Composition for Odor Suppression

Abstract

The present disclosure provides a composition. In an embodiment, the composition includes an olefin-based polymer and from 0.15 wt % to 15 wt % of an odor suppressant. The odor suppressant includes (i) from 0.05 wt % to 2 wt % of a metal oxide having a band gap greater than 5.0 electron volts (eV), and (ii) from 0.1 wt % to 13 wt % of an acid copolymer. The ratio of metal oxide to acid copolymer is from 1:20 to 1:1. Weight percents are based on the total weight of the composition.

Claims

1. A composition comprising: an ethylene-based polymer; from 0.15 wt % to 15 wt % of an odor suppressant based on total weight of the composition, the odor suppressant comprising (i) from 0.05 wt % to 2 wt % based on the total weight of the composition of a metal oxide having a band gap greater than 5.0 electron volts (eV); and (ii) from 0.1 wt % to 13 wt % based on the total weight of the composition of an acid copolymer composed of (i) ethylene monomer and (ii) a carboxylic acid comonomer or ester derivative thereof; and the ratio of metal oxide to acid copolymer is from 1:20 to 1:1.

2. The composition of claim 1 wherein the composition exhibits at least a 20% reduction in a volatile hetero-carbonyl species compared to the olefin-based polymer without the odor suppressant, as measured by normalized gas chromatography.

3. The composition of claim 1 wherein the metal oxide is selected from the group consisting of calcium oxide and magnesium oxide.

4. The composition of claim 1 wherein the acid polymer is selected from the group consisting of, ethylene ethyl acrylate copolymer, ethylene butyl acrylate copolymer, ethylene acrylic acid copolymer, ethylene/(meth)acrylic acid copolymer, and combinations thereof.

5. The composition of claim 1 wherein the odor suppressant is a blend of the metal oxide particles dispersed in the acid copolymer.

6. The composition of claim 1 wherein the composition comprises an ethylene-based polymer; from 0.55 wt % to 5 wt % of an odor suppressant based on total weight of the composition, the odor suppressant comprising (i) from 0.05 wt % to 1 wt % based on total weight of the composition of a metal oxide having a band gap greater than 5.0 electron volts (eV); and (ii) from 0.5 wt % to 4 wt % based on total weight of the composition of an acid copolymer; and the ratio of metal oxide to acid copolymer is from 1:4 to 1:1.

7. The composition of claim 1 wherein the metal oxide is particles of calcium oxide.

8. The composition of claim 1 wherein the acid copolymer is ethylene acrylic acid.

9. A process comprising: providing an ethylene-based polymer, the ethylene-based polymer having an amount of at least one volatile carbonyl-containing species; adding to the ethylene-based polymer from 0.15 wt % to 15 wt % of an odor suppressant comprising (i) from 0.05 wt % to 2 wt % of a metal oxide having a band gap greater than 5.0 electron volts (eV); and (ii) from 0.1 wt % to 13 wt % of an acid copolymer composed of (i) ethylene monomer and (ii) a carboxylic acid comonomer or ester derivative thereof, the ratio of metal oxide to acid copolymer is from 1:20 to 1:1; and neutralizing, with the odor suppressant, at least some of the volatile hetero-carbonyl species to form an odor-reduced composition and weight percents are based on total weight of the odor-reduced composition.

10. The process of claim 9 comprising forming an odor-reduced composition exhibiting at least a 20% reduction in the amount of a volatile hetero-carbonyl species compared to the ethylene-based polymer without the odor suppressant, as measured by normalized gas chromatography.

11. The process of claim 9 comprising dispersing, before the adding, particles of the metal oxide in the acid copolymer to form an odor suppressant pre-blend; adding the odor suppressant pre-blend to the ethylene-based polymer; and forming the odor-reduced composition.

Description

BRIEF DESCRIPTION OF THE DRAWING

[0042] FIG. 1 is a schematic representation of a tray of water samples identified with random three digit codes for presentation to sensory panelists in accordance with an embodiment of the present disclosure.

DETAILED DESCRIPTION

[0043] The present disclosure provides a composition. In an embodiment, a composition for suppressing odors is provided and includes an olefin-based polymer and an odor suppressant. The composition includes from 0.15 wt % to 15 wt % of the odor suppressant based on total weight of the composition. The odor suppressant includes (i) from 0.05 wt % to 2 wt % based on total weight of the composition of a metal oxide having a band gap greater than 5.0 electron volts (eV). The odor suppressant further includes (ii) from 0.1 wt % to 13 wt % based on total weight of the composition of an acid copolymer. The ratio of metal oxide to acid copolymer is from 1:20 to 1:1.

