Ethylene polymers having improved melt strength and thermal stability

Abstract

An ethylene-based polymer formed by reacting at least the following: ethylene, and at least one asymmetric polyene of Structure 1 described herein: [Selection diagram] None

Description

Background Art

[0001] The present invention relates to an ethylene-based polymer such as an LDPE-type polymer having improved melt strength and improved thermal stability and reducing taste and odor. Such polymers are useful for extrusion coating and film applications. Conventional low-density polyethylene (LDPE) has good processability, but there is still a need for improvement in melt strength and thermal stability when used in extrusion coating and film applications.

[0002] Low-density polyethylene is disclosed in the following references. US Patent Publication No. 2015 / 0197590 discloses an ethylene-based polymer formed by reacting at least the following ethylene and an asymmetric polyene containing at least one "alpha, beta-unsaturated end" and "C-C double bond end", and the reaction is carried out in the presence of at least one free radical initiator. US Patent Publication No. 2008 / 0242809 discloses a process for preparing a copolymer of ethylene and a comonomer, and the comonomer is a di- or higher-functional (meth)acrylate. US Patent No. 3,542,749 discloses an ethylene copolymer containing polymerized ethylene and polymerized oleyl acrylate, elsyl acrylate, N-oleyl acrylamide, nelsyl acrylamide, or any mixture thereof.

[0003] Additional polymerization is disclosed in the following references: Tung, L.H., et al., Preparation of Polystyrene with Long Chain Branches via Free Radical Polymerization, J. Polym. Sci., Polym. Chem. Ed., (1981), 19, 2027-39; Tung, L.H., Branching Kinetics in Copolymerization of Styrene with a Chain-Transfer Monomer, J. Polym. Sci., Polym. Chem. Ed., (1981), 19, 3209-3217; Liu, J., et al., Branched Polymer via Free Radical Polymerization of Chain Transfer Monomer: A Theoretical and Experimental Investigation, J. Polym. Sci. Part A: Polym. Chem., (2007), 46, 1449-59; U.S. Patent Publication No. 2009 / 0253878; U.S. Patent No. 5,763,629; U.S. Patent No. 5,539,075; International Patent Publication No. WO 2012 / 084787; International Patent Publication No. WO 2007 / 110127; International Patent Publication No. WO 97 / 45465.

[0004] However, as discussed, there remains a need for ethylene-based polymers having improved melt strength and improved thermal stability for use in extrusion coating and film applications. These needs are met by the following invention.

Summary of the Invention

[0005] An ethylene-based polymer formed by reacting at least ethylene and at least one asymmetric polyene of Structure 1 below,

Chemical formula

Brief Description of the Drawings

[0006]

Figure 1

Modes for Carrying Out the Invention

[0007] The ethylene-based polymers described herein have been discovered, and they have excellent melt strength and thermal stability (e.g., LDPE polymerized in the presence of isoprenyl methacrylate (IPMA) is thermally more stable during melt processing than LDPE polymerized in the presence of polypropylene glycol allyl ether methacrylate (PPG AEMA)). These polymers are well-suited for extrusion coating and film applications.

[0008] As described above, an ethylene-based polymer is provided, and the ethylene-based polymer is formed by reacting at least ethylene and at least one of the following asymmetric polyenes of Structure 1:

Chemical formula

[0009] The ethylene-based polymer may include a combination of two or more of the embodiments described herein.

[0010] The asymmetric polyene may include a combination of two or more of the embodiments described herein.

[0011] In one embodiment or a combination of the embodiments described herein, the asymmetric polymer is an asymmetric diene.

[0012] In one embodiment or a combination of the embodiments described herein, Structure 1 is Structure 1A. [Chemical formula] .

[0013] In one embodiment or a combination of the embodiments described herein, the ethylene-based polymer has a density of ≥ 0.900, or ≥ 0.905, or ≥ 0.910 grams per cubic centimeter (g / cc or g / cm 3 ³). In a further embodiment, the asymmetric polyene is an asymmetric diene.

[0014] In one embodiment or a combination of the embodiments described herein, the ethylene-based polymer has a density of ≤ 0.950, or ≤ 0.945, or ≤ 0.940 grams per cubic centimeter (g / cc or g / cm 3 ³). In a further embodiment, the asymmetric polyene is an asymmetric diene.

[0015] In one embodiment or a combination of the embodiments described herein, the ethylene-based polymer has a density of 0.900 to 0.940 g / cc, or 0.905 to 0.935 g / cc, or 0.910 to 0.930 g / cc (1 cc = 1 cm 3 ³). In a further embodiment, the asymmetric polyene is an asymmetric diene.

[0016] In one embodiment or a combination of the embodiments described herein, the ethylene-based polymer has a melt index (I2) of 0.10 to 100 g / 10 min, or 0.50 to 80 g / 10 min, or 1.0 to 60 g / 10 min, or 5.0 to 40 g / 10 min, or 10 to 20 g / 10 min. In a further embodiment, the asymmetric polyene is an asymmetric diene.

[0017] In one embodiment or a combination of the embodiments described herein, the ethylene-based polymer has a melt index (I 2 ) of 0.5 to 60 g / 10 min, or 1.0 to 40 g / 10 min, or 2.0 to 20 g / 10 min, or 5.0 to 10 g / 10 min. In a further embodiment, the asymmetric polyene is an asymmetric diene.

[0018] In one embodiment or a combination of the embodiments described herein, the ethylene-based polymer has a melt index (I 10 ) of 45 to 100 g / 10 min, or 50 to 90 g / 10 min, or 55 to 85 g / 10 min, or 60 to 80 g / 10 min. In a further embodiment, the asymmetric polyene is an asymmetric diene.

[0019] In one embodiment or a combination of the embodiments described herein, the ethylene-based polymer has a melt index ratio (I 10 / I 2 ) of 8.0 to 14.0, or 9.0 to 13, or 10 to 11. In a further embodiment, the asymmetric polyene is an asymmetric diene.

[0020] In one embodiment or a combination of the embodiments described herein, the ethylene-based polymer has a melt strength (MS) of ≧10, or ≧11, or ≧12, or ≧13. In a further embodiment, the asymmetric polyene is an asymmetric diene.

[0021] In one embodiment or a combination of the embodiments described herein, the ethylene-based polymer has a melt strength (MS) of ≦50, or ≦40, or ≦30, or ≦20. In a further embodiment, the asymmetric polyene is an asymmetric diene.

[0022] In one embodiment or a combination of the embodiments described herein, the ethylene-based polymer has a melt strength to melt index ratio (MS / I 2) has. In a further embodiment, the asymmetric polyene is an asymmetric diene.

[0023] In one embodiment or a combination of embodiments described herein, the ethylene-based polymer has a molecular weight distribution (MWD) of 7.0 to 13, or 8.0 to 12, or 9.0 to 11. In a further embodiment, the asymmetric polyene is an asymmetric diene.

[0024] In one embodiment or a combination of embodiments described herein, the ethylene-based polymer has a number average molecular weight (Mn) of 10,000 to 22,000 g / mol, or 12,000 to 20,000 g / mol, or 14,000 to 18,000 g / mol. In a further embodiment, the asymmetric polyene is an asymmetric diene.

[0025] In one embodiment or a combination of embodiments described herein, the ethylene-based polymer has a weight average molecular weight (Mw) of 140,000 to 180,000 g / mol, or 145,000 to 175,000 g / mol, or 150,000 to 170,000 g / mol. In a further embodiment, the asymmetric polyene is an asymmetric diene.

[0026] In one embodiment or a combination of embodiments described herein, the ethylene-based polymer has a z-average molecular weight (Mz) of 800,000 to 1,200,000 g / mol, or 850,000 to 1,150,000 g / mol, or 900,000 to 1,100,000 g / mol. In a further embodiment, the asymmetric polyene is an asymmetric diene.

