CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application is filed under the Patent Cooperation Treaty, which claims benefit of priority to U.S. Provisional Application No. 62/556,167, filed September 8, 2017, the contents of which are incorporated herein by reference in their entirety.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

[0002] Not applicable.

FIELD OF THE INVENTION

[0003] Embodiments of the present disclosure generally relate to polyolefin based adhesive compositions.

BACKGROUND OF THE INVENTION

[0004] This section introduces information that may be related to or provide context for some aspects of the techniques described herein and/or claimed below. This information is background for facilitating a better understanding of that which is disclosed herein. Such background may include a discussion of "related" art. That such art is related in no way implies that it is also "prior" art. The related art may or may not be prior art. The discussion is to be read in this light, and not as an admission of prior art.

[0005] Multi-layer films are widely used in a variety of applications, including packaging applications. Depending on the intended end-use application, the number and arrangement of layers and type of resin employed in each layer will vary.

[0006] One challenge experienced in the fabrication of multi-layer films is achieving sufficient bond strength between the various layers of the multi-layer film. In order to improve bonding between layers, a tie-layer may be disposed between one or more layers of the multi-layer film. However, even when multi-layer films include tie-layers, difficulties in adhering dissimilar layers can occur. Thus, it is desirable to develop adhesive compositions for use in tie-layers that are capable of sufficiently adhering dissimilar layers within a multi-layer film.

SUMMARY OF THE INVENTION

[0007] Various embodiments of the technology described herein are directed to resolving, or at least reducing, one or more of the problems mentioned above. Some embodiments of the technology include processes of forming adhesive compositions. The processes generally include contacting an olefin monomer with a catalyst system within a polymerization zone to form an olefin based polymer under polymerization conditions sufficient to form the olefin based polymer, the catalyst system including a metal component generally represented by the formula:

wherein M is a transition metal, R is a halogen, an alkoxy, or a hydrocarboxyl group and x is the valence of the transition metal, wherein the catalyst system further includes an internal donor (ID) comprising a C3-C6 cyclic ether; and withdrawing the olefin based polymer from the polymerization zone; and blending the olefin based polymer with a grafted polyolefin copolymer formed from and/or containing at least a grafted polyolefin, an olefin elastomer and a long-chain branched polyolefin, so as to form a polyolefin based adhesive composition. In one embodiment, the blending step of the process is performed in-line (described in greater detail below). In another embodiment, the blending step of the process is performed off-line (described in greater detail below), whereby the olefin based polymer withdrawn from the polymerization zone is cooled (e.g., pelletized) before it is subsequently employed as the olefin based polymer in the blending step.

[0008] One or more embodiments include a process of the preceding paragraph, wherein the olefin based polymer contacts the grafted polyolefin copolymer prior to pelletization of the olefin based polymer.

[0009] One or more embodiments include the process of any preceding paragraph and further include melt blending the olefin based polymer and the grafted polyolefin copolymer in the presence of an adhesion promoting additive.

[0010] One or more embodiments include the process of any preceding paragraph, wherein the transition metal is selected from titanium, chromium and vanadium.

[0011] One or more embodiments include the process of any preceding paragraph, wherein the metal component is selected from TiC , TiBn, Ti(OC2H5)3Cl, Ti(OC3H7)2Ci2, Ti(OC6Hi3)2Ch, Ti(OC ₂ H ₅ )2Br2 and Ti(OCi2H ₂₅ )Cl3.

[0012] One or more embodiments include the process of any preceding paragraph, wherein the catalyst system further includes an organoaluminum compound selected from trimethyl aluminum (TMA), triethyl aluminum (TEA1) and triisobutyl aluminum (TiBAl).

[0013] One or more embodiments include the process of any preceding paragraph, wherein the cyclic ether is selected from tetrahydrofuran, dioxane, methyltetrahydrofuran and combinations thereof.

[0014] One or more embodiments include the process of any preceding paragraph, wherein the catalyst system further includes a support material including a magnesium halide. [0015] One or more embodiments include the process of any preceding paragraph, wherein the catalyst system exhibits a molar ratio Mg:Ti of greater than 5: 1.

[0016] One or more embodiments include the process of any preceding paragraph, wherein the catalyst system exhibits a molar ratio Mg:ID of less than 3: 1.

[0017] One or more embodiments include the process of any preceding paragraph, wherein the olefin based polymer exhibits a density (determined in accordance with ASTM D-792) of from 0.86 g/cm ³ to 0.94 g/ cm ³ .

[0018] One or more embodiments include the process of any preceding paragraph, wherein the olefin based polymer exhibits a melt index (Mh) (determined in accordance with ASTM D-1238) in a range of 0.1 dg/min to 15 dg/min.

[0019] One or more embodiments include the process of any preceding paragraph, wherein the polyolefin based adhesive composition includes the grafted polyolefin copolymer in a range of 0.5 wt.% to 50 wt.%, based on the total weight of the polyolefin based adhesive composition.

[0020] One or more embodiments include an adhesive composition including a polyolefin based adhesive composition formed with a single heat cycle and including an olefin based copolymer of ethylene and a co-monomer selected from propylene, 1-butene, 1-hexene, 1-octene and combinations thereof formed with a catalyst system including a metal component generally represented by the formula:

wherein M is a transition metal, R is a halogen, an alkoxy, or a hydrocarboxyl group and x is the valence of the transition metal, wherein the catalyst system further includes an internal donor including a C3-C6 cyclic ether; and supported on MgCh; and a grafted polyolefin copolymer formed from and/or containing at least a grafted polyolefin, an olefin elastomer and a long -chain branched polyolefin.

[0021] One or more embodiments include the adhesive composition of the preceding paragraph exhibiting a lower gel count and lower yellowness index than an identical composition formed via an off-line process.

[0022] One or more embodiments include the adhesive composition of any preceding paragraph, wherein the cyclic ether is selected from tetrahydrofuran, dioxane, methyltetrahydrofuran and combinations thereof.