[0044] A. Olefin-Based Polymer

[0045] The present composition includes an olefin-based polymer. The olefin-based polymer includes an amount of at least one volatile hetero-carbonyl species. It is understood the olefin-based polymer may contain two, three, four or more different volatile hetero-carbonyl species. In an embodiment, the olefin-based polymer is a propylene-based polymer, an ethylene-based polymer, or combinations thereof. Nonlimiting examples of propylene-based polymer include propylene copolymer, propylene homopolymer, and combinations thereof. In an embodiment, the propylene-based polymer is a propylene/α-olefin copolymer. Nonlimiting examples of suitable α-olefins include C.sub.2 and C.sub.4-C.sub.20 α-olefins, or C.sub.4-C.sub.10 α-olefins, or C.sub.4-C.sub.8 α-olefins. Representative α-olefins include ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene.

[0046] In an embodiment, the propylene/α-olefin copolymer is a propylene/ethylene copolymer containing greater than 50 wt % units derived from propylene, or from 51 wt %, or 55 wt %, or 60 wt % to 70 wt %, or 80 wt %, or 90 wt %, or 95 wt %, or 99 wt % units derived from propylene, based on the weight of the propylene/ethylene copolymer. The propylene/ethylene copolymer contains a reciprocal amount of units derived from ethylene, or from less than 50 wt %, or 49 wt %, or 45 wt %, or 40 wt % to 30 wt %, or 20 wt %, or 10 wt %, or 5 wt %, or 1 wt %, or 0 wt % units derived from ethylene, based on the weight of the propylene/ethylene copolymer.

[0047] In an embodiment, the olefin-based polymer is an ethylene-based polymer. The ethylene-based polymer can be an ethylene homopolymer or an ethylene/α-olefin copolymer.

[0048] In an embodiment, the ethylene-based polymer is an ethylene/α-olefin copolymer. Nonlimiting examples of suitable α-olefins include C.sub.3-C.sub.20 α-olefins, or C.sub.4-C.sub.10 α-olefins, or C.sub.4-C.sub.8 α-olefins. Representative α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene.

[0049] In an embodiment, the ethylene/α-olefin copolymer is an HDPE that is an ethylene/C.sub.4-C.sub.8 α-olefin copolymer. The HDPE has one, some, or all of the following properties:

[0050] (i) a density from 0.940 g/cc to 0.960 g/cc; and/or

[0051] (ii) a Tm from 128° C. to 132° C.; and/or

[0052] (iii) a melt index from 0.5 g/10 min to 2.0 g/10 min.

[0053] A nonlimiting example of a suitable HDPE is DMDA-1250 available from The Dow Chemical Company.

[0054] In an embodiment, the ethylene/α-olefin copolymer is an LDPE having one, some, or all of the following properties:

[0055] (i) a density from 0.910 to 0.920 g/cc; and/or

[0056] (ii) a Tm from 105° C. to 110° C.; and/or

[0057] (iii) a melt index from 5.0 g/10 min to 10.0 g/10 min.

[0058] A nonlimiting example of a suitable LDPE is LDPE 722 available from The Dow Chemical Company.

[0059] B. Odor Suppressant

[0060] The present composition includes an odor suppressant. The odor suppressant is a blend of metal oxide (Bi) and an acid copolymer (Bii).

[0061] B(i) Metal Oxide

[0062] The odor suppressant includes metal oxide. The metal oxide has a band gap greater than 5.0 electron volts (eV). A “band gap,” as used herein, is an energy range in a solid where no electron states exist. The band gap is the energy required to promote a valence electron to a conduction electron, which is free to move within the crystal lattice and serve as a charge carrier to conduct electric current. An “electron volt” or “eV,” is a unit of energy equal to approximately 1.6×10.sup.−19 joules. Band gap for metal oxides are described in detail in Surface and Nanomolecular Catalysis, Ryan Richards (ed), Taylor & Francis 2006, the contents of which are incorporated by reference herein.

[0063] Bounded by no particular theory, it is believed that a large band gap (i.e., greater than 5.0 eV) translates to a bond with very little covalent character in which electrons are shared disproportionately. This may result in metal ions in the lattice with a net positive charge and oxide ions with a net negative charge. The magnitude of the charge can therefore be proportional to the band gap. The electron-starved metal ions may consequently be free to act as Lewis acids, accepting electrons from slightly basic moieties present in the volatile hetero-carbonyl odorant molecules. Additionally, the crystalline oxide ions may be able to act as Lewis bases donating electrons into slightly acidic moieties in the volatile hetero-carbonyl odorant molecules.