[0027] In one embodiment or a combination of embodiments described herein, the ethylene-based polymer has an OS rank as described herein of ≤2 and a VOC rank as described herein of ≤3. In a further embodiment, the asymmetric polyene is an asymmetric diene.

[0028] In one embodiment or a combination of embodiments described herein, the ethylene-based polymer has a neck-in of ≦ 2.0 at a line speed of 440 fpm and a screw speed of 90 rpm. In a further embodiment, the asymmetric polyene is an asymmetric diene.

[0029] In one embodiment or a combination of embodiments described herein, in the reaction, the asymmetric polyene is present in an amount of ≧ 100 ppm by mass, or ≧ 150 ppm by mass, or ≧ 200 ppm by mass, based on the total amount of ethylene. In a further embodiment, the asymmetric polyene is an asymmetric diene.

[0030] In one embodiment or a combination of embodiments described herein, in the reaction, the asymmetric polyene is present in an amount of ≦ 5,000 ppm by mass, or ≦ 2,000 ppm by mass, or ≦ 1,000 ppm by mass, based on the total amount of ethylene. In a further embodiment, the asymmetric polyene is an asymmetric diene.

[0031] In one embodiment or a combination of embodiments described herein, the ethylene-based polymer is a low-density polyethylene containing polyene in the reacted form. In a further embodiment, the asymmetric polyene is an asymmetric diene.

[0032] In one embodiment or a combination of embodiments described herein, the ethylene-based polymer contains ethylene and polyene as the only monomer species in the polymerized form. In a further embodiment, the asymmetric polyene is an asymmetric diene.

[0033] In one embodiment or a combination of embodiments described herein, the ethylene-based polymer includes at least one structure selected from Structure I, [Chemical formula] , wherein R1 is selected from H or alkyl. In a further embodiment, the asymmetric polyene is an asymmetric diene.

[0034] In the above structure l, the notation

Chemical formula

[0035] In one embodiment or a combination of embodiments described herein, the ethylene-based polymer, in the reacted form, contains ≧0.075 mol, or ≧0.100 mol, or ≧0.150 mol, or ≧0.200 mol of asymmetric polyene per 1000 mol of ethylene-based polymer backbone carbons, based on the weight of the polymer. In a further embodiment, the asymmetric polyene is an asymmetric diene.

[0036] In one embodiment or a combination of embodiments described herein, the ethylene-based polymer, in the reacted form, contains ≦10.0 mol, or ≦5.00 mol, or ≦2.00 mol, or ≦1.00 mol of asymmetric polyene per 1000 mol of ethylene-based polymer backbone carbons, based on the weight of the polymer. In a further embodiment, the asymmetric polyene is an asymmetric diene.

[0037] In one embodiment or a combination of embodiments described herein, the ethylene-based polymer, in the reacted form, contains ≦2.00 mol, or ≦1.50 mol, or ≦1.00 mol, or ≦0.500 mol of asymmetric polyene per 1000 mol of ethylene-based polymer backbone carbons, based on the weight of the polymer. In a further embodiment, the asymmetric polyene is an asymmetric diene.

[0038] In one embodiment or a combination of embodiments described herein, the ethylene-based polymer, in the reacted form, contains ≧0.03 wt%, or ≧0.04 wt%, or ≧0.05 wt% of asymmetric polyene, based on the weight of the polymer. In a further embodiment, the asymmetric polyene is an asymmetric diene.

[0039] In one embodiment or a combination of embodiments described herein, the ethylene-based polymer, in its reacted form, contains ≦1.5 wt%, or ≦1.2 wt%, or ≦1.0 wt%, or ≦0.8 wt%, or ≦0.6 wt%, or ≦0.4 wt% of an asymmetric polyene based on the weight of the polymer. In a further embodiment, the asymmetric polyene is an asymmetric diene.

[0040] In one embodiment or a combination of embodiments described herein, the ethylene-based polymer, in its reacted form, contains ≦0.50 wt%, or ≦0.20 wt%, or ≦0.10 wt% of an asymmetric polyene based on the weight of the polymer. In a further embodiment, the asymmetric polyene is an asymmetric diene.

[0041] In one embodiment or a combination of embodiments described herein, the ethylene-based polymer contains ethylene and at least one asymmetric polyene as the only monomer units. In a further embodiment, the asymmetric polyene is an asymmetric diene.

[0042] In one embodiment or a combination of embodiments described herein, the ethylene-based polymer contains ethylene and at least two asymmetric polyenes as the only monomer units. In a further embodiment, each asymmetric polyene is an asymmetric diene.

[0043] In one embodiment or a combination of embodiments described herein, the ethylene-based polymer contains ethylene and one asymmetric polyene as the only monomer units. In a further embodiment, the asymmetric polyene is an asymmetric diene.

[0044] In one embodiment or a combination of embodiments described herein, the ethylene-based polymer contains ethylene and two asymmetric polyenes as the only monomer units. In a further embodiment, each asymmetric polyene is an asymmetric diene.

[0045] Compositions comprising an ethylene polymer of any one or more of the embodiments described herein are also provided.

[0046] In one embodiment or a combination of embodiments described herein, the composition further comprises at least one other polymer. In a further embodiment, the at least one other polymer is different from the ethylene polymer of the present invention in one or more properties, such as density, melt index (I2), Mw, Mn, or Mw / Mn.

[0047] In one embodiment or a combination of embodiments described herein, the at least one other polymer is a linear low density ethylene / alpha-olefin copolymer. In a further embodiment, the linear low density ethylene / alpha-olefin copolymer has a density of 0.910 to 0.940 g / cc and a melt index (I2) of 0.5 to 50 g / 10 min.

[0048] The present invention also provides an article comprising at least one component formed from the composition of the present invention.

[0049] In one embodiment or a combination of embodiments described herein, the article is a film or a coating.

[0050] In one embodiment or a combination of embodiments described herein, the article is a film.

[0051] In one embodiment or a combination of embodiments described herein, the article is a coating.

[0052] The ethylene polymer of the present invention may comprise a combination of two or more of the embodiments described herein.

[0053] The composition of the present invention may comprise a combination of two or more of the embodiments described herein.

[0054] The article of the present invention may include a combination of two or more embodiments described herein.

[0055] The present invention also provides a method for forming an ethylene polymer as described herein, the method including polymerizing ethylene in the presence of an asymmetric polyene as described above.

[0056] In one embodiment or a combination of embodiments described herein, ethylene is polymerized in the presence of at least 50 mol ppm of an asymmetric polyene (based on the total amount of monomers in the reaction feed). In a further embodiment, the asymmetric polyene is an asymmetric diene.

[0057] In one embodiment or a combination of embodiments described herein, the polymerization pressure is ≧100 MPa. In a further embodiment, the polymerization is carried out at a pressure of 150 MPa to 350 MPa. In a further embodiment, the polymerization is carried out at a temperature of 100 °C to 380 °C. In a further embodiment, the method is carried out in a reactor configuration including at least one tubular reactor.

[0058] In one embodiment or a combination of embodiments described herein, the polymerization is carried out at a temperature of 100 °C to 380 °C. In a further embodiment, the method is carried out in a reactor configuration including at least one tubular reactor.

[0059] In one embodiment or a combination of embodiments described herein, the polymerization is carried out in a reactor configuration including at least one tubular reactor or at least one autoclave.

[0060] In one embodiment or a combination of embodiments described herein, the polymerization is carried out in a reactor configuration including at least one autoclave.

[0061] In one embodiment or a combination of embodiments described herein, the polymerization is carried out in a reactor configuration including at least one tubular reactor.

