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Title:
ADHESIVE COMPOSITION
Document Type and Number:
WIPO Patent Application WO/2017/210507
Kind Code:
A1
Abstract:
The present disclosure provides a composition. In an embodiment an adhesive composition is provided and includes (A) a propylene-based interpolymer having a density from 0.850 g/cc to 0.900 g/cc; (B) an ethylene-based polymer composition having a melt viscosity at 140°C from 10 mPa*s to 1,000 mPa*s; and (C) a tackifier. The composition has a molecular weight distribution ratio from 1.00 to 1.40, wherein the molecular weight distribution ratio is the molecular weight distribution of the propylene-based interpolymer of component (A) compared to the molecular weight distribution of the ethylene-based polymer composition of component (B). The composition has a density ratio from 0.93 to 1.30, wherein the density ratio is the density of the propylene-based interpolymer of component (A) compared to the density of the ethylene-based polymer composition of component (B).

Inventors:
ZHANG-WATSON LING (US)
JIN YI (US)
Application Number:
PCT/US2017/035593
Publication Date:
December 07, 2017
Filing Date:
June 02, 2017
Export Citation:
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Assignee:
DOW GLOBAL TECHNOLOGIES LLC (US)
International Classes:
C09J123/14; C08L23/06; C08L23/14
Domestic Patent References:
WO2012149391A12012-11-01
WO2010138253A22010-12-02
WO2014046834A12014-03-27
WO2016029006A12016-02-25
Foreign References:
US201562235185P2015-09-30
Other References:
"Periodic Table of Elements", 1990, CRC PRESS, INC.
EDITH A. TURI: "Thermal Characterization of Polymeric Materials, 2nd ed.,", vol. 92, 1997, article BERNHARD WUNDERLICH: "The Basis of Thermal Analysis", pages: 277 - 278
EDITH A. TURI: "Thermal Characterization of Polymeric Materials, 2nd ed.,", vol. 92, 1997, article BERNHARD; WUNDERLICH: "The Basis of Thermal Analysis", pages: 278 - 279
TH.G. SCHOLTE; N.L.J. MEIJERINK; H.M. SCHOFFELEERS; A.M.G. BRANDS, J. APPL. POLYM. SCI., vol. 29, 1984, pages 3763 3782
E.P. OTOCKA; R.J. ROC; N.Y. HELLMAN; P.M. MUGLIA, MACROMOLECULES, vol. 4, 1971, pages 507
S. DI MARTINO; M. KELCHTERMANS, APPL. POLYM. SCI., vol. 56, 1995, pages 1781 - 1787
V. BUSICO; R. CIPULLO, PROG. POLYM. SCI., vol. 26, 2001, pages 443 - 533
JACK L. KOENIG: "Spectroscopy of Polymers, 2nd ed.,", 1999
Attorney, Agent or Firm:
BARTHEL, Ted, J. (555 East Wells Street Suite 190, Milwaukee WI, US)
Download PDF:
Claims:
We Claim :

1 . A composition comprising:

A) a propylene-based interpolymcr having a density from 0.850 g/cc to 0.900 g/cc;

B) an ethy1ene-based polymer composition having a melt viscosity at 140°C from 10 mPa●s to 1 ,000 mPa●s; and

C) a tackifier; and

the composition has a molecular weight distribution ratio from 1 .00 to 1 .40, wherein the molecular weight distribution ratio is the molecular weight distribution of the propylene-based interpolymcr of component (A) to the molecular weight distribution of the ethyl en c-based polymer composition of component (B); and

the composition has a density ratio from 0.93 to 1 .30, wherein the density ratio is the density of the propylene-based interpolymcr of component (A) compared to the density of the ethylene-based polymer composition of component (B).

2. The composition of claim I , wherein the ethylene-based polymer composition has a density from 0.880 g/cc to 0.930 g/cc and a molecular weight distribution from greater than 1 .25 to 3.0.

3. The composition of any one of the previous claims, wherein the propylene-based interpolymer has a melt viscosity at 1 77°C from 700 mPa●s to 10,000 mPa●s.

4. The composition of any one of the previous claims, wherein the propylene-based interpolymer has: (i) a density from 0.870 g/cc to 0.890 g/cc; (i i) a melt viscosity at I 77°C from 700 m Pa●s to 5,000 m Pa●s; (ii i) a Koenig B-value less than 1 .0; (iv) a total unsaturation per mole of propylene from 0.01 0% to 0.030%; and (v) a weight average molecular weight from 20,000 to 50,000 g/mol .

5. The composition of any one of the previous claims, the composition comprising:

(A) from 55 wt % to 90 wt % propylene-based interpolymer;

(B) from 1 wt % to 30 wt % ethylene-based polymer composition;

(C) from 5 wt % to 30 wt % tackifier; and

(D) from 0.01 wt % to 1 .0 wt % antioxidant.

6. The composition of any one of the previous claims, wherein the ethylene-based polymer composition has a melt viscosity at 140°C from 20 mPa●s to 800 mPa.s

7. The composition of any one of the previous claims, wherein the ethylene-based polymer composition has a molecular weight distribution from 1 .5 to 2.0.

8. The composition of any one of the previous claims, wherein the composition has a melt viscosity at 1 77°C from 300 mPa●s to 4,000 mPa●s.

9. The composition of any one of the previous claims, wherein the composition has: (i) a fiber tear from greater than 55% to 1 00% at a temperature from -40°C to 60°C; (ii) a peel adhesion failure temperature (PAF'I") from 45°C to 80°C; (iii) a set time from 0.5 seconds to 9 seconds; and (iv) an open time from 25 seconds to 60 seconds.

10. An article comprising at least one component formed from the composition of any one of the previous claims.

Description:
ADHESIVE COMPOSITION

REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application No. 62/345,433, filed June 3, 2016, and incorporated herein by reference.

BACKGROUND

[0002] Compositions for conventional hot-melt adhesive (HMA) formulations follow a general rule of thumb of containing 1/3 polymer, 1/3 tackifter and 1/3 wax. An HMA formulation using propylene-based polymer can be formulated into an ( IMA formulation with sufficient adhesion performance, but propylene-based polymers arc less compatible with conventional ethylenc- bascd waxes and Fischer-Tropsch waxes which often results in failure of adhesion performance. HMA formulations using propylene-bascd polymers conventionally include a propolync-bascd wax to overcome the compatibility issues. However, propylene-based waxes arc more expeasive than conventional ethylcnc-based waxes and typically result in longer set times. Known arc HMA compositions including propolync-bascd polymer and high density (i.e., at least 0.950 g/cc) ethyleno-ba.scd wax. The high density limits the selection of ethylcnc-based wax that is suitable for HMA compositions.

[0003] A need exists for a HMA composition with a propylene-based polymer and a low density eihylene-bascd wax, while maintaining suitable adhesion properties and a rapid set time compatible with high-speed line processing applications.

[0004] A need further exists for a HMA composition with a propolync-bascd polymer and a low density ethylcne-bascd wax having improved high temperature resistance, improved adhesion properties- improved substrate compatibility, and/or improved thermal stability.

SUMMARY

[0005] The instant disclosure provides a composition suitable for adhesive applications, and further tor holt-melt adhesive applications.

[0006] The present composition provides a composition. In an embodiment, an adhesive composition is provided and includes (A) a propylene-bascd interpolymer having a density from 0.850 g/cc to 0.900 g/cc; (B) an ethylene-basecl polymer composition having a melt viscosity at 140°C from 10 mPa●s to 1 ,000 mPa●s ; and (C) a tackifier. The composition has a molecular weight distribution ratio from 1.00 to 1.40, wherein the moleculur weight distribution ratio is the molecular weight distribution of the propolync-bascd interpolymer of component (A) compared to the molecular weight distribution of the ethylcne-bascd polymer composition of component (B). The composition has a density ratio from 0.03 to 1.30, wherein the density ratio is the density of the propylene-based interpolymer of component (A) compared to the density of the ethylene-based polymer composition of component (B).

DEFINITIONS

[0009] Any reference to the Periodic fable of Elements is that as published by CRC Press, Inc., 1 990 1 99 1 . Reference to a group of elements in this table is by the new notation for numbering groups.

[0008] For purposes of United States patent practice, the contents of any referenced patent, patent application or publication arc incorporated by reference in their entirety (or its equivalent US version is so incorporated by reference) especially with respect to the disclosure of definitions (to the extent not inconsistent with any definitions specifically provided in this disclosure) and general knowledge in the art.

[0009] The numerical ranges disclosed herein include all values from, and including, the lower and upper value. For ranges containing explicit values (e.g., 1 or 2; or 3 to 5; or 6; or 7), any subrange between any two explicit values is included (e.g., 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6; etc.).

[0010] Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percents are based on weight and all test methods are current as of the filing date of this disclosure.

[0011] The term "composition" refers to a mixture of materials which comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0012] The terms "comprising," "including," "having" and their derivatives, are not intended to exclude the presence of any additional component, step or procedure, whether or not the same is specifically disclosed. In order to avoid any doubt, all compositions claimed through use of the term "comprising" may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless stated to the contrary. In contrast, the term "consisting essentially of" excludes from the scope of any succeeding recitation any other component, step, or procedure, excepting those that are not essential to operability. The term "consisting of excludes any component, step, or procedure not speci fically delineated or listed. The term "or," unless stated otherwise, refers to the listed members individually as well as in any combination. Use of the singular includes use of the plural and vice versa.

[0013] A "polymer" is a polymeric compound prepared by polymerizing monomers, whether of the same or a di fferent type. The generic term polymer thus embraces the term "homopolymer" (employed to refer to polymers prepared from only one type of monomer, with the understanding (.hat trace amounts of impurities can be incorporated into the polymer structure), and the term " interpolymer," as defined hereinafter. Trace amounts of impurities, for example, catalyst residues, may be incorporated into and/or within the polymer. It also embraces all forms of copolymer, e.g., random, block, etc. The terms "ethylene/a-olefin polymer" and "propylene/a- olefin polymer" are indicative of copolymer as described above prepared from polymerizing ethylene or propylene respectively and one or more additional, polymerizable a-olefin monomer. It is noted that although a polymer is often referred to as being "made of one or more specified monomers, "based on" a speci fied monomer or monomer type, "containing" a specified monomer content, or the like, in this context the term "monomer" is understood to be referring to the polymerized remnant of the speci fied monomer and not to the unpolymerized species. I n general, polymers herein are referred to has being based on "units" that are the polymerized form of a corresponding monomer.

[0014] An "interpolymer" is a polymer prepared by the polymerization of at least two different types of monomers. The generic term interpolymer thus includes copolymers (employed to refer to polymers prepared from two different types of monomers), and polymers prepared from more than two different types of monomers.

