contacting the propylene-based elastomers with oxygen (usually air) at a temperature greater than the melting point of the propylene-based elastomer, thereby forming new and novel functionalized propylene-based elastomers with increased polarity. As further shown by these examples, these new molecules generated by the oxidation treatment during processing not only allow for improved polarity, but also further allow for tailored oxidation treatment due to the formation of polar carbonyl functional groups in the chain.

[0203] As confirmed by the data below, these functionalized propylene-based elastomers exhibit excellent adhesion characteristics to polar materials while maintaining the elastomeric nature of the non-polar, non-reactive backbone provided by the elastomer.

[0204] Additionally, these improved properties can be obtained in melt blends with polar polymers and / or other materials such as fillers or organic fillers. It has also been discovered that the functionalized propylene-based elastomers also affect the surface properties of the blend, which allows for the modification of the surface properties during the formation of the blend.

[0205] Typically, during compounding applications, elevated temperatures lead to chain scission, which generally degrades the properties of the material. Contrary to expectations, it was discovered that intentionally increasing the processing temperature while compounding the propylene-based elastomers involved in the presence of oxygen leads to an oxidatively tailored process.

[0206] Table 1 lists the MFR and weight % ethylene for the propylene-based elastomers used in the following examples.

[0207] Table 1

[0208] PBE MFR Weight% Ethylene VM6102 3 16 VM6202 20 15 VM3980 8 9 VM3588 8 4 VM6502 48 13 VM7020 20 17 VM7050 48 13

[0209] The oxidative functionalization of two PBE samples was evaluated. Samples of VM 6201 and VM 6202 were prepared for FTIR analysis and observed over a period of 30 minutes while heated at 200 °C on a hot air stage of an FT-IR microscope in air. The resulting infrared spectra are shown in Figure 1 As shown in the figure, when heated at 1,773cm -1 -1,719cm -1 and 1,080cm -1 -1,000cm -1 Absorptions attributed to carbonyl compounds gradually appear in the region. These absorptions are attributed to the different carbonyl group stretches in the functionalized propylene-based elastomer according to the following:

[0210] Table 2

[0211]

[0212] Thus, a method of improving polarity is to increase the temperature to greater than 200°C in the presence of oxygen without any additional antioxidants during the compounding process. The degree of polarity is related to the relative proportion of carbonyl groups and / or other oxygen-containing functional groups generated on or in the polymer. The relative weight percent of oxygen incorporated into the functionalized propylene-based elastomer is shown to be dependent on temperature and reaction time.

[0213] Figure 2 Display heating ratio Figure 1 The effect of two different samples of propylene-based elastomers with those lower ethylene contents is shown in . As these data confirm, propylene-based elastomers with lower ethylene contents achieve functionalization in less time than those with higher ethylene concentrations.

[0214] Figure 3 Shown are FT-IR spectra of VM6102 taken at various time intervals while heated in air at 200° C. As these data show, absorptions consistent with the formation of carbonyl functional groups as well as other oxygen-containing functional groups appear over time.

[0215] Figure 4Display relative to Figure 3 The data shown are plots of normalized relative peak areas of infrared absorption attributable to oxygen-containing functional groups with respect to reaction time at 200° C. As shown in these data, the ratio of carbonyl groups to pristine or unfunctionalized PBE is about 0-30% based on these data. Figure 4 It is also recognized that the amount of functionalization can be controlled by selecting an appropriate reaction time for preparing the functionalized propylene-based elastomer at a specific temperature or within a specific temperature range.

[0216] Examples of the types of reaction products believed to be formed during the functionalization process include the following, which are further shown by the infrared data:

[0217]

[0218] i) Ethers:

[0219]

[0220] ii) Ketones

[0221]

[0222] iii) Esters

[0223]

[0224] iv) Lactone

[0225]

[0226] v) Anhydride

[0227]

[0228] vi) carboxylic acid; and

[0229]

[0230] vii) Carbonates.

[0231]

[0232] For simplicity, functionalization is shown within a single polymer chain, however, it is understood that such functionalization may be present at the terminus of each polymer chain, as shown with respect to ketones, and / or between two or more polymer chains, as shown with respect to ether functional groups.

[0233] Table 3A lists GPC data for untreated propylene-based elastomers (PBE) and functionalized propylene-based elastomers (f-PBE) after heat treatment with oxygen (air) at the indicated temperatures. For these examples, the air present was generated by air entrained into the extruder during operation. No additional air was supplied to the extruder, and the nitrogen purge provided by the extruder was turned off. The PBE was fed into a twin screw extruder operating at a screw speed of 180 RPM at the indicated temperature with a residence time of 10 minutes.

