Ethylene-Based Polymer Composition with Branching and Process for Producing the Same

Abstract

The present disclosure provides a polymer composition. In an embodiment, an ethylene-based polymer composition is provided and is formed by high pressure (greater than or equal to 100 MPa), free-radical polymerization, by reacting: ethylene monomer and a mixture of hydrocarbon-based molecules, with each hydrocarbon-based molecule comprising three or more terminal alkene groups.

Claims

1. An ethylene-based polymer composition formed by high pressure (greater than or equal to 100 MPa), free-radical polymerization, by reacting: ethylene monomer and a mixture of hydrocarbon-based molecules, each hydrocarbon-based molecule comprising three or more terminal alkene groups.

2. The ethylene-based polymer composition of claim 1, wherein the hydrocarbon-based molecules have the Structure I: ##STR00010## wherein n is from 3 to 160, and m is from 0 to 50.

3. The ethylene-based polymer composition of claim 2, wherein the mixture of hydrocarbon-based molecules based on Structure I has a molecular weight distribution from 1.2 to 10.

4. The ethylene-based polymer composition of claim 1, wherein the hydrocarbon-based molecules have the Structure II: ##STR00011## wherein n is from 3 to 160, and m is from 0 to 50; x is from 0 to 160, and y is from 0 to 50.

5. The ethylene-based polymer composition of claim 4, wherein the mixture of hydrocarbon-based molecules based on Structure II has a molecular weight distribution from 1.2 to 10.

6. The ethylene-based polymer composition of claim 1 5 wherein the ethylene-based polymer composition has a G′ value that meets the following relationship:
G′≥C+D log(I.sub.2), wherein C is 185 Pascal and D is −90 Pa/log(g/10 min), and I.sub.2 is the melt index of the ethylene-based polymer composition, measured in grams/10 minutes (g/10 min).

7. The ethylene-based polymer composition of claim 1, wherein the ethylene-based polymer composition comprises, in polymerized form, from 95 wt % to 99.98 wt % of ethylene, based on the total weight of the ethylene-based polymer composition.

8. The ethylene-based polymer composition of claim 1, wherein the ethylene-based polymer composition comprises, in polymerized form, from 0.02 wt % to 5.0 wt % of the mixture of hydrocarbon-based molecules, based on the total weight of the ethylene-based polymer composition.

9. The ethylene-based polymer composition of claim 1, wherein the ethylene-based polymer composition has a melt index (I.sub.2) from 0.10 g/10 min to 200 g/10 min.

10. The ethylene-based polymer composition of claim 1, wherein the ethylene-based polymer composition has an alkenes content from 0.05/1000 carbons to 3.0/1000 carbons.

11. The ethylene-based polymer composition of claim 1, wherein the ethylene-based polymer composition has a GI200 value from 0 mm.sup.2/24.6 cm.sup.3 to 20 mm.sup.2/24.6 cm.sup.3.

12. The ethylene-based polymer composition of claim 1, wherein the ethylene-based polymer composition has a density from 0.909 g/cc to 0.940 g/cc.

13. The ethylene-based polymer composition of claim 1, wherein the ethylene-based polymer composition is a low density polyethylene comprising, in polymerized form, ethylene monomer and the mixture of hydrocarbon-based molecules.

14. The ethylene-based polymer composition of claim 1, further comprising a blend component, wherein the blend component does not include the mixture of hydrocarbon-based molecules.

15. An article comprising the composition of claim 1.

16. The article of claim 15, wherein the article is selected from the group consisting of a film, a coating, a coating for a cable, a coating for a wire, and a coated sheet.

17. A process comprising: reacting, in a polymerization reactor under free-radical polymerization conditions and at a pressure greater than or equal to 100 MPa, ethylene monomer and a mixture of hydrocarbon-based molecules, each hydrocarbon-based molecule comprising three or more terminal alkene groups; and forming an ethylene-based polymer composition.

18. The process of claim 17 comprising reacting ethylene monomer with a mixture of hydrocarbon-based molecules, each the hydrocarbon-based molecule having the Structure I: ##STR00012## wherein n is from 3 to 160, and m is from 0 to 50; and forming an ethylene-based polymer.

19. The process of claim 17, wherein the polymerization takes place in a reactor configuration comprising at least one tubular reactor.

20. The process of claim 17, wherein the polymerization takes place in a reactor configuration comprising at least one autoclave reactor.

Description

DETAILED DESCRIPTION

[0059] The present disclosure provides an ethylene-based polymer composition. The ethylene-based polymer composition includes the polymerization product of ethylene monomer and a mixture of hydrocarbon-based molecules having three or more terminal alkene groups.

[0060] In an embodiment, the ethylene-based polymer composition is formed from a process involving high pressure (greater than 100 MPa) and free-radical polymerization. Ethylene monomer and a mixture of hydrocarbon-based molecules having three or more terminal alkene groups are reacted together to form the ethylene-based polymer composition. The polymerization process is discussed in detail below.

[0061] Hydrocarbon-Based Molecule

[0062] The ethylene-based polymer composition is the polymerization reaction product of ethylene and the mixture of hydrocarbon-based molecules having three or more terminal alkene groups. The hydrocarbon-based molecules have only carbon atoms and hydrogen atoms, and have three or more terminal alkene groups. The term “hydrocarbon-based molecules comprising three or more terminal alkene groups,” (or interchangeably referred to as “hydrocarbon-based molecules”) as used herein, refers to a chemical component that is a polymer chain composed of only carbon atoms and hydrogen atoms, the polymer chain being branched and having three or more terminal ends wherein an alkene group (i.e. carbon-carbon double) bond is present at each terminal end. The term “mixture of hydrocarbon-based molecules,” as used herein, refers to two or more hydrocarbon-based molecules, wherein at least two of the molecules differ in structure, property, and/or composition.

[0063] In an embodiment, the number of terminal alkene groups present in each of the hydrocarbon-based molecules is from 3, or 5, or 7, or 8 to 17, or 18. In a further embodiment, the number of terminal alkene groups present in each of the hydrocarbon-based molecules is from 3 to 40, or from 5 to 40, or from 10 to 40, or from 12 to 20. By way of example, the mixture of hydrocarbon-based molecules may include a first hydrocarbon-based molecule having three terminal alkene groups and a second hydrocarbon-based molecule having twelve terminal alkene groups.

[0064] In an embodiment, each of the hydrocarbon-based molecules in the mixture has the Structure I:

##STR00002## [0065] wherein n (the number of terminal alkene groups) from 3 to 160, and m (the number of internal alkene groups) is from 0 to 50. In another embodiment, n is from 3, or 5, or 10, or 20, or 30, or 40, and m is from 0, or 10, or 20, or 40, or 50. In a further embodiment, n is from 3 to 160, or from 5 to 100, or from 9 to 40, and m is from 0 to 30, or from 1 to 20, or from 2 to 10.

