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US-12617935-B2 - Polymers of ethylene and monocyclic organosiloxane

US12617935B2US 12617935 B2US12617935 B2US 12617935B2US-12617935-B2

Abstract

An ethylene-based polymer composition includes units derived from ethylene, units derived from a comonomer, and an optionally units derived from a termonomer. The comonomer is a monocyclic organosiloxane (MOCOS) of formula (I) [R 1 , R 2 SiO 2/2 ] n wherein n is an integer greater than or equal to 3, each R 1 is independently a (C 2 -C 4 ) alkenyl or a H 2 C═C(R 1a )—C(═O)—O—(CH 2 ) m — wherein R 1a is H or methyl, m is an integer from 1 to 4, and each R 2 is independently H, (C 1 -C 4 ) alkyl, phenyl, or R 1 .

Inventors

  • Jeffrey M. Cogen
  • Yabin Sun
  • Timothy J. Person
  • Arkady L. Krasovskiy
  • Pyung Lee
  • Hayley A. Brown
  • Sean W. Ewart

Assignees

  • DOW GLOBAL TECHNOLOGIES LLC

Dates

Publication Date
20260505
Application Date
20200729

Claims (8)

  1. 1 . An ethylene-based polymer composition comprising: units derived from ethylene, units derived from a comonomer, and an optionally units derived from a termonomer; and the comonomer is polymerized into the polymer backbone and is a monocyclic organosiloxane (MOCOS) of formula (I) [R 1 ,R 2 SiO 2/2 ] n wherein n is an integer greater than or equal to 3, each R 1 is independently a (C 2 -C 4 ) alkenyl or a H 2 C═C(R 1a )—C(═O)—O—(CH 2 ) m — wherein R 1a is H or methyl; m is an integer from 1 to 4; and each R 2 is independently H, (C 1 -C 4 ) alkyl, phenyl, or R 1 .
  2. 2 . The ethylene-based polymer composition of claim 1 comprising from 0.01 wt % to 0.5 wt % of the MOCOS comonomer.
  3. 3 . The ethylene-based polymer composition of claim 1 wherein the MOCOS comonomer is selected from the group consisting of 2,4,6-trimethyl-2,4,6-trivinyl-cyclotrisiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetravinyl-cyclotetrasiloxane, 2,4,6,8,10-pentamethyl-2,4,6,8,10-pentavinyl-cyclopentasiloxane, and combinations thereof.
  4. 4 . The ethylene-based polymer composition of claim 1 wherein the ethylene-based polymer is an ethylene/MOCOS copolymer having (i) a Mw/Mn from 7.5 to 9.5, (ii) a vinyls content from 0.3600/1000 carbons to 0.6200/1000 carbons, and (iii) a trans content from 0.1000/1000 carbon atoms to 0.3100/1000 carbon atoms.
  5. 5 . The ethylene-based polymer composition of claim 1 wherein the ethylene/MOCOS copolymer has (iv) an MI from 2.0 g/10 min to 5.0 g/10 min, and (v) a melt strength from 5.0 to 8.5 cN.
  6. 6 . The ethylene-based polymer composition of claim 1 wherein the termonomer is present and is selected from the group consisting of an olefin, an unsaturated ester, a functionalized alkene, and combinations thereof.
  7. 7 . The ethylene-based polymer of claim 6 wherein the ethylene-based polymer comprises from 0.01 wt % to 0.5 wt % of the MOCOS comonomer; and from 0.5 wt % to 20 wt % of the termonomer.
  8. 8 . An article comprising the ethylene-based polymer composition of claim 1 .

Description

BACKGROUND The level of branching in an ethylene-based polymer, such as low density polyethylene (LDPE) for example, is due predominantly to the reactor design (autoclave or tubular) and the polymerization conditions used to make the LDPE. Known are branching agents for increasing the level of branching in an LDPE. However, the process conditions required to achieve a modified LDPE with a high level of branching, often result in a final product with inferior properties, including a higher content of a low molecular weight extractable fraction. Thus, the art recognizes the on-going need for LDPE with increased melt strength vis-h-vis increased branching levels, the LDPE prepared under polymerization conditions that maintain good polymer properties. SUMMARY The present disclosure is directed to an ethylene-based polymer composition. In an embodiment, the ethylene-based polymer composition includes units derived from ethylene, units derived from a comonomer, and an optionally units derived from a termonomer. The comonomer is a monocyclic organosiloxane (MOCOS) of formula (I) [R1,R2SiO2/2]n wherein n is an integer greater than or equal to 3,each R1 is independently a (C2-C4)alkenyl or a H2C═C(R1a)—C(═O)—O—(CH2)m—wherein R1a is H or methyl,m is an integer from 1 to 4, andeach R2 is independently H, (C1-C4)alkyl, phenyl, or R1. DEFINITIONS Any reference to the Periodic Table of Elements is that as published by CRC Press, Inc., 1990-1991. Reference to a group of elements in this table is by the new notation for numbering groups. For purposes of United States patent practice, the contents of any referenced patent, patent application or publication are incorporated by reference in their entirety (or its equivalent U.S. version is so incorporated by reference) especially with respect to the disclosure of definitions (to the extent not inconsistent with any definitions specifically provided in this disclosure). The numerical ranges disclosed herein include all values from, and including, the lower and upper value. For ranges containing explicit values (e.g., from 1 or 2, or 3 to 5, or 6, or 7), any subrange between any two explicit values is included (e.g., the range 1-7 above includes subranges of from 1 to 2; from 2 to 6; from 5 to 7; from 3 to 7; from 5 to 6; etc.). Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percents are based on weight and all test methods are current as of the filing date of this disclosure. An “acrylate” as used herein, is a monomer containing the Structure (A) below: wherein R1 is a hydroxyl group or a C-Cis alkoxy group and R2 is H or CH3. Acrylate-based monomers include acrylates and methacrylates. An “alkane” is a saturated hydrocarbon. An “alkyl” (or “alkyl group”) is an alkane having a valence (typically univalent). An “alkene” is a hydrocarbon containing a carbon-carbon double bond. An “alkenyl” (or “alkenyl group”) is an alkene having a valence (typically univalent) The term “allyl” (or “allyl group”) is a univalent unsaturated C3H5 hydrocarbon. In other words, an allyl group is propene minus one hydrogen atom. The terms “blend” or “polymer blend,” as used, refers to a mixture of two or more polymers. A blend may or may not be miscible (not phase separated at molecular level). A blend may or may not be phase separated. A blend may or may not contain one or more domain configurations, as determined from transmission electron spectroscopy, light scattering, x-ray scattering, and other methods known in the art. The blend may be effected by physically mixing the two or more polymers on the macro level (for example, melt blending resins or compounding), or the micro level (for example, simultaneous forming within the same reactor). The term “composition” refers to a mixture of materials which comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition. The terms “comprising,” “including,” “having” and their derivatives, are not intended to exclude the presence of any additional component, step or procedure, whether or not the same is specifically disclosed. In order to avoid any doubt, all compositions claimed through use of the term “comprising” may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless stated to the contrary. In contrast, the term “consisting essentially of” excludes from the scope of any succeeding recitation any other component, step, or procedure, excepting those that are not essential to operability. The term “consisting of” excludes any component, step, or procedure not specifically delineated or listed. The term “or,” unless stated otherwise, refers to the listed members individually as well as in any combination. Use of the singular includes use of the plural and vice versa. An “ethylene-based polymer” is a polymer that contains more than 50 weight percent (wt %) polymerized ethylene monomer (based on the t