Propylene-ethylene copolymer and adhesive containing propylene-ethylene copolymer

Abstract

A propylene-ethylene copolymer is provided that exhibits excellent tensile strength and mechanical properties due to specific propylene and ethylene contents, triad tacticity, viscosity, and crystallinity. Furthermore, the inventors of the present application have discovered that specific processing conditions such as polymerization temperature and the ratio of external donor to catalyst can facilitate the production of the high tensile strength propylene-ethylene copolymer described herein. Additionally, 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 Application) This PCT patent application was filed on July 26, 2022, and claims the benefit of priority to U.S. Patent Application No. 17 / 873,916, filed previously under the name "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.

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

Background Art

[0003] Generally, most polyolefin polymers exhibit one or more characteristics, such as low viscosity and / or cohesive strength, that make them unsuitable for use alone in forming adhesives. Therefore, hot melt adhesives contain more than one type of polyolefin polymer. Thus, most hot melt adhesives require a blend of a low viscosity polyolefin polymer and a high viscosity polyolefin polymer to meet the specific performance criteria for the intended use of the adhesive and to meet the viscosity window for adhesive sprayability.

[0004] Due to the deficiencies of 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 for their use by themselves without the need for a secondary polymer when forming an adhesive composition. These secondary polymers containing higher tensile and mechanical properties also typically have a higher ring and ball softening point temperature and a higher viscosity, which melt the adhesive more slowly and energy-intensively, making processing more difficult. In addition, when higher tensile strength 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. In addition, there is a need for polyolefin polymers having 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 comprising propylene and ethylene. Further, the propylene-ethylene copolymer comprises (a) at least 77 wt% and less than 89 wt% propylene, (b) 52% - 75% triad tacticity (mm%), (c) exhibits a ring and ball softening point of 100°C to 155°C, (d) has a Brookfield viscosity at 190°C greater than 15,000 cP and less than 88,000 cP, and (e) exhibits a tensile strength at break of at least 2.5 MPa.

[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 shown above, the propylene-ethylene copolymer: (a) comprises at least 77% by weight and less than 89% by weight of propylene; (b) comprises 52% to 75% triad tacticity (mm%); (c) exhibits a ring and ball softening point of 100°C to 155°C; (d) has a Brookfield viscosity at 190°C greater than 15,000 cP and less than 88,000 cP; and (e) exhibits a tensile strength at break of at least 2.5 MPa. Further, the adhesive comprises: (a) 5 to 100% by weight of the propylene-ethylene copolymer; (b) 0 to 55% by weight of at least one second polymer; (c) at most 70% by weight of at least one tackifier; (d) at most 20% by weight of a processing oil; and (e) at most 35% by weight of at least one wax.

[0008] The following description refers to various aspects of the present disclosure. The following description 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 a 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, wherein the propylene-ethylene copolymer (a) comprises 77 to 90% by weight of propylene, (b) comprises 52% to 75% triad tacticity (mm%), (c) has a Brookfield viscosity at 190°C of at least 4,000 cP, (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 relation to the first aspect, the propylene-ethylene copolymer may comprise 10 to 23% by weight of ethylene.

[0011] In addition to, or in place of, this, the triad tacticity of the propylene-ethylene copolymer is 53% to 70%.

[0012] In addition to, or in place of, this, the propylene-ethylene copolymer has a Brookfield viscosity of 4,000 to 88,000 cP at 190°C.

[0013] In addition to, or in place of, this, 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] In addition to, or in place of, this, the propylene-ethylene copolymer exhibits a ring-and-ball softening point of 100 to 135°C and a needle penetration of 2 to 24 dmm.

[0015] In addition to, or in place of, this, 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] In addition to, or in place of, this, the propylene-ethylene copolymer may contain less than 1 wt% of 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 wt% of 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, and (v) exhibits a needle 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% by weight of propylene, (b) having a triad tacticity (mm%) of 52% to 75%, (c) showing 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, a propylene-ethylene copolymer containing propylene and ethylene, wherein the propylene-ethylene copolymer (a) contains 77 to 90% by weight of propylene, (b) contains a triad tacticity (mm%) of 52% to 75%, (c) has a Brookfield viscosity of 7,000 to 15,000 cP at 190°C, (d) shows a ring-and-ball softening point of 90 to 135°C, (e) shows a tensile strength at break of at least 2 MPa, a propylene-ethylene copolymer is provided.

[0020] According to a fifth aspect of the present disclosure, a propylene-ethylene copolymer containing propylene and ethylene, wherein the propylene-ethylene copolymer (a) contains 77% by weight and less than 89% by weight of propylene, (b) contains a triad tacticity (mm%) of 52% to 75%, (c) has a Brookfield viscosity of greater than 15,000 cP and less than 88,000 cP at 190°C, (d) shows a ring-and-ball softening point of 100 to 155°C, (e) A propylene-ethylene copolymer is provided that exhibits a breaking point tensile strength of at least 2.5 MPa.

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

[0022] According to a seventh aspect of the present disclosure, a method for producing the propylene-ethylene copolymers of the first through fifth aspects, as well as additives and alternatives related to these aspects, the method including polymerizing ethylene and propylene at a temperature of 160° C. or less, the polymerizing occurring in the presence of a catalyst system having a molar ratio of aluminum to titanium in the range of 1:1 to 100:1, is provided.

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

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

[0025] In addition to, or in place of, this, the triad tacticity of the propylene-ethylene copolymer is 53% to 70%.

[0026] In addition to, or in place of, this, the propylene-ethylene copolymer has a Brookfield viscosity of 4,000 to 88,000 cP at 190 °C.

[0027] In addition to, or in place of, this, 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] In addition to, or in place of, this, the propylene-ethylene copolymer exhibits a ring and ball softening point of 100 to 135 °C and a needle penetration of 2 to 24 dmm.

[0029] In addition to, or in place of, this, 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] In addition to, or in place of, this, the composition contains 20 to 80% by weight of a propylene-ethylene copolymer.

[0031] In addition to, or in place of, this, the composition (a) 25 to 45% by weight of a propylene-ethylene copolymer, and (b) 0 to 15% by weight of a second polymer, and (c) 45 to 50% by weight of a tackifier, and (d) 0 to 15% by weight of a processing oil, and (e) 0 to 10% by weight of a wax.

[0032] In addition to, or in place of, this, 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 (a) 5 to 100% by weight of a propylene-ethylene copolymer, wherein the propylene-ethylene copolymer (i) contains 77 to 90% by weight of propylene, (ii) contains 52% to 75% triad tacticity (mm%), (iii) exhibits a ring and ball softening point of 90°C to 135°C, (iii) has a Brookfield viscosity of 7,000 cP to 15,000 cP at 190°C, and (iv) exhibits a tensile strength at break of at least 2 MPa, a propylene-ethylene copolymer, and (b) 0 to 55% by weight of at least one second polymer, and (c) 70% by weight or less of at least one tackifier, and (d) 20% by weight or less of processing oil, and (e) 35% by weight or less of at least one wax, a composition is provided.

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

[0035] In addition to or instead of this, the composition (a) 35 to 55% by weight of a propylene-ethylene copolymer, and (b) 35 to 55% by weight of a tackifier, and (c) 0 to 15% by weight of processing oil, and (d) 0 to 7% by weight of wax, and contains.

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

[0037] In addition to, or in place of, this, the composition exhibits a peel strength that is at least 80% of the initial peel strength of the composition after 24 hours of aging.

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

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

[0040] In addition to, or in place of, this, the composition exhibits a peel strength that is at least 80% of the initial peel strength of the composition after 24 hours of aging.