[0066] In an embodiment, mixture of hydrocarbon-based molecules consist of two or more hydrocarbon-based molecules having Structure I:

##STR00003## [0067] wherein n is the number of terminal alkene groups, m is the number of internal alkene groups, and the average n content in the mixture of hydrocarbon-based molecules is from 9 to 40, and the average m content is from 1 to 10. The “average n content” is calculated by dividing the number average molecular weight (Mn) by the weight average molecular weight (Mw) of the hydrocarbon-based molecule, then multiplying by the fractional amount of terminal alkene groups. The “average m content” is calculated by dividing the number average molecular weight (Mn) by the weight average molecular weight (Mw) of the hydrocarbon-based molecule, then multiplying by the fractional amount of internal alkene groups.

[0068] In an embodiment, mixture of hydrocarbon-based molecules has respective average n content and average m content (denoted as “n/m”, see Structure I for each hydrocarbon-based molecule) as follows: 9-40/1-10, or 12-38/2-8, or 13-37/2-6, or 15-35/2-6, or 19/3, or 33/5.

[0069] In an embodiment, the mixture of hydrocarbon-based molecules based on Structure I has a molecular weight distribution from 1.2 to 20. In another embodiment, the mixture of hydrocarbon-based molecules based on Structure I has a molecular weight distribution from 1.2, or 1.3, or 1.4 to 2, or 5 to 10 or 20. In a further embodiment, the mixture of hydrocarbon-based molecules based on Structure I has a molecular weight distribution from 1.2 to 20, or from 1.3 to 10, or from 1.5 to 5.

[0070] In an embodiment, each of the hydrocarbon-based molecules has the Structure II:

##STR00004##

wherein n is from 3 to 160, and m is from 0 to 50; x is from 0 to 160, and y is from 0 to 50. In another embodiment, n is from 3, or 5, or 10, or 20, or 30, or 40, or 50 to 60, or 70 to 80, or 90, or 100, or 110, or 120, or 130, or 140, or 150, or 160, and m is from 0, or 10, or 20 to 30, or 40, or 50; x is from 0, or 1, or 5, or 10, or 20, or 30, or 40, or 50 to 60, or 70 to 80, or 90, or 100, or 110, or 120, or 130, or 140, or 150, or 160, and y is from 0, or 1, or 10, or 20 to 30, or 40, or 50. In a further embodiment, n is from 3 to 160, or from 5 to 150, or from 9 to 140, or from 9 to 100, or from 9 to 50, or from 9 to 30, m is from 0 to 30, or from 1 to 20, or from 1 to 10, x is from 0 to 160, or from 1 to 50, or from 1 to 20, or from 1 to 10, and y is from 0 to 50, or from 1 to 20, or from 1 to 10.

[0071] The hydrocarbon-based molecules of Structure I and/or Structure II are hereafter interchangeably referred to as “branching agent.”

[0072] The notation “” in Structure I and in Structure II represents a cis alkyl group or a trans alkyl group with respect to the double bond.

[0073] In an embodiment a mixture of hydrocarbon-based molecules having the Structure I and/or the Structure II, with differing molecular weights, is used.

[0074] It is understood that the present ethylene-based polymer composition may include (i) Structure I only, (ii) Structure II only, or (iii) a combination of Structure I and Structure II. It is understood that the term “ethylene-based polymer composition,” as used herein, refers to the polymer that is the reaction product of ethylene with Structure I and/or Structure II.

[0075] In an embodiment, the ethylene-based polymer composition includes, in polymerized form, from 95 wt %, or 96 wt %, or 97 wt %, or 98 wt % to 99 wt %, or 99.5 wt %, or 99.7 wt %, or 99.9 wt % of ethylene, and a reciprocal amount of the mixture of hydrocarbon-based molecules, or from 5.0 wt %, or 4.0 wt %, or 3.0 wt %, or 2.0 wt % to 1.0 wt %, or 0.5 wt %, or 0.3 wt %, or 0.1 wt % of the mixture of the hydrocarbon-based molecules. Weight percent is based on total weight of the ethylene-based polymer composition. In a further embodiment, the ethylene-based polymer composition includes, in polymerized form, from 95.0 wt % to 99.9 wt %, or from 96 wt % to 99.8 wt %, or from 98 wt % to 99.8 wt % of ethylene, and the mixture of hydrocarbon-based molecules is present in an amount from 5.0 wt % to 0.1 wt %, or from 4.0 wt % to 0.2 wt %, or from 2.0 wt % to 0.2 wt %.

[0076] The ethylene-based polymer composition has a density from 0.909 g/cc to 0.940 g/cc. In an embodiment, the ethylene-based polymer composition has a density from 0.909 g/cc, or 0.915 g/cc, or 0.920 g/cc to 0.930 g/cc, or 0.935 g/cc, or 0.940 g/cc. In another embodiment, the ethylene-based polymer composition has a density from 0.910 g/cc to 0.940 g/cc, or from 0.915 g/cc to 0.935 g/cc, or from 0.917 g/cc to 0.930 g/cc, or from 0.917 g/cc to 0.926 g/cc.

[0077] In an embodiment, the ethylene-based polymer composition has a melt index (I.sub.2) from 0.10 g/10 min to 200 g/10 min. In another embodiment, the ethylene-based polymer composition has a melt index from 0.1 g/10 min, or 1.0 g/10 min, or 5.0 g/10 min, or 10 g/10 min, or 20 g/10 min, or 30 g/10 min, or 40 g/10 min, to 50 g/10 min, or 60 g/10 min, 70 g/10 min, or 75 g/10 min, or 80 g/10 min, or 90 g/10 min, or 100 g/10 min. In a further embodiment, the ethylene-based polymer composition has a melt index from 0.1 g/10 min to 200 g/10 min, or from 0.1 g/10 min to 100 g/10 min, or from 0.1 g/10 min to 80 g/10 min, or from 0.1 g/10 min to 20 g/10 min.

[0078] In an embodiment, the ethylene-based polymer composition has a melt index (I.sub.2) from 0.1 g/10 min to 8.0 g/10 min.

[0079] In an embodiment, the ethylene-based polymer composition has an alkenes content from 0.05/1000 carbons, or 0.15/1000 carbons, or 0.3/1000 carbons, or 0.4/1000 carbons, to 1.0/1000 carbons, or 2.0/1000 carbons, or 3.0/1000 carbons. In an embodiment, the ethylene-based polymer composition has an alkenes content from 0.05/1000 carbons to 3.0/1000 carbons, or from 0.05/1000 carbons to 1/1000 carbons, or from 0.08/1000 carbons to 1/1000 carbons.

[0080] In an embodiment, the ethylene-based polymer composition has a melt elasticity from 0.1 cN to 100 cN, and a melt index from 0.1 g/10 min to 100 g/10 min.

[0081] In an embodiment, the ethylene-based polymer composition has a G′ value greater than or equal to C+D log(I.sub.2), wherein C is 185 Pa and D is −90 Pa/log(g/10 min), wherein I.sub.2 is the melt index of the ethylene-based polymer composition, Pa is Pascals (N/m.sup.2), and log(g/10 min) is the logarithm of the melt index of the ethylene-based polymer composition.