[0023] One or more embodiments include a multi-layer polymeric structure (e.g., a multi-layer film, multi-layer sheet or a rigid multi-layer structure) including a plurality of resin layers; and one or more tie-layers disposed between at least two of the resin layers, wherein the tie layers are formed of the adhesive composition of any preceding paragraph. [0024] While multiple embodiments are disclosed, still other embodiments will become apparent to those skilled in the art from the following detailed description. As will be apparent, certain embodiments, as disclosed herein, are capable of modifications in various obvious aspects, all without departing from the spirit and scope of the claims as presented herein. Accordingly, the accompanying drawing and detailed description are to be regarded as illustrative in nature and not restrictive.

BRIEF DESCRIPTION OF DRAWING

[0025] The claimed subject matter may be understood by reference to the following description taken in conjunction with the accompanying drawing, in which like reference numerals identify like elements, and in which:

[0026] FIGURE 1 illustrates an embodiment of an in-line process of forming an adhesive composition.

[0027] While the claimed subject matter is susceptible to various modifications and alternative forms, the specific embodiments described in detail below are by way of example. It should be understood that the description herein of specific embodiments of the technology is not intended to limit the claimed subject matter to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope as defined by the appended claims.

DETAILED DESCRIPTION

[0028] Illustrative embodiments of the subject matter claimed below will now be disclosed. In the interest of clarity, not all features of an actual implementation are described in this specification. It will be appreciated that in the development of any such actual embodiment, numerous implementation-specific decisions must be made to achieve the developers' specific goals, such as compliance with system-related and business-related constraints, which will vary from one implementation to another. Moreover, it will be appreciated that such a development effort, even if complex and time-consuming, would be a routine undertaking for those of ordinary skill in the art having the benefit of this disclosure.

[0029] The embodiments illustratively disclosed herein may be practiced in the absence of any element that is not specifically disclosed herein and/or any optional element disclosed herein. While compositions and methods are described in terms of "comprising," "containing," or "including" various components or steps, the compositions and methods can also "consist essentially of or "consist of the various components and steps. Further, various ranges and/or numerical limitations may be expressly stated below. It should be recognized that unless stated otherwise, it is intended that endpoints are to be interchangeable. Further, any ranges include iterative ranges of similar magnitude falling within the expressly stated ranges or limitations disclosed herein is to be understood to set forth every number and range encompassed within the broader range of values. It is to be noted that the terms "range" and "ranging" as used herein generally refer to a value within a specified range and encompass all values within that entire specified range.

[0030] Furthermore, various modifications may be made within the scope of the disclosure as herein intended, and embodiments of the disclosure may include combinations of features other than those expressly claimed.

[0031] Various terms as used herein are shown below. To the extent a term used in a claim is not defined below, it should be given the broadest definition skilled persons in the pertinent art have given that term as reflected in printed publications and issued patents at the time of filing. Further, unless otherwise specified, all compounds described herein may be substituted or unsubstituted and the listing of compounds includes derivatives thereof.

[0032] Unless otherwise designated herein, all testing methods specified herein are the current methods at the time of filing.

[0033] Polyolefin based adhesive compositions and methods of making and using the same are described herein. The polyolefin based adhesive compositions are generally formed of an olefin based polymer and a grafted polyolefin copolymer.

[0034] Grafted polyolefin copolymers as used herein are a copolymer made from and/or containing at least (i) a grafted polyolefin, (ii) an olefin elastomer, and (iii) a long-chain branched polyolefin. In at least one aspect of the invention, the grafted polyolefin is coupled to the olefin elastomer to form a first couplet, and the olefin elastomer is present an amount from about 0.2 to about 60 weight percent of the grafted polyolefin copolymer. In at least one aspect of the invention, the first couplet of the grafted polyolefin and the olefin elastomer is coupled to the long- chain branched polyolefin to form a second couplet of grafted polyolefin, olefin elastomer, and long-chain branched polyolefin. In at least one aspect of the invention, the long-chain branched polyolefin is present in an amount from about 1.5 to about 50 weight percent of the grafted polyolefin copolymer.

[0035] The use of the terms "first" and "second" in the preceding paragraph are not intended to indicate sequence but rather difference. As such, the grafted polyolefin could be coupled to the long-chain branched polyolefin to form the first couplet. Alternatively, the couplet components may combine simultaneously to from a single couplet of grafted polyolefin, olefin elastomer, and long-chain branched polyolefin. Moreover, the couplets can be formed in any order or simultaneously. [0036] In at least some embodiments, the grafted polyolefin copolymer composition is made from and/or contains a high-density polyethylene (HDPE) grafted with (a) maleic anhydride, (b) an olefin elastomer composition made from and/or containing ethylene propylene rubbers (EPR) and/or ethylene-propylene-diene monomer rubbers (EPDM), and (c) a long-chain branched polyolefin composition made from and/or containing a low density polyethylene (LDPE).

[0037] Grafted polyolefins suitable for use in making the grafted polyolefin copolymer are prepared by reacting polyolefins with unsaturated monomers at elevated temperatures, with or without a free-radical initiator, under conditions effective to graft unsaturated monomer units onto the polyolefin backbone. Preferably, the grafting reaction occurs under an inert gas, such as nitrogen.

[0038] Polyolefins suitable for making the grafted polyolefins include high density polyethylenes (HDPE), medium density polyethylenes (MDPE), low density polyethylenes (LDPE), linear low density polyethylenes (LLDPE), polypropylenes, ethylene-propylene copolymers, impact-modified poly-propylenes, and the like, and blends thereof. Preferred polyolefins for making the grafted polyolefin are polyethylenes, more preferably, HDPE and LLDPE, and even more preferably, HDPE. Typically, the even more preferred HDPE has a density from about 0.940 to about 0.970 g/cm ³ .

