# US 2016/0355653 A1 · Porous Propylene Polymers

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- Number: US 2016/0355653 A1
- Document ID: US20160355653A1
- Status: Published application
- Kind: A1
- Application number: 15/142,021
- Filed: 2016-04-29
- Published: 2016-12-08
- Earliest claimed: 2015-06-05
- Assignees: ExxonMobil Chemical Patents Inc.
- Applicants: ExxonMobil Chemical Patents Inc.
- Inventors: Matthew W. Holtcamp; Gregory S. Day; Jian Yang; Lubin Luo; Steven D. Brown; Rohan A. Hule
- Web page: https://patentgrep.com/patent/US20160355653A1

## CPC

- C08J 9/00: Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof (mechanical aspects of shaping of plastics or substances in a plastic state for the production of porous or cellular articles B29C)
- C08F 4/02: Carriers therefor
- C08F 10/06: Propene
- C08F 4/65912: {in combination with an organoaluminium compound}
- C08F 4/65927: {two cyclopentadienyl rings being mutually bridged}
- C08F 2410/06: Catalyst characterized by its size
- C08J 2205/044: Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
- C08J 2323/12: Polypropene
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

This invention relates to high porosity (≧15%) and/or low pore diameter (PD<165 μm) propylene polymers and propylene polymerization processes using single site catalyst systems with supports having high surface area (SA≧400 m2/g), low pore volume (PV≦2 mL/g), a specific mean pore diameter range (PD=1-20 nm), and high average particle size (PS≧30 μm).

## Claims

### Claim 1

A propylene polymer comprising:
at least 50 mol % propylene;
a 1% Secant flexural modulus of at least 1000 MPa, determined according to ASTM D 790 (A, 1.0 mm/min);
greater than 5 and less than 200 regio defects per 10,000 propylene units, determined by 13C NMR;
if comonomer is present, a composition distribution breadth index (CDBI) of 50% or more;
a matrix comprising a porosity of 15% or more and a median pore diameter of between greater than 6 and less than 160 μm, as determined by mercury intrusion porosimetry.

### Claim 2 (depends on 1)

The propylene polymer of claim 1, wherein the porosity is 30% or more.

### Claim 3 (depends on 1)

The propylene polymer of claim 1, comprising a multimodal molecular weight distribution.

### Claim 4 (depends on 1)

The propylene polymer of claim 1, wherein the polymer is in a particulated form wherein at least 95% by volume has a particle size greater than about 120 μm.

### Claim 5 (depends on 1)

The propylene polymer of claim 1, comprising a multimodal particle size distribution.

### Claim 6 (depends on 1)

The propylene polymer of claim 1, further comprising an active catalyst system dispersed in the matrix, the catalyst system comprising a single site catalyst precursor compound, an activator for the precursor compound, and a support having a specific surface area of 400 m2/g or more, a pore volume of from 0.5 to 2 mL/g, and a mean pore diameter of from 1 to 20 nm (10 to 200 Å).

### Claim 7 (depends on 1)

The propylene polymer of claim 1, comprising a heterophasic copolymer comprising a fill phase at least partially filling the pores in the matrix.

### Claim 8 (depends on 1)

The propylene polymer of claim 1, further comprising:
a total propylene content of at least 75 wt %;
if comonomer is present, a total co-monomer content from about 3 wt % up to about 25 wt %;
if comonomer is present, a CDBI of at least 60%;
a matrix porosity of at least 35%;
a matrix median pore diameter greater than 8 μm and less than 150 μm, as determined by mercury intrusion porosimetry;
at least 50% isotactic pentads;
more than 10 regio defects per 10,000 propylene units, determined by 13C NMR;
a 1% Secant flexural modulus of at least 1800 MPa;
a melting point (Tm, DSC peak second melt) of at least 145° C.;
an Mw/Mn as measured by GPC-DRI of greater than 1 up to 5;
a multimodal molecular weight distribution with an overall Mw/Mn of greater than 1 to 20 and at least one mode having an Mw/Mn of greater than 1 to 5;
at least 95% by volume having a particle size greater than 150 μm up to 10 mm;
a melt flow rate (MFR, ASTM 1238, 230° C., 2.16 kg) from about 0.1 dg/min up to about 300 dg/min;
an Mw (as measured by GPC-DRI) from 50,000 to 1,000,000 g/mol; or
a combination thereof.

