Propylene-ethylene copolymer and adhesive containing the propylene-ethylene copolymer

Abstract

There is provided a propylene-ethylene copolymer which exhibits excellent tensile strength and mechanical properties due to their specific propylene and ethylene contents, triad tacticity, viscosity, and crystallinity. Further, the inventors have discovered that certain processing conditions such as polymerization temperature and external donor to catalyst ratio can promote the production of the high tensile strength propylene-ethylene copolymer described herein. Further, the high tensile strength propylene-ethylene copolymer can be used to produce various hot melt adhesives, such as those for hygienic applications, woodworking applications, laminating applications, and packaging applications, which exhibit unique and excellent mechanical properties.

Description

Technical Field

[0001] Related Applications This PCT patent application was filed on July 26, 2022, and claims the benefit of priority to the previously filed U.S. Patent Application No. 17 / 873,929, entitled "PROPYLENE-ETHYLENE COPOLYMERS AND ADHESIVES CONTAINING PROPYLENE-ETHYLENE COPOLYMERS". The entire previously filed U.S. patent application identified above is incorporated herein by reference into this PCT patent application.

Background Art

[0002] (Field of the Invention) The present invention generally relates to propylene-ethylene copolymers and adhesives containing such copolymers. Specifically, but not exclusively, the present invention generally relates to propylene-ethylene copolymers that exhibit excellent tensile properties and adhesives containing such copolymers.

[0003] (Description of Related Art) Generally, hot melt adhesives contain two or more polyolefin polymers because most polyolefin polymers exhibit one or more properties such as low viscosity and / or low cohesive strength, making them unsuitable for use by themselves when forming an adhesive. Thus, most hot melt adhesives require a blend of a low viscosity polyolefin polymer and a high viscosity polyolefin polymer to meet certain performance criteria for the intended use of the adhesive and to meet the viscosity range for adhesive sprayability.

[0004] Due to deficiencies in existing polyolefin polymers, several manufacturers have attempted to modify the propylene and ethylene content of polyolefin polymers to form polymers that exhibit a specific ratio of needle penetration to softening point. However, despite the improvements associated with such polymers, these polymers generally do not exhibit the tensile strength and mechanical properties necessary to be utilized on their own without the need for a secondary polymer when forming an adhesive composition. These secondary polymers, which contain higher tensile and mechanical properties, also typically have a higher ring and ball softening point temperature and a higher viscosity, which slows down the adhesive, requires more energy to melt, and makes processing more difficult. Additionally, when higher tensile polyolefin polymers are utilized, the high initial adhesive strength generally decreases unacceptably with aging, particularly in sanitary applications such as diaper adhesives.

[0005] Accordingly, there remains a need for polyolefin polymers that exhibit desirable tensile strength and manageable processing characteristics for use in adhesive compositions. Additionally, there is a need for polyolefin polymers that have desirable tensile strength and adhesive strength that do not decrease unacceptably with aging. SUMMARY OF THE INVENTION

[0006] One or more aspects of the present disclosure generally relate to propylene-ethylene copolymers that include propylene and ethylene. Further, the propylene-ethylene copolymer includes (a) 77 to 90 weight percent ethylene, (b) 52% to 75% triad tacticity (mm%), (c) exhibits a ring and ball softening point of 95°C to 125°C, (d) has a Brookfield viscosity of 2,000 to 7,000 cP at 190°C, and (e) (i) exhibits a breaking point tensile strength of at least 4 MPa, or (ii) exhibits a breaking point tensile strength of at least 1 MPa and a breaking point elongation of at least 100%.

[0007] Regarding the propylene-ethylene copolymer disclosed above, one or more aspects of the present disclosure generally relate to adhesives comprising the propylene-ethylene copolymer referenced above. As described above, the propylene-ethylene copolymer comprises (a) 77 to 90 weight percent ethylene, (b) 52% to 75% triad tacticity (mm%), (c) a ring-and-ball softening point of 95°C to 125°C, (d) a Brookfield viscosity of 2,000 to 7,000 cP at 190°C, and (e) (i) a tensile strength at break of at least 4 MPa, or (ii) a tensile strength at break of at least 1 MPa and an elongation at break of at least 100%. Further, the adhesive comprises (a) 5 to 100 weight percent of the propylene-ethylene copolymer, (b) 0 to 55 weight percent of at least one second polymer, (c) at most 70 weight percent of at least one tackifier, (d) at most 20 weight percent of a processing oil, and (e) at most 35 weight percent of at least one wax.

[0008] The following description refers to various aspects of the present disclosure. The following descriptions of the aspects may be combined in any combination or may be applied separately to related aspects (e.g., one of the following limitations may be applicable to the first aspect, while another limitation may not be applicable to the first aspect).

[0009] According to a first aspect of the present disclosure, there is provided a propylene-ethylene copolymer comprising propylene and ethylene, the propylene-ethylene copolymer (a) comprises 77 to 90 weight percent propylene, (b) comprises 52% to 75% triad tacticity (mm%), (c) has a Brookfield viscosity of at least 4,000 cP at 190°C, (d) exhibits a ring-and-ball softening point of 90 to 155°C, (e) exhibits a tensile strength at break of at least 2.5 MPa.

[0010] In connection with the first aspect, the propylene-ethylene copolymer may contain 10 to 23 weight percent ethylene.

[0011] Additionally or alternatively, the triad tacticity of the propylene-ethylene copolymer is 53% to 70%.

[0012] Additionally or alternatively, the propylene-ethylene copolymer has a Brookfield viscosity of 4,000 to 88,000 cP at 190 °C.

[0013] Additionally or alternatively, the propylene-ethylene copolymer exhibits a heat of crystallization of 15 to 42 J / g and a heat of fusion of 9 to 33 J / g.

[0014] Additionally or alternatively, the propylene-ethylene copolymer exhibits a ring-and-ball softening point of 100 to 135 °C and a penetration of 2 to 24 dmm.

[0015] Additionally or alternatively, the propylene-ethylene copolymer exhibits an elongation at break of 100% to 1,000% and a tensile strength at break of 2.5 to 20 MPa.

[0016] Additionally or alternatively, the propylene-ethylene copolymer may contain less than 1 weight percent C4-C 10 alpha-olefin.

[0017] According to a second aspect of the present disclosure, alone or in combination with the first aspect, the propylene-ethylene copolymer (i) contains 10 to 23 weight percent ethylene, (ii) has a triad tacticity (mm%) of 53% to 70%, (iii) has a Brookfield viscosity of 4,000 to 88,000 cP at 190 °C, (iv) exhibits a tensile strength at break of 2.5 to 20 MPa, (v) exhibits a penetration of 3 to 23 dmm.

[0018] According to a third aspect of the present disclosure, alone or in combination with the first and second aspects, the propylene-ethylene copolymer is (a) containing 77 to 90 weight percent of propylene, (b) having a triad tacticity (mm%) of 52% to 75%, (c) having a ring-and-ball softening point of 95°C to 125°C, (d) having a Brookfield viscosity of 2,000 to 7,000 cP at 190°C, (e) (i) a tensile strength at break of at least 4 MPa, or (ii) showing a tensile strength at break of at least 4 MPa and an elongation at break of at least 100%.

[0019] According to a fourth aspect of the present disclosure, there is provided a propylene-ethylene copolymer containing propylene and ethylene, the propylene-ethylene copolymer being (a) containing 77 to 90 weight percent of propylene, (b) containing a triad tacticity (mm%) of 52% to 75%, (c) having a Brookfield viscosity of 7,000 to 15,000 cP at 190°C, (d) showing a ring-and-ball softening point of 90°C to 135°C, (e) showing a tensile strength at break of at least 2 MPa.

[0020] According to a fifth aspect of the present disclosure, there is provided a propylene-ethylene copolymer containing propylene and ethylene, the propylene-ethylene copolymer being (a) containing less than 77 to 89 weight percent of propylene, (b) containing a triad tacticity (mm%) of 52% to 75%, (c) having a Brookfield viscosity of more than 15,000 cP and less than 88,000 cP at 190°C, (d) showing a ring-and-ball softening point of 100°C to 155°C, (e) showing a tensile strength at break of at least 2.5 MPa.

[0021] According to a sixth aspect of the present disclosure, there is provided a composition comprising the propylene-ethylene copolymers contemplated in the first to fifth aspects, as well as additions and alternatives related to these aspects.

[0022] According to a seventh aspect of the present disclosure, there is provided a method for producing the propylene-ethylene copolymers of the first to fifth aspects and additional or alternative ones related to these aspects, the method comprising polymerizing ethylene and propylene at a temperature of 160 °C or lower, wherein the polymerization occurs in the presence of a catalyst system having a molar ratio of aluminum to titanium in the range of 1:1 to 100:1.

[0023] According to an eighth aspect of the present disclosure, there is provided a composition comprising: (a) 5 to 100 weight percent of a propylene-ethylene copolymer, (i) containing 77 to 90 weight percent of propylene, (ii) containing 52% to 75% triad tacticity (mm%), (iii) having a Brookfield viscosity of at least 4,000 cP at 190 °C, (iv) showing a ring and ball softening point of 90 to 135 °C, (v) showing a tensile strength at break of at least 2.5 MPa, (b) 0 to 55 weight percent of at least one second polymer, (c) at most 70 weight percent of at least one tackifier, (d) at most 20 weight percent of processing oil, (e) at most 35 weight percent of at least one wax.

[0024] In connection with the eighth aspect, the propylene-ethylene copolymer may contain 10 to 23 weight percent of ethylene.

[0025] Additionally or alternatively, the triad tacticity of the propylene-ethylene copolymer is 53% to 70%.

[0026] Additionally or alternatively, the propylene-ethylene copolymer has a Brookfield viscosity of 4,000 to 88,000 cP at 190 °C.

[0027] Additionally or alternatively, the propylene-ethylene copolymer exhibits a heat of crystallization of 15 to 42 J / g and a heat of fusion of 9 to 33 J / g.

[0028] Additionally or alternatively, the propylene-ethylene copolymer exhibits a ring and ball softening point of 100 to 135 °C and a penetration of 2 to 24 dmm.

[0029] Additionally or alternatively, the propylene-ethylene copolymer exhibits an elongation at break of 100% to 1,000% and a tensile strength at break of 2.5 to 20 MPa.

[0030] Additionally or alternatively, the composition comprises 20 to 80 weight percent of a propylene-ethylene copolymer.

[0031] Additionally or alternatively, the composition (a) 25 to 45 weight percent of a propylene-ethylene copolymer, and (b) 0 to 15 weight percent of a second polymer, and (c) 45 to 50 weight percent of a tackifier, and (d) 0 to 15 weight percent of a processing oil, and (e) 0 to 10 weight percent of a wax.

[0032] Additionally or alternatively, the composition has a Brookfield viscosity in the range of 500 to 20,000 cP at 190 °C.

[0033] According to a ninth aspect of the present disclosure, a composition comprising (a) 5 to 100 weight percent of a propylene-ethylene copolymer, wherein (i) contains 77 to 90 weight percent of propylene, and (ii) contains 52% to 75% of triad tacticity (mm%). (iii) showing a ring-and-ball softening point of 90°C to 135°C, (iii) having a Brookfield viscosity of 7,000 to 15,000 cP at 190°C, (iv) showing a breaking point tensile strength of at least 2 MPa, a propylene-ethylene copolymer, and (b) 0 to 55 weight percent of at least one second polymer, and (c) at most 70 weight percent of at least one tackifier, and (d) at most 20 weight percent of processing oil, and (e) at most 35 weight percent of at least one wax, a composition is provided.

[0034] In connection with the ninth aspect, the composition (a) 35 to 50 weight percent of a propylene-ethylene copolymer, and (b) 0 to 15 weight percent of a second polymer, and (c) 35 to 50 weight percent of a tackifier, and (d) 0 to 15 weight percent of processing oil, and (e) 0 to 10 weight percent of a wax, and includes.

[0035] Additionally or alternatively, the composition (a) 35 to 55 weight percent of a propylene-ethylene copolymer, and (b) 35 to 55 weight percent of a tackifier, and (c) 0 to 15 weight percent of processing oil, and (d) 0 to 7 weight percent of a wax, and includes.

[0036] Additionally or alternatively, the composition has a Brookfield viscosity in the range of 1,000 to 4,000 cP at 150°C.

[0037] Additionally or alternatively, the composition shows a peel strength after 24 hours of aging that is at least 80 percent of the initial peel strength of the composition.

[0038] According to a tenth aspect of the present disclosure, a composition comprising: (a) 30 to 45 weight percent of a propylene-ethylene copolymer, (i) containing 77 to 90 weight percent of propylene, (ii) containing 52% to 75% triad tacticity (mm%), (iii) showing a ring-and-ball softening point of 90°C to 135°C, (iii) having a Brookfield viscosity of 7,000 to 15,000 cP at 190°C, (iv) showing a tensile strength at break of at least 2 MPa, and a propylene-ethylene copolymer, (b) 0 to 15 weight percent of a second polymer, (c) 40 to 50 weight percent of a tackifier, (d) 0 to 20 weight percent of a processing oil, (e) 0 to 10 weight percent of a wax, is provided.

[0039] In connection with the tenth aspect, the composition has a Brookfield viscosity in the range of 1,000 to 5,000 cP at 150°C.

[0040] Additionally or alternatively, the composition exhibits a peel strength after 24 hours of aging that is at least 80 percent of the initial peel strength of the composition.

[0041] According to an eleventh aspect of the present disclosure, a composition comprising: (a) 5 to 100 weight percent of a propylene-ethylene copolymer, (i) containing at least 77 weight percent and less than 89 weight percent of propylene, (ii) containing 52% to 75% triad tacticity (mm%), (iii) showing a ring-and-ball softening point of 100°C to 155°C, (iii) having a Brookfield viscosity at 190°C greater than 15,000 cP and less than 88,000 cP, (iv) A propylene-ethylene copolymer exhibiting a breaking point tensile strength of at least 2.5 MPa, and (b) at least one second polymer of 0 to 55 weight percent, and (c) at least one tackifier of 70 weight percent or less, and (d) processing oil of 20 weight percent or less, and (e) at least one wax of 35 weight percent or less, a composition is provided.

[0042] In relation to the 11th aspect, the composition (a) 30 to 45 weight percent of a propylene-ethylene copolymer, and (b) 0 to 15 weight percent of a second polymer, and (c) 40 to 50 weight percent of a tackifier, and (d) 10 to 20 weight percent of processing oil, and (e) 0 to 10 weight percent of a wax, and includes. The composition has a Brookfield viscosity in the range of 1,000 to 5,000 cP at 150 °C.

[0043] In relation to the 11th aspect, the composition has a Brookfield viscosity in the range of 1,000 to 5,000 cP at 150 °C.

[0044] Additionally or alternatively, the composition has a Brookfield viscosity in the range of 1,000 to 20,000 cP at 190 °C.

[0045] Additionally or alternatively, the composition exhibits a peel strength after 24 hours of aging that is at least 80 percent of the initial peel strength of the composition.

[0046] According to a twelfth aspect of the present disclosure, there is provided an article comprising the propylene-ethylene copolymer of the first to fifth aspects and / or the composition of the sixth and / or eighth to eleventh aspects, the article being selected from the group consisting of adhesives, sealants, caulking materials, roofing membranes, waterproof membranes and liners, carpets, laminates, laminate articles, tapes, labels, mastics, polymer blends, wire coatings, molded articles, heat-seal coatings, disposable sanitary articles, insulating glass (IG) units, bridge decks, electronic enclosures, waterproof membranes, waterproof compounds, liners, cable flooding / filling compounds, sheet molding compounds, dough molded compounds, overmold compounds, rubber compounds, polyester composites, glass composites, glass fiber reinforced plastics, wood plastic composites, polyacrylic blend compounds, lost wax precision casting, investment casting wax compositions, book binding, candles, windows, tires, films, gaskets, seals, O-rings, motor vehicles, motorcycles, motor vehicle molded parts, motor vehicle extruded parts, clothing articles, rubber additives / processing aids, and fibers. When the article is an adhesive, the adhesive is a packaging adhesive, a food contact grade adhesive, an indirect food contact packaging adhesive, a product assembly adhesive, a woodworking adhesive, an edge banding adhesive, a profile wrapping adhesive, a flooring adhesive, an automotive assembly adhesive, a structural adhesive, a flexible lamination adhesive, a rigid lamination adhesive, a flexible film adhesive, a flexible packaging adhesive, a water-activated adhesive, a household repair adhesive, an industrial adhesive, a construction adhesive, a furniture adhesive, a mattress adhesive, a pressure sensitive adhesive (PSA), a PSA tape, a PSA label, a PSA protective film, a self-adhesive film, a lamination adhesive, a flexible packaging adhesive, a heat-seal adhesive, an industrial adhesive, a sanitary nonwoven construction adhesive, a sanitary core integrity adhesive, or a sanitary elastic attachment adhesive.

Brief Description of the Drawings

[0047] Embodiments of the present invention are described herein with reference to the following drawings.

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Mode for Carrying Out the Invention

[0048] The inventors have found that a propylene-ethylene copolymer having a triad tacticity, in combination with a specific propylene content and ethylene content, and other characteristics such as viscosity and crystallinity, can exhibit excellent tensile strength and mechanical properties. Furthermore, the inventors have found that certain processing conditions, such as polymerization temperature and external donor-to-catalyst ratio, can promote the production of the propylene-ethylene copolymers of the present invention described herein. Furthermore, the inventors have found that using these propylene-ethylene copolymers with excellent tensile strength, various compositions can be produced, including adhesives for sanitary applications, woodworking applications, laminating applications, and packaging applications, which exhibit unique and excellent mechanical properties (e.g., excellent peel strength and peel strength after aging).

[0049] The viscosity of the polymer is the 3.4th power of the entangled polymer melt (M 3.4) is known to be proportional to the increased molecular weight. It is also known that the mechanical strength of a polymer increases with its molecular weight as long polymer chains become entangled and increase the strength of the bulk polymer. As a result, polymers with similar monomer compositions and viscosities (molecular weights) have similar tensile strengths. The inventors have discovered that the tensile strength and elongation at break of the propylene-ethylene copolymers of the present invention were unexpectedly high at a given propylene content and viscosity.