[0064] Table A below provides band gap values for several metal oxides from Surface and Nanomolecular Catalysis, Ryan Richards (ed), Taylor & Francis 2006.

TABLE-US-00001 TABLE A Band gap thresholds for some metal oxides Metal oxide Band gap (eV) MgO 7.7 CaO 6.9 SrO 5.3 BaO 4.4 ZnO ~3.2 TiO.sub.2 ~3.2 Al.sub.2O.sub.3 ~7 CuO 1.2 Cu.sub.2O 2.1

[0065] In an embodiment, the metal oxide is in the form of particles (powder), has a band gap greater than 5.0 eV and the metal oxide is selected from calcium oxide (CaO), magnesium oxide (MgO), strontium oxide (SrO), aluminum oxide Al.sub.2O.sub.3, and combinations thereof.

[0066] In an embodiment, the metal oxide is in the form of particles (powder) and has a band gap greater than 6.0 eV. In a further embodiment, the metal oxide is selected from calcium oxide (CaO), magnesium oxide (MgO), and combinations thereof. In yet a further embodiment, the metal oxide is calcium oxide (CaO).

[0067] In an embodiment, the metal oxide is calcium oxide (6.9 eV), in the form of particles (powder), the calcium oxide powder having a D50 particle size from 100 nm, or 125 nm, or 150 nm to 250 nm, or 500 nm, or 1000 nm, or 3000 nm. In a further embodiment, the calcium oxide powder has a D50 from 100 nm to 3000 nm, or from 125 nm to 1000 nm, or from 150 nm to 500 nm, or from 175 nm to 250 nm, or from 125 to 160 nm, or from 150 to 160 nm.

[0068] In an embodiment, the metal oxide is hygroscopic and includes surface bound moisture. In a further embodiment, the metal oxide is CaO.H.sub.2O.

[0069] B(ii) Acid Copolymer

[0070] The odor suppressant includes an acid copolymer along with the metal oxide. The term “acid copolymer,” (or “AC”) as used herein, is a copolymer containing (i) ethylene monomer and (ii) a carboxylic acid comonomer or ester derivative thereof (hereafter referred to as “acid comonomer”). The acid copolymer contains the acid comonomer in an amount from 1 wt %, or 5 wt %, or 10 wt %, or 15 wt % to 20 wt %, or 25 wt %, or 30 wt % and a reciprocal wt % amount of ethylene monomer. It is understood that the acid copolymer contains greater than 50 wt %, or greater than 60 wt % ethylene monomer. In a further embodiment, the acid copolymer includes from 1 wt % to 30 wt % acid comonomer (and reciprocal amount ethylene), or from 5 wt % to 30 wt % acid comonomer (and reciprocal amount ethylene), or from 10 wt % to 25 wt % acid comomomer (with reciprocal amount of ethylene), or from 15 wt % to 20 wt % acid comonomer (and reciprocal amount ethylene), or from 5 wt % to 10 wt % acid comonomer (with reciprocal amount ethylene).

[0071] In an embodiment, the acid comonomer is an acrylate-based moiety. Nonlimiting examples of suitable acid copolymers wherein the acid comonomer is an acrylate-based moiety include ethylene ethyl acrylate copolymer (EEA), ethylene butyl acrylate copolymer (EBA), ethylene acrylic acid copolymer (EAA), ethylene/(meth)acrylic acid copolymer (EMA), and combinations thereof.

[0072] In an embodiment, the acid copolymer is an ethylene/acrylic acid copolymer having from 5 wt % to 30 wt % acrylic acid comonomer. Nonlimiting examples of suitable acid copolymers include Nucrel® polymers, available from E. I. du Pont de Nemours and Company (Wilmington, Del.).

[0073] In an embodiment, the odor suppressant is a pre-blend of the metal oxide powder dispersed in the acid copolymer. Mechanical blending and/or melt blending can be used to homogeneously disperse the metal oxide particles throughout the acid copolymer. The pre-blend that is the odor suppressant is subsequently added to the olefin-based polymer (A).

