US 5,866,663 A · Processes of polymerizing olefins

Abstract

Disclosed herein are processes for polymerizing ethylene, acyclic olefins, and/or selected cyclic olefins, and optionally selected olefinic esters or carboxylic acids, and other monomers. The polymerizations are catalyzed by selected transition metal compounds, and sometimes other co-catalysts. Since some of the polymerizations exhibit some characteristics of living polymerizations, block copolymers can be readily made. Many of the polymers produced are often novel, particularly in regard to their microstructure, which gives some of them unusual properties. Numerous novel catalysts are disclosed, as well as some novel processes for making them. The polymers made are useful as elastomers, molding resins, in adhesives, etc. Also described herein is the synthesis of linear .alpha.-olefins by the oligomerization of ethylene using as a catalyst system a combination a nickel compound having a selected .alpha.-diimine ligand and a selected Lewis or Bronsted acid, or by contacting selected .alpha.-diimine nickel complexes with ethylene.

Claims309

Dependent claims

A process for the polymerization of olefins, comprising, contacting a transition metal complex of a bidentate ligand selected from the group consisting of ##STR93## with an olefin wherein:

said olefin is selected from the group consisting of ethylene, an olefin of the formula R.sup.17 CH.dbd.CH.sub.2 and R.sup.17 CH.dbd.CHR.sup.17, cyclobutene, cyclopentene, norbornene, or a substituted norbornene;
said transition metal is selected from the group consisting of Ti, Zr, Sc, V, Cr, a rare earth metal, Fe, Co, Ni and Pd;
R.sup.2 and R.sup.5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R.sup.3 and R.sup.4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R.sup.3 and R.sup.4 taken together are hydrocarbylene or substituted hydrocarbylene to form a carbocyclic ring;
R.sup.44 is hydrocarbyl or substituted hydrocarbyl, and R.sup.28 is hydrogen, hydrocarbyl or substituted hydrocarbyl or R.sup.44 and R.sup.28 taken together form a ring;
R.sup.45 is hydrocarbyl or substituted hydrocarbyl, and R.sup.29 is hydrogen, substituted hydrocarbyl or hydrocarbyl, or R.sup.45 and R.sup.29 taken together form a ring;
R.sup.46 and R.sup.47 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R.sup.48 and R.sup.49 are each independently hydrogen, hydrocarbyl, or substituted hydrocarbyl;
R.sup.31 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
each R.sup.30 is independently hydrogen, substituted hydrocarbyl or hydrocarbyl, or two of R.sup.30 taken together form a ring;
R.sup.20 and R.sup.23 are independently hydrocarbyl or substituted hydrocarbyl;
R.sup.21 and R.sup.22 are each in independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
each R.sup.17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
R.sup.1 is hydrogen, hydrocarbyl or substituted hydrocarbyl;
n is 2 or 3;
and provided that:
when said bidentate ligand is (XXX) M is not Pd;
when M is Pd a diene is not present;
and
said transition metal also has bonded to it a ligand that may be displaced by said olefin or add to said olefin;
when said olefin comprises norbornene or substituted norbornene no other olefin is present.

18 more elements

A process for the polymerization of olefins, comprising, contacting, at a temperature of about -100.degree. C. to about +200.degree. C.:

a first compound W, which is a neutral Lewis acid capable of abstracting either Q.sup.- and S.sup.- to form WQ.sup.- or WS.sup.-, provided that the anion formed is a weakly coordinating anion;
or a cationic Lewis or Bronsted acid whose counterion is a weakly coordinating anion;
a second compound of the formula ##STR95## and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R.sup.17 CH.dbd.CH.sub.2 or R.sup.17 CH.dbd.CHR.sup.17, cyclobutene, cyclopentene, substituted norbornene, or norbornene;
wherein:
M is Ti, Zr, Sc, V, Cr, a rare earth metal, Fe, Co, Ni or Pd in the m oxidation state;
y+z=m
R.sup.2 and R.sup.5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R.sup.3 and R.sup.4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R.sup.3 and R.sup.4 taken together are hydrocarbylene or substituted hydrocarbylene to form a carbocyclic ring;
each R.sup.17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
Q is alkyl, hydride, chloride, iodide, or bromide;
S is alkyl, hydride, chloride, iodide, or bromide;
and
provided that;
when norbornene or substituted norbornene is present, no other monomer is present;
when M is Pd a diene is not present;
and
except, when both Q and S are each independently chloride, bromide or iodide w is capable of transferring a hydride or alkyl group to M.