[0050] More specifically, the inventors have discovered that the triad tacticity of propylene-ethylene copolymers can be important in controlling tensile strength, elongation at break, crystallinity, penetration, and adhesive aging properties. Further, the inventors have discovered that the triad tacticity must be selectively controlled along with the ethylene content of the copolymers of the present invention, because the crystal defects caused by the ethylene content also affect these important physical properties. Further, as will be discussed in more detail below, the inventors have discovered that polymerization temperature and external donor to catalyst ratio can be effective ways to control the triad tacticity of the resulting propylene-ethylene copolymers.

[0051] Furthermore, the inventors have discovered that the propylene-ethylene copolymers of the present invention can be used as the sole polymer or as the main polymer when producing a desired adhesive. The inventors have discovered that an adhesive formulation containing the propylene-ethylene copolymers of the present invention can exhibit desirable softening points and viscosities that allow the adhesive to be sprayed at 150 °C. Further, such adhesives were able to exhibit stable or increasing peel strengths after aging for 24 hours, 4 hours (38 °C), 2 weeks (55 °C), and 1 month (25 °C).

[0052] Important features of the propylene-ethylene copolymer of the present invention are described in more detail below. Most of the following features and properties of the propylene-ethylene copolymer and the adhesive of the present invention can be listed separately, but each of the following features and / or properties of the copolymer and the adhesive is not mutually exclusive and is assumed to be combinable and can exist in any combination as long as such a combination does not result in a contradiction (e.g., incompatible weight percentage ranges).

[0053] According to various embodiments, the propylene-ethylene copolymer described herein may contain various amounts of ethylene. In certain embodiments, or in combination with any of the embodiments referred to herein, the propylene-ethylene copolymer may contain at least 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 weight percent ethylene, based on the total weight of the copolymer. Additionally, or alternatively, the propylene-ethylene copolymer may contain less than 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 20, 19, or 18 weight percent ethylene, based on the total weight of the copolymer.

[0054] In certain embodiments, or in combination with any of the embodiments referred to herein, the propylene-ethylene copolymer may contain ethylene in the range of 0.5 to 30, 0.5 to 25, 0.5 to 23, 0.5 to 21, 0.5 to 18, 5 to 30, 5 to 25, 5 to 23, 5 to 21, 5 to 18, 8 to 30, 8 to 25, 8 to 23, 8 to 21, 8 to 18, 10 to 30, 10 to 25, 10 to 23, 10 to 21, 10 to 18, 15 to 30, 15 to 25, 15 to 23, 15 to 21, 15 to 18, 18 to 30, 18 to 25, 18 to 23, or 18 to 21 weight percent, based on the total weight of the copolymer.

[0055] Furthermore, in various embodiments, the propylene-ethylene copolymer may contain various amounts of propylene. In certain embodiments, or in combination with any of the embodiments referred to herein, the propylene-ethylene copolymer may contain at least 72, 75, 77, 78, 79, 80, 81, or 82 weight percent propylene, based on the total weight of the copolymer. Additionally, or alternatively, the propylene-ethylene copolymer may contain less than 90, 89, 88, 87, 86, 85, 84, 83, or 82 weight percent propylene, based on the total weight of the copolymer.

[0056] In certain embodiments, or in combination with any of the embodiments referred to herein, the propylene-ethylene copolymer may contain from 72 to 90, 72 to 89, 72 to 88, 77 to 90, 77 to 89, 77 to 88, 77 to 86, 77 to 84, 77 to 82, 79 to 90, 79 to 89, 79 to 88, 79 to 86, 79 to 84, 79 to 82, 82 to 90, 82 to 89, or 82 to 88 weight percent propylene, based on the total weight of the copolymer.

[0057] The ethylene and propylene content of the copolymer was determined by NMR via techniques described in Macromolecules 2000, 33, 1157 - 1162 by Wang et al. (incorporated herein by reference in its entirety).

[0058] In certain embodiments, or in combination with any of the embodiments referred to herein, the propylene-ethylene copolymer may contain one or more C4 - C 10 alpha-olefins. Generally, C4 - C 10 alpha-olefins, when utilized in adhesives, can be used to increase the resulting bond strength of the copolymer. These C4 - C 10 alpha-olefins can include, for example, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and combinations thereof.

[0059] In one embodiment, or in combination with any of the embodiments referred to herein, the copolymer comprises at least one C4-C 10 alpha-olefin of 10, 8, 5, 3, 2, 1, 0.5, or 0.1 weight percent or less, based on the total weight of the copolymer. Further, in various embodiments, the copolymer comprises at least one C4-C 10 alpha-olefin in the range of 0.5 to 10, 1 to 10, 2 to 10, 3 to 10, 4 to 10, or 5 to 10 weight percent, based on the total weight of the copolymer.

[0060] In certain embodiments, the propylene-ethylene copolymer may not contain any C4-C 10 alpha-olefin.

[0061] In one embodiment, or in combination with any of the embodiments referred to herein, the propylene-ethylene copolymer may have a triad tacticity of at least 52, 53, 54, 55, 56, 57, 58, 59, 60, or 61 mm content % or more. Additionally or alternatively, the propylene-ethylene copolymer may have a triad tacticity of less than 75, 74, 73, 72, 71, 70, 69, 68, 67, 66, 65, 64, 63, 62, 61, or 60 mm content %.

[0062] In one embodiment, or in combination with any of the embodiments referred to herein, the propylene-ethylene copolymer may have a triad tacticity in the range of 52 to 75, 52 to 74, 52 to 70, 52 to 65, 52 to 60, 53 to 75, 53 to 74, 53 to 70, 53 to 65, 53 to 60, 54 to 75, 54 to 74, 54 to 70, 54 to 67, 54 to 66, 54 to 65, 54 to 60, 55 to 75, 55 to 74, 55 to 70, 55 to 65, 55 to 60, 58 to 75, 58 to 74, 58 to 70, 58 to 68, 60 to 75, 60 to 74, 60 to 70, 60 to 68, 61 to 75, 61 to 74, 61 to 70, or 61 to 68 mm content %.

[0063] The equations for measuring the triad tacticity can be found in U.S. Patent No. 5,504,172 and the paper by Tsutsui et al. (Polymer 1989, 30, 1350 - 1356), both of which are hereby incorporated by reference in their entirety. The triad tacticity of a polymer is the relative tacticity of the sequence of three adjacent propylene units, which is a chain consisting of head - to - tail linkages and is represented as a binary combination of meso (m) and racemic (r) sequences. The triad tacticity represented herein as "mm" is determined by 13C nuclear magnetic resonance (NMR) and the following equation:

[0064]

Number

[0065]

Chemistry

[0066] In one embodiment, or in combination with any of the embodiments referred to herein, the propylene-ethylene copolymer may have a Brookfield viscosity of at least 2,000, 3,000, 4,000, 5,000, 6,000, 7,000, 8,000, 9,000, 10,000, 11,000, 12,000, 13,000, 14,000, 15,000, 16,000, 20,000, 25,000, 27,000, 30,000, 35,000, 40,000, 45,000, 50,000, 55,000, 60,000, 65,000, 70,000, 75,000, 80,000, 85,000, 90,000 cp at 190°C. Additionally, or alternatively, the propylene-ethylene copolymer may have a Brookfield viscosity of less than 120,000, 110,000, 100,000, 90,000, 88,000, 80,000, 70,000, 60,000, 50,000, 40,000, 35,000, 30,000, 27,000, 26,000, 25,000, 20,000, 18,000, 17,000, 16,000, 15,000, 14,000, 13,000, 12,000, 11,000, 10,000, 7,000, 6,000, 5,000, 4,000, 3,000, or 2,000 cP at 190°C as measured according to ASTM D-3236.

[0067] In one embodiment, or in combination with any of the embodiments referred to herein, the propylene-ethylene copolymer may have a higher Brookfield viscosity in the range of 4,000 to 88,000, 15,000 to 88,000, 15,000 to 60,000, 15,000 to 26,000, 27,000 to 40,000, 27,000 to 35,000, 27,000 to 30,000, 15,000 to 26,000, 4,000 to 60,000, or 27,000 to 120,000 cP at 190°C as measured according to ASTM D-3236. Additionally, or alternatively, the propylene-ethylene copolymer may have a higher Brookfield viscosity greater than 15,000 cP and less than 88,000 cP at 190°C.

[0068] In one embodiment, or in combination with any of the embodiments referred to herein, the propylene-ethylene copolymer may have a midpoint Brookfield viscosity in the range of 7,000 to 15,000, 7,000 to 14,000, 7,000 to 13,000, or 7,000 to 12,000 cP at 190 °C as measured according to ASTM D-3236.

[0069] In one embodiment, or in combination with any of the embodiments referred to herein, the propylene-ethylene copolymer may have a low Brookfield viscosity in the range of 2,000 to 7,000, 3,000 to 7,000, 4,000 to 7,000, 4,000 to 27,000, 7,000 to 12,000, or 4,000 to 6,000 cP at 190 °C as measured according to ASTM D-3236.

[0070] In one embodiment, or in combination with any of the embodiments referred to herein, the propylene-ethylene copolymer may have a peak Tm of at least 70, 72, 74, 75, 76, 78, 80, 82, 84, 85, 86, 88, or 90 °C. Additionally or alternatively, the propylene-ethylene copolymer may have a peak Tm of 121, 120, 118, 116, 114, 112, 110, 108, 106, 104, 102, 100, 98, 96, 94, 92, 90, 89, 88, 87, 86, or 85 °C. The peak Tm may be measured according to the procedure outlined in "DSC as Problem Solving Tool: Measurement of Percent Crystallinity of Thermoplastics" by Sichina et al., which is hereby incorporated by reference in its entirety. The peak Tm refers to the assigned temperature that the DSC software identifies as the integral peak of the melting transition from the Tm endotherm.

[0071] In one embodiment, or in combination with any of the embodiments referred to herein, the propylene-ethylene copolymer may have a peak Tm in the range of 70 - 90 °C, 70 - 89 °C, 70 - 88 °C, 70 - 87 °C, 70 - 86 °C, 70 - 85 °C, 74 - 85 °C, 85 - 121 °C, or 90 - 110 °C.

[0072] Generally, the softening point of the propylene-ethylene copolymer can be modified and optimized by controlling the comonomer content, triad tacticity, crystallinity, and viscosity of the propylene-ethylene copolymer. It may be desirable for the copolymer to have a lower softening point so that it can be utilized and processed at lower application temperatures. In one embodiment, or in combination with any of the embodiments referred to herein, the propylene-ethylene copolymer, when measured according to ASTM E28 Standard Test Method for Softening Point of Resins Derived from Pine Chemicals and Hydrocarbons using a Ring-and-Ball apparatus with a heating rate of 5 °C per minute and a bath solution of USP glycerin, may exhibit a ring-and-ball softening point of at least 90 °C, 94 °C, 95 °C, 100 °C, 105 °C, 110 °C, 113 °C, or 115 °C. Additionally or alternatively, the propylene-ethylene copolymer, when measured according to ASTM E28 Standard Test Method for Softening Point of Resins Derived from Pine Chemicals and Hydrocarbons using a Ring-and-Ball apparatus with a heating rate of 5 °C per minute and a bath solution of USP glycerin, may exhibit a ring-and-ball softening point of less than 160 °C, 155 °C, 150 °C, 145 °C, 140 °C, 138 °C, 135 °C, 134 °C, 133 °C, 130 °C, 125 °C, 120 °C, 117 °C, 115 °C, or 110 °C.

[0073] In one embodiment, or in combination with any of the embodiments referred to herein, the propylene-ethylene copolymer has a ring-and-ball softening point in the range of 90 to 155 °C, 90 to 135 °C, 94 to 154 °C, 94 to 110 °C, 94 to 135 °C, 95 to 155 °C, 95 to 135 °C, 95 to 125 °C, 105 to 155 °C, 105 to 140 °C, 100 to 135 °C, 100 to 134 °C, 100 to 133 °C, 100 to 130 °C, 100 to 125 °C, 100 to 120 °C, 100 to 117 °C, 100 to 110 °C, 105 to <120> °C, or 113 to 138 °C when measured according to ASTM E28 Standard Test Method for Softening Point of Resins Derived from Pine Chemicals and Hydrocarbons using a Ring-and-Ball apparatus with a heating rate of 5 °C per minute and a bath solution of USP glycerin or silicone oil.

[0074] Generally, the penetration of the propylene-ethylene copolymer can be modified and optimized by controlling the comonomer content, triad tacticity, crystallinity, and viscosity of the propylene-ethylene copolymer. In one embodiment, or in combination with any of the embodiments referred to herein, the propylene-ethylene copolymer can have a penetration of at least 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, or 175 decimillimeters (dmm). Additionally, or alternatively, the propylene-ethylene copolymer can have a penetration of less than 35, 30, 26, 25, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, or 11 dmm when measured according to ASTM D5 Standard Test Method for Penetration of Bituminous Materials.

[0075] In one embodiment, or in combination with any of the embodiments referred to herein, the propylene-ethylene copolymer may have a penetration in the range of 2 to 26 dmm, 2 to 23 dmm, 3 to 23 dmm, 3 to 20 dmm, 5 to 23 dmm, 6 to 23 dmm, 10 to 23 dmm, 13 to 23 dmm, 6 to 22 dmm, 15 to 21 dmm, 17 to 22 dmm, 2 to 17 dmm, 2 to 15 dmm, 2 to 13 dmm, or 2 to 11 dmm.

[0076] Generally, the breaking point tensile strength of a propylene-ethylene copolymer can be modified and optimized by controlling the comonomer content, triad tacticity, crystallinity, and viscosity of the propylene-ethylene copolymer. In certain embodiments, or in combination with any of the embodiments referred to herein, the propylene-ethylene copolymer has a breaking point tensile strength of at least 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, or 4.0 MPa as measured according to ASTM D412 Standard Test Methods for Vulcanized Rubber and Thermoplastic Elastomers-Tension. Additionally, or alternatively, the propylene-ethylene copolymer has a breaking point tensile strength of less than 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2.5, or 2 MPa as measured according to ASTM D412.In one embodiment, or in combination with the embodiments referred to herein, the propylene-ethylene copolymer may exhibit a breaking tensile strength in the range of 2 to 20 MPa, 2 to 17 MPa, 2 to 15 MPa, 2 to 12 MPa, 2 to 10 MPa, 2 to 9 MPa, 2 to 8 MPa, 2 to 6 MPa, 2 to 4 MPa, 2 to 3 MPa, 2 to 2.3 MPa, 2.5 to 20 MPa, 2.5 to 17 MPa, 2.5 to 15 MPa, 2.5 to 12 MPa, 2.5 to 10 MPa, 2.5 to 9 MPa, 2.5 to 8 MPa, 2.6 to 20 MPa, 2.6 to 17 MPa, 2.6 to 15 MPa, 2.6 to 12 MPa, 2.6 to 10 MPa, 2.6 to 9 MPa, 2.6 to 8 MPa, 2.8 to 20 MPa, 2.8 to 17 MPa, 2.8 to 15 MPa, 2.8 to 12 MPa, 2.8 to 10 MPa, 2.8 to 9 MPa, 2.8 to 8 MPa, 3 to 20 MPa, 3 to 17 MPa, 3 to 15 MPa, 3 to 12 MPa, 3 to 10 MPa, 3 to 9 MPa, 3.5 to 20 MPa, 3.5 to 17 MPa, 3.5 to 15 MPa, 3.5 to 12 MPa, 3.5 to 10 MPa, 3.5 to 9 MPa, 3.5 to 8 MPa, 4 to 20 MPa, 4 to 15 MPa, 4 to 12 MPa, 4 to 10 MPa, 4 to 9 MPa, 4 to 8 MPa, or 4 to 6 MPa when measured according to ASTM D412.

[0077] Generally, the elongation at break of the propylene-ethylene copolymer can be modified and optimized by controlling the comonomer content, triad tacticity, crystallinity, and viscosity of the propylene-ethylene copolymer. In one embodiment, or in combination with any of the embodiments referred to herein, the propylene-ethylene copolymer may exhibit an elongation at break of at least 70, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, or 600% when measured according to ASTM D412. Additionally, or alternatively, the propylene-ethylene copolymer may exhibit an elongation at break of less than 1,000, 900, 800, 700, 600, or 500% when measured according to ASTM D412.

[0078] In one embodiment, or in combination with any of the embodiments referred to herein, the propylene-ethylene copolymer can exhibit a breaking elongation in the range of 70 to 1,000%, 70 to 800%, 70 to 500%, 100 to 1,000%, 100 to 800%, 200 to 1,000%, 200 to 800%, 300 to 1,000%, 300 to 800%, 450 to 1,000%, 450 to 800%, 500 to 1,000%, or 500 to 800% when measured according to ASTM D412.

[0079] In one embodiment, or in combination with any of the embodiments referred to herein, the propylene-ethylene copolymer has a heat of crystallization (H c , cooling rate 20 °C / min) of at least 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, or 23 J / g. Additionally or alternatively, the propylene-ethylene copolymer has a heat of crystallization (H c , cooling rate 20 °C / min) of less than 50, 45, 42, 40, 38, 36, 34, 33, 32, 31, 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 20, 19, or 18 J / g. For example, the propylene-ethylene copolymer has a heat of crystallization (H c , cooling rate 20 °C / min) in the range of 15 to 42, 15 to 33, 15 to 25, 15 to 24, 15 to 23, 15 to 22, 15 to 21, 15 to 20, 15 to 19, 15 to 18, 16 to 36, 16 to 33, 16 to 29, 16 to 22, 16 to 21, 16 to 20, 20 to 30, 20 to 28, 20 to 26, 23 to 42, or 24 to 29 J / g.