[0041] According to an eleventh aspect of the present disclosure, a composition comprising: (a) 5 to 100% by weight of a propylene-ethylene copolymer, wherein the propylene-ethylene copolymer: (i) contains at least 77 and less than 89% by weight of propylene, (ii) contains 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, and (iv) showing a breaking point tensile strength of at least 2.5 MPa, a propylene-ethylene copolymer, and (b) 0 to 55 wt% of at least one second polymer, and (c) 70 wt% or less of at least one tackifier, and (d) 20 wt% or less of processing oil, and (e) 35 wt% or less of at least one wax, a composition is provided.

[0042] In relation to the 11th aspect, the composition (a) 30 to 45 wt% of a propylene-ethylene copolymer, and (b) 0 to 15 wt% of a second polymer, and (c) 40 to 50 wt% of a tackifier, and (d) 10 to 20 wt% of processing oil, and (e) 0 to 10 wt% of a wax, and includes.

[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] In addition to, or in place of, this, the composition has a Brookfield viscosity in the range of 1,000 to 20,000 cP at 190°C.

[0045] In addition to, or in place of, this, the composition shows a peel strength that is at least 80% of the initial peel strength of the composition after 24 hours of aging.

[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, wherein the article is selected from the group consisting of an adhesive, a sealant, a caulking material, a roofing membrane, a waterproof membrane and backing, a carpet, a laminate, a laminated article, a tape, a label, a mastic, a polymer blend, a wire coating, a molded article, a heat-sealing coating, a disposable sanitary article, an insulating glass (IG) unit, a bridge deck, an electronic housing, a waterproof membrane, a waterproof compound, a backing, a cable flooding / filling compound, a sheet molding compound, a dough molding compound, an overmold compound, a rubber compound, a polyester composite, a glass composite, a glass fiber reinforced plastic, a wood plastic composite, a polyacrylic blend compound, a lost wax precision casting, an investment casting wax composition, bookbinding, a candle, a window, a tire, a film, a gasket, a seal, an o-ring, an automobile, a motorcycle, an automotive molded part, an automotive extruded part, a clothing item, a rubber additive / processing aid, and a fiber. When the article is an adhesive, the adhesive includes 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 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 pressure-sensitive film, a lamination adhesive, a flexible packaging adhesive, a heat-sealing 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.

[0048]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Mode for Carrying Out the Invention

[0049] The inventors of the present application have discovered that a propylene-ethylene copolymer having a specific propylene content, ethylene content, and triad tacticity, in combination with other characteristics such as viscosity and crystallinity, can exhibit excellent tensile strength and mechanical properties. Furthermore, the inventors of the present application have discovered that specific processing conditions such as polymerization temperature and the ratio of external donor to catalyst can facilitate the production of the propylene-ethylene copolymer of the present invention described herein. Furthermore, the inventors of the present application have discovered that these excellent high-tensile strength propylene-ethylene copolymers can be used to produce various compositions including adhesives for hygienic 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).

[0050] The viscosity of the polymer is the 3.4th power of the molecular weight of the entangled polymer melt (M 3.4) is known to be proportional. It is also known that as long polymer chains become intertwined and increase the strength of the bulk polymer, the mechanical strength of the polymer increases with the molecular weight. As a result, polymers with similar monomer compositions and viscosities (molecular weights) have similar tensile strengths. The inventors of the present application have discovered that the tensile strength and elongation at break of the propylene-ethylene copolymer of the present invention are unexpectedly high at a given propylene content and viscosity.

[0051] More specifically, the inventors of the present application have discovered that the triad tacticity of the propylene-ethylene copolymer can be important for controlling tensile strength, elongation at break, crystallinity, needle penetration, and adhesive aging characteristics. Furthermore, the inventors of the present application have discovered that since the crystal defects caused by the ethylene content also affect the important physical properties of the copolymer, the triad tacticity must be selectively controlled together with the ethylene content of the copolymer of the present invention. Furthermore, as will be discussed in more detail below, the inventors of the present application have discovered that the polymerization temperature and the ratio of external donor to catalyst can be effective ways to control the triad tacticity of the resulting propylene-ethylene copolymer.

[0052] Furthermore, the inventors of the present application have discovered that the propylene-ethylene copolymer of the present invention can be used as the only polymer or as the main polymer when producing a desired adhesive. The inventors of the present application have discovered that an adhesive formulation containing the propylene-ethylene copolymer of the present invention can exhibit a desirable softening point and viscosity that enable the adhesive to be sprayed at 150°C. Furthermore, such an adhesive was able to exhibit a stable peel strength or an increasing peel strength after aging for 24 hours, 4 hours (38°C), 2 weeks (55°C), and 1 month (25°C).

[0053] 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 it should be noted that 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 exist in any combination as long as such combinations are not contradictory (e.g., incompatible weight % ranges).

[0054] 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 wt% ethylene, based on the total weight of the copolymer. In addition to this, or as an alternative, the propylene-ethylene copolymer may contain less than 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 20, 19, or 18 wt% ethylene, based on the total weight of the copolymer.

[0055] 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 wt%, based on the total weight of the copolymer.

[0056] 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. In addition to this, 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.

[0057] 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.

[0058] The ethylene and propylene contents of the copolymer are determined by NMR via techniques described in Macromolecules 2000, 33, 1157 - 1162 by Wang et al. (incorporated herein by reference in its entirety).

[0059] 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 can be used to increase the resulting bond strength of the copolymer when utilized in adhesives. 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.

[0060] In one embodiment, or in combination with any of the embodiments referred to herein, the propylene-ethylene copolymer is at least one C4-C having 10, 8, 5, 3, 2, 1, 0.5, or 0.1 wt% or less based on the total weight of the copolymer. 10 alpha-olefin may be included. Further, in various embodiments, the copolymer is at least one C4-C in the range of 0.5-10, 1-10, 2-10, 3-10, 4-10, or 5-10 wt% based on the total weight of the copolymer. 10 alpha-olefin may be included.

[0061] In certain embodiments, the propylene-ethylene copolymer may not contain any C4-C 10 alpha-olefin.

[0062] 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 greater than those. In addition to this, or as an alternative, 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%.

[0063] 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 52-75, 52-74, 52-70, 52-65, 52-60, 53-75, 53-74, 53-70, 53-65, 53-60, 54-75, 54-74, 54-70, 54-67, 54-66, 54-65, 54-60, 55-75, 55-74, 55-70, 55-65, 55-60, 58-75, 58-74, 58-70, 58-68, 60-75, 60-74, 60-70, 60-68, 61-75, 61-74, 61-70, or 61-68 mm content%.

[0064] 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 arrangement of three adjacent propylene units that are chains consisting of head-to-tail linkages, which 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,

[0065]

Number

[0066]

Chemistry

[0067] 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. In addition to this, or as an alternative, 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 when measured in accordance with ASTM D-3236.

[0068] 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 when measured in accordance with ASTM D-3236. In addition to this, or as an alternative, the propylene-ethylene copolymer may have a higher Brookfield viscosity greater than 15,000 cP and less than 88,000 cP at 190 °C.

[0069] In one embodiment, or in combination with any of the embodiments referred to herein, the propylene-ethylene copolymer may have an intermediate 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 when 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 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 when measured according to ASTM D-3236.

[0071] 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. In addition to this, or as an alternative, the propylene-ethylene copolymer may have a peak Tm of less than 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 temperature assigned by the DSC software as the integral peak of the melting transition from the Tm endotherm.

[0072] 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 to 90 °C, 70 to 89 °C, 70 to 88 °C, 70 to 87 °C, 70 to 86 °C, 70 to 85 °C, 74 to 85 °C, 85 to 121 °C, or 90 to 110 °C.

