Low molecular weight ethylene interpolymers and polymerization process
Low molecular weight olefin polymers are prepared by a polymerization process employing titanium complexes comprising a 3-aryl-substituted cyclopentadienyl ring or substituted derivatives thereof as polymerization catalysts.
1. A polymerization process comprising contacting one or more addition polymerizable monomers selected from the group consisting of ethylene and one or more C 4-10 α-olefins under polymerization conditions including a temperature from 95 to 160° C. with a catalyst composition comprising a metal complex corresponding to the formula:
wherein,
Ar is an aryl group of from 6 to 30 atoms not counting hydrogen;
R independently each occurrence is hydrogen, Ar, or a group other than Ar selected from hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylgermyl, halide, hydrocarbyloxy, trihydrocarbylsiloxy, bis(trihydrocarbylsilyl)amino, di(hydrocarbyl)amino, hydrocarbadiylamino, hydrocarbylimino, di(hydrocarbyl)phosphino, hydrocarbadiylphosphino, hydrocarbylsulfido, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, trihydrocarbylsilyl-substituted hydrocarbyl, trihydrocarbylsiloxy-substituted hydrocarbyl, bis(trihydrocarbylsilyl)amino-substituted hydrocarbyl, di(hydrocarbyl)amino-substituted hydrocarbyl, hydrocarbyleneamino-substituted hydrocarbyl, di(hydrocarbyl)phosphino-substituted hydrocarbyl, hydrocarbylenephosphino-substituted hydrocarbyl, or hydrocarbylsulfido-substituted hydrocarbyl, said R group having up to 40 atoms not counting hydrogen atoms;
M is titanium;
Z′ is SiR 6 2 , CR 6 2 , SiR 6 2 SiR 6 2 , CR 6 2 CR 6 2 , CR 6 ═CR 6 , CR 6 2 SiR 6 2 , BR 6 , BR 6 L″, or GeR 6 2 ;
Y is —O—, —S—, —NR 5 —, —PR 5 —; —NR 5 2 , or —PR 5 2 ;
R 5 , independently each occurrence, is hydrocarbyl, trihydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl, said R 5 having up to 20 atoms other than hydrogen, and optionally two R 5 groups or R 5 together with Y form a ring system;
R 6 , independently each occurrence, is hydrogen, or a member selected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl, —NR 5 2 , and combinations thereof, said R 6 having up to 20 non-hydrogen atoms, and optionally, two R 6 groups form a ring system;
L″ is a monodentate or polydentate Lewis base optionally bonded to R 6 ;
X is hydrogen or a monovalent anionic ligand group having up to 60 atoms not counting hydrogen;
L independently each occurrence is a neutral ligating compound having up to 20 atoms, other than hydrogen, and optionally L and X are bonded together;
X′ is a divalent anionic ligand group having up to 60 atoms other than hydrogen;
z is 0, 1 or 2;
x is 0, 1, 2, or 3;
l is a number from 0 to 2, and
x′ is 0 or 1,
to prepare a polymer having a melt index greater than 1.0 and a comonomer incorporation greater than 5 weight percent.
2. A process according to claim 1 , wherein at least one R is selected from the group consisting of Ar.
3. A process according to claim 2 , wherein the cyclopentadienyl group is substituted at the 3- and 4-position with an Ar group.
4. A process according to any one of claims 1 - 3 , wherein:
Ar is phenyl, naphthyl, 4-bisphenyl, 3-(N,N-dimethylamino)phenyl, 4-methoxyphenyl, 4methylphenyl, pyrrol-1-yl, or 1-methylpyrrol-3-yl;
R is hydrogen, methyl or Ar;
X is chloride, methyl or benzyl;
X′ is 2,3-dimethyl-1,3-butenediyl;
L is 1,3-pentadiene or 1,4-diphenyl-1,3-butadiene;
Y is —NR 5 —;
Z′ is SiR 6 2 ;
R 5 each occurrence is independently hydrocarbyl;
R 6 each occurrence is independently methyl;
x is 0 or 2;
l is 0 or 1; and
x′ is 0 or 1;
with the proviso that:
when x is 2, x′ is zero, and M is in the +4 formal oxidation state,
when x is 0 and x′ is 1, M is in the +4 formal oxidation state, and
when x and x′ are both 0, l is 1, and M is in the +2 formal oxidation state.
5. A process according to claim 1 wherein the metal complex is selected from the group consisting of:
(3,4-diphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium dichloride,
(3,4-diphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium dimethyl, and
(3,4-diphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II) 1,3-pentadiene.