[0015] An "olefin-based polymer" or "polyolefin" is a polymer that contains equal to or greater than 50 wt%, or a majority amount of polymerized olefin monomer, for example, ethylene or propylene, (based on the weight of the polymer), and optional ly, may contain at least one comonomer. Nonlimiting examples of an olefin-based polymer include an ethylene-based polymer and a propylene-based polymer.

[0016] An "ethylene-based polymer" or "ethylene polymer" is a polymer that contains equal to or greater than 50 wt%, or a majority amount of polymerized ethylene based on the weight of the polymer, and, optionally, may comprise at least one comonomer.

[0017] A "propylene-based polymer" is a polymer that contains equal to or greater than 50 wt%, or a majority amount of polymerized propylene based on the weight of the polymer, and, optionally, may comprise at least one comonomer.

[0018] An "ethylene/α-olefin interpolymer" is an interpolymer that contains a majority amount of polymerized ethylene, based on the weight of the interpolymer, and at least one a-olefin.

[0019] An "ethylene/a-olefin copolymer" is an interpolymer that contains greater than 50 vvt%, or a majority amount of polymerized ethylene, based on the weight of the copolymer, and an a- olefin, as the only two monomer types.

[0020] A "propylene-based interpolymer" is an interpolymer that contains, in polymerized form, equal to or greater than 50 wt%, or a majority amount of propylene, based on the weight of the intcrpolymer, and at least one comonomer.

[0021 ] A "propylene/a-olefin interpolymer" is an interpolymer that contains, in polymerized form, equal to or greater than 50 wt%, or a majority amount of propylene, based on the weight of the interpolymer, and at least one α-olefin.

[0022] A "propylene/a-olefin copolymer" is a copolymer that contains, in polymerized form, greater than 50 wt% propylene, based on the weight of the copolymer, and an a-olel m, as the only two monomer types.

DETAI LE- D DESCRI PTION

|0023] The instant disclosure provides a composition suitable for holt-melt adhesive applications. The composition includes:

(A) a propylene-based interpolymer having a density from 0.850 g/cc to 0.900 g/cc;

(B) an ethylene-based polymer composition having a melt viscosity at 140°C from 1 0 m Pa●s to 1 ,000 mPa●s; and

(C) a tackifier; and

(D) optional antioxidant, and

the composition has (i) a molecular weight distribution ratio from 1 .00 to 1 .40, wherein the molecular weight distribution ratio is the molecular weight distribution of the propylene-based interpolymer of component (A) compared to the molecular weight distribution of the ethylene- based polymer composition of component (B); and (ii) a density ratio from 0.93 to 1 .30, wherein the density ratio is the density of the propylene-based interpolymer of component (A) compared to the density of the ethylene-based polymer composition of component (B).

[0024] In an embodiment, the composition is an adhesive composition, or further a hot melt adhesive (HMA) composition. An "adhesive composition" is a mixture of components that is capable of joining substrates o f interest together under an application of heat and/or pressure. A nonlimiting example of a suitable adhesive composition is a hot melt adhesive (HM A) composition. A "hot melt adhesive (HMA) composition" is a mixture of components that is capable of joining substrates of interest together under the application of heat, or more typically, the application of heat and pressure. In an embodiment, the composition is a HMA composition. Although the following disclosure is directed to I IMA compositions, it is understood that the fol lowing disclosure is applicable to other adhesive compositions, such as pressure sensitive adhesive compositions, for example.

A. Propylene-based interpolymer

[0025] The present composition includes a propylene-based interpolymer.

[0026] In an embodiment, the propylene-based intcrpolymer is selected from a propolyne/a-olefin interpolymer, or a propolync/α-olefin copolymer. Non limiting examples of suitable α-olefins include, for example, ethylene, C 4 , C 5 , C 6 and C 8 α-olef ins. In an embod iment, the propylene-based interpolymer is selected from a propylene/ethylene interpolymer, or a propylene/ethylene copolymer. In an embodiment, the propylenc-based interpolymer is a propylenc-bascd plastomer or elastomer (or "PBPE").

[0027] In an embodiment, the propylene-based interpolymer contains greater than 50 vvt% units derived from propylene, or from 5 1 wt%, or 55 wt%, or 60 wt%, or 65 \vt% to 70 wt%, or 75 wl%, or 80 wt%, or 85 wt%, or 90 wt%, or 95 wt%, or 98 wt%, or 99 wt% units derived from propylene, based on the weight of the propylene-based interpolymer.

[0028] In an embodiment, the propylene-based interpolymer is a propylene-based plastomer or elastomer. A "propylene-based plastomer or elastomer" (or "PBPE") is a propylene/ethylene copolymer and includes at least 50 weight percent of units derived from propylene and up to 10 wt% ethylene comonomer. In an embodiment, PBPE includes from 1 wt%, or 3 wt%, or 4 wt%, or 5 wt% to 7 wt%, or 8 wt%, or 9 wt%, or 10 wt% ethylene comonomer. in an embodiment, the PBPE includes from 50 wt%, or 60 wt%, or 70 wt%, or 80 wt%, or 90 wt%, or 91 wt%, or 92 wt%, or 93 wt% to 95 wt%, or 96 wt%, or 97 wt%. or 98 wt%, or 99 wt% propylene comonomer. In an embodiment, the PBPE includes greater than 50 wt% propylene comonomer. In another embodiment, the PB PE includes from 90 wt%, or 91 wt %, or 92 wt%, or 93 wl%, or 94 wt% to 95 wt%, or 96 wt%, or 97 wt%, or 98 wt %, or 99 wt% units derived from propylene and from 1 wt%, or 2 wt%, or 3 wt%, or 4 wt%, or 5 wt% to 6 wt%, or 7 wl%, or 8 wt%, or 9 wt%, or 10 wt% units derived from ethylene.

[0029] I n an embodiment, the propylene-based interpolymer has a total unsaturation per mole of propylene from 0.01 0%, or 0.01 5% to 0.025%, or 0.030%. The total unsaturation per mole of propylene is measured by 1 H NMR analysis, as described below in the test methods section. In a further embodiment, the propylene-based interpolymer is a propylenc/a-olefin interpolymer, and further a propylene/a-olefin copolymer, and further a PBPE, Nonlimiting examples of suitable a- olefins include, for example, ethylene. C 4 , C 5 , C 6 .and C 8 α-olefins.

[0030] In an embodiment, the propylene-based interpolymer has a melt viscosity at 1 77°C from 700 mi lliPascal-second (mPa●s), or 800 mPa●s, or 900 mPa●s, or 1 ,000 mPa●s, or 1 ,500 m Pa●s to 2,000 mPa●s, or 2,500 mPa●s, or 4,000 m Pa●s, or 5,000 mPa●s, or 7,000 mPa●s, or 1 0,000 mPa●s. In a further embodiment, the propylene-based interpolymer has a melt viscosity at 1 77°C from 700 mPa●s to 5,000 mPa●s. In a further embodiment, the propylene-based interpolymer is a propylene/a-olefin interpolymer, and further a propylene/a-olefin copolymer, and further a PBPE. Nonlimiting examples of suitable α-olefins include, for example, ethylene. C 4 , C 5 , C 6 , and C 8 α-olefins.

[0031] I n an embodiment, the propylene-based interpolymer has a crystallinity from 1 wt%, or 10 wt%. or 1 5 wt%, or 20 vvt% to 25 wt%, or 30 wt%, or 35 wt%, or 40 wt%. In an embodiment, the propylene-based interpolymer has a crystallinity from 10 to 40 wt%, or 20 to 39 wt%. In an embodiment, a PBPE that is propylene/ethylene copolymer may have a crystallinity in the range from 10 to 40 wt %, or 20 to 39 wt %. Crystallinity is measured via DSC method, as described below in the test methods section. In a further embodiment, the propylene-based interpolymer is a propylene/a-olefin interpolymer, and further a propylene/α-olefin copolymer, and further a PBPE. The propylene/ethylene copolymer includes units derived from propylene and polymeric units derived from ethylene comonomer and optional C 4 -C 1 0 α-olefin. Nonl imiting examples of suitable a-olefins include, for example, ethylene, C 4 , C 5 , C 6 and C 8 α-olefins.

[0032] In an embodiment, the propylene-based interpolymer has a heat of fusion (Mr) from 40 J/g, or 45 J/g to 50 J/g, or 55 J/g, or 60 J/g, or 65 J/g, or 70 J/g, or 75 J/g, or 80 J/g. In a further embodiment, the propylene-based interpolymer is a propylene/a-olefin interpolymer, and further a propylene/a-olefin copolymer, and further a PBPE. Nonlimiting examples of suitable a-olefins include, for example, ethylene, C 4 , C 5 , C 6 and C 8 α-olefins.

[0033] In an embodiment, the propylene-based interpolymer has a density from 0.850 g/cc, or 0.860 g/cc, or 0.865 g/cc, or 0.870 g/cc to 0.880 g/cc, or 0.885 g/cc, or 0.890 g/cc. In a further embodiment, the propylene-based interpolymer is a propylene/a-olefin interpolymer, and further a propylenc/a-olefin copolymer, and further a PBPE. Nonlimiting examples of suitable a-olefins include, for example, ethylene, C 4 , C 5 , C 6 and C 8 α-olefins.

[0034] In an embodiment, the propylene-based interpolymer has a melting temperature, Tm, from 85°C, or 90°C, or 95°C, or 100°C to 1 05°C, or 1 10°C, or 1 1 5°C, or 120°C. In a further embodiment, the propylene-based interpolymer is a propylene/α-olefin interpolymer, and further a propylene/a-olefin copolymer, and further a PBPE. Nonlimiting examples of suitable α-olefins include, for example, ethylene, C 4 , C 5 , C 6 and C 8 α-olefins.

[0035] In an embodiment, the propylene-based interpolymer has a weight average molecular weight (Mw) from 20,000 g/mol, or 24,000 g/mol, or 30,000 g/mol to 35,000 g/mol, or 40,000 g/mol, or 48,000 g/mol, or 50,000 g/mol. In a further embodiment, the propylene-based interpolymer is a propylene/a-olefin interpolymer, and further a propylene/a-olefin copolymer, and further a PBPE. Nonlimiting examples of suitable α-olefins include, for example, ethylene, C 4 , C 5 , C 6 and C 8 α-olefins.

[0036] In an embodiment, the propylene-based interpolymer has a Mw/Mn from 2.0, or 2.1 , or 2.2, or 2.3 to 2.5, or 2.7, or 3.0, or 3.5, or 4.0. In a further embodiment, the propylene-based interpolymer is a propylene/α-ole fm interpolymer, and further a propylene/a-olefin copolymer, and further a PBFE. Nonlimiting examples of suitable a-olefins include, for example, ethylene, C 4 , C 5 , C 6 and C 8 α-olefins.