[0062] In one embodiment or a combination of the embodiments described herein, the polymerization is carried out in a reactor configuration comprising at least one tubular reactor and at least one autoclave reactor.

[0063] In one embodiment or a combination of the embodiments described herein, the asymmetric diene is added to the polymerization in an amount of 0.002 to 0.300 mole percent, and further 0.005 to 0.300 mole percent, based on the total molar amount of ethylene and asymmetric diene added to the polymerization.

[0064] The process of the present invention may include a combination of two or more of the embodiments described herein.

[0065] Process To produce the ethylene-based polymers of the present invention, a high-pressure free-radical initiated polymerization process is typically used. Two different types of high-pressure free-radical initiated polymerization processes are known. In the first type, a stirred autoclave vessel having one or more reaction zones is used. The autoclave reactor typically has several injection points for the initiator or monomer feed, or both. In the second type, a jacketed tube is used as a reactor having one or more reaction zones. The length of the reactor, which is suitable but not limited thereto, can be 100 to 3000 meters (m) or 1000 to 2000 meters. The start of the reaction zone is typically defined by a side injection of any of the reaction initiator, ethylene, chain transfer agent (or telomer), comonomer(s), and combinations thereof, for both types of reactors. The high-pressure process can be carried out in an autoclave or tubular reactor, each having one or more reaction zones, or in a combination of an autoclave and a tubular reactor, each having one or more reaction zones.

[0066] Often, conventional chain transfer agents are used to control the molecular weight. In a preferred embodiment, one or more conventional chain transfer agents (CTAs) are added to the polymerization process of the present invention. Typical CTAs that can be used include, but are not limited to, propylene, isobutane, n-butane, 1-butene, methyl ethyl ketone, acetone, ethyl acetate, propionaldehyde, ISOPAR (ExxonMobil Chemical), and isopropanol. In one embodiment or a combination of the embodiments described herein, the amount of CTA used in the process is from 0.03 to 10 weight percent of the total reaction mixture.

[0067] In one embodiment or a combination of embodiments described herein, the process includes a recycle loop process to improve conversion efficiency. In one embodiment or a combination of embodiments described herein, polymerization can be carried out in a tubular reactor as described in International Patent Application No. PCT / US12 / 059469, filed October 10, 2012. This patent application describes a multi-zone reactor and describes alternative locations for supplying fresh ethylene to control the ratio of ethylene to CTA and thus control polymer properties. Fresh ethylene can be added simultaneously at multiple locations to achieve the desired ethylene to chain transfer ratio. Similarly, as described in International Application No. PCT / US12 / 064284 (filed November 9, 2012), the addition of fresh CTA can be carefully selected to control polymer properties. Fresh CTA can be added simultaneously at multiple locations to achieve the desired CTA to ethylene ratio. Similarly, the addition points and amounts of fresh polyolefin described herein can be used to control gel formation while maximizing the desired properties of improved melt strength and performance in the intended application. Fresh polyolefin can be added simultaneously at multiple locations to achieve the desired polyolefin to ethylene ratio. The use of polyolefin to broaden the molecular weight distribution and improve melt strength places additional requirements on the distribution of CTA and polyolefin along the reactor system while minimizing potential adverse effects such as gel formation, reactor fouling, process instability, and low efficiency of polyolefin to achieve the desired changes in product properties.

[0068] In one embodiment or a combination of embodiments described herein, polymerization is carried out in a reactor configuration that includes at least one autoclave reactor and at least one tubular reactor. In a multi-reactor system, the autoclave reactor is typically upstream of the tubular reactor. The addition points and amounts of fresh ethylene, fresh CTA, and fresh polyolefin can be appropriately controlled to achieve the desired ratios of CTA to ethylene and polyolefin to ethylene in the feed and / or within the reaction zone.

[0069] In one embodiment or a combination of embodiments described herein, the asymmetric diene is added to the polymerization in an amount of 0.002 to 0.300 mole percent, and further 0.005 to 0.300 mole percent, based on the total number of moles of ethylene and asymmetric diene added to the polymerization. In a further embodiment, the polymerization is carried out in two reactors. In another embodiment, the polymerization is carried out in one reactor having a plurality or at least two reaction zones.

[0070] The ethylene used for the production of the ethylene-based polymer can be purified ethylene obtained by removing polar components from the loop recycle stream or obtained by using a reaction system configuration such that only fresh ethylene is used to make the polymers of the present invention. It is not typical to require purified ethylene to make an ethylene-based polymer. In such cases, ethylene from the recycle loop may be used.

[0071] In one embodiment or a combination of embodiments described herein, the ethylene-based polymer comprises ethylene and one or more comonomers, preferably one comonomer. Comonomers include, but are not limited to, α-olefins, acrylates, methacrylates and anhydrides, each typically having 20 or fewer carbon atoms. The α-olefin comonomer can have 3 to 10 carbon atoms, or alternatively, the α-olefin comonomer can have 3 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.

[0072] In one embodiment or a combination of embodiments described herein, the ethylene-based polymer comprises ethylene and at least one asymmetric polyene as the only monomer units.

[0073] Initiator Free radical initiators are generally used to produce the ethylene polymers of the present invention. Exemplary organic peroxides include, but are not limited to, cyclic peroxides, diacyl peroxides, dialkyl peroxides, hydroperoxides, peroxicarbonates, peroxydicarbonates, peroxy esters, and peroxyketals. Preferred initiators are t-butyl peroxypivalate, di-t-butyl peroxide, t-butyl peroxyacetate and t-butyl peroxy-2- hexanoate, or mixtures thereof. In one embodiment, these organic peroxide initiators are used in an amount of 0.001 to 0.2 weight percent based on the weight of the polymerizable monomer.

[0074] In one embodiment or a combination of embodiments described herein, the initiator is added to at least one polymerization reaction zone where the initiator has a "half-life temperature in 1 second" above 255 °C, preferably above 260 °C. In a further embodiment, such initiator is used at a peak polymerization temperature of 320 °C to 350 °C. In another embodiment, the initiator comprises at least one peroxide group incorporated in a cyclic structure. Examples of such initiators include TRIGONOX 301 (3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonan) and TRIGONOX 311 (3,3,5,7,7-pentamethyl-1,2,4-trioxepane), both of which are available from Akzo Nobel, and HMCH-4-AL (3,3,6,6,9,9-hexamethyl-1,2,4,5-tetroxonan) available from United Initiators, but are not limited thereto. See International Patent Application Publication Nos. WO02 / 14379 and WO01 / 68723.

[0075] Additive The composition of the present invention may contain one or more additives. Examples of additives include, but are not limited to, stabilizers, plasticizers, antistatic agents, pigments, dyes, nucleating agents, fillers, lubricants, flame retardants, processing aids, smoke suppressants, viscosity control agents, and antiblocking agents. The polymer composition may contain, for example, less than 10 percent by weight of a combination of one or more additives, based on the weight of the polymer of the present invention.

[0076] In one embodiment, the ethylene-based polymer of the present invention is treated with one or more stabilizers, such as antioxidants like IRGANOX 1010, IRGANOX 1076, and IRGAFOS 168. Generally, the polymer is treated with one or more stabilizers prior to extrusion or other melt processes.