6. A process according to any one of claims 1 - 3 which is a solution polymerization.
7. A process according to claim 4 which is a solution polymerization.
8. A polymerization process comprising contacting ethylene, propylene, and optionally one or more of norbornadiene, ethylidene-norbornene, or a C 4-40 diene or contacting ethylene, a C 4-10 α-olefin, and one or more of norbornadiene, ethylidene-norbornene, or a C 4-40 diene under polymerization conditions including a temperature from 95 to 160° C. with a catalyst composition comprising a metal complex corresponding to the formula:
wherein,
Ar is an aryl group of from 6 to 30 atoms not counting hydrogen;
R independently each occurrence is hydrogen, Ar, or a group other than Ar selected from hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylgermyl, halide, hydrocarbyloxy, trihydrocarbylsiloxy, bis(trihydrocarbylsilyl)amino, di(hydrocarbyl)amino, hydrocarbadiylamino, hydrocarbylimino, di(hydrocarbyl)phosphino, hydrocarbadiylphosphino, hydrocarbylsulfido, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, trihydrocarbylsilyl-substituted hydrocarbyl, trihydrocarbylsiloxy-substituted hydrocarbyl, bis(trihydrocarbylsilyl)amino-substituted hydrocarbyl, di(hydrocarbyl)amino-substituted hydrocarbyl, hydrocarbyleneamino-substituted hydrocarbyl, di(hydrocarbyl)phosphino-substituted hydrocarbyl, hydrocarbylenephosphino-substituted hydrocarbyl, or hydrocarbylsulfido-substituted hydrocarbyl, said R group having up to 40 atoms not counting hydrogen atoms;
M is titanium;
Z′ is SiR 6 2 , CR 6 2 , SiR 6 2 SiR 6 2 , CR 6 2 CR 6 2 , CR 6 ═CR 6 , CR 6 2 SiR 6 2 , BR 6 , BR 6 L″, or GeR 6 2 ;
Y is —O—, —S—, —NR 5 —, —PR 5 —; —NR 5 2 , or —PR 5 2 ;
R 5 , independently each occurrence, is hydrocarbyl, trihydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl, said R 5 having up to 20 atoms other than hydrogen, and optionally two R 5 groups or R 5 together with Y form a ring system;
R 6 , independently each occurrence, is hydrogen, or a member selected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl, —NR 5 2 , and combinations thereof, said R 6 having up to 20 non-hydrogen atoms, and optionally, two R 6 groups form a ring system;
L″ is a monodentate or polydentate Lewis base optionally bonded to R 6 ;
X is hydrogen or a monovalent anionic ligand group having up to 60 atoms not counting hydrogen;
L independently each occurrence is a neutral ligating compound having up to 20 atoms, other than hydrogen, and optionally L and X are bonded together;
X′ is a divalent anionic ligand group having up to 60 atoms other than hydrogen;
z is 0, 1 or 2;
x is 0, 1, 2, or 3;
l is a number from 0 to 2, and
x′ is 0 or 1,
to prepare a polymer having a Mooney Viscosity from 0.01 to 10 and a comonomer incorporation greater than 5 weight percent.
9. A process according to claim 8 , wherein at least one R is selected from the group consisting of Ar.
10. A process according to claim 8 , wherein the cyclopentadienyl group is substituted at the 3- and 4-position with an Ar group.
11. A process according to any one of claims 8 - 10 , wherein:
Ar is phenyl, naphthyl, 4-bisphenyl, 3-(N,N-dimethylamino)phenyl, 4-methoxyphenyl, 4-methylphenyl, pyrrol-1-yl, or 1-methylpyrrol-3-yl;
R is hydrogen, methyl or Ar;
X is chloride, methyl or benzyl;
X′ is 2,3-dimethyl-1,3-butenediyl;
L is 1,3-pentadiene or 1,4-diphenyl-1,3-butadiene;
Y is —NR 5 —;
Z′ is SiR 6 2 ;
R 5 each occurrence is independently hydrocarbyl;
R 6 each occurrence is independently methyl;
x is 0 or 2;
l is 0 or 1; and
x′ is 0 or 1;
with the proviso that:
when x is 2, x′ is zero, and M is in the +4 formal oxidation state,
when x is 0 and x′ is 1, M is in the +4 formal oxidation state, and
when x and x′ are both 0, l is 1, and M is in the +2 formal oxidation state.
12. A process according to claim 8 wherein the metal complex is selected from the group consisting of:
(3,4-diphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium dichloride,
(3,4-diphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium dimethyl, and
(3,4-diphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II) 1,3-pentadiene.
13. A process according to any one of claims 8 - 10 which is a solution polymerization.
14. A process according to claim 12 which is a solution polymerization.