[0074] C. Composition

[0075] In an embodiment, the present composition includes (A) from 85 wt % to 99.85 wt % of the olefin-based polymer and (B) from 15 wt %, or 13 wt %, or 11 wt %, or 10 wt %, or 9 wt %, or 7 wt %, or 5 wt % to 2 wt %, or 1 wt %, or 0.6 wt %, or 0.5 wt %, or 0.3 wt %, or 0.2 wt %, or 0.15 wt % of the odor suppressant. The odor suppressant is mixed, or otherwise is blended, into the olefin-based polymer matrix. The odor suppressant contains (i) from 0.05 wt %, or 0.1 wt %, or 0.15 wt %, or 0.2 wt %, or 0.25 wt %, or 0.3 wt %, or, 0.4 wt %, or 0.5 wt %, or 0.7 wt %, or 0.9 wt % to 1.0 wt %, or 1.5 wt %, or 2 wt % of particles of the metal oxide (with band gap greater than 5.0 eV); and (ii) from 0.1 wt %, or 0.5 wt %, or 1.0 wt %, or 3 wt %, or 4 wt. %, or 5 wt %, or 7 wt %, or 9 wt % to 10 wt %, or 11 wt %, or 13 wt % of the acid copolymer. Weight percents are based on total weight of the composition. The ratio of metal oxide to acid copolymer is from 1:20, or 1:15, or 1:10, or 1:8, or 1:6 to 1:4, or 1:2, or 1:1. The composition exhibits at least a 5% reduction in at least one volatile hetero-carbonyl species compared to the olefin-based polymer without the odor suppressant (i.e., the olefin-based polymer (A) alone).

[0076] The reduction in volatile hetero-carbonyl species is a quantitative comparison of (i) the amount of a pre-determined volatile hetero-carbonyl species present in the neat olefin-based polymer (i.e., the olefin-based polymer (A) without any odor suppressant) to (ii) the amount of the pre-determined volatile hetero-carbonyl species in the present composition composed of (A) the olefin-based polymer and (B) the odor suppressant. The reduction in volatile hetero-carbonyl species is measured by normalized gas chromatography as previously disclosed herein.

[0077] A “volatile hetero-carbonyl species,” as used herein, is a hydrocarbon compound having from 1 carbon atom to 16 carbon atoms (i) and contains at least one heteroatom selected from S, O, N, and/or P, (ii) and has a molecular weight from 30 Daltons to 250 Daltons, (iii) and has a vapor pressure greater than 0.01 millimeters mercury (mm Hg) at standard temperature and pressure, or “STP.” In an embodiment, the volatile hetero-carbonyl species has a C—O bond and/or a C═O bond. Nonlimiting examples of volatile hetero-carbonyl species include volatile C.sub.1-C.sub.16 aldehydes, volatile C.sub.1-C.sub.16 ketones, volatile C.sub.1-C.sub.16 carboxylic acids, volatile C.sub.1-C.sub.16 esters, volatile C.sub.1-C.sub.16 alcohols, volatile C.sub.1-C.sub.16 ethers and combinations thereof.

[0078] Nonlimiting examples of volatile C.sub.1-C.sub.16 aldehydes include formaldehyde, acetalaldehyde, propanal, hexanal, furfural, heptanal, benzaldehyde, octanal, nonanal, decanal, undecanal, and combinations thereof.

[0079] Nonlimiting examples of volatile C.sub.3-C.sub.16 ketones include 2-pentanone, 2-hexanone, 2-octanone, 2-nonanone, 2-decanone, 2-acetophenone, 2-undecanone, and combinations thereof.

[0080] Nonlimiting examples of volatile C.sub.1-C.sub.16 carboxylic acids include hexanoic acid, butyric acid, heptanoic acid, octanoic acid, benzoic acid, nonanoic acid, decanoic acid, and combinations thereof.

[0081] Nonlimiting examples of volatile C.sub.1-C.sub.16 alcohols include methanol, ethanol, propanol, 2-methyl butanol, and combinations thereof.

[0082] Nonlimiting examples of volatile C.sub.1-C.sub.16 ethers include tetrahydrofuran (THF) and alkyl derivatives thereof.

[0083] In an embodiment, the composition includes (A) an olefin-based polymer that is an ethylene-based polymer. The ethylene-based polymer contains an amount of at least one volatile hetero-carbonyl species. The composition includes (B) from 0.55 wt % to 5 wt % of the odor suppressant based on total weight of the composition. The odor suppressant includes (Bi) from 0.05 wt % to 1 wt % of a metal oxide having a band gap greater than 5.0 electron volts (eV) that is particles of CaO, (Bii) from 0.5 wt % to 4 wt % based on total weight of the composition of an acid copolymer; and the ratio of metal oxide to acid copolymer is from 1:4 to 1:1. The composition exhibits at least a 5% reduction in at least one volatile hetero-carbonyl species compared to the olefin-based polymer (A) without the odor suppressant as measured by normalized gas chromatography.

