Process for the preparation of a polyolefin having one or multiple end-functionalized branches

Patent metadata

Field	Value
Publication number	US-10465018-B2
Application number	US-201515537933-A
Country	US
Kind code	B2
Filing date	Dec 23, 2015
Priority date	Dec 23, 2014
Publication date	Nov 5, 2019
Grant date	Nov 5, 2019

Abstract

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

First claim

The invention claimed is:

1. A process for the preparation of a polyolefin having one or multiple end-functionalized branches, 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 containing a main group metal hydrocarbyl chain transfer agent functionality according to Formula 1a:
R 100 (n-2) R 101 M n+ R 102   (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 metal catalyst precursor comprising a metal from Group 3-10 of the IUPAC Periodic Table of elements, and
ii) optionally a co-catalyst;
iii) an additional chain transfer and/or chain shuttling agent 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;
wherein
M is a main group metal;
n is the oxidation state of M;
R 100 , R 101 and R 102 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 R 100 , R 101 and R 102 is a hydrocarbyl group Q, wherein hydrocarbyl group Q is according to Formula 1b:

wherein
Z is bonded to M and Z is a C1-C18 hydrocarbylene group;
R 105 optionally forms a cyclic group with Z;

R 103 and R 104 and R 105 are each independently selected from hydrogen or a hydrocarbyl group;
B) an oxidizing step comprising contacting said polyolefin having one or multiple main group metal end-functionalized branches obtained in step A) with an oxidizing agent to obtain a polyolefin having one or multiple main group metal end-functionalized oxidized branches; and
C) contacting said polyolefin having one or multiple main group metal end-functionalized oxidized branches obtained in step B) with a quenching agent to remove the main group metal from the oxidized branch ends to obtain the polyolefin having one or multiple end-functionalized branches.

2. The process according to claim 1 , wherein said oxidizing agent used in step B) is an oxidizing agent according to Formula I:
XY a Z 1 b Z 2 c   (Formula I)

wherein a is 1, b and c are each independently 0 or 1 and X, Y, Z 1 and Z 2 are independently selected from carbon, hydrocarbyl, heteroatom and halogen.

3. The process according to claim 1 , wherein the oxidizing agent used in step B) is selected from the group consisting of fluorine, chlorine, iodine, bromine, O 2 , CO, O 3 , CO 2 , CS 2 , COS, R 2 NCO, R 2 NCS, R 2 NCNR 3 , CH 2 ═C(R 2 )C(═O)OR 3 , CH 2 ═C(R 2 )(C═O)N(R 3 )R 4 , CH 2 ═C(R 2 )P(═O)(OR 3 )OR 4 , N 2 O, R 2 CN, R 2 NC, epoxide, aziridine, cyclic anhydride, R 3 R4C═NR 2 , R 2 C(═O)R 3 , ClC(═O)OR 2 and SO 3 .

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

5. The process according to claim 1 ,
wherein at least one of R 100 , R 101 and R 102 is a hydrocarbyl group Q and the remaining groups of R 100 , R 101 and R 102 are each a C1-C4 hydrocarbyl group or
wherein two groups of R 100 , R 101 and R 102 are each a hydrocarbyl group Q and the remaining group of R 100 , R 101 and R 102 is a C1-C4 hydrocarbyl group or
wherein all of R 100 , R 101 and R 102 are a hydrocarbyl group Q.

6. The process according to claim 1 , wherein the hydrocarbyl group Q according to Formula 1b attached to a main group metal is a linear α-olefin group or a cyclic unsaturated hydrocarbyl group.

7. The process according to claim 1 , wherein the at least one second type of olefin monomer 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.

8. 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 borate.

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

10. The process according to claim 9 , wherein said metal catalyst precursor is a an indenyl substituted zirconium dihalide.

11. The process according to claim 9 , wherein said metal catalyst precursor is [Me 2 Si(C 5 Me 4 )N(tBu)]TiCl 2 or [N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium dimethyl.

12. 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.

13. A polyolefin obtained by a process according to claim 1 having one or multiple end-functionalized branches, having a number average molecular weight (Me) between 500 and 1,000,000 g/mol and having a polydispersity index (D) of between 1.1 and 10.0 and wherein said polyolefin has a degree of functionalization of at least 30%,
wherein said polyolefin having one or multiple end-functionalized branches is according to Formula I.I:
Pol-XY a Z 1 b Z 2 c R 1 d   (Formula I.I),

wherein
a, b, c and d are each independently 0 or 1,
X, Y, Z 1 , Z 2 are each independently selected from carbon, hydrocarbyl, heteroatom and halogen, and
R 1 is hydride or hydrocarbyl,

with the proviso that at least one of X, Y, Z 1 , Z 2 is a heteroatom.

14. The polyolefin according to claim 13 , wherein a, b and d are 1, c is 0, and X is C, Y and Z 1 are O and R 1 is H.

15. The process according to claim 1 , wherein the hydrocarbyl group Q according to Formula 1b attached to a main group metal is but-3-en-1-yl, pent-4-en-1-yl, hex-5-en-1-yl, hept-6-en-1-yl or oct-7-en-1yl, 5-ethylenebicyclo[2.2.1]hept-2-ene or 5-propylenebicyclo[2.2.1]hept-2-ene.

16. The process according to claim 15 , wherein the metal catalyst or metal catalyst precursor used in step A) comprises Ti, Zr or Hf.

17. The process according to claim 16 , wherein
said oxidizing agent used in step B) is selected from the group consisting of O 2 , O 3 , N 2 O, CO 2 and SO 3 ;
the additional chain transfer and/or shuttling agent used in step A) is selected from the group consisting of hydr

Assignees

• Sabic Global Technologies Bv

Inventors

• Duchateau Robbert R
• Bouyahyi Miloud
• Jasinska-Walc Lidia
• Zuideveld Martin Alexander

Classifications

• C08F2/38 Primary

  Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation} · CPC title

• C08F4/65927

  two cyclopentadienyl rings being mutually bridged · CPC title

• C08F210/16 Primary

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title

• C08F210/14

  Monomers containing five or more carbon atoms · CPC title

• C08F8/00

  Chemical modification by after-treatment (graft polymers, block polymers, crosslinking with unsaturated monomers or with polymers C08F251/00 - C08F299/00; of conjugated diene rubbers C08C) · CPC title