[0039] Suitable unsaturated monomers are also well known. Preferred unsaturated monomers are ethylenically unsaturated carboxylic acids and acid derivatives, particularly esters, anhydrides, acid salts, and the like. Examples include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, maleic anhydride, tetrahydrophthalic anhydride, norborn-5-ene-2,3- dicarboxylic acid anhydride, nadic anhydride, himic anhydride, and the like, and mixtures thereof. Maleic anhydride is particularly preferred. Other suitable unsaturated monomers are described in U.S. Patent No. 6,385,777 and U.S. Patent Application Publication No. 2007/0054142, the teachings of which are incorporated herein by reference.

[0040] The relative amounts of polyolefin and unsaturated monomer used will vary and depend on factors such as the nature of the polyolefin and the unsaturated monomer, the desired tie-layer properties, the reaction conditions, the available equipment, and other factors. Usually, the unsaturated monomer is used in an amount within the range of about 0.1 to about 15 weight percent, based on the total weight of the grafted polyolefin, preferably from about 0.5 to about 6 weight percent, and most preferably from about 1 to about 3 weight percent.

[0041] Grafting of the unsaturated monomer (s) to the polyolefin is accomplished according to known procedures, generally by heating a mixture of the unsaturated monomer(s) and the polyolefin. Most typically, the grafted polyolefin is prepared by melt blending the polyolefin with the unsaturated monomer in a shear-imparting extruder/reactor. Twin screw extruders such as those marketed by Coperion under the designations ZSK-53, ZSK-83, ZSK-90 and ZSK-92 are especially useful for performing the grafting step. A free-radical initiator such as an organic peroxide can be employed but is not necessary.

[0042] Grafting of the unsaturated monomer to the polyolefin is performed at elevated temperatures, preferably within the range of 180 degrees Celsius to 400 degrees Celsius, more preferably from 200 degrees Celsius to 375 degrees Celsius, and most preferably from 230 degrees Celsius to 350 degrees Celsius. Shear rates in the extruder can vary over a wide range, preferably from 30 to 1000 rpm, more preferably from 100 to 600 rpm, and most preferably from 200 to 400 rpm. Preferably, the grafting reaction occurs under an inert gas, such as nitrogen.

[0043] Suitable olefin elastomers include ethylene-propylene rubber (EPR), ethylene- propylene-diene monomer rubber (EPDM), the like, and mixtures thereof. Preferably, the olefin elastomers contain from about 10 to about 80 weight percent of ethylene recurring units, based upon the total weight of the olefin elastomer. More preferred olefin elastomers contain from about 10 to about 70 weight percent of ethylene units.

[0044] Commercially available olefin elastomers include Lanxess Corporation's Buna™ EP T2070 (68 weight percent ethylene and 32 weight percent propylene, based on the total weight of the copolymer); Buna EP T2370 (3 weight percent ethylidene norbornene, 72 weight percent ethylene, and 25 weight percent propylene, based on the total weight of the copolymer); Buna EP T2460 (4 weight percent ethylidene norbornene, 62 weight percent ethylene, and 34 weight percent propylene, based on the total weight of the copolymer); ExxonMobil Chemical's Vistalon™ 707 (72 weight percent ethylene and 28 weight percent propylene, based on the total weight of the copolymer); Vistalon 722 (72 weight percent ethylene and 28 weight percent propylene, based on the total weight of the copolymer); and Vistalon 828 (60 weight percent ethylene and 40 weight percent propylene, based on the total weight of the copolymer).

[0045] Suitable ethylene -propylene elastomers also include Exxon Mobil Chemical's Vistamaxx™ elastomers, particularly grades 6100, 1100, and 3000, and Dow Chemical's Versify™ elastomers, particularly grades DP3200.01, DP3300.01, and DP3400.01, which have ethylene contents of 9 weight percent, 12 weight percent, and 15 weight percent, respectively, based upon the total weight of the copolymer.

[0046] Additional EPDM rubbers include Dow's Nordel™ hydrocarbon rubber, e.g., the 3722P, 4760P, and 4770R grades.

[0047] Long-chain branched polyolefins suitable for making the grafted polyolefin copolymer have at least 1 long chain branch per 1000 carbons. In the present description, the term "long- chain" refers to carbon chains that are C6 or longer. "Long chain branching (LCB)" can be determined by conventional techniques known in the industry, such as 13C nuclear magnetic resonance (13C NMR) spectroscopy, using, for example, the method of Randall (Rev. Micromole. Chem. Phys., C29 (2&3) 1989, p. 285-297). Two other methods are gel permeation chromatography, coupled with a low angle laser light scattering detector (GPC-LALLS), and gel permeation chromatography, coupled with a differential viscometer detector (GPC-DV). The use of these techniques for long chain branch detection, and the underlying theories, have been well documented in the literature. See, for example, Zimm, B. H. and Stockmayer, W. H., J. Chem. Phys., 17,1301(1949) and Rudin, A., Modern Methods of Polymer Characterization, John Wiley & Sons, New York (1991) pp. 103-112. Suitable long-chain branched polyolefins include polyethylenes having long-chain branching. Preferably, the long-chain branched polyolefin is a low density polyethylene (LDPE). The LDPE can be an ethylene homopolymer or ethylene copolymerized with one or more monomers, such as vinyl acetate, methyl acrylate, acrylic acid, ethyl acrylate, or a C3 to CIO a-olefin.

[0048] As used herein, a "live, grafted polyolefin," refers to a grafted polyolefin that can further react with added olefin elastomer and long chained branched polyolefin, and any residual polyolefin, unsaturated monomer, and/or free-radical initiator used to make the grafted polyolefin. Commercially available grafted polyolefins are not "live" because the free-radical content has fully reacted or has been quenched during workup of the product, for instance during pelletization. A live, grafted polyolefin contains active free-radical species generated thermally by visbreaking or from peroxide decomposition. The residual radical content allows reaction to continue upon combination of the freshly made grafted polyolefin, including while the polyolefin is still molten, with an added olefin elastomer and long chain branched polyolefin. One or more of the grafted polyolefin, olefin elastomer, long chain branched polyolefin, residual polyolefin, and residual unsaturated monomer may be involved in a secondary reaction. Without being bound to theory, it is believed that live, grafted polyolefin allows the polyolefin to better react with the olefin elastomer, the long-chain branched polyolefin and the free radicals from the polyolefin, e.g., from HDPE.