[0077] In addition to the ethylene-based polymer of the present invention, the composition of the present invention can further contain at least one other polymer. Blends and mixtures of the polymer of the present invention with other polymers can be prepared. Polymers suitable for blending with the polymer of the present invention include natural and synthetic polymers. Exemplary polymers for blending include propylene-based polymers (both impact-modified polypropylene, isotactic polypropylene, atactic polypropylene, and random propylene / ethylene copolymers), various types of ethylene-based polymers, such as high-pressure, free-radical LDPE, heterogeneously branched LLDPE (typically via a Ziegler-Natta catalyst), homogeneously branched linear or substantially linear PE (typically via a single-site, e.g., metallocene catalyst), e.g., multiple reactor PE (a composition of heterogeneously branched PE and homogeneously branched PE “in the reactor,” e.g., the products disclosed in U.S. Patent Nos. 6,545,088 (Kolthammer et al.), 6,538,070 (Cardwell et al.), 6,566,446 (Parikh et al.), 5,844,045 (Kolthammer et al.), 5,869,575 (Kolthammer et al.), and 6,448,341 (Kolthammer et al.)), ethylene vinyl acetate (EVA), ethylene / vinyl alcohol copolymer, polystyrene, impact-modified polystyrene, ABS, styrene / butadiene block copolymer, and hydrogenated derivatives thereof (SBS and SEBS), and thermoplastic polyurethane. Other ethylene-based polymers include homogeneous polymers, such as olefin plastomers and elastomers (e.g., polymers available under the trade names AFFINITY Plastomers and ENGAGE Elastomers (The Dow Chemical Company), and EXACT (ExxonMobil Chemical Co.)).Propylene-based copolymers (e.g., polymers available under the trade names VERSIFY Plastomers&Elastomers (The Dow Chemical Company) and VISTAMAXX (ExxonMobil Chemical Co.)) may also be useful as components in blends containing the polymers of the present invention.

[0078] Use The polymers of the present invention can be used in various conventional thermoplastic manufacturing processes for producing useful articles, including single-layer and multilayer films; molded articles such as blow-molded, injection-molded, or rotomolded articles; coatings such as extrusion coatings; fibers; and woven or non-woven fabrics.

[0079] The polymers of the present invention can be used as various films, including, but not limited to, transparent shrink films, collation shrink films, cast stretch films, silage films, stretch hoods, sealants, and diaper backsheets. Other suitable applications include, but are not limited to, wires and cables, gaskets and profiles, adhesives, footwear components, and automotive interior parts.

[0080] Definition Unless otherwise indicated, implied by context, or not conventional in the art, all parts and percentages are by weight and all test methods are the latest as of the filing date of this application.

[0081] As used herein, the term "composition" includes the composition and mixtures of materials including reaction products and decomposition products formed from the materials of the composition.

[0082] As used herein, the terms "blend" or "polymer blend" refer to a mixture of two or more polymers. The blend may or may not be miscible (not phase-separated at the molecular level). The blend may or may not be phase-separated. The blend may or may not contain one or more domain configurations, as determined by transmission electron spectroscopy, light scattering, X-ray scattering, and other methods known in the art. The blend can be achieved by physically mixing two or more polymers at the macro level (e.g., melt blend resin or compounding) or at the micro level (e.g., simultaneous molding in the same reactor).

[0083] The term "polymer" refers to a compound prepared by polymerizing monomers, whether of the same kind or different kinds. Thus, the general term "polymer" encompasses the term "homopolymer" (which refers to a polymer prepared from only one kind of monomer, with the understanding that trace amounts of impurities may be incorporated into the polymer structure), and the term "interpolymer" as defined below. Trace amounts of impurities may be incorporated in and / or into the polymer.

[0084] The term "interpolymer" refers to a polymer prepared by the polymerization of at least two different kinds of monomers. The general term "interpolymer" includes copolymers (which refer to polymers prepared from two different monomers) and polymers prepared from more than two different kinds of monomers.

[0085] The term "ethylene-based polymer" refers to a polymer that contains 50 wt% or more than half of polymerized ethylene, based on the weight of the polymer, and optionally may contain at least one comonomer.

[0086] The term "ethylene-based interpolymer" refers to an interpolymer that contains 50 wt% or more than half of polymerized ethylene, based on the weight of the interpolymer, and contains at least one comonomer.

[0087] The term "ethylene-based copolymer" refers to a copolymer that, based on the weight of the copolymer, contains 50 wt% or a majority of polymerized ethylene and a comonomer as the only monomer species.

[0088] The term "propylene-based polymer" refers to a polymer that, based on the weight of the polymer, contains a majority amount of polymerized propylene and optionally may contain at least one comonomer.

[0089] The term "reaction zone", as used herein, refers to a reaction zone in which a polymerization reaction is initiated or restarted by the addition of a free radical or a component that dissociates into and / or generates a free radical. Typically, the reaction medium is heated and / or cooled by a heat transfer medium flowing through a jacket surrounding the reactor. The reaction zone may also be initiated by the addition of fresh ethylene and / or recycled ethylene and a free radical or a component that dissociates into and / or generates a free radical.

[0090] The term "fresh", as used herein in relation to an ethylene-based feed component (i.e., "fresh ethylene", "fresh CTA", "fresh polyene"), refers to a reactant that is provided from an external source(s) and not internally provided from a recycled source(s).

[0091] The term "reactor system", as used herein, refers to a device used to polymerize and isolate a polymer. Such devices include, but are not limited to, one or more reactors, reactor preheater(s), monomer reactor cooling device(s), hypercompressor(s), primary compressor(s), and / or booster compressor(s).

[0092] As used herein, the term "reactor configuration" refers to one or more reactors used to polymerize a polymer, and optionally, one or more reactor preheaters and ethylene feed cooling devices. Such reactors include, but are not limited to, autoclave reactors (plural possible), tubular reactors (plural possible), and combinations of autoclave and tubular reactors.

[0093] The terms "comprising," "including," "having," and their derivatives are not intended to exclude the presence of any additional components, steps, or procedures, whether or not they are specifically disclosed. To avoid any ambiguity, all compositions claimed through the use of the term "comprising" may include the compound, whether or not it is an additional additive, adjuvant, or polymeric compound, unless there is a conflicting description. In contrast, the term "consisting essentially of" excludes any other components, steps, or procedures from the scope of any subsequent reference, except for those that are not operationally essential. The term "consisting of" excludes any component, step, or procedure that is not specifically described or listed.

[0094] Test Methods Density The sample for density measurement was prepared according to ASTM D1928. The sample was pressed at 374°F (190°C) and 30,000 psi for 3 minutes, then at 70°F (21°C) and 30,000 psi for 1 minute. The density measurement was performed within 1 hour of sample pressing using ASTM D792, Method B.

[0095] Melt Index The melt index, or I2, was measured according to ASTM D1238, Condition 190°C / 2.16 kg and reported as grams eluted per 10 minutes. I10 was measured according to ASTM D 1238, Condition 190°C / 10 kg and the amount eluted per 10 minutes was reported in grams.

[0096] Melt strength Melt strength was measured at 190°C using a Goettfert Rheotens 71.97 (Goettfert Inc.; Rock Hill, SC). A melt sample (about 25 - 50 grams) was fed through a Goettfert Rheotester 2000 capillary rheometer with a flat entry angle (180 degrees) 30 mm in length and 2 mm in diameter. The sample was fed into, compressed, and melted for 10 minutes in a barrel (length = 300 mm, diameter = 12 mm) before being extruded at a constant piston speed of 0.265 mm / second corresponding to a wall shear rate of 38.2 seconds -1 The extrudate was passed through a Rheotens wheel located 100 mm below the die exit and pulled downward by the wheel at an acceleration of 2.4 mm / second 2 The force (cN) applied to the wheel was recorded as a function of the wheel speed (in mm / s). The sample was repeated at least twice until two curves of force (in cN) as a function of strand speed (in mm / second) overlapped, and then the curve with the highest speed at which the strand broke was recorded. The melt strength was reported as the plateau force (cN) before the strand broke.

[0097] Dynamic mechanical spectroscopy (DMS) The resin was compression molded into a "3 mm thick x 1 inch" circular plaque at 350°F for 6.5 minutes under 20,000 lb f in air. The sample was then removed from the compression machine, placed on a counter, and cooled.

