Polyolefin-based ionomers and production thereof
This invention relates to a process to produce an ionomer comprising: 1) contacting, in a reactor, one or more C 2 -C 60 α-olefins, an optional diene, and a metal alkenyl with a catalyst system comprising an activator, a catalyst compound, and a support; 2) forming a copolymer comprising one or more C 2 -C 60 α-olefin monomers and about 0.01 wt % to about 20 wt %, based on the weight of the copolymer, of metal alkenyl; 3) functionalizing and quenching the polymerization reaction with one or more electrophilic groups; and 4) obtaining ionomer.
1. A process to produce an ionomer comprising:
1) contacting, in a reactor, one or more C 2 -C 60 α-olefin monomers, an optional diene, and a metal alkenyl represented by the formula: Q(R′) z-v (R) v
where Q is a group 1, 2, 12 or 13 metal,
R is a hydrocarbenyl group containing 4 to 20 carbon atoms having an allyl chain end,
R′ is a hydrocarbyl group containing 1 to 30 carbon atoms,
z is 1, 2, or 3, and
v is 1, 2 or 3, where z-v is 0, 1 or 2,
with a catalyst system comprising an activator, a catalyst compound, and a support;
2) forming a copolymer comprising one or more C 2 -C 60 α-olefin monomers and about 0.01 wt % to about 20 wt %, based on a weight of the copolymer, of metal alkenyl, wherein the copolymer optionally has a melting point of 100° C. or more and or an Mw of 100,000 g/mol;
3) quenching a polymerization reaction with one or more electrophilic groups thereby functionalizing the copolymer; and
4) introducing a metal cation and obtaining ionomer comprising an ionic group.
2. The process of claim 1 , wherein Q is Al.
3. The process of claim 1 , wherein R is butenyl, pentenyl, heptenyl, or octenyl and R′ is methyl, ethyl, propyl, isobutyl, butyl, octyl, or n-octyl.
4. The process of claim 1 , wherein the metal alkenyl is one or more of isobutyl-di(oct-7-en-1-yl)-aluminum, isobutyl-di(dec-9-en-1-yl)-aluminum, isobutyl-di(non-8-en-1-yl)-aluminum, isobutyl-di(hept-6-en-1-yl)-aluminum, dimethyl(oct-7-en-1-yl)aluminum, diethyl(oct-7-en-1-yl)aluminum, dibutyl(oct-7-en-1-yl)aluminum, diisobutyl(oct-7-en-1-yl)aluminum, diisobutyl(non-8-en-1-yl) aluminum, diisobutyl(dec-9-en-1-yl)aluminum, diisobutyl(dodec-10-en-1-yl)aluminum, diisobutyl(hept-6-en-1-yl)aluminum, diethyl(hept-6-en-1-yl)aluminum, dimethyl(hept-6-en-1-yl)aluminum, di-n-octyl(7-octen-1-yl)aluminum, n-octyl(di-7-octen-1-yl)aluminum, or diisobutyl(6-hepten-1-yl)aluminum.
5. The process of claim 1 , where the C 2 -C 60 α-olefins are one or more of ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene or isomers thereof.
6. The process of claim 1 , where the diene comprises one or more of butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, cyclopentadiene, vinylnorbornene, norbornadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, divinylbenzene, dicyclopentadiene, or combination(s) thereof.
7. The process of claim 1 , where copolymer comprises:
1) 50 wt % to about 99.99 wt % of a first α-olefin monomer,
2) up to about 50 wt % of an optional second α-olefin comonomer different from the first α-olefin monomer,
3) up to about 20 wt % of an optional diene, and
4) 0.01 wt % to about 20 wt % of a metal alkenyl, based on a weight of the copolymer.
8. The process of claim 1 , where copolymer has an Mw/Mn of from about 2 to about 4 Mw of about 50,000 g/mol or more and an Mn of about 21,000 g/mol or more.
9. The process of claim 1 , wherein reaction conditions comprise a temperature of about 50° C. to about 100° C. and a time of about 5 minutes to about 30 minutes.
10. The process of claim 1 , wherein quenching the polymerization reaction comprises introducing a quench agent comprising the one or more electrophilic groups at a pressure of about 50 psi to about 150 psi, at a temperature of about 50° C. to about 100° C., and for a time of about 5 minutes to about 30 minutes.