[0049] As with selection of the relative amounts of the polyolefin and the unsaturated monomer for preparation of the grafted polyolefin previously described, the amount of olefin elastomer and the amount of the long-chain branched polyolefin used depends on the nature of the grafted polyolefin, the olefin elastomer, and the long-chain branched polyolefin, the desired tie- layer properties, the coupling conditions, equipment, and other factors. Generally, however, the amount of olefin elastomer used will be in an amount from about 0.2 to about 60 weight percent, based on the weight of the grafted polyolefin copolymer composition produced, preferably from about 0.8 to about 50 weight percent, more preferably from about 1 to about 35 weight percent, most preferably from about 1 to about 30 weight percent. Generally, the amount of the long-chain branched polyolefin used will be in an amount from about 1.5 to about 50 weight percent, based on the weight of the grafted polyolefin copolymer composition produced, preferably from about 2 to about 40 weight percent.

[0050] In the process for making the grafted polyolefin copolymer, the grafted polyolefin, the olefin elastomer, and the long-chain branched polyolefin are coupled, in the presence of free radicals. The coupling of the olefin elastomer to the grafted polyolefin may precede, occur simultaneously with, or follow the coupling of the long-chain branched polyolefin to the grafted polyolefin. These couplings can be performed using any suitable reactor. Preferably, the couplings occur under an inert gas, such as nitrogen.

[0051] Conveniently, the couplings are performed by combining freshly-prepared grafted polyolefin with the olefin elastomer and the long-chain branched polyolefin in a shear-imparting extruder/reactor as described earlier. In one particularly preferred approach, the grafted polyolefin is transferred while still molten from an outlet of a first extruder directly to a second extruder in which the couplings with the olefin elastomer and the long-chain branched polyolefin occur.

[0052] The grafted polyolefin, the olefin elastomer, and the long-chain branched polyolefin couple at elevated temperature, preferably at temperatures between 120 degrees Celsius to 300 degrees Celsius, more preferably from 135 degrees Celsius to 260 degrees Celsius. Preferably, the temperature for the coupling used to make this graft composition is lower than that used to make the grafted polyolefin. Shear rates in the extruder for this step can vary over a wide range, preferably from 30 to 1000 rpm, more preferably from 100 to 600 rpm, and most preferably from 200 to 500 rpm.

[0053] The resulting grafted polyolefin copolymer is conveniently quenched and pelletized at this point, but it can be combined immediately after preparation with the olefin based polymer (base resin) composition as is described further below.

[0054] Off-line processes for forming polyolefin based adhesive compositions generally included extruding olefin based polymers upon withdrawal from a polymerization zone to form polyolefin pellets in a first extrusion process and then contacting those polyolefin pellets with a functionalized polyolefin in a second (or subsequent) extrusion process to form the polyolefin based adhesive composition.

[0055] Each extrusion process is generally referred to herein as a "heat cycle." A heat cycle generally refers to heating a respective polymer to a temperature sufficient to at least partially melt the polymer and form a molten polymer, and then cooling the molten polymer to a temperature sufficient to at least partially solidify the molten polymer.

[0056] In contrast, in the in-line embodiments described herein, the olefin based polymer undergoes a single heat cycle in the formation of the polyolefin based adhesive composition. For example, in one or more embodiments, the olefin based polymer recovered from a polymerization zone is directly contacted with the graft polyolefin copolymer to form the polyolefin based adhesive composition. For example, olefin based polymer may be withdrawn from the polymerization zone and melt blended with the graft polyolefin copolymer to form the polyolefin based adhesive composition. Such melt blending may occur via extrusion, for example. In such embodiments, it is to be noted that while the olefin based polymer contacts the graft polyolefin copolymer during the melt blending, the initial contact of the olefin based polymer and the graft polyolefin copolymer may occur prior to melt blending, such as in a mixer, a feeder or a storage vessel, for example.

[0057] As used herein, the term "directly" refers to withdrawing the olefin based polymer from the polymerization zone and contacting the olefin based polymer with the grafted polyolefin copolymer without an intervening heat cycle. In such embodiments, the olefin based polymer contacts the grafted polyolefin copolymer prior to pelletization of the olefin based polymer and thus, the olefin based polymer undergoes a single heat cycle in the formation of the polyolefin based adhesive composition.

[0058] An illustrative schematic of such an embodiment is illustrated in FIGURE 1, which illustrates in-line process 100 for forming an adhesive composition. Within the process 100, olefin monomer (not shown) and optionally co-monomer (not shown) is introduced into a polymerization zone (or reactor) 200 via a reactor feed line 104. The olefin monomer contacts a polymerization catalyst system (not shown) disposed within the polymerization zone 200 under polymerization conditions sufficient to form an olefin based polymer (not shown). The olefin based polymer (not shown) is withdrawn or recovered from the polymerization zone 200 via reactor exit line 106 and passes through an optional powder silo (vessel or bin) 202 to an extruder 204 via first an extruder- feed line 108. A grafted polyolefin copolymer (not shown) is introduced into an optional graft silo (vessel or bin) 206 via graft-feed line 110. The grafted polyolefin copolymer (not shown) is fed to the extruder 204 via a second extruder-feed line 1 12. The grafted polyolefin copolymer (not shown) and the olefin based polymer (not shown) are mixed in the extruder 204 (optionally under shear mixing sufficient to blend the components and any additives). The mixed grafted polyolefin copolymer and olefin based polymer form the polyolefin based adhesive composition (not shown) within the extruder 204. The adhesive composition (not shown) is fed (optionally by an un-shown melt pump) from the extruder 204 to a pelletizer 208 via a pelletizer feed line 1 14. The adhesive composition (not shown) is pelletized in the pelletizer 208 and recovered as product via product line 1 18. Optionally, the pelletized adhesive composition may be accumulated in bins (not shown) and shipped to customers. Additional equipment components, such as feeders, additive bins, degassers, screen packs, and storage tanks are contemplated for use but are known in the art and thus not shown in Figure 1.

