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BR-112022012386-B1 - PROCESS FOR PREPARING AN ALPHA COMPOSITION

BR112022012386B1BR 112022012386 B1BR112022012386 B1BR 112022012386B1BR-112022012386-B1

Abstract

PROCESS FOR PREPARING AN ALPHA COMPOSITION, COMPOSITION, AND, ARTICLE. The present invention relates to a process for preparing an alpha composition comprising a first ethylene/alpha-olefin/interpolymer fraction and a second ethylene/alpha-olefin/interpolymer fraction; wherein said process comprises polymerizing, in a reactor, a reaction mixture comprising ethylene and an alpha-olefin, a biphenylphenol metal complex selected from Structure 1, as described herein, and a biphenylphenol metal complex selected from Structure 2, as described herein; and the alpha compositions prepared therefrom.

Inventors

  • JOHNATHAN E. DELORBE
  • Daniela Ferrari
  • THOMAS WESLEY KARJALA JR.
  • Sylvie Vervoort
  • JEFFREY C. MUNRO
  • Lisa MADENJIAN

Assignees

  • DOW GLOBAL TECHNOLOGIES LLC

Dates

Publication Date
20260317
Application Date
20201216
Priority Date
20191226

Claims (10)

  1. 1. Process for preparing an alpha composition, characterized in that it comprises a first fraction of ethylene/alpha-olefin interpolymer and a second fraction of ethylene/alpha-olefin interpolymer; wherein said process comprises polymerizing, in a reactor, a reaction mixture comprising ethylene, an alpha-olefin, a metal complex selected from a) below and a metal complex selected from b) below: a) a biphenylphenol metal complex selected from the following Structure 1: Structure 1, in which: M is a metal chosen from zirconium (Zr) or hafnium (Hf), the metal being in a formal oxidation state of +2, +3 or +4; n is 0, 1 or 2; when n is 1, X is a monodentate ligand or a bidentate ligand; when n is 2, each X is a monodentate ligand chosen independently; The metal complex generally has a neutral charge; each of -Z1- and -Z2- is independently selected from -O-, -S-, -N(RN)-, or -P(RP)-; R1 and R8 are independently selected from the group consisting of -H, hydrocarbyl (C1-C40), heterohydrocarbyl (C1-C40), -Si(RC)3, -Ge(RC)3, -P(RP)2, -N(RN)2, -ORC, -SRC, -NO2, -CN, -CF3, RCS(O)-, RCS(O)2-, (RC)2C=N-, RCC(O)O-, RCOC(O)-, RCC(O)N(R)-, (RC)2NC(O)-, halogen, radicals having formula (I), radicals having formula (II), and radicals having formula (III): wherein each of R31-35, R41-48, and R51-59 is independently selected from hydrocarbyl (C1-C40), heterohydrocarbyl (C1-C40), -Si(RC)3, -Ge(RC)3, -P(RP)2, -N(RN)2, -N=CHRC, -ORC, -SRC, -NO2, -CN, -CF3, RCS(O)-, RCS(O)2-, (RC)2C=N-, RCC(O)O-, RCOC(O)-, RCC(O)N(RN)-, (RC)2NC(O)-, halogen or -H; each of R2-7, R9-16 is independently selected from hydrocarbyl (C1-C40), heterohydrocarbyl (C1-C40), -Si(RC)3, -Ge(RC)3, -P(RP)2, -N(RN)2, -N=CHRC, -ORC, -SRC, -NO2, -CN, -CF3, RCS(O)-, RCS(O)2-, (RC)2C=N-, RCC(O)O-, RCOC(O)-, RCC(O)N(RN)-, (RC)2NC(O)-, halogen or -H; L is hydrocarbylene (C1-C40) or heterohydrocarbylene (C1-C40), wherein the hydrocarbylene (C1-C40) has a portion comprising a main chain linking 1 carbon atom to 10 carbon atoms, linking the two Z groups in Structure 1 (to which L is attached); or the heterohydrocarbylene (C1-C40) has a portion comprising a linking backbone of 1 to 10 atoms linking the two Z groups in Structure 1, wherein each of the 1 to 10 atoms of the 1 to 10-atom linking backbone of the heterohydrocarbylene (C1-C40) independently is a carbon atom or a group of heteroatoms, wherein each group of heteroatoms is independently O, S, S(O), S(O)2, Si(RC)2, Ge(RC)2, P(RC), or N(RC), wherein each RC independently is (C1-C30)hydrocarbyl or (C1-C30)heterohydrocarbyl; wherein for Structure 1, L is selected from the following: i) -CH2Si(Ra)(Rb)CH2- or -CH2Ge(Ra)(Rb)CH2-, wherein Ra and Rb are each independently a hydrocarbyl (C1-C30) or a heterohydrocarbyl (C1-C30); ii) 1,3-dimethylpropan-1,3-di-yl; or iii) propan-1,3-di-yl; and each remaining RP, RN, and RC in Structure 1 is independently a hydrocarbyl (C1-C30), a heterohydrocarbyl (C1-C30), or -H; b) a biphenylphenol metal complex selected from Structure 2: Structure 2, in which M is Zr or Hf, with the metal in a formal oxidation state of +2, +3, or +4; n is 0, 1, or 2; when n is 1, X is a monodentate ligand or a bidentate ligand; when n is 2, each X is a monodentate ligand chosen independently; The metal complex generally has a neutral charge; each of -Z1- and -Z2- is independently selected from -O-, -S-, -N(RN)-, or -P(RP)-; R1 and R8 are independently selected from the group consisting of -H, hydrocarbyl (C1-C40), heterohydrocarbyl (C1-C40), -Si(RC)3, -Ge(RC)3, -P(RP)2, -N(RN)2, -ORC, -SRC, -NO2, -CN, -CF3, RCS(O)-, RCS(O)2-, (RC)2C=N-, RCC(O)O-, RCOC(O)-, RCC(O)N(R)-, (RC)2NC(O)-, halogen, radicals having formula (I), radicals having formula (II), and radicals having formula (III): wherein each of R31-35, R41-48, and R51-59 is independently selected from hydrocarbyl (C1-C40), heterohydrocarbyl (C1-C40), -Si(RC)3, -Ge(RC)3, -P(RP)2, -N(RN)2, -N=CHRC, -ORC, -SRC, -NO2, -CN, -CF3, RCS(O)-, RCS(O)2-, (RC)2C=N-, RCC(O)O-, RCOC(O)-, RCC(O)N(RN)-, (RC)2NC(O)-, halogen or -H; each of R2-7, R9-16 is independently selected from hydrocarbyl (C1-C40), heterohydrocarbyl (C1-C40), -Si(Rc)3, -Ge(Rc)3, -P(RP)2, -N(RN)2, -N=cHRc, -ORc, -SRc, -NO2, -cN, -cF3, RcS(O)-, RcS(O)2-, (Rc)2c=N-, Rcc(O)O-, RcOc(O)-, Rcc(O)N(RN)-, (Rc)2Nc(O)-, halogen or -H; Y is any -(cH2)n-, where n = 0 to 2; -cRaRb-, where Ra and Rb are each independently hydrocarbyl (c1-c40), heterohydrocarbyl (c1-c40), or -H; -Ge(RD)2- or -Si(RD)2-, wherein each RD is independently selected from