[0073] 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 by a Ring-and Ball Apparatus using a heating rate of 5 °C / min and a bath solution of USP glycerin in accordance with ASTM E28 Standard Test Method for Softening Point of Resins Derived from Pine Chemicals and Hydrocarbons, 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. In addition to this, or as an alternative, the propylene-ethylene copolymer, when measured by a Ring-and Ball Apparatus using a heating rate of 5 °C / min and a bath solution of USP glycerin in accordance with ASTM E28 Standard Test Method for Softening Point of Resins Derived from Pine Chemicals and Hydrocarbons, 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.

[0074] In one embodiment, or in combination with any of the embodiments referred to herein, the propylene-ethylene copolymer may exhibit 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 heating rate of 5 °C / min and a bath solution of USP glycerin in a ring-and-ball apparatus.

[0075] 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. In one embodiment, or in combination with any of the embodiments referred to herein, the propylene-ethylene copolymer may have a needle penetration of at least 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, or 17 decimillimeters ("dmm") when measured according to ASTM D5. In addition to this, or as an alternative, the propylene-ethylene copolymer may have a needle 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.

[0076] In one embodiment, or in combination with any of the embodiments referred to herein, the propylene-ethylene copolymer may have a needle 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.

[0077] 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 may exhibit 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 when measured according to ASTM D412 Standard Test Methods for Vulcanized Rubber and Thermoplastic Elastomers-Tension. In addition to this, or alternatively, the propylene-ethylene copolymer may exhibit 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 when measured according to ASTM D412.In one embodiment, or in combination with any of 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.

[0078] 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. In addition to this, or as an alternative, 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.

[0079] In one embodiment, or in combination with any of the embodiments referred to herein, the propylene-ethylene copolymer may 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.

[0080] 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 , at a cooling rate of 20 °C / min) of at least 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, or 23 J / g. In addition to this, or as an alternative, the propylene-ethylene copolymer has a heat of crystallization (H c , at a cooling rate of 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 , at a cooling rate of 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.

[0081] 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 cooling 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 cooling rate of 20 °C / min).

[0082] Additionally, the propylene-ethylene copolymers described herein can be amorphous or semi-crystalline. As used herein, "amorphous" means that the copolymer has a crystallinity of less than 5% when measured using differential scanning calorimetry ("DSC") in accordance with ASTM E794-85. As used herein, "semi-crystalline" means that the copolymer has a crystallinity in the range of 5 - 40% when measured using DSC at a scanning 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 a crystallinity of at least 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20% when measured using DSC in accordance with ASTM E794-85. In addition to this, or as an alternative, the copolymer can have a crystallinity of less than 60, 50, 45, 40, 35, 30, 25, 24, 23, or 22% when measured using DSC in accordance with ASTM E794-85. For example, the copolymer can have a 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% when measured using DSC in accordance with ASTM E794-85.

[0083] 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. In addition or alternatively, after heat 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 long-term storage and exposure.

[0084] In one embodiment, or in combination with any of the embodiments referred to herein, the propylene-ethylene copolymer may contain ethylene in the range of 8 to 25 weight percent, based on the total weight of the copolymer, may have a triad tacticity in the range of 55 to 70 mm%, may have a tensile strength at break in the range of 0.9 to 10 MPa when measured according to ASTM D412, may have a ring and ball softening point in the range of 100° C. to 135° C. when measured according to ASTM E28, and may have a viscosity at 190° C. in the range of 15,000 to 30,000 cP when measured according to ASTM D-3236.

[0085] Exemplary propylene-ethylene copolymer compositions having high viscosity, high tensile strength and high elongation for use in various adhesives such as woodworking adhesives are shown 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 and / or narrow ranges). Further, while wide, intermediate, and narrow ranges are provided in Table 1A, 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 so long as such ranges do not result in contradictions.

[0086]

Table 1

[0087] Exemplary propylene-ethylene copolymer compositions having high viscosity and intermediate tensile strength for use in various adhesives such as laminating adhesives and woodworking adhesives are shown 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 and / or narrow ranges). Further, while wide, intermediate, and narrow ranges are provided in Table 1B, 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 so long as such ranges do not result in contradictions.

[0088]

Table 2

[0089] An exemplary propylene-ethylene copolymer composition for use in various adhesives such as sanitary adhesives, having an intermediate viscosity and exhibiting an intermediate tensile strength, is shown in Table 1C below. As shown below, Table 1C provides wide, intermediate, and narrow ranges for various characteristics of these intermediate 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 and / or narrow ranges). Further, while wide, intermediate, and narrow ranges are provided in Table 1C, it is envisioned 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 contradictions.

[0090] [Table 3]

[0091] An exemplary propylene-ethylene copolymer composition for use in various adhesives such as packaging adhesives and sanitary adhesives, having a low viscosity and exhibiting an intermediate tensile strength, is shown 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, 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 and / or narrow ranges). Further, while wide, intermediate, and narrow ranges are provided in Table 1D, it is envisioned 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 contradictions.

[0092] [Table 4]

[0093] Process for producing a propylene-ethylene copolymer As discussed 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 used in various adhesives. Without wishing to be bound by theory, these unique tensile properties and ring-and-ball softening points are believed to be obtained due to combinations 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. In addition to this, it has been observed that certain process conditions can also facilitate the production of the copolymers of the present invention described herein. As discussed below, it has been observed that certain reaction conditions (e.g., polymerization temperature) and catalyst system components (e.g., the ratio of external donor to catalyst) can have a significant impact on the resulting propylene-ethylene copolymer.

[0094] A 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.

[0095] 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 embodiments, the catalyst includes titanium chloride on a magnesium chloride support.

[0096] 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 triethyl aluminum ("TEAL").

[0097] In one embodiment, or in combination with any of the embodiments referred to herein, the catalyst system may have a molar ratio of aluminum to titanium 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. In addition or alternatively, the catalyst system may have a molar ratio of aluminum to titanium 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.

[0098] In one embodiment, or in combination with any of the embodiments referred to herein, the catalyst system may have a molar ratio of aluminum to silicon 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. In addition or alternatively, the catalyst system may have a molar ratio of aluminum to silicon 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.

[0099] 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 may include, for example, organic esters, ethers, alcohols, amines, ketones, phenols, phosphines, and / or organosilanes. Further, the catalyst system may include an internal donor and / or an external donor.

[0100] 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.

[0101] 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 may 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 co-catalysts 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.

[0102] 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 may be added to the catalyst system. The internal 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 tetracoordinated Mg atoms on the (110) plane of MgCl2 or a binuclear complex with two pentacoordinated Mg atoms on the (100) plane.

[0103] Ziegler-Natta Catalyst, Fifth Generation (Diether and Succinate): Certain diether compounds, particularly 2,2-disubstituted-1,3-dimethoxypropane with an oxygen-oxygen distance in the range of 2.8 to 3.2 Å, 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 fifth-generation diether catalyst system, high stereospecificity can be obtained even in the absence of an external donor. The fifth-generation diether catalyst system can exhibit particularly high polymerization activity and good stability. They also provide 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, particularly succinate and polyol esters, have been used. Alkoxysilane is often used as an external donor.

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

[0105] In certain embodiments, or in combination with any of the embodiments referred to herein, the catalyst system may comprise a third-generation Ziegler-Natta catalyst, a fourth-generation Ziegler-Natta catalyst, a fifth-generation Ziegler-Natta catalyst, or a sixth-generation Ziegler-Natta catalyst.

[0106] In certain embodiments, 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 includes at least one external electron donor. In certain embodiments, or in combination with any of the embodiments referred to herein, the external electron donor includes 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 can comprise, consist essentially of, or consist 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 needle 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., more than 95%) 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 can be produced that has a higher ethylene content but still exhibits a desired balance between softening point and hardness.

[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. In addition to this, or as an alternative, 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] In addition to this, or as an alternative, 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: l to 15:1, 2:1 to 10:1, or 2:1 to 8:1.

