Reverse staged impact copolymers

Patent metadata

Field	Value
Publication number	US-9376559-B2
Application number	US-201414525766-A
Country	US
Kind code	B2
Filing date	Oct 28, 2014
Priority date	Nov 22, 2013
Publication date	Jun 28, 2016
Grant date	Jun 28, 2016

Abstract

This invention relates to processes to prepare impact copolymers having an ethylene content of greater than 20 wt % using a process where ethylene polymer is made in the first stage and propylene polymer is made in the second stage.

First claim

What is claimed is:

1. A process for producing ethylene-based in-reactor compositions comprising:
a) contacting ethylene and optionally a C 3 to a C 12 alpha-olefin comonomer under polymerization conditions in a first stage in the presence of a first metallocene catalyst system to form Component A;
b) contacting Component A of step (a) with a C 3 to a C 12 alpha-olefin monomer under polymerization conditions in a second stage in the presence of a second metallocene catalyst system to form Component B, wherein the first metallocene catalyst system is present in both steps a and b and/or additional metallocene catalyst is added to the reaction mixture between steps a and b and the first metallocene catalyst system may be the same as the second metallocene catalyst system; and
c) obtaining an ethylene-based in-reactor composition comprising Component A and Component B, wherein the ethylene-based in-reactor composition has from greater than 20% to about 85% of ethylene on a mole percentage basis and wherein the polymer composition has a multimodal melting point.

2. The process of claim 1 , wherein Component A is produced by the first metallocene catalyst system which is the same as or different from the second metallocene catalyst system, wherein each metallocene catalyst system, independently, comprises: (i) a metallocene compound comprising a group 4, 5, or 6 metal; (ii) an activator; and (iii) a support material.

3. The process of claim 2 , wherein the first metallocene catalyst system is the same as the second metallocene catalyst system.

4. The process of claim 2 , wherein the process comprises 0 wt % diene monomer.

5. The process of claim 1 , wherein each metallocene catalyst system, independently, comprises a metallocene compound represented by the following formula:

wherein:
M 1 is selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten;
R 1 and R 2 are selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C 1 to C 10 alkyl groups, substituted or unsubstituted C 1 to C 10 alkoxy groups, substituted or unsubstituted C 6 to C 14 aryl groups, substituted or unsubstituted C 6 to C 14 aryloxy groups, substituted or unsubstituted C 2 to C 10 alkenyl groups, substituted or unsubstituted C 7 to C 40 arylalkyl groups, substituted or unsubstituted C 7 to C 40 alkylaryl groups and substituted or unsubstituted C 7 to C 40 arylalkenyl groups; optionally R 1 and R 2 are joined together to form a C 4 to C 40 alkanediyl group or a conjugated C 4 to C 40 diene ligand which is coordinated to M 1 in a metallacyclopentene fashion; optionally R 1 and R 2 represent a conjugated diene, optionally, substituted with one or more groups independently selected from hydrocarbyl, trihydrocarbylsilyl, and trihydrocarbylsilylhydrocarbyl groups, said diene having a total of up to 40 atoms not counting hydrogen and forming a π complex with M 1 ;
each R 3 and RB is independently selected from hydrogen, halogen, substituted or unsubstituted C 1 to C 10 alkyl groups, substituted or unsubstituted C 6 to C 14 aryl groups, substituted or unsubstituted C 2 to C 10 alkenyl groups, substituted or unsubstituted C 7 to C 40 arylalkyl groups, substituted or unsubstituted C 7 to C 40 alkylaryl groups, substituted or unsubstituted C 8 to C 40 arylalkenyl groups, and —NR′ 2 , —SR′, —OR′, —SiR′ 3 , —OSiR′ 3 , and —PR′ 2 radicals wherein each R′ is independently selected from halogen, substituted or unsubstituted C 1 to C 10 alkyl groups and substituted or unsubstituted C 6 to C 14 aryl groups;
R 4 , R 5 , R 6 , and R 7 are each selected from the group consisting of hydrogen, halogen, hydroxy, substituted or unsubstituted C 1 to C 10 alkyl groups, substituted or unsubstituted C 1 to C 10 alkoxy groups, substituted or unsubstituted C 6 to C 14 aryl groups, substituted or unsubstituted C 6 to C 14 aryloxy groups, substituted or unsubstituted C 2 to C 10 alkenyl groups, substituted or unsubstituted C 7 to C 40 arylalkyl groups, substituted or unsubstituted C 7 to C 40 alkylaryl groups and C 7 to C 40 substituted or unsubstituted arylalkenyl groups; and
R 13 is selected from:

—B(R 14 )—, —Al(R 14 )—, —Ge—, —Sn—, —O—, —S—, —SO—, —SO 2 —, —N(R 14 )—, —CO—, —P(R 14 )—, and —P(O)(R 14 )—;
wherein R 14 , R 15 , and R 16 are each independently selected from hydrogen, halogen, C 1 to C 20 alkyl groups, C 6 to C 30 aryl groups, C 1 to C 20 alkoxy groups, C 2 to C 20 alkenyl groups, C 7 to C 40 arylalkyl groups, C 8 to C 40 arylalkenyl groups and C 7 to C 40 alkylaryl groups, optionally R 14 and R 15 , together with the atom(s) connecting them, form a ring; and M 3 is selected from carbon, silicon, germanium, and tin; or
R 13 is represented by the formula:

wherein R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 are each independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C 1 to C 10 alkyl groups, substituted or unsubstituted C 1 to C 10 alkoxy groups, substituted or unsubstituted C 6 to C 14 aryl groups, substituted or unsubstituted C 6 to C 14 aryloxy groups, substituted or unsubstituted C 2 to C 10 alkenyl groups, substituted or unsubstituted C 7 to C 40 alkylaryl groups, substituted or unsubstituted C 7 to C 40 alkylaryl groups and substituted or unsubstituted C 8 to C 40 arylalkenyl groups; optionally two or more adjacent radicals R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 , including R 20 and R 21 , together with the atoms connecting them, form one or more rings; and
M 2 represents one or more carbon atoms, or a silicon, germanium, or tin atom.

6. The process of claim 1 , wherein each metallocene catalyst system, independently, comprises a metallocene compound by the following formula:
(Cp) m R A n M 4 Q k
wherein each Cp is a cyclopentadienyl or a cyclopentadienyl substituted by one or more hydrocarbyl radical having from 1 to 20 carbon atoms;
R A is a structural bridge between two Cp rings;
M 4 is a transition metal selected from groups 4 or 5;
Q is a hydride or a hydrocarbyl group having from 1 to 20 carbon atoms or an alkenyl group having from 2 to 20 carbon atoms, or a halogen;
m is 1, 2, or 3, with the proviso that if m is 2 or 3, each Cp may be the same or different;
n is 0 or 1, with the proviso that n=0 if m=1; and
k is such that k+m is equal to the oxidation state of M, with the proviso that if k is greater than 1, each Q may be the same or different.

7. The process of claim 1 , wherein each metallocene catalyst system, independently, comprises a metallocene compound represented by the formula:
R A (CpR″ p )(CpR* q )M 5 Q r

wherein:
each Cp is a cyclopentadienyl or substituted cyclopentadienyl ring;
each R* and R″ is a hydrocarbyl group having from 1 to 20 carbon atoms and may the same or different;
p is 0, 1, 2, 3, or 4;
q is 1, 2, 3, or 4;
R A is a structural bridge between the Cp rings imparting stereorigidity to the metallocene compound;
M 5 is a group 4, 5, or 6 metal;
Q is a hydrocarbyl radical having 1 to 20 carbon atoms or is a halogen;
r is s−2, where s is the valence of M 5 ;
wherein (CpR* q ) has bilateral or pseudobilateral symmetry; R* q is selected such that (CpR* q ) forms a fluorenyl, alkyl substituted indenyl, or tetra-, tri-, or dialkyl

Assignees

• Exxonmobil Chem Patents Inc

Inventors

• Holtcamp Matthew W
• Mccullough Laughlin G
• Perez Jr Celestino M
• Mattler Sarah J

Classifications

• C08L2205/025

  containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure · CPC title

• C08J2323/06

  Polyethene · CPC title

• C08J2323/04

  Homopolymers or copolymers of ethene · CPC title

• C08J2323/14

  Copolymers of propene (C08J2323/16 takes precedence) · CPC title

• C08J5/18 Primary

  Manufacture of films or sheets · CPC title