[0084] In an embodiment, the composition includes (A) from 97 wt % to 98.9 wt % of an olefin-based polymer that is an ethylene-based polymer. The ethylene-based polymer contains an amount of at least one volatile hetero-carbonyl species. The composition includes from 3 wt %, or 2.8 wt % to 1.1 wt % of the odor suppressant wherein the odor suppressant contains (Bi) metal oxide that is particles of CaO in an amount from 0.01 wt %, or 0.05 wt %, or 0.07 wt % to 0.5 wt %, or 0.7 wt %, or 0.9 wt % and (Bii) acid copolymer that is an ethylene/acrylic acid copolymer in an amount from 0.1, or 0.2, or 0.5, or 0.7, or 0.9 to 1.0, or 1.3, or 1.5, or 1.7, or 1.9 and the ratio of metal oxide to acid copolymer is from 1:10, or 1:8, or 1:6 to 1:4, or 1:2, or 1:1. Weight percents are based on the total weight of the composition. The composition exhibits at least a 20% reduction in at least one volatile hetero-carbonyl species compared to the olefin-based polymer (A) without the odor suppressant. The reduction in volatile hetero-carbonyl species is measured by normalized gas chromatography.

[0085] In an embodiment, the composition includes (A) from 99.8 wt % to 99.85 wt % of an olefin-based polymer that is an ethylene-based polymer. The ethylene-based polymer contains an amount of at least one volatile hetero-carbonyl species. The composition includes from 0.2 wt % to 0.15 wt % of the odor suppressant wherein the odor suppressant contains (Bi) metal oxide that is particles of CaO in an amount from 0.05 wt %, or 0.06 wt % to 0.08 wt %, or 0.1 wt %, and (Bii) acid copolymer that is an ethylene/acrylic acid copolymer in an amount from 0.1 wt %, or 0.12 wt % to 0.15 wt %, or 0.18 wt % and the ratio of metal oxide to acid copolymer is from 1:4 to 1:2 and is hereafter referred to as composition1. Weight percents are based on total weight of the composition. Composition1 exhibits from 20% to 25% reduction in at least one volatile hetero-carbonyl species compared to the olefin-based polymer (A) without the odor suppressant. The reduction in volatile hetero-carbonyl species is measured by normalized gas chromatography.

[0086] In an embodiment, composition1 includes (A) 98.92 wt % ethylene-based polymer and 0.18 wt % of the odor suppressant. The odor suppressant contains (Bi) metal oxide that is particles of CaO in an amount of 0.06 wt % and (Bii) acid copolymer that is an ethylene/acrylic acid copolymer in an amount of 0.12 wt %, and the ratio of metal oxide to acid copolymer is 1:2. Composition1 exhibits a 20% reduction in propanal compared to the amount of propanal present in the olefin-based polymer (A) alone over an exposure period of 20 hours. The percent reduction in propanal is measured by normalized gas chromatography.

[0087] In an embodiment, the composition includes (A) from 98.5 wt % to 99.0 wt % of an olefin-based polymer that is an ethylene-based polymer. The ethylene-based polymer contains an amount of at least one volatile hetero-carbonyl species. The composition includes from 1.5 wt %, or 1.3 wt % to 1.1 wt %, or 1.0 wt % of the odor suppressant wherein the odor suppressant contains (Bi) metal oxide that is particles of CaO in an amount from 0.05 wt %, or 0.08 wt % to 0.1 wt %, or 0.13 wt %, or 0.15 wt % and (Bii) acid copolymer that is an ethylene/acrylic acid copolymer in an amount from 1.0 wt %, or 1.1 wt % to 1.2 wt %, or 1.3 wt % and the ratio of metal oxide to acid copolymer is from 1:15, or 1:12 to 1:10, or 1:8 and is hereafter referred to as composition2. Weight percents are based on total weight of the composition. Composition2 exhibits from 25% to 30% reduction in at least one volatile hetero-carbonyl species compared to the olefin-based polymer (A) without the odor suppressant. The reduction in volatile hetero-carbonyl species is measured by normalized gas chromatography.