[0234] Table 3A

[0235]

[0236] Table 3B shows the relative percent change ("Δ %") of the values ​​for f-PBE relative to untreated PBE according to the following formula:

[0237] Δ%=[(PBE–f-PBE) / PBE]*100%

[0238] Table 3B

[0239]

[0240] As these data show, no significant chain scission or other damage to the PBE occurs during the functionalization process by compounding, even at 270° C. These data are consistent with other data showing that the physical properties of f-PBE are not significantly altered by functionalization, except for those that depend on the polarity of the elastomer, such as the water contact angle, and that stable blends are formed with other materials.

[0241] Hydrophobicity

[0242] Several compositions were prepared from the three components listed in Table 4.

[0243] Table 4

[0244] Components Material describe PP PP3155E3 Isotactic polypropylene, MFR 35 (ExxonMobil) VM7050 Vistamaxx 7050 Propylene-based elastomer, 13 wt% ethylene, MFR 48 (ExxonMobil) VM7020 Vistamaxx 7020 Propylene-based elastomer, 17 wt% ethylene, MFR 20 (ExxonMobil)

[0245] The following exemplary and comparative blends were prepared according to the table below.

[0246] According to the embodiments disclosed herein, blends are prepared by preparing blends (or single materials) of the indicated materials and then directing the feed mixture to a twin screw extruder with an 11 cm barrel heated to the indicated temperature. The inventive examples are mixed in the extruder by purging the extruder with compressed air in the presence of oxygen. The comparative examples are mixed in the extruder under nitrogen. All blends are mixed at 200 rpm at the indicated temperature for a total residence time of 10 minutes. For the inventive samples, functionalized propylene-based elastomers are formed in the presence of polyalphaolefins (i.e., isotactic polypropylene).

[0247] Samples suitable for determining static contact angles were prepared by compression molding at 190°C for 5 minutes. The static contact angles were then determined according to ASTM D7490. To prevent functionalization, comparative examples for contact angle measurements were prepared by compression molding at 180°C for 5 minutes under nitrogen. These data are shown in Table 5.

[0248] Table 5

[0249]

[0250] Table 5 (continued)

[0251]

[0252]

[0253] As these data show, the comparative examples of neat material that has not undergone any processing (Comparative Examples 1, 2, and 3) show that the material is hydrophobic prior to functionalization. Comparative Example 4 confirms that the melt mixed blend remains hydrophobic without functionalization.

[0254] Comparative Examples 6, 7, 9, 13, and 21 confirm that propylene-based elastomers are converted to hydrophilic materials when functionalized with oxygen at the temperatures indicated. Comparative Examples 8 and 10 confirm that the hydrophobic characteristics of polyalphaolefins (iPP) are not altered when reacted with oxygen according to embodiments of the present disclosure. The remaining examples also demonstrate that the hydrophobic characteristics of various blend compositions can be adjusted by controlling the functionalization temperature, residence time, and relative proportion of the functionalized propylene-based elastomer present in the material.

[0255] Certain embodiments and features have been described using a set of numerical upper limits and a set of numerical lower limits. It should be appreciated that, unless otherwise indicated, ranges from any lower limit to any upper limit are contemplated. Certain lower limits, upper limits, and ranges appear in one or more of the claims below. All numerical values ​​are "about" or "approximately" the indicated value, and take into account experimental errors and deviations expected by a person of ordinary skill in the art.

[0256] As used herein, the phrases "substantially free" and "substantially free of" are intended to mean that the item in question is not intentionally used or added in any amount, but may be present in very small amounts as impurities resulting from environmental or process conditions.

[0257] To the extent a term used in a claim is not defined above, it should be given the broadest definition persons skilled in the relevant art have given that term as reflected in at least one printed publication or issued patent. In addition, all patents, test procedures, and other documents cited in this application are fully incorporated by reference for all jurisdictions where such incorporation is permitted, to the extent such disclosure is not inconsistent with this application.

[0258] While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof and the scope of the invention is determined by the claims appended hereto.

Claims

1. A composition comprising: i) C2-C 12 Polyalphaolefins; and ii) a functionalized propylene-based elastomer comprising 4 to 25 wt.% of one or more C2 or C4-C 12 α-olefin units and a plurality of oxygen-containing functional groups selected from carboxylic acids, anhydrides, ketones, esters, ethers, and combinations thereof; wherein the functionalized propylene-based elastomer has a triad tacticity greater than 90% and a heat of fusion less than 75 J / g.

2. The composition of claim 1, wherein the functionalized propylene-based elastomer comprises 0.01 wt% to 10 wt% oxygen, based on the total amount of functionalized propylene-based elastomer present.