11. The process of claim 1 , wherein the catalyst compound comprises a metallocene represented by the formula:
Cp A Cp B M′X′ n , (MCN-I)
Cp A (T)Cp B M′X′ n , or (MCN-II)
T y Cp m MG n X q (MCN-III)
wherein each Cp A and Cp B is independently selected from cyclopentadienyl ligands or ligands isolobal to cyclopentadienyl, one or both Cp A and Cp B may contain heteroatoms, and one or both Cp A and Cp B may be substituted by one or more R″ groups;
M′ is selected from Groups 3 through 12 atoms or lanthanide Group atoms;
X′ is an anionic leaving group; n is 0 or an integer from 1 to 4;
each R″ is independently selected from alkyl, substituted alkyl, heteroalkyl, alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, aryloxy, alkylthio, arylthio, aryl, substituted aryl, heteroaryl, aralkyl, aralkylene, alkaryl, alkarylene, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocycle, heteroaryl, a heteroatom-containing group, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, silyl, boryl, phosphino, phosphine, amino, amine, ether, or thioether;
(T) is a bridging group selected from divalent alkyl, divalent substituted alkyl, divalent heteroalkyl, divalent alkenyl, divalent substituted alkenyl, divalent heteroalkenyl, divalent alkynyl, divalent substituted alkynyl, divalent heteroalkynyl, divalent alkoxy, divalent aryloxy, divalent alkylthio, divalent arylthio, divalent aryl, divalent substituted aryl, divalent heteroaryl, divalent aralkyl, divalent aralkylene, divalent alkaryl, divalent alkarylene, divalent haloalkyl, divalent haloalkenyl, divalent haloalkynyl, divalent heteroalkyl, divalent heterocycle, divalent heteroaryl, a divalent heteroatom-containing group, divalent hydrocarbyl, divalent substituted hydrocarbyl, divalent heterohydrocarbyl, divalent silyl, divalent boryl, divalent phosphino, divalent phosphine, divalent amino, divalent amine, divalent ether, or divalent thioether;
Cp is independently a substituted or unsubstituted cyclopentadienyl ligand or substituted or unsubstituted ligand isolobal to cyclopentadienyl;
M is a Group 4 transition metal;
G is a heteroatom group represented by the formula JR* z where J is N, P, O or S, and R* is a linear, branched, or cyclic C 1 -C 20 hydrocarbyl; z is 1 or 2;
T is a bridging group; y is 0 or 1; X is a leaving group; m=1, n=1, 2 or 3, q=0, 1, 2 or 3, and the sum of m+n+q is equal to the coordination number of the Group 4 transition metal.
12. The process of claim 1 , wherein the catalyst compound is represented by Formula (A):
wherein:
M is a group 3, 4, 5, or 6 transition metal or a Lanthanide;
E and E′ are each independently O, S, or NR 9 , where R 9 is independently hydrogen, C 1 -C 40 hydrocarbyl, C 1 -C 40 substituted hydrocarbyl, or a heteroatom-containing group;
Q is group 14, 15, or 16 atom that forms a dative bond to metal M;
A 1 QA 1′ are part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms that links A 2 to A 2′ via a 3-atom bridge with Q being the central atom of the 3-atom bridge;
A 3 A 2 is a divalent group containing 2 to 40 non-hydrogen atoms that links A 1 to the E-bonded aryl group via a 2-atom bridge;
A 2′ A 3′ is a divalent group containing 2 to 40 non-hydrogen atoms that links A 1′ to the E′-bonded aryl group via a 2-atom bridge;
each L is independently a Lewis base;
each X is independently an anionic ligand;
n is 1, 2 or 3;
m is 0, 1, or 2;
n+m is not greater than 4;
each of R 1* , R 2* , R 3* , R 4* , R 1′ , R 2′ , R 3′ , and R 4′ is independently hydrogen, C 1 -C 40 hydrocarbyl, C 1 -C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or one or more of R 1* and R 2* , R 2* and R 3* , R 3* and R 4* , R 1′ and R 2′ , R 2′ and R 3′ , R 3′ and R 4′ may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atoms, and where substitutions on the ring can join to form additional rings;
any two L groups may be joined together to form a bidentate Lewis base;
an X group may be joined to an L group to form a monoanionic bidentate group; and
any two X groups may be joined together to form a dianionic ligand group.
13. The process of claim 1 , wherein the ionomer has a maximum elastic range of from about 400% elongation to about 500% elongation.
14. The process of claim 1 , wherein the ionomer has an elongation at breakage of about 500% or greater.
15. The process of claim 1 , wherein the ionomer has a tensile set, at 200% deformation, of from about 40% to about 50%.
16. The process of claim 1 , wherein the ionomer has a tensile strength, at 25° C., of from about 0.1 MPa to about 10 MPa.
17. The process of claim 1 , wherein the ionomer has a Young's modulus, at 40° C. of from about 0.5 MPa to about 10 MPa, the ionomer has a glass transition temperature of from about −100° C. to about −10° C., the ionomer has a complex viscosity as measured by oscillatory shear at an angular frequency of 0.1 rad/s of about 500,000 Pa-s to about 800,000 Pa-s, the copolymer comprising a propylene copolymer that has a complex viscosity as measured by oscillatory shear at an angular frequency of 100 rad/s of about 100 to 500 Pa-s, the ionomer has a shear thinning index of about 1,000 to 5,000, and the ionomer has a strain hardening ratio of about 5 to about 15 when measured at Hencky strain rate of 10 sec −1 , of about 10 to about 20 when measured at Hencky strain rate of 1.0 sec −1 , of about 15 to about 30 when measured at Hencky strain rate of 0.1 sec −1 , of about 30 to about 100 when measured at Hencky strain rate of 0.01 sec −1 , and/or of about 100 to about 200 when measured at Hencky strain rate of 0.001 sec −1 .