[0037] In an embodiment, the propy1ene-based interpolymer has a Mw/Mn from 2.00, or 2.05. or 2. 1 0, or 2.1 5, or 2.20, or 2.25, or 2.30, or 2.35, or 2.40 to 2.50, or 2.55, or 2.60, or 2.65, or 2.70, or 2.75, or 2.80, or 2.85, or 2.90, or 2.95, or 3.00, or 3. 1 0, or 3.20. or 3.30, or 3.40, or 3.50. or 3.60, or 3.70, or 3.80. or 3.90 or 4.00. In a further embodiment, the propolyne-based interpolymer is a propolyne/α-olefin interpolymer, and further a propylene/a-olefin copolymer, and further a PBPE, Non limiting examples of suitable α-olclins include, for example, ethylene, C 4 , C 5 , C 6 and C 8 α-olefins.

[0038] In an embodiment, the propylene-based interpolymer, further the propylene/ethylene interpolymer, further the propylene/ethylene copolymer, and further the PBPE, is characterized as having substantially isotactic propylene sequences. "Substantially isotactic propylene sequences" are sequences having an isotactic triad (mm) measured by 13 C NMR of greater than 0.85, or greater than 0.90, or greater than 0.92, or greater than 0.93. Isotactic triads refer to the isotactic sequence in terms of a triad unit in the copolymer molecular chain determined by 13 C NMR spectroscopy.

1 . B-Value

[0039] The term "B-value" is a measure of randomness and measures the distribution of the propylene and comonomcr across the polymer chain of the propylene-based interpolymer. For a propylene/ethylene copolymer, the "B-valuc" is a measure of randomness and measures the distribution of the propylene and ethylene across the polymer chain of the propylene/ethylene copolymer. B-values range from 0 to 2. The higher the B-value, the more alternating the ethylene distribution in the copolymer. The lower the B-value, the more blocky or clustered the ethylene distribution in the propylene/ethylene copolymer.

[0040] In an embodiment, the propylene-based interpolymer has a B-valuc of less than 1 .0, or less than 0.99, or less than 0.98, or less than 0.97. In an embodiment, the propylene-based interpolymer has a B-value from 0.90, or 0.92, or 0.93, or 0.94 to 0.95, or 0.96, or 0.97, or 0.98, or 0.99. In a further embodiment, the propylene-based interpolymer is a propylene/a-olefin interpolymer and further propylene/a-olefin copolymer. Nonlimiting examples of suitable α-olefins include, for example, ethylene, C 4 , C 5 , C 6 and C 8 α-olefins.

[0041] In an embodiment, the propylene-based interpolymer is a PBPE with a Koenig B-value of less than 1 .0, or less than 0.99, or less than 0.98, or less than 0.97. The lower the B-value, the more blocky or clustered the ethylene distribution in a PBPE propylene/ethylene copolymer. For PB PE polymers made with a Group IV metal complex of a polyvalent aryloxyelher catalyst, the B-values are less than 1 .0. In an embodiment, the PBPE has a B-value from 0.90, or 0.92, or 0.93, or 0.94 to 0.95, or 0.96, or 0.97, or 0.98, or 0.99. Thus, for PBPE made with the Group IV metal complex of a polyvalent aryloxyether catalyst, not only is the propylene block length relatively long for a given percentage of ethylene, but a substantial amount of long sequences of three or more sequential ethylene insertions are present in the PBPE.

[0042] T he B-value as described by Koenig (Spectroscopy of Polymers (2d ed. 1 999) is calculated as follows. B is defined for a propylene/ethylene copolymer as:

where the sum of the EP and PE diad fractions; and Fe and Fp - the mole fraction

of ethylene and propylene in the copolymer, respectively. The diad fraction can be derived from triad data according to: f(EP + PE) = [ EPEj + [EPP+PPEj/2 + [PEP] + | EEP+PEEJ/2. The B-values can be calculated for other copolymers in an analogous manner by assignment of the respective copolymer diads. For example, calculation of the B-value for a propylene/ 1 -octene copolymer uses the following equation:

[0043] In an embodiment, the propolyne-based interpolymcr, and further the PBPE has one, some, or all of the following properties: (i) from 90 wt % to 99 wt % units derived from propylene and from 1 0 wt % to 1 wt % units derived from ethylene; (ii) an isotactic triad (mm) measured by 13 C NMR greater than 0.85 ; (iii) a Koenig B-value from 0.90 to 0.99; (iv) a total mol % unsaturation propylene from 0.0 10% to 0.030%; (iii) a density from 0.850 g/cc to 0.890 g/cc; (iv) a melt viscosity at 1 77°C from 700 mPa●s to 10,000 mPa●s; (v) a melting temperature, Tm from 85°C to 1 20°C; (vi) a heat of fusion (I I f ) from 40 J/g to 80 J/g; (vii) a crystallinity from 1 % to 40%; (viii) an Mw from 20,000 to 50,000 g/mol; and/or (ix) a Mw/Mn from 2.0 to 4.0.

[0044 j In an embodiment, the propylene-based interpolymcr, and further the PBPE has one, some, or all of the following properties: (i) from 93 wt % to 95 wt % units derived from propylene and from 5 wt %> to 7 wt % units derived from ethylene; (ii) an isotactic triad (mm) measured by 13 C N MR greater than 0.90; (iii) a Koenig B-valuc from 0.90 to 0.96; (iv) a total mol % unsaturation propylene from 0.010% to 0.020%; (iii) a density from 0.870 g/cc to 0.890 g/cc; (iv) a melt viscosity at 1 77°C from 700 mPa'S to 5,000 mPa●s; (v) a melting temperature, Tm from 90°C to 1 1 0°C; (vi) a heat of fusion (H f ) from 40 J/g to 70 J/g; (vii) a crystallinity from 20% to 40%; (viii) an Mw from 20,000 to 40,000 g/mol; and/or (ix) a Mw/Mn from 2.0 to 3.0. 2. Suitable catalyst for the propylene-based interpolymer

[0045] In an embodiment, the propylene-based interpolymer, further the propylene/ethylene interpolymer, further the propylene/ethylene copolymer, and further the PBPH, is made with a (i) catalyst that is a Group IV metal complex of a polyvalent aryloxyether, (ii) an activator, and/or (iii) a cocatalyst. The catalyst is capable of producing polymers from propylene containing monomer mixtures having extremely high molecular weight and isotacticity, at catalyst efficiencies of greater than 0.5 gpolymer/μgmetal, allowing the use of a chain transfer agent to control molecular weight without sacri ficing molecular weight distribution. A sufficient quantity of chain transfer agent is used so that a substantial decrease in molecular weight (>30 percent) occurs compared to a comparative polymerization without the use of chain transfer agent. When the chain transfer agent is hydrogen, at least 0.01 mol percent (based on propylene) is used, and a maximum of 2 mole percent is used. Nonlimiting examples of suitable Group IV metals include titanium, zirconium, and hafnium. In an embodiment, the Group IV metal complex is a hafnium- based polyvalent aryloxyether. A nonl imiting example of a suitable Group I V metal complex of a polyvalent aryloxyether includes [| 2',2"'-[ 1 ,3-propanediylbis(oxy-KO)]bis-{3-[9H -3,6-di-( l , l - dimethylethyl)-carbazol-9-yl]} -5'-fiuoro-5-( l , l ,3,3-tetramethylbutyl)-| 1 , 1 '-biphenyl ]-2-olato- KO |](2-)]dimethyl hafnium.

[0046] The metal complexes are activated in various ways to yield catalyst compounds having a vacant coordination site that will coordinate, insert, and polymerize addition polymerizable monomers, especially olefin(s). For the purposes of this patent speci fication and appended claims, an "activator" or "cocatalyst" is any compound or component or method which can activate the metal complex in the foregoing manner. Non-limiting examples of suitable activators include Lewis acids, non-coordinating ionic activators, ionizing activators, organometallic compounds, and combinations of the foregoing substances capable of converting the neutral metal complex to a catalytical ly active species.

[0047] Ionizing cocatalysts may contain an active proton, or some other cation associated with, but not coordinated to or only loosely coordinated to, an anion of the ionizing compound. Non l im iting examples include ammonium cation containing salts, especially those containing trihydrocarbyl-substituted ammonium cations containing one or two C 10-40 alkyl groups, especially methylbis(octodecyl)-ammonium- and methylbis(tetradecyr)-ammonium-cations and a non- coordinating anion, especially a tctrakis(perfiuoro)arylborate anion, especial ly tetrakis(pentafluorophenyl)borate. The cation may comprise a mixture of hydrocarbyl groups of di ffering lengths. For example, the protonated ammonium cation derived from the commercially available long-chain amine comprising a mixture of two C 14 , C 16 or C 18 alky groups and one methyl group. Such amines are available from Chemtura Corp., under the trade name Kemamine™ T9701 , and from Akzo Nobel under the trade name Armeen™ M2HT. In an embodiment, the ammonium salt activator is methyl di(C 1 4-20 alkyl)ammonium tctrakis(pentafluorophenyl)borate, such as methyl di(octadecyl)ammonium tetrakis(pentafluorophenyI)borate (MDB).

[0048] Another suitable class of organometallic activators or cocatalysts is alumoxanes, also referred to as alkylaluminoxanes. Alumoxanes are well known activators for use with mctallocene type catalyst compounds to prepare addition polymerization catalysts. Non1im iling examples include alumoxanes that are Lewis acid modified a lumoxanes, especial ly tri(C 3-6 )alkylaluminum modified methylalumoxane, including tri(isobutyl)aluminum modified methalumoxane (MMAO), available commercially as MMAO-3A, from Akzo Nobel, or tri(n- octyl)alum inum modi fied methalumoxane, available commercially as MMAO- 12, from Akzo Nobel.

[0049] Combinations of activators are also contemplated by the present disclosure, for example, alumoxanes and ionizing activators in combination.

[0050] In an embodiment, the propylene-based interpolymer, further the propylene/a-oleifn interpolymer, further the propylene/a-olefin copolymer, and further the PBPE is produced as disclosed in International Application Number PCT/US201 5/046094 fi led 20 August 2015 (published as International Publication No. WO 2016/029006) or co-pending application IJ SSN 62/235, 1 85 filed 30 September 201 5, the entire content of each is incorporated by reference herein to the extent that the language is not inconsistent with the instant application.

[0051 ] The propylene-based interpolymer, and further the propylene/a-olefin copolymer, and further the PBPE, is present in the composition in an amount from 50 wt%, or 5 1 wt%, or 55 wt%, or 60 wt %, or 65 wt %, or 69 wt % to 70 wt %, or 71 wt %, or 75 wt %, or 80 wt %, or 85 wt %, or 90 wt %. In an embodiment, the PBPE is present in the composition in an amount that is equal to or greater than 50 wt%. Weight percent is based on total weight of the composition.