[0059] In an embodiment, the processes described herein are in-line processes to form adhesive resins (also called adhesive compositions). In an embodiment, an in-line process is a process in which an adhesive resin is formed using a polyolefin from a reactor (also called the olefin based polymer) that undergoes a single heat cycle (or a single heat history, or a single pelletization step). In an embodiment, the in-line process includes withdrawing (by pump, pressure, fluid flow, or gravity) polyolefin powder off of a reactor and melt mixing it (optionally in an extruder) - without prior pelletization of the polyolefin powder - with an adhesive graft (also called a grafted polyolefin copolymer) to form an adhesive resin, which is then pelletized.

[0060] The adhesive graft (also called a grafted polyolefin copolymer) may be pelletized separately from (and optionally prior to) the in-line process. In other words, the single heat history of the in-line process refers to the melt history of the olefin based polymer and does not include the formation (or melt history) of the adhesive graft (also called a grafted polyolefin copolymer).

[0061] In embodiments of in-line processes, virgin polyolefin powder may be melt mixed with the adhesive graft; and optionally, additives are introduced to the polyolefin powder before it is melt mixed with the adhesive graft. In some embodiments associated with in-line processes, the virgin polyolefin (or polyolefin stabilized with additives) may undergo cooling as it is transported from the reactor to the melt mixer; alternatively the cooling is minimized (by, for example, insulating the pipes, or using a relatively short distance of pipe - as is practical within a commercial chemical plant). In alternative embodiments of in-line processes, the virgin polyolefin (or polyolefin stabilized with additives) is stored in a vessel (such as a silo) before it is melt mixed with the adhesive graft. In this alternative embodiment, the virgin polyolefin (or polyolefin stabilized with additives) is allowed to cool more significantly and optionally to ambient or near ambient temperature.

[0062] In an alternative embodiment, an in-line process is a closed, continuous, and/or connected process for melt mixing polyolefin powder with an adhesive graft to form an adhesive resin. In one or more embodiments, a closed system is one with minor exposure to oxygen. It is to be noted that closed systems may inevitably include the exposure to oxygen either through the external introduction of oxygen and/or oxygen containing compounds to the system, leaks in pipes, via in situ generation of oxygen containing compounds within the system, or via minor amounts of oxygen that may be introduced to the reactor (for example, oxygen may be used as a catalyst terminator in the reactor) and carried through to the melt mixer (also called extruder). However, such oxygen levels are at "minor" levels such that detrimental effect/degradation is not observed in the olefin based polymer. In one or more embodiments, a connected system is one in which the olefin based polymer is manufactured and extruded on-site without the need for being moved (for example, by truck or rail) to another compounding facility (for example, a toll compounder or a compounding facility located onsite). In an embodiment, continuous and connected systems are those in which the polyolefin is carried (optionally directly) from the reactor to the melt mixer without an intermediate transportation step (by, for example, rail or truck) to a separate facility. In an embodiment, continuous and connected systems may include some intermittent storage of the polyolefin in a vessel or silo.

[0063] The in-line system embodiments are in contrast to an "off-line" system in other embodiments, wherein, in one or more embodiments, the olefin based polymer is produced and pelletized on one plant site. The pelletized olefin based polymer is then moved (optionally by truck or rail) to a second location for compounding with a grafted polyolefin copolymer. The second location can be a new toll compounder (i.e. , a new company) or can be a separate part of a single plant site. Thus, an in-line system may utilize a single extruder, whereas an off-line system utilizes multiple extruders. As mentioned above and in various embodiments, in both the in-line and off-line processes the grafted polyolefin copolymer is pelletized separately (optionally in a prior system).

[0064] The in-line processes of the embodiments herein result in polyolefin based adhesive compositions exhibiting improved properties, such as reduced yellowness and/or gels, in comparison to off-line systems. Visually, yellowness is associated with product degradation by light, chemical exposure and processing. The yellowness index is calculated by the Hunter colorimeter per ASTM method D1925.

[0065] The polyolefin based adhesive composition may include the grafted polyolefin copolymer in a range of 0.5 wt.% to 50 wt.%, or 1 wt.% to 20 wt.%, or 2 wt.% to 15 wt.%, or 5 wt. % to 15 wt. %, or 6 wt. % to 11 wt. %, or 12 wt. % to 17 wt. %, or 20 wt.% to 30 wt.%, based on the total weight of the polyolefin based adhesive composition, for example.

[0066] In one or more embodiments, the polyolefin based adhesive composition may contain additives to impart desired physical properties, such as printability, increased gloss, or a reduced blocking tendency. Examples of additives may include, without limitation, stabilizers, ultra-violet screening agents, oxidants, anti-oxidants, anti-static agents, ultraviolet light absorbents, fire retardants, processing oils, mold release agents, coloring agents, pigments/dyes, fillers or combinations thereof, for example. These additives may be included in amounts effective to impart desired properties.

[0067] It is further contemplated that the additives may include one or more adhesion- promoting resins, such as thermoplastic elastomers.

[0068] In one or more embodiments, the additives are melt blended with the olefin based polymer and the grafted polyolefin copolymer. Such melt blending may occur when the olefin based polymer is melt blended with the grafted polyolefin copolymer, for example.

