Producing high comonomer content propylene-based polymers
View Patent ↗A gas-phase process for making a propylene-based polymer in a fluidized-bed reactor, the reactor containing a fluidized bed including polymer product particles and a catalyst, the process having a set of quantitative criteria for maximum monomer partial pressure, maximum reactor temperature, and comonomer content(s) in the propylene-based polymer. The propylene-based polymer may be EBPT or BPRCP. The catalyst may include a catalyst/donor system comprising (1) a supported Ziegler-Natta pro-catalyst, (2) a co-catalyst, and (3) a mixed external electron donor system including (a) an activity limiting agent including at least one carboxylate ester functional group, and (b) a selectivity control agent.
1. A process of producing a propylene-based polymer, the process comprising contacting, under copolymerization conditions, (A) propylene, butene and optionally ethylene, in a fluidized-bed reactor, the reactor containing (B) a fluidized bed comprising propylene-based polymer product particles and a catalyst, the propylene-based polymer having a seal initiation temperature (SIT) of 75° C. to 110° C., the process conducted under copolymerization conditions comprising a reactor temperature that is 20° C. to 40° C. less than the SIT of the propylene-based polymer; and wherein the catalyst comprises (1) a Ziegler-Natta pro-catalyst composition, (2) a co-catalyst, and (3) a mixed external electron donor (M-EED) system comprising (a) an activity limiting agent, and (b) a selectivity control agent, the process having a propylene partial pressure in a range of 80% to 120% of the maximum partial pressure, PP C3 _ max , as determined by the following equation:
PP C3 _ max =625−43.7 E t −20.0 B t −2.2 T
where E t , the ethylene content in the propylene-based polymer, is in a range of 0 to 2.5 wt %,
B t , the butene content in the propylene-based polymer, is in a range of 8 to 20 wt %, and where (2*E t +B t ) is less than or equal to 21 wt %, and T is the reactor temperature with a unit of ° C., and the partial pressure is with a unit of psi.
2. The process of claim 1 in which the activity limiting agent comprises at least one carboxylate ester functional group.
3. The process of claim 1 in which the selectivity control agent is selected from the group consisting of dicyclopentyldimethoxysilane, n-propyltrimethoxysilane, and methylcyclohexyldimethoxysilane.
4. The process of claim 1 in which the fluidized-bed reactor is fluidized with a pressurized gas having a gas velocity that is in a range of 5 times the minimum fluidization velocity to 1.6 times the flow regime transition velocity necessary to change the flow regime of the fluidized bed from turbulent fluidization to fast fluidization.
5. The process of claim 1 in which E t is in a range of 0 to 1.5 wt % and B t is in a range of 8 to 18 wt %.
6. The process of claim 1 in which the propylene-based polymer is one of EBPT and BPRCP.
7. A process of producing a propylene-based polymer in a fluidized-bed reactor comprising propylene-based polymer product particles and a catalyst, the propylene-based polymer having a seal initiation temperature (SIT) of 75° C. to 110° C., the process conducted under copolymerization conditions comprising a reactor temperature and a propylene partial pressure in a range of 80% to 120% of the maximum partial pressure, PP C3 _ max , as determined by the following equation:
PP C3 _ max =625−43.7 E t −20.0 B t −2.2 T
where E t , the ethylene content in the propylene-based polymer, is in a range of 0 to 2.5 wt %, B t , the butene content in the propylene-based polymer, is in a range of 8 to 20 wt %, and where (2*E t +B t ) is less than or equal to 21 wt %, and T is the reactor temperature with a unit of ° C., the partial pressure is with a unit of psi, and wherein the catalyst comprises (1) a Ziegler-Natta pro-catalyst composition, (2) a co-catalyst, and (3) a mixed external electron donor (M-EED) system comprising (a) an activity limiting agent, and (b) a selectivity control agent.
8. The method of claim 7 in which the process is conducted at a maximum reactor temperature that is 20° C. less than the SIT of the propylene-based polymer.
9. The method of claim 7 in which the process is conducted at a maximum reactor temperature that is 10° C. less than the crystallization temperature (T c ) of the propylene-based polymer.
10. The process of claim 7 in which the fluidized-bed reactor is fluidized with a pressurized gas having a gas velocity that is in a range of 5 times the minimum fluidization velocity to 1.6 times the flow regime transition velocity necessary to change the flow regime of the fluidized bed from turbulent fluidization to fast fluidization.
11. The process of claim 7 in which the propylene-based polymer is one of EBPT and BPRCP.
12. The process of claim 7 in which the activity limiting agent comprises at least one carboxylate ester functional group.
13. The process of claim 7 in which the selectivity control agent is selected from the group consisting of dicyclopentyldimethoxysilane, n-propyltrimethoxysilane, and methylcyclohexyldimethoxysilane.