Vinyl terminated polyethylene with long chain branching

Patent metadata

Field	Value
Publication number	US-9464148-B2
Application number	US-201514702216-A
Country	US
Kind code	B2
Filing date	May 1, 2015
Priority date	Aug 3, 2012
Publication date	Oct 11, 2016
Grant date	Oct 11, 2016

Abstract

Vinyl terminated polyolefins with long chain branching produced with Salan catalysts having carbazole moieties.

First claim

What is claimed is:

1. A polyolefin comprising:
a) at least 50% allylic vinyl chain ends;
b) an Mn of at least 200 g/mol, as determined by 1 H NMR;
c) a ratio of long chain branching of at least 7 carbons per 1000 carbon atoms as determined by 13 C NMR of greater than 0.5; and
d) at least 50 mole % ethylene.

2. The polyolefin of claim 1 , comprising:
a melting point (T m ) of 100° C. or more determined by differential scanning calorimetry (DSC).

3. The polyolefin of claim 1 , comprising an Mn of at least 250 g/mol as determined by 1 H NMR.

4. The polyolefin of claim 1 , comprising a ratio of long chain branching of at least 7 carbons per 1000 carbon atoms as determined by 13 C NMR of greater than 1.0.

5. The polyolefin of claim 1 , comprising a melting point (T m ) of 110° C. or more determined by differential scanning calorimetry (DSC).

6. The polyolefin of claim 1 , comprising less than 1400 ppm aluminum as determined by inductively coupled plasma emission spectrometry (ICPES), less than 1400 ppm of a Group 3, 4, 5, or 6 transition metal, as determined by inductively coupled plasma emission spectrometry (ICPES), or a combination thereof.

7. The polyolefin of claim 1 , comprising a density of greater than 0.96 g/cc.

8. The polyolefin of claim 1 , comprising a branching index g'vis of 0.90 or less.

9. The polyolefin of claim 1 , comprising propylene.

10. The polyolefin of claim 1 , comprising a ratio of saturated chain ends to allylic vinyl chain ends of 1:1 to 5:1.

11. The polyolefin of claim 1 , wherein at least 80 wt % of the polyolefin has one allylic vinyl group per molecule.

12. The polyolefin of claim 1 , comprising a weight average molecular weight (M w ) of 5,000 to 1,000,000 g/mol.

13. The polyolefin of claim 1 , comprising an Mw/Mn of greater than 1 to 4.

14. The polyolefin of claim 1 , comprising at least 99.9 mole percent ethylene.

15. The polyolefin of claim 1 , wherein the polyolefin is produced by a process comprising contacting one or more olefins with a catalyst system at a temperature, a pressure, and for a period of time sufficient to produce the polyolefin, wherein the catalyst system comprises an activator and a salan catalyst precursor compound.

16. The polyolefin of claim 15 , wherein the catalyst compound is according to Formula I represented by:

M is a Group 4, 5 or 6 transition metal;
each X is, independently, a univalent C 1 to C 20 hydrocarbyl radical, a functional group comprising elements from Groups 13-17 of the periodic table of the elements, or X 1 and X 2 join together to form a C 4 to C 62 cyclic or polycyclic ring structure;
each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 ,R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , and R 28 is, independently, a hydrogen, a C 1 -C 40 hydrocarbyl radical, a functional group comprising elements from Groups 13-17 of the periodic table of the elements, or two or more of R 1 to R 28 may independently join together to form a C 4 to C 62 cyclic or polycyclic ring structure, or a combination thereof, or a combination thereof; and
Y is a divalent C 1 to C 20 hydrocarbyl.

17. The polyolefin of claim 15 , wherein the catalyst compound is according to Formula II represented by:

M is a Group 4, 5 or 6 transition metal;
each X is, independently, a univalent C 1 to C 20 hydrocarbyl radical, a functional group comprising elements from Groups 13-17 of the periodic table of the elements, or X 1 and X 2 join together to form a C 4 to C 62 cyclic or polycyclic ring structure;
each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , and R 21 is, independently, a hydrogen, a C 1 -C 40 hydrocarbyl radical, a functional group comprising elements from Group 13-17 of the periodic table of the elements, or two or more of R 1 to R 21 may independently join together to form a C 4 to C 62 cyclic or polycyclic ring structure, or a combination thereof; subject to the proviso that R 19 is not a carbazole or a substituted carbazole radical, and
Y is a divalent C 1 to C 20 hydrocarbyl radical.

18. A polyolefin comprising:
a) a ratio of long chain branching of at least 7 carbons per 1000 carbon atoms as determined by 13 C NMR of greater than 0.5;
b) a melting point (T m ) of 100° C. or more determined by differential scanning calorimetry (DSC);
c) a ratio of saturated chain ends to allylic vinyl chain ends of 1:1 to 5:1;
d) a ratio of vinyl groups per molecule as determined by 13 C NMR of at least 50%;
e) an Mn of at least 250 g/mol as determined by 1 H NMR; and
f) at least 50 mole % ethylene.

19. The polyolefin of claim 18 , wherein:
the ratio of long chain branching of at least 7 carbons per 1000 carbon atoms as determined by 13 C NMR is greater than 1;
the melting point (T m ) is 110° C. or more determined by differential scanning calorimetry (DSC;
at least 80 wt % of the polyolefin has one allylic vinyl group per molecule;
the ratio of saturated chain ends to allylic vinyl chain ends is 1:1 to 4:1;
a density is greater than 0.96 g/ml;
a branching index g'vis is 0.90 or less;
a weight average molecular weight (M w ) is 5,000 to 1,000,000 g/mol;
an Mw/Mn is greater than 1 to 4;
at least 99.9 mole percent of the polyolefin is ethylene; or
a combination thereof.

Assignees

• Exxonmobil Chemical Patents Inc
• Ramot At Tel-Aviv Univ Ltd

Inventors

• Giesbrecht Garth R
• Holtcamp Matthew W
• Kol Moshe

Classifications

• C08F4/76

  selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum · CPC title

• C08F4/52

  selected from boron, aluminium, gallium, indium, thallium or rare earths (C08F4/14 takes precedence) · CPC title

• C08F110/02 Primary

  Ethene · CPC title

• C08F2500/09

  Long chain branches · CPC title

• C08F4/64189

  ONNO · CPC title