[0052] The propylene-based interpolymer, further the propylene/a-olefin interpolymer, further the propylene/a-olefin copolymer, and further the PBPE, may comprise two or more embodiments disclosed herein.

B. Ethylene-Based Polymer composition

[0053] The present composition includes an ethylene-based polymer composition . The ethylenc- based polymer composition may be used to reduce the melt viscosity of the 1 IMA composition. An "ethylene-based polymer composition" includes an ethylene-based polymer or a blend of ethylene-based polymers. The ethylene-based polymer composition comprises a majority amount of units derived from ethylene, based on the weight of the ethylene-based polymer composition, In an embodiment, the ethylene-based polymer composition includes from 50 wt%, or greater than 50 wt%, or 60 wt%, or 70 wt% to 75 wt%, or 80 wt%, or 90 wt%, or 95 wt%, or 99 wt%, or 100 wt% units derived from ethylene, based on the weight of the ethylene-based polymer composition. In an embodiment, the ethylene-based polymer composition includes from 90 wt%, or 95 wt%, or 97 wt% to 99 wt%, or 1 00 wt% units derived from ethylene, based on the weight of the ethylene-based polymer. The ethylene-based polymer composition may optionally include additives such as an antioxidant. In an embodiment, the ethylene-based polymer composition is composed solely of ethylene-based polymer and excludes additives. Nonlimiting examples of suitable ethylene-based polymer compositions include ethylene homopolymer, ethylene-based interpolymer, and combinations thereof.

[0054] The ethylene-based polymer composition excludes microcrystalline wax (i.e., by-product polyethylene wax), Fischer-Tropsch wax, and oxidized Fischer-Tropsch wax. Ethylene-based polymer is structurally distinct from m icrocrystalline wax because microcrystal line wax has a lower density and more branching than ethylene-based polymer. Ethylene-based polymer is structurally distinct from Fischer-Tropsch wax because Fischer-Tropsch wax is more linear (i.e., has less branching) than ethylene-based polymer.

[0055] The ethylene-based polymer composition may or may not be functionalized. In an embodiment, the ethylene-based polymer composition is not functionalized.

[0056] The ethylene-based polymer composition may or may not be oxidized to create polarity. Oxidation inserts an oxygen molecule into the structure of the ethylene-based polymer composition, which may be in the form of a carbonyl for example. In an embodiment, the ethylene-based polymer composition is not oxidized.

[0057] The ethylene homopolymer is produced by way of Ziegler-Natta catalyst polymerization or metallocene catalyst polymerization yielding a Ziegler-Natta catalyzed ethylene-based polymer or a metal locene-catalyzed ethylene-based polymer, respectively. In an embodiment, the ethylene-based polymer is a low density polyethylene homopolymer.

[0058] The ethylene-based interpolymer is selected from an ethylene/a-olefin interpolymer, or an ethylene/a-olefin copolymer. Nonlimiting examples of suitable α-olefins include, for example, C 3 , C 4 , C 5 , C 6 , and C 8 α-olefins.

[0059] The ethylene-based polymer composition has a density from 0.880 g/cc, or 0.885 g/cc, or 0.890 g/cc, or 0.895 g/cc, or 0.900 g/cc, or 0.905 g/cc, or 0.9 1 0 g/cc to 0.9 1 5 g/cc, or 0.920 g/cc, or 0.925 g/cc, or 0.930 g/cc. [0060] The ethylene-based polymer composition has a melt viscosity at 140°C from 10 mPa●s, or 30 mPa●s to 50 mPa●s, 100 mPa●s, or 1 80 mPa●s, or 200 mPa●s, or 250 mPa●s, or 300 mPa●s, or 350 mPa●s, or 400 mPa●s, or 450 mPa●s, or 475 mPa●s, or 500 mPa●s, or 550 mPa●s, or 600 mPa●s, or 700 mPa●s, or 800 mPa●s, or 900 mPa●s, or 1 ,000 mPa●s. In a further embodiment, the ethylene-based polymer composition has a melt viscosity at 140°C from 20 mPa●s to 450 mPa●s.

[0061] The ethylene-based polymer composition has a molecular weight distribution (Mw/Mn) from greater than 1.25, or 1 .30, or 1 .35. or 1 .40, or 1 .45, or 1.50, or 1 .60, or 1.70, or 1.75, or 1 .80, or 1 .85, or 1.90 to 1 .94, or 1 .95, or 1 .96, or 1 .99, or 2.00, or 2.10, or 2.50, or 2.60, or 2.70, or 2.80, or 2.90, or 3.00. In a further embodiment, the ethylene-bascd polymer composition has a molecular weight distribution from 1 .80 to 1.96.

[0062] In an embodiment, the ethylene-based polymer composition has a weight average molecular weight (Mw) from 800 g/mol, or 1 ,000 g/mol, or 2,000 g/mol, or 3,000 g/mol, or 4,000 g/mol, or 5,000 g/mol, or 6,000 g/mol to 7,000 g/mol, or 8,000 g/mol, or 9,000 g/mol, or 10,000 g/mol.

[0063] In an embodiment, the ethylene-based polymer composition has a number average molecular weight (Mn) from 270 g/mol, or 300 g/mol, or 350 g/mol, or 400 g/mol, or 450 g/mol, or 500 g/mol, or 550 g/mol, or 600 g/mol, or 650 g/mol, or 700 g/mol, or 800 g/mol, or 900 g/mol, or 1 ,000 g/mol, or 1 .200 g/mol, or 1 ,500 g/mol, or 2,000 g/mol, or 2, 100 g/mol, or 2,500 g/mol, or 3,000 g/mol, or 3,300 g/mol to 3,500 g/mol, or 4,000 g/mol, or 5,000 g/mol, or 6,000 g/mol, or 7.000 g/mol, or 8,000 g/mol.

[0064] In an embodiment, the ethylene-based polymer composition has a Z average molecular weight (Mz) from 1 ,000 g/mol, or 2,000 g/mol, or 3,000 g/mol, or 3,500 g/mol, or 4.000 g/mol, or 5,000 g/mol, or 6,000 g/mol to 7,000 g/mol, or 8,000 g/mol, or 9,000 g/mol, or 10,000 g/mol, or 1 1 ,000 g/mol. The "Z average molecular weight"(Mz) is the third moment average molar mass.

[0065] In an embodiment, the ethylene-based polymer composition has a total mole percent unsaturation per 1 ,000 carbon bonds that is from 0.001 %, or 0.005%, or 0.010%, or 0.050%, or 0.100%), or 0.200%, or 0.300%, or 0.400%.or 0.500%, or 0.600%, or 0.700%, or 0.800%, or 0.900% to 1 .000%, or 1.050%, or 1.100%, or 1.200%, or 1 .300%, or 1 .400%, or 1 .500%, or 1.600%, or 1 .700%), or 1 .800%, or 1.900%, or 1 .950%, or 2.000%. In another embodiment, the ethylene-based polymer composition has a total mole percent unsaturation per 1 ,000 carbon bonds that is less than 2.000%), or less than 1 .500%, or less than 2.000%.

[0066] In an embodiment, the ethylene-based polymer composition has a drop point of from 80°C, or 85°C, or 90°C, or 95°C, or 100°C to 105°C, or 1 10°C, or 1 13°C, or 1 15°C, or 120°C, or 125°C, or 1 30°C, or 1 35°C, or 140°C, or 145°C, or 1 50°C.

[0067] In an embodiment, the ethylene-based polymer composition has one, some, or all of the following properties: (i) a density from 0.880 g/cc to 0.930 g/cc; (ii) a melt viscosity at 140°C from 10 mPa●s to 1 ,000 mPa●s; (in) a molecular weight distribution from greater than 1 .25 to 3.00; (vi) a weight average molecular weight (Mw) from 800 g/mol to 10,000 g/mol; (v) a number average molecular weight (Mn) from 270 g/mol to 8,000 g/mol; (vi) a Z average molecular weight (Mz) from 1 ,000 g/mol to 1 1 ,000 g/mol; (vii) a drop point from 80°C to 1 50°C; and/or (vi i i) a total mole percent unsaturation per 1 ,000 carbon bonds from 0.00 1 % to 2.000%.

[0068] In an embodiment, the ethylenc-bascd polymer composition has one, some, or all of the following properties: (1) a density from 0.880 g/cc to 0.930 g/cc; (ii) a melt viscosity at 140°C from 30 mPa●s to 500 m Pa●s; (ii i) a molecular weight distribution from 1 .80 to 2.00; (vi) a weight average molecular weight (Mw) from 2,000 g/mol to 7,000 g/mol; (v) a number average molecular weight (Mn) from 1 ,000 g/mol to 4,000 g/mol; (vi) a Z average molecular weight (Mz) from 3,000 g/mol to 10,000 g/mo1; (vii) a drop point from 90°C to 1 1 5°C; and/or (vi ii) a total mole percent unsaturation per 1 ,000 carbon bonds from 0.380% to 1 .999%.

[0069] Nonlimiting examples of suitable ethylene-based polymer compositions include low density polyethylene homopolymers A-C™ 8, A-C™ 6 1 7, and A-C™ 1 702, avai lable from Honeywell.

[0070] The ethylene-based polymer composition is present in the composition in an amount from 1 wt %, or 2 wt %, or 5 wt %, or 7 wt %, or 9 wt % to 10 wt %, or 1 1 wt %, or 15 wt %, or 20 wt %, or 30 wt %. Weight percent is based on total weight of the composition.

[0071] The ethylene-bascd polymer composition may comprise two or more embodiments disclosed herein.

C . Tackifier

[0072] The present composition includes a tacki fier. The tackifier has a Ring and Ball softening temperature (measured in accordance with ASTM E 28) from 90°C, or 93°C, or 95°C, or 97°C, or 100°C, or 1 05°C, or 1 1 0°C to 120°C, or 130°C, or 140°C, or 1 50°C. The tackiiier may modify the properties of the composition such as viscoelastic properties (e.g., tan delta), rheological properties (e.g., viscosity), tackiness (e.g., ability to stick), pressure sensitivity, and wetting property. In some embodiments, the tackifier is used to improve the tackiness of the composition. In other embodiments, the tackiiier is used to reduce the viscosity of the composition. In particular embodiments, the tackifier is used to wet out adherent surfaces and/or improve the adhesion to the adherent surfaces. [0073] Tackifiers suitable for the compositions disclosed herein can be sol ids, semi-solids, or liquids at room temperature. Non-lim iting examples of suitable tackifiers include ( 1 ) natural and modi fied rosins (e.g., gum rosin, wood rosin, tal l oil rosin, distilled rosin, hydrogenated rosin, dimerized rosin, and polymerized rosin); (2) glycerol and pentaerythritol esters of natural and modified rosins (e.g., the glycerol ester of pale, wood rosin, the glycerol ester of hydrogenated rosin, the glycerol ester of polymerized rosin, the pentaerythritol ester of hydrogenated rosin, and the phenolic-modified pentaerythritol ester of rosin); (3) copolymers and terpolymcrs of natured terpenes (e.g., styrene/terpene and alpha methyl styrene/terpcne); (4) polyterpene resins and hydrogenated polyterpene resins; (5) phenolic modified icrpene resins and hydrogenated derivatives thereof (e.g., the resin product resulting from the condensation, in an acidic medium, of a bicyclic Icrpene and a phenol); (6) aliphatic or cycloahphatic hydrocarbon resins and the hydrogenated derivatives thereof (e.g., resins resulting from the polymerization of monomers consisting primarily of olefins and diolcfins); (7) aromatic hydrocarbon resins and the hydrogenated derivatives thereof; (8) aromatic modi fied aliphatic or cycloahphatic hydrocarbon resins and the hydrogenated derivatives thereof; and combinations thereof.