[0098] Under nitrogen purge, a constant temperature frequency sweep was performed using a TA Instruments "Advanced Rheometric Expansion System (ARES)" equipped with 25 mm (diameter) parallel plates. The sample was placed on the plate and melted at 190 °C for 5 minutes. Then, the plates were closed to a 2 mm gap, and the sample was trimmed (removing the excess sample extending beyond the circumference of the "25 mm diameter" plate), and then the test was started. This method incorporated an additional 5-minute delay to allow for temperature equilibration. This experiment was performed at 190 °C over a frequency range of 0.1 to 100 radians / second. The strain amplitude was constant at 10%. The complex viscosity η*, tan(δ) or tandelta, the viscosity at 0.1 radians / second (V0.1), the viscosity at 100 radians / second (V100), and the viscosity ratio (V0.1 / V100) were measured.

[0099] Triple detector gel permeation chromatography (TDGPC) The chromatography system consisted of a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph equipped with a Precision Detectors (now Agilent Technologies) dual-angle laser light scattering (LS) detector model 2040 and subsequently an internal IR5 infrared detector (IR5) coupled to a PolymerChar 4-capillary viscosity detector (three detectors in series). For all light scattering measurements, a 15-degree angle was used for measurement purposes. The autosampler oven compartment was set to 160 °C and the column compartment was set to 150 °C. The columns used were four Agilent "Mixed A" columns, each 30 cm long and filled with 20 micron linear mixed-bed particles. The chromatography solvent used was 1,2,4-trichlorobenzene containing 200 mass ppm of butylated hydroxytoluene (BHT). The solvent source was nitrogen-injected. The injection volume was 200 microliters and the flow rate was 1.0 milliliter / minute.

[0100] The calibration of the GPC column set was performed with polystyrene standards having 21 narrow molecular weight distributions and molecular weights in the range of 580 to 8,400,000 g / mol. These standards were arranged in six "cocktail" mixtures with at least a 10 separation between individual molecular weights. The standards were purchased from Agilent Technologies. The polystyrene standards were prepared at "0.025 grams in 50 milliliters of solvent" for molecular weights of 1,000,000 g / mol and above, and "0.05 grams in 50 milliliters of solvent" for molecular weights below 1,000,000 g / mol. The polystyrene standard solution was dissolved at 80 degrees Celsius for 30 minutes with gentle stirring. The polystyrene standard peak molecular weight (IR5 detector) was converted to polyethylene molecular weight using Equation 1 (described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)): [Number] , where M is the molecular weight, A has a value of 0.4315, and B is equal to 1.0.

[0101] The fifth-degree polynomial was used to fit each polyethylene equivalent calibration point. A slight adjustment (about 0.415 - 0.44) to A was made to correct for column resolution and band broadening effects so that the NIST standard NBS1475 was obtained at 52,000 g / mol (Mw).

[0102] The total plate count of the GPC column set was performed with EICOSANE (prepared at 0.04 g in 50 milliliters of "TCB stabilizing solvent" and dissolved for 20 minutes with gentle stirring). The plate count (Equation 2) and symmetry (Equation 3) were measured with a 200 microliter injection according to the following equations. [Number] Wherein, RV is the retention volume in milliliters, the peak width is in milliliters, the peak maximum is the maximum height of the peak, and the half height is half the height of the peak maximum. [Number] Wherein, RV is the retention volume in milliliters, the peak width is in milliliters, the "peak maximum" is the maximum IR signal height corresponding to the "RV position" on the chromatogram, the "one-tenth height" is one-tenth the height of the peak maximum, the "rear peak" refers to the peak tail at the signal retention volume after the peak maximum (at one-tenth the height of the peak maximum), and the "front peak" refers to the peak front at the signal retention volume before the peak maximum (at one-tenth the height of the peak maximum). The plate count of the chromatography system should be more than 24,000, and the symmetry should be between 0.98 and 1.22.

[0103] The sample was prepared in a semi-automatic mode using PolymerChar's "Instrument Control" software, with the target weight of the sample set to 2 mg / ml. Through the PolymerChar high-temperature autosampler, a solvent (containing 200 ppm of BHT) was added to a vial with a septum cap that had been pre-nitrogen sparged. Decane (flow marker) was added to each sample (about 5 microliters). The sample was dissolved at 160 °C for 2 hours under "low-speed" shaking.

[0104] IR5 Chromatogram The calculations of Mn (converted), Mw (converted), and Mz (converted) were based on GPC results using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph, the IR chromatogram with the baseline subtracted at each equally spaced data collection point (i) according to Equations 4 - 6, and the polyethylene equivalent molecular weights obtained from the narrow standard calibration curve at point (i) of Equation 1, using the PolymerChar GPCOne™ software (version 2013G). Table 3 lists the conventional GPC results of the examples and comparative examples using the following Equations 4 - 6 for conventional GPC. [Number] 。

[0105] To monitor the deviation over time, a flow marker (decane) was introduced into each sample via a micropump controlled by the PolymerChar GPC-IR system. Using this flow marker (FM, decane here), the pump flow rate (flow rate (nominal)) of each sample was linearly corrected by aligning the RV value of each decane peak in the sample (RV(FM sample)) with the RV value of the decane peak in the narrow standard calibration (RV(calibrated FM)). Subsequently, it was assumed that any time change in the decane marker peak was related to a linear shift in the flow rate (flow rate (effective)) for the entire experiment. To facilitate the highest accuracy in RV measurement of the flow marker peak, a least-squares fitting routine was used to fit the peak of the flow marker concentration chromatogram to a quadratic equation. Subsequently, the first derivative of the quadratic equation was used to determine the true peak position. After calibrating the system based on the flow marker peak, the effective flow rate (relative to the narrow standard calibration) was calculated using Equation 7. The processing of the flow marker peak was performed via the PolymerChar GPCOne™ software. The acceptable flow correction should be such that the effective flow rate is within + / - 2% of the nominal flow rate. Flow rate (effective) = Flow rate (nominal) * (RV(calibrated FM) / RV(FM sample)) (Equation 7).

[0106] The systematic approach for determining the multiple detector offset was performed in a manner consistent with that published by Balke, Mourey et al. (Mourey and Balke, Chromatography Polym. Chpt12, (1992)) (Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym. Chpt13, (1992)). The alignment of the triple detector log (MW and IV) results (generated from broad homopolymer polyethylene standards (Mw / Mn = 3)) to the narrow standard column calibration results (generated from narrow standard calibration curves) was performed using PolymerChar's GPCOne™ software.

[0107] Light scattering chromatogram Absolute molecular weight data (MW absolute) was obtained using PolymerChar's GPCOne™ software in a manner consistent with that published by Zimm (Zimm, B.H., J. Chem. Phys., 16, 1099 (1948)) and Kratochvil (Kratochvil, P., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NY (1987)). The overall injection concentration used for molecular weight determination was derived from the mass detector area and mass detector constant obtained from one of a suitable linear polyethylene homopolymer or a polyethylene standard of known weight average molecular weight (traceable to the NBS 1475 homopolymer polyethylene reference sample). The molecular weight calculated (using GPCOne™) was obtained using the light scattering constant and a refractive index concentration coefficient, dn / dc, of 0.104, derived from one or more of the polyethylene standards described below. Generally, the mass detector response (IR5) and light scattering constant (determined using GPCOne™) should be determined from linear standards having a molecular weight in excess of about 50,000 g / mol. Table 5 lists the light scattering GPC results for the examples and comparative examples.

[0108] The equation for Mw (absolute) is an area-based result that uses the 15-degree light scattering signal minus the baseline and the IR5 measurement sensor signal minus the baseline (applying mass and light scattering constants), as determined from GPCOne (trademark) software: [Number] .