[0080] In one embodiment, or in combination with any of the embodiments referred to herein, the propylene-ethylene copolymer has a heat of fusion (H f, and can exhibit a heating rate of 20 °C / min. For example, the propylene-ethylene copolymer has a heat of fusion (H) in the range of 8 - 40, 8 - 35, 9 - 33, 9 - 20, 9 - 18, 9 - 16, 9 - 15, 9 - 14, 10 - 29, 10 - 21, 11 - 29, 11 - 19, 11 - 16, 11 - 15, 11 - 14, 12 - 33, or 13 - 20 J / g. f , and can exhibit a heating rate of 20 °C / min.

[0081] Additionally, the propylene-ethylene copolymers described herein can be amorphous or semi-crystalline. As used herein, "amorphous" means that the copolymer has less than 5 percent crystallinity when measured using differential scanning calorimetry ("DSC") in accordance with ASTM E 794-85. As used herein, "semi-crystalline" means that the copolymer has crystallinity in the range of 5 - 40 percent when measured using DSC at a scan rate of 20 °C / min in accordance with ASTM E794-85. In certain embodiments, or in combination with any of the embodiments referred to herein, the copolymer can have at least 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 percent crystallinity when measured in accordance with ASTM E794-85. Additionally or alternatively, the copolymer can have less than 60, 50, 45, 40, 35, 30, 25, 24, 23, or 22 percent crystallinity when measured using DSC in accordance with ASTM E794-85. For example, the copolymer can have crystallinity in the range of 2 - 50, 3 - 46, 4 - 40, 4 - 30, 4 - 20, 16 - 25, 16 - 23, 17 - 25, 17 - 23, 20 - 35, or 20 - 30 percent when measured using DSC in accordance with ASTM E794-85.

[0082] In one embodiment, or in combination with any of the embodiments referred to herein, the propylene-ethylene copolymer does not exhibit a substantial change in color when subjected to storage conditions at elevated temperatures over an extended period of time. Prior to any aging resulting from storage, the copolymer of the present invention may have an initial Gardner color of less than 4, 3, 2, or 1 when measured according to ASTM D1544. Additionally, or alternatively, after thermal aging at 177° C. for at least 96 hours, the copolymer of the present invention may exhibit a final Gardner color of less than 7, 5, 3, or 2 when measured according to ASTM D1544. Thus, the copolymer of the present invention can retain a desirable color even after extended storage and exposure.

[0083] In one embodiment, or in combination with any of the embodiments referred to herein, the propylene-ethylene copolymer can contain ethylene in the range of 8 to 25 weight percent based on the total weight of the copolymer, can have a triad tacticity in the range of 55 to 70 mm%, can have a tensile strength at break in the range of 0.9 to 10 MPa when measured according to ASTM D412, a ring and ball softening point in the range of 100° C. to 135° C. when measured according to ASTM E28, and a viscosity at 190° C. in the range of 15,000 to 30,000 cP when measured according to ASTM D-3236.

[0084] Exemplary propylene-ethylene copolymer compositions having high viscosity, high tensile strength and high elongation for use in various adhesives such as woodworking adhesives are provided in Table 1A below. As shown below, Table 1A provides wide, intermediate, and narrow ranges for various characteristics of these high-viscosity propylene-ethylene copolymers, and these ranges can be combined in any combination regardless of their categories (e.g., one or more wide ranges can be combined with one or more intermediate ranges and / or narrow ranges). Further, wide, intermediate, and narrow ranges are provided in Table 1A, but it is contemplated that any of the ranges described above for general propylene-ethylene copolymers may be applicable to the copolymer compositions provided in Table 1A as long as such ranges do not create contradictions.

[0085]

Table 1

[0086] Exemplary propylene-ethylene copolymer compositions having high viscosity and medium tensile strength for use in various adhesives such as laminating adhesives and woodworking adhesives are provided in Table 1B below. As shown below, Table 1B provides wide, intermediate, and narrow ranges for various characteristics of these high-viscosity propylene-ethylene copolymers, and these can be combined in any combination regardless of their categories (e.g., one or more wide ranges can be combined with one or more intermediate ranges and / or narrow ranges). Further, wide, intermediate, and narrow ranges are provided in Table 1B, but it is contemplated that any of the ranges described above for general propylene-ethylene copolymers may be applicable to the copolymer compositions provided in Table 1B as long as such ranges do not create contradictions.

[0087]

Table 2

[0088] Exemplary propylene-ethylene copolymer compositions for use in a variety of adhesives, such as sanitary adhesives, having medium viscosity and exhibiting medium tensile strength are provided in Table 1C below. As shown below, Table 1C provides wide, intermediate, and narrow ranges for various characteristics of these medium viscosity propylene-ethylene copolymers, which may be combined in any combination regardless of their categories (e.g., one or more wide ranges may be combined with one or more intermediate ranges and / or narrow ranges). Further, while wide, intermediate, and narrow ranges are provided in Table 1C, it is contemplated that any of the ranges described above for general propylene-ethylene copolymers may be applicable to the copolymer compositions provided in Table 1C so long as such ranges do not create a contradiction.

[0089]

Table 3

[0090] Exemplary propylene-ethylene copolymer compositions for use in a variety of adhesives, such as packaging and sanitary adhesives, having low viscosity and exhibiting medium tensile strength are provided in Table 1D below. As shown below, Table 1D provides wide, intermediate, and narrow ranges for various characteristics of these low viscosity propylene-ethylene copolymers, which may be combined in any combination regardless of their categories (e.g., one or more wide ranges may be combined with one or more intermediate ranges and / or narrow ranges). Further, while wide, intermediate, and narrow ranges are provided in Table 1D, it is contemplated that any of the ranges described above for general propylene-ethylene copolymers may be applicable to the copolymer compositions provided in Table 1D so long as such ranges do not create a contradiction.

[0091]

Table 4

[0092] Process for Producing Propylene-Ethylene Copolymer As described above, the present disclosure relates to a group of propylene-ethylene copolymers that exhibit desirable tensile properties at a processable viscosity and a suitable ring and ball softening point, and can thus be utilized in various adhesives. Without wishing to be bound by theory, it is believed that these unique tensile properties and ring and ball softening point are obtained due to a combination of several different copolymer characteristics such as the propylene / ethylene content of the copolymer, the triad tacticity content (mm%) of the copolymer, the crystallinity of the copolymer, and the viscosity of the copolymer. Additionally, it has been observed that certain process conditions can also facilitate the production of the copolymers of the present invention described herein. As will be discussed below, it has been observed that certain reaction conditions (e.g., polymerization temperature) and catalyst system components (e.g., external donor to catalyst ratio) can have a significant impact on the resulting propylene-ethylene copolymer.

[0093] The propylene-ethylene copolymer can be produced by reacting a propylene monomer and an ethylene monomer in the presence of a catalyst system comprising at least one electron donor.

[0094] In certain embodiments, or in combination with any of the embodiments referred to herein, the catalyst system can include a Ziegler-Natta catalyst. Generally, a Ziegler-Natta catalyst can contain a titanium-containing component, an aluminum component, and an electron donor. In certain specific embodiments, the catalyst includes titanium chloride on a magnesium chloride support.

[0095] In certain embodiments, or in combination with any of the embodiments referred to herein, the catalyst system can include a heterogeneous supported catalyst system formed from a titanium compound in combination with an organoaluminum cocatalyst. Generally, the cocatalyst can include an alkylaluminum cocatalyst such as triethylaluminum ("TEAL").

[0096] In one embodiment, or in combination with any of the embodiments referred to herein, the catalyst system can have an aluminum to titanium molar ratio of at least 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, or 15:1, and / or 100:1, 50:1, 35:1, or 25:1 or less. Additionally, or alternatively, the catalyst system can have an aluminum to titanium molar ratio in the range of 1:1 to 100:1, 5:1 to 50:1, 10:1 to 35:1, or 15:1 to 25:1.

[0097] In one embodiment, or in combination with any of the embodiments referred to herein, in various embodiments, the catalyst system can have an aluminum to silicon molar ratio of at least 0.1:1, 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, or 6:1, and / or 100:1, 50:1, 35:1, 20:1, 15:1, 10:1, or 8:1 or less. Additionally, or alternatively, the catalyst system can have an aluminum to silicon molar ratio in the range of 0.5:1 to 100:1, 1:1 to 50:1, 2:1 to 35:1, 2:1 to 20:1, 2:1 to 15:1, 2:1 to 10:1, or 2:1 to 8:1.

[0098] Generally, electron donors can increase the stereospecificity of the copolymer. However, it can be important to precisely regulate the content of electron donors as they can suppress the catalytic activity to an unacceptable level in some situations. Examples of electron donors used during the polymerization process can include, for example, organic esters, ethers, alcohols, amines, ketones, phenols, phosphines, and / or organosilanes. Further, the catalyst system can include an internal donor and / or an external donor.

[0099] As defined in 「Stereospecific α-Olefin Polymerization with Heterogeneous Catalysts,」 by J. Severn and R. L. Jones Jr, Handbook of Transition Metal Polymerization Catalysts, (2018) Chapter 9, p229 - 312 (incorporated herein by reference in its entirety), there are multiple generations of internal donors for Ziegler - Natta catalyst systems. The Ziegler - Natta catalysts can be divided into multiple generations, which are described in more detail below.

[0100] Ziegler - Natta Catalyst, 3rd Generation (Benzoate): The 3rd generation catalysts typically contain MgCl2, TiCl4, and an internal electron donor, which are combined with an aluminum alkyl co - catalyst such as Al(CH2CH3)3. An "external" electron donor can be added to the catalyst system. The internal donor in the 3rd generation catalysts is typically ethyl benzoate, which is used in combination with a second aromatic ester such as methyl p - toluate or ethyl p - ethoxybenzoate (PEEB) as an external donor. An external donor is required because most of the internal donor is lost as a result of reactions involving the co - catalyst such as alkylation and / or complexation reactions. In most cases, the external donor replaces the internal donor in the solid catalyst and maintains high catalyst stereospecificity.

[0101] Ziegler - Natta Catalyst, 4th Generation (Phthalate): The 4th generation catalysts contain MgCl2, TiCl4, and an internal electron donor, which are combined with an aluminum alkyl co - catalyst such as Al(CH2CH3)3. An external electron donor can be added to the catalyst system. The internal electron donor in the 4th generation catalysts is a phthalate / alkoxysilane system. It has been found that the bidentate phthalate donor can form a strong chelate complex with the four - coordinate Mg atom on the (110) plane of MgCl2 or a binuclear complex with two five - coordinate Mg atoms on the (100) plane.

[0102] Ziegler-Natta Catalyst, 5th Generation (Diether and Succinate): Certain diether compounds, specifically, 2,2-disubstituted-1,3-dimethoxypropane with an oxygen-oxygen distance in the range of

[0103] [Number] have been found not to be extracted when the catalyst is contacted with Al(CH2CH3)3 cocatalyst, similar to those of alkoxysilane external donors. As a result, in the 5th generation diether catalyst system, high stereospecificity can be obtained even in the absence of an external donor. The 5th generation diether catalyst system can exhibit particularly high polymerization activity and good stability. They also give a relatively narrow molecular weight distribution (MWD) and show high sensitivity to hydrogen. Recently, new types of internal donor compounds based on aliphatic dicarboxylic acid esters such as malonate and glutarate, specifically, succinate and polyol esters, have been used. Alkoxysilane is often used as an external donor.

[0104] Ziegler-Natta Catalyst, 6th Generation (Phthalate Substitution): The new 1,2-phenylenedibenzoate internal donor used in the 6th generation Ziegler-Natta catalyst is important as a phthalate substitution. In addition, the disclosure of mixed internal donors, for example, blends of succinate and diether, or blends of succinate and dimethoxytoluene, is increasing. The 6th generation catalyst can also result in high stereospecificity in the absence of an external donor. Thus, depending on the crystalline target, the external donor may or may not be used to achieve the desired crystalline target.

[0105] In certain embodiments, or in combination with any of the embodiments recited herein, the catalyst system can include a 3rd generation Ziegler-Natta catalyst, a 4th generation Ziegler-Natta catalyst, a 5th generation Ziegler-Natta catalyst, or a 6th generation Ziegler-Natta catalyst.

[0106] In one embodiment, or in combination with any of the embodiments referred to herein, the catalyst system may comprise a third generation Ziegler-Natta catalyst or a fourth generation Ziegler-Natta catalyst.

[0107] Generally, the catalyst system comprises at least one external electron donor. In one embodiment, or in combination with any of the embodiments referred to herein, the external electron donor comprises at least one alkoxysilane such as a "D" donor (e.g., dicyclopentyldimethoxysilane), a "C" donor (e.g., cyclohexylmethyldimethoxysilane), or combinations thereof. Further, in some embodiments, the alkoxysilane may comprise, consist essentially of, or consist entirely of a "D" donor or a "C" donor.

[0108] It has been observed that the addition of the above external donor to the catalyst system can increase the hardness of the copolymer (i.e., decrease the penetration), and increase the viscosity. However, contrary to what has been previously observed in the art, the above electron donor can decrease rather than increase the softening point of the resulting copolymer. Further, it has been observed that substantially all (i.e., greater than 95 percent) of the ethylene added to the reactor during the polymerization process can react when the above electron donor is used. Thus, this can result in a copolymer having a higher ethylene content and a lower propylene content. As a result, when the above electron donor is used, a propylene-ethylene copolymer having a higher ethylene content but still exhibiting a desired balance between softening point and hardness can be produced.

[0109] In one embodiment, or in combination with any of the embodiments referred to herein, the catalyst system may have a molar ratio of external electron donor to titanium of at least 0.1:1, 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, or 4:1, and / or less than 10:1, 9:1, or 8:1. Additionally or alternatively, the catalyst system may have a molar ratio of external electron donor to titanium in the range of 0.1:1 to 10:1, 0.5:1 to 10:1, 1:1 to 10:1, 1.5:1 to 10:1, 2:1 to 10:1, 2.5:1 to 10:1, 3:1 to 10:1, 3.5:1 to 10:1, 4:1 to 10:1, 0.5:1 to 9:1, 1:1 to 9:1, 1.5:1 to 9:1, 2:1 to 9:1, 2.5:1 to 9:1, 3:1 to 9:1, 3.5:1 to 9:1, 4:1 to 9:1, 0.5:1 to 8:1, 1:1 to 8:1, 1.5:1 to 8:1, 2:1 to 8:1, 2.5:1 to 8:1, 3:1 to 8:1, 3.5:1 to 8:1, or 4:1 to 8:1.

[0110] Additionally or alternatively, in one embodiment, or in combination with any of the embodiments referred to herein, the catalyst system may include a molar ratio of TEAL cocatalyst to electron donor of at least 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, or 6:1, and / or 100:1, 50:1, 35:1, 20:1, 15:1, 10:1, or 8:1 or less. Further, the catalyst system may include a molar ratio of TEAL cocatalyst to electron donor in the range of 0.5:1 to 100:1, 1:1 to 50:1, 2:1 to 35:1, 2:1 to 20:1, 2:1 to 15:1, 2:1 to 10:1, or 2:1 to 8:1.

[0111] In certain embodiments, the type of electron donor can affect the required TEAL / electron donor ratio. For example, in embodiments where the electron donor is a "D" donor or a "C" donor, the TEAL / electron donor ratio can be less than 20:1.

[0112] The catalyst system can exhibit a catalyst activity in the range of 200 to 2,000, 400 to 1,200, 500 to 1,000, 1,000 to 6,000, or 6,000 to 18,000 g / g. The catalyst activity is calculated by measuring the ratio of the weight of the polymer produced in the reactor to the weight of the catalyst loaded in the reactor. These measurements are based on a reaction time of 1 hour.

[0113] The addition of an external donor can increase the viscosity and molecular weight, so the addition of hydrogen may be required to act as a chain terminator during polymerization. For example, the process can be carried out at a hydrogen pressure in the range of 5 to 100, 10 to 80, or 15 to 50 psig.

[0114] Turning now to the polymerization process conditions, in one embodiment, or in combination with any of the embodiments referred to herein, the polymerization reaction can occur at a temperature in the range of 160 °C or less, 155 °C or less, 150 °C or less, or 100 to 200, 110 to 180, 110 to 155, 120 to 160, or 120 to 150 °C. Further, the polymerization reaction can be carried out at a pressure in the range of 500 to 2,000, 600 to 1,500, 700 to 1,250, or 800 to 1,100 psig.

[0115] In certain embodiments, or in combination with any of the embodiments referred to herein, the ratio of the ethylene flow rate to the propylene flow rate to the polymerization reaction may be in the range of 0.1:100 to 18:100, 0.1:100 to 10:100, 0.1:100 to 5:100, 0.1:100 to 4:100, 0.5:100 to 3:100, 0.5:100 to 2:100, 0.5:100 to 1.5:100, 0.5:100 to 1:100, 1:100 to 4:100, 1:100 to 3:100, 1:100 to 2:100, 1.5:100 to 4:100, 1.5:100 to 3:100, 1.5:100 to 2:100, 2:100 to 4:100, 2:100 to 3:100, 3:100 to 18:100, 3:100 to 14:100, 3:100 to 12:100, 3:100 to 10:100, 4:100 to 18:100, 4:100 to 14:100, 4:100 to 12:100, 4:100 to 10:100, 7:100 to 18:100, 7:100 to 14:100, 7:100 to 12:100, 7:100 to 10:100, 8:100 to 18:100, 8:100 to 14:100, 8:100 to 12:100, or 8:100 to 10:100.

[0116] In certain embodiments, or in combination with any of the embodiments referred to herein, the ratio of the hydrogen flow rate to the propylene flow rate to the polymerization reaction may be in the range of 0.03:100 to 0.5:100, 0.04:100 to 0.4:100, 0.15:100 to 0.4:100, 0:100 to 0.3:100, 0:100 to 0.2:100, 0:100 to 0.02:100, 0:100 to 0.01:100, 0.01:100 to 0.02:100, 0.04:100 to 0.2:100, 0.05:100 to 0.1:100, 0.07:100 to 0.3:100, or 0.08:100 to 0.4:100.