3. The composition of claim 1 or claim 2, wherein the functionalized propylene-based elastomer has an MFR greater than or equal to 20 g / 10 min when measured according to ASTM D-1238, Condition L, ie, 230°C with a 2.16 kg weight.

4. The composition of claim 1 or claim 2, wherein the functionalized propylene-based elastomer comprises ethylene.

5. The composition of claim 4, wherein the functionalized propylene-based elastomer comprises greater than or equal to 10 weight percent ethylene, based on the total amount of functionalized propylene-based elastomer present.

6. The composition of claim 1 or claim 2 having a static water contact angle of less than 90° when measured according to ASTM D7490.

7. The composition of claim 1 or claim 2, wherein the functionalized propylene-based elastomer is the reaction product of: i) oxygen-containing gas; and ii) a first propylene-based elastomer comprising 4 to 25 wt.% of one or more C2 or C4-C 12 α-olefin units and have a triad tacticity greater than 90% and a heat of fusion less than 75 J / g.

8. The composition of claim 1 or claim 2, wherein the polyalphaolefin comprises greater than 50 mol% propylene.

9. The composition of claim 8, wherein the polyalphaolefin further comprises ethylene, butene, pentene, hexene, 4-methyl-1-pentene, octene, decene, or a combination thereof.

10. The composition of claim 1 or claim 2, comprising 10 wt% to 40 wt% of the functionalized propylene-based elastomer, based on the total amount of functionalized propylene-based elastomer and polyalphaolefin present.

11. The composition of claim 1 or claim 2, comprising 70 wt% to 90 wt% of the functionalized propylene-based elastomer, based on the total amount of functionalized propylene-based elastomer and polyalphaolefin present.

12. The composition of claim 1, wherein the esters are selected from the group consisting of carbonates, lactones, and combinations thereof.

13. Methods, comprising: contacting a first propylene-based elastomer with an oxygen-containing gas at a temperature greater than or equal to 200° C. for a period of time sufficient to form a functionalized propylene-based elastomer comprising 4 to 25 weight percent of one or more C2 or C4-C 12 alpha-olefin units and greater than 0.1 weight percent of oxygen-containing functional groups selected from carboxylic acids, anhydrides, ketones, esters, ethers, and combinations thereof, wherein the functionalized propylene-based elastomer has a triad tacticity greater than 90 percent and a heat of fusion less than 75 J / g; and Melt mixing the functionalized propylene-based elastomer with one or more C2-C 12 polyalphaolefin to form a blend composition.

14. The method of claim 13, wherein the first propylene-based elastomer is contacted with the oxygen-containing gas at a temperature of 230°C to 260°C for a period of time greater than 5 minutes.

15. The method of claim 13, wherein the first propylene-based elastomer is contacted with the oxygen-containing gas at a temperature greater than or equal to 200°C in the absence of an antioxidant and / or antioxidant package.

16. The method of claim 13 or claim 14, wherein the first propylene-based elastomer comprises greater than 10 weight percent ethylene, based on the total amount of first propylene-based elastomer present.

17. The method of claim 13 or claim 14, wherein the first propylene-based elastomer is mixed with the polyalphaolefin prior to or melt mixed with the oxygen-containing gas at a temperature greater than or equal to 200°C for a period of time sufficient to form the functionalized propylene-based elastomer.

18. The method of claim 17, wherein the first propylene-based elastomer and the polyalphaolefin are blended together prior to said melt mixing and fed into an extruder, wherein said contacting of the first propylene-based elastomer with the oxygen-containing gas is conducted at a temperature greater than or equal to 200° C. for a period of time sufficient to form a functionalized propylene-based elastomer.

19. The method of claim 13 or claim 14, wherein the blend composition has a static water contact angle of less than 90° when measured according to ASTM D7490.

20. The method of claim 13, wherein the esters are selected from the group consisting of carbonates, lactones, and combinations thereof.

21. Finished products, including: i) C2-C 12 Polyalphaolefins; and ii) a functionalized propylene-based elastomer comprising 4 to 25 wt.% of one or more C2 or C4-C 12 α-olefin units and a plurality of oxygen-containing functional groups selected from carboxylic acids, anhydrides, ketones, esters, ethers, and combinations thereof, wherein the functionalized propylene-based elastomer has a triad tacticity greater than 90% and a heat of fusion less than 75 J / g.

22. The article of claim 21 having a static water contact angle of less than 90° when measured according to ASTM D7490.

23. The article of any one of claims 21-22, wherein the article is a nonwoven fabric, a diaper or a film.

24. The article of claim 21, wherein the esters are selected from the group consisting of carbonates, lactones, and combinations thereof.

Images