[0111] In certain embodiments, the type of electron donor may 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 may 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 charged into the reactor. These measurements are based on a reaction time of 1 hour.

[0113] Since the addition of an external donor can increase the viscosity and molecular weight, 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] Returning to the polymerization process conditions, in certain embodiments, or in combination with any of the embodiments referred to herein, the polymerization reaction can be carried out 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 one embodiment, 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 one embodiment, 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 one embodiment, 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 certain embodiments, 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 certain embodiments, 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. End uses including propylene-ethylene copolymers

[0120] The propylene-ethylene copolymers of the present invention described herein and the compositions containing these copolymers can be used in a variety of applications, such as adhesives (e.g., automotive adhesives, woodworking adhesives, and packaging adhesives), sealants, caulking materials, roofing membranes, waterproof membranes, compounds and linings, carpets, laminates, laminated articles, tapes (e.g., tamper-evident tapes, water-activated tapes, pressure-sensitive tapes, sealing tapes, scrim-reinforced tapes, veneer tapes, reinforced and non-reinforced pressure-sensitive paper tapes, box maker's tapes, paper tapes, packaging tapes, HVAC duct tapes, masking tapes, invisible tapes, insulating tapes, gaffer tapes, hockey tapes, medical tapes, etc.), labels (e.g., general-purpose labels, beverage labels, freezer labels, smart labels, for household appliances, etc.), mastics, polymer blends, wire coatings, molded articles, heat-seal coatings, disposable sanitary articles, insulated 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 molded parts, automotive extruded parts, clothing items, rubber additives / processing aids, and fibers.

[0121] Examples of the films containing the propylene-ethylene copolymers of the present invention described herein and the compositions containing these copolymers include, but are not limited to, multilayer films, coextruded films, calendered films, and cast films. Examples of the laminates containing the propylene-ethylene polymers of the present invention or the 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] Adhesive compositions comprising the propylene-ethylene copolymers of the present invention described herein and compositions containing these copolymers 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, adhesive films, lamination adhesives, flexible packaging adhesives, heat seal adhesives, industrial adhesives, hygiene non-woven building adhesives, hygiene core integrity adhesives, and hygiene elastic attachment adhesives.

[0123] In certain embodiments, or in combination with any of the embodiments referred to herein, the propylene-ethylene 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 non-woven / hygiene adhesives, hot melt product assembly adhesives, hot melt woodworking adhesives, hot melt automotive parts assembly adhesives, hot melt lamination adhesives, and hot melt packaging adhesives. More particularly, adhesives produced from the copolymers of the present invention can be utilized in a very wide variety of end products including hygiene packaging, household appliances, automotive parts, woodworking, and packaging applications due to the unique combination of tensile strength, elongation at break, softening point, and needle penetration as described above. Generally, the various properties of the copolymers of the present invention (e.g., tensile strength, elongation at break, softening point, and needle penetration) can be selected to suit the intended end use of the composition into which the copolymer is incorporated.

[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. A 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, mixers, and users generally desire a thermally stable, low-color 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 desired balance of 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, e.g., a coating die or nozzle.

[0128] Hot melt adhesive compositions are useful for bonding a variety of substrates including, for example, cardboard, coated cardboard, paperboard, fiberboard, virgin and recycled kraft, high density and low density kraft, chipboard, treated and coated kraft and chipboard, their corrugated forms, 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, may be 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 including, for example, articles such as packaging, bags, boxes, cartons, cases, trays, multiwall bags, accessories (e.g., straws attached to beverage cartons), shrink wrap, cigarettes (e.g., plug wrap), filters (e.g., pleated filters and filter frames), bookbinding, 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 webs, 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 fibers, as a coating (e.g., continuous or discontinuous coating), as beads, as a film (e.g., continuous or discontinuous film), and combinations thereof. Further, the hot melt adhesive may 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., applying beads, fine wire extrusion, single screw extrusion, and twin screw extrusion), wheel coating, non-contact coating, contact coating, gravure, 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 producing laminates and multilayer laminates. As used herein, the terms "laminate" and "multilayer laminate" may be used interchangeably.

[0134] The compositions of the present invention can be bonded to various substrates including, but not limited to, cellulosic polymer materials such as paper, cotton, linen, cloth, and wood boards; synthetic polymer materials including 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), 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; metal materials; plastic materials; elastomeric materials; composite materials; cloth 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 as 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.), parts for household appliances (e.g., casings of personal computers, frames of thin TVs, etc.), and casing materials (e.g., interior wall panels, decorative films, etc.).

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

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

[0138] Furthermore, in certain embodiments, or in combination with any of the embodiments recited herein, the copolymers of the present invention may also be used to modify existing polymer blends typically utilized in plastic, elastomer applications, roofing applications, asphalt modification, cable filling, and tire modification. The copolymers of the present invention may improve the adhesion, processability, stability, viscoelasticity, thermal properties, and mechanical properties of these polymer blends.

[0139] In certain embodiments, or in combination with any of the embodiments recited herein, the propylene-ethylene copolymer of the present invention may be modified to produce a graft copolymer. In such embodiments, the copolymers of the present invention may 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 may 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 copolymers of the present invention by themselves or can combine them with other additives and polymers. Suitable polymers that can form a polymer blend in combination with the copolymers 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; acrylic resins; polyacrylates; acrylate copolymers, such as, 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 rubber; ethylene vinyl acetate copolymers; butyl rubber; styrene butadiene rubber; butadiene acrylonitrile rubber; natural rubber; polyisoprene; polyisobutylene; polyvinyl acetate; 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 linear or branched C4-C 10 a copolymer produced from an alpha-olefin monomer, ethylene and 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] Examples of 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 and typically forming succinic anhydride), and the like.

[0143] It has been found that blends of the propylene-ethylene copolymer of the present invention with various types of polyolefins can 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 discussed above, the propylene-ethylene copolymer of the present invention described herein 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 may comprise, based on the total weight of the adhesive, 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 % of one or more of the propylene-ethylene copolymers. In addition to this, or as an alternative, the adhesive composition may comprise, based on the total weight of the adhesive, less than 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 % of one or more of the propylene-ethylene copolymers.

[0145] In certain embodiments, or in combination with any of the embodiments referred to herein, the adhesive composition may comprise, based on the total weight of the adhesive, from 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 % of one or more of the propylene-ethylene copolymers. In certain embodiments, the adhesive composition may consist entirely of the copolymer of the present invention.

[0146] In certain embodiments, or in combination with any of the embodiments referred to herein, the adhesive may contain at least 1, 2, or 3 propylene-ethylene copolymers of the present invention selected from Table 1A, 1B, 1C, and / or 1D. In such embodiments, the copolymers 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 certain embodiments, or in combination with any of the embodiments recited 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 copolymers of the present invention. In addition to, 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 copolymers of the present invention. For example, the adhesive may include at least one second polymer different from the copolymers of the present invention in the range of 10 to 90, 20 to 80, 30 to 70, 40 to 55, 1 to 15, 1 to 3, 1 to 5, 1 to 20, 2 to 15, or 2 to 10 weight percent.

[0149] In certain embodiments, or in combination with any of the embodiments recited 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 copolymers 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 10Copolymers produced from alpha-olefin monomers, functionalized polyolefins, isoprene-based block copolymers, butadiene-based block copolymers, hydrogenated block copolymers, styrene-ethylene / butylene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene / propylene-styrene (SEPS), ethylene vinyl acetate copolymer, polyester, polyester-based copolymers, neoprene, urethane, acrylic resin, polyacrylate, ethylene acrylic acid copolymer, ethylene n-butyl acrylate copolymer, ethylene methyl acrylate copolymer, polyether ether ketone, polyamide, styrene block copolymer, hydrogenated styrene block copolymer, random styrene copolymer, ethylene-propylene rubber, ethylene vinyl acetate copolymer, butyl rubber, styrene butadiene rubber, butadiene acrylonitrile rubber, natural rubber, polyisoprene, polyisobutylene, and polyvinyl acetate, or combinations thereof may be included.

