Process for the preparation of a branched polyolefin

• US 10,450,388 B2
• Filed: 12/23/2015
• Issued: 10/22/2019
• Est. Priority Date: 12/23/2014
• Status: Active Grant

• Current Assignee: SABIC Global Technologies BV (Government of Saudi Arabia)
• Original Assignee: SABIC Global Technologies BV (Government of Saudi Arabia)
• Inventors: Duchateau, Robbert R., Bouyahyi, Miloud, Jasinska-Walc, Lidia, Zuideveld, Martin Alexander
• Primary Examiner(s): Bullock, In Suk C
• Assistant Examiner(s): Fadhel, Ali Z
• Application Number:
  US15/537,926
• Publication Number:
  US 20170355786A1
• Time in Patent Office: 1,399 Days
• CPC Class Codes: C08F 10/00 Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 2/38 Polymerisation using regulators, e.g. chain terminating agents , e.g. telomerisation
• CPC Class Codes: C08F 210/14 Monomers containing five or more carbon atoms
• CPC Class Codes: C08F 210/16 Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 2500/09 Long chain branches
• CPC Class Codes: C08F 4/65927 two cyclopentadienyl rings being mutually bridged

Abstract

The present invention relates to a process for the preparation of a branched polyolefin via the polymerization of an olefin monomer and an olefin monomer comprising a main group metal hydrocarbyl chain transfer agent. The invention moreover relates to polyolefins obtained by said process.

Claims

1. A process for the preparation of a branched polyolefin, said process comprising the step of:

A) a polymerization step comprising copolymerizing at least one first type of olefin monomer and at least one second type of olefin monomer comprising a main group metal hydrocarbyl chain transfer agent functionality according to Formula 1a;

R¹⁰⁰_(n-2)R¹⁰¹Mⁿ⁺R¹⁰² 

 

(Formula 1a)

using a catalyst system to obtain a polyolefin having one or multiple main group metal end-functionalized branches;

wherein said catalyst system comprises;

i) a metal catalyst or catalyst precursor comprising a metal from Group 3-10 of the IUPAC Periodic Table of elements;

ii) optionally a co-catalyst; and

iii) an additional chain transfer and/or chain shuttling agent comprising a main group metal hydrocarbyl or hydride;

wherein

M is a main group metal;

n is the oxidation state of M; and

R¹⁰⁰, R¹⁰¹ and R¹⁰² of Formula 1a are each independently selected from the group consisting of a hydride, a C1-C18 hydrocarbyl group, or a hydrocarbyl group Q with the proviso that at least one of R¹⁰⁰, R¹⁰¹ and R¹⁰² is a hydrocarbyl group Q, wherein hydrocarbyl group Q is according to Formula 1b;

2. The process according to claim 1, wherein the quenching agent in step B) is a protic reagent.

3. The process according to claim 1,

wherein R¹⁰⁰, R¹⁰¹ and R¹⁰² are hydrocarbyl group Q or

wherein R¹⁰⁰ is a C2-C4 hydrocarbyl group and R¹⁰¹ and R¹⁰² is hydrocarbyl group Q or

wherein R¹⁰⁰ and R¹⁰¹ are a C2-C4 hydrocarbyl group and R¹⁰² is hydrocarbyl group Q.

4. The process according to any claim 1, wherein the hydrocarbyl group Q according to Formula 1b is a linear α

-olefin group or a cyclic unsaturated hydrocarbyl group.

5. The process according to claim 1, wherein the at least one second type of olefin monomer comprising a main group metal hydrocarbyl chain transfer agent is selected from the group consisting of bis(isobutyl)(5-ethylen-yl-2-norbornene) aluminum, di(isobutyl)(7-octen-1-yl) aluminum, di(isobutyl)(5-hexen-1-yl) aluminum, di(isobutyl)(3-buten-1-yl) aluminum, tris(5-ethylen-yl-2-norbornene) aluminum, tris(7-octen-1-yl) aluminum, tris(5-hexen-1-yl) aluminum, or tris(3-buten-1-yl) aluminum, ethyl(5-ethylen-yl-2-norbornene) zinc, ethyl(7-octen-1-yl) zinc, ethyl(5-hexen-1-yl) zinc, ethyl(3-buten-1-yl) zinc, bis(5-ethylen-yl-2-norbornene) zinc, bis(7-octen-1-yl) zinc, bis(5-hexen-1-yl) zinc, and bis(3-buten-1-yl) zinc.