[0117] In certain embodiments, or in combination with any of the embodiments referred to herein, the polymerization reactor may include a stirred reactor, and the polymerization reaction may have a residence time in the reactor in the range of 0.1 to 6, 0.5 to 4, 1 to 2, 6 to 72, 16 to 36, 16 to 24, 12 to 48, or 12 to 24 hours.

[0118] In one embodiment, or in combination with any of the embodiments referred to herein, the polymerization reactor may include a loop reactor, and the polymerization reaction may have a residence time in the reactor in the range of 8 to 72, 12 to 48, 12 to 24, or 16 to 36 hours.

[0119] In one embodiment, or in combination with any of the embodiments referred to herein, ethylene may be added to the reactor as a gas and propylene may be added as a liquid.

[0120] End use including propylene-ethylene copolymer The propylene-ethylene copolymers of the present invention described herein and compositions containing these copolymers can be used in a wide variety of applications, such as adhesives (e.g., automotive adhesives, woodworking adhesives, and packaging adhesives), sealants, caulking materials, roofing membranes, waterproof membranes and linings, carpets, laminates, laminated articles, tapes (e.g., tamper evident tapes, water-activated tapes, gum tapes, sealing tapes, scrim-reinforced tapes, veneer tapes, reinforced and non-reinforced adhesive paper tapes, box maker's tapes, paper tapes, packaging tapes, HVAC duct tapes, masking tapes, mending tapes, insulating tapes, gaffer tapes, hockey tapes, medical tapes, etc.), labels (e.g., multi-purpose labels, beverage labels, freezer labels, smart labels, household appliances, etc.), mastics, polymer blends, wire coatings, molded articles, heat-seal coatings, disposable sanitary articles, insulating glass (IG) units, bridge decks, waterproof membranes, waterproof compounds, bitumen modification, asphalt modification, cable flooding / filling compounds, sheet molding compounds, dough molding compounds, overmold compounds, rubber compounds, polyester composites, glass composites, glass fiber reinforced plastics, plastic fiber reinforced compounds, wood plastic composites, polyacrylic blend compounds, lost wax precision casting, investment casting wax compositions, candles, windows, films, gaskets, seals, O-rings, automotive vehicle molded parts, automotive vehicle extruded parts, clothing articles, rubber additives / processing aids, and fibers.

[0121] Examples of films containing the propylene-ethylene copolymers of the present invention described herein and compositions containing these copolymers include, but are not limited to, multilayer films, coextruded films, calendered films, and cast films. Examples of laminates containing the propylene-ethylene polymers of the present invention or compositions containing the propylene-ethylene polymers of the present invention include, but are not limited to, paper-foil laminates, paper-film laminates, and nonwoven-film laminates.

[0122] The adhesive compositions comprising the propylene-ethylene copolymers of the present invention described herein and compositions containing these copolymers can include packaging adhesives, food contact grade adhesives, indirect food contact packaging adhesives, product assembly adhesives, woodworking adhesives, edge banding adhesives, profile wrapping adhesives, flooring adhesives, automotive assembly adhesives, structural adhesives, mattress adhesives, pressure sensitive adhesives (PSA), PSA tapes, PSA labels, PSA protective films, self-adhesive films, laminating adhesives, flexible packaging adhesives, heat seal adhesives, industrial adhesives, sanitary nonwoven architectural adhesives, sanitary core integrity adhesives, and sanitary elastic attachment adhesives.

[0123] In certain embodiments, or in combination with any of the embodiments referred to herein, the copolymers described herein can be utilized in adhesives such as, for example, hot melt adhesives, aqueous adhesives, solvent-based adhesives, hot melt pressure sensitive adhesives, solvent-based pressure sensitive adhesives, hot melt nonwoven / sanitary adhesives, hot melt product assembly adhesives, hot melt woodworking adhesives, hot melt automotive part assembly adhesives, hot melt laminating adhesives, and hot melt packaging adhesives. More specifically, due to their particular combinations of tensile strength, elongation at break, softening point, and penetration as described above, the adhesives produced from the copolymers of the present invention can be utilized in a very large number of end products including sanitary packaging, household appliances, automotive parts, woodworking, and packaging applications. Generally, the various properties of the copolymers of the present invention, such as tensile strength, elongation at break, softening point, and penetration, can be selected to be compatible with the intended end use of the composition incorporating the copolymer.

[0124] In one embodiment, or in combination with any of the embodiments referred to herein, the copolymers of the present invention can be used to produce adhesive compositions useful for packaging, product assembly, heat sealing, lamination, gap sealing (e.g., cable filling), caulking, window sealing, woodworking, edge banding, and / or profile wrapping. As used herein, the terms "adhesive", "adhesive composition" and "composition" can be used interchangeably.

[0125] In one embodiment, or in combination with any of the embodiments referred to herein, the adhesive composition includes a hot melt adhesive. The hot melt adhesive can be applied to a substrate while in its molten state and cooled to cure the adhesive layer. Such adhesives are widely used in various commercial and industrial applications such as product assembly, lamination, and packaging. In these applications, the adhesive is applied to at least one substrate to bond the substrate to a second similar or different substrate.

[0126] Adhesives, sealants, and other formulators and users generally desire a thermally stable, low-coloring hot melt adhesive having a favorable balance of physical properties including temperature resistance, chemical resistance, cohesive strength, viscosity, adhesion to various substrates, and open time and cure time that can be tailored to specific use and application conditions. The balance of desired properties varies depending on the application, and the hot melt compositions of the present invention described herein provide an improved balance of properties for multiple end uses.

[0127] The hot melt adhesive composition can have a melt rheology and thermal stability suitable for use in conventional hot melt adhesive application equipment. In one embodiment, or in combination with any of the embodiments referred to herein, the blended components of the hot melt adhesive composition have a low melt viscosity at the application temperature, thereby facilitating the flow of the composition through a coating device, such as a coating die or nozzle.

[0128] Hot melt adhesive compositions are useful for bonding a variety of substrates, such as paperboard, coated paperboard, cardboard, fiberboard, virgin and recycled kraft, high density and low density kraft, chipboard, treated and coated kraft and chipboard, and their corrugated versions, clay coated chipboard carton stock, composites, leather, polymer films (e.g., polyolefin films, polyvinylidene chloride films, ethylene vinyl acetate films, polyester films, metallized polymer films, multilayer films, and combinations thereof), fibers and substrates made from fibers (e.g., virgin fibers, recycled fibers, synthetic polymer fibers, cellulose fibers, and combinations thereof), release liners, porous substrates (e.g., woven webs, nonwoven webs, nonwoven scrims, and perforated films), cellulose substrates, sheets (e.g., paper and fiber sheets), paper products, tape backings, and combinations thereof. Useful composites include, for example, chipboard laminated to a metal foil (e.g., aluminum foil) (optionally, laminated to at least one layer of polymer film), chipboard bonded to a film, kraft bonded to a film (e.g., polyethylene film), and combinations thereof.

[0129] Hot melt adhesive compositions are useful for bonding a first substrate to a second substrate in a variety of applications and structures, such as articles including packaging, bags, boxes, cartons, cases, trays, multiwall bags, accessories (e.g., straws attached to beverage cartons), reel wrap, cigarettes (e.g., plug wrap), filters (e.g., pleated filters and filter frames), bookbinding materials, footwear, disposable absorbent articles (e.g., disposable diapers, sanitary napkins, medical drapes, bandages, surgical pads, drapes, gowns, and meat packaging products), paper products (e.g., paper towels, toilet paper, facial tissue, wipes, tissues, and sheets), veneer, mattress covers, automotive foils, and components of absorbent articles (e.g., absorbent elements, absorbent cores, impermeable layers, capture layers, woven fabrics, and nonwoven webs), and combinations thereof.

[0130] The hot melt adhesive composition is also useful for forming laminates of porous substrates and polymer films, such as those used in the manufacture of disposable articles including, for example, medical drapes, medical gowns, sheets, feminine hygiene products, diapers, adult incontinence articles, absorbent pads for animals (e.g., pet pads) and humans (e.g., body and cadavers), and combinations thereof.

[0131] The hot melt adhesive composition can be applied to a substrate in any useful form, including, for example, as a fiber, as a coating (e.g., continuous or discontinuous coating), as a bead, as a film (e.g., continuous or discontinuous film), and combinations thereof. Further, the hot melt adhesive can be applied using any suitable application method, including, for example, slot coating, curtain coating, spray coating (e.g., spiral spray, random spray, and melt blowing), foaming, extrusion (e.g., bead application, wire extrusion, single screw extrusion, and twin screw extrusion), wheel application, non-contact coating, contact coating, gravure printing, engraved roller, roll coating, transfer coating, screen printing, flexographic printing, and combinations thereof.

[0132] In certain embodiments, or in combination with any of the embodiments recited herein, the hot melt adhesive can be used to form automotive interior materials.

[0133] Generally, the hot melt adhesives of the present invention can be used to form bonds for generating laminates and multilayer laminates. As used herein, the terms "laminate" and "multilayer laminate" can be used interchangeably.

[0134] The composition of the present invention of the present disclosure can be bonded to various substrates including, but not limited to, cellulosic polymer materials such as paper, cotton, linen, cloth, and wooden boards; polyolefin resins such as polypropylene (PP) and polyethylene (PE), polystyrene, styrene-butadiene block copolymer (SBS resin), styrene-acrylonitrile copolymer (AS resin), acrylonitrile-ethylene / propylene styrene copolymer (AES resin), and acrylonitrile-butadiene-styrene copolymer (ABS resin) and other styrene resins, polycarbonate resin (PC resin), PC-ABS resin, (meth)acrylic resin, polyester resin, polyamide resins such as nylon and polyurethane, phenolic resin, and epoxy resin; wood materials; metal materials; plastic materials; elastomer materials; composite materials; textile materials; glass materials; leather materials, and combinations thereof. The material of the substrate can be a mixture or combination of two or more different materials. When forming a laminate by bonding two different substrates through an adhesive layer containing the propylene-ethylene polymer of the present invention or the hot melt adhesive of the present disclosure, the materials of the two substrates may be the same or different from each other.

[0135] The laminate containing the polymer or composition of the present invention can be suitably used in applications where coating materials and formed articles are used as substrates such as interior materials of automobiles (e.g., ceiling materials for automobile interiors, door parts for automobile interiors, dashboard parts for automobile interiors, instrument panels, etc.), home appliance parts (e.g., casings of personal computers, frames of thin TVs, etc.), and housing materials (e.g., interior wall panels, decorative films, etc.).

[0136] In one embodiment, or in combination with any of the embodiments referred to herein, the multilayer laminate can be prepared by bonding a covering material such as a decorative sheet and a formed article through an adhesive layer containing the propylene-ethylene polymer or hot melt adhesive composition of the present invention. Various preparation methods such as thermal lamination, vacuum forming, vacuum pressure forming, hot pressing, hot rolling, and / or hot stamping can be used.

[0137] Typical but non-limiting industrial applications of the hot melt adhesive composition include packaging, wood processing, assembly of interior parts of vehicles (e.g., automobiles), and conventional end uses (e.g., bookbinding materials, sanitary disposable consumer articles, and labeling).

[0138] Furthermore, in one embodiment, or in combination with any of the embodiments referred to herein, the copolymers of the present invention described herein can also be used to modify existing polymer blends typically utilized in plastic, elastomeric applications, roofing applications, cable filling, and tire modification. The copolymers of the present invention can improve the adhesiveness, processability, stability, viscoelasticity, thermal properties, and mechanical properties of these polymer blends.

[0139] In one embodiment, or in combination with any of the embodiments referred to herein, the propylene-ethylene copolymer of the present invention can be modified to produce a graft copolymer. In such embodiments, the copolymers of the present invention can be grafted with maleic anhydride, fumaric acid esters and maleic acid esters, methacrylic acid esters (e.g., glycidyl methacrylate and hydroxyethyl methacrylate), methacrylic acid, vinyl derivatives, silane derivatives, or combinations thereof. These graft copolymers can be produced using any conventional process known in the art, including, for example, transesterification and free radical induced coupling.

[0140] The various end uses and end products described above can utilize the copolymer of the present invention by itself or can combine it with other additives and polymers. Suitable polymers that can form a polymer blend in combination with the copolymer of the present invention include, for example, isoprene-based block copolymers; butadiene-based block copolymers; hydrogenated block copolymers; styrene-ethylene / butylene-styrene block copolymers (SEBS); styrene-isoprene-styrene block copolymers (SIS); styrene-ethylene / propylene-styrene (SEPS); ethylene vinyl acetate copolymers; polyesters; polyester-based copolymers; neoprene; urethanes; acrylates; polyacrylates; acrylate copolymers, for example, but not limited to, ethylene acrylic acid copolymers, ethylene n-butyl acrylate copolymers, and ethylene methyl acrylate copolymers; polyether ether ketones; polyamides; styrene block copolymers; hydrogenated styrene block copolymers; random styrene copolymers; ethylene-propylene rubbers; ethylene vinyl acetate copolymers; butyl rubbers; styrene butadiene rubbers; butadiene acrylonitrile rubbers; natural rubbers; polyisoprenes; polyisobutylenes; polyvinyl acetates; polyolefins; and combinations thereof.

[0141] Polyolefins useful with the propylene-ethylene copolymer of the present invention can be any known in the art. In certain embodiments, or in combination with any of the embodiments recited herein, the polyolefin can be an amorphous polyolefin, a semi-crystalline polyolefin, an alpha-polyolefin, a reactor-ready polyolefin, a metallocene-catalyzed polyolefin polymer and elastomer, a reactor-made thermoplastic polyolefin elastomer, an olefin block copolymer, a thermoplastic polyolefin, an atactic polypropylene, a polyethylene, an ethylene-propylene polymer, a propylene-hexene polymer, an ethylene-butene polymer, an ethylene-octene polymer, a propylene-butene polymer, a propylene-octene polymer, a metallocene-catalyzed polypropylene polymer, a metallocene-catalyzed polyethylene polymer, a propylene-based terpolymer, propylene and a linear or branched C4-C 10 copolymer produced from an alpha-olefin monomer, ethylene and a linear or branched C4-C 10 It can be at least one selected from the group consisting of a copolymer produced from an alpha-olefin monomer, and a functionalized polyolefin.

[0142] Functionalized olefin polymers and copolymers can include maleated polyethylene, maleated metallocene polyethylene, maleated metallocene polypropylene, maleated ethylene propylene rubber, maleated polypropylene, maleated ethylene copolymer, functionalized polyisobutylene (typically functionalized with maleic anhydride to typically form succinic anhydride), and the like.

[0143] Blends of the various types of polyolefins with the propylene-ethylene copolymer of the present invention have been found to provide improved adhesion, cohesive strength, temperature resistance, viscosity, and open time and cure time to adhesives. Thus, in various embodiments, the propylene-ethylene polymer of the present invention can be combined with at least one polyolefin.

[0144] As described above, the propylene-ethylene copolymer of the present invention described in this specification can be used to produce a hot melt adhesive. In certain embodiments, or in combination with any of the embodiments referred to herein, the adhesive composition can comprise one or more of at least 1, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 30, 32, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50 weight percent of the propylene-ethylene copolymer, based on the total weight of the adhesive. Additionally, or alternatively, the adhesive composition can comprise less than one or more of 95, 90, 85, 80, 76, 75, 70, 66, 63, 60, 59, 56, 55, 52, 50, 45, 40, 35, 30, 25, 20, 15, or 10 weight percent of the propylene-ethylene copolymer, based on the total weight of the adhesive.

[0145] In certain embodiments, or in combination with any of the embodiments referred to herein, the adhesive composition can comprise one or more of the propylene-ethylene copolymer in the range of 1 to 95, 5 to 90, 5 to 100, 8 to 52, 8 to 50, 8 to 45, 8 to 35, 10 to 80, 20 to 70, 25 to 52, 25 to 50, 25 to 45, 30 to 45, 30 to 60, 35 to 50, 35 to 55, 40 to 55, 50 to 80, 50 to 70, 30 to 90, 30 to 80, 30 to 70, 30 to 60, 30 to 50, or 30 to 40 weight percent, based on the total weight of the adhesive. In certain specific embodiments, the adhesive composition can consist entirely of the copolymer of the present invention.

[0146] In one embodiment, or in combination with any of the embodiments referred to herein, the adhesive may contain at least one, two, or three propylene-ethylene copolymers of the present invention selected from Table 1A, 1B, 1C, and / or 1D. In such embodiments, the copolymer may include any combination of high-viscosity copolymers (i.e., Table 1B), medium-viscosity copolymers (i.e., Table 1C), and / or low-viscosity copolymers (i.e., Table 1D).

[0147] Furthermore, depending on the intended end use, the hot melt adhesive composition may also include various additives such as, for example, a second polymer, tackifier, processing oil, wax, antioxidant, plasticizer, pigment, and filler.

[0148] In one embodiment, or in combination with any of the embodiments referred to herein, the adhesive composition may include at least 1, 2, 3, 4, 5, 10, 12, 15, 20, 30, 40, 50, or 55 weight percent of at least one second polymer different from the copolymer of the present invention. Additionally, or alternatively, the adhesive composition may include 90, 80, 70, 55, 40, 35, 30, 25, 20, 15, 14, 13, 12, 11, or 10 weight percent or less of at least one second polymer different from the copolymer of the present invention. For example, the adhesive may include at least one second polymer different from the copolymer of the present invention in the range of 10 - 90, 20 - 80, 30 - 70, 40 - 55, 1 - 15, 1 - 3, 1 - 5, 1 - 20, 2 - 15, or 2 - 10 weight percent.

[0149] In one embodiment, or in combination with any of the embodiments referred to herein, the adhesive composition may include at least 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 15, 17, 20, 23, 25, 30, 35, 40, 45, 47, or 50 weight percent of at least one second polymer different from the copolymer of the present invention.