[0151] In certain embodiments, or in combination with any of the embodiments recited herein, an adhesive containing at least one second polymer may also contain at least one, two, or three of the propylene-ethylene copolymers of the present invention selected from Tables 1A, 1B, 1C, and / or 1D. In such embodiments, the copolymers may include any combination of high viscosity copolymers (i.e., Table 1B), intermediate 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, 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 in addition to the propylene-ethylene copolymer of the present invention. In addition to or alternatively, the adhesive composition may include at least one polyolefin in an amount of 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, based on the total weight of the adhesive, 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 of the adhesive.

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

[0154] Some examples of metallocene catalyst 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 certain embodiments, or in combination with any of the embodiments recited herein, the olefin polymer can include a mixture of at least two different olefin polymers, such as a blend comprising an olefin homopolymer and an olefin copolymer, a blend comprising different olefin homopolymers of the same or different monomers, a blend comprising 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 their wide availability, the addition of the above polyolefins can reduce the production cost of the composition.

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

[0158] In one embodiment, or in combination with any of the embodiments referred to herein, the added polymer and / or polyolefin may 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 may be added to the adhesive composition of the present invention may be prepared by Ziegler-Natta catalysts, single-site catalysts (metallocenes), multiple single-site catalysts, non-metallocene heteroaryl catalysts, or combinations thereof. The additional polymers may include combinations of amorphous, semi-crystalline, random, branched-chain, linear, or block structures.

[0160] Generally, the additional polyolefin components can be prepared by any conventional polymerization synthesis process. In one embodiment, 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. Polymerization methods may include high pressure, slurry, gas, bulk, suspension, supercritical, or solution phase, or combinations thereof. The catalysts may be in the form of homogeneous solutions, supported forms, or combinations thereof. The polymerization may be carried out by continuous, semi-continuous, or batch processes and may include the use of chain transfer agents, scavengers, or other such additives that may be applicable.

[0161] In certain embodiments, or in combination with any of the embodiments referred to herein, additional polymers are produced in a single or multiple polymerization zones using a single polymerization catalyst. Metallocene (or heterogeneous) polymers are typically made using multiple metallocene catalyst blends 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 a crystalline content over time that is sufficient to achieve good cohesive strength in the formulation.

[0163] In certain embodiments, 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. In addition to, or alternatively, the adhesive composition can include 90, 80, 70, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, or 5 weight percent or less of at least one tackifier, based on the total weight of the adhesive. For example, the adhesive 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 of the adhesive.

[0164] Generally, tackifiers can improve the tack and adhesion of adhesives and can also reduce the viscosity of adhesives. A lower viscosity can improve the application flow characteristics, enabling 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 types of olefin copolymers and additional polymers used.

[0165] Suitable tackifiers can include, for example, alicyclic hydrocarbon resins, C5 hydrocarbon resins; C5 / C9 hydrocarbon resins; aromatic modified C5 resins; C9 hydrocarbon resins; copolymers or pure monomer resins such as styrene with alpha-methylstyrene, vinyltoluene, para-methylstyrene, indene, methylindene, C5 resins, and C9 resins; 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 can 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 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 of at least one processing oil, based on the total weight of the adhesive. For example, the adhesive 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 processing oils 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 one of ordinary skill in the art, processing oils 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 oils.

[0167] In one embodiment, or in combination with any of the embodiments referred to herein, the adhesive composition may comprise 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. In addition to, or in the alternative, the adhesive composition may comprise up to 40, 30, 25, 20, 15, 10, 7, 5, or 3 weight percent of at least one wax, based on the total weight of the adhesive. For example, the adhesive may comprise at least one wax in the range 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. 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 conventional 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 manufactured by 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 ΜΑΡΡ 40 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, and 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 wt% or more, preferably 10 wt% or more, and a functional group content of up to 10 wt%. 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 embodiment mentioned 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 wt% of wax, such as, but not limited to, polyethylene wax and / or Fischer-Tropsch wax.

[0173] In one embodiment, or in combination with any embodiment mentioned 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 wt% 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 wt%.

[0174] In one embodiment, or in combination with any embodiment mentioned herein, the adhesive composition may contain at least 0.5, 1, 2, or 3 and / or 20, 10, 8, or 5 wt% 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 wt%. Suitable plasticizers 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 include, for example, Benzoflex™ plasticizer (Eastman Chemical); Eastman 168™ (Eastman Chemical); Oppanol® 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, plasticoater, Brabender mixer, twin screw extruder, or 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, nonwoven 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 when measured according to ASTM D3236. For example, the hot melt adhesive may have a Brookfield viscosity in the range of 100 to 60,000, 300 to 10,000, 500 to 5,000, 750 to 2,500, 400 to 3,000, 500 to 1,000, 500 to 5,000, 500 to 10,000, 500 to 15,000, 500 to 20,000, 1,000 to 5,000, 1,000 to 10,000, 1,000 to 15,000, 1,000 to 20,000, 1,000 to 40,000, or 1,000 to 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 when 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, 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 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 100, 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 when 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° (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. In addition to this, or as an alternative, the hot melt adhesive composition may have a 90° (T-peel) peel strength of 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 been cured at room temperature for 24 hours, after the adhesive has been cured at 38 °C for 4 hours, after the adhesive has been cured at 55 °C for 2 weeks, and / or after the adhesive has been 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 shown above, due to the unique propylene-ethylene copolymer, the hot melt adhesive composition can exhibit desirable peel strength even after aging. In certain embodiments, or in combination with any of the embodiments referred to herein, the hot melt adhesive composition, after curing the adhesive at room temperature for 24 hours, then at 38 °C for 4 hours, then at 55 °C for 2 weeks, and / or after curing the adhesive at 25 °C for 1 month, when measured according to ASTM D903, may exhibit a 90° (T-peel) 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. In addition to this, or as an alternative, the hot melt adhesive composition may exhibit a 90° (T-peel) peel strength that is at least 50, 55, 60, 65, 70, 75, 80, 85, or 90% of the initial 90° (T-peel) peel strength after aging for 4 hours, 24 hours, 2 weeks, or 1 month.

[0185] Generally, the adhesive composition containing the copolymer of the present invention may have a wide range of operating windows and may have an application window of 80 to 230 °C. This wide range of operating windows 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 referred to herein, the hot melt adhesive composition may exhibit a holding force of at least 5, 15, 20, or 25 minutes and / or 150 minutes or less at 60 °C. In addition to this, or as an alternative, the hot melt adhesive may 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 to 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 specimen.

[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 when measured in accordance with ASTM D4498-07. In addition to, or in the alternative, 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 when measured in accordance with 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 when measured in accordance with 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 when measured in accordance with ASTM D1002. For example, the hot melt adhesive composition may exhibit a lap shear in the range of 25-300, 50-275, 75-250, 100-250, or 100-225 lbf when measured in accordance with 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% 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 before tearing. When 80% of the fibers of the substrate are 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 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 as measured by ASTM method E-28. For example, the hot melt adhesive composition may exhibit a ring and ball softening point of 100 - 200°C, 110 - 180°C, 125 - 160°C, or 130 - 150°C as measured by ASTM method E-28.

[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 - 200°C, 90 - 175°C, 100 - 140°C, or 100 - 125°C.