[0082] In an embodiment, the ethylene-based polymer composition has a GI200 value from 0 mm.sup.2/24.6 cm.sup.3 to 20 mm.sup.2/24.6 cm.sup.3. In an embodiment, the ethylene-based polymer composition has a GI200 value from 0 mm.sup.2/24.6 cm.sup.3, or 0.05 mm.sup.2/24.6 cm.sup.3, or 0.3 mm.sup.2/24.6 cm.sup.3, to 0.7 mm.sup.2/24.6 cm.sup.3, 5 mm.sup.2/24.6 cm.sup.3, or 20 mm.sup.2/24.6 cm.sup.3. In a further embodiment, the ethylene-based polymer composition has a GI200 value from 0 mm.sup.2/24.6 cm.sup.3 to 20 mm.sup.2/24.6 cm.sup.3, or from 0.05 mm.sup.2/24.6 cm.sup.3 to 5 mm.sup.2/24.6 cm.sup.3, or from, 0.3 mm.sup.2/24.6 cm.sup.3 to 0.7 mm.sup.2/24.6 cm.sup.3.

[0083] In an embodiment, the ethylene-based polymer composition has a density from 0.900 g/cc to 0.940 g/cc, and a melt index from 0.1 g/10 min to 200 g/10 min. In another embodiment, the ethylene-based polymer composition has a density from 0.900 g/cc, or 0.910 g/cc, or 0.920 g/cc to 0.925 g/cc, or 0.930 g/cc, and a melt index from 0.1 g/10 min, or 2.0 g/10 min, or 3.0 g/10 min to 9.0 g/10 min, or 10 g/10 min, or 100 g/10 min. In a further embodiment, the ethylene-based polymer composition has a density from 0.900 g/cc to 0.940 g/cc, or from 0.910 g/cc to 0.930 g/cc, or from 0.917 g/cc to 0.925 g/cc, and a melt index from 0.1 g/10 min to 200 g/10 min, or from 0.1 g/10 min to 100 g/10 min, or from 0.1 g/10 min to 20.0 g/10 min.

[0084] In an embodiment, the ethylene-based polymer composition has one, some, or all of the following properties:

[0085] (i) an alkenes content from 0.05/1000 carbons, or 0.15/1000 carbons, or 0.3/1000 carbons, or 0.4/1000 carbons, to 1.0/1000 carbons, or 2.0/1000 carbons, or 3.0/1000 carbons; and/or

[0086] (ii) a melt elasticity from 0.1 cN to 100 cN, and a melt index from 0.1 g/10 min to 200 g/10 min; and/or

[0087] (iii) a G′ value greater than or equal to C+D log(I.sub.2), wherein C is 185 Pa and D is −90 Pa/log(g/10 min); and/or

[0088] (iv) a GI200 value from 0.05 mm.sup.2/24.6 cm.sup.3 to 20 mm.sup.2/24.6 cm.sup.3; and/or

[0089] (v) a density from 0.909 g/cc to 0.940 g/cc.

[0090] In an embodiment, the ethylene-based polymer composition has a Mw(abs) versus I.sub.2 relationship, with Mw(abs) less than or equal to A+B(I.sub.2), wherein A is 2.65×10.sup.5 g/mol and B is −8.00×10.sup.−3 (g/mol)/(dg/min) (hereafter Equation A) and the ethylene-based polymer composition has a G′ versus I.sub.2 relationship, wherein G′ is greater than or equal to N C+D log(I.sub.2), where C is 185 Pa and D is −90 Pa/log(g/10 min) (hereafter Equation B). In other words, the present ethylene-based polymer has a Mw(abs) value less than the value from Equation A and G′ value greater than the value from Equation B.

[0091] In an embodiment, the ethylene-based polymer composition is a low density polyethylene (LDPE) that includes, in polymerized form, ethylene monomer and the mixture of hydrocarbon-based molecules.

[0092] The present ethylene-based polymer composition is produced via in-reactor high pressure polymerization. Bound by no particular theory, it is believed that copolymerization of ethylene monomer and the mixture of hydrocarbon-based molecules may occur by multiple scenarios. Two possible scenarios are (i) reaction of propagating polymer chain (PC) with terminal alkene group of the hydrocarbon-based molecules followed by further propagation and termination, and (ii) reaction of propagating polymer chain (PC) with internal alkene group of the hydrocarbon-based molecules followed up by further propagation and termination.

##STR00005##

The resultant ethylene-based polymer composition (Structure III) has polyethylene chain (LDPE) bonded directly to a hydrocarbon-based molecule. Single terminal alkene group or multiple terminal alkene groups can be attacked by propagating polymer chain (PC) leading to single or multiple LDPEs been attached to the hydrocarbon-based molecule. In an embodiment, two or more terminal alkene groups undergo copolymerization, while the remaining terminal alkene groups remain unreacted.

##STR00006##

[0093] The resultant ethylene-based polymer composition (Structure IV) has two polyethylene chains bonded to a hydrocarbon-based molecule at the internal alkene group reaction point (in the “m” section of a hydrocarbon-based molecule) that combine to form an LDPE unit. Single internal alkene group or multiple internal alkene groups can be attacked by propagating polymer chain (PC) leading to single or multiple LDPEs that are copolymerized with the hydrocarbon-based molecule. In an embodiment, two or more internal alkene groups undergo reaction, while the remaining internal alkene groups remain unreacted. A single internal and/or terminal alkene group or multiple internal and/or external alkene groups can be attacked by propagating polymer chain (PC) leading to single or multiple LDPEs that are copolymerized with the hydrocarbon-based molecule. In an embodiment, two or more alkene groups undergo reaction, while the remaining internal alkene groups remain unreacted.

[0094] Final product of the in-reactor reaction of the growing polymer chain at the terminal alkene group (scenario I above) followed by further propagation and termination differs from post-reactor terminal alkene group grafting. Post-reactor terminal alkene group grafting is shown below:

##STR00007##

[0095] In post-reactor terminal alkene group grafting, LDPE is bonded to a hydrocarbon-based molecule at the terminal alkene group reaction point. A separate molecule, normally another LDPE, reacts with the intermediate product to form the resultant ethylene-based polymer composition.

[0096] Final product of the in-reactor reaction of the growing polymer chain at the internal alkene group followed by further propagation and termination (scenario ii above) differs from post-reactor internal alkene grafting. Post-reactor internal alkene grafting is shown below:

##STR00008##

[0097] In post-reactor internal alkene grafting reaction, LDPE is bonded to a hydrocarbon-based molecule at the internal alkene group reaction point. A separate molecule, typically another LDPE, reacts with the intermediate product to form the resultant ethylene-based polymer composition.