[0088] In an embodiment, composition2 includes (A) 98.9 wt % ethylene-based polymer and 1.1 wt % of the odor suppressant. The ethylene-based polymer contains an amount of at least one volatile hetero-carbonyl species. The odor suppressant contains (Bi) metal oxide that is particles of CaO in an amount of 0.1 wt % and (Bii) acid copolymer that is an ethylene/acrylic acid copolymer in an amount of 1.0 wt %, and the ratio of metal oxide to acid copolymer is 1:10. Composition2 exhibits a 28% reduction in propanal compared to the amount of propanal present in the olefin-based polymer (A) alone over an exposure period of 20 hours. The percent reduction in propanal is measured by normalized gas chromatography.

[0089] In an embodiment, the composition includes (A) from 94 wt % to 96 wt % of an olefin-based polymer that is an ethylene-based polymer. The composition includes from 6 wt % to 4 wt % of the odor suppressant wherein the odor suppressant contains (Bi) metal oxide that is particles of CaO in an amount from 0.8 wt % to 1.0 wt %, or 1.2 wt % and (Bii) acid copolymer that is an ethylene/acrylic acid copolymer in an amount from 3.0 wt % to 5.0 wt % and the ratio of metal oxide to acid copolymer is from 1:3 to 1:5 and is hereafter referred to as composition3. Weight percents are based on total weight of the composition. Composition3 exhibits from 28% to 32% reduction in at least one volatile hetero-carbonyl species compared to the olefin-based polymer (A) without the odor suppressant. The reduction in volatile hetero-carbonyl species is measured by normalized gas chromatography.

[0090] In an embodiment, composition3 includes (A) 95 wt % ethylene-based polymer and 5 wt % of the odor suppressant. The odor suppressant contains (Bi) metal oxide that is particles of CaO in an amount of 1.0 wt % and (Bii) acid copolymer that is an ethylene/acrylic acid copolymer in an amount of 4.0 wt %, and the ratio of metal oxide to acid copolymer is 1:4. Composition3 exhibits a 30% reduction in propanal compared to the amount of propanal present in the olefin-based polymer (A) alone over an exposure period of 20 hours. The percent reduction in propanal is measured by normalized gas chromatography.

[0091] D. Applications

[0092] The present composition may be used in any application wherein a polymeric material, and an olefin-based polymer in particular, is exposed to volatile hetero-carbonyl species. Nonlimiting examples of suitable applications for the present composition include trash liners, fabrics used in clothing, automotive interiors, and food packaging such as caps & closures, bottles, and wraps.

[0093] Surprisingly, the present composition (i.e., composition1 and/or composition2 and/or composition3) exhibits the same, or better, odor suppression capability without compromising processability and without compromising film properties. Applicant discovered the metal oxide with band gap of greater than 5.0 eV works synergistically with the acid copolymer to improve odor suppression with less total metal oxide (and less CaO in particular) compared to polymer matrix systems containing metal oxide only. The ability of acid copolymer to synergistically improve odor suppression when combined with metal oxide with band gap of greater than 5.0 eV (and CaO in particular) is unexpected.

[0094] The present disclosure provides a process. In an embodiment, the process includes providing an olefin-based polymer (A). The olefin-based polymer (A) has an amount of at least one volatile hetero-carbonyl species. The process includes adding to the olefin-based polymer (A) from 0.15 wt % to 15 wt % of an odor suppressant (B). The odor suppressant (B) includes (Bi) from 0.05 wt % to 2 wt % of a metal oxide having a band gap greater than 5.0 electron volts (eV), and (Bii) from 0.1 wt % to 13 wt % of an acid copolymer, the ratio of metal oxide to acid copolymer is from 1:20 to 1:1. The process includes neutralizing, with the odor suppressant, at least some of volatile hetero-carbonyl species in olefin-based polymer (A) to form an odor-reduced composition. Weight percents are based on total weight of the odor-reduced composition.

[0095] In an embodiment, the process includes forming an odor-reduced composition exhibiting at least a 20% reduction in the amount of a volatile hetero-carbonyl species compared to the olefin-based polymer (A), as measured by normalized gas chromatography.

[0096] In an embodiment, the process includes dispersing, before the adding, particles of the metal oxide in the acid copolymer to form an odor suppressant pre-blend. The process includes adding the odor suppressant pre-blend to the olefin-based polymer (A) to form the odor-reduced composition.

[0097] By way of example, and not limitation, some embodiments of the present disclosure will now be described in detail in the following Examples.

Examples

[0098] Materials used in the examples are provided in Table 1 below.