[0109] The equation for Mz (absolute) is dependent on the point-by-point determination of the absolute molecular weight, which is derived from the ratio of the 15-degree light scattering signal minus the baseline and the IR5 measurement sensor signal minus the baseline using GPCOne (trademark) software and factored for mass and light scattering constants. Linear regression was used to extrapolate the absolute molecular weight where either detector (IR5 or LS) has a relative peak signal height (maximum peak height) of less than about 4%. [Number] .

[0110] Viscosity chromatogram Absolute intrinsic viscosity data (IV (absolute)) was obtained using the area of the specific viscosity chromatogram obtained from a PolymerChar viscometer detector when calibrated against the known intrinsic viscosity of NBS1475. The overall injection concentration used for the determination of the intrinsic viscosity was derived from either a suitable linear polyethylene homopolymer or one of the polyethylene standards of known intrinsic viscosity (resulting from the NBS 1475 homopolymer polyethylene reference sample), obtained from the mass detector area and the mass detector constant.

[0111] The equation for IV (absolute value) is an area-based result using the specific viscosity signal minus the baseline (DV) and the IR5 measurement sensor signal minus the baseline (applying mass and viscosity constants), as determined from GPCOne (trademark) software. [Number] .

[0112] Differential Scanning Calorimetry (DSC) Using Differential Scanning Calorimetry (DSC), the melting and crystallization behavior of polymers over a wide range of temperatures can be measured. For example, this analysis is performed using a TA Instruments Q2000 DSC equipped with an RCS (Refrigerated Cooling System) and an autosampler. During the test, a nitrogen purge gas flow rate of 50 ml / min is used. Each sample is melt-pressed into a thin film at about 190 °C and then air-cooled to room temperature (about 25 °C). A sample of "0.5 - 0.9 grams" is pressed at 190 °C and 20,000 lb f for 10 seconds to form a film of "0.1 - 0.2 mil thickness", thereby forming a film sample. Test pieces with a diameter of 6 mm and weighing 3 - 10 mg are extracted from the cooled polymer, weighed, placed in an aluminum dish (about 50 mg), and crimped shut. Then, an analysis was performed to determine its thermal properties.

[0113] The thermal behavior of the sample was determined by raising and lowering the temperature of the sample to create a heat flow vs. temperature profile. To remove its thermal history, first, the sample was rapidly heated to 180 °C and held isothermally for 5 minutes. Next, the sample was cooled to -40 °C at a cooling rate of 10 °C / min and held isothermally at -40 °C for 5 minutes. Then, the sample was heated to 150 °C at a heating rate of 10 °C / min (this is the "second heating" gradient). The cooling curve and the second heating curve were recorded. The cooling curve was analyzed by setting the baseline end point from the start of crystallization to -20 °C. The heating curve was analyzed by setting the baseline end point from -20 °C to the end of melting. The determined values were the peak melting temperature (Tm), the peak crystallization temperature (Tc), the heat of fusion (Hf) (joules per gram), and the degree of crystallinity % of the ethylene-based polymer sample calculated using the following equation: Degree of crystallinity % = ((Hf) / (292 J / g)) × 100 (Equation 16).

[0114] The heat of fusion and peak melting temperature are reported from the second heat curve. The peak crystallization temperature is determined from the cooling curve.

[0115] Nuclear magnetic resonance ( 1 H NMR) Each NMR sample was prepared by adding approximately "0.10 g of an ethylene-based polymer" into a "NORELL 1001 - 710 mm NMR tube" containing "2.7 g of tetrachloroethane-d 3 (tris(acetylacetonato)-chromium(III)) (Cr(AcAc) 2 (TCE)". The sample was purged by bubbling nitrogen through the solvent via a pipette, inserted into the tube for about 5 minutes to prevent oxidation, then capped and sealed with TEFLON tape, and then immersed overnight at room temperature to facilitate dissolution of the sample. The sample was kept in a nitrogen-purged box during storage before and after preparation to minimize exposure to oxygen. The sample was heated and mixed at 115 °C with a vortex mixer to ensure homogeneity. Each sample was visually inspected to ensure homogeneity.

[0116] Data were collected at a sample temperature of 120 °C using a BRUKER AVANCE 400 MHz NMR spectrometer equipped with a BRUKER DUAL DUL high-temperature cryoprobe. Each analysis was performed with a ZG pulse, 32 scans, SWH 10,000 Hz, AQ 1.64 seconds, and D1 14 seconds. The acquisition was repeated using a D1 of 28 seconds to check quantification, and the results were the same.

[0117] GC analysis Headspace water extraction and preparation - solid-phase microextraction (HS-SPME) Each film was prepared as described in the "Extrusion Coating" of the experimental section. Each sample of 2 grams (approx. 1 inch × 1 inch) (approx. 1.3 mil polymer coated on a release liner, with the release liner removed to provide a self-standing film) was weighed into individual "20 mL" headspace vials, and the vials were sealed. The vials with the film were equilibrated at 75 °C for 10 minutes, and the headspace was extracted by SPME for analysis by gas chromatography using a quadrupole mass spectrometer (GC / qMS).

[0118] Preparation of HS-SPME Each film of 10 grams (see above) was weighed into a "40 mL" glass bottle (I-Chem, high purity). The vial was completely filled with high purity water (ASTM type I, reagent grade, Mill-Q Integral 3, 18.2 MΩ, <5 ppb TOC). The vial was sealed with a PTFE-lined cap, and the film was extracted at 40 °C for 48 hours. After 48 hours, the bottle was removed from the oven and the contents were allowed to return to room temperature (approx. 4 hours). HS-SPME analysis was performed using 20 mL headspace vials. Each vial was prepared with "3.5 g" of sodium sulfate (Sigma-Aldrich, ACS reagent grade, purified by heating in a furnace at 1050 °F for 12 hours) and 10 grams of the water extract (without film). The mixture was vigorously mixed and sonicated for 15 minutes to dissolve the sodium sulfate. The vial was then equilibrated at 75 °C for 10 minutes, and the headspace was extracted by SPME for analysis by gas chromatography using a quadrupole mass spectrometer (GC / qMS).

[0119] GC / ODP / qMS Analysis Conditions The headspace within each vial was sampled by SPME and analyzed by GC / qMS. Quantification was performed using an external standard calibration procedure. Automated sample analysis was performed using a Gerstel Multipurpose Sampler (MPS), an Agilent 7890A gas chromatography, and an Agilent 5975C inert XL quadrupole mass spectrometer. The MPS was controlled using Gerstel's Maestro software. The control and data collection of GC / qMS were performed using Agilent's Chemstation software. The headspace of the water extract was a sample that was equilibrated with water at 75 °C and stirred for 10 minutes using a "2 cm x 50 / 30 μm" divinylbenzene / carboxen / polydimethylsiloxane (Supleco) SPME fiber. The components of the SPME fiber were desorbed at a split / splitless inlet at 250 °C, followed by separation using an Agilent, VF-WAXms, "30 m x 250 μm x 0.5 μm" capillary column with an oven temperature program of 50 °C (held for 2 minutes) to 260 °C (held for 6 minutes), at 15 °C / min, and an initial column flow of 2.0 mL / min of helium.

[0120] The samples were then comparatively ranked on a scale of 1 to 5 (where 1 indicates the minimum and 5 indicates the maximum) for the oxygenated species (OS) or total volatile organic compounds (VOC) detected within the materials.

[0121] Experiment Synthesis of Isoprenyl Methacrylate (IPMA) [Chemical formula] A 1000 mL five-neck LabMax reaction vessel was equipped with an overhead stirrer, a thermocouple, an 8% O2 / N2 purge tube, and a 10-plate Oldershaw distillation column / distillation head, along with an automatic reflux splitter / controller. The flask was charged with 86.5 g of isoprenol (1.0 mol) and 321 g of MMA (3.2 mol). Inhibitors (MEHQ and 4-HT) were added to the flask contents at concentrations of 1040 ppm and 85 ppm, respectively, in the final product. The purge tube was turned on at a rate of 1 - 2 bubbles / second.