6. The process according to claim 1, wherein the co-catalyst is selected from the group consisting of MAO, DMAO, MMAO, SMAO, fluorinated aryl borane and fluorinated aryl borane borate.

7. The process according to claim 1, wherein the metal catalyst used in step A) comprises a metal selected from the group consisting of Ti, Zr, Hf, V, Cr, Fe, Co, Ni, and Pd.

8. The process according to claim 7, wherein said metal catalyst is a Group 4 single-site catalyst, optionally a metallocene or a post-metallocene.

9. The process according to claim 8, wherein said catalyst is a C_s-, C₁-, or C₂-symmetric zirconium metallocene.

10. The process according to claim 1, wherein the additional chain transfer and/or chain shuttling agent is selected from the group consisting of hydrocarbyl aluminum, hydrocarbyl magnesium, hydrocarbyl zinc, hydrocarbyl gallium, hydrocarbyl boron, hydrocarbyl calcium, aluminum hydride, magnesium hydride, zinc hydride, gallium hydride, boron hydride, calcium hydride and a combination thereof.

11. The process according to claim 1, wherein the at least one first type of olefin monomer used in step A) is selected from the group consisting of ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-cyclopentene, cyclopentene, cyclohexene, norbornene, ethylidene-norbornene, vinylidene-norbornene, and a combination thereof.

12. The process according to claim 1, wherein the branched polyolefin has a number average molecular weight (Mn) between 500 and 1,000,000 g/mol and a polydispersity index (Ð

=M_w/M_n) of between 1.1 and 5.0.

13. The process according to claim 1, wherein R¹⁰⁰ and R¹⁰¹ are isobutyl and R¹⁰² is hydrocarbyl group Q.

14. The process according to claim 13, wherein the hydrocarbyl group Q according to Formula 1b is oct-7-en-1-yl or 5-alkylenebicyclo[2.2.1]hept-2-ene.

15. The process according to claim 11, wherein the at least one second type of olefin monomer comprising a main group metal hydrocarbyl chain transfer agent is selected from the group consisting of bis(isobutyl)(5-ethylen-yl-2-norbornene) aluminum, di(isobutyl)(7-octen-1-yl) aluminum, di(isobutyl)(5-hexen-1-yl) aluminum, di(isobutyl)(3-buten-1-yl) aluminum, tris(5-ethylen-yl-2-norbornene) aluminum, tris(7-octen-1-yl) aluminum, tris(5-hexen-1-yl) aluminum, or tris(3-buten-1-yl) aluminum, ethyl(5-ethylen-yl-2-norbornene) zinc, ethyl(7-octen-1-yl) zinc, ethyl(5-hexen-1-yl) zinc, ethyl(3-buten-1-yl) zinc, bis(5-ethylen-yl-2-norbornene) zinc, bis(7-octen-1-yl) zinc, bis(5-hexen-1-yl) zinc, and bis(3-buten-1-yl) zinc.

16. The process according to claim 15, wherein

the co-catalyst is selected from the group consisting of MAO, DMAO, MMAO, SMAO, fluorinated aryl borane and fluorinated aryl borane borate;

the metal catalyst used in step A) comprises Ti, Zr or Hf; and

the additional chain transfer and/or chain shuttling agent is selected from the group consisting of hydrocarbyl aluminum, hydrocarbyl magnesium, hydrocarbyl zinc, hydrocarbyl gallium, hydrocarbyl boron, hydrocarbyl calcium, aluminum hydride, magnesium hydride, zinc hydride, gallium hydride, boron hydride, calcium hydride, and a combination thereof.

17. The process according to claim 16, wherein the at least one first type of olefin monomer used in step A) is selected from the group consisting of ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-cyclopentene, cyclopentene, cyclohexene, norbornene, ethylidene-norbornene, vinylidene-norbornene, and a combination thereof.

18. The process of according to claim 17, wherein the branched polyolefin has a number average molecular weight (Mn) between 500 and 1,000,000 g/mol and a polydispersity index (Ð

=M_w/M_n) of between 1.1 and 5.0.

19. The process according to claim 17, wherein said catalyst is a bridged bis-indenyl zirconium dihalide.

20. The process according to claim 19, wherein the branched polyolefin has a number average molecular weight (Mn) between 500 and 1,000,000 g/mol and a polydispersity index (Ð

=M_w/M_n) of between 1.1 and 5.0.