Process for homo—or copolymerization of conjugated olefins
View Patent ↗Metal complexes, catalyst compositions containing the metal complexes, and processes for making the metal complexes and the catalyst compositions are described for the manufacture of polymers from ethylenically unsaturated addition polymerizable monomers. The metal complexes have chemical structures corresponding to one of the following formulae: wherein M I and M II are metals; T is nitrogen or phosphorus; P is a carbon, nitrogen or phosphorus atom; groups R 1 , R 2 and R 3 may be linked to each other; Y is a divalent bridging group; X, X 1 , and X 2 are anionic ligand groups with certain exceptions; D is a neutral Lewis base ligand; and s, o, k, i, ii, p, m, a, b, c, d, c, t, and y are numbers as further described in the claims.
1. A metal complex catalyst, which is a reaction product of:
A) at least one metal complex represented by Formula I:
wherein:
M I is lanthanum, cerium, praseodymium, neodymium, or promethium;
M II is lithium, sodium, or potassium;
N is nitrogen;
X, independently in each occurrence, is fluoride, chloride, bromide or iodide, or an —OR group, wherein R, independently in each occurrence, is hydrogen, or a group having from 1 to 80 atoms, not counting hydrogen, selected from hydrocarbyl, hydrocarbylsilyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, acyl-substituted hydrocarbyl, arylcarbonyl-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl-substituted hydrocarbyl, acyl, or arylcarbonyl;
D is THF, DME, TEA, TMEDA, Et 2 O;
s is the number 0 or 1;
y is the number 1, 2, 3, 4, 5, or 6;
o is the number 1;
p is the number 1;
t is the number 0, 1, 2 or 3;
R A and R B , independently in each occurrence are hydrogen, a halide atom or a group having from 1 to 80 atoms not counting hydrogen, selected from the group consisting of hydrocarbyl, hydrocarbylsilyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, or hydrocarbylsilyl-substituted hydrocarbyl;
wherein the two ligands (R A )(R B )N are only linked via M I ; and
B) at least one activator selected from:
a) C 1-30 organoboron or organoaluminum compounds,
b) polymeric or oligomeric alumoxanes,
c) non-polymeric compatible, non-coordinating, ion-forming compounds, and
d) hydrocarbyl sodium, hydrocarbyllithium, hydrocarbyl zinc, hydrocarbyl magnesium halide, and dihydrocarbyl magnesium; and
wherein A) and B) are brought together in a reaction medium at a temperature from −78° C. to 250° C.
2. The catalyst of claim 1 , wherein the reaction medium is selected from at least one of the following: an aliphatic hydrocarbon, an aromatic hydrocarbon or a halohydrocabon; at a temperature from −5° C. to 160° C.
3. The catalyst of claim 1 , wherein M I is neodymium.
4. The catalyst of claim 1 , wherein M II is lithium, sodium or potassium;
D is THF, DME or Et 2 O;
X is fluorine, chlorine, bromine or iodine;
s is the number 0; and
y is the number 1, 2, 3 or 4.
5. The catalyst of claim 1 , further comprising a support.
6. The catalyst of claim 5 , wherein the support is selected from at least one of the following: clay, silica, layered silicates, alumina, activated carbon, graphite or carbon black.
7. The catalyst of claim 1 , wherein the activator comprises a combination of the following:
a) a trialkyl aluminum compound having from 1 to 4 carbon atoms in each alkyl group, and
b) a halogenated tri(hydrocarbyl)boron compound or halogenated tetrakis(hydrocarbyl)boron or -aluminum compound, each having from 1 to 20 carbon atoms in each hydrocarbyl group.
8. The catalyst of claim 1 , wherein the activator comprises a combination of the following:
a) a tris(pentafluorophenyl)borane, tetrakis(pentafluorophenyl)borate, or tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and
b) a polymeric or oligomeric alumoxane.
9. The catalyst of claim 1 , wherein the activator comprises a combination of the following:
a) a trialkyl aluminum or dialkyl aluminum hydride compound, and
b) boron trifluoride, boron trichloride, boron tribromide, aluminum trifluoride, aluminum trichloride, aluminum tribromide, scandium trifluoride, or titanium tetrafluoride.