EP-4735523-A1 - TRIMODAL ETHYLENE-BASED POLYMERS

Abstract

Embodiments of the present disclosure are directed to a trimodal ethylene-based polymer comprising first, second, and third polymer fractions wherein the first, second, and third polymer fractions each comprise the polymerized reaction product of ethylene monomer and optionally C 3 -C 14 alpha-olefin comonomer with the proviso that at least one of the first, second, and third polymer fractions comprise the polymerized reaction product of ethylene monomer, polyene comonomer, and optionally C 3 -C 14 alpha-olefin comonomer.

Inventors

• FROESE, Robert D.J.
• LU, Keran
• WEINHOLD, JEFFREY D.
• DEN DOELDER, CORNELIS F.J.
• MARTINETTI, LUCA
• HOU, JIANBO
• PEREIRA, Joana Amaral
• BAZEN, Jan
• KLOSIN, JERZY

Assignees

• Dow Global Technologies LLC

Dates

Publication Date

20260506

Application Date

20240612

Claims (1)

1. 85099-WO-PCT/DOW 85099 WO CLAIMS 1. A trimodal ethylene-based polymer comprising first, second, and third polymer fractions wherein: the first, second, and third polymer fractions each comprise the polymerized reaction product of ethylene monomer and optionally C 3 -C 14 alpha-olefin comonomer with the proviso that at least one of the first, second, and third polymer fractions comprise the polymerized reaction product of ethylene monomer, polyene comonomer, and optionally C3-C14 alpha-olefin comonomer. 2. The trimodal ethylene-based polymer of claim 1, wherein the trimodal ethylene-based polymer has a melt strength (MS) from 4.0 to 25.0 cN, and a rheology ratio V0.1/V100 from 4.0 to 12.0, wherein V 0.1 is the viscosity of the trimodal ethylene-based polymer at 190 °C at an angular frequency of 0.1 radians/second, and V100 is the viscosity of the trimodal ethylene-based polymer at 190 °C at an angular frequency of 100 radians/second, and wherein MS is the melt strength in cN (Rheotens device, 190°C, 2.4 mm/s 2 , 120 mm from the die exit to the center of the wheels, extrusion rate of 38.2 s -1 , capillary die of 30 mm length, 2 mm diameter and 180° entrance angle). 3. The trimodal ethylene-based polymer of claim 1, wherein the polyene comprise acyclic unconjugated dienes. 4. The trimodal ethylene-based polymer of any preceding claim, wherein the rheology ratio V0.1/V100 is from 4.0 to 8.0. 5. The trimodal ethylene-based polymer of any preceding claim, wherein the trimodal ethylene-based polymer has an I 2 of 0.5 to 2.0 dg/min. 6. The trimodal ethylene-based polymer of any preceding claim, wherein the trimodal ethylene-based polymer has a density of 0.910 to 0.935 g/cc. 7. The trimodal ethylene-based polymer of any preceding claim, wherein the trimodal ethylene-based polymer has an MWD of 3.0 to 5.0, MWD is defined as M w /M n with M w being a weight average molecular weight and Mn being a number average molecular weight as measured according to conventional Gel Permeation Chromatography. 85099-WO-PCT/DOW 85099 WO 8. The trimodal ethylene-based polymer of any preceding claim, wherein the first fraction has a density of less than 0.925 g/cc, a melt index (I2) less than 0.5 dg/min, and an MWD less than 3.0. 9. The trimodal ethylene-based polymer of any preceding claim, wherein at least one of the first, second, and third polymer fractions are substantially free of long chain branching. 10. The trimodal ethylene-based polymer of any preceding claim, wherein the trimodal ethylene-based polymer comprises from 45 to 65 wt.% first fraction and 35 to 55 wt.% of the sum of the second and third polymer fractions. 11. The trimodal ethylene-based polymer of any preceding claim, wherein the melt strength (MS) is from 8.0 to 15 cN. 12. A film comprising the trimodal ethylene-based polymer of any preceding claim. 13. The film of claim 12, wherein the film is a monolayer or multilayer film. 14. The film of claims 12 or 13, wherein the film has a normalized dart strength (DS) from 750 to 1750 gram/mil (g/mil) as measured according to ASTM D1709. 15. The film of any of claims 11-14, wherein the film has an average cross-direction (CD) tear from 40 to 70 gram-force (gf) and the film has an average thickness of 1-3 mil.