[0098] In an embodiment, the ethylene-based polymer composition has Structure III and/or Structure IV as discussed above, and has one, some, or all of the following properties:

[0099] (i) an alkenes content from 0.05/1000 carbons, or 0.15/1000 carbons, or 0.3/1000 carbons, or 0.4/1000 carbons to 1.0/1000 carbons, or 2.0/1000 carbons, or 3.0/1000 carbons; and/or

[0100] (ii) a melt elasticity from 0.1 cN to 100 cN, and a melt index from 0.1 g/10 min to 200 g/10 min; and/or

[0101] (iii) a G′ value greater than or equal to C+D log(I.sub.2), where C is 185 Pa and D is −90 Pa/log(g/10 min); and/or

[0102] (iv) a GI200 value from 0 mm.sup.2/24.6 cm.sup.3 to 20 mm.sup.2/24.6 cm.sup.3; and/or

[0103] (v) a density from 0.909 g/cc to 0.940 g/cc, and a melt index from 0.1 g/10 min to 200 g/10 min.

[0104] In an embodiment, the ethylene-based polymer composition has a hexane extractable from 1.0 wt % to 5.0 wt %, based on the weight of the ethylene-based polymer composition. In another embodiment, the ethylene-based polymer composition has a hexane extractable from 1.0 wt %, or 1.1 wt %, or 1.5 wt % to 2.6 wt %, or 3.5 wt %, or 5.0 wt %. In a further embodiment, the ethylene-based polymer composition has a hexane extractable from 1.0 wt % to 4.5 wt %, or from 1.1 wt % to 3.5 wt %, or from 1.5 wt % to 2.6 wt %.

[0105] In an embodiment, the ethylene-based polymer composition includes a blend component. The blend component is a polymer that does not include the mixture of the hydrocarbon-based molecules.

[0106] In an embodiment, the blend component is an ethylene-based polymer that does not include the mixture of the hydrocarbon based molecules. Nonlimiting examples of suitable ethylene-based polymers include ethylene/alpha-olefin copolymer, ethylene/C.sub.3-C.sub.8 alpha-olefin copolymer, ethylene/C.sub.4-C.sub.8 alpha-olefin copolymer, and copolymers of ethylene and one or more of the following comonomers: acrylate, (meth)acrylic acid, (meth)acrylic ester, carbon monoxide, maleic anhydride, vinyl acetate, vinyl propionate, mono esters of maleic acid, diesters of maleic acid, vinyl trialkoxysilane, vinyl trialkyl silane, and any combination thereof.

[0107] In an embodiment, the blend component is an ethylene-based polymer having a density from 0.890 g/cc, or 0.900 g/cc, or 0.905 g/cc, or 0.910 g/cc, or 0.915 g/cc, or 0.917 g/cc to 0.925 g/cc, or 0.930 g/cc, or 0.935 g/cc, or 0.940 g/cc, or 1.05 g/cc. In a further embodiment, the ethylene-based polymer that is the blend component has a density from 0.900 g/cc to 0.940 g/cc, or from 0.905 g/cc to 0.935 g/cc, or from 0.910 g/cc to 0.930 g/cc, or from 0.915 g/cc to 0.925 g/cc, or from 0.917 g/cc to 0.925 g/cc.

[0108] In an embodiment, the blend component has a melt index (I.sub.2) from 0.1 to 200 g/10 min.

[0109] In an embodiment, the blend component is a high density polyethylene (HDPE).

[0110] In an embodiment, the blend component is linear low density polyethylene (LLDPE).

[0111] In an embodiment, the blend component is a low density polyethylene (LDPE).

[0112] In another embodiment, the blend component is an ethylene/alpha-olefin copolymer. In a further embodiment, the alpha-olefin of the blend component is a C.sub.3-C.sub.8 alpha-olefin, or a C.sub.4-C.sub.8 alpha-olefin.

[0113] The present disclosure also provides an article comprising at least one component formed from the composition of an embodiment, or a combination of two or more embodiments, described herein.

[0114] In an embodiment, the article is a coating of a film.

[0115] In an embodiment, the article is a coating.

[0116] In an embodiment, the article is a film.

[0117] The ethylene-based polymer composition includes a combination of two or more embodiments as described herein.

[0118] The article includes a combination of two or more embodiments as described herein.

[0119] The present disclosure also provides a process of producing the present ethylene-based polymer composition. The process includes reacting, in a polymerization reactor under free-radical polymerization conditions and at a pressure greater than 100 MPa, ethylene monomer in the presence of the mixture of hydrocarbon-based molecules that have three or more terminal alkene groups. The process includes forming the present ethylene-based polymer composition.

[0120] In an embodiment, the polymerization takes place in a reactor configuration comprising at least one tubular reactor or at least one autoclave reactor.

[0121] In an embodiment, the polymerization takes place in a reactor configuration that includes at least one tubular reactor.

[0122] In an embodiment, the polymerization takes place in a reactor configuration that includes at least one autoclave reactor.

[0123] In an embodiment, the ethylene monomer is polymerized in the presence of at least 2 mole ppm (based on amount of total monomers in reaction feed) of the additive of the mixture of hydrocarbon-based molecules.

[0124] In an embodiment, the polymerization pressure is greater than, or equal to, 100 MPa.

[0125] In another embodiment, the polymerization takes place with at least one polymerization pressure from 100 MPa to 360 MPa.

[0126] In a further embodiment, the polymerization takes place with at least one temperature from 100° C. to 380° C.

[0127] In order to produce a highly branched ethylene-based polymer composition, a high pressure, free-radical initiated polymerization process is used. Two different high pressure free-radical initiated polymerization process types are known. In the first process type, an agitated autoclave reactor having one or more reaction zones is used. The autoclave reactor normally has several injection points for initiator or monomer feeds, or both. In the second process type, a jacketed tube is used as a reactor, which has one or more reaction zones. Suitable, but not limiting, reactor lengths may be from 100 meters to 3000 meters (m), or from 1000 meters to 2000 meters. The beginning of a reaction zone, for either type of reactor, is typically defined by the side injection of either initiator of the reaction, ethylene, chain transfer agent (or telomer), comonomer(s), as well as any combination thereof. A high pressure process can be carried out in autoclave reactors or tubular reactors having one or more reaction zones, or in a combination of autoclave reactors and tubular reactors, each comprising one or more reaction zones.

[0128] In an embodiment, an initiator is injected prior to the reaction zone where free radical polymerization is to be induced.

[0129] In an embodiment, a conventional chain transfer agent (CTA) is used to control molecular weight.

[0130] In another embodiment, one or more conventional CTAs are added to an inventive polymerization process. Non-limiting examples of CTAs include propylene, isobutane, n-butane, 1-butene, methyl ethyl ketone, acetone, ethyl acetate, propionaldehyde, ISOPAR (ExxonMobil Chemical Co.), and isopropanol. In an embodiment, the amount of CTA used in the process is from 0.01 weight percent to 10 weight percent of the total reaction mixture.

[0131] In an embodiment, the process includes a process recycle loop to improve conversion efficiency.