[0150] Exemplary second polymers include amorphous polyolefins, semi-crystalline polyolefins, alpha-polyolefins, reactor-ready polyolefins, metallocene-catalyzed polyolefin polymers and elastomers, reactor-made thermoplastic polyolefin elastomers, olefin block copolymers, thermoplastic polyolefins, atactic polypropylene, polyethylene, ethylene-propylene polymers, propylene-hexene polymers, ethylene-butene polymers, ethylene-octene polymers, propylene-butene polymers, propylene-octene polymers, metallocene-catalyzed polypropylene polymers, metallocene-catalyzed polyethylene polymers, propylene-based terpolymers including ethylene-propylene-butylene terpolymers, propylene and linear or branched C4-C 10 Copolymers produced from alpha-olefin monomers, ethylene and linear or branched C4-C 10 Copolymers produced from alpha-olefin monomers, functionalized polyolefins, isoprene-based block copolymers, butadiene-based block copolymers, hydrogenated block copolymers, styrene-ethylene / butylene-styrene block copolymers (SEBS), styrene-isoprene-styrene block copolymers (SIS), styrene-ethylene / propylene-styrene (SEPS), ethylene vinyl acetate copolymers, polyesters, polyester-based copolymers, neoprene, urethanes, acrylates, polyacrylates, ethylene acrylic acid copolymers, ethylene n-butyl acrylate copolymers, ethylene methyl acrylate copolymers, polyether ether ketones, polyamides, styrene block copolymers, hydrogenated styrene block copolymers, random styrene copolymers, ethylene-propylene rubber, ethylene vinyl acetate copolymers, butyl rubber, styrene butadiene rubber, butadiene acrylonitrile rubber, natural rubber, polyisoprene, polyisobutylene, polyvinyl acetate, or combinations thereof.

[0151] In one embodiment, or in combination with any of the embodiments referred to herein, the adhesive containing at least one second polymer may also contain at least one, two, or three propylene-ethylene copolymers of the present invention selected from Tables 1A, 1B, 1C, and / or 1D. In such embodiments, the copolymer may include any combination of high viscosity copolymers (i.e., Table 1B), medium viscosity copolymers (i.e., Table 1C), and / or low viscosity copolymers (i.e., Table 1D).

[0152] In one embodiment, or in combination with any of the embodiments referred to herein, in addition to the propylene-ethylene copolymer of the present invention, the adhesive may include at least 1, 2, 3, 4, 5, 10, 12, 15, 20, 25, 30, 35, 40, 45, or 50 weight percent of at least one polyolefin. Additionally, or alternatively, the adhesive composition may include 99, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 12, 11, 10, 5, or 2 weight percent or less of at least one polyolefin in addition to the propylene-ethylene copolymer of the present invention. For example, the adhesive composition may include at least one polyolefin in the range of 1 to 90, 1 to 60, 1 to 40, 1 to 20, 10 to 90, 20 to 80, 20 to 40, 30 to 70, 30 to 40, 40 to 55, 10 to 15, 1 to 3, 1 to 5, 1 to 15, 1 to 10, 2 to 15, or 2 to 10 weight percent based on the total weight.

[0153] Examples of commercially available polyolefins that are acceptable include Aerafin™ 17 by Eastman; Aerafin™ 180 by Eastman; Rextac™ polymers made by REXtac LLC, including Rextac™ Ε-63, E-65, 2760, 2815, 2730, and 2830; polymers made by Evonik Industries, including Vestoplast®, Vestoplast® 408 and 708; and Eastoflex® by Eastman, including Eastoflex® E1060 and P1010.

[0154] Some examples of metallocene-catalyzed polymers include polyolefins such as polyethylene, polypropylene, and their copolymers. Exemplary polypropylene-based elastomers include those sold under the trade name VISTAMAXX™ by ExxonMobil Chemical and those sold under the trade name L-MODU™ by Idemitsu Kosan (Japan). Exemplary polyethylene-based elastomers and plastomers include those sold under the trade names AFFINITY™, AFFINITY™ GA, INFUSE™, and ENGAGE™ by Dow Chemical Company; those sold under the trade name VISTAMAXX™ by ExxonMobil Chemical Company (Houston, Texas); and those sold under the trade name LlCOCENE™ by Clariant.

[0155] In one embodiment, or in combination with any of the embodiments referred to herein, the olefin polymer can include a mixture of at least two different olefin polymers, for example, a blend including an olefin homopolymer and an olefin copolymer, a blend including different olefin homopolymers of the same or different monomers, a blend including different olefin copolymers, and various combinations thereof. Useful olefin polymers can also include, for example, modified, unmodified, grafted, and ungrafted olefin polymers, unimodal olefin polymers, multimodal olefin polymers, and combinations thereof.

[0156] In many cases, these added polyolefins can increase the cohesive strength, adhesion properties, tackiness, low-temperature flexibility, total crystallinity, and / or temperature resistance of the adhesive composition of the present invention. Further, due to the wide availability of the above polyolefins, the production cost of the composition can be reduced.

[0157] In one embodiment, or in combination with any of the embodiments referred to herein, the adhesive composition can include the propylene-ethylene copolymer and metallocene-catalyzed polyethylene copolymer of the present invention, for example, an ethylene-octene copolymer. In such an embodiment, the propylene-ethylene copolymer of the present invention can be used to replace polyethylene in various types of adhesives such as those used for packaging applications.

[0158] In one embodiment, or in combination with any of the embodiments referred to herein, the added polymer and / or polyolefin can be functionalized at the polymer chain ends and / or at pendant positions within the polymer with groups including, but not limited to, silane, acid anhydrides such as maleic anhydride, hydroxyl, ethoxy, epoxy, siloxane, amine, aminosiloxane, carboxy, and acrylate.

[0159] Additional polymers and polyolefins that can be added to the adhesive composition of the present invention can be prepared by Ziegler-Natta catalysts, single-site catalysts (metallocenes), multiple single-site catalysts, non-metallocene heteroaryl catalysts, or combinations thereof. The additional polymers can include combinations of amorphous, semi-crystalline, random, branched-chain, linear, or block structures.

[0160] Generally, any conventional polymerization synthesis process can prepare the additional polyolefin component. In certain embodiments, or in combination with any of the embodiments referred to herein, one or more catalysts, typically metallocene catalysts or Ziegler-Natta catalysts, are used for the polymerization of olefin monomers or monomer mixtures. The polymerization methods can include high pressure, slurry, gas, bulk, suspension, supercritical, or solution phase, or combinations thereof. The catalyst can be in the form of a homogeneous solution, a supported form, or a combination thereof. The polymerization can be carried out by continuous, semi-continuous, or batch processes and can include the use of chain transfer agents, scavengers, or other such additives that are considered applicable.

[0161] In certain embodiments, or in combination with any of the embodiments referred to herein, the additional polymer is produced in one or more polymerization zones using a single polymerization catalyst. Metallocene (or heterogeneous) polymers are typically made using blends of multiple metallocene catalysts to obtain the desired heterogeneous structure.

[0162] In certain embodiments, or in combination with any of the embodiments referred to herein, the crystalline content of the added polymer or polyolefin can increase the cohesive strength of the adhesive composition. Generally, formulations based on metallocene-polymerized semi-crystalline copolymers can ultimately build up over time a crystalline content sufficient to achieve good cohesive strength in the formulation.

[0163] In one embodiment, or in combination with any of the embodiments referred to herein, the adhesive composition can include at least 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 46, 47, 48, 50, 55, or 60 weight percent of at least one tackifier, based on the total weight of the adhesive. Additionally, or alternatively, the adhesive composition can include up to 90, 80, 70, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, or 5 weight percent of at least one tackifier, based on the total weight of the adhesive. For example, the adhesive composition can include at least one tackifier in the range of 5 to 90, 20 to 80, 20 to 40, 20 to 30, 30 to 70, 35 to 50, 35 to 55, 35 to 60, 40 to 50, 40 to 55, 40 to 60, or 45 to 50 weight percent, based on the total weight.

[0164] Generally, tackifiers can improve the tack and adhesion of the adhesive and also reduce the viscosity of the adhesive. A lower viscosity can improve the application flow characteristics, allowing for easier processing, lower energy requirements, and lower processing temperatures. A lower viscosity also helps the adhesive to "wet out" or coat the surface substantially uniformly and penetrate the substrate. Tack is required in most adhesive formulations to enable proper bonding of articles before the hot melt adhesive solidifies. The desirability and selection of a particular tackifier can depend on the specific type of olefin copolymer and additional polymers used.

[0165] Suitable tackifiers include, for example, alicyclic hydrocarbon resins, C5 hydrocarbon resins; C5 hydrocarbon resins; C5 / C9 hydrocarbon resins; aromatic modified C5 resins; C9 hydrocarbon resins; copolymers of alpha-methylstyrene, vinyltoluene, para-methylstyrene, indene, methylindene, C5 resins, and C9 resins or pure monomer resins such as styrene; terpene resins; terpene phenol resins; terpene styrene resins; rosin esters; modified rosin esters; liquid resins of fully or partially hydrogenated rosin; fully or partially hydrogenated rosin esters; fully or partially hydrogenated modified rosin resins; fully or partially hydrogenated rosin alcohols; fully or partially hydrogenated C5 resins; fully or partially hydrogenated C5 / C9 resins; fully or partially hydrogenated aromatic modified C5 resins; fully or partially hydrogenated C9 resins; fully or partially hydrogenated pure monomer resins; fully or partially hydrogenated C5 / alicyclic resins; fully or partially hydrogenated C5 / alicyclic / styrene / C9 resins; fully or partially hydrogenated alicyclic resins; and combinations thereof. Exemplary commercially available hydrocarbon resins include Regalite™ hydrocarbon resins. In certain embodiments, the tackifier may include a functionalized tackifier.

[0166] In one embodiment, or in combination with any of the embodiments referred to herein, the adhesive composition may include at least one processing oil of at least 1, 2, 3, 4, 5, 7, 8, 9, or 10, and / or 40, 30, 25, 20, 15, 10.5, 10, 6, or 5 weight percent or less, based on the total weight of the adhesive. For example, the adhesive composition may include at least one processing oil in the range of 2 to 40, 2 to 20, 2 to 15, 2 to 10.5, 2 to 5, 5 to 30, 8 to 25, 1 to 15, or 10 to 20 weight percent, based on the total weight of the adhesive. Examples of the processing oil may include, for example, mineral oil, naphthenic oil, paraffin oil, aromatic oil, castor oil, rapeseed oil, triglyceride oil, or combinations thereof. As would be understood by those skilled in the art, the processing oil may also include extender oils commonly used in adhesives. The use of oil in the adhesive may be desirable when the adhesive is used as a pressure-sensitive adhesive for producing tapes or labels, or as an adhesive for bonding nonwoven articles. In certain embodiments, the adhesive may not include any processing oil.

[0167] In one embodiment, or in combination with any of the embodiments referred to herein, the adhesive composition may include at least 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 15, 16, 17, 18, 19, 20, 21, 22, 23, or 25 weight percent of at least one wax, based on the total weight of the adhesive. Additionally, or alternatively, the adhesive composition may include at least one wax in an amount of 40, 30, 25, 20, 15, 10, 7, 5, or 3 weight percent or less. For example, the adhesive may include at least one wax in an amount of 1 to 40, 5 to 30, 8 to 25, 10 to 20, 3 to 7, 2 to 5, 2 to 7, 2 to 40, 2 to 30, 2 to 25, 2 to 20, 2 to 10, 1 to 25, 1 to 20, 1 to 15, 1 to 10, 1 to 7, or 1 to 5 weight percent. The wax serves to reduce the overall viscosity of the adhesive, thereby liquefying the adhesive and enabling proper application or coating of the hot melt adhesive onto the intended substrate. The type and melting point of the wax, as well as its compatibility with the other components of the adhesive composition, control the open time and cure rate of the adhesive. The open time is known in the art as the length of time after application that the adhesive wets out and bonds to the substrate. Any conventionally known wax suitable for use in formulating hot melt adhesives may be used in the practice of the present invention.

[0168] Suitable waxes may include, for example, microcrystalline waxes, paraffin waxes, waxes produced by the Fischer-Tropsch process, functionalized waxes (such as maleated waxes, fumarated waxes, or waxes having functional groups), polyolefin waxes, petroleum waxes, polypropylene waxes, polyethylene waxes, ethylene vinyl acetate waxes, and vegetable waxes. When the adhesive is used as a hot melt packaging adhesive, the use of wax in the adhesive may be desirable.

[0169] Non-limiting examples of commercially available waxes suitable for the present invention include Sasol® H-1 available from Sasol Wax Americas, Inc.; A-C®-9, AC-596, and A-C 810 available from Honeywell International Inc.; EPOLENE® N-15, E-43, C-10, and C-18 available from Westlake; and POLYWAX® 400, 850, 1000, and 3000 from Baker Hughes Inc. Other exemplary waxes include, but are not limited to, the microcrystalline waxes Be Square® 195 and Clariant Licocene® PE4201.

[0170] As used herein, "functionalized" means that the relevant component is prepared in the presence of a functional group incorporated into the component or is contacted with a functional group and optionally a catalyst, heat, initiator, or free radical source to incorporate, graft, bond, physically attach, and / or chemically attach all or a portion of the functional group (such as maleic acid or maleic anhydride) to the polymer.

[0171] Exemplary functionalized wax polymers useful as functional components include those modified with alcohols, acids, ketones, anhydrides, etc. Commercially available functionalized waxes include maleated polypropylene, available under the trade name MAPP40 from Chusei; maleated metallocene waxes such as TP LICOCENE PP1602 available from Clariant; maleated polyethylene waxes and maleated polypropylene waxes available under the trade names EPOLENE C-16, EPOLENE C-18, EPOLENE E43 from Westlake; EASTMAN G-3003 from Eastman Chemical; maleated polypropylene wax LICOMONT AR 504 available from Clariant; grafted functional polymers available under the trade names AMPLIFY EA 100 and AMPLIFY VA 200 from Dow Chemical Co.; and CERAMER maleated ethylene polymers available under the trade names CERAMER 1608, CERAMER 1251, CERAMER 67, and CERAMER 24 from Baker Hughes. Useful waxes also include polyethylene and polypropylene waxes with an Mw of less than 15,000, preferably 3,000 to 10,000, a crystallinity of 5 weight percent or more, preferably 10 weight percent or more, and a functional group content of up to 10 weight percent. Additional functionalized polymers that can be used as functional components include A-C 575P, A-C 573P, A-C Χ596Α, A-C Χ596Ρ, A-C Χ597Α, A-C Χ597Ρ, A-C Χ950Ρ, A-C Χ1221, A-C 395Α, A-C 395Α, A-C 1302Ρ, A-C 540, A-C 54A, A-C 629, A-C 629Α, A-C 307, and A-C 307Α available from Honeywell International.

[0172] In one embodiment, or in combination with any of the embodiments referred to herein, the adhesive composition may not contain wax. For example, the adhesive composition may contain less than 10, 7, 5, 4, 3, 2, 1, or 0.5 weight percent of wax, such as, but not limited to, polyethylene wax and / or Fischer-Tropsch wax.

[0173] In one embodiment, or in combination with any of the embodiments referred to herein, the adhesive composition may contain at least 0.1, 0.2, 0.5, 1, 2, or 3, and / or 20, 10, 8, 5, 1, or 0.5 weight percent or less of at least one antioxidant, based on the total weight of the adhesive. For example, the adhesive composition may contain at least one antioxidant in the range of 0.1 to 20, 1 to 10, 2 to 8, 3 to 5, or 0.5 to 2 weight percent.

[0174] In one embodiment, or in combination with any of the embodiments referred to herein, the adhesive composition may contain at least 0.5, 1, 2, or 3, and / or 20, 10, 8, or 5 weight percent or less of at least one plasticizer, based on the total weight of the adhesive. For example, the adhesive may contain at least one plasticizer in the range of 0.5 to 20, 1 to 10, 2 to 8, or 3 to 5 weight percent. Suitable plasticizers may include, for example, olefin oligomers, low molecular weight polyolefins, such as liquid polybutylene, polyisobutylene, mineral oil, dibutyl phthalate, dioctyl phthalate, chlorinated paraffin, and phthalate-free plasticizers. Commercially available plasticizers may include, for example, Benzoflex (trademark) plasticizers (Eastman Chemical); Eastman 168 (trademark) (Eastman Chemical); Oppanol (registered trademark) B10 (BASF); REGALREZ 1018 (Eastman Chemical); Calsol 5550 (Calumet Lubricants); Kaydol oil (Chevron); or ParaLux oil (Chevron).

[0175] In one embodiment, or in combination with any of the embodiments referred to herein, the adhesive composition may include at least one filler in an amount of at least 5, 10, 20, 30, or 40, and / or 90, 80, 70, or 55 weight percent or less, based on the total weight of the adhesive. For example, the adhesive may include at least one filler in the range of 1 to 90, 20 to 80, 30 to 70, or 40 to 55 weight percent. Suitable fillers may include, for example, carbon black, calcium carbonate, clay, titanium oxide, zinc oxide, or combinations thereof.

[0176] The adhesive composition can be produced using conventional techniques and equipment. For example, the components of the adhesive composition can be blended in a mixer such as a sigma blade mixer, a plasticoater, a Brabender mixer, a twin screw extruder, or an in-can blend (pint can). In one embodiment, or in combination with any of the embodiments referred to herein, the adhesive can be formed into a desired form such as a tape or sheet by suitable techniques including, for example, extrusion, compression molding, calendering, or roll coating techniques (e.g., gravure, reverse roll, etc.), curtain coating, slot die coating, or spray coating.

[0177] Furthermore, the adhesive composition can be applied to a substrate by a solvent casting process or by melting the adhesive and then using conventional hot melt adhesive application equipment known in the art. Suitable substrates may include, for example, non-woven fabrics, woven fabrics, paper, glass, plastics, films, wood, and metals. Generally, 0.1 to 100 g / m 2 or 1 to 1,000 g / m 2 of the adhesive composition can be applied to the substrate.