[0122] Azeotropic drying under atmospheric pressure The reaction vessel was heated in distillation mode using the LabMax unit with settings of Tj = 140 °C and Tj - Tr = 30 °C. The LabMax unit was maintained at a vessel temperature of approximately 106 - 107 °C and a vapor temperature of approximately 92 - 99 °C during distillation. Some water droplets were observed in the return tube. After 30 minutes of reflux, 55 mL of distillate was removed using a reflux ratio of 2.5:1 (40% recovery). The reaction vessel was then cooled to 40 °C.

[0123] Transesterification reaction Anhydrous LiOH (0.49 g, 0.02 mol) was added to the above reaction vessel contents. The pressure in the flask was maintained at 760 mmHg using a vent to air. The pot contents were heated using settings of Tj = 140 °C and Tj - Tr = 27 °C, and the vessel temperature steadily increased from 105 °C to 120 °C as the distillate was removed. The vapor temperature was lowered from 71 °C to 64 °C in the first reflux. When the vapor temperature reached 64.0 °C, the MMA - methanol azeotropic mixture was distilled off using a reflux ratio of 30 / 70. After 1 hour, approximately 50 mL of distillate was collected and the vapor temperature rose to 75 °C. The vessel contents were cooled to 50 °C and sampled for NMR analysis. The proton NMR of the vessel contents showed that the isoprenol conversion was >99%.

[0124] Removal of MMA The pressure was reduced to 40 mmHg, and the vessel contents were heated using a setting of Tj = 140 °C and Tj - Tr = 27 °C. As MMA was removed, the vessel temperature steadily increased from 50 °C to 105 °C. MMA was collected in a vapor temperature range of 30 - 32 °C using a reflux ratio of 30 / 70. Note: Such a reflux ratio was found to be important for reducing / avoiding the loss of IPMA during the MMA stripping stage. When the vapor temperature exceeded 50 °C, the vessel contents were cooled to 50 °C and the pressure was released to atmospheric pressure. Approximately "140 grams of MMA" was collected.

[0125] Filtration of the catalyst The vessel contents were cooled to 0 °C over 3 hours using a setting of Tr = 0 °C, held at that temperature for 1 hour, and then filtered through moderately fine P4 filter paper. As determined by proton NMR spectroscopy, approximately 146 grams (95% yield) of IPMA was produced with a purity of >97.5%.

[0126] Distillation of IPMA MMA was removed and the pressure was reduced to less than 5 mmHg. The vessel contents were heated using Tj = 110 °C and Tj - Tr = 27 °C. As IPMA was distilled overhead in a vapor temperature range of 49 - 52 °C, the vessel temperature steadily increased from 50 °C to 75 °C. The weight of the distilled IPMA was 147 grams (yield 95%) and the purity was >98.5%.

[0127] Polymerization Asymmetric diene - isoprenyl methacrylate (IPMA) was charged into a 316 stainless - steel feed tank, diluted with ethyl acetate to produce a final concentration of 7.8 wt%. This tank was nitrogen - purged for 3 hours before use and maintained at 70 psig nitrogen fill during operation.

[0128] Initiators - The peroxide initiators tert-butyl peroxyacetate (TPA, 20 wt% solution in ISOPAR™ H) and di-tert-butyl peroxide (DTBP, 20 wt% solution in ISOPAR™ H) were mixed with ISOPAR E in a second 316 stainless steel feed tank to produce "1500 mass ppm" TPA and "415 mass ppm" DTBP (TPA molar / DTBP molar ratio of 4:1). Prior to using the tank, nitrogen filling and removal at 70 psig were performed five times and maintained under nitrogen filling during polymerization.

[0129] Ethylene was injected at 5480 g / h at a pressure of 1930 bar into a stirred (1600 rpm) 300 mL high-pressure CSTR reactor equipped with an externally heated jacket set at 220 °C. The mixture was compressed to 1930 bar and propylene (CTA) was added to the ethylene stream at a pressure of 62 bar at a rate of 232 g / h prior to injecting into the reactor (referenced above). Prior to injecting the mixture into the reactor, an ethyl acetate solution of IPMA was pumped at a rate of 2.79 g / h into the ethylene-propylene mixture at a pressure of 1930 bar. The peroxide initiators were added directly to the reactor through the sidewall at a pressure of 1930 bar at a rate of 5.5×10 -2 g / h (0.42 mmol / h) for TPA and 1.5×10 -2 g / h (0.1 mmol / h) for DTBP. The conversion of ethylene to polymer was 9.2 wt% based on the mass of ethylene flowing into the reactor and the average reaction temperature was about 220 °C. An ethylene-based polymer (LDPE / IPMA, Example 1 of the present invention) was formed. The polymerization conditions are summarized in Table 1 below. The polymer properties are shown in Tables 2 - 4 below.

[0130] Refer to the control - the above reactor (316 stainless steel feed vessel) and initiator. Ethylene was injected at 5452 g / hour into a stirred (1600 rpm) 300 mL high - pressure CSTR reactor equipped with an outer heating jacket set at 220 °C at a pressure of 1930 bar. The mixture was compressed to 1930 bar, and propylene (chain transfer agent) was added to the ethylene stream at a pressure of 62 bar at a rate of 120 grams / hour before injecting into the reactor. The peroxide initiator mixture was added directly to the reactor through the sidewall of the CSTR reactor at a pressure of 1930 bar at a rate of 5×10 -2 grams / hour (0.4 millimoles / hour) of TPA, and 1.4×10 -2 grams / hour (0.1 millimoles / hour) of DTBP. The conversion of ethylene to polymer was 11.2 wt% based on the mass of ethylene flowing into the reactor, and the average reaction temperature was about 221 °C. The reaction polymerization conditions are summarized in Table 1 below. The polymer properties are shown in Tables 2 - 4 below.

Table 1

[0131] Polymer properties The polymerization conditions are described in Tables 2 and 3 below.

Table 2

Table 3

[0132] Extrusion coating All coating experiments were conducted on a Black-Clawson extrusion coating line. The extruder was equipped with a single-flight screw of 3.5 inches, 30:1 L / D, and 4:1 compression ratio, and two spiral Mattock mixing sections. A 91 cm (36 inch) nominal die width was deckled to a 61 cm (24 inch) open die width (a metal dam used at the die exit around the outer edge of the die to block the flow within the die and reduce the die width, thus reducing the flow of the polymer from the die). In extrusion coating, the deckle is a die insert that sets the coating width of the slot die coater or the extrusion width of the extrusion die. This functions by restricting the flow as the material exits the die.

[0133] For the evaluation of extrusion coating, a constant 15.2 cm (6 inch) air gap was set for all resins. The die gap was set at "20 mils", but slight adjustments were required to maintain a constant coating thickness. The temperature of each zone of the extruder was 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 an output rate of "250 pounds / hour". The line speed was "440 ft / min (fpm)", resulting in a "1.3 mil" coating on kraft paper with a width of 61 cm (24 inches) (kraft paper, unbleached) at a rate of "50 pounds / run". Self-standing strips of polymer film for analytical testing (e.g., HS-SPME) were obtained by coating the resin on a release liner. Before the molten polymer curtain contacted the paper substrate, a strip of silicon-coated release liner approximately "61 cm (24 inches)" wide was inserted between the polymer coating and the paper substrate to form a "polymer coating / release liner / kraft paper" configuration, where the paper and the release liner were not adhered to each other. The "polymer coating / release liner" sub-configuration was wound up and wrapped with food-grade aluminum foil. The solidified polymer coating was peeled from the release liner for analytical testing.

