Process to produce polymers from pyridyldiamido transition metal complexes and use thereof

Patent metadata

Field	Value
Publication number	US-9260552-B2
Application number	US-201414515810-A
Country	US
Kind code	B2
Filing date	Oct 16, 2014
Priority date	Nov 15, 2013
Publication date	Feb 16, 2016
Grant date	Feb 16, 2016

Abstract

Processes to produce ethylene copolymers using pyridyldiamido transition metal complexes, a chain transfer agent, and an activator are disclosed.

First claim

What is claimed is:

1. A process to polymerize ethylene and one or more C3 to C20 comonomers comprising contacting ethylene, one or more C3 to C20 comonomers, an activator, a chain transfer agent, and a pyridyldiamido transition metal complex represented by the formula: (A), (B), (C), or (D):

wherein:
M is a Group 3 or 4 metal;
Q 1 is a three atom bridge with the central of the three atoms being a group 15 or 16 element (said group 15 element may or may not be substituted with an R 30 group) represented by the formula: -G 1 -G 2 -G 3 - where G 2 is a group 15 or 16 atom (said group 15 element may be substituted with a R 30 group), G 1 and G 3 are each a group 14, 15, or 16 atom (each group 14, 15, and 16 element may or may not be substituted with one or more R 30 groups), where G 1 , G 2 and G 3 , or G 1 and G 2 , or G 1 and G 3 , or G 2 and G 3 may form a singular or multi ring system;
each R 30 group is, independently, hydrogen or a C 1 to C 100 hydrocarbyl group or a silyl group;
Q 2 is —NR 17 or —PR 17 , where R 17 is selected from hydrocarbyls, substituted hydrocarbyls, silyls, or germyls;
Q 3 is -(TT)- or -(TTT)- where each T is carbon or a heteroatom, and said carbon or heteroatom may be unsubstituted or substituted with one or more R 30 groups that together with the “—C-Q 3 =C—” fragment, forms a 5- or 6-membered cyclic group or a polycyclic group including the 5 or 6-membered cyclic group;
R 1 is selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups;
R 3 , R 4 , and R 5 are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, aryloxy, halogen, amino, and silyl, and wherein adjacent R groups (R 3 & R 4 and/or R 4 & R 5 ) may be joined to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings;
R 2 is -E(R 12 )(R 13 )— with E being carbon, silicon, or germanium;
Y is selected from oxygen, sulfur, or -E*(R 6 )(R 7 )—, with E* being carbon, silicon, or germanium;
R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen, amino, and silyl, and wherein adjacent R groups (R 6 & R 7 , and/or R 8 & R 9 , and/or R 9 & R 10 , and/or R 10 & R 11 and/or R 12 & R 13 ) may be joined to form a saturated, substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings;
L is an anionic leaving group, where the L groups may be the same or different and any two L groups may be linked to form a dianionic leaving group;
n is 1 or 2;
L′ is a neutral Lewis base; and
w is 0, 1, 2, 3 or 4.

2. The process of claim 1 , wherein M is Ti, Zr, or Hf.

3. The process of claim 1 , wherein R 2 is selected from CH 2 , CH(aryl), CH(2-isopropylphenyl), CH(2,6-dimethylphenyl), CH(2,4-6-trimethylphenyl), CH(alkyl), CMe 2 , SiMe 2 , SiEt 2 , or SiPh 2 .

4. The process of claim 1 , wherein T is C, O, S, or N.

5. The process of claim 1 , wherein E and E* are carbon and each R 6 , R 7 , R 12 , and R 13 are a C 1 to C 30 substituted or unsubstituted hydrocarbyl group.

6. The process of claim 1 , wherein E and E* are carbon and each R 6 , R 7 , R 12 , and R 13 are a C 6 to C 30 substituted or unsubstituted aryl group.

7. The process of claim 1 , wherein Q 2 is —NR 17 .

8. The process of claim 1 , wherein E and E* are carbon and R 1 and R 17 are independently selected from phenyl groups that are substituted with 0, 1, 2, 3, 4, or 5 substituents selected from the group consisting of F, Cl, Br, I, CF 3 , NO 2 , alkoxy, dialkylamino, hydrocarbyl, and substituted hydrocarbyl groups with from one to ten carbons.

9. The process of claim 1 , wherein Q 1 is selected from:

where the

symbols indicate the connections to R 2 and the aromatic ring, and alkyl is an alkyl group.

10. The process of claim 1 , wherein each L is independently selected from the group consisting of halide, alkyl, aryl, alkoxy, amido, hydrido, phenoxy, hydroxy, silyl, allyl, alkenyl, triflate, alkylsulfonate, arylsulfonate, and alkynyl; and each L′ is independently selected from the group consisting of ethers, thio-ethers, amines, nitriles, imines, pyridines, and phosphines.

11. The process of claim 1 , wherein Q 3 is CHCHCH, CH 2 CH, CHN(alkyl), CH—S, CHC(alkyl)=CH, C(alkyl)CH═C(alkyl), CH—O, or NO.

12. The process of claim 1 , wherein the complex is represented by formula (A).

13. The process of claim 1 , wherein the complex is represented by formula (B).

14. The process of claim 1 , wherein the complex is represented by formula (C).

15. The process of claim 1 , wherein the complex is represented by formula (D).

16. The process of claim 1 , wherein the complex is one or more of the compounds represented by the formula:

17. The process of claim 1 , wherein the activator comprises an alumoxane.

18. The process of claim 1 , wherein the activator comprises a non-coordinating anion.

19. The process of claim 1 , wherein the activator comprises one or more of:
trimethylammonium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-diethylanilinium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, trimethylammonium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluorophenyl)borate, [Me 3 NH + ][B(C 6 F 5 ) 4 ], 1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium, triphenylcarbenium tetraphenylborate, and triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate.

20. The process of claim 1 wherein the monomer comprises ethylene.

21. The process of claim 1 wherein the monomer comprises propylene.

22. The process of claim 1 wherein the pyridyldiamido transition metal complex is supported.

23. The process of claim 1 wherein the chain transfer agent is dialkyl zinc, trialkyl aluminum, or a mixture thereof.

24. The process of claim 1 wherein the chain transfer agent is one or more of diethylzinc, tri(n-octyl)aluminum, or di(n-propyl)zinc.

25. The process of claim 1 further comprising obtaining an ethylene copolymer having an Mw(LS)/Mn(Dri) of from 1 to 2.5.

26. The process of claim 1 further comprising obtaining an ethylene copolymer having:
1) an Mw(LS)/Mn(Dri) of from 1 to 2.5;
2) an Mw of from 3,000 to 300,000 g/mol;
3) a g′vis of 0.90 or more;
4) an ethylene content of 35 to 85 mol % or more;
5) an C3 to C20 alpha olefin content of 15 to 65 mol %;
6)

Assignees

• Exxonmobil Chem Patents Inc

Inventors

• Hagadorn John R
• Farng Liehpao O
• Palafox Patrick J
• Yang Jian
• Stewart Ian C

Classifications

• C10M143/04 Primary

  containing propene · CPC title

• C10M2205/022

  Ethene · CPC title

• C08F4/64148

  NN(R)N · CPC title

• C08F2800/10

  as molar percentages · CPC title

• C08F2500/03

  Narrow molecular weight distribution, i.e. Mw/Mn < 3 · CPC title