[0074] In an embodiment, the tacki fier includes aliphatic, cycloahphatic and aromatic hydrocarbons and modified hydrocarbons and hydrogenated versions; terpenes and modified terpenes and hydrogenated versions; and rosins and rosin derivatives and hydrogenated versions; and mixtures of two or more of these tackifiers. These tacki fying resins have a ring and ball softening point from 70°C, or 100°C to 130°C, or 1 50°C, and wil l typical ly have a melt viscosity, at 190°C, as measured using a Brookfield viscometer, of from 1 mPa●s, or 1 00 mPa●s, or 500 mPa●s to 1 ,000 mPa●s, or 1 ,500 mPa●s, or 2,000 mPa●s. They are also avai lable with di ffering levels of hydrogenation, or saturation, which is another commonly used term. Nonlimiting examples of suitable tackifying resins include Eastotac™ 1 1-100, 1 1- 1 1 5 and 1 1- 130 from Eastman Chemical Co. in Kingsport, Tcnn., which are partially hydrogenated cycloahphatic petroleum hydrocarbon resins with softening points of 100°C, 1 1 5°C and 130°C, respectively. These are available in the B grade, the R grade, the 1., grade and the W grade, indicating differing levels of hydrogenation with E being the least hydrogenated and W being the most hydrogenated. The E grade has a brom ine number of 15, the R grade a brom ine number of 5, the L grade a bromine number of 3 and the W grade has a bromine number of 1 . Eastotac™ I 1- 142R from Eastman Chemical Co. has a softening point of 1 40°C. Other nonlimiting examples of suitable tackifying resins include Escorcz™ 5300, 5400, and 5637, partially hydrogenated aliphatic petroleum hydrocarbon resins, and Escorez™ 5600, a partially hydrogenated aromatic modi fied petroleum hydrocarbon resin all available from Exxon Chemical Co. in Houston, Tex.; Wingtack™ Extra, which is an aliphatic, aromatic petroleum hydrocarbon resin available from Goodyear Chemical Co. in Akron, Ohio; Hercolite™ 2100, a partially hydrogenated cycloaliphatic petroleum hydrocarbon resin available from Hercules, Inc. in Wilmington, Del.; Norsolene™ hydrocarbon resins from Cray Valley; and Arkon™ water white, hydrogenated hydrocarbon resins available from Arakawa Europe GmbH.

[0075] In an embodiment, the tacki fier includes aliphatic hydrocarbon resins such as resins resulting from the polymerization of monomers consisting of olefins and diolefins (e.g., Escorez™ 13 10EC, Escorez™ 2596 from ExxonMobil Chemical Company, Houston, Tex. or PICCOTAC™ 1095, PICCOTAC™ 9095 from Eastman Chemical Company, Kingsport, Tenn.) and the hydrogenated derivatives thereof; alicyclic petroleum hydrocarbon resins and the hydrogenated derivatives thereof (e.g., Escorez™ 5300 and 5400 series from ExxonMobil Chemical Company; EASTOTAC™ resins from Eastman Chemical Company). In some embodiments, the tackifiers include hydrogenated cyclic hydrocarbon resins (e.g., REGAEREZ™ and R EGAEITE™ resins from Eastman Chemical Company).

[0076] In an embodiment, the tack i fying agent is a rosin-based tackifier selected from a partial ly hydrogenated glycerol ester, a fully hydrogenated pentaerythritol ester, a fully hydrogenated glycerol ester, a non-hydrogenated ester with a glass transition temperature (Tg) from 30°C, or 35°C, or 40°C to 45°C or 50°C, and combinations thereof.

[0077] In an embodiment, the tacki fier is an aliphatic hydrogenated hydrocarbon resin. In a further embodiment, the aliphatic hydrogenated hydrocarbon tackifier is a hydrogenated cyclopentadiene-bascd tacki fier. In a further embodiment, the aliphatic hydrogenated hydrocarbon tacki fier is a hydrogenated cyclopentadiene-based tacki fier with a ring and ball softening point of 1 1 5°C and a melt viscosity at 1 90°C of 400 mPa●s, available commercial ly under the trade name Eastotac™ H- 115W (available from Eastman Chemical).

[0078] The tackifier is present in the composition in an amount from 1 wt%, or 5 wt %, or 9 wt%, or 10 wt %, or 1 5 wt %, or 1 9 wt % to 20 wt %, or 2 1 wt %, or 23 wt%, or 25 wt %, or 30 wt %, or 35 wt%, or 40 wt%, or 45 wt%, or 49 wt%. In a further embodiment, the tacki fier is present in the composition in an amount that is less than 50 wt%. Weight percent is based on the total weight of the composition.

[0079] The tackifier may comprise two or more embodiments disclosed herein.

D. Additives

[0080] The present composition may include one or more additives. Nonlimiting examples of suitable additives include plasticizcrs, oils such as mineral oil, stabilizers, antioxidants, pigments, dyestuffs, antiblock additives, polymeric additives, defoamers, preservatives, thickeners, rheology modifiers, humectanls, fil lers, solvents, nucleating agents, surfactants, chelating agents, gelling agents, processing aids, cross-linking agents, neutral izing agents, (lame retardants, fluorescing agents, compatibilizers, antimicrobial agents, and water.

[0081] I n an embodiment, the composition includes polymeric additives. Nonlimiling examples of suitable polymeric additives include styrenic block copolymer such as those available from Kraton under the trade name KRATON™ polymers; ethylene/α-olefin copolymer such as those available from The Dow Chemical Company under the trade name ENGAGE™; ethylene/ix- olefin terpolymers, such as an ethylene-based polymer containing two types of a-olefins; and combinations thereof.

[0082 ] In an embodiment, the composition includes an antioxidant. The antioxidant protects the composition from degradation caused by reaction with oxygen induced by such things as heat, light, or residual catalyst from the raw materials such as the tacki fying resin. Suitable antioxidants include high molecular weight hindered phenols and multifunctional phenols such as sulfur and phosphorous-containing phenol. Representative hindered phenols include; 1 ,3,5- trimethyl-2,4,6-tris-(3,5-di-tert-butyl-4~hydroxybenzyl)-ben zene; pentaerythrityl tetrakis-3(3,5-di- lerl-butyl-4-hydroxypheny])-propionate; n-octadecyl-3(3,5-di-tei1-butyl-4-hydroxyphenyl)- propionate; 4,4'-methylenebis(2,6-tert-butyl-phenol); 4,4'-thiobis(6-tert-butyl-o-cresol); 2,6-di- tertbutylphenol; 6-(4-hydroxyphenoxy)-2,4-bis(n-octyl-thio)-l,3,5 triazine; di-n-octylthio)elhyl 3,5-di-tert-butyl-4-hydroxy-benzoate; and sorbitol hexa| 3-(3,5-di-tert-butyl-4-hydiOxy-phcnyl)- propionate].

[0083] Such antioxidants are commercially available from Ciba Specialty Chemicals and include lrganox™ 565, 1 01 0, 1 076 and 1 726, which are hindered phenols. These are primary antioxidants act as radical scavengers and may be used alone or in combination with other antioxidants such as phosphite antioxidants like Irgafos™ 168, available from Ciba Specialty Chemicals. Phosphite catalysts are considered secondary catalysts and are not generally used alone. These are primarily used as peroxide decomposers. Other avai lable catalysts are Cyanox™ LTDP, avai lable from Cytec Industries, and Ethanox™ 330, available from Albemarle Corp. Many such antioxidants are available either to be used alone or in combination with other such antioxidants.

[0084] In an embodiment, the composition contains from 0.1 wt %, or 0.2 wt %, or 0.3 wt %, or 0.4 wt% to 0.5 wt%, or 0.6 wt %, or 0.7 wt%, or 0.8 wt %, or 1 .0 wt %, or 2.0 wt%, or 2.5 wt%, or 3.0 wt% additive, based on total weight of the composition.

[0085] In an embodiment, the composition contains from 0.1 wt %. or 0.2 wt %, or 0.3 wt %, or 0.4 wt% to 0.5 wt%, or 0.6 wt %, or 0.7 wt%, or 0.8 wt %, or 1 .0 wt %, or 2.0 wt%, or 2.5 wt%, or 3.0 wt% antioxidant, based on total weight of the composit ion.

[0086] The additive may comprise two or more embodiments disclosed herein.

E. Composition

[0087] In an embodiment, the composition includes: (A) equal to or greater than 50 wt% propylene-based interpolymcr, such as PBPE, having a density from 0.850 g/cc to 0,900 g/cc: (13) an ethylene-based polymer composition having a melt viscosity at 140°C from 10 mPa●s to 1 ,000 mPa●s; and (C) a tackifier; and (D) optional antioxidant, and the composition has a molecular weight distribution ratio from 1 .00 to 1 .40; and a density ratio from 0.93 to 1 .30,

[0088] The propylene-based interpolymcr, ethylene-based polymer composition, tacki fier, and antioxidant may be any respective propylene-based interpolymcr, ethylene-based polymer composition, tacki fier and antioxidant disclosed herein.

[0089] In an embodiment, the combined amount of (A) propylene-based interpolymer, (B) ethylene-based polymer, and (C) tacki fier equals from 95 wt%, or 97 wt% to 98 wt%, or 99 wt%, or 100 wt% of the composition.

[0090] In an embodiment, the weight ratio of (A) propylene-based interpolymcr to (B) ethylene- based polymer is from 2.00. or 3.00, or 4.00, or 5.00, or 6.00 to 7.00, or 8.00. or 9.00, or 1 0.00.

[009] ] In an embodiment, the composition has a melt viscosity, at 1 77°C, from 300 mPa●s, or 350 mPa●s, or 400 mPa●s, or 500 mPa●s, or 600 mPa●s, or 700 mPa●s, or 800 mPa●s, or 850 mPa●s, or 900 mPa●s, or 1 .000 m Pa●s, or 1 ,200 mPa●s, or 1 ,400 mPa●s to 1 ,500 mPa●s, or 1 ,600 mPa●s, or 1 ,800 mPa●s, or 2,000 mPa●s, or 2,500 mPa●s, or 3,000 mPa●s, or 3,500 mPa●s, or 4,000 mPa●s.