[0134] The amount of neck-in (the difference between the actual coating width and the deckle width (61 cm)) was measured at line speeds of "440 feet per minute" and "880 feet per minute (fpm)", resulting in coating thicknesses of "1.3 mils" and "0.65 mils", respectively. The amperage and horsepower of the extruder were recorded. Without changing the position of the backpressure valve, the amount of backpressure for each polymer was also recorded. Drawdown is the line speed at which edge defects (typically, the width of the polymer coating that vibrates along the edge of the polymer coating) are noticed on the polymer coating, or the line speed at which the melt curtain completely tears from the die. The reduced rate drawdown (RRDD) of all resins was measured at a screw speed of "45 rpm" by increasing the line speed until edge defects or web tears were noticed. The extrusion coating results are shown in Table 4 below.

Table 4

[0135] As can be seen in Tables 2 - 4 above, the polymers of the present invention (Example 1 of the present invention, LDPE / IPMA) have excellent melt strength (MS), excellent thermal stability (low OS and VOC levels), and good extrusion coating properties. Compared with the PPG AEMA-containing resin, the polymers of the present invention (LDPE / IPMA) are thermally more stable during melt processing, do not decompose into species that produce a pungent odor during processing, and do not impart an off-taste or bad odor to food.

[0136] Description of the Flow Diagram (Tubular Reactor) Figure 1 shows a generalized flow scheme of a high-pressure polymerization plant configuration containing a tubular reactor. Stream (1) is fresh ethylene make-up, which is compressed by a primary compressor into stream (2) together with the booster discharge. Stream (2) is combined with the high-pressure recycle stream (18) and the feed (3) and distributed to the suction inlet of the hyper compressor. The hyper pressurizes the ethylene feed stream to a level sufficient to supply the high-pressure tubular reactor (reactor). Although not shown, the flow scheme may include partial combinations of stream (2) and stream (18) and / or distribution to the inlet of the hyper compressor.

[0137] Stream (4) and / or (5) represent the CTA system make-up feed. The CTA make-up can, in principle, be freely distributed to the main compression stream supplied and / or distributed to the lateral stream (8) and the front stream (9). The CTA make-up stream (4) and / or (5) can be supplied at the inlet(s) of the hyper compressor, between stages (if any), at the outlet(s) and / or at the inlet(s) of the reaction zone(s). The CTA system may consist of single and / or multiple components and may contain various compositions.

[0138] Stream (6) and / or stream (7) represent the polyene feed. The polyene feed can, in principle, be freely distributed to the main compression stream supplied and / or distributed to the lateral stream (8) and / or the front stream (9). The polyene stream (6) and / or (7) can be supplied at the inlet(s) of the hyper compressor, between stages (if any), at the outlet(s), to the individual ethylene feed streams to the reactor, and / or directly into the reaction zone. The discharge temperature of the hyper is typically in the range of 60 to 100 °C. The ethylene feed to the first reaction zone is typically preheated to a temperature of 130 to 180 °C, while the ethylene of the lateral feed is supplied to the reactor at the hyper compressor discharge temperature or cooled before being supplied to the reactor.

[0139] The dimensions and configuration of the reactor can be, as follows, an inner diameter of the tube of 40 - 60 mm and a length (distribution) of the Rx zone of 1000 - 200 m. In the reactor, polymerization is initiated with the assistance of a free radical initiator system and is injected and / or activated at the inlet of each reaction zone. The maximum temperature of each reaction zone is controlled at a set point by adjusting the concentration and / or feed rate of the initiator system at the start of each reaction zone.

[0140] After the reaction is completed and a plurality of cooling steps are applied, the reaction mixture is depressurized and / or cooled at (10) and separated in a high-pressure separator (HPS). The HPS separates the reaction mixture into an ethylene-rich stream (15) containing a small amount of wax and / or entrained polymer and a polymer-rich stream (11) that is sent to the LPS for further separation. The ethylene stream (15) is cooled and washed in stream (17). Stream (16) is a purge stream for removing impurities and / or inert substances. The polymer separated in the LPS is further processed at (12). The ethylene removed in the LPS (13) is fed to a booster where condensates such as solvent, lubricating oil, and others are collected during compression and removed through stream (14). The outlet of the booster is combined with a make-up ethylene stream (1) and further compressed by a primary compressor. The present application also relates to the following aspects. (1) An ethylene polymer formed by reacting at least ethylene and at least one asymmetric polyene of the following Structure 1,

Chem.

Chem.

Chem.

Claims

1. A method for reacting ethylene and at least one asymmetric polyene of the following Structure 1 to form an ethylene-based polymer, 【Chemical 1】 In the formula, R １ is selected from H or C １ to C ５ alkyl, wherein the ethylene-based polymer, in the reacted form, contains 1.5 wt% or less of the asymmetric polyene based on the weight of the polymer, and, the ethylene-based polymer contains ethylene and one kind of asymmetric polyene as the only monomer units, Method.

2. The method according to Claim 1, wherein Structure 1 is Structure 1A [Chemical Formula 2] 。

3. The method according to any one of Claims 1 to 2, wherein the ethylene-based polymer has a z-average molecular weight (Mz) of 800,000 g / mol to 1,200,000 g / mol.

4. The method according to any one of Claims 1 to 3, wherein the ethylene-based polymer has a melt strength (MS) of 10 cN or more to 40 cN or less (at 190 °C).

5. The method according to any one of Claims 1 to 4, wherein the ethylene-based polymer has a weight-average molecular weight (Mw) of 145,000 to 175,000 g / mol.

6. The method according to any one of Claims 1 to 5, wherein the ethylene-based polymer has a molecular weight distribution (MWD) of 8.0 to 12.

7. The polymer has a melt index (I ２ ) of 5.0 g / 10 min to 10 g / 10 min, and the method according to any one of claims 1 to 6.

8. The ethylene polymer has a melt index (I １０ ) of 50 g / 10 min to 90 g / 10 min, and the method according to any one of claims 1 to 7.

9. The ethylene polymer has a melt index ratio (I １０ / I ２ ) of 9.0 to 13, the method according to claim 8.

10. The ethylene polymer has a ratio of melt strength to melt index (MS / I) of 2.0 to 4.0 ２ ), the method according to any one of claims 1 to 9.

11. The method according to any one of Claims 1 to 10, wherein the polymer has a density of 0.905 g / cc to 0.935 g / cc.

12. The method according to any one of Claims 1 to 11, wherein the ethylene-based polymer, in the reacted form, contains 0.01 wt% or more to 0.20 wt% or less of the asymmetric polyene based on the weight of the ethylene-based polymer.

13. The method according to any one of Claims 1 to 12, wherein the ethylene-based polymer has a detected oxygenated species (OS) rank of 2 or less and a total volatile organic compound (VOC) rank of 2 or less.

14. A method comprising: reacting ethylene and at least one asymmetric polyene of the following Structure 1 to form an ethylene-based polymer, 【Chemical Formula 3】 wherein, R １ is selected from H or C １ to C ５ alkyl wherein the ethylene-based polymer, in the reacted form, contains 1.5 wt% or less of the asymmetric polyene based on the weight of the polymer, and, the ethylene-based polymer contains ethylene and one kind of asymmetric polyene as the only monomer units, the step wherein the ethylene-based polymer contains at least one structure selected from the following Structure I 【Chemical 4】 The step of extruding and coating the ethylene-based polymer onto a substrate, The step of forming a coating composed of the ethylene-based polymer on the substrate, A method comprising:

15. Extrusion coating at a line speed of 440 fpm and a screw speed of 90 rpm, Forming a coating with a neck-in of 2.0 inches or less, The method according to claim 14, comprising:

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