[0132] In an embodiment, the polymerization takes place in a tubular reactor, such as described in international patent application PCT/US12/059469 (WO2013059042(A1), filed Oct. 10, 2012. This patent application describes a multi zone reactor which describes alternate locations of feeding fresh ethylene to control the ethylene to CTA ratio and therefore control polymer properties. Fresh ethylene monomer is simultaneously added in multiple locations to achieve the desired ethylene monomer to chain transfer ratio as described in international patent application PCT/US12/064284 (filed Nov. 9, 2012) (WO2013078018(A2). In a similar way addition of fresh CTA addition points is carefully selected to control polymer properties. Fresh CTA is simultaneously added in multiple locations to achieve the desired CTA to ethylene monomer ratio. Likewise, the addition points and the amount of fresh branching agents, described in this application, are controlled to control gel formation while maximizing the desired property of increased melt strength and performance in targeted applications. Fresh branching agent is simultaneously added in multiple locations to achieve the desired branching agent to ethylene monomer ratio. The use of a branching agent and/or coupling agent to broaden molecular weight distribution and to increase the melt strength of the polymer will put further requirements on the distribution of the CTA and the branching agent along a reactor system in order to achieve the desired change in product properties without or minimizing potential negative impacts such as gel formation, reactor fouling, process instabilities, and minimizing the amount of branching agent.

[0133] In an embodiment, the polymerization takes place in at least one tubular reactor. In a multi reactor system, the autoclave reactor precedes the tubular reactor. The addition points and amounts of fresh ethylene, fresh CTA, and fresh branching agent are controlled to achieve the desired ratios of CTA to ethylene monomer and branching agent to ethylene monomer in the feeds to and or in the reaction zones.

[0134] In an embodiment, the branching agent is fed through a compression stage directly into the reaction zone or directly into the feed to the reaction zone. The choice of feed point into the reaction and/or a reaction zone depends on several factors, including, but not limited to, the solubility of the polyene in pressurized ethylene and/or solvent, the condensation of the polyene in pressurized ethylene, and/or fouling by premature polymerization of the branching agent in the pre-heater used to heat the reactor contents prior to injection of initiator.

[0135] In an embodiment, the branching agent is fed directly into the reaction zone or directly into the feed to the reaction zone.

[0136] In an embodiment, branching agent is added prior to, or simultaneously with, the addition of the free-radical initiator, at the inlet of the reaction zone. In another embodiment, the branching agent is added prior to the initiator addition to allow for a good dispersion of the polyene.

[0137] In an embodiment, the branching agent is fed only to reaction zone 1.

[0138] In an embodiment, more branching agent, by mass, is added to reaction zone 1 as compared to the amount of polyene, by mass, added to a subsequent reaction zone.

[0139] In an embodiment, the ethylene fed to the first reaction zone is from 10 percent to 100 percent of the total ethylene fed to the polymerization. In a further embodiment, the ethylene fed to the first reaction zone is from 20 percent to 80 percent, further from 25 percent to 75 percent, further from 30 percent to 70 percent, further from 40 percent to 60 percent, of the total ethylene fed to the polymerization.

[0140] In an embodiment, the process takes place in a reactor configuration that comprises at least one tubular reactor. In a further embodiment, the maximum temperature in each reaction zone is from 150° C. to 360° C., further from 170° C. to 350° C., further from 200° C. to 340° C.

[0141] In an embodiment, the polymerization pressure at the first inlet of the reactor is from 100 MPa to 360 MPa, further from 150 MPa to 340 MPa, further from 185 MPa to 320 MPa.

[0142] In an embodiment, the ratio of “the concentration of the CTA in the feed to reaction zone i” to “the concentration of the CTA in the feed added to reaction zone 1” is greater than, or equal to, 1.

[0143] In an embodiment, the ratio of “the concentration of the CTA in the feed to reaction zone i” to “the concentration of the CTA in the feed added to reaction zone 1” is less than 1, further less than 0.8, further less than 0.6, further less than 0.4.

[0144] In an embodiment the number of reaction zones range from 3 to 6.

[0145] Non-limiting examples of ethylene monomer used for the production of the ethylene-based polymer composition include purified ethylene, which is obtained by removing polar components from a loop recycle stream, or by using a reaction system configuration, such that only fresh ethylene is used for making the inventive polymer. Further examples of ethylene monomer include ethylene monomer from a recycle loop.

[0146] In an embodiment, the ethylene-based polymer composition includes ethylene monomer, the mixture of hydrocarbon-based molecules (Structure I or Structure II), and one or more comonomers, and preferably one comonomer. Non-limiting examples of suitable comonomers include α-olefins, acrylates, carbon monoxide, methacrylates, (meth)acrylic acid, monoesters of maleic acid, diesters of maleic acid, anhydrides, vinyl acetate, vinyl propionate, vinyl trialkoxysilanes, vinyl trialkyl silanes each having no more than 20 carbon atoms. The α-olefin comonomers have from 3 to 10 carbon atoms, or in the alternative, the α-olefin comonomers have from 4 to 8 carbon atoms. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene.

[0147] In an embodiment, the ethylene-based polymer composition includes ethylene monomer and at least one hydrocarbon-based molecules (Structure I or Structure II) as the only monomeric units.

[0148] Free Radical Initiators

[0149] In an embodiment, free radical initiators are used to produce the inventive ethylene-based polymer compositions. Non-limiting examples of organic peroxides cyclic peroxides, diacyl peroxides, dialkyl peroxides, hydroperoxides, peroxycarbonates, peroxydicarbonates, peroxyesters, peroxyketals, t-butyl peroxy pivalate, di-t-butyl peroxide, t-butyl peroxy acetate and t-butyl peroxy-2-hexanoate, and combinations thereof. In an embodiment, these organic peroxy initiators are used in an amount from 0.001 wt % to 0.2 wt %, based upon the weight of polymerizable monomers.

[0150] In an embodiment, an initiator is added to at least one reaction zone of the polymerization, and wherein the initiator has a “half-life temperature at one second” greater than 255° C., or greater than 260° C.

[0151] In another embodiment, such initiators are used at a peak polymerization temperature from 320° C. to 350° C.

[0152] In a further embodiment, the initiator includes at least one peroxide group incorporated in a ring structure. Non-limiting examples of initiators include TRIGONOX 301 (3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonaan) and TRIGONOX 311 (3,3,5,7,7-pentamethyl-1,2,4-trioxepane), both available from Akzo Nobel, and HMCH-4-AL (3,3,6,6,9,9-hexamethyl-1,2,4,5-tetroxonane) available from United Initiators.

[0153] In an embodiment, the configuration of the tubular reactor includes three to five reaction zones, with fresh ethylene fed to the front of the tubular reactor, and recycled ethylene fed to the side of the tubular reactor. Fresh CTA is fed to the side of the tubular reactor. The mixture of hydrocarbon-based molecules is fed to the front of the tubular reactor, with direct feed of the mixture of hydrocarbon-based molecules after preheating of the tubular reactor.

[0154] Additives

[0155] In an embodiment, the composition includes one or more additives. Non-limiting examples of additives include stabilizers, plasticizers, antistatic agents, pigments, dyes, nucleating agents, fillers, slip agents, fire retardants, processing aids, smoke inhibitors, viscosity control agents and anti-blocking agents. The polymer composition may, for example, comprise less than 10 percent of the combined weight of one or more additives, based on the weight of the ethylene-based polymer composition.