14 more elements

A process for the production of polyolefins, comprising, contacting, at a temperature of about -100.degree. C. to about +200.degree. C., one or more monomers selected from the group consisting of ethylene, an olefin of the formula R.sup.17 CH.dbd.CH.sub.2 or R.sup.17 CH.dbd.CHR.sup.17, cyclobutene, cyclopentene, substituted norbornene, and norbornene;

and a compound of the formula ##STR96## wherein:
R.sup.2 and R.sup.5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R.sup.3 and R.sup.4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R.sup.3 and R.sup.4 taken together are hydrocarbylene or substituted hydrocarbylene to form a carbocyclic ring;
T.sup.2 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R.sup.15 C(.dbd.O)-- or R.sup.15 OC(.dbd.O)--;
Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur or oxygen, provided that if the donating atom is nitrogen then the pKa of the conjugate acid of that compound is less than about 6;
X is a weakly coordinating anion;
R.sup.15 is hydrocarbyl not containing olefinic or acetylenic bonds;
each R.sup.17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
M is Ni(II) or Pd(II);
each R.sup.16 is independently hydrogen or alkyl containing 1 to 10 carbon atoms;
n is 1, 2, or 3;
R.sup.8 is hydrocarbyl;
and
T.sup.2 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, hydrocarbyl substituted with keto or ester groups but not containing olefinic or acetylenic bonds, R.sup.15 C(.dbd.O)-- or R.sup.15 OC(.dbd.O)--;
provided that:
when M is Pd, or (II) or (VII) are present, a diene is not present;
and
when norbornene or substituted norbornene is used no other monomer is present.

15 more elements

A process for the production of polyolefins, comprising contacting, at a temperature of about -100.degree. C. to about +200.degree. C., one or more monomers selected from the group consisting of ethylene, an olefin of the formula R.sup.17 CH.dbd.CH.sub.2 or R.sup.17 CH.dbd.CHR.sup.17, cyclobutene, cyclopentene, substituted norbornene, and norbornene;

with a compound of the formula ##STR97## wherein:
R.sup.20 and R.sup.23 are independently hydrocarbyl or substituted hydrocarbyl;
R.sup.21 and R.sup.22 are each in independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
T.sup.1 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R.sup.15 C(.dbd.O)-- or R.sup.15 OC(.dbd.O)--;
M is Ti, Zr, Sc, Cr, a rare earth metal, V, Fe, Co, Ni or Pd in the m oxidation state;
for (XIII), m is 2;
T.sup.2 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, hydrocarbyl substituted with keto or ester groups but not containing olefinic or acetylenic bonds, R.sup.15 C(.dbd.O)-- or R.sup.15 OC(.dbd.O)--;
R.sup.15 is hydrocarbyl not containing any olefinic or acetyleneic bonds;
each R.sup.17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur or oxygen, provided that if the donating atom is nitrogen then the pKa of the conjugate acid of that compound is less than about 6;
and
X is a weakly coordinating anion.

9 more elements

A process for the production for polyolefins, comprising contacting, at a temperature of about -100.degree. C. to about +200.degree. C.,

a first compound W, which is a neutral Lewis acid capable of abstracting either Q.sup.- or S.sup.- to form WQ.sup.- or WS.sup.-, provided that the anion formed is a weakly coordinating anion;
or a cationic Lewis or Bronsted acid whose counterion is a weakly coordinating anion;
a second compound of the formula ##STR99## and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R.sup.17 CH.dbd.CH.sub.2 or R.sup.17 CH.dbd.CHR.sup.17, cyclobutene, cyclopentene, substituted norbornene, and norbornene;
wherein:
M is Ti, Zr, V, Cr, a rare earth metal, Co, Fe, Sc, or Ni, of oxidation state m;
R.sup.44 is hydrocarbyl or substituted hydrocarbyl, and R.sup.28 is hydrogen, substituted hydrocarbyl or hydrocarbyl, or R.sup.44 and R.sup.28 taken together form a ring;
R.sup.45 is hydrocarbyl or substituted hydrocarbyl, and R.sup.29 is hydrogen, substituted hydrocarbyl or hydrocarbyl, or R.sup.45 and R.sup.29 taken together form a ring;
each R.sup.30 is independently hydrogen, substituted hydrocarbyl or hydrocarbyl, or two of R.sup.30 taken together form a ring;
n is 2 or 3;
y and z are positive integers;
y+z=m;
each R.sup.17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
Q is alkyl, hydride, chloride, iodide, or bromide;
S is alkyl, hydride, chloride, iodide, or bromide;
and
provided that;
when norbornene or substituted norbornene is present, no other monomer is present.