### Claim 9

A process to polymerize propylene comprising:
(a) contacting propylene monomer under polymerization conditions with a catalyst system, the catalyst system comprising a single site catalyst precursor compound, an activator, and a support, wherein the support has an average particle size of from 30 microns up to 200 microns, a surface area of 400 m2/g or more, a pore volume of from 0.5 to 2 mL/g, and a mean pore diameter of from 1 to 20 nm (10 to 200 Å), as determined by BET nitrogen adsorption; and
(b) forming a matrix of propylene polymer comprising at least 50 mol % propylene and a porosity of 15% or more as determined by mercury intrusion porosimetry.

### Claim 10 (depends on 9)

The process of claim 9, wherein the support comprises agglomerates of a plurality of primary particles.

### Claim 11 (depends on 10)

The process of claim 10, further comprising fragmenting the agglomerates to disperse catalyst sites in the propylene polymer matrix.

### Claim 12 (depends on 9)

The process of claim 9, wherein the support comprises spray dried silica, the spray dried silica having an average particle size of more than 50 μm, a specific surface area less than 1000 m2/g, or a combination thereof.

### Claim 13 (depends on 9)

The process of claim 9, wherein the specific surface area is more than 650 m2/g and the mean pore diameter is less than 7 nm (70 Å).

### Claim 14 (depends on 9)

The process of claim 9, wherein the specific surface area is less than 650 m2/g or the mean pore diameter is greater than 7 nm (70 Å).

### Claim 15 (depends on 9)

The process of claim 9, wherein the activator comprises alumoxane.

### Claim 16 (depends on 9)

The process of claim 9, wherein the catalyst system further comprises a co-activator, selected from the group consisting of: trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-octylaluminum, trihexylaluminum, and diethylzinc.

### Claim 17 (depends on 9)

The process of claim 9, wherein the contacting of the propylene monomer with the catalyst system is carried out in a slurry.

### Claim 18 (depends on 9)

The process of claim 9, wherein the polymerization conditions comprise a pressure of from about 0.96 MPa (140 psi) to about 7 MPa (1 kpsi), a temperature of from about −20° C. to 150° C., a residence time from 15 to 720 minutes, with or without hydrogen present, and with or without an ethylene or C4 to C20 comonomer present.

### Claim 19 (depends on 9)

The process of claim 9, wherein the propylene monomer in (a) is essentially free of ethylene and C4 to C20 alpha olefins, and the propylene polymer formed is a propylene homopolymer.

### Claim 20 (depends on 9)

The process of claim 9, further comprising varying a concentration of hydrogen or other chain transfer agent in (a), and wherein the propylene polymer formed in (b) comprises a multimodal molecular weight distribution.

### Claim 21 (depends on 9)

The process of claim 9, further comprising contacting the propylene polymer matrix from (b) with one or more alpha-olefin monomers under polymerization conditions to form a heterophasic copolymer comprising a fill phase at least partially filling the pores in the matrix.

### Claim 22 (depends on 9)

The process of claim 9, further comprising melt processing the propylene polymer at a shear rate of 1000 sec−1 or more.

### Claim 23 (depends on 9)

The process of claim 9, wherein the single site catalyst precursor compound is represented by the following formula:
(Cp)mRAnM4Qk
wherein:
each Cp is a cyclopentadienyl moiety or a substituted cyclopentadienyl moiety substituted by one or more hydrocarbyl radicals having from 1 to 20 carbon atoms;
RA is a structural bridge between two Cp moieties;
M4 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 M4, with the proviso that if k is greater than 1, each Q may be the same or different.

### Claim 24 (depends on 9)

The process of claim 9, wherein the single site catalyst precursor compound is represented by the formula:
RA(CpR″p)(CpR*q)M5Qr
wherein:
each Cp is a cyclopentadienyl moiety or substituted cyclopentadienyl moiety;
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;
RA is a structural bridge between the Cp moieties imparting stereorigidity to the metallocene compound;
M5 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 minus 2, where s is the valence of M5;
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 substituted cyclopentadienyl radical; and (CpR″p) contains a bulky group in one and only one of the distal positions;
wherein the bulky group is of the formula ARwv; and
where A is chosen from group 4 metals, oxygen, or nitrogen, and Rw is a methyl radical or phenyl radical, and v is the valence of A minus 1.

### Claim 25 (depends on 9)

The process of claim 9, wherein the single site catalyst precursor compound is represented by the formula:
where:
M is a group 4, 5, or 6 metal;
T is a bridging group;
each X is, independently, an anionic leaving group;
each R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, and R13 is, independently, halogen atom, hydrogen, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, substituted germylcarbyl substituent or a —NR′2, —SR′, —OR′, —OSiR′3, or —PR′2 radical, wherein R′ is one of a halogen atom, a C1-C10 alkyl group, or a C6-C10 aryl group.