[0156] In an embodiment the ethylene-based polymer composition is treated with one or more stabilizers, for example, antioxidants, such as IRGANOX 1010, IRGANOX 1076 and IRGAFOS 168. In general, the ethylene-based polymer composition is treated with one or more stabilizers before extrusion or other melt processes.

[0157] In an embodiment, the ethylene-based polymer composition further includes at least one other polymer, in addition to the inventive ethylene-based polymer with the mixture of hydrocarbon-based molecules (Structure I or Structure II). Blends and mixtures of the ethylene-based polymer composition with other polymers may be prepared. Suitable polymers for blending with the inventive polymers include natural and synthetic polymers. Exemplary polymers for blending include propylene-based polymers, ethylene/alkene alcohol copolymers, polystyrene, impact modified polystyrene, ABS, styrene/butadiene block copolymers and hydrogenated derivatives thereof (SBS and SEBS), and thermoplastic polyurethanes.

[0158] Other ethylene-based polymer compositions for blending with the present ethylene-based polymer composition include homogeneous polymers, such as olefin plastomers and elastomers (for example, polymers available under the trade designations AFFINITY Plastomers and ENGAGE Elastomers (The Dow Chemical Company) and EXACT (ExxonMobil Chemical Co.), Propylene-based copolymers (for example, polymers available under the trade designation VERSIFY Plastomers & Elastomers (The Dow Chemical Company) and VISTAMAXX (ExxonMobil Chemical Co.) can also be useful as components in blends comprising an inventive polymer.

[0159] Applications

[0160] The ethylene-based polymer composition of the present disclosure may be employed in a variety of conventional thermoplastic fabrication processes to produce useful articles, including but not limited to monolayer and multilayer films; molded articles, such as blow molded, injection molded, or rotomolded articles; coatings; fibers; and woven or non-woven fabrics, cables, pipes, green house films, silo bag films, collation Shrink films, food packaging films, foams.

[0161] The ethylene-based polymer composition may be used in a variety of films, including but not limited to, clarity shrink films, collation shrink films, cast stretch films, silage films, stretch hood, sealants, and diaper backsheets. Other suitable applications include, but are not limited to, wires and cables, gaskets and profiles, adhesives; footwear components, and auto interior parts.

[0162] Applicant unexpectedly discovered that a mixture of hydrocarbon-based molecules that has either Structure I or Structure II used in-reactor, with n is greater than three (or n greater than 5), resulted in an ethylene-based polymer composition having an increased number of branching points, which results in a greater change in melt rheology. The higher branch levels, as seen in the GPC and melt rheology data and improved solubility of the ethylene-based polymer composition, results in reduced reactor fouling and reduced gel formation of the ethylene-based polymer composition. The resultant ethylene-based polymer composition also has improved (reduced) taste and odor performance, as compared to some other polymer compositions modified with other types of branching agents including for example PPG-AEMA.

Examples

[0163] Commercially Available Reagents

[0164] LDPE 5004i, PG7004, PT7007, and PT7009 each is LDPE ethylene homopolymer produced in an autoclave reactor. Each is available from The Dow Chemical Company. Isopar E, Isopar H, and Isopar L are available from Exxon Chemicals.

[0165] Polybutadiene (Additive A: Nisso PB B-1000, Additive B: Nisso PB B-2000) were supplied from Nippon Soda, Co. Properties for these materials are listed in Table 1 below.

TABLE-US-00001 TABLE 1 % terminal % internal Avg n Avg m Mn (g/mol).sup.1 Mw/Mn.sup.2 alkene.sup.1 alkene.sup.1 content.sup.3 content.sup.3 Additive A 1200 1.47 85 15 19 3 Additive B 2100 1.56 88 12 33 5 .sup.1Provided by Nippon Soda .sup.2Determined by GPC .sup.3Calculated by dividing Mn by Mw of butadiene monomer (hydrocarbon-based molecule) and multiplying by fractional amount of terminal alkene groups for n, and internal alkene groups for m. Example: Mn = 1200 g/mol, Avg n = (1200 g/mol)/(54.09 g/mol butadiene monomer) = 22 repeat units*0.85 (terminal /total alkene) = 18.8 terminal vinyl groups per chain on average

[0166] 1. Polymerization I: Autoclave Reactor

[0167] Preparation of Solutions

[0168] Asymmetrical Diene Comparative Sample I: Isoprenyl Methacrylate (IPMA), shown below

##STR00009##

[0169] Comparative branching agent 1

was loaded into a 316 stainless steel supply vessel, and diluted with ethyl acetate, to produce a final concentration of 7.8 wt %. This vessel was purged with nitrogen for three hours before use and kept under 70 psig nitrogen pad.

Inventive Example I

[0170] Additive A was loaded into a 316 stainless steel supply vessel, and diluted with Isopar™ E to produce a final concentration of 1.7 wt %. This vessel was purged with nitrogen for three hours before use and kept under 70 psig nitrogen pad during operation.

[0171] Various feed levels of this solution were introduced into the reactor to produce polymer samples. Additive B was added to the reactor in the same manner as Additive A.

[0172] Initiators: Peroxide initiator tert-butyl peroxyacetate (TPA, 20% by weight solution in ISOPAR™ H), and peroxide initiator di-tert-butyl peroxide (DTBP, 20% by weight solution in ISOPAR™ H), were combined with ISOPAR E, in a second 316 stainless steel supply vessel, to produce 1500 mass ppm TPA and 415 mass ppm DTBP (a ratio of 4:1 mole TPA/mole DTBP). The vessel was padded, de-padded, five times with 70 prig nitrogen before use, and kept under nitrogen pad during operation.

[0173] Ethylene was injected at 5500 gm/hr, at a pressure of 193 MPa, into an agitated (1600 rpm) 300 mL high pressure CSTR reactor, with an external heating jacket set to control the internal reactor temperature at 220° C. Propylene (CTA) was added to the ethylene stream at a pressure of 6.2 MPa, and controlled at a rate to produce a final product with a MI of .sup.˜4 g/10 min, before the mixture was compressed to 193 MPa, and injected into the reactor. The solution of the appropriate additive solution was pumped at a pressure of 193 MPa directly into the reactor via a high pressure pump. The peroxide initiator solution was added directly to the reactor, through the sidewall, at a pressure of 193 MPa at a rate to control the ethylene conversion near 12%.

[0174] The details of the polymerization procedure for each experiment are shown in Table 2 below.

TABLE-US-00002 TABLE 2 Autoclave Polymerization Conditions (at ethylene feed 5,500 g/hr and at 220° C.) t-butyl peroxy- di-t-butyl IPMA Additive Ethylene Polymer Propylene acetate peroxide feed A feed Conversion Collected Experiment (g/hr) (g/hr) (g/hr) (g/hr) (g/hr) (%) (g/hr) Control 120 0.38 0.08 0 0 12.1 660 Comparative 232 0.18 0.04 2.79 0 11.6 640 Sample I Inventive 135 0.15 0.03 0 2.72 13.0 700 Example I

[0175] Properties of ethylene homopolymer produced in the autoclave reactor are provided in Table 3 below.