[0178] In one embodiment, or in combination with any of the embodiments referred to herein, the hot melt adhesive composition may have a Brookfield viscosity of at least 100, 300, 500, 750, or 1,000, and / or 60,000, 40,000, 30,000, 20,000, 10,000, 5,000, 4,000, 3,000, or 2,500 cps or less at 177 °C as measured according to ASTM D3236. For example, the hot melt adhesive may have a Brookfield viscosity in the range of 100 - 60,000, 300 - 10,000, 500 - 5,000, 750 - 2,500, 400 - 3,000, 500 - 1,000, 500 - 5,000, 500 - 10,000, 500 - 15,000, 500 - 20,000, 1,000 - 5,000, 1,000 - 10,000, 1,000 - 15,000, 1,000 - 20,000, 1,000 - 40,000, or 1,000 - 60,000 cps at 177 °C.

[0179] In one embodiment, or in combination with any of the embodiments referred to herein, the hot melt adhesive composition may have a Brookfield viscosity of at least 100, 500, 1,000, 2,000, 3,000, 4,000, 5,000, 6,000, 7,000, 8,000, or 9,000, and / or 60,000, 40,000, 30,000, 20,000, or 15,000 cps or less at 140 °C as measured according to ASTM D3236. For example, the hot melt adhesive may have a Brookfield viscosity in the range of 100 - 60,000, 500 - 20,000, 3,000 - 15,000, 4,000 - 15,000, 5,000 - 15,000, 5,000 - 15,000, or 6,000 - 15,000 cps at 140 °C.

[0180] In one embodiment, or in combination with any of the embodiments referred to herein, the hot melt adhesive composition may have a Brookfield viscosity of at least 100, 500, 1,000, 1,500, 2,000, 3,000, 4,000, 5,000, 6,000, 7,000, 8,000, or 9,000, and / or 60,000, 40,000, 30,000, 20,000, or 15,000 cps or less at 150 °C as measured according to ASTM D3236. For example, the hot melt adhesive may have a Brookfield viscosity in the range of 100 to 60,000, 500 to 20,000, 1,000 to 15,000, 1,000 to 4,000, 2,000 to 15,000, 3,000 to 15,000, 4,000 to 15,000, or 4,000 to 10,000 cps at 150 °C.

[0181] In one embodiment, or in combination with any of the embodiments referred to herein, the hot melt adhesive composition may have a Brookfield viscosity of at least 10, 500, 1,000, 1,500, 2,000, 2,500, 3,000, 3,500, or 4,000, and / or 60,000, 40,000, 30,000, 20,000, 10,000, 9,000, or 8,000 cps or less at 160 °C as measured according to ASTM D3236. For example, the hot melt adhesive may have a Brookfield viscosity in the range of 100 to 60,000, 500 to 10,000, 1,000 to 10,000, 1,500 to 10,000, 2,000 to 10,000, 1,000 to 8,000, 1,000 to 5,000, 1,000 to 4,000, or 2,000 to 10,000 cps at 160 °C.

[0182] In one embodiment, or in combination with any of the embodiments referred to herein, the hot melt adhesive composition may have a Brookfield viscosity of at least 100, 500, 1,000, 2,000, 3,000, 4,000, 5,000, 6,000, 7,000, 8,000, or 9,000, and / or 60,000, 50,000, 40,000, 30,000, 20,000, or 15,000 cps or less at 190 °C as measured according to ASTM D3236. For example, the hot melt adhesive may have a Brookfield viscosity in the range of 100 to 60,000, 500 to 20,000, 1,000 to 5,000, 1,000 to 4,000, or 2,000 to 10,000, 1,000 to 20,000, 3,000 to 15,000, 4,000 to 15,000, 5,000 to 15,000, 5,000 to 15,000, or 6,000 to 15,000 cps at 190 °C.

[0183] In one embodiment, or in combination with any of the embodiments referred to herein, the hot melt adhesive composition may have a 90-degree (T-peel) peel strength of at least 1, 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, or 150 g / 25 mm as measured according to ASTM D903. Additionally, or alternatively, the hot melt adhesive composition may have a 90-degree (T-peel) peel strength of at least 200, 190, 180, 170, 160, 150, 140, 130, 120, 110, 100, 95, 90, 85, or 80 g / 25 mm or less as measured according to ASTM D903. The foregoing peel strength values may be applicable after the adhesive has cured at room temperature for 24 hours, after the adhesive has cured at 38 °C for 4 hours, after the adhesive has cured at 55 °C for 2 weeks, and / or after the adhesive has cured at 25 °C for 1 month. For example, the hot melt adhesive may have a peel strength in the range of 1 to 200, 10 to 180, 20 to 150, 30 to 140, 40 to 120, 55 to 200, 55 to 100, 55 to 150, 55 to 200, 70 to 200, 100 to 200, or 115 to 200 g / 25 mm as measured according to ASTM D903.

[0184] As described above, due to the unique propylene-ethylene copolymer, the hot melt adhesive composition can exhibit a desirable peel strength even after aging. In certain embodiments, or in combination with any of the embodiments recited herein, the hot melt adhesive composition has a 90-degree (T-peel) peel strength in the range of 1-200, 10-180, 20-150, 30-140, 40-120, 55-200, 55-100, 55-150, 55-200, 70-200, 100-200, or 115-200 g / 25 mm when measured according to ASTM D903 after the adhesive has cured at room temperature for 24 hours, after the adhesive has cured at 38 °C for 4 hours, after the adhesive has cured at 55 °C for 2 weeks, and / or after the adhesive has cured at 25 °C for 1 month. Additionally, or alternatively, the hot melt adhesive composition can exhibit a 90-degree (T-peel) peel strength after aging for 4 hours, 24 hours, 2 weeks, or 1 month that is at least 50, 55, 60, 65, 70, 75, 80, 85, or 90 percent of the initial 90-degree (T-peel) peel strength.

[0185] Generally, the adhesive composition containing the copolymer of the present invention can have a wide operating window and can have an application window of 80-230 °C. This wide operating window can be demonstrated by the peel strength of the adhesive at different temperatures.

[0186] In certain embodiments, or in combination with any of the embodiments recited herein, the hot melt adhesive composition can exhibit a holding force of at least 5, 15, 20, or 25 minutes and / or 150 minutes or less at 60 °C. Additionally, or alternatively, the hot melt adhesive can exhibit a holding force of at least 400, 600, 800, or 1,000 minutes at 50 °C. The holding forces at 50 °C and 60 °C can be measured by stabilizing the adhered carton substrate at room temperature (usually 20-23 °C) overnight and then suspending the substrate in a shear bank oven in the peel mode. Then, a weight is suspended under the adhered substrate. The time at which the weight falls due to breakage is recorded for each test piece.

[0187] In one embodiment, or in combination with any of the embodiments referred to herein, the hot melt adhesive composition may exhibit a shear adhesion failure temperature ("SAFT") of at least 75, 80, 85, 90, 95, 100, 110, 120, 130, or 135 °C as measured according to ASTM D4498-07. Additionally or alternatively, the hot melt adhesive composition may exhibit a shear adhesion failure temperature ("SAFT") of 200, 160, 155, 150, 140, 135, 134, 133, 130 or 135 °C or less as measured according to ASTM D4498-07. For example, the hot melt adhesive may exhibit a SAFT in the range of 2-200, 50-150, 75-125, 130-160, 130-155, 130-150, 130-145, 135-155, 135-150, 140-160, 140-155, 140-150, 145-160, 145-155, or 145-150 °C as measured according to ASTM D4498-07.

[0188] In one embodiment, or in combination with any of the embodiments referred to herein, the hot melt adhesive composition may exhibit a lap shear of at least 25, 50, 75, or 100 and / or 300, 275, 250, 225, 200, 175, 150, or 125 lbf or less as measured according to ASTM D1002. For example, the hot melt adhesive may exhibit a lap shear in the range of 25-300, 50-275, 75-250, 100-250, or 100-225 lbf as measured according to ASTM D1002.

[0189] In one embodiment, or in combination with any of the embodiments referred to herein, the hot melt adhesive composition may exhibit at least 50, 65, 70, 75, 80, 85, 90, or 95 percent high temperature performance fiber tear (HTFT) at 60°C. The HTFT test consists of manually tearing by hand a glued cardboard (carton) substrate under conditions of 60°C. The glued carton substrate must be stabilized for 4 hours ± 5 minutes under conditions of 60°C prior to tearing. When 80% of the substrate is broken, the test is considered a pass, and thus the hot melt adhesive is considered to function well. In some applications, when 50% of the fibers of the substrate are broken, the test is considered a pass, and the adhesive is considered to function well at 60°C.

[0190] In one embodiment, or in combination with any of the embodiments referred to herein, the hot melt adhesive composition may exhibit a ring and ball softening point measured by ASTM method E-28 of at least 100, 105, 110, 115, 120, 125, or 130°C, and / or 200, 190, 180, 170, 160, 150, or 140°C or less. For example, the hot melt adhesive composition may exhibit a ring and ball softening point measured by ASTM method E-28 of 100 to 200°C, 110 to 180°C, 125 to 160°C, or 130 to 150°C.

[0191] In one embodiment, or in combination with any of the embodiments referred to herein, the hot melt adhesive composition may exhibit heat resistance of at least 80, 85, 90, 95, or 100°C, and / or 200, 175, 150, 140, 130, 125, or 120°C or less. For example, the hot melt adhesive composition may exhibit heat resistance of 80 to 200°C, 90 to 175°C, 100 to 140°C, or 100 to 125°C.

[0192] In certain embodiments, or in combination with any of the embodiments referred to herein, the adhesives containing the copolymers of the present invention do not exhibit a substantial change in color when subjected to high-temperature storage conditions over a long period of time. Before any aging due to storage occurs, the adhesive may have an initial Gardner color of less than 18, 15, 10, 8, 5, 4, 3, 2, or 1 as measured according to ASTM D1544. After heat aging at 177 °C for about 96 hours, the adhesive may exhibit a final Gardner color of less than 18, 15, 10, 7, 5, 3, 2, or 1 as measured according to ASTM D1544. Thus, the adhesive can retain a desirable color even after long-term storage and exposure.

[0193] Exemplary adhesive formulations for use on various substrates and for various applications are provided in Table 2 below. In addition, Table 2 provides broad, intermediate, and narrow ranges for various characteristics of the adhesive formulations, which can be combined in any combination regardless of their categories (e.g., one or more broad ranges can be combined with one or more intermediate and / or narrow ranges). Further, while broad, intermediate, and narrow ranges are provided in Table 2, it is contemplated that any of the above ranges regarding the composition of the adhesive formulation (e.g., polymer content, tackifier content, etc.) and the attendant performance characteristics may be applicable to the adhesive formulations provided in Table 2 as long as such combinations do not result in contradictions.

[0194]

Table 5

[0195] In certain embodiments, or in combination with any of the embodiments referred to herein, the propylene-ethylene copolymers of the present invention can be utilized in adhesive compositions as described above in the present disclosure. Specifically, the propylene-ethylene copolymers of the present invention can be utilized to produce hot melt adhesives having a wide process window and high peel strength for laminated materials such as, but not limited to, hygiene products.

[0196] As discussed above, the adhesive compositions described herein can be used to bond various substrates and adherends, thereby forming a multilayer laminate. For example, an article can be manufactured using the adhesive composition by (a) applying the adhesive composition to at least a portion of the surface of a substrate, and (b) contacting the treated surface with another surface, thereby forming a laminate.

[0197] A variety of articles can be manufactured using the adhesive compositions described herein. Exemplary articles that can be manufactured with the adhesive compositions described herein include articles where the article is an adhesive, sealant, caulking material, roofing membrane, waterproof membrane, compound, and underlayment, carpet, laminate, laminated article, tape, label, mastic, polymer blend, wire coating, molded article, heat seal coating, disposable hygiene article, insulating glass (IG) unit, bridge deck, bitumen modification, asphalt modification, electronic housing, waterproof membrane, cable flooding / filling compound, sheet molding compound, dough molding compound, overmold compound, rubber compound, polyester composite, glass composite, glass fiber reinforced plastic, wood plastic composite, polyacrylic blend compound, lost wax precision casting, investment casting wax composition, bookbinding material, candle, window, tire, film, gasket, seal, O-ring, motor vehicle (automobile), motorcycle (bike), bus, and tram, truck, motor vehicle molded parts, motor vehicle extruded parts, clothing article, rubber additive / processing aid, and fiber.

[0198] Exemplary adhesives that can be produced with the adhesive compositions described herein include packaging adhesives, food contact grade adhesives, indirect food contact packaging adhesives, product assembly adhesives, woodworking adhesives, edge banding adhesives, profile wrapping adhesives, flooring adhesives, automotive assembly adhesives, structural adhesives, flexible lamination adhesives, rigid lamination adhesives, flexible film adhesives, flexible packaging adhesives, water-activated adhesives, household repair adhesives, industrial adhesives, construction adhesives, furniture adhesives, mattress adhesives, pressure sensitive adhesives (PSA), PSA tapes, PSA labels, PSA protective films, self-adhesive films, lamination adhesives, flexible packaging adhesives, heat seal adhesives, industrial adhesives, hygienic nonwoven construction adhesives, hygienic core integrity adhesives, and hygienic elastic attachment adhesives.

[0199] The present invention can be further illustrated by the following examples of this embodiment, which are included for illustrative purposes only and are not intended to limit the scope of the present invention unless otherwise specifically stated.

Examples

[0200] Example 1 - High Viscosity Propylene-Ethylene Copolymers with High and Moderate Tensile Strengths Various propylene-ethylene copolymers of the present invention having high viscosities and exhibiting moderate tensile strengths were produced. The propylene-ethylene copolymers were produced according to the following polymerization process.

[0201] The reactants propylene, ethylene, and hydrogen, along with a diluent, an external donor, and a catalyst, were fed to a 5-gallon continuously stirred tank reactor (CSTR) at the ratios, flow rates, and temperatures provided in Table 3 below for each of the generated samples. The samples of the present invention and the comparative samples (i.e., the generated comparative samples) were prepared using a third-generation (Benozate) catalyst and an alkoxysilane as the external electron donor described above. The reactor was operated at a pressure in the range of 790 - 850 psi. Further, a hot oil system provided a trace of the reactor jacket. The dip tube carried the product out of the reactor, and the equilibar was pressurized by pressure control maintaining helium in the reactor.

[0202] The diluent was then stripped from the copolymer in the let-down tank, and then steam and nitrogen were used to deactivate the residual catalyst in a heat oil jacketed exchanger. The molten copolymer was then collected from the bottom of the inactivation unit and pumped to the final product collection tank. The copolymers of the present invention (i.e., samples starting with a number, e.g., "1A") and the comparative copolymers (i.e., samples starting with "C", e.g., "C1") obtained were produced according to the reaction conditions listed in Table 3.

[0203]

Table 6

[0204] The copolymers of the present invention and the comparative samples produced under the conditions shown in Table 3 were subjected to tests to verify the characteristics and features of the copolymers. Various properties were tested using the described test methods unless otherwise specified.

[0205] Ethylene content and triad tacticity Techniques for determining ethylene and propylene (「PP」) composition and triad tacticity by NMR were performed according to the techniques outlined in the aforementioned references. More specifically, a sample was prepared by adding 0.4 g of copolymer sample and 100 mg of Cr(acac)3 to a 4-dram vial, followed by the addition of 0.5 mL of orthodichlorobenzene-d4 and 3.5 mL of trichlorobenzene (non-deuterated). The resulting solution was magnetically stirred at 120 °C until complete dissolution of the copolymer was observed by visual inspection. Dissolution typically completed within 1 hour. A 10 mm NMR tube was warmed to 80 °C. While wearing heat-resistant gloves, the warm solution was poured into the 10 mm NMR tube until the sample height was approximately 4.5 - 5 cm. The tube was then capped with a push-on cap. It was important to transfer the solution to the NMR tube while it was still warm so that it did not solidify before the transfer was complete. The spectrum was analyzed using MNova software. After applying Fourier transform to the FID data, the spectrum was phase-adjusted, the baseline was corrected, and calculations were performed as described in the aforementioned references. It was determined that the standard deviation of PP% was 0.7 and the standard deviation of mm% was 0.3.

[0206] Preparation of Tensile Strength Samples A film sample for tensile testing was prepared using a Carver press. First, 20 grams of the molten sample was placed into a 5”×5” inch (137 mm×137 mm) aluminum square casting frame with a thickness of 1 mm. Subsequently, the sample was sandwiched between a silicone-coated PET film, release paper, and a metal plate, and then heated in the Carver press with zero pressure applied. The sample was compression molded at 177 °C to 188 °C for 12 minutes, then a pressure of 6000 PSI was applied for 5 seconds and released. Thereafter, the pressure was increased to 12000 PSI and released again. Finally, a pressure of 18000 PSI was applied and held for 2 minutes. Then, the sample was removed from the press and quickly transferred from the hot metal plate to a set of room-temperature plates with a 10 kg weight block acting as a heat sink on top. After applying an 8-minute cooling time, the weight block and metal plate were removed. Then the film was stored in a room with controlled temperature and humidity (25 °C, 50% RH) for 24 hours, and then cut using a dumbbell-shaped cutter based on ASTM-D412 die C.

[0207] Tensile test Tensile strength and elongation at break were determined at 20 inches per minute (51 cm per minute) following the procedure described in ASTM D412 (die C). All tests were conducted on an MTS tensile testing machine at 25 °C, 50% RH in a temperature- and humidity-controlled (CTH) room. Tensile strength at break was calculated by dividing the magnitude of the force at break by the cross-sectional area of the sample without strain. Elongation at break was calculated by the recorded elongation distance at the break point and normalized by the original standard gauge length of 62.5 mm within the tensile grip.

[0208] Table 4 below provides the measured characteristics and properties of the measured copolymers. In addition, Table 4 also lists the characteristics and properties of two commercially available propylene-ethylene copolymers labeled "CAC1" and "CAC2". In the table below, "NP" refers to penetration, "SP" refers to ring and ball softening point, "PP" refers to propylene, "TT" refers to triad tacticity, "TSB" refers to tensile strength at break, "EB" refers to elongation at break, "H F " refers to heat of fusion, and "H C " refers to heat of crystallization.