[0069] Catalyst systems useful for polymerizing olefin monomers include any suitable catalyst system. For example, the catalyst system may include chromium based catalyst systems, single site transition metal catalyst systems including metallocene catalyst systems, Ziegler-Natta (Z-N) catalyst systems or combinations thereof, for example. The catalysts may be activated for subsequent polymerization and may or may not be associated with a support material, for example. A brief discussion of such catalyst systems is included below, but is in no way intended to limit the scope of the disclosure to such catalysts.

[0070] Catalyst systems useful for polymerizing olefin monomers may include Ziegler-Natta catalyst systems, for example. Ziegler-Natta catalyst systems are generally formed from the combination of a metal component (e.g., a potentially active catalyst site) with one or more additional components, such as a catalyst support, a co-catalyst and/or one or more electron donors, for example.

[0071] A specific example of a Ziegler-Natta catalyst includes a metal component generally represented by the formula:

wherein M is a transition metal, R is a halogen, an alkoxy, or a hydrocarboxyl group and x is the valence of the transition metal. For example, x may be from 1 to 4.

[0072] The transition metal may be selected from Groups IV through VIB (e.g., titanium, chromium or vanadium) of the Periodic Table of Elements, for example. R may be selected from chlorine, bromine, carbonate, ester, or an alkoxy group in various embodiments. Examples of catalyst components include TiC , TiBn, Ti(OC2H5)3Cl, Ti(OC3H7)2Cl2, Ti(OC6Hi3)2Ch, Ti(OC2H5)2Br2 and Ti(OCi2H25)Cb, for example.

[0073] Those skilled in the art will recognize that a catalyst may be "activated" in some way before it is useful for promoting polymerization. As discussed further below, activation may be accomplished by contacting the catalyst with an activator, which is also referred to in some instances as a "co-catalyst". Embodiments of such Z-N activators include organoaluminum compounds, such as trimethyl aluminum (TMA), triethyl aluminum (TEA1) and triisobutyl aluminum (TiBAl), for example.

[0074] The Ziegler-Natta catalyst system may further include one or more electron donors, such as internal electron donors and/or external electron donors. The internal electron donors may include amines, amides, esters, ketones, nitriles, ethers, thioethers, thioesters, aldehydes, alcoholates, salts, organic acids, phosphines, diethers, succinates, phthalates, malonates, maleic acid derivatives, dialkoxybenzenes or combinations thereof, for example.

[0075] In one or more embodiments, the internal donor includes a C3-C6 cyclic ether, or a C3- C5 cyclic ether. For example, the cyclic ethers may be selected from tetrahydrofuran, dioxane, methyltetrahydrofuran and combinations thereof. (See, WO2012/025379, which is incorporated by reference herein.)

[0076] The external electron donors may include monofunctional or polyfunctional carboxylic acids, carboxylic anhydrides, carboxylic esters, ketones, ethers, alcohols, lactones, organophosphorus compounds and/or organosilicon compounds. In one embodiment, the external donor may include diphenyldimethoxysilane (DPMS), cyclohexylmethyldimethoxysilane (CMDS), diisopropyldimethoxysilane (DIDS) and/or dicyclopentyldimethoxysilane (CPDS), for example. The external donor may be the same or different from the internal electron donor used. However, in one or more embodiments, the catalyst system is absent external donor.

[0077] The components of the Ziegler-Natta catalyst system (e.g., catalyst, activator and/or electron donors) may or may not be associated with a support, either in combination with each other or separate from one another. In one or more embodiments, the Z-N support materials may include a magnesium dihalide, such as magnesium dichloride or magnesium dibromide or silica, for example.

[0078] In one or more embodiments, the support may include a magnesium compound represented by the general formula:

wherein R" is a C1-C10 alkyl and m is in a range of 0.5 to 3.

[0079] In one or more embodiments, the Ziegler-Natta catalyst system exhibits a molar ratio of support to metal component (measured as the amount of metal of each component) Mg:Ti of greater than 5 : 1, or in a range of 7: 1 to 50: 1, or 10: 1 to 25 : 1, for example.

[0080] In one or more embodiments, the Ziegler-Natta catalyst system exhibits a molar ratio of support to internal donor Mg:ID of less than 3 : 1, or less than 2.9: 1, or less than 2.6: 1, or less than 2.1 : 1, or less than 2: 1, or from 1.1 : 1 to 1.4: 1, for example. [0081] In one or more embodiments, the Ziegler-Natta catalyst system exhibits an X-ray diffraction spectrum in which the range of 2Θ diffraction angles between 5.0° and 20.0°, at least three main diffraction peaks are present at diffraction angles 2Θ of 7.2 ± 0.2°, and 11.5 ± 0.2° and 14.5 ± 0.2°, the peak at 2Θ of 7.2 ± 0.2° being the most intense peak and the peak at 11.5 ± 0.2° having an intensity less than 0.9 times the intensity of the most intense peak.

[0082] In one or more embodiments, the intensity of the peak at 11.5° has an intensity less than 0.8 times the intensity of the diffraction peak at 2Θ diffraction angles of 7.2 ± 0.2°. In one or more embodiments, the intensity of the peak at 14.5 ± 0.2° is less than 0.5 times, or less than 0,4 times the intensity of the diffraction peak at 2Θ diffraction angles of 7.2 ± 0.2°.

[0083] In one or more embodiments, another diffraction peak is present at diffraction angles 2Θ of 8,2 ± 0.2° having an intensity equal to or lower than the intensity of the diffraction peak at 2Θ diffraction angles of 7.2 ± 0.2°. For example, the intensity of the peak at diffraction angles 2Θ of 8,2 ± 0.2° is less than 0.9, or less than 0.5 times the intensity of the diffraction peak at 2Θ diffraction angles of 7.2 ± 0.2°.

[0084] In one or more embodiments, an additional broad peak is observed at diffraction angles 2Θ of 18.2 ± 0.2° having an intensity less than 0.5 times the intensity of the diffraction peak at 2Θ diffraction angles of 7.2 ± 0.2°. As referenced herein, the X-ray diffraction spectra are collected by using a Bruker D8 advanced powder diffractometer.

