Multimodal and broad molecular weight high density polyethylene
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.
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.