[0209]

Table 7

[0210] As shown in Table 4, the copolymers of the present invention exhibited desirable tensile strength (TSB) superior to that of the comparative examples and existing commercial products of similar viscosity. More specifically, as shown above, the propylene / ethylene content, triad tacticity, viscosity, peak T m , heat of fusion, and heat of crystallization of the copolymers were all important features in producing copolymers with excellent tensile strength. For example, Table 4 emphasizes the importance of ethylene content, which can affect the crystallinity and elongation of the copolymer, and triad tacticity, which can affect the tensile profile, elongation, crystallinity, and penetration of the resulting copolymer.

[0211] The inventors have observed that ethylene is generally inserted into the copolymer mainly as crystal defects in the amorphous phase, and thus higher ethylene typically disrupts the average crystal sequence length of isotactic polypropylene (iPP) and reduces the percentage of crystallinity of the copolymer. Generally, higher strength propylene-ethylene copolymers such as those shown in Tables 3 and 4 provide higher initial peel strength in adhesives.

[0212] Figure 1 is a chart comparing the propylene content of the copolymers in Table 4 with the resulting tensile strength at break. As shown in Figure 1, the propylene and ethylene content of the copolymers was important in obtaining excellent tensile strength.

[0213] Example 2 - Medium-viscosity propylene-ethylene copolymers having high and medium tensile strength Various propylene-ethylene copolymers of the present invention having medium viscosity and showing medium tensile strength were produced. The propylene-ethylene copolymers were produced according to the polymerization method described in Example 1.

[0214] The obtained copolymers of the present invention (e.g., "2A") and comparative copolymers (e.g., "C6") were produced according to the reaction conditions listed in Table 5. Unless otherwise specified, the copolymers were tested and their properties and characteristics were verified using the aforementioned test methodology.

[0215] [Table 8]

[0216] The copolymers of the present invention (i.e., samples starting with numbers) and comparative samples (i.e., samples starting with "C") produced under the conditions shown in Table 5 were tested to verify the properties and characteristics of the copolymers. Unless otherwise specified, various properties were tested using the test methodology described above.

[0217] The following Table 6 provides the measured characteristics and properties of the measured copolymers and two commercially available propylene-ethylene copolymers designated "CAC3" and "CAC4" having similar viscosities.

[0218] [Table 9]

[0219] As shown above in Table 6, the copolymers of the present invention included higher viscosities and exhibited desirable tensile strengths superior to existing commercially available products. More specifically, as shown above, the propylene / ethylene content, triad tacticity, viscosity, peak T m , heat of fusion, and heat of crystallization were all important features in producing copolymers that exhibited excellent tensile strength and elongation at a desirable ring and ball softening point. For example, Table 6 emphasizes the importance of ethylene content, which can affect the crystallinity and elongation of the copolymer, and triad tacticity, which can affect the tensile profile, elongation, crystallinity, and penetration of the resulting copolymer. Generally, higher strength propylene-ethylene copolymers, such as those shown in Tables 5 and 6, provide higher initial peel strength in adhesives.

[0220] Figure 2 is a chart comparing the propylene content of the copolymers in Table 6 to the resulting tensile strength at break. As shown in Figure 2, the propylene and ethylene content of the copolymers were important in obtaining excellent tensile strength. It is particularly interesting to compare Example 2O of the present invention with CAC4, which had similar viscosities and propylene content. Higher polymer molecular weights are known to contribute to higher viscosities and tensile strengths. Example 2O of the present invention can be shown to have an unexpectedly high tensile strength (10.4 MPa, 8133 cP) relative to its viscosity, which is evident when compared to the values of CAC4 (i.e., 3.8 MPa, 7570 cP). Without wishing to be bound by theory, similar viscosities indicate similar molecular weights, and thus the unexpectedly high tensile strength of Example 2O of the present invention is likely the result of the inventive combination of propylene content and tacticity (mm%).

[0221] Example 3 - Low Viscosity Propylene-Ethylene Copolymers with High and Medium Tensile Strengths Various propylene-ethylene copolymers of the present invention were produced that had low viscosities and exhibited medium tensile strengths. The propylene-ethylene copolymers were produced according to the polymerization method described in Example 1.

[0222] The obtained copolymers of the present invention (e.g., "3A") and comparative copolymers (e.g., "C11") were produced according to the reaction conditions listed in Table 7 below.

[0223]

Table 10

[0224] The copolymers of the present invention (i.e., samples starting with numbers) and comparative samples (i.e., samples starting with "C") produced under the conditions shown in Table 7 were subjected to tests to verify the properties and characteristics of the copolymers. Unless otherwise specified, various properties were tested using the test methods described above. Table 8 below provides the measured characteristics and properties of the measured copolymers. In addition, Table 8 also lists the characteristics and properties of commercially available propylene-ethylene copolymers listed as "CAC5", "CAC6", "CAC7", "CAC8", and "CAC9".

[0225]

Table 11

[0226] As shown in Table 8, the copolymers of the present invention have a low viscosity and exhibit a desirable tensile strength superior to existing commercially available products. More specifically, as shown above, the propylene / ethylene content, triad tacticity, viscosity, peak T m , heat of fusion, and heat of crystallization were all important characteristics in producing copolymers exhibiting excellent tensile strength. For example, Table 8 emphasizes the importance of the ethylene content, which can affect the crystallinity and elongation of the copolymer, and the triad tacticity, which can affect the tensile profile, elongation, crystallinity, and penetration of the resulting copolymer.

[0227] Figure 3 is a chart comparing the propylene content of the copolymers in Table 6 with the resulting tensile strength at break. As shown in Figure 3, the propylene and ethylene content of the copolymers were important in obtaining excellent tensile strength. It is particularly interesting to compare Examples 3E and 3F of the present invention with CAC5. Examples 3E and 3F of the present invention have a tensile strength approximately twice that of CAC5 (2.4 MPa), namely 4.2 MPa and 5.0 MPa respectively, while the three copolymers have similar viscosities and propylene contents. Without wishing to be bound by theory, similar viscosities indicate similar molecular weights, and thus the unexpectedly high tensile strength of Examples 3E and 3F of the present invention is probably the result of the combination of propylene content and tacticity (mm%) of the present invention.

[0228] Figure 4 is a chart comparing the tensile strengths of all the high-tensile-strength copolymers and medium-tensile-strength copolymers of the present invention with the viscosities of the corresponding copolymers. The copolymers in Figure 4 include those from Examples 1 to 3, together with the above-mentioned comparative copolymers and commercially available copolymers (CAC). As shown in Figure 4, the viscosity of the copolymers of the present invention had a positive effect on the tensile strength of the resulting copolymers.

[0229] Example 4 - Woodworking Adhesive Various hot melt adhesives were produced for woodworking applications to test the copolymers of the present invention. Using the copolymers 1B, 1C, 1D, and 2N of the present invention, woodworking adhesives having the formulations provided in Table 16 were produced. Additionally, for comparison purposes, adhesive formulations were also produced using Aerafin™ 180 from Eastman and Vestoplast® 828 from Evonik Industries. Vestoplast® 828 has a viscosity of 25,000 cP at 190 °C, a penetration of 22 dmm, a softening point of 161 °C, a Tm of 159 °C, a breaking point tensile strength of 0.9 MPa, an elongation at break of 468%, and a heat of crystallization of 8.3 J / g. The adhesives also contained an antioxidant (Irganox® 1076 from BASF), a tackifier (Eastotac™ H100R from Eastman), and a wax (Epolene® E-43 from Westlake Chemical). All of the following amounts in Table 9 regarding the listed components are provided as weight percentages based on the total weight of the adhesive. The amount of antioxidant added was based on the total weight of the other components.

[0230] The adhesives were made based on the following process. First, the heating block was preheated to about 180 °C. Subsequently, the copolymer, wax, resin, and antioxidant were weighed into a 1-pint aluminum container. Subsequently, the container was placed in the heating block. When the mixture showed signs of melting, a stir bar was inserted and mixed at a speed of about 50 rpm until homogeneous. When the mixture became homogeneous, the stirring speed was increased to 150 rpm for 30 minutes. Then the speed was decreased to about 30 rpm and mixed for an additional 15 minutes while removing bubbles (if any) before removal. The heating block temperature was maintained at about 180 °C throughout the blending process. The adhesive was poured onto silicon-coated release paper and cooled to room temperature.

[0231] Table 9 provides the formulations and characteristic features of the comparative woodworking adhesive ( 「CA」) and the inventive adhesive ( 「IA」).

[0232]

Table 12

[0233] Measurement of the Viscosity of the Adhesive The viscosity was measured according to an in - house method compliant with ASTM D - 3236 using a Brookfield DV2Textra viscometer equipped with a Thermosel (trademark) and a No. 27 spindle. 10.5 grams of the adhesive was placed in the Brookfield tube, and the sample was heated to the temperature (if not already molten) for 10 minutes. Then, the sample was equilibrated under shear for 20 minutes at each respective test temperature. The spindle rpm was adjusted so that the motor % was maximized, and no adjustment was made during the last 20 minutes of the shear equilibration time. The values were reported in centipoise (cP). The viscosity readings were taken from low temperature to high temperature.

[0234] Adhesive Ring and Ball Softening Point (RBSP) The adhesive Ring and Ball Softening Point was measured using a Herzog ring and ball softening point apparatus according to ASTM method E - 28. The formulated adhesive was decanted into a brass ring and cooled overnight or for more than 16 hours. The sample was trimmed flat before the test. The silicone oil was heated at 5 °C per minute until the ball passed through the softened specimen, and the temperature was measured at the moment of passage. The reported value is the average of two readings.

[0235] Shear Adhesion Failure Temperature (SAFT) - Wood Processing Sample Preparation: Two basswood wood substrates (size 1” x 1”) were joined with an adhesive. The adhesive was melted at 180 - 200 °C for at least 20 minutes and then applied to one surface of the basswood wood substrate with a laboratory spatula. Immediately afterwards, another basswood wood substrate was placed on top of the adhesive and gentle pressure was applied to ensure a 1” x 1” bond area. A 100 g weight was placed on the bond area at 350 °C for 30 seconds. The final adhesive thickness was 1.5 - 2.0 mils.

[0236] SAFT temperature measurement was carried out in accordance with ASTM D4498 - 07 “Standard Test Method for Heat - Fail Temperature in Shear of hot Melt Adhesives”. After conditioning at room temperature for at least 24 hours, the specimens were placed in a programmable oven equipped with a Cheminstruments 30 - Bank tester (West Chester Township, OH). The static load was 500 g. The heating program was set to run from 20 °C to 150 °C at a ramp rate of 0.5 °C / min. The program recorded the time when the bond broke (the weight fell) and converted it to the bond failure temperature. A total of three specimens were tested and the average was reported. The standard deviation was 6 °C.

[0237] Lap Shear Strength Test - Woodworking Two veneer panels were joined using an adhesive bead of 3 ± 0.9 grams / m2 applied at 190 °C using an Adhesive Testing Unit manufactured by ITW Dynatec GmbH, Mettmann, Germany. Prior to testing, the samples were conditioned for 24 hours in a temperature and humidity controlled (CTH) chamber at 25 °C, 50% RH. Strength was measured on an MTS Criterion Model 43 Electromechanical Universal Test System at a rate of 12.7 mm / min. A minimum of five specimens per sample were tested and the average value was reported. The test was carried out in accordance with ASTM D1002.

[0238] Heat Resistance - Woodworking Heat resistance was measured using a 1” x 8” MDF board and a laminate paper substrate bonded with approximately 5 mils of adhesive pressed at 350 °C for 1.5 minutes. The laminate was horizontally mounted in an oven and a 10 g weight was suspended from the end of the paper laminate. The oven was set at 50 °C and the temperature was increased by 10 °C per hour up to a maximum of 150 °C. The failure temperature was the temperature at which the paper peeled more than 7 cm from the MDF board. The average of three measurements was reported.

[0239] As shown in Table 9, all of the adhesives of the present invention showed heat resistance exceeding 100 °C. In contrast, CA1 had only a heat resistance of 95 °C. Furthermore, Adhesive 4 of the present invention showed an unexpected 114% increase in lap shear strength compared to the comparative adhesives, while also providing a decreased viscosity. Most surprisingly, the increased heat resistance and lap shear of the adhesives of the present invention were accompanied by a decreased SAFT temperature.

[0240] Example 5 - Woodworking Adhesive Various hot melt adhesives for woodworking applications were produced to test the copolymers of the present invention. Using Copolymers 1B, 1C, 1D, and 2N of the present invention, woodworking adhesives having the formulations provided in Table 10 below were produced. In addition, for comparison purposes, adhesive formulations were also produced using Aerafin™ 180 from Eastman and Vestoplast® 828 from Evonik Industries. The adhesives also contained an antioxidant (Irganox® 1076 from BASF) and a tackifier (Eastotac™ H130R from Eastman). The adhesives were produced and tested according to the procedures previously described in Example 4. All of the following amounts in Table 10 regarding the listed components are provided as weight percentages based on the total weight of the adhesive. The amount of antioxidant added was based on the total weight of the other components. Table 10 provides the formulations and characteristic features of the comparative woodworking adhesives (“CA”) and the adhesives of the present invention (“IA”).

[0241]

Table 13

[0242] As shown in Table 10, all of the adhesives of the present invention showed desirable lap shear as compared to the comparative adhesives. Additionally, the adhesives of the present invention showed lower RBSP, which allows for faster melting and easier processing.

[0243] Example 6 - Hygiene Adhesive with High Viscosity Propylene - Ethylene Copolymer Various hot melt adhesives for hygiene applications were produced and the copolymers of the present invention having high viscosity (i.e., 1A and 1I from Example 1) were tested. Additionally, for comparison purposes, adhesive formulations were also produced using Araffin™ 180 by Eastman. The adhesives also contained an antioxidant (Irganox® 1010 from BASF), a tackifier (Eastotac™ H100R or Regalite™ R1090 from Eastman), a wax (Sasolwax® H - 1 from Sasol), and a processing oil (Kaydol Oil from Chevron or Seration 1820 by Sasol). Unless otherwise specified, the adhesives were produced and tested according to the procedure described in Example 4. All of the following amounts in Table 11 regarding the listed components are provided as weight percentages based on the total weight of the adhesive. The amount of antioxidant added was based on the total weight of the other components. Table 11 provides the formulations and characteristic features of the comparative hygiene adhesives ("CA") and the adhesives of the present invention ("IA").

[0244]

Table 14

[0245] Measurement of Non - Woven Laminate Peel Strength (T - Peel) A polyethylene (「PE」) backsheet with a thickness of 1 mil (24.4 gsm) from Berry Global and a hydrophobic nonwoven sheet with a thickness of 15 gsm from Midwest Filtration were adhered together using a Catbridge high-speed coater as described below, and a laminate sample was formed by applying a hot-melt adhesive at 3 gsm between the two sheets through a signature nozzle head at 130 - 160 °C. The PE backsheet and the hydrophobic nonwoven sheet were peeled from each other using an Instron 3365 tensile strength tester at an angle of 180° and a speed of 300 mm / min. Except for the immediate peel strength, the laminate was conditioned at 25 °C and 50% relative humidity after the hot-melt adhesive was applied and before the peel test. The following T-peel tests were performed: · Immediate peel strength - g / 25 mm · Peel strength - g / 25 mm, 24 hours, · Peel strength - g / 25 mm, 4 hours at 38 °C, · Peel strength - g / 25 mm, 2 weeks at 55 °C, and · Peel strength - g / 25 mm, 1 month at 25 °C.

[0246] The PE backsheet and the hydrophobic nonwoven sheet were pulled 6.5 inches apart and the force was recorded as the T-peel strength of the hot-melt adhesive. Five replicates of test specimens were performed for each test and the mean value / standard deviation was recorded.

[0247] Additionally, the adhesives shown in Table 11 were subjected to further Catbridge test runs to analyze the effect of the oil content on the peel strength of the adhesives.

[0248] Catbridge Calibration and Lance Step The Catbridge high-speed coater (PL59188) was manufactured by Catbridge Machinery and was equipped with a Nordson applicator having an Acumeter tank / pump and a signature nozzle. The Acumeter pump speed was calibrated based on three pump ratios, namely 20%, 30%, and 50%, controlled by Catbridge. A timer was used to dispense and weigh the adhesive onto a peeled liner for 1 minute. Using the weights, a graph of weight versus pump speed was plotted. An equation with an R 2 higher than 0.98 was acceptable, and the slope and constant were obtained. Depending on the line speed, additional weight, and pattern width, the amount of adhesive dispensed was determined using the following equation. Amount of adhesive (g / min) = Line speed (m / min) × Adhesion weight (g / m 2 ) × Pattern width (m)

[0249] Using the slope and constant from the calibration, the pump ratio (%) and the pump speed in rpm were determined for the required amount of adhesive. Catbridge was then run at the required pump speed by adjusting the air pressure to achieve a good adhesive pattern and good edge control. The adhesive was sprayed onto a PE backsheet and combined with the non-woven fabric using a nip roll set at 30 psi. The line was run for about 30 - 40 seconds to obtain a good representative sample over several seconds as the line stabilized. If the pattern was not good enough, i.e., there was not enough entanglement or fibrillation when viewed under UV light, the air pressure was gradually adjusted until a good pattern was achieved. Typically, a higher air pressure was required for a higher line speed or a higher viscosity adhesive.

[0250] The results of the Catbridge test runs in IA8, IA9, CA5, IA10, and IA12 are shown in Figure 5, which shows the immediate peel strength and the peel strength at 2 hours, 4 hours (aging at 38°C), 2 weeks (aging at 55°C), and 1 month (aging at 25°C).

