Propylene copolymers obtained using transition metal bis(phenolate) catalyst complexes and homogeneous process for production thereof
This invention relates to a homogeneous process to produce propylene copolymers, such as propylene ethylene copolymers, using transition metal complexes of a dianionic, tridentate ligand that features a central neutral heterocyclic Lewis base and two phenolate donors, where the tridentate ligand coordinates to the metal center to form two eight-membered rings. Preferably the bis(phenolate) complexes are represented by Formula (I): where M, L, X, m, n, E, E′, Q, R 1 , R 2 , R 3 , R 4 , R 1′ , R 2′ , R 3′ , R 4′ , A 1 , A 1′ , and are as defined herein, where 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.
1 . A polymerization process comprising contacting, in a homogeneous phase, at least one C 3 -C 40 alpha olefin and ethylene with a catalyst system comprising activator and catalyst compound represented by Formula (I):
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, a C 1 -C 40 hydrocarbyl, a 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 1 and A 1′ are independently C, N, or C(R 22 ), where R 22 is selected from hydrogen, C 1 -C 20 hydrocarbyl, C 1 -C 20 substituted hydrocarbyl;
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;
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;
L is a Lewis base;
X is 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, a C 1 -C 40 hydrocarbyl, a C 1 -C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group,
and 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 may 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;
any two X groups may be joined together to form a dianionic ligand group; and
obtaining a copolymer comprising up to 35 mole % ethylene.
2 . The polymerization process of claim 1 , wherein the C 3 -C 40 alpha olefin is propylene and the copolymer comprises 0.1 to 35 mol % ethylene and 99.9 to 65 mol % propylene.
3 . The polymerization process of claim 1 , wherein Mis Hf, Zr, or Ti.
4 . The polymerization process of claim 1 where the catalyst compound represented by Formula (II):
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, a C 1 -C 40 hydrocarbyl, a C 1 -C 40 substituted hydrocarbyl, or a heteroatom-containing group;
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 may 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;
any two X groups may be joined together to form a dianionic ligand group;
each of R 5 , R 6 , R 7 , R 8 , R 5′ , R 6′ , R 7′ , R 8′ , R 10 , R 11 , and R 12 is independently hydrogen, a C 1 -C 40 hydrocarbyl, a C 1 -C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or one or more of R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , R 5′ and R 6′ , R 6′ and R 7′ , R 7′ and R 8′ , R 10 and R 11 , or R 11 and R 12 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 may join to form additional rings.
5 . The polymerization process of claim 4 , wherein M is Hf, Zr, or Ti.
6 . The polymerization process of claim 1 , wherein E and E′ are each O.
7 . The polymerization process of claim 1 , wherein R 1 and R 1′ is independently selected from the group consisting of a C 4 -C 40 tertiary hydrocarbyl group, a C 4 -C 40 cyclic tertiary hydrocarbyl group, and a C 4 -C 40 polycyclic tertiary hydrocarbyl group.
8 . The polymerization process of claim 1 wherein each X is, independently, selected from the group consisting of substituted or unsubstituted hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, and a combination thereof, and optionally wherein two X's may form a part of a fused ring or a ring system.
9 . The polymerization process of claim 1 wherein each L is, independently, selected from the group consisting of: ethers, thioethers, amines, phosphines, ethyl ether, tetrahydrofuran, dimethylsulfide, triethylamine, pyridine, alkenes, alkynes, allenes, carbenes and a combination thereof, and optionally wherein two or more L's may form a part of a fused ring or a ring system.
10 . The polymerization process of claim 1 , wherein M is Zr or Hf, Q is nitrogen, both A 1 and A 1′ are carbon, both E and E′ are oxygen, and both R 1 and R 1′ are independently selected from the group consisting of C 4 -C 20 cyclic tertiary alkyl, adamantan-1-yl, and substituted adamantan-1-yl.
11 . The polymerization process of claim 1 , wherein Q is carbon, A 1 and A 1′ are both nitrogen, and both E and E′ are oxygen.
12 . The polymerization process of claim 1 , wherein Q is carbon, A 1 is nitrogen, A 1′ is C(R 22 ), and both E and E′ are oxygen, where R 22 is selected from hydrogen, C 1 -C 20 hydrocarbyl, C 1 -C 20 substituted hydrocarbyl.
13 . The polymerization process of claim 1 , wherein the heterocyclic Lewis base is selected from the groups represented by the following formulas:
where each R 23 is independently selected from hydrogen, C 1 -C 20 alkyl, or C 1 -C 20 substituted alkyl.
14 . The polymerization process of claim 1 wherein the catalyst compound is represented by one or more of the following formulas:
15 . The polymerization process of claim 1 , wherein the polymerization process is a solution process.
16 . The polymerization process of claim 1 , wherein the polymerization process occurs at a temperature of from about 140° C. to about 65° C. and a catalyst activity is 100,000 kg polymer per kg of catalyst or more.
17 . The polymerization process of claim 1 wherein a catalyst activity is 200,000 kg polymer per kg of catalyst or more.
18 . The polymerization process of claim 1 , wherein the copolymer has a branching index, g′ vis of 0.95 or less.
19 . The polymerization process of claim 1 , wherein the copolymer has an Mn of 25,000 g/mol or more.
20 . The polymerization process of claim 1 , wherein the copolymer has an Mw/Mn of 1.5 to 15.
21 . The polymerization process of claim 1 , wherein the copolymer has a melt flow rate of 1500 g/10 min or less.
22 . The polymerization process of claim 1 , wherein the copolymer has a Brookfield viscosity of 500 mPa·sec or more.
23 . The polymerization process of claim 1 , wherein the copolymer has an ethylene content of 5 to 26 mol %.
24 . The polymerization process of claim 1 , wherein the copolymer has a Tm of 155° C. or less.
25 . The polymerization process of claim 1 , wherein the copolymer has a heat of fusion of 100 J/g or less.
26 . The polymerization process of claim 1 , wherein r 1 r 2 of the copolymer is in range of 0.8 to 3.0.
27 . The polymerization process of claim 1 , wherein the copolymer has regio defects of from 0.01 to 1.2 mol %.
28 . The polymerization process of claim 1 , wherein the copolymer has an mm triad tacticity of 75% or greater.