Description

85099-WO-PCT/DOW 85099 WO TRIMODAL ETHYLENE-BASED POLYMERS CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application claims the benefit of U.S. Provisional Application Serial No. 63/510,769 filed June 28, 2023, the contents of which are incorporated in their entirety herein. TECHNICAL FIELD [0002] Embodiments are generally related to multimodal ethylene-based polymers and are particularly related to trimodal ethylene-based polymers having processibility and mechanical properties. BACKGROUND [0003] Linear Low Density Polyethylenes (LLDPE) made via solution or gas phase processes typically have excellent mechanical properties, but poor melt strength and processibility in film fabrication. Therefore, to increase processibility, some amount of LDPE may typically be blended with LLDPE in order to improve the processibility and melt strength of LLDPE resins. Unfortunately, the addition of LDPE leads to decreased mechanical properties of the resulting blends when compared with pure LLDPE resin. [0004] Accordingly, there are needs for ethylene-based polymers suitable to provide processibility and excellent mechanical properties (e.g., dart) without blending with LDPE. SUMMARY [0005] The present trimodal ethylene-based polymers achieve this need for processibility and mechanical strength by including at least one polymer fraction having increased long chain branching. Without being limited by theory, this long chain branching provides increased melt strength necessary in film processing, while the trimodal ethylene-based polymers still maintain excellent abuse resistance properties in films. [0006] According to one or more embodiments, a trimodal ethylene-based polymer comprising first, second, and third polymer fractions is provided. The first, second, and third polymer fractions each comprise the polymerized reaction product of ethylene monomer and optionally C3-C14 alpha-olefin comonomer with the proviso that at least one of the first, second, 85099-WO-PCT/DOW 85099 WO and third polymer fractions comprise the polymerized reaction product of ethylene monomer, polyene comonomer, and optionally C3-C14 alpha-olefin comonomer. [0007] These and other embodiments are described in more detail in the following Detailed Description in conjunction with the appended drawings. BRIEF DESCRIPTION OF THE DRAWINGS [0008] The following detailed description of specific embodiments of the present disclosure can be best understood when read in conjunction with the following drawings, where like structure is indicated with like reference numerals and in which: [0009] FIG. 1 graphically depicts the molecular weight distribution of the present trimodal ethylene-based polymers according to one or more embodiments presently described; and [0010] FIG. 2 graphically illustrates the relationship between melt strength and normalized dart strength for the present trimodal ethylene-based polymers according to one or more embodiments presently described. DETAILED DESCRIPTION [0011] Specific embodiments of a process for synthesizing polymer and polymers synthesized by the process of this disclosure will now be described. It should be understood that the process for synthesizing polymers of this disclosure may be embodied in different forms and should not be construed as limited to the specific embodiments set forth in this disclosure. Rather, embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art. [0012] DEFINITIONS [0013] The term “polymer” refers to a polymeric compound prepared by polymerizing monomers, whether of the same or a different type. The generic term polymer thus embraces the term “homopolymer,” usually employed to refer to polymers prepared from only one type of monomer as well as “copolymer” which refers to polymers prepared from two or more different monomer types. 85099-WO-PCT/DOW 85099 WO [0014] “Polyethylene” or “ethylene-based polymer” shall mean polymers comprising greater than 50% by weight of units which have been derived from ethylene monomer. This includes polyethylene homopolymers or copolymers (meaning units derived from two or more monomer types). Common forms of polyethylene known in the art include Low Density Polyethylene (LDPE); Linear Low Density Polyethylene (LLDPE); Ultra Low Density Polyethylene (ULDPE); Very Low Density Polyethylene (VLDPE); single-site catalyzed Linear Low Density Polyethylene, including both linear and substantially linear low density resins (m-LLDPE); Medium Density Polyethylene (MDPE); and High Density Polyethylene (HDPE). [0015] The term “LDPE” may also be referred to as “high pressure ethylene polymer” or “highly branched polyethylene” and is defined to mean that the polymer is partly or entirely homopolymerized or copolymerized in autoclave or tubular reactors at pressures above 14,500 psi (100 MPa) with the use of free-radical initiators, such as peroxides (see, for exam