[0192] In one embodiment, or in combination with any of the embodiments referred to herein, the adhesive containing the copolymer of the present invention does not exhibit a substantial change in color when subjected to storage conditions at high temperatures 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 when 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 when 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 shown in Table 2 below. In addition to this, Table 2 provides wide, intermediate, and narrow ranges for various characteristics of the adhesive formulations, which can be combined in any combination regardless of their category (e.g., one or more wide ranges can be combined with one or more intermediate and / or narrow ranges). Further, while wide, intermediate, and narrow ranges are provided in Table 2, it is contemplated that any of the ranges described above with respect to the composition of the adhesive formulation (e.g., polymer content, tackifier content, etc.) may be applicable to the adhesive formulations provided in Table 2 as long as the attached performance characteristics do not result in a contradiction for such ranges.

[0194]

Table 5

[0195] In one embodiment, or in combination with any of the embodiments referred to herein, the propylene-ethylene copolymer of the present invention can be utilized in an adhesive composition as described above in the present disclosure. In particular, the propylene-ethylene copolymer 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 multilayer laminates. For example, an article can be manufactured using an 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 produced using the adhesive compositions described herein. Exemplary articles that can be produced using the adhesive compositions described herein include 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 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, candles, windows, tires, films, gaskets, seals, o-rings, automobiles, motorcycles, buses, streetcars, trucks, automotive molded parts, automotive extruded parts, clothing items, rubber additives / processing aids, and fibers.

[0198] Exemplary adhesives that can be produced using 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, household repair adhesives, industrial adhesives, construction adhesives, furniture adhesives, mattress adhesives, pressure sensitive adhesives (PSA), PSA tapes, PSA labels, PSA protective films, adhesive films, lamination adhesives, flexible packaging adhesives, heat seal adhesives, industrial adhesives, hygienic non-woven 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, but it is understood that these examples 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 Copolymer with High Tensile Strength and Intermediate Tensile Strength Various propylene-ethylene copolymers of the present invention having high viscosities and exhibiting intermediate tensile strengths were produced. The propylene-ethylene copolymers were produced according to the following polymerization process.

[0201] Propylene, ethylene, and hydrogen, which are reactants, were fed into a 5-gallon continuously stirred tank reactor (CSTR) at the ratios, flow rates, and temperatures provided in Table 3 below for each of the samples to be produced, together with a diluent, an external donor, and a catalyst. Samples of the present invention and comparative samples (i.e., the produced comparative samples) were prepared using a third-generation (benzoate) 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 tracking of the reactor jacket. The dip tube carried the product out of the reactor, and the equilibar was pressurized by the pressure maintained by helium to control the reactor.

[0202] The diluent was then stripped from the copolymer in the let-down tank, and then the residual catalyst was deactivated in a heat oil jacketed exchanger using steam and nitrogen. The molten copolymer was then collected from the bottom of the inactivation device 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 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 comparative samples produced under the conditions shown in Table 3 were tested to verify the properties and characteristics 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 (propylene, "PP") composition and triad tacticity by NMR were carried out 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 occurred 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 the Fourier transform to the FID data, the spectrum was phase-adjusted, the baseline was corrected, and calculations were performed as described in the references above. The standard deviation of PP% was determined to be 0.7 and the standard deviation of mm% was determined to be 0.3.

[0206] Preparation of Tensile Strength Samples Using a Carver press, film samples for tensile testing were prepared. First, 20 grams of the molten sample was placed into a 5-inch × 5-inch (137 mm × 137 mm) aluminum square mold frame with a thickness of 1 mm. Then, 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. Then, 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 hammer block acting as a heat sink on top. After applying an 8-minute cooling time, the hammer 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 / min) according to the procedure described in ASTM D412 (die C). All tests were conducted on an MTS tensile testing machine at 25 °C and 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 specimen 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 shows the measured characteristics and properties of the measured copolymers. In addition to this, Table 4 also lists the characteristics and properties of two commercially available propylene-ethylene copolymers labeled "CAC1" and "CAC2". In the following table, "NP" refers to needle 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 showed desirable tensile strength (TSB) superior to that of comparative examples and existing commercial products of similar viscosities. 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 showing excellent tensile strength. For example, Table 4 emphasizes the importance of ethylene content, which can affect the crystallinity and elongation of the copolymers, and triad tacticity, which can affect the tensile profile, elongation, crystallinity, and needle penetration of the resulting copolymers.

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

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

[0213] Example 2 - Intermediate Viscosity Propylene-Ethylene Copolymer with High and Intermediate Tensile Strengths Various propylene-ethylene copolymers of the present invention having intermediate viscosities and exhibiting intermediate tensile strengths were produced. The propylene-ethylene copolymers were produced according to the polymerization process 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 using the aforementioned test methods to verify their properties and characteristics.

[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 methods described above.

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

[0218] [Table 9]

[0219] As shown in Table 6 above, the copolymer of the present invention contained a higher viscosity and exhibited 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 features in producing a copolymer that exhibited excellent tensile strength and elongation at a desired ring and ball softening point. For example, Table 6 emphasizes the importance of the ethylene content that can affect the crystallinity and elongation of the copolymer, as well as the triad tacticity that can affect the tensile profile, elongation, crystallinity, and needle penetration of the resulting copolymer. Generally, higher strength propylene-ethylene copolymers such as those shown in Tables 5 and 6 provide a higher initial peel strength in adhesives.

[0220] Figure 2 is a chart comparing the propylene content of the copolymer in Table 6 with the obtained tensile strength at the break point. As shown in Figure 2, the propylene content and ethylene content of the copolymer were important in obtaining excellent tensile strength. It is particularly interesting to compare Example 2O and CAC4 of the present invention having similar viscosities and propylene contents. A higher polymer molecular weight is known to contribute to higher viscosity and tensile strength. It was found that Example 2O of the present invention had an unexpectedly high tensile strength (10.4 MPa, 8,133 cP) for its viscosity, which is evident when compared with the values of CAC4 (i.e., 3.8 MPa, 7,570 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 probably the result of the combination of the propylene content and tacticity (mm%) of the present invention.

[0221] Example 3 - Low Viscosity Propylene-Ethylene Copolymers with High and Intermediate Tensile Strengths Various propylene-ethylene copolymers of the present invention having a low viscosity and exhibiting an intermediate tensile strength were produced. The propylene-ethylene copolymers were produced according to the polymerization process described in Example 1.

[0222] The obtained copolymer of the present invention (e.g., "3A") and the comparative copolymer (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 the comparative samples (i.e., samples starting with "C") produced under the conditions shown in Table 7 were tested 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 shows 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 had a low viscosity and exhibited 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 of the copolymer were all important characteristics in producing copolymers with 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 needle penetration of the obtained 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 content and ethylene content of the copolymers were important in obtaining excellent tensile strength. Comparing Examples 3E and 3F of the present invention with CAC5 is particularly interesting. Examples 3E and 3F of the present invention have a tensile strength (4.2 MPa and 5.0 MPa respectively) approximately twice that of CAC5 (2.4 MPa), although 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 the propylene content and tacticity (mm%) of the present invention.

[0228] Figure 4 is a chart comparing the tensile strength of all high-tensile-strength copolymers and medium-tensile-strength copolymers of the present invention with the viscosity of the corresponding copolymers. The copolymers in Figure 4 include those from Examples 1-3, along 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 resulting tensile strength of the copolymers.

[0229] Example 4 - Woodworking Adhesive To test the copolymers of the present invention, various hot melt adhesives for woodworking applications were produced. Using copolymers 1B, 1C, 1D, and 2N of the present invention, woodworking adhesives having the formulations provided in Table 16 were produced. In addition to this, for comparison, adhesive formulations using Eastman's Aerafin™ 180 and Evonik Industries' Vestoplast™ 828 were also produced. Vestoplast™ 828 has a viscosity of 25,000 cP at 190°C, a needle 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 for 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 according to the following process. First, the heating block was preheated to about 180°C. Then, the copolymer, wax, resin, and antioxidant were weighed and placed into a 1-pint aluminum container. Then, the container was placed inside the heating mantle. 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 over 30 minutes. Then, the speed was decreased to about 30 rpm and mixed for an additional 15 minutes, after which it was removed to remove air bubbles (if any). The heating block temperature was maintained at about 180°C by the blending process. The adhesive was poured onto silicon-coated release paper and cooled to room temperature.