[0085] The Ziegler-Natta catalyst may be formed by any method known to one skilled in the art. For example, the Ziegler-Natta catalyst may be formed by contacting a transition metal halide with a metal alkyl or metal hydride. (See, U.S. Patent Nos. 4,298,718; 4,298,718; 4,544,717; 4,767,735; and 4,544,717; which are incorporated by reference herein.)

[0086] Olefin based polymers formed by catalyst systems having the specific internal donors discussed herein have been found to exhibit low levels of xylene solubles. Xylene solubles refers to the portion of a polymer that is soluble in xylene and that portion is thus termed the xylene soluble fraction (XS%). In determining XS%, the polymer is dissolved in boiling xylene and then the solution is cooled to 0 °C. The XS% is that portion of the dissolved polymer that remains soluble in the cold xylene.

[0087] In one or more embodiments, the olefin based polymer exhibits a xylene soluble fraction (determined in accordance with ASTM D-5492-98) of less than 1.5%, or less than 1.0%, or less than 0.5%, for example.

[0088] Gels can originate from a number of sources, including crosslinking reactions during polymerization, insufficient mixing, homogenization during melt blending and homogenization and crosslinking during film extrusion, for example. Gels are generally undesirable as they can negatively affect subsequent film performance and appearance. For example, high concentrations of gels may cause the film to break in the film production line or during subsequent stretching. As used herein, "gels" are defined as particles having a size greater than 200 μπι.

[0089] In one or more embodiments, the olefin based polymer exhibits a gel defect area of 25 ppm or less, or 20 ppm or less, for example. As used herein "gel defect area" refers to the measurement of gels in films and is measured via commercially available gel measurement systems commercially available by Optical Control Systems (OCS) GmbH, the Optical Control Systems film scanning system FS-5.

[0090] As indicated elsewhere herein, the catalyst systems are used to form olefin based polymer compositions (which may be interchangeably referred to herein as poly olefins). Once the catalyst system is prepared, as described above and/or as known to one skilled in the art, a variety of processes may be carried out using that composition to form olefin based polymers. The equipment, process conditions, reactants, additives and other materials used in polymerization processes will vary in a given process, depending on the desired composition and properties of the polymer being formed. Such processes may include solution phase, gas phase, slurry phase, bulk phase, high pressure processes or combinations thereof, for example.

[0091] In certain embodiments, the processes described above generally include polymerizing one or more olefin monomers to form olefin based polymers. The olefin monomers may include C2 to C30 olefin monomers, or C2 to C12 olefin monomers (e.g., ethylene, propylene, butene, pentene, 4-methyl-l-pentene, hexene, octene and decene), for example. It is further contemplated that the monomers may include olefinic unsaturated monomers, C4 to Cis diolefins, conjugated or nonconjugated dienes, polyenes, vinyl monomers and cyclic olefins, for example. Non-limiting examples of other monomers may include norbornene, norbornadiene, isobutylene, isoprene, vinylbenzylcyclobutane, styrene, alkyl substituted styrene, ethylidene norbornene, dicyclopentadiene and cyclopentene, for example. The formed polymer may include homopolymers, copolymers or terpolymers, for example.

[0092] The olefin based polymers may include, but are not limited to, linear low density polyethylene, elastomers, plastomers, high density polyethylenes, low density polyethylenes, medium density polyethylenes, polypropylene and polypropylene copolymers, for example.

[0093] In one or more embodiments, the olefin based polymers include ethylene based polymers. As used herein, the term "ethylene based" is used interchangeably with the terms "ethylene polymer" or "polyethylene" and refers to a polymer having at least 50 wt.%, or at least 70 wt.%, or at least 75 wt.%, or at least 80 wt.%, or at least 85 wt.% or at least 90 wt.% polyethylene relative to the total weight of polymer, for example. [0094] The ethylene based polymers may include one or more co-monomers, such as those discussed previously herein. For example, the ethylene based polymers may include one or more co-monomers selected from propylene, 1-butene, 1-hexene, 1-octene and combinations thereof. In one or more embodiments, the ethylene based polymer includes one or more co-monomers selected from 1-butene, 1-hexene and combinations thereof. The ethylene based polymer may include co-monomer in a range of 5 wt.% to 10 wt.%, based on the total weight of the olefin based polymer.

[0095] The ethylene based polymers may have a density (determined in accordance with ASTM D-792) of from 0.86 g/cc to 0.94 g/cc, or from 0.91 g/cc to 0.94 g/cc, or from 0.915 g/cc to 0.935 g/cc, for example.

[0096] The ethylene based polymers may have a melt index (Mh) (determined in accordance with ASTM D-1238) of from 0.1 dg/min to 15 dg/min, from 0.1 dg/min to 10 dg/min, or from 0.05 dg/min to 8 dg/min.

[0097] In one or more embodiments, the olefin based polymers include high density polyethylene. As used herein, the term "high density polyethylene" refers to ethylene based polymers having a density of from about 0.94 g/cm ³ to about 0.97 g/cm ³ .

[0098] In one or more embodiments, the olefin based polymers include low density polyethylene. As used herein, the term "low density polyethylene" refers to ethylene based polymers having a density in a range of 0.88 g/cm ³ to 0.925 g/cm ³ .

[0099] In one or more embodiments, the olefin based polymers include linear low density polyethylene. As used herein, the term "linear low density polyethylene" refers to substantially linear low density polyethylene characterized by the absence of long -chain branching.

[00100] In one or more embodiments, the olefin based polymers include medium density polyethylene. As used herein, the term "medium density polyethylene" refers to ethylene based polymers having a density of from 0.92 g/cm ³ to 0.94 g/cm ³ or from 0.926 g/cm ³ to 0.94 g/cm ³ .