TABLE-US-00002 TABLE 1 Material Material/Description Abbreviation Properties Source DMDA-1250 PE1 HDPE, ethylene/octene copolymer; The Dow (HDPE) density = 0.955 g/cc; MI 1.5 g/10 min, Chemical Tm = 130° C. Company LDPE722 (LDPE) PE2 LDPE, broad molecular weight The Dow distribution homopolymer, density = Chemical 0.918 g/cc; MI 8.0 g/10 min, Tm = Company 107° C. Calcium Oxide CaO density = 3.3 g/cc; Sigma- (CaO) Loss on Ignition 1000° C. after 2 Aldrich hours ≤ 10% Chemical Company Nucrel ® 3990 AC ethylene/acrylic acid copolymer; DuPont (acid copolymer) 9.5 wt % acrylic acid comonomer; density = 0.940 g/cc; Tm = 78° C.; MI = 10 g/10 min Surlyn ® 9150 Ionomer Zn salt of ethylene/methacrylic acid DuPont (ionomer) copolymer; density = 0.970 g/cc; Tm = 82° C.; MI = 4.5 g/10 min Propanal (volatile Volatile C.sub.3 Molecular weight 58.08 g/mol (Daltons) carbonyl containing aldehyde Density 0.866 g/cc species) Boiling point 49° C. at 760 mm Hg 235 mm Hg at STP

[0099] 1. Sample Preparation

[0100] Individual additives were ground as needed to ensure similar particle size distributions between the polyolefin resin and the intended additives. The polyolefin material which was to be tested is dry blended with antioxidant loading (CaSt-600 ppm\Igrafos 168-500 ppm\Irganox 1010-500 ppm). Dry blending included addition of powdered additives to powder resin into a large bag and shaking the bag repeatedly. The additized resin was then split into aliquots. Each aliquot was then treated with powdered AC, and CaO in the same fashion as the antioxidants etc. Aliquots and control samples were stored in glass jars with PTFE-lined caps until they were introduced into the pelletizing extruder.

[0101] Samples were pelletized by feeding each powder aliquot into a Brabender Micro16 twin screw extruder. The melt temperature was set to 190° C. and the feed hopper is blanketed with nitrogen to prevent oxidative degradation of the extruded polymer. The molten extrudate was routed through chilled cooling water, and into an automated strand-cutting apparatus. The resulting pellets were collected as soon as practical into glass jars with PTFE-lined caps to avoid any possible off-gassing.

[0102] 2. Odor Suppression—Reduction in Volatile Hetero-Carbonyl Species

[0103] Samples were prepared by adding 2 grams of sample pellets to separate headspace vials. A 0.5 mL, 1700 ppmv sample of propanal was added separately to each headspace vial. Samples were sealed for 20 hrs at room temperature, and shaken for 4 hours. Headspace gas was withdrawn for testing as described above.

[0104] Comparative sample (CS1) was prepared. CS1 is a control sample with LDPE722 (LDPE) and no odor suppressant.

[0105] IE1-IE3 are inventive examples of the present composition composed of LDPE722 and odor suppressant composed of varying amounts CaO and acid copolymer (AC).

[0106] The percent of propanal reduction (volatile hetero-carbonyl species) using CS1 as control and compared to respective IE1-IE3 is provided in Table 2 below.

[0107] Table 2. Headspace GC reductions in propanal upon exposure to compositions (all results normalized to control sample, CS1 using normalized gas chromotography)

TABLE-US-00003 TABLE 2 Wt %* % Propanal Odor reduction suppres- CaO:AC compared Composition sant ratio to control CS1 PE2 n/a n/a 0 (control) IE1 PE2 + 0.06 wt % 0.18 1:2 20 CaO + 0.12 wt % AC IE2 PE2 + 0.1 wt % 1.1  1:10 28 CaO + 1 wt % AC IE3 PE2 + 1 wt % 5 1:4 30 CaO + 4 wt % AC *wt % based on total weight composition

[0108] Normalized gas chromatography is determined using Equation (1) as follows.

(GC.sub.(propanal at 20 hrs,CE1)−GC.sub.(propanal at 20 hrs,IEx))/GC.sub.(propanal at 20 hrs,CE1)*100;

[0109] where GC.sub.(propanal at 20 hrs, CE1) is the area under the curve associated with propanal and t is a time point of 20 hrs exposure to an initial concentration of 38 ppmv for CS1. The term “IEx” indicates IE1, IE2, and IE3.

GC.sub.(propanal at 20 hrs,CE1)−GC.sub.(propanal at 20 hrs,IE1))/GC.sub.(propanal at 20 hrs,CE1)*100=(980088−800827)/(980088)*100=18

[0110] Data presented in Table 2 are the average of two samples for each sample. The greater the % odor reduction value, the greater the odor suppression.