[0231] Table 9 shows the formulations and characteristic features of the comparative woodworking adhesives ("CA") and the adhesives of the present invention ("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. The sample was then 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] Ring and Ball Softening Point (RBSP) of the adhesive The Ring and Ball Softening Point of the adhesive 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 testing. 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 passing point. The reported value is the average of two readings.

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

[0236] The SAFT temperature measurement was conducted 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 dropped) and converted this 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 - for Woodworking Two coverstock panels were bonded using adhesive beads applied at 3 ± 0.9 grams / m2 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 and 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 conducted in accordance with ASTM D1002.

[0238] Heat Resistance - for Woodworking Heat resistance was measured using a 1-inch x 8-inch 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 inside the oven and a 10 g weight was suspended from the end of the paper laminate. The oven was set to 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 exhibited 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 relative to the comparative adhesive, while also providing a decrease in viscosity. Most surprisingly, the increased heat resistance and lap shear of the adhesives of the present invention were accompanied by a decrease in the SAFT temperature.

[0240] Example 5 - Woodworking Adhesive To test the copolymers of the present invention, various hot melt adhesives for woodworking applications were produced. 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 to this, for comparison, adhesive formulations using Aerafin™ 180 from Eastman and Vestoplast™ 828 from Evonik Industries were also produced. 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 procedure already described in Example 4. All of the following amounts in Table 10 for 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 shows 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 compared to the comparative adhesives. In addition to this, the adhesives of the present invention showed a lower RBSP, which allows for faster melting and easier processing.

[0243] Example 6 - Sanitary Adhesive with High Viscosity Propylene - Ethylene Copolymer Various hot melt adhesives for hygienic use were produced and the copolymers of the present invention having high viscosities (i.e., 1A and 1I from Example 1) were tested. In addition to this, for comparison, adhesive formulations were also produced using Aerafin™ 180 by Eastman. The adhesives also contained an antioxidant (Irganox® 1010 manufactured by BASF), a tackifier (Eastotac™ H100R or Regalite™ R1090 manufactured by Eastman), a wax (Sasolwax® H-1 manufactured by Sasol), and a processing oil (Kaydol Oil manufactured by 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 shows the formulation and characteristic features of the comparative hygienic adhesive (“CA”) and the adhesive of the present invention (“IA”).

[0244]

Table 14

[0245] Measurement of nonwoven 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 conducted. · Immediate peel strength - g / 25 mm · Peel strength - g / 25 mm at 24 hours, · Peel strength - g / 25 mm at 38 °C for 4 hours, · Peel strength - g / 25 mm at 55 °C for 2 weeks, · Peel strength - g / 25 mm at 25 °C for 1 month.

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

[0247] In addition to this, to analyze the peel strength of the adhesive and compare the effect of oil content on it, further Catbridge trial runs were conducted on the adhesives shown in Table 11.

[0248] Catbridge Calibration and Lance Step The Catbridge high-speed coater (PL 59188) was manufactured by Catbridge Machinery and was equipped with a Nordson applicator with an Acumeter tank / pump and a signature nozzle. The Acumeter pump speed was calibrated based on three pump ratios controlled by Catbridge, namely 20%, 30%, and 50%. A timer was used to dispense and weigh the adhesive onto a peeled liner for 1 minute. Using that weight, 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 intercept 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 amount (g / m 2 ) × Pattern width (m)

[0249] Using the slope and intercept from the calibration, the pump ratio (%) and the pump speed in rpm were determined for the required amount of adhesive. Then, the Catbridge was 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 a non-woven fabric using nip rolls set at 30 psi. Since it took a few seconds for the line to stabilize, the line was run for about 30 - 40 seconds to obtain a good representative specimen. 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 increased and adjusted until a good pattern was achieved. Typically, higher line speeds or adhesives with higher viscosities required higher air pressures.

[0250] The results of the Catbridge trial runs for IA8, IA9, CA5, IA10, and IA12 are shown in Figure 5, which shows the immediate peel strength and peel strength at 24 hours, 4 hours (aged at 38°C), 2 weeks (aged at 55°C), and 1 month (aged at 25°C).

[0251] As shown in Table 11 above, an adhesive viscosity range for spraying was obtained with a polymer addition of 32 - 35 wt% having a single copolymer type. Further, as shown in Table 11 and Figure 5, adhesives with lower oil content were able to maintain higher peel strength, which was aided 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. In particular, the high viscosity copolymer has 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 and increased peel strength at 24 hours, 4 hours (aged at 38°C), 2 weeks (aged at 55°C), and 1 month (aged at 25°C). It has been found that it can be used as the only polymer in an adhesive formulation. Certain adhesives can 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] Accordingly, an appropriate range of propylene / ethylene comonomer content, in combination with a specific level of propylene tacticity, provides a propylene-ethylene copolymer having a unique balance of intermediate tensile strength, viscosity, needle penetration, and elongation properties that are particularly advantageous for sanitary adhesive applications. More specifically, it has been observed that the tensile strength of the copolymers of the present invention is high enough to contribute to the adhesive bond strength in the formulated adhesive, but not so high that the bond strength is significantly lost after aging. Further, by maintaining a specific triad tacticity in the copolymers of the present invention, the tensile strength, elongation, crystallinity, and needle 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 invention from Example 2 having intermediate viscosities, various hot melt adhesives for hygiene applications were produced. In addition thereto, for comparison, 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), a possible additional propylene-ethylene copolymer (Eastoflex™ E1003 from Eastman), and a processing oil (Kaydol Oil from Chevron). In addition thereto, the adhesives IA 20 and IA 21 of the invention each 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.

[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 formulations and characteristic features of comparative hygiene adhesives (“CA”) and adhesives of the invention having a high oil content (“IA”), while the following Table 13 provides the formulations and characteristic features of comparative hygiene adhesives (“CA”) and adhesives of the invention having a low oil content (“IA”).

[0255]

Table 15

[0256]

Table 16

[0257] To analyze the peel strength of the adhesive and compare the effect of oil content thereon, Catbridge trial runs were performed on the adhesives shown in Tables 12 and 13. The results of the Catbridge trial runs for CA 6, IA 9, IA 20, IA 21, C 10, IA 23, IA 24, and IA 26 are shown in Figure 6, which shows the immediate peel strength and 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 a single polymer when 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 a medium viscosity were able to produce desirable adhesives both as the only polymer in the adhesive and as the main polymer present in the adhesive. In addition to this, the adhesive formulations of the present invention have desirable RBSP and viscosities, can be sprayed well at 150 °C, and can exhibit stable or increasing peel strength after aging for 24 hours, 4 hours (38 °C), 2 weeks (55 °C), and 1 month (25 °C). Generally, in order to obtain a higher polymer addition amount (for example, 50% by weight), a higher addition amount of oil was required to meet the viscosity required for adhesive spraying.

[0259] It was also observed that using Eastoflex™ E1003 to replace part 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 higher viscosity copolymers such as IA 20 and IA 21 could maintain the peel strength of the adhesive and withstand a greater amount of processing oil. Generally, to use less processing oil, the copolymer content had to be reduced, as in IA 23, IA 24, and IA 25. As a result, in certain cases, this increased the peel strength. For example, as shown in Table 13, IA 23 and IA 24 exhibited higher peel strength compared to CA 7. However, the peel strength of IA 25 decreased by 60% the next day, and the adhesive was hard and unable to complete the aging test. IA 24 also exhibited a softer feel, which may be desirable for hygienic applications.