14 more elements

A process for the polymerization of olefins, comprising, contacting, at a temperature of about -100.degree. to about +200.degree. C.:

a first compound W, which is a neutral Lewis acid capable of abstracting either Q.sup.- or S.sup.- to form WQ.sup.- or WS.sup.-, provided that the anion formed is a weakly coordinating anion;
or a cationic Lewis or Bronsted acid whose counterion is a weakly coordinating anion;
a second compound of the formula ##STR101## and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R.sup.17 CH.dbd.CH.sub.2 or R.sup.17 CH.dbd.CHR.sup.17, 4-vinylcyclohexene, cyclobutene, cyclopentene, substituted norbornene, and norbornene;
wherein:
M is Ni(II), Co(II), Fe(II) or Pd(II);
R.sup.2 and R.sup.5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R.sup.3 and R.sup.4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R.sup.3 and R.sup.4 taken together are hydrocarbylene or substituted hydrocarbylene to form a carbocyclic ring;
each R.sup.17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
Q is alkyl, hydride, chloride, iodide, or bromide;
S is alkyl, hydride, chloride, iodide, or bromide;
and
provided that:
when norbornene or substituted norbornene is present, no other monomer is present, and further provided that when 4-vinylcyclohexene is present M is Ni;
when M is Pd a diene is not present;
and when both Q and S are each independently chloride, bromide or iodide W is capable of transferring a hydride or alkyl group to M.

12 more elements

A polymerization process, comprising, contacting:

a Ni0!, Pd0! or NiI! compound containing a ligand which may be displaced by a ligand of the formula (VIII), (XXX), (XXXII) or (XXIII);
a second compound of the formula ##STR103## an oxidizing agent;
a source of a relatively weakly coordinating anion;
and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R.sup.17 CH.dbd.CH.sub.2 or R.sup.17 CH.dbd.CHR.sup.17, cyclopentene, cyclobutene, substituted norbornene, and norbornene;
wherein:
R.sup.2 and R.sup.5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R.sup.3 and R.sup.4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R.sup.3 and R.sup.4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
each R.sup.17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
each R.sup.31 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
R.sup.44 is hydrocarbyl or substituted hydrocarbyl, and R.sup.28 is hydrogen, hydrocarbyl or substituted hydrocarbyl or R.sup.44 and R.sup.28 taken together form a ring;
R.sup.45 is hydrocarbyl or substituted hydrocarbyl, and R.sup.29 is hydrogen, substituted hydrocarbyl or hydrocarbyl, or R.sup.45 and R.sup.29 taken together form a ring;
each R.sup.30 is independently hydrogen, substituted hydrocarbyl or hydrocarbyl, or two of R.sup.3 taken together form a ring;
R.sup.46 and R.sup.47 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
n is 2 or 3;
R.sup.48 and R.sup.49 are each independently hydrogen, hydrocarbyl, or substituted hydrocarbyl;
R.sup.20 and R.sup.23 are independently hydrocarbyl or substituted hydrocarbyl;
R.sup.21 and R.sup.22 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
and
provided that;
when norbornene or substituted norbornene is present, no other monomer is present;
when a Pd0! compound is used, a diene is not present;
and
when said second compound is (XXX) only an Ni0! or NiI! compound is used.

20 more elements

A process for the polymerization of olefins, comprising, contacting, at a temperature of about -100.degree. C. to about +200.degree. C.:

a first compound W, which is a neutral Lewis acid capable of abstracting either Q.sup.- or S.sup.- to form WQ.sup.- or WS.sup.-, provided that the anion formed is a weakly coordinating anion;
or a cationic Lewis or Bronsted acid whose counterion is a weakly coordinating anion;
a second compound of the formula ##STR109## and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R.sup.17 CH.dbd.CH.sub.2 or R.sup.17 CH.dbd.CHR.sup.17, cyclopentene, cyclobutene, substituted norbornene, and norbornene;
wherein:
R.sup.46 and R.sup.47 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R.sup.48 and R.sup.49 are each independently hydrogen, hydrocarbyl, or substituted hydrocarbyl;
each R.sup.31 is independently hydrocarbyl, substituted hydrocarbyl, or hydrogen;
M is Ti, Zr, V, Cr, a rare earth metal, Co, Fe, Sc, Ni, or Pd of oxidation state m;
y and z are positive integers;
y+z=m;
each R.sup.17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
Q is alkyl, hydride, chloride, iodide, or bromide;
S is alkyl, hydride, chloride, iodide or bromide;
and
provided that;
when norbornene or substituted norbornene is present, no other monomer is present;
when M is Pd a diene is not present;
and
except when both Q and S are each independently chloride, bromide or iodide W is capable of transferring a hydride or alkyl group to M.