TABLE-US-00003 TABLE 3 Ethylene Homopolymer Properties MI (I.sub.2) I.sub.10 MS Example (g/10 min) (g/10 min) (cN, 190° C.) MI* MS Control 4.3 47.4 12.4 53.3 Comparative 6.7 70.4 13.0 87.1 Sample I Inventive 5.1 55.0 14.6 74.5 Example I

[0176] 2. Melt Strength Experimentation

[0177] Additional samples were made under the autoclave polymerization conditions of Polymerization I, disclosed above. In particular, both Additive A and Additive B feed rates were varied while holding melt index (MI) constant (at or near 4 g/10 min). Applicant discovered that while holding melt index constant, increasing the amount of either Additive A or Additive B increased the melt strength of the polymer. The results of the melt strength experimentation are shown in Table 4 below.

TABLE-US-00004 TABLE 4 Melt Strength Experimentation Results Amount fed MI (I.sub.2) ME MS Additive (mol ppm) (g/10 min) (cN, 190° C.) (cN, 190° C.) None 0 3.7 3.6 5.8 None 0 5.2 3.6 5.4 None 0 5.6 3.5 4.9 Additive A 2 3.5 4.9 7.8 Additive A 2 3.6 5.0 7.8 Additive A 2 4.2 5.0 7.2 Additive A 4 4.2 5.3 7.9 Additive A 4 4.7 5.2 7.3 Additive A 4 4.4 6.0 8.4 Additive A 6 4.8 5.8 7.9 Additive A 6 3.7 7.1 8.4 Additive A 6 3.0 7.5 10.2 Additive A 6 3.7 5.8 6.6 Additive A 6 3.0 6.9 8.0 Additive A 6 3.5 4.5 6.4 Additive A 8 3.5 4.8 6.7 Additive A 8 3.6 4.4 6.3 Additive A 8 4.0 4.1 3.1 Additive A 10 4.6 4.3 6.5 Additive A 10 3.9 4.6 6.5 None 0 3.8 3.1 5.1 None 0 4.9 2.1 3.9 None 0 4.6 2.6 4.4 Additive B 4 4.7 3.0 5.9 Additive B 4 5.5 2.7 4.9 Additive B 7 4.6 4.2 6.3 Additive B 7 4.5 4.2 6.4 Additive B 7 3.6 5.1 8.8

[0178] 3. Extrusion Coating

[0179] Each of the polymer compositions, Control, Comparative Sample I, and Inventive Example I, is subjected to extrusion coating, temperature, and shear to determine thermal stability and breakdown product. All coating experiments were performed on a Black-Clawson Extrusion Coating Line. The extruder was equipped with a 3.5 inch, 30:1 LID, 4:1 compression ratio single flight screw with two spiral Mattock mixing sections. The nominal die width of 91 cm (36 inches) was deckled (metal dam to block the flow in the die at the die exit around the outer edges of the die, and used to decrease the die width, and thus decrease the polymer flow out of the die) to an open die width of 61 cm (24 inches). In extrusion coating, a deckle is a die insert that sets the coating width of a slot die coater or the extrusion width of an extrusion die. It works by constraining the flow as the material exits the die.

[0180] For the extrusion coating evaluation, a constant 15.2 cm (6 inches) air gap was set for all resins. The die gap was set to 20 mil, however small adjustments were needed to maintain a constant coating thickness. The temperatures in each zone of the extruder were 177, 232, 288, and 316° C. (die) (350, 450, 550 and 600° F. (die)), respectively, leading to a target melt temperature of 318° C. (605° F.). The screw speed was 90 rpm, resulting in 250 lb/hr output rate. Line speed was at 440 ft/min (fpm) resulting in a 1.3 mil coating onto a 50 lb/ream KRAFT paper (the width of the KRAFT paper was 61 cm (24 inches); unbleached). A free standing piece of polymer film for analytical testing (e.g., HS-SPME) was obtained by coating the resin onto a release liner. A piece of silicon coated release liner 61 cm (24 inches) wide was inserted between the polymer coating and the paper substrate before the molten polymer curtain touched the paper substrate to form a “polymer coating/release liner/KRAFT paper” configuration in which the paper and release liner are not adhered to each other. The “polymer coating/release liner” sub-configuration was rolled and wrapped in food grade aluminum foil. The solidified polymer coatings were detached from the release liner for analytical testing.

[0181] The amount of neck-in (the difference in actual coating width versus deckle width (61 cm)) was measured at line speeds of 440 feet per min and 880 feet per minute (fpm), resulting in a “1.3 mil” and a “0.65 mil” coating thickness, respectively. Amperage and Horse Power of the extruder were recorded. The amount of backpressure was also recorded for each polymer without changing the back pressure valve position. Draw down is the line speed at which edge imperfections on the polymer coating (typically the width of the polymer coating oscillating along the edges of the polymer coating) were noticed, or the line speed at which the molten curtain completely tears from the die. A reduced rate draw down (RRDD) was measured for all resins at 45 rpm screw speed by ramping up the line speed until edge imperfections or web tear was noticed. Extrusion coating results are shown in Table 5 below.

TABLE-US-00005 TABLE 5 Extrusion coating results 440 NI.sup.1 880 NI.sup.2 RRDD.sup.3 HP.sup.4 AMPS.sup.5 PRESS.sup.6 Control 2.75 2.5 925 26 130 1142 Comparative 2 Nd.sup.7 625 23 120 999 Sample I Inventive 2.125 2 800 25 125 1134 Example I .sup.1 Neck-in at line speed of 440 fpm and screw speed of 90 rpm .sup.2 Neck-in at line speed of 880 fpm and screw speed of 90 rpm .sup.3 Reduced rate draw down at screw speed of 45 rpm .sup.4 Horse power .sup.5 Amperage .sup.6 Back pressure in psi .sup.7 Not determined

TABLE-US-00006 TABLE 6 Extrusion coating polymer properties Example OS.sup.1 rank VOC.sup.2 rank Control 1 2 Comparative 2 3 Sample I Inventive 1 2 Example I .sup.1OS = oxygenated species (OS); VOC = total volatile organic compounds .sup.2See WO2014/003837

[0182] As seen in Tables 3 and 5-6, Inventive Example I has excellent melt strength (MS), excellent thermal stability (low OS and VOC levels), and good extrusion coating properties. It is noted that Inventive Example I is more thermally stable during melt processing than Comparative Sample I and does not decompose into chemical species that produce a pungent odor during processing and could also impart bad taste and odor to foodstuff.

