Multimodal and broad molecular weight high density polyethylene

Patent metadata

Field	Value
Publication number	US-10590212-B2
Application number	US-201615564559-A
Country	US
Kind code	B2
Filing date	Apr 20, 2016
Priority date	Apr 20, 2015
Publication date	Mar 17, 2020
Grant date	Mar 17, 2020

Abstract

This invention relates to new multimodal and/or broad molecular weight high density polyethylene polymers. The polymers may be made in a single reactor, preferably a gas phase reactor using a dual catalyst system comprising a pyridyldiamido transition metal compound, a metallocene compound, a support, and optionally an activator.

First claim

What is claimed is:

1. A multimodal ethylene polymer comprising a low molecular weight fraction, LMWF, having a molecular weight of less than 100 kg/mol and a high molecular weight fraction, HMWF, having a molecular weight of more than 700 kg/mol, the polymer having:
a. at least 50 mol% ethylene;
b. a density of 0.938 to 0.965 g/cm 3 according to ASTM D1505;
c. a medium load melt index, I 5 , measured according to ASTM D1238(190° C., 5 kg weight), of 0.05 to 50 g/10 min;
d. a flow index, I 21 , measured according to ASTM D1238(190° C., 21.6 kg weight), of 0.1 to 100 g/10 min;
e. a ratio of Mz/Mw of greater than 5.5;
f. at least two inflection points in a GPC-4D trace; and
g. a strain hardening ratio, SHR, via SER of greater than 10 at a Hencky strain rate of 0.1 s −1 and/or 1 s −1 .

2. The polymer of claim 1 comprising from 0.1 to 50 wt% of the HMWF.

3. The polymer of claim 1 having a molecular weight distribution, Mw/Mn, of from 18 to 50.

4. The polymer of claim 1 having a melt strength via RHEOTENS at a 190° C. die temperature of greater than 22 cN.

5. The polymer of claim 1 having a melt index, I 2 measured according to ASTM D1238(190° C., 2.16 kg weight), of 0.01 to 10 g/10 min.

6. The polymer of claim 1 having at least three inflection points in a GPC-4D trace.

7. A process to produce the polymer of claim 1 , wherein the polymer is produced using a supported catalyst system comprising:
(i) at least one first catalyst component comprising a pyridyldiamido transition metal complex;
(ii) at least one second catalyst component comprising a metallocene compound;
(iii) a support material; and
(iv) optionally, an activator.

8. The process of claim 7 , wherein the pyridyldiamido transition metal complex has the general formula (I):

wherein,
M is Ti, Zr, or Hf;
Z is —(R 14 ) p C—C(R 15 ) q —,
where R 14 and R 15 are independently selected from the group consisting of hydrogen, hydrocarbyls, and substituted hydrocarbyls, and wherein adjacent R 14 and R 15 groups may be joined to form an aromatic or saturated, substituted or unsubstituted hydrocarbyl 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,

p is 0, 1 or 2, and q is 0, 1 or 2;
R 1 and R 11 are independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups;
R 2 and R 10 are each, independently, —E(R 12 )(R 13 )— with E being carbon, silicon, or germanium, and each R 12 and R 13 being independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and phosphino, R 12 and R 13 may be joined to each other or to R 14 or R 15 to form a saturated, substituted or unsubstituted hydrocarbyl ring, where the ring has 4, 5, 6, or 7 ring carbon atoms and where substitutions on the ring can join to form additional rings, or R 12 and R 13 may be joined to form a saturated heterocyclic ring, or a saturated substituted heterocyclic ring where substitutions on the ring can join to form additional rings;
R 3 , R 4 , and R 5 are independently selected from the group consisting of hydrogen, hydrocarbyls (such as alkyls and aryls), 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;
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 0, 1, 2, 3, or 4;
L′ is neutral Lewis base; and
w is 0, 1, 2, 3 or 4.

9. The process of claim 7 , wherein the metallocene compound is represented by the formula Cp A Cp B M′X′ n , wherein Cp A and Cp B are each independently selected from the group consisting of cyclopentadienyl ligands and ligands isolobal to cyclopentadienyl, either or both Cp A and Cp B optionally contain heteroatoms, and either or both Cp A and Cp B optionally are substituted; wherein M′ is Ti, Zr, or Hf; wherein X′ may be any leaving group; wherein n is 0, 1, 2, 3, or 4.

10. The process of claim 7 , wherein the polymer is produced in situ in a single reactor and the single reactor is a single gas phase reactor.

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Doufas Antonios K
• Sanders David F
• Norman Alexander I
• Holtcamp Matthew W
• Green Keith R
• Hule Rohan A
• Thurman Derek W

Classifications

• C08F2500/05

  Bimodal or multimodal molecular weight distribution · CPC title

• C08F210/16 Primary

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

• C08F4/65916

  supported on a carrier, e.g. silica, MgCl2, polymer · CPC title

• C08F2500/04

  Broad molecular weight distribution, i.e. Mw/Mn > 6 · CPC title

• C08F2500/12

  Melt flow index or melt flow ratio · CPC title