[0092] In an embodiment, the composition has a fiber tear greater than 50%, or greater than 55%, or greater than 60%), or greater than 70%, or greater than 75%, or greater than 80%, or greater than 85%,or greater than 90% to 1 00% at a temperature from -40°C to 60°C. High fiber tear is especially advantageous for I IMA compositions utilized in the packaging industry because, during transportation and storage of a package, the package is regularly exposed to extreme temperatures (as low as -40°C and as high as 60°C). Adhesive compositions used in packages, such as boxes or cartons, must maintain sufficient adhesion across the entire range of the extreme temperatures (-40°C to 60°C).

[0093] In an embodiment, the composition has a fiber tear after aging for 24 hours at 1 77°C from greater than 50%, or greater than 55%, or greater than 60%, or greater than 70%, or greater than 75%, or greater than 80%), or greater than 85%, or greater than 90% to 1 00%> at a temperature from -40°C to 60°C.

[0094] In an embodiment, the composition has a peel adhesion failure temperature (ΡAFΤ) of from 40°C, or 45°C, or 50°C, or 55°C, or 60°C, or 65°C to 70°C, or 75°C, or 80°C. In an embodiment, the composition has a peel adhesion failure temperature (PA FT) greater than or equal to 45°C, or greater than or equal to 55°C, or greater than or equal to 60°C.

[0095] In an embodiment, the composition has a set time from 0.5 sec, or 1 .0 sec, or 1.5 sec, or 2.0 sec. to 3.0 sec, or 3.5 sec, or 4.0 sec, or 4.5 sec, or 4.9 sec, or 5.0 sec, or 6.0 sec, or 7.0 sec, or 8.0 sec, or 9.0 sec, or 9.5 sec, or 9.9 sec, or 10.0 sec.

[0096] In an embodiment, the composition has an open time from 20 sec, or 25 sec, or 27 sec, or 30 sec, or 35 sec, or 37 sec, or 39 sec.to 40 sec, or 45 sec, or 50 sec, or 60 sec. In a further embodiment, the composition has an open time of equal to or greater than 20 sec.

[0097] In an embodiment, the ratio of the density of the propylene-based interpolymer to the density of the ethylene-based polymer composition (the "density ratio") is from 0.90, or 0.91. or 0.92, or 0.93, or 0.94, or 0.95 to 0.96, or 0.97, or 0.98, or 0.99, or 1 .00, or 1 .01 , or 1 .02, or 1 .03, or 1 .04, or 1 .05, or 1 .06, or, 1 .07, or 1 .08, or 1 .09, or 1 .10, or 1 .20, or 1 .30. The density ratio is calculated in accordance with the Equation below:

[0098] In an embodiment, the ratio of the molecular weight distribution (Mw/Mn) of the propylene-based interpolymer to the molecular weight distribution of the ethylene-based polymer composition (the "molecular weight distribution ratio", or the "MWDp/M WDe ratio") is from 1.00, or 1 .10, or 1.15, or 1 .16 to 1.17, or 1.18, or 1 .19, or 1 .20, or 1 .21 , or 1.22, or 1 .23, or 1.24, or 1 .25, or 1 .26, or 1 .27, or 1 .28, or 1.29, or 1 .30, or 1 .35, or 1 .40. The MWDp/MWDe ratio is calculated in accordance with the Equation below:

[0099] In an embodiment, the composition has a density ratio from 0.90, or 0.93, or 0.95 to 1 .1 , or 1 .30 and a MWDp/MWDe ratio from 1.00, or 1 .10 to 1 .30, or 1 .40.

[00100] In an embodiment, the composition has a melt viscosity at 177°C from 300 mPa●s to 4,000 mPa●s; a fiber tear greater than 50% at a temperature from -40°C to 60°C; a fiber tear after aging for 24 hours at 177°C greater than 50% at a temperature from -40°C to 60°C; a PA FT from 40°C to 80°C; a set time less than or equal to 10 sec; an open time equal to or greater than 20 sec; a density ratio from 0.90, or 0.93 to 1 .30; and/or a MWDp/MWDe ratio from 1.00 to 1 .40.

[00101] Not wishing to be bound by any particular theory, Applicants believe that an ethylene- based polymer composition with a density from 0.880 g/cc to 0.930 g/cc and a broad molecular weight distribution (from greater than 1.25 to 3.00) results in improved compatibility between the propylene-based interpolymer and the ethylene-based polymer composition. The unexpected compatibility of the propylene-based inlerpolymer, and further the PBPE, and the ethylene-based polymer composition having a melt viscosity at 140°C of 1 0 1 ,000 mPa●s, the composition having a MWDp/MWDe ratio from 1 .00 to 1 .40 and a density ratio of 0.93 to 1 .30, is exemplified by the composition exhibiting sufficient adhesive performance (fiber tear greater than 50% at a temperature from -40°C to 60°C), as well as an open time greater than 20 sec. and a set time less than 10 sec. Applicants believe a MWDp/MWDe from 1 .00 to i .40,and further a broader ethylene-based polymer molecular weight distribution, results in improved homogenous distribution of the ethylene-based polymer in the propylene-basecl inlerpolymer.

[00102] The composition is prepared by blending the components in a melt at a temperature from 1 70°C to 190°C, or from 1 70°C to 1 80°C to form a homogeneous blend.

100103] In an embodiment, the composition is an adhesive composition, and further a hot melt adhesive (HMA) composition, which includes:

(A) from 50 wt% to 90 wt% propylene-based polymer, such as PBPE, having a density from 0.850 g/ce to 0.900 g/cc;

(B) from 1 wt% to 30 wt% ethylene-based polymer composition having: (i) a density from 0.880 g/cc to 0.930 g/cc; (ii) a melt viscosity at 140°C from 10 inPa●s to 1 ,000 mPa●s; and (i ii) a molecular weight distribution from greater than 1 .25 to 3.0;

(C) from 1 wt% to 49 wt% tackifier; and

(D) from 0 wt%, or 0. 1 wt% to 3 ,0 wt% antioxidant,

wherein the combined amount of (A) propylene-based inlerpolymer, (B) ethylene-based polymer, and (C) tackifier equals at least 95 wt% of the composition; the composition has a density ratio from 0.90, or 0.93 to 1 .30 and a MWDp/MWDe ratio from 1 .00 to 1 .40; and the composition has one, some, or al1 of the following properties:

(i) a melt viscosity at 1 77°C from 300 mPa●s to 4,000 mPa●s;

(i i) a fiber tear from greater than 50% to 1 00% at a temperature from -40°C to 60°C;

( iii) a fiber tear alter aging for 24 hours at 1 77°C from greater than 50% to 100% at a temperature from -40°C to 60°C;

(iv) a peel adhesion failure temperature (PAFT) from 40°C to 80°C;

(v) a set time from 0.5 seconds (sec.) to 10 sec.; and/or

(vi) an open time from 20 sec. to 60 sec.

(00104] In an embodiment, the composition is an adhesive composition, and further a hot melt adhesive (I IMA) composition, which includes:

(A) from 55 wt% to 90 wl% propylene-based polymer, such as PBPE, having a density from 0.860 g/cc to 0.900 g/cc; (B) from 1 wt% to 30 \vt% ethylenc-based polymer composition having: (i) a density from 0.880 g/cc to 0.930 g/cc; (ii) a melt viscosity at 140°C from 10 mPa●s to 500 mPa●s; and (iii) a molecular weight distribution from 1 .8 to 2.0;

(C) from 5 wt% to 30 wt% tackifier; and

(D) from 0. 1 wt% lo 1 .0 wt% antioxidant,

wherein the combined amount of (A) propylene-based interpolymer, (B) ethylenc-based polymer, and (C) tacki fier equals at least 97 wt% of the composition; the composition has a density ratio from 0.95 to 1 .0 and a MWDp/MWDe ratio from 1 .10 to 1 .30; and the composition has one. some, or all of the following properties:

(i) a melt viscosity at 177°C from 300 mPa●s to 2,000 mPa●s;

(ii) a fiber tear from greater than 55% to 100% at a temperature from -40°C to 60°C;

(iii) a fiber tear after aging for 24 hours at 177°C from greater than 55% to 100% at a temperature from -40°C to 60°C;

(iv) a peel adhesion failure temperature (PAFT) from 45°C to 80°C;

(v) a set time from 0.5 sec. to 9 sec; and/or

(vi) an open time from 25 sec. to 60 sec,

[00105] It is understood that the sum of the components (A)-(D) in each of the foregoing adhesive compositions yields 100 weight percent.

[00107] The composition may comprise two or more embodiments disclosed herein.

F. Article

[00107] The present disclosure provides an article. The article includes at least one component formed from the present composition. The composition can be any composition as disclosed above. In an embodiment, the composition is an HMA composition. Nonlimiting examples of suitable articles include HMA bonded cardboard packaging boxes, multilayer articles, wood articles and non-woven articles.

[00108] In an embodiment, that article includes a substrate. The composition is on at least one surface of the substrate. Nonlimiting examples of suitable substrates include film, sheets, fabric, cardboard and wood.

[00109] In an embodiment, the composition forms a seal between the at least one surface of the substrate and at least one surface of another substrate.

[00110] The present article may comprise two or more embodiments disclosed herein.

TEST METHODS

[00111] Density is measured in accordance with ASTM D792, Method B. The result is recorded in grams (g) per cubic centimeter (g/ec or g/cm 3 ). [00112] Drop point is measured in accordance with ASTM D 3954.

[001 13] Ring-and-ball softening point is measured using a Mettler Toledo FP900 Thermosystem according to ASTM E28.

[001 14] Melt viscosity was measured using a Brookfield Viscometer Model, and a Brookfield RV-DV-II-Pro viscometer spindle 3 1 , at 177°C for the PBPlv, at 177°C for the composition, at 140°C for the ethylene-based polymer composition, and at 1 90° for the tackifier. The sample was poured into the chamber, which was, in turn, inserted into a Brookfield Thermosel, and locked into place. The sample chamber has a notch on the bottom that fits the bottom of the Brookfield Thermosel, to ensure that the chamber is not al lowed to turn, when the spindle is inserted and spinning. The sample (approximately 8- 1 0 grams of resin) was heated to the required temperature until the melted sample was one inch below the lop of the sample chamber. The viscometer apparatus was lowered, and the spindle submerged into the sample chamber. Lowering was continued, until the brackets on the viscometer align on the Thermosel. The viscometer was turned on, and set to operate at a shear rate, which leads to a torque reading in the range of 40 to 60 percent of the total torque capacity, based on the rpm output of the viscometer. Readings were taken every minute for 15 minutes, or until the values stabi lize, at which point, a final reading was recorded.