[0260] As shown in Tables 12 and 13, together with Figure 6, there is an advantage in using the intermediate viscosity copolymers of the present invention over the low viscosity copolymers because the intermediate viscosity copolymers of the present invention have better tensile properties and thus may require less (or no) additional polymer to add strength. Further, polymers with intermediate tensile strength such as 2A have been demonstrated to be well-suited as single polymers in hygienic adhesives because they can provide excellent peel strength both immediately and after aging.

[0261] Example 8 - Comparison of the Adhesive of the Present Invention with Commercial Adhesives Adhesives IA 10 of the present invention from Example 6, Adhesive IA 23 of the present invention from Example 7, and Adhesive IA 24 of the present invention from Example 7 were compared with existing commercially available adhesives, namely, Safemelt™ DP830H / ST (SBS-based) manufactured by Savare, 5603N2P (mPO-based) manufactured by HB Fuller, and Safemelt™ VV25F / SW (butene-APO-based) manufactured by 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] To analyze and compare the peel strength of the adhesives, Catbridge trial runs were performed on the adhesives shown in Table 14. The results of the Catbridge trial runs are shown in Figure 7, which shows 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 were suitable as single polymers in producing hygiene adhesives showing excellent peel strength, especially after aging. Furthermore, the peel strength performance of the adhesives of the present invention was comparable to that of currently commercially available adhesives. Moreover, the adhesives of the present invention were sprayed very well and did not require high air pressure to obtain a good pattern. In contrast, the commercially available butene-APO-based adhesive was not sprayed well at low temperatures and required high air pressure to obtain a good pattern. In addition to this, the adhesives of the present invention showed sufficient cohesive strength to operate on high-speed lines up to 600 m / min.

[0265] In view of the above, 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, an overly high tensile strength was observed, which caused a decrease in the 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 "about" specific value. For example, "about 10" provides support for the specific value of "10" and values in the range of 9 - 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 A only, B only, C only, 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 up to the entire amount or 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 recited 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 "comprising," "comprises," and "comprise" provided above.

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

[0274] Numerical ranges When a series of numbers is recited, 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 is optionally "at least" or "below," and each number is in an "or" relationship. In an exemplary scenario, "at least 10, 20, 30, 40, 50, 75 wt%..." means the same as "at least 10 wt%, or at least 20 wt%, or at least 30 wt%, or at least 40 wt%, or at least 50 wt%, or at least 75 wt%."

[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 claims that recite only the lower limit of the range, as well as claims 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" (no upper limit) and claims that recite "less than 100" (no 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 as examples 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 hereby state their intention to rely on the doctrine of equivalents to determine and evaluate the reasonable and fair scope of the present invention, since the devices related thereto are outside the scope of the present invention but do not substantially depart from the literal scope of the present invention as recited in the following claims. Further, while specific embodiments of the present invention are 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 is (a) containing at least 77% by weight and less than 89% by weight of propylene, (b) containing 52% to 75% of triad tacticity (mm%), (c) showing a ring-and-ball softening point of 100°C to 155°C, (d) having a Brookfield viscosity at 190°C greater than 15,000 cP and less than 88,000 cP, and (e) showing a tensile strength at break of at least 2.5 MPa, a propylene-ethylene copolymer.

2. The propylene-ethylene copolymer according to claim 1, wherein the propylene-ethylene copolymer contains 10 to 22% by weight of ethylene.

3. The propylene-ethylene copolymer according to claim 1, wherein the propylene-ethylene copolymer has a Brookfield viscosity at 190°C of 15,000 to 60,000 cP.

4. The propylene-ethylene copolymer according to claim 1, wherein the propylene-ethylene copolymer shows a heat of crystallization of 16 to 36 J / g and a heat of fusion of 11 to 29 J / g.

5. The propylene-ethylene copolymer according to claim 1, wherein the propylene-ethylene copolymer shows a ring-and-ball softening point of 105°C to 140°C and a needle penetration of 3 to 20 dmm.

6. The propylene-ethylene copolymer according to claim 1, wherein the propylene-ethylene copolymer shows an elongation at break of 300% to 1,000% and a tensile strength at break of 2.5 to 20 MPa.

7. The propylene-ethylene copolymer is (a) containing 10 to 22% by weight of ethylene, (b) having a Brookfield viscosity at 190°C of 15,000 to 60,000 cP, (c) showing a ring-and-ball softening point of 105°C to 140°C, (d) showing a needle penetration of 3 to 20 dmm, and (e) showing an elongation at break of 300% to 1,000%, the propylene-ethylene copolymer according to claim 1.

8. 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.

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

10. 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.

11. 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, candles, windows, tires, films, gaskets, seals, o-rings, automobiles, motorcycles, automotive molded parts, automotive extruded parts, clothing items, rubber additives / processing aids, and fibers. 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 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, an 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.

12. A composition comprising a propylene-ethylene copolymer containing propylene and ethylene, the composition being (a) 5 to 100% by weight of the propylene-ethylene copolymer, wherein the propylene-ethylene copolymer is (i) contains at least 77% and less than 89% by weight of propylene, (ii) contains 52% to 75% triad tacticity (mm%), (iii) shows a ring-and-ball softening point of 100°C to 155°C, (iv) has a Brookfield viscosity at 190°C greater than 15,000 cP and less than 88,000 cP, and (v) shows a tensile strength at break of at least 2.5 MPa, a propylene-ethylene copolymer, and (b) 0 to 55% by weight of at least one second polymer, (c) 70% by weight or less of at least one tackifier, (d) 20% by weight or less of processing oil, (e) 35% by weight or less of at least one wax, a composition.

13. The composition according to claim 12, wherein the propylene-ethylene copolymer contains 10 to 22% by weight of ethylene.

14. The composition according to claim 12, wherein the propylene-ethylene copolymer has a viscosity at 190°C of 15,000 to 60,000 cP.

15. The composition according to claim 12, wherein the propylene-ethylene copolymer shows a heat of crystallization of 16 to 36 J / g and a heat of fusion of 11 to 29 J / g.

16. The composition according to claim 12, wherein the propylene-ethylene copolymer shows a ring-and-ball softening point of 105 to 140°C and a needle penetration of 3 to 20 dmm.

17. The composition according to claim 12, wherein the propylene-ethylene copolymer shows an elongation at break of 300% to 1,000% and a tensile strength at break of 2.5 to 20 MPa.

18. The propylene-ethylene copolymer is (a) contains 10 to 22% by weight of ethylene, (b) has a Brookfield viscosity at 190°C of 15,000 to 60,000 cP, (c) shows a ring-and-ball softening point of 105 to 140°C, (d) shows a needle penetration of 3 to 20 dmm, and (e) shows an elongation at break of 300% to 1,000%, the composition according to claim 12.

19. The composition according to claim 12, wherein the composition contains 20 to 80% by weight of the propylene-ethylene copolymer.

20. The composition is (a) 30 to 45% by weight of the propylene-ethylene copolymer, and (b) 0 to 15% by weight of the second polymer, (c) 40 to 50% by weight of said tackifier, (d) 10 to 20% by weight of said processing oil, (e) 0 to 10% by weight of said wax, and the composition according to claim 12.

21. The composition according to claim 12, wherein the composition has a Brookfield viscosity in the range of 1,000 to 20,000 cP at 190°C.

22. An article comprising the composition according to claim 12, wherein the article is 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, candles, windows, tires, films, gaskets, seals, O-rings, automobiles, motorcycles, automotive molded parts, automotive extruded parts, clothing items, rubber additives / processing aids, and fibers, 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, an automotive 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, an 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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