[0251] As shown in Table 11 above, a polymer loading of 32 - 35 wt% with a single copolymer type gave an adhesive viscosity range for spraying. Further, as shown in Table 11 and Figure 5, adhesives with lower oil content were able to maintain higher peel strength, assisted by the tensile strength of the copolymers of the present invention. Further, the adhesives formed from Copolymer 1A of the present invention showed the best overall performance for all adhesives. Specifically, the high viscosity copolymer had a desirable RBSP, a desirable viscosity at a spraying temperature of about 130 °C to about 160 °C, a desirable nonwoven / PE immediate peel strength, and stable or increasing peel strength at 24 hours, 4 hours (aging at 38 °C), 2 weeks (aging at 55 °C), and 1 month (aging at 25 °C). It was found that it could be used as the only polymer in the adhesive formulation. Certain adhesives could contain 30 - 45 wt% propylene-ethylene copolymer, 35 - 55 wt% of at least one tackifier, 5 - 25 wt% processing oil, and 0 - 15 wt% of at least one wax.

[0252] Thus, a suitable range of propylene / ethylene comonomer content having a particular level of propylene tacticity together provided a propylene-ethylene copolymer with a unique balance of moderate tensile strength, viscosity, penetration, and elongation properties that was particularly advantageous for sanitary adhesive applications. More specifically, it was observed that the tensile strength of the copolymers of the present invention was high enough to contribute to the adhesive bond strength in the formulated adhesives, but not so high that the bond strength was significantly lost after aging. Further, by maintaining a particular triad tacticity in the copolymers of the present invention, the tensile strength, elongation, crystallinity, and penetration of the resulting copolymers were able to form adhesives with excellent aging properties.

[0253] Example 7 - Sanitary Adhesive with Medium Viscosity Propylene-Ethylene Copolymer To test the copolymers of the present invention from Example 2 having medium viscosity, various hot melt adhesives for sanitary applications were produced. Additionally, for comparison, the adhesive formulations were also produced using comparative copolymers C8 and C9. The adhesives also contained an antioxidant (Irganox® 1010 from BASF), a tackifier (Eastotac™ H100R or Regalite™ R1090 from Eastman), a wax (Sasolwax® H-1 from Sasol), and a processing oil (Kaydol Oil from Chevron). Additionally, the adhesives IA20 and IA21 of the present invention contained a small amount of one additional high viscosity copolymer, namely, Kraton D1657 SEBS styrene block copolymer from Kraton and INFUSE™ 9807 olefin block copolymer from Dow, respectively.

[0254] Adhesives were produced and tested according to the procedures described in Examples 4 and 6. All of the following amounts in Tables 12 and 13 for the listed components are provided as weight percentages based on the total weight of the adhesive. The following Table 12 provides the formulation and characteristic features of a comparative sanitary adhesive ("CA") and an adhesive of the present invention having a high oil content ("IA"), while the following Table 13 provides the formulation and characteristic features of a comparative sanitary adhesive ("CA") and an adhesive of the present invention having a low oil content ("IA").

[0255]

Table 15

[0256]

Table 16

[0257] The adhesives shown in Tables 12 and 13 were subjected to Catbridge test runs to analyze the effect of oil content on the peel strength of the adhesives. The results of the Catbridge test runs for CA6, IA9, IA20, IA21, C10, IA23, IA24, and IA26 are shown in Figure 6, showing the immediate peel strength and the peel strength at 24 hours, 4 hours (38 °C), 2 weeks (55 °C), and 1 month (25 °C).

[0258] Generally, medium-viscosity olefin copolymers are not used as the sole polymer in producing adhesives because their cohesive strength is not sufficiently good. However, as shown in Tables 12 and 13 above, the copolymers of the present invention having medium viscosity were able to produce desirable adhesives both as the sole polymer in the adhesive and as the major polymer present in the adhesive. Additionally, the adhesive formulations of the present invention had desirable RBSP and viscosities and could be sufficiently sprayed at 150 °C and showed stable or increased peel strength after aging for 24 hours, 4 hours (38 °C), 2 weeks (55 °C), and 1 month (25 °C). Generally, to obtain a higher polymer load (e.g., 50 wt%), a higher amount of oil was required to meet the viscosity required for adhesive spraying.

[0259] It was also observed that using Eastoflex™ E1003 to replace a portion of the processing oil provided no advantages; rather, it significantly increased the viscosity of the adhesive, thereby reducing the propylene-ethylene copolymer content and adversely affecting the peel strength. It was also observed that adding high-viscosity copolymers such as IA20 and IA21 enabled the adhesive to maintain peel strength and withstand larger amounts of processing oil. Generally, in order to use less processing oil, the copolymer content had to be reduced, as in IA23, IA24, and IA25. As a result, in certain cases, this led to an increase in peel strength. For example, as shown in Table 13, IA23 and IA24 exhibited higher peel strength compared to CA7. However, the peel strength of IA25 decreased by 60% the next day, and the adhesive was hard, preventing it from completing the aging test. IA24 also exhibited a softer feel, which may be desirable for hygienic applications.

[0260] As shown in Tables 12 and 13 together with FIG. 6, the medium-viscosity copolymers of the present invention have better tensile properties and thus may require little (if any) additional polymer to add strength, providing an advantage over using low-viscosity copolymers. Furthermore, polymers with medium tensile strength, such as 2A, have been demonstrated to be well-suited as single polymers in hygienic adhesives since they can provide excellent peel strength both immediately and after aging.

[0261] Example 8 - Comparison of the Adhesive of the Present Invention with Commercially Available Adhesives The adhesives IA10 of the present invention from Example 6, the adhesives IA23 of the present invention from Example 7, and the adhesives IA24 of the present invention from Example 7 were compared with existing commercially available adhesives, namely, Safemelt™ DP830H / ST (SBS-based) from Savare, 5603N2P (mPO-based) from HB Fuller, and Safemelt™ VV25F / SW (butene-APO-based) from Savare. The adhesives were tested according to the procedures described in Examples 4 and 6. Table 14 below provides the characteristic features of the adhesives of the present invention and the commercially available adhesives.

[0262]

Table 17

[0263] The adhesives shown in Table 14 were subjected to a Catbridge test run to analyze and compare the peel strength of the adhesives. The results of the Catbridge test run are shown in Figure 7, indicating the peel strength at 24 hours, 4 hours (38 °C), 2 weeks (55 °C), and 1 month (25 °C).

[0264] As shown in Table 14 together with Figure 7, the copolymers of the present invention are suitable as single polymers in producing sanitary adhesives and showed excellent peel strength, especially after aging. Furthermore, the peel strength performance of the adhesives of the present invention was comparable to that of the commercially available adhesives currently on the market. Additionally, the adhesives of the present invention were sprayed very well and did not require high air pressure to obtain a good pattern, whereas, in contrast, the commercially available butene-APO-based adhesives were not sprayed well at low temperatures and required high air pressure to obtain a good pattern. Additionally, the adhesives of the present invention showed sufficient cohesive strength to run on high-speed lines up to 600 m / min.

[0265] From the above viewpoints, it was observed that there was a direct correlation between the mechanical properties of the propylene-ethylene copolymer and the peel strength of the adhesive. However, it was observed that too high a tensile strength caused a decrease in peel strength during aging.

[0266] Definition It should be understood that the following is not intended to be an exclusive list of defined terms. Other definitions may be provided in the foregoing description, such as when used in the context of the defined terms.

[0267] As used herein, the terms "a", "an", and "the" mean one or more.

[0268] As used herein, the term "about" refers to any value within the range of 90% to 110% of the specified value. However, it should be noted that all values related to "about" include the specific value itself and the support of the range related to the specific value of "about". For example, "about 10" provides support for the specific value of "10" and values in the range of 9 to 11. Further, the term "about" can be associated with any specific value listed herein.

[0269] As used herein, the term "and / or" when used in a list of two or more items means that any one of the listed items can be used alone or any combination of two or more of the listed items can be used. For example, if a composition is described as containing components A, B, and / or C, the composition can contain only A, only B, only C, a combination of A and B, a combination of A and C, a combination of B and C, or a combination of A, B, and C.

[0270] As used herein, the phrase "at least a portion" includes at least a portion and the greatest portion, including the entire amount or entire period.

[0271] As used herein, the terms "comprising", "comprises", and "comprise" are open - ended transitional terms used to move from the subject matter recited before the term to one or more elements recited after the term, and the elements listed after the transitional term are not necessarily the only elements that constitute the subject matter.

[0272] As used herein, the terms "having", "has", and "have" have the same open - ended meaning as the terms "comprising", "comprises", and "comprise" provided above.

[0273] As used herein, the terms "including", "include", and "included" have the same open - ended meaning as the terms "comprising", "comprises", and "comprise" provided above.

[0274] Numerical ranges When a series of numbers is presented, each number should be understood to be modified in the same way as the first or last number in the series or sentence. For example, each number may be, in some cases, "at least" or "less than or equal to", and each number is in an "or" relationship. In an exemplary scenario, "at least 10, 20, 30, 40, 50, 75 weight percent..." means the same as "at least 10 weight percent, or at least 20 weight percent, or at least 30 weight percent, or at least 40 weight percent, or at least 50 weight percent, or at least 75 weight percent".

[0275] This description uses numerical ranges to quantify certain parameters related to the present invention. When a numerical range is provided, such a range is to be understood as being construed to provide literal support for claim limitations that recite only the lower limit of the range, as well as for claim limitations that recite only the upper limit of the range. For example, the disclosed numerical range of 10 to 100 provides literal support for claims that recite "greater than 10" (without an upper limit) and for claims that recite "less than 100" (without a lower limit).

[0276] The claims are not limited to the disclosed embodiments The preferred forms of the present invention described above should be used only by way of illustration and should not be used in a limiting sense for interpreting the scope of the present invention. Modifications to the above exemplary embodiments can be readily made by those skilled in the art without departing from the spirit of the present invention.

[0277] The inventors state herein their intention to rely on the doctrine of equivalents to determine and evaluate the reasonable fair scope of the present invention, because, as recited in the following claims, they are related to devices that are not substantially outside but are outside the literal scope of the present invention. Further, while particular embodiments of the present invention are being considered, the present invention encompasses any combination of those embodiments.

Claims

1. A propylene-ethylene copolymer containing propylene and ethylene, wherein the propylene-ethylene copolymer has (a) contains 77 to 90 weight percent of propylene, (b) contains 52% to 75% of triad tacticity (mm%), (c) shows a ring-and-ball softening point of 95°C to 125°C, (d) has a Brookfield viscosity of 2,000 to 7,000 cP at 190°C, (e) (i) a tensile strength at break of at least 4 MPa, or (ii) shows a tensile strength at break of at least 1 MPa and an elongation at break of at least 100%, a propylene-ethylene copolymer.

2. The propylene-ethylene copolymer according to claim 1, wherein the propylene-ethylene copolymer contains 10 to 23 weight percent of ethylene.

3. The propylene-ethylene copolymer according to claim 1, wherein the triad tacticity of the propylene-ethylene copolymer is 54% to 67%.

4. The propylene-ethylene copolymer according to claim 1, wherein the propylene-ethylene copolymer has a viscosity of 3,000 to 7,000 cP at 190°C.

5. The propylene-ethylene copolymer according to claim 1, wherein the propylene-ethylene copolymer shows a heat of crystallization of 16 to 33 J / g and a heat of fusion of 11 to 19 J / g.

6. The propylene-ethylene copolymer according to claim 1, wherein the propylene-ethylene copolymer shows a softening point of 100 to 120°C and a penetration of 6 to 22 dmm.

7. The propylene-ethylene copolymer according to claim 1, wherein the propylene-ethylene copolymer shows an elongation at break of 100% to 1,000% and a tensile strength at break of 4 to 9 MPa.

8. The propylene-ethylene copolymer has (a) contains 54% to 67% of triad tacticity (mm%), (b) shows a ring-and-ball softening point of 100 to 120°C, (c) has a Brookfield viscosity of 3,000 to 7,000 cP at 190°C, (d) shows a tensile strength at break of 4 to 9 MPa, (e) shows an elongation at break of 100 to 1,000%, (f) contains 10 to 23 weight percent of ethylene, (g) shows a penetration of 6 to 22 dmm, the propylene-ethylene copolymer according to claim 1.

9. The propylene-ethylene copolymer contains less than 1% by weight of C ４ -C １０ The propylene-ethylene copolymer according to claim 1, which contains an alpha-olefin.

10. A composition containing the propylene-ethylene copolymer according to claim 1.

11. A method for producing a propylene-ethylene copolymer according to claim 1, the method comprising polymerizing ethylene and propylene at a temperature of 160 ° C or lower, the polymerizing occurring in the presence of a catalyst system, the catalyst system having a molar ratio of aluminum to titanium in the range of 1:1 to 100:

1.

12. An article comprising the propylene-ethylene copolymer according to claim 1, the article being selected from the group consisting of adhesives, sealants, caulking materials, roofing membranes, waterproof membranes and liners, carpets, laminates, laminate articles, tapes, labels, mastics, polymer blends, wire coatings, molded articles, heat seal coatings, disposable sanitary articles, insulated glass (IG) units, bridge decks, electronic enclosures, waterproof membranes, waterproof compounds, liners, cable flooding / filling compounds, sheet molding compounds, dough molding compounds, overmold compounds, rubber compounds, polyester composites, glass composites, glass fiber reinforced plastics, wood plastic composites, polyacrylic blend compounds, lost wax precision casting, investment casting wax compositions, bookbinding materials, candles, windows, tires, films, gaskets, seals, O-rings, motor vehicles, motorcycles, motor vehicle molded parts, motor vehicle extruded parts, clothing articles, rubber additives / processing aids, and fibers. The adhesive comprises a packaging adhesive, a food contact grade adhesive, an indirect food contact packaging adhesive, a product assembly adhesive, a woodworking adhesive, an edge banding adhesive, a profile wrapping adhesive, a flooring adhesive, a motor vehicle assembly adhesive, a structural adhesive, a flexible lamination adhesive, a rigid lamination adhesive, a flexible film adhesive, a flexible packaging adhesive, a household repair adhesive, an industrial adhesive, a construction adhesive, a furniture adhesive, a mattress adhesive, a pressure sensitive adhesive (PSA), a PSA tape, a PSA label, a PSA protective film, a self-adhesive film, a lamination adhesive, a flexible packaging adhesive, a heat seal adhesive, an industrial adhesive, a sanitary non-woven fabric construction adhesive, a sanitary core integrity adhesive, or a sanitary elastic attachment adhesive.

13. A composition comprising a propylene-ethylene copolymer comprising propylene and ethylene, the composition being (a) 5 to 100 weight percent of a propylene-ethylene copolymer, wherein (i) containing 77 to 90 weight percent of propylene, (ii) containing 52% to 75% triad tacticity (mm%), (iii) showing a ring and ball softening point of at least 95°C to 125°C, (iv) having a Brookfield viscosity of 2,000 to 7,000 cP at 190°C, (v) (1) a breaking point tensile strength of at least 4 MPa, or (2) showing a breaking point tensile strength of at least 1 MPa and a breaking point elongation of at least 100%, a propylene-ethylene copolymer, (b) 0 to 55 weight percent of at least one second polymer, (c) at most 70 weight percent of at least one tackifier, (d) at most 20 weight percent of a processing oil, (e) at most 35 weight percent of at least one wax, a composition comprising.

14. The composition according to claim 13, wherein the propylene-ethylene copolymer contains 10 to 23 weight percent of ethylene.

15. The composition according to claim 13, wherein the triad tacticity of the propylene-ethylene copolymer is 54% to 67%.

16. The composition according to claim 13, wherein the propylene-ethylene copolymer has a viscosity of 3,000 to 7,000 cP at 190°C.

17. The composition according to claim 13, wherein the propylene-ethylene copolymer shows a heat of crystallization in the range of 16 to 33 J / g and a heat of fusion of 11 to 19 J / g.

18. The composition according to claim 13, wherein the propylene-ethylene copolymer shows a softening point of 100 to 120°C and a penetration of 6 to 22 dmm.

19. The composition according to claim 13, wherein the propylene-ethylene copolymer shows a breaking point elongation of 100% to 1,000% and a breaking point tensile strength of 4 to 9 MPa.

20. The composition according to claim 13, wherein the composition contains 20 to 80 weight percent of the propylene-ethylene copolymer.

21. The composition according to claim 13, wherein the composition has a Brookfield viscosity in the range of 500 to 10,000 cP at 177°C.

22. An article comprising the composition according to claim 13, wherein the article is selected from the group consisting of adhesives, sealants, caulking materials, roofing membranes, waterproof membranes and linings, carpets, laminates, laminate articles, tapes, labels, mastics, polymer blends, wire coatings, molded articles, heat-seal coatings, disposable sanitary articles, insulating glass (IG) units, bridge decks, electronic enclosures, waterproof membranes, waterproof compounds, linings, cable flooding / filling compounds, sheet molding compounds, dough molding compounds, overmold compounds, rubber compounds, polyester composites, glass composites, glass fiber reinforced plastics, wood plastic composites, polyacrylic blend compounds, lost wax precision casting, investment casting wax compositions, bookbinding materials, candles, windows, tires, films, gaskets, seals, O-rings, motor vehicles, motorcycles, motor vehicle molded parts, motor vehicle extruded parts, clothing articles, rubber additives / processing aids, and fibers. The article, wherein the adhesive comprises a packaging adhesive, a food contact grade adhesive, an indirect food contact packaging adhesive, a product assembly adhesive, a woodworking adhesive, an edge banding adhesive, a profile wrapping adhesive, a flooring adhesive, a motor vehicle assembly adhesive, a structural adhesive, a flexible lamination adhesive, a rigid lamination adhesive, a flexible film adhesive, a flexible packaging adhesive, a household repair adhesive, an industrial adhesive, a construction adhesive, a furniture adhesive, a mattress adhesive, a pressure sensitive adhesive (PSA), a PSA tape, a PSA label, a PSA protective film, a self-adhesive film, a lamination adhesive, a flexible packaging adhesive, a heat seal adhesive, an industrial adhesive, a sanitary non-woven construction adhesive, a sanitary core integrity adhesive, or a sanitary elastic attachment adhesive.

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