[001 15[ Peel adhesion failure temperature (PA FT) was tested according to ASTM D 4498 with a 100 gram weight in the peel mode. The tests were started at room temperature (25°C/77°F) and the temperature was increased at an average rate of 0.5°C/minute. Samples for PA FT testing were prepared using two sheets of 40 pound Kraft paper, each of 6 x 12 in ( 152 x 305 mm) dimensions. On the bottom sheet, lengthwise and separated by a gap of 1 in (25 mm), were adhered in paral lel fashion two 1 .75 in or 2 in (45 mm or 5 1 mm) wide strips of a one sided, pressure-sensitive tape such as masking tape. The composition sample to be tested was heated to 1 77°C (350°F) and drizzled in an even manner down the center of the gap formed between the tape strips. Then, before the composition can unduly thicken, two glass rods, one rod riding immediately upon the tapes and shimmed on each side of the gap with a strip of the same tape followed by the second rod and (between the two rods) the second sheet of paper, were slid down the length of the sheets. This was done in a fashion such that the first rod evenly spreads the composition in the gap between the tape strips and the second rod evenly compresses the second sheet over the top of the gap and on top of the tape strips. Thus, a single 1 inch (25.4 mm) wide strip of sample composition was created between the two tape strips, and bonding the paper sheets. The sheets so bonded were cut crosswise into strips of width 1 inch (25.4 mm) and length of 3 inches (76.2 mm), each strip having a 1 x 1 in (25 x 25 mm) adhesive sample bond in the center. The strips were then employed in the PAFT testing, as desired.

[001 16] Differential Scanning Calorimetry (DSC) can be used to measure the melting, crystallization, and glass transition behavior of a polymer over a wide range of temperature. For example, the TA Instruments Q 1000 DSC, equipped with an RCS (refrigerated cool ing system) and an autosampler was used to perform this analysis. During testing, a nitrogen purge gas flow of 50 ml/min was used. Bach sample was melt pressed into a thin film at 190°C; the melted sample was then air-cooled to room temperature (25°C). A 5-8 mg, 6 mm diameter specimen was extracted from the cooled polymer, weighed, placed in a light aluminum pan (50 mg), and crimped shut. The sample pan was placed in a DSC cell, and then heated, at a rate of approximately 10°C/min, to a temperature of 1 80°C for PE (230°C for polypropylene or "PP"). The sample was kept at this temperature for 3 minutes in order to remove its thermal history. Then, the sample was cooled at a rate of 1 0°C/min to -60°C for PE (-40°C for PP), and kept isolhermally at that temperature for 3 minutes. The sample was next heated to 1 80°C (this is the "second heat" ramp) at a rate of 10°C/min, until complete melting (second heat). The cooling and second heating curves were recorded. The values determined are extrapolated onset of melting, T m , and extrapolated onset of crystallization, T c . Heat of fusion (H f ) (in Joules per gram), and the calculated % crystallinity for polyethylene samples using the Equation below:

% Crystallinity = ((H r )/292 J/g) x 100

[001 17] The heat of fusion (Fl ( ) and the peak melting temperature were reported from the second heat curve. Peak crystallization temperature was determined from the cool ing curve.

[001 18] Melting point, T m , was determined from the DSC heating curve by first drawing the baseline between the start and end of the melting transition. A tangent line was then drawn to the data on the low temperature side of the melting peak. Where this line intersects the baseline is the extrapolated onset of melting (T m ). This is as described in Bernhard Wunderlich, The Basis of Thermal Analysis, in Thermal Characterization of Polymeric Materials 92, 277- 278 (Edith A. Turi ed., 2d ed. 1997).

[00119] Crystallization temperature, T c , was determined from a DSC cooling curve as above except the tangent line was drawn on the high temperature side of the crystallization peak. Where this tangent intersects the baseline is the extrapolated onset of crystallization (T c ),

[00120] Glass transition temperature, T g , was determined from the DSC heating curve where half the sample has gained the liquid heat capacity as described in Bernhard Wunderlich, The Basis of Thermal Analysis, in Thermal Characterization of Polymeric Materials 92, 278-279 (Edith A. Turi ed., 2d ed. 1997). Baselines were drawn from below and above the glass transition region and extrapolated through the T g region. The temperature at which the sample heat capacity was half-way between these baselines is the T g .

[00121 ] A high temperature gel permeation chromatography (GPC) system, equipped with Robotic Assistant Deliver (RAD) system was used for sample preparation and sample injection. The concentration detector was an Infra-red detector (IR-5) from Polymer Char Inc. (Valencia, Spain). Data collection was performed using a Polymer Char DM i 00 Data acquisition box, The carrier solvent was 1 ,2,4-trichlorobenzenc (TCB). The system was equipped with an on-line solvent degas device from Agilent. The column compartment was operated at 1 50°C. The columns were four Mixed A LS 30 cm, 20 micron columns. The solvent was nitrogen-purged 1 ,2,4-trichlorobenzene (TCB) containing approximately 200 ppm 2,6-di-t-bulyl-4-melhylphenol (BH ' f). The flow rate was 1 .0 mL/min, and the injection volume was 200 μl. A "2 mg/mL " sample concentration was prepared by dissolving the sample in N 2 purged and preheated TCB (containing 200 ppm BH ' f), for 2.5 hours at 1 60°C, with gentle agitation.

[00122] The GPC column set was calibrated by running twenty narrow molecular weight distribution polystyrene standards. The molecular weight (MW) of the standards ranges from 580 g/mol to 8,400,000 g/mo1, and the standards were contained in six "cocktail" mixtures. Each standard mixture had at least a decade of separation between individual molecular weights. The equivalent polypropylene molecular weights of each PS standard were calculated by using fol lowing equation, with reported Mark-1 louwink coefficients for polypropylene ( T h.G. Scholte,

N.E.J. Meijerink, H.M. Schoffeleers, & A.M.G. Brands, J. Appl. Polym . Sci., 29, 3763 3782

( 1984)) and polystyrene (E.P. Otocka, R.J . Roe, N.Y. 1 lellman, & P.M. Muglia, Macromolecules, 4, 507 ( 1 971 )):

where M pp is PP equivalent MW, M PS is PS equivalent MW, log K and a values of Mark 1 louwink coefficients for PP and PS are l isted below.

[00123] A logarithmic molecular weight calibration was generated

polynomial fit as a function of elution volume. Number average and weight average molecular weights were calculated according to the following equations:

Z average molecular weight was calculated according to the fol lowing equation

where M is the molecular weight at a slice of i (elution component i), and Wf i is the weight fraction of the polymer chains having a molecular weight of M,.

[00124] For the ethylene-based polymers and the comparative waxes, the high temperature GPC method described above was modified. For the ethylene-based polymers and the comparative waxes, molecular weight and molecular weight distribution were characterized using an In fra-red detector (I R-5) from Polymer Char Inc. (Valencia, Spain). The system was equipped with a solvent delivery pump, an on-line solvent degas device, and a column oven from Agilent. The auto-sampler was model 1 12400. The column compartment and detector compartment were operated at 1 50°C. The columns were two PLgel Mixed-F, columns, 3 micron columns, from Agilent. The solvent was nitrogen-purged 1 ,2,4-trichlorobenzene (TCB) containing approximately 200 ppm 2,6-di-t-butyl-4-methylphenol (BUT). The flow rate was 0.7 mL/min, and the injection volume was 200 μΐ. A "2 mg/mL" sample concentration was prepared by dissolving the sample in N 2 purged and preheated TCB (containing 200 ppm BUT), for 0.5 hours at 1 50°C, with gentle agitation on the auto-sampler prior to injection. Calibration of the two Mixed-B column set was performed with live low molecular weight, narrow polydispersed polyethylene references (from Polymer Laboratories, now Agilent) and two saturated hydrocarbon monomers (Bicosane and Decane, from Aldrich). The molecular weights of the references ranged from 142 to 32,000 g/mo1. A third order polynomial was used to establish the molecular weight-elution volume calibration curve. The correlation coefficient is 0.9999, based on the r-square.

[00125] 13 C NMR was used for ethylene content, Koenig B-value, triad distribution, and triad tacticity and is performed as follows:

[00126] The samples were prepared by adding approximately 2.7g of a 50/50 mixture of tetrachloroethane-do/orthodichlorobenzene containing 0.025 M Cr(AcAc)3 to 0.20 0.3()g sample in a Norcll 1001 -7 1 0mm NMR tube. The samples were dissolved and homogenized by heating the tube and its contents to 1 50°C using a heating block and heat gun. Bach sample was visually inspected to ensure homogeneity.

[00127] The data was col lected using a Bruker 400 MHz spectrometer equipped with a Bruker Dual DUL high-temperature CryoProbe. The data was acquired using 320 transients per data file, a 6 sec. pulse repetition delay, 90° flip angles, and inverse gated decoupling with a sample temperature of I 20°C. All measurements were made on non-spinning samples in locked mode. Samples were allowed to thermally equilibrate for 7 minutes prior to data acquisition. Percent mm tacticity and wt% ethylene was then determined according to methods commonly used in the art.*

*Reierences:

For composition (wl% F): S. l)i Martino and M. Kclchtermans; J. Appl. Polym. Sci., V 56, 178 1 - 1 787 ( 1995)

Tacticity, detailed assignments: V. Busico, R. Cipullo; Prog. Polym. Sci. V 26, 443-533 (2001 )

The "Koenig B-value" or chi statistic is one measure of randomness or blockiness in a propylene ethylene random copolymer. A value of 1 .0 indicates a random copolymer and a value of zero indicates complete blocks of monomers A and B. A B-value of 2 indicates an alternating copolymer. B : | FP ]/(2[P |[ E]), where [ FP] is the total mole fraction of FP dimers (FP+PF, or (FFP+ PPF+PFP i- EPE)), and | F] is the mole fraction ethylene, and Jack F. Koenig, Spectroscopy of Polymers (2d ed. 1999).

Analysis ~ Total Unsaturation Per Mole Propylene

[00128] Samples were prepared by adding approximately 3.25g of a 50/50 m ixture of tetrachloroethane-d2/perchlorethylene that is 0.0015M in chromium acetylacetonale (relaxation agent) to 0.1 30g sample in a 10mm NM R tube. The samples were dissolved and homogenized by heating the tube and its contents to 1 1 0°C. The data was collected using a Brukcr 400 MHz spectrometer equipped with a Bruker Dual DIJL high-temperature CryoProbe. The unsaturation data was collected using 4 scans per data file, a 15.6 sec. pulse repetition delay with a sample temperature of I 20°C. The acquisition was carried out using spectral width of 10,000Hz and a file size of 16K. data points, The pre-saturation experiment was run with a modified pulse sequence, lc l prl2.zz l using 1 00 scans per data file.

