Process for Making Branched EPDM and the EPDM Therefrom

Patent metadata

Field	Value
Publication number	US-2018223022-A1
Application number	US-201615749866-A
Country	US
Kind code	A1
Filing date	Aug 17, 2016
Priority date	Sep 14, 2015
Publication date	Aug 9, 2018
Grant date	—

Abstract

Branched ethylene-propylene-diene elastomers (bEPDM) and processes for making the bEPDM's comprising combining a catalyst precursor and an activator at a temperature within a range from 90° C. to 160° C. with ethylene, a C3 to C12 α-olefin, a non-conjugated diene, and a dual-polymerizable diene, where the catalyst precursor is a metallocene catalyst precursor, preferably according to one of various structures including any two ligands selected from cyclopentadienyl ligands and ligands isolobal to the cyclopentadienyl group.

First claim

What is claimed is:

1 . A process comprising combining a catalyst precursor and an activator at a temperature within a range from 90° C. to 160° C. and a pressure greater than 8.0 MPa with a feed comprising ethylene, a C3 to C12 α-olefin, a non-conjugated diene, and a dual-polymerizable diene; and obtaining a branched ethylene propylene diene elastomer (bEPDM); where the catalyst precursor is selected from one of the following structures:

wherein:
M is a Group 4 metal;
Q is silicon or carbon;
R′ and R″ are selected from phenyl, alkyl substituted phenyl, and silyl substituted phenyl;
each X is independently selected from C1 to C10 alkyls, phenyls, and halogens;
each of R 1 to R 8 is independently selected from hydrogen, C1 to C10 alkyls, phenyls, and alkylphenyls; and

each of R 1′ to R 6′ is independently selected from hydrogen, C to C10 alkyls, and phenyls; and wherein the activator comprises a tetra(perfluorinated aromatic)borate.

2 . The process of claim 1 , wherein R 1 , R 3 to R 6 , and R 8 are hydrogen and the R 2 and R 7 groups are selected from the group consisting of iso-propyl, iso-butyl, tert-butyl, phenyl, alkylphenyl, and dialkylphenyl.

3 . The process of claim 1 , wherein the catalyst precursor has the following structure:

4 . The process of claim 3 , wherein R′ and R″ are each independently C1 to C5 alkylsilyl-p-phenyl; R 1 , R 3 to R 6 , and R 8 are each hydrogen; and R 2 and R 7 are selected from the group consisting of iso-propyl, iso-butyl, tert-butyl, phenyl, alkylphenyl, and dialkylphenyl.

5 . The process of claim 4 , wherein R 2 and R 7 are each tert-butyl, R 1 , R 3 to R 6 , and R 8 are each hydrogen, R 1 to R 4′ are each hydrogen, Q is silicon, and R′ and R″ are each triethylsilyl-p-phenyl.

6 . (canceled)

7 . The process of claim 1 , wherein the activator also comprises a bulky organic cation.

8 . The process of claim 1 , where the combining occurs at a pressure of at least 11.3 MPa.

9 . The process of claim 1 , where the mol percent of the dual-polymerizable diene is less than 0.30 mol % relative to the other monomers in the feed.

10 . The process of claim 1 , wherein the non-conjugated diene is 5-ethylidene-2-norbornene.

11 . The process of claim 1 , further comprising recovering an effluent comprising from 2 wt % to 20 wt % bEPDM based on the weight of the effluent.

12 . The process of claim 1 , satisfying the relationship [P-DPD]<0.244[M-DPD]+0.012, where [P-DPD] is the mol % of dual-polymerizable diene as measured by 13 C NMR, and [M-DPD] is the mol % dual-polymerizable diene monomer relative to monomers in the feed.

13 . The process of claim 1 , wherein the bEPDM has less than 2.0 mol % propylene region-errors as measured by 13 C NMR.

14 . A branched ethylene-propylene-diene elastomer (bEPDM) made by the process of claim 1 .

15 . A branched ethylene-propylene-diene elastomer (bEPDM) comprising:
within the range from 35 wt % to 65 wt % ethylene derived monomer units; within the range from 2 wt % to 12 wt % of non-conjugated diene derived monomer units; and within the range from 0.060 mol % to 0.20 mol % dual-polymerizable diene derived monomer units; wherein the remainder of monomer derived units are a C3 to C12 α-olefin derived units.

16 . The bEPDM of claim 15 , having a branching index (Bi) within the range from 4 to 12.

17 . The bEPDM of claim 15 , having an uncured Mooney MLRA (1+4 at 125° C.) within the range from 500 MU to 1600 MU.

18 . The bEPDM of claim 15 , having an uncured Mooney ML (1+4 at 125° C.) of less than 140 MU.

19 . The bEPDM of any claim 15 , having a compound Mooney Viscosity ML (1+4 at 125° C.) within the range from 65 MU to 72 MU.

20 . The bEDPM of any claim 15 , having less than 2.0 mol % propylene regio-errors as measured by 13 C NMR.

21 . The bEDPM of claim 15 , wherein the non-conjugated diene derived unit is 5-ethylidene-2-norbornene.

22 . The bEDPM of claim 15 , wherein the dual-polymerizable diene derived unit is 5-vinyl-2-norbornene.

23 . A sheet or molded article, foamed or non-foamed, comprising the bEPDM of claim 15 .

24 . A process comprising polymerizing a polymerization feed comprising ethylene, a C3 to C12 α-olefin, a non-conjugated diene, and a dual-polymerizable diene in a polymerization reactor at temperatures greater than 100° C. and pressure greater than 10 MPa so as to obtain a branched ethylene propylene diene elastomer (bEPDM);
wherein the polymerization feed comprises [M-DPD] mol % dual-polymerizable diene monomer relative to monomers in the feed;
the bEPDM comprises [P-DPD] mol % dual-polymerizable derived diene units as measured by 13 C NMR; and
[P-DPD]<0.244[M-DPD]+0.012.

25 . The process of claim 24 , wherein one or more of the following conditions is met:
(a) the polymerizing produces a polymerization effluent comprising the bEPDM within a range of 3 to 12 wt %, based on the mass of the polymerization effluent; (b) [P-DPD] is less than 0.1; (c) [M-DPD] is within the range from 0.05 to 0.25; and (d) the bEPDM comprises less than 1.9 mol % regioerrors as measured by 13 C NMR.

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Kiss Gabor
• Canich Jo Ann M
• Wouters Guy J
• Reynolds Robert P
• Kolb Rainer
• Lohse David J
• Barsan Florin

Classifications

• C08F210/18 Primary

  with non-conjugated dienes, e.g. EPT rubbers · CPC title

• C08F2420/10

  Heteroatom-substituted bridge, i.e. Cp or analog where the bridge linking the two Cps or analogs is substituted by at least one group that contains a heteroatom · CPC title

• C08F4/65908

  in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+ · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title