[0183] 4. Polymerization II: Tubular Reactor

[0184] Comparative Sample A′ and Comparative Sample B′

[0185] The polymerization was carried out in a tubular reactor with three reaction zones. In each reaction zone, pressurized water was used for cooling and/or heating the reaction medium, by circulating this water through the jacket of the reactor. The inlet-pressure was 222 MPa, and the pressure drop over the whole tubular reactor system was about 30 MPa. Each reaction zone had one inlet and one outlet. Each inlet stream consisted of the outlet stream from the previous reaction zone and/or an added ethylene-rich feed stream. The non-converted ethylene, and other gaseous components in the reactor outlet, were recycled through a high pressure recycle and a low pressure recycle, and were compressed and distributed through a booster, a primary and a hyper (secondary) compressors. Organic peroxides (tert-Butyl peroxy-2-ethyl hexanoate and Di-tert-butyl peroxide) were fed into each reaction zone. Propionaldehyde (PA) was used as a chain transfer agent (CTA), and it was present in each reaction zone inlet, originating from the low pressure and high pressure recycle flows. The fresh PA was added only to the second and third reactions zones in the ratio equivalent to 0.8 and 0.2 respectively. Fresh ethylene was directed towards the first reaction zone.

[0186] After reaching the first peak temperature (maximum temperature) in reaction zone 1, the reaction medium was cooled with the aid of the pressurized water. At the outlet of reaction zone 1, the reaction medium was further cooled by injecting cold, ethylene-rich feed and the reaction was re-initiated by feeding an organic peroxide system. This process was repeated at the end of the second reaction zone to enable further polymerization in the third reaction zone. The polymer was extruded and pelletized (about 30 pellets per gram), using a single screw extruder at a melt temperature around 230-250° C. The weight ratio of the ethylene-rich feed streams to the three reaction zones was 1.00:0.80:0.20. The internal process velocity was approximately 12.5, 9 and 11 m/sec for respectively the first, second, and third reaction zone. Additional information can be found in Tables 7-10 below.

Inventive Example 1′

[0187] The polymerization was carried out in a tubular reactor with three reaction zones, as discussed above for Comparative Sample A′. All process conditions are the same as for Comparative Sample A′, except for inventive example 1′, Additive A was added to the first zone. The amount can be found in Table 8. Additional information can be found in Tables 7 and 9.

Inventive Example 2′

[0188] The polymerization was carried out in a tubular reactor with three reaction zones, as discussed above for Inventive Example 1′. All process conditions are the same as for Inventive Example 1′, except additional Additive A was fed to the first zone. Additional information can be found in Tables 7-9 below.

Inventive Example 3′

[0189] The polymerization was carried out in a tubular reactor with three reaction zones, as discussed above for Inventive Example 1′. All process conditions are the same as for Inventive Example 1′, except additional Additive A was fed to the first zone and additional propionaldehyde (PA) was fed to adjust the melt index of the material. Additional information can be found in Tables 7-9 below.

TABLE-US-00007 TABLE 7 Pressure and temperature conditions of comparative and inventive examples Inlet- Start- reinitiation reinitiation pressure, temp., temp. temp. 1st Peak 2nd Peak 3rd Peak Mpa ° C. 2nd zone, ° C. 3rd zone, ° C. temp., ° C. temp.,° C. temp. ° C. CS A′ 222.5 145 145 227 295 294 292 CS B′ 222 145 145 222 295 294 294 IE 1′ 222.5 145 145 227 295 294 293 IE 2′ 222 145 145 229 295 293 293 IE 3′ 222 145 145 222 295 294 294

TABLE-US-00008 TABLE 8 Additional information of the comparative and inventive examples Additive A flow/kg h.sup.−1 MI (I.sub.2) Melt Elasticity (1.sup.st zone) g/10 min Conversion % cN CS A′ 0 3.9 37.7 2.6 CS B′ 0 7.0 38.1 1.3 IE 1′ 25 3.8 38.0 3.5 IE 2′ 36 3.7 38.2 4.1 IE 3′ 36 6.8 38.5 2.4

TABLE-US-00009 TABLE 9 Polymer properties of the examples GI-200 A + B(I.sub.2)* Is Mw unit = mm.sup.2 G′ (at C + Is G′ MI (I.sub.2) units = (abs) less gel per 170° C.; Dlog(I.sub.2)** greater g/10 Mw (abs) g/mol than Eq. A 24.6 cm.sup.3 G″ = 500 Pa) unit = Pa than Eq. B Density min g/mol (Eq. 1) value? of film unit = Pa (Eq. B) value? g/cm.sup.3 PG7004 4.1 >300000 232200 No N.D. 146 130 yes 0.9215 (fail) (pass) PT7007 7.5 355000 205000 No N.D. 129 106 yes 0.9174 (fail) (pass) PT7009 8.7 346000 195400 No N.D. 120 100 yes 0.9188 (fail) (pass) A′ 3.9 193,145 234200 Yes 0.37 124 132 no 0.9238 (pass) (fail) B′ 7.0 167,809 235080 Yes 0.19 102 109 no 0.9241 (pass) (fail) IE 1′ 3.8 211,580 236440 Yes 0.1 146 133 yes 0.9232 (pass) (pass) IE 2′ 3.7 232,324 235800 Yes 0.6 160 134 yes 0.9230 (pass) (pass) IE ′ 6.8 203,214 234520 Yes 0.4 117 110 yes 0.9231 (pass) (pass) *A = 2.65 × 10.sup.5 g/mole, and B = −8.00 × 10.sup.3 (g/mole)/(dg/min) **C = 185 Pa and D = −90 Pa/log(dg/min)

[0190] As shown in Table 9, comparative samples (CS) PG7004, PT7007, PT7009 have higher Mw(abs) compared to each respective Equation A value thereby indicating that comparative samples PG7004, PT7007, PT7009 are produced in an autoclave configuration. Comparative samples A′, B′ and inventive examples 1′, 2′ and 3′ each have an Mw(abs) value less than the Equation A value denoting polymerization in a tubular reactor configuration. PG7004, PT7007, PT7009 and inventive examples (1E) 1′, 2′, 3′ each have a higher G′ value than respective value calculated from Equation B (“pass” Equation B) indicating greater longer chain branching than would be possible in a tubular reactor under the same temperature/pressure reactor conditions and without an additive, as indicated by comparative samples A′, B′ (no additive), A′, B′ failing the G′ requirement (“fail” for Equation B) set forth in Equation B. Inventive examples 1′, 2′, 3′ unexpectedly exhibit the combination of enhanced branching (i.e., passing Equation B) and production in a tubular reactor (i.e., passing Equation A) thereby providing a branched polymer in a low energy efficient production process.

[0191] The Inventive Examples exhibit enhanced branching with addition of the additive (Additive A) in multiple reactor types. The enhanced branching resulted in materials with superior melt elasticity and melt strength, which is advantageous in a variety of polymer applications including extrusion coating. In particular, the use of the additives in a tubular reactor enables melt strength in the Inventive Examples compared to materials produced in an autoclave reactor. The resultant ethylene-based polymer composition also had improved (reduced) taste and odor performance, as compared to other polymer compositions modified with other types of branching agents.

[0192] 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.