the group consisting of -H, hydrocarbyl (c1-c40), heterohydrocarbyl (c1-c40), -Si(Rc)3, -Ge(Rc)3, -P(RP)2, -N(RN)2, -ORc, -SRc, -NO2, -cN, -cF3, RcS(O)-, RcS(O)2-, (Rc)2c=N-, Rcc(O)O-, RcOc(O)-, Rcc(O)N(RN)-, and (RN)2Nc(O)-; each Rc, RP, and RN in Structure 2 is independently a hydrocarbyl (c1-c30), a heterohydrocarbyl (c1-c30), or -H; with the condition that for either Structure 1 or Structure 2, R12 and R13 cannot both be halo groups, where R1 and R8 are each a radical having formula (II), where R43 = R46 = t-Bu, and R41-42 = R44-45 = R47-48 = -H; and with the condition that when Structure 1 and Structure 2 have the same R groups, Z groups, X group(s), and linker group between Z1 and Z2, these structures do not have the same metal (M), such that if M is Hf for one structure, M is Zr for the other structure.
  2. 2. Process according to claim 1, characterized in that for Structure 1, R1 and R8 are identical and selected from the group consisting of radicals having formula (I), radicals having formula (II) and radicals having formula (III).
  3. 3. Process, according to any one of claims 1 or 2, characterized in that for Structure 2, R1 and R8 are identical and selected from the group consisting of radicals having formula (I), radicals having formula (II) and radicals having formula (III).
  4. 4. Process, according to any one of claims 1 to 3, characterized in that for Structure 2, Y is selected from the following: i) -SiRcRd-, or -GeRcRd- wherein Rc and Rd are each independently a hydrocarbyl (C1-C30) or a heterohydrocarbyl (C1-C30); ii) -(CH2)n-, wherein n = 0 to 2; or iii) -CRaRb-, wherein Ra and Rb are each independently a hydrocarbyl (C1-C30), a heterohydrocarbyl (C1-C30) or -H.
  5. 5. Process, according to any one of claims 1 to 4, characterized in that Structure 1 is selected from the following structures 1a or 1c:
  6. 6. Process, according to any one of claims 1 to 5, characterized in that Structure 2 is selected from the following structures 2a or 2b:
  7. 7. Process, according to any one of claims 1 to 6, characterized in that it has an overall catalyst efficiency > 2.8 x 106 [(alpha composition in grams) per (total catalyst metal in grams)], at a reactor temperature > 150 °C.
  8. 8. Process, according to any one of claims 1 to 7, characterized in that it has an overall catalyst efficiency > 2.8 x 106 [(alpha composition in grams) per (total catalyst metal in grams)], at an alpha composition density of 0.855 g/cm3 to 0.890 g/cm3.
  9. 9. Process, according to any one of claims 1 to 8, characterized in that the mass flow ratio between the (hydrogen reactor feed) and the (ethylene reactor feed) is < 6.00 x 10-4 g/g.
  10. 10. Process, according to any one of claims 1 to 9, characterized in that it is carried out at a reactor temperature > 150 °C.