[00101] In one or more embodiments, the olefin based polymer is a linear low density polyethylene, the grafted polyolefin is high density polyethylene and the long-chain branched polyolefin is low density polyethylene.

[00102] The polyolefin based adhesive compositions are useful in applications known to one skilled in the art to be useful for conventional polymeric compositions, such as forming operations (e.g. , film, sheet, pipe and fiber extrusion and co-extrusion as well as blow molding, injection molding and rotary molding). Films include blown, oriented or cast films formed by extrusion or co-extrusion or by lamination useful as shrink film, cling film, stretch film, sealing films, oriented films, snack packaging, heavy duty bags, grocery sacks, baked and frozen food packaging, medical packaging, industrial liners, and membranes, for example, in food-contact and non-food contact applications. Fibers include slit-films, monofilaments, melt spinning, solution spinning and melt blown fiber operations for use in woven or non-woven form to make sacks, bags, rope, twine, carpet backing, carpet yarns, filters, diaper fabrics, medical garments and geotextiles, for example. Extruded articles include medical tubing, wire and cable coatings, sheets such as thermoformed sheets (including profiles and plastic corrugated cardboard), geomembranes and pond liners. Molded articles include single and multi-layered constructions in the form of bottles, tanks, large hollow articles, rigid food containers and toys.

[00103] In some embodiments, the homogeneous distribution of co-monomer in and among the polymer chains is important for subsequent film production. Thus, the polyolefin composition may generally exhibit a substantially homogeneous co-monomer distribution.

[00104] The polyolefin based adhesive composition can be utilized in the production of composite polymeric structures, e.g. , multi-layer films, sheets or rigid structures, wherein a layer of the polyolefin based adhesive composition is applied to one or more layers of the multi-layer structure by methods known in the art, such as co-extrusion, for example. The multi-layer films or other structures may include one or more layers formed from nylon, polyolefins, polar substrates such as ethylene vinyl alcohol (EVOH) and polyamides with one or more styrene polymers, including styrene homopolymers, copolymers, and impact modified polystyrenes. The polyolefin based adhesive compositions may be utilized as tie-layers in the multi-layer films. Tie-layers are generally utilized as a layer disposed between two additional layers to improve the adhesion therebetween.

[00105] Tie-layers in the composite structures may experience significant stresses which are created at an interface between the tie-layer and the layer to which the tie-layer is adhered. However, the tie-layer adhesives of the embodiments described herein exhibit substantial and unexpected adhesive properties even under significant stresses.

[00106] The multi-layer film or other structure may include any number of layers sufficient to satisfy its application. For example, the multi-layer film may include at least 2, or 3, or 4, or 5 or 6, or 7, or 9, or 11 layers.

[00107] The polyolefin based adhesive compositions disclosed herein exhibit excellent adhesion under a variety of conditions to non-polar polyolefins, polar polymers and styrenic substrates.

Examples [00108] To facilitate a better understanding of the disclosure, the following examples of embodiments are given. In no way should the following examples be read to limit, or to define, the scope of the appended claims.

[00109] An adhesive composition was evaluated for use as tie-layers in multi-layer films. The adhesive composition included about 73.5 wt.% ethylene hexene LLDPE and about 26.5 wt.% grafted polyolefin copolymer and exhibited a density of about 0.918 g/cm ³ . and a melt index of 2 dg/min. The LLDPE was prepared with the Ziegler-Natta catalyst described herein.

[00110] The grafted polyolefin copolymer was a graft of (a) a live graft of high density polyethylene grafted with maleic anhydride, (b) elastomer comprising ethylene-propylene rubber (EPR), and (c) a long -chain branched polyolefin in the form of a low density polyethylene. The grafted polyolefin copolymer had a maleic anhydride content of 1.5 wt.%.

[00111] The in-line samples were prepared via a single heat cycle by discharging a polyolefin from a polymerization reactor in the form of a powder and feeding the polyolefin into an accumulator bin in-line with the reactor. The grafted polyolefin copolymer was introduced into a second accumulator bin and then both components were fed together into a mixer where they were mixed and heated to a temperature of about 400-450 °F (204.4 - 232.2 °C), subjected to shear mixing and pelletized. The off-line samples were prepared via multiple heat cycles (e.g. , previously manufactured and pelletized resin mixed with grafted polyolefin copolymer in a twin screw extruder heated to a temperature of about 400-450 °F (204.4 - 232.2 °C), subjected to shear mixing and pelletized).

[00112] To determine the gel counts and distribution of gels in the various adhesive compositions, samples of each adhesive composition were separately introduced into a single screw extruder and extruded into 2 mil monolayer cast films. The content of gelled polymer in the resulting films was determined by counting the number of gels in a given area (10 m ² ) and normalizing the count by a laser gel scanner (/ ^' . e. , film inspection methods commercially available through OCS (Optical Control Systems) GmbH). The yellowness index of the various samples was further measured via ASTM method D 1925. The results are set forth in TABLE 1 and TABLE 2 below.

Table 1

Total Gel Count

Inventive (No./sq. Yellow Index Examples Gel Area (ppm) meter) (D1925-70)

In-line- 1 21.8 269 2.3

In-line-2 21.8 269 2.3

In-line-3 25.3 269.4 1.5

In-line-4 18.7 223.1 1 In-line-5 20.5 221.7 0.9

In-line-6 16.6 194.2 0.9

In-line-7 15.8 190.2 0.2

In-line- 8 15.1 187.4 0.7

In-line-9 16.2 201.4 1.4

In-line- 10 16.1 197.8 0.9

In-line- 1 1 15.3 189.6 0.4

In-line- 12 16.7 192.2 0.5

In-line- 13 15.6 196.6 0.8

215

Average 18.1 (13 count) (13 Count) 1.06 (13 count)

Table 2

[00113] While the foregoing is directed to embodiments of the present disclosure, further embodiments of the disclosure may be devised without departing from the scope of the present disclosure.