Calculations

Moles of H from propylene Mol fraction propylene * (integral area δ 3.5

0.2ppm)

Mol % vinylidene unsaturation/mol propylene

Total mol % unsaturation/mol propylene

1 IT NMR Analysis Total Unsaturation Per 1, 000 Carbon Bonds

[00129] Samples were prepared by Ή NM R experimental procedures: samples were dissolved in NMR tubes to concentrations of approximately 0.05 g/mL. The solvent used was chlorolbrm- d with 0.02 M Cr(acae)j (chromium(III) acetylacetone) added. The tubes were then heated in a heating block set at 50°C. The samples were vortexed and heated to ensure homogeneous solutions were achieved. The Ή NMR was taken in a Vairan Inova 600MHz spectrometer equipped with an 8 mm inverse probe. The relaxation time used is 35sec., 90 deg pulse of 7.8 us, 64 scans. The spectra were centered at 4 ppm with spectral width of 1 6.7 ppm,

[00130] Fiber Tear (%) Percent fiber tear (FT) of compositions using Inland corrugated cardboard was determined according to a standardized method. A bead of sample composition was applied on to a cardboard coupon (5 x 6 cm) using an Olinger Bond Tester, and a second coupon was quickly placed on top of the sample composition. Light finger pressure, for about 3 sec, was applied to hold the bond in place. Ten samples of each composition were prepared.

[00131 ] Five samples of each composition were conditioned for at least 4 hours at room temperature and 50 % relative hum idity. The samples were pulled apart by hand and the failure mode (fiber tear, cohesive failure, adhesive failure) was recorded. The average of the five samples was calculated.

[00132] The other five samples of each composition were conditioned at a temperature of 177°C for 24 hrs. The samples were pul led apart by hand and the failure mode (fiber tear, cohesive- failure, adhesive failure) was recorded. The average of the five samples was calculated.

[00133] Set Time and Open Time properties were determined using the Olinger Bond Tester, a mechanical testing device used to form and tear test bonds. The Olinger Bond ' fester was heated to 350°C ( 177°C). The bottom substrate, 2.5" (63.5 mm) x 2" (50.8 mm) corrugated board, moved on a track under the adhesive pot which delivered a bead of polymer approximately 1 /16" ( 1 .6 mm) to 1 /8" (3.2 mm) wide, and 1 " (25.4 mm) long. The adhesive pot pressure was increased, or decreased, in order to maintain consistent bead size, A top substrate, 2.5" (63.5 mm) x 2" (50.8 mm), was applied to the bottom substrate, with a pressure of 2 bars. The Olinger has 2 timers, capable of measuring set-time and open-time potential to the nearest second.

[00134] Open Time measurement is the longest time period between adhesive application to one substrate, and the bonding with a second substrate, that results in a 75% fiber-tearing bond. For testing, compression time (or set time) was set to the time determined by set time measurement to achieve 100% fiber tear. Open time was set at 10 sec. and increased in 10 sec. intervals until less than 50% fiber tear was achieved. The open time was decreased by 5 sec and % fiber tear determined. Finally, open time was changed by 1 sec. interval to determine the maximum allowable time to achieve 75% or greater fiber tear.

[00135] Set Time measurement.— is the minimum compression time required to achieve a fiber- tearing bond. For testing, open time was set at 2 sec. A bond was formed as the top substrate was compressed onto the bottom substrate. After a preset compression time, a tear test was executed as the top substrate was pulled from the bottom substrate. A visual assessment was then made to determine the percentage of liber tear achieved under the preset test conditions. The set time was changed in 1 see. intervals, determining the time to achieve 100% fiber tear and less than 75% fiber tear. The set time was recorded as the shortest time, to the nearest second, at which a minimum of 75%) fiber tear was obtained.

[00136] By way of example, and not limitation, some embodiments of the present disclosure will now be described in detail in the following Examples.

EXAMPLES

Preparation of PBPE

[00137] A propylene-based interpolymer (for example, a PBPE) was produced utilizing Catalyst A, a hafnium metal complex of a polyvalent aryloxyether catalyst, fable 1 below provides the name and structure for Catalyst A.

[00138] The PBPE was made according to the following procedure. Catalyst A and cocatalyst component solutions were metered using pumps and mass flow meters and were combined with the catalyst flush solvent and introduced into the bottom of the reactor. The cocatalyst used was a long-chain alkyl ammonium borate of approximate stoichiometry equal to methyl di(octadecyl)ammonium tetrakis(pentafluorophenyI)borate (MDB) combined with a tertiary component, tri(isobutyl)aluminum modi fied methalumoxane (MMAO) containing a molar ratio of i-butyl/methyl groups of 1 /3. For Catalyst A, the cocatalyst was in a molar ratio based on Hf of 1 .2/1 , and MMAO (25/ 1 Al/l l l).

[00139] The polymerization process was exothermic. About 900 British thermal units (BTUs) were released per pound (2009 kJ/kg) of propylene polymerized and about 1 ,500 BTUs released per pound (3489 kJ/kg) of ethylene polymerized. The primary process design consideration was the removal of the heat of reaction. The propylene-ethylene (P-E) copolymers were produced in a low-pressure, solution polymerization loop reactor, made up of a 3 inch (76mm) loop pipe plus two heat exchanges, the total volume of which is 31 .4 gallons ( 1 1 8.9 liter). Solvent and monomer (propylene) were injected into the reactor as a liquid. The comonomcr (ethylene) gas was fully dissolved in the liquid solvent. The feed was cooled to 5°C before injection into the reactor. The reactor operated at polymer concentration from 1 5 wt % to 20 wt %. The adiabatic temperature rise of the solution accounted for some of the heat removal from the polymerization reaction. Heat exchangers within the reactor were utilized to remove the remaining heat of reaction allowing for reactor temperature control at the reaction temperatures.

[00140] The solvent used was a high purity iso-paraffinic fraction available from Exxon under the trademark Isopar E. Fresh propylene was passed through a bed of Selexsorb COS for puri fication before mixing with a recycle stream containing solvent, propylene, ethylene, and hydrogen. After mixing with the recycle stream, the combined stream was passed through a bed of 75 wt % Molecular Sieve 13X and 25 wt % Selexsorb CD for further puri fication before using a high pressure 700 psig (4826 kPa) feed pump to pass the contents to the reactor. Fresh ethylene was passed through a Selexsorb COS bed for puri fication before compressing the stream to 750 psig (5 1 71 kPa). Hydrogen (a telogen used to reduce molecular weight) was mixed with the compressed ethylene before the two were mixed/dissolved into the liquid feed. The total stream was cooled to an appropriate feed temperature (5"C). The reactor operated at 500 525 psig

(3447-3619 kPa) and the control temperature is reported in T able 1 A. The propylene conversion in the reactor was maintained by controlling the catalyst injection rate. The reaction temperature was maintained by controlling the water temperature across the shell side of the heat exchanger at 85°C. The residence time in the reactor was short ( 1 0 minutes). The propylene conversion per reactor pass is reported in Table 1 A.

[00141 ] Upon exiting the reactor, water and additive were injected into the polymer solution. The water hydrolyzes the catalyst, terminating the polymerization reaction. The additives consist of antioxidants, i.e., 500 ppm of a phenolic and 1 000 ppm of a phosphite, which remained with the polymer and acted as stabilizers to prevent polymer degradation while in storage before subsequent fabrication at an end-user's facility. The post-reactor solution was super-heated from reactor temperature to 230°C in preparation for a two-stage devolalilization. The solvent and unreacted monomers were removed during the devolalilization process. The polymer melt was pumped to a die for underwater pellet cutting.

[00142] Solvent and monomer vapors exiting the top of the devolatilizers were sent to a coalcscer. The coalescer removes polymer entrained in the vapor during devolalilization. The clean vapor stream leaving the eoalescer was partially condensed through a series of heat exchangers. The two-phase mixture entered a separation drum . The condensed solvent and monomers were purified (this is the recycle stream described above) and re-used in the reaction process. The vapors leaving the separating drum, mostly containing propylene and ethylene, were sent to a block flare and burned.

[00143] The process conditions for the PB PH produced by the foregoing process are provided in ' fable 1 A below, and the properties are provided in Table 2 below.

[00144] Isotacticty in ' fable 2 was determ ined with ' 'C NM R. ' Fhe samples were prepared by adding approximately 2.6g of a 50/50 mixture of tetrachloiOethane-d2/orthodichlorobenzene that is 0.025M in chromium acetylacetonate (relaxation agent) to a 0.2g sample in a 10mm NM R lube. The samples were dissolved and homogenized by heating the tube and its contents to 1 50°C. ' fhe data was collected using a Bruker 400 MHz spectrometer equipped with a Bruker Dual DUL high-temperature CryoProbe. The data was acquired using 160 scans per data fi le, a 6 sec. pulse repetition delay with a sample temperature of 120°C. The acquisition was carried out using spectral width of 25,000Hz and a file size of 32K data points.

2. Production of compositions

[00145] The properties of the ethylene-based polymers and the comparative waxes are provided in Table 3 below. The term "ND" denotes "not detectable."

[00146] The starting materials from Tables 2 and 3, a tacki fier, and an antioxidant were weighed and then blended at 1 77°C for 30 min at 1 00 rounds per minute (rpm) using a smal l bowl I laake blender. No visual separation was detected for any of the compositions. The compositions and their application performance data are provided in ' fable 4 below. The term "CS" denotes "comparative sample."

[00147] ' fable 4 shows inventive compositions containing the present ethyienc-based polymer composition, a PBPE and a tacki fier that have a density ratio from 0.93 to 1 .30 and a MWDp/MWDe ratio from 1 .00 to 1 .40 (Ex. 1 , Ex. 2, Ex. 3) unexpectedly exhibit adhesive properties comparable to compositions with a density ratio of less than 0.93 (CS 1 , CS 2, CS 3), such as a ΡAFΤ greater than 45°C, while also exhibiting excellent (i.e., long) open times of greater than 25 sec. Further, the inventive compositions (Ex. 1 , Ex. 2, Ex. 3) exhibit adhesive properties comparable to compositions containing a PBPE, tackifier, and a propylene-based polymer (PI 5 6 102) (CS 4), such as a fiber tear greater than 55% at a temperature from -40°C to 60°C. Ex. 1 , Ex. 2, and Ex. 3 are suitable for packaging applications. In contrast, compositions containing a PBPE and a Fischer-Tropsch wax (1 11 ) (CS 5) exhibit a fiber tear less than 50% at a temperature from -40°C to 60°C and an open time less than 25 sec, indicating CS 5 is unsuitable for packaging applications.

[00148] It is specifically intended that the present disclosure nol be limited to the embodiments and illustrations contained herein, but include modi fied forms of those embodiments including portions of the embodiments and combinations of elements of di fferent embodiments as come within the scope of the following claims.