16 more elements

A process for the production of polyolefins, comprising, contacting, at a temperature of about -100.degree. C. to about +200.degree. C., a compound of the formula ##STR110## with one or more monomers selected from the group consisting of ethylene, an olefin of the formula R.sup.17 CH.dbd.CH.sub.2 or R.sup.17 CH.dbd.CHR.sup.17, cyclobutene, cyclopentene, substituted norbornene, and norbornene,

wherein:
M is Ni(II) or Pd(II);
R.sup.2 and R.sup.5 are hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it;
R.sup.3 and R.sup.4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R.sup.3 and R.sup.4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
each R.sup.11 is independently hydrogen, alkyl or --(CH.sub.2).sub.m CO.sub.2 R.sup.1 ;
T.sup.3 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, or --CH.sub.2 CH.sub.2 CH.sub.2 CO.sub.2 R.sup.8 ;
P is a divalent group containing one or more repeat units derived from the polymerization of one or more monomers selected from the group consisting of ethylene, an olefin of the formula R.sup.17 CH.dbd.CH.sub.2 or R.sup.17 CH.dbd.CHR.sup.17, cyclopentene, cyclobutene, substituted norbornene, and norbornene, and, when M is Pd(II), optionally one or more of:
a compound of the formula CH.sub.2 .dbd.CH(CH.sub.2).sub.m CO.sub.2 R.sup.1, CO, or a vinyl ketone;
R.sup.8 is hydrocarbyl;
each R.sup.17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
R.sup.1 is hydrogen, or hydrocarbyl or substituted hydrocarbyl containing 1 to 10 carbon atoms;
m is 0 or an integer of 1 to 16;
and X is a weakly coordinating anion;
provided that when norbornene or substituted norbornene is present no other monomer is present;
when M is Pd a diene is not present;
and
further provided that when M is Ni(II) R.sup.11 is not --CO.sub.2 R.sup.8.

14 more elements

A process for the production of polyolefins, comprising, contacting, at a temperature of about -100.degree. C. to about +200.degree. C., a compound of the formula ##STR111## and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R.sup.17 CH.dbd.CH.sub.2 or R.sup.17 CH.dbd.CHR.sup.17, cyclobutene, cyclopentene, substituted norbornene, and norbornene,

wherein:
M is Zr, Ti, Sc, V, Cr, a rare earth metal, Fe, Co, Ni or Pd of oxidation state m;
R.sup.2 and R.sup.5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it;
R.sup.3 and R.sup.4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R.sup.3 and R.sup.4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
each R.sup.11 is independently hydrogen or alkyl, or both of R.sup.11 taken together are hydrocarbylene to form a carbocyclic ring;
T.sup.3 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, or --CH.sub.2 CH.sub.2 CH.sub.2 CO.sub.2 R.sup.8 ;
Q is a monoanion;
P is a divalent group containing one or more repeat units derived from the polymerization of one or monomers selected from the group consisting of ethylene, an olefin of the formula R.sup.17 CH.dbd.CH.sub.2 or R.sup.17 CH.dbd.CHR.sup.17, cyclopentene, cyclobutene, substituted norbornene, and norbornene, and, when M is Pd(II), optionally one or more of:
a compound of the formula CH.sub.2 .dbd.CH(CH.sub.2).sub.m CO.sub.2 R.sup.1, CO, or a vinyl ketone;
R.sup.8 is hydrocarbyl;
a is 1 or 2;
y+a+1=m;
each R.sup.17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
R.sup.1 is hydrogen, or hydrocarbyl or substituted hydrocarbyl containing 1 to 10 carbon atoms;
m is 0 or an integer of 1 to 16;
and X is a weakly coordinating anion;
provided that, when norbornene or substituted norbornene is present, no other monomer is present;
when M is Pd a diene is not present;
and further provided that, when M is Ni(II), T.sup.3 is not --CH.sub.2 CH.sub.2 CH.sub.2 CO.sub.2 R.sup.8.

16 more elements

Dependencies are inferred from the claim text.

Processes of polymerizing olefins

Life of this patent

Processes of polymerizing olefins

Life of this patent

Abstract

Claims309