Description

Cross-referencing related requests [0001] This application claims priority benefit from US patent application No. 62/953,707, filed December 26, 2019, which is incorporated herein in its entirety by reference. Background of the invention [0002] Enhanced processability of elastomers is a key requirement for end-use manufacturers of various elastomeric products, such as automotive parts, photovoltaic components, wire and cable components, and footwear components. There is a need for new elastomeric resins with enhanced processability, as indicated by excellent shear thinning behavior. Such resins must polymerize in low-cost and high-efficiency processes. [0003] US publication 2011/0290317 discloses the preparation and electronic applications of bimodal and multimodal ethylene-based polymers. These polymers are prepared in two reactors, adding complexity and capital costs to the polymerization process as a whole. International publication WO2018/022588 discloses the polymerization of multimodal elastomers, primarily synthesized in the presence of a biphenylphenol catalyst and a restricted geometry catalyst (CGC). A comparative example (Comp. C), using two biphenylphenol catalysts, had a low overall catalyst efficiency of 1.4 x 10⁶ g of polymer per g of total catalyst metal. Additional in situ bimodal ethylene-based polymers and post-reactor blends are disclosed in the following references: WO2001/014434 (polymerization using a mixed geometry-restricted catalyst system), WO2002/074817 (polymerization using a mixed geometry-restricted catalyst system), US20160115264 (metallocene-catalyzed polymers), US5849823 (blends of homogeneously branched linear or substantially linear ethylene/alpha-olefin interpolymers), US6451894 (blends including a crystalline or semicrystalline polyolefin or a copolymer of ethylene and a C3 to C10 olefin, and a multimodal elastomer of sequentially polymerized ethylene-alpha-olefin monomers; see also US6610408). However, the cited technique does not promote elastomeric resins with excellent behavior of thinning by shearing, and which can be polymerized in low-cost and high-efficiency processes. These needs were met by the following invention. Summary of the invention [0004] A process for preparing an alpha composition comprising a first fraction of ethylene/alpha-olefin interpolymer and a second fraction of ethylene/alpha-olefin interpolymer; wherein said process comprises polymerizing, in a reactor, a reaction mixture comprising ethylene, an alpha-olefin, a metal complex selected from a) below and a metal complex selected from b) below: a) a biphenylphenol metal complex selected from the following Structure 1: Structure 1, in which: M is a metal chosen from zirconium (Zr) or hafnium (Hf), the metal being in a formal oxidation state of +2, +3, or +4; n is 0, 1, or 2; when n is 1, X is a monodentate ligand or a bidentate ligand; when n is 2, each X is a monodentate ligand chosen independently; the metal complex generally has a neutral charge; each of -Z1- and -Z2- is independently selected from -O-, -S-, -N(RN)-, or -P(RP)-; R1 and R8 are independently selected from the group consisting of -H, hydrocarbyl (C1-C40), heterohydrocarbyl (C1-C40), -Si(RC)3, -Ge(RC)3, -P(RP)2, -N(RN)2, -ORC, -SRC, -NO2, -CN, -CF3, RCS(O)-, RCS(O)2-, (RC)2C=N-, RCC(O)O-, RCOC(O)-, RCC(O)N(R)-, (RC)2NC(O)-, halogen, radicals having formula (II), radicals having formula (II) and radicals having formula (III): wherein each of R31-35, R41-48, and R51-59 is independently selected from hydrocarbyl (C1-C40), heterohydrocarbyl (C1-C40), -Si(RC)3, -Ge(RC)3, -P(RP)2, -N(RN)2, -N=CHRC, -ORC, -SRC, -NO2, -CN, -CF3, RCS(O)-, RCS(O)2-, (RC)2C=N-, RCC(O)O-, RCOC(O)-, RCC(O)N(RN)-, (RC)2NC(O)-, halogen or -H; each of R2-7, R9-16 is independently selected from hydrocarbyl (C1-C40), heterohydrocarbyl (C1-C40), -Si(RC)3, -Ge(RC)3, -P(RP)2, -N(RN)2, -N=CHRC, -ORC, -SRC, -NO2, -CN, -CF3, RCS(O)-, RCS(O)2-, (RC)2C=N-, RCC(O)O-, RCOC(O)-,RCC(O)N(RN)-, (RC)2NC(O)-, halogen or -H; L is hydrocarbylene (C1-C40) or heterohydrocarbylene (C1-C40), wherein the hydrocarbylene (C1-C40) has a portion comprising a main chain linking 1 carbon atom to 10 carbon atoms, linking the two Z groups in Structure 1 (to which L is attached); or the heterohydrocarbylene (C1-C40) has a portion comprising a main linking chain of 1 to 10 atoms, linking the two Z groups in Structure 1, wherein each of the 1 to 10 atoms of the main linking chain of 1 to 10 atoms of heterohydrocarbylene (C1-C40), independently, is a carbon atom or a group of heteroatoms, wherein each group of heteroatoms is, independently, O, S, S(O), S(O)2, Si(RC)2, Ge(RC)2, P(RC), or N(RC), wherein, independently, each RC is (C1-C30)hydrocarbyl or (C1-C30)heterohydrocarbyl; Each remaining RP, RN, and RC in Structure 1 is independently a hydrocarbyl (C1-C30), a heterohydrocarbyl (C1-C30), or -H; b) a biphenylphenol metal complex selected from Structure 2: Structure 2, in which M is Zr or Hf, w