[0111] Odor suppression capability for CaO is known to be linear whereby the more CaO added to a polyolefin, the greater is the odor suppression. However, high loadings (greater than 5 wt %) of CaO are unfavorable because metal oxide, and CaO in particular, can interfere with the melt processing of polyolefin.

[0112] In Table 2, IE1 (odor suppressant at 0.18 wt %, 0.06 wt % CaO and 0.12 wt % AC, CaO:AC ratio 1:2) demonstrates that only at small load (less than 0.2 wt %, in IE1 specifically 0.06 wt %) of CaO in conjunction with a 1:2 CaO:AC ratio exhibits a significant amount (20% reduction) of odor suppression after 20 hours.

[0113] IE2 (odor suppressant at 1.1 wt %, 0.1 wt % CaO and 1.0 wt % CaO:AC ratio 1:10) demonstrates further that at small load (less than 0.2 wt % CaO and in IE2 specifically 0.1 wt %) of CaO odor suppressant in conjunction with a 1:10 CaO:AC ratio exhibits a significant amount (28% reduction) of odor suppression after 20 hours.

[0114] IE3 (odor suppressant at 5 wt %, 1.0 wt % CaO and 4.0 wt % CaO:AC ratio 1:4) exhibits 30% odor reduction after 20 hours. Compared to IE2, IE3 increases CaO concentration 10× (CaO in IE2 is 0.1 wt %, CaO in IE3 is 1 wt %), and IE3 increases AC concentration 4× (IE2 AC is 1 wt %, IE3 AC is 4 wt %), for in an increase in odor suppression of 7%.

[0115] IE1-IE3 show that 0.15-15 wt % CaO/AC odor suppressant (and in particular 0.18-5.0 wt % odor suppressant) with (i) 0.05-2 wt % CaO, (ii) 0.5-13 wt % AC, and (iii) CaO:AC ratio from 1:20 to 1:1 significantly reduces carbonyl-containing species (i.e., at least 20% reduction in carbonyl-containing species compared to the same polyolefin containing no CaO/AC odor suppressant).

[0116] 3. Sensory Panel

[0117] Ten grams of resin floated in 900 mL of Nestle Purified drinking water in a glass jar secured with a PTFE lined lid. The samples were stored at 40° C. for twenty hours. The resin was then removed and the water was poured into a large glass container to make a homogenous mix. For the evaluation, forty milliliters was poured into seven ounce polystyrene cups and served at room temperature.

TABLE-US-00004 TABLE 3 Taste Preparation Test medium Nestle Pure Life purified water (900 ml) Sample Resin (10 g) Contact time 20 hours Contact temperature 40° C. Serving temperature Room temperature Serving amount 40 mL in 7 oz cup

[0118] Test Method Panelists smelled the back of their hand and used water between taste samples to reduce fatigue and carry over affect. Random three digit codes were used as blind sample identification. A balanced block design was used to ensure all samples were served equally often and in all positions. The replicate set of samples provided a measure of test reproducibility. FIG. 1 shows a representation of a tray with water samples provided to the panelists, the tray using random three digit codes to identify the water samples.

TABLE-US-00005 TABLE 4 Number of panelists 24 Sensory questionnaire Paired Comparison, Hedonic Acceptability, and Descriptive Analysis Sample codes Random 3 digit Test design Random order of presentation Fatigue minimization Nestle water Replicate served Yes

[0119] The procedure of the taste and odor evaluations by the human sensory panel follow protocols suggested by ASTM and ISO and incorporates the scientific method and good statistical practices.

TABLE-US-00006 TABLE 5 Taste and odor panel results Taste of water: Taste of water: Odor Paired Paired Ranking comparison: comparison: Composition Intensity* Set 1 (%).sup.a Set 2 (%).sup.a IE4 PE1 + 0.1 wt % CaO + 1.5 83 79 1 wt % AC CS2 PE1 2.1 17 21 CS3 PE1 + 0.1 wt % CaO 2.3 NT NT NT = not tested, i.e. not a choice in the pair comparison *Odor intensity ranking is rated from 1 to 5, with 1 being “least intense” and 5 being “most intense” .sup.aHigher percentage scores means is preferred, means that more participants chose that sample as the better sample

[0120] It is specifically intended that the present disclosure not be limited to the embodiments and illustrations contained herein, but include modified forms of those embodiments including portions of the embodiments and combinations of elements of different embodiments as come within the scope of the following claims.