US2002111445A1PendingUtilityA1
Copolymerization of olefins
Est. expiryMay 29, 2018(expired)· nominal 20-yr term from priority
C08F 10/00C08F 210/16C08F 210/06C08F 210/02C08F 4/7054
43
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Claims
Abstract
Ethylene and/or propylene, and α-olefins may be copolymerized by contacting then with certain iron or cobalt complexes of selected 2,6-pyridinecarboxaldehydebis(imines) and 2,6-diacylpyridinebis(imines). The polymers produced, some of which are novel, are useful as molding resins.
Claims
exact text as granted — not AI-modifiedWhat is claimed is:
1 . A polymerization process, comprising, contacting, at a temperature of about −10° C. to about +200° C., a compound of the formula
with one or both of ethylene and propylene, an α-olefin of the formula H 2 C═CHR 21 , and:
(a) a first compound W, which is a neutral Lewis acid capable of abstracting X − and alkyl group or a hydride group from M to form WX − , WR 20 or WH and which is also capable of transferring an alkyl group or a hydride to M, provided that WX − is a weakly coordinating anion; or
(b) a combination of a second compound which is capable of transferring an alkyl or hydride group to M and a third compound which is a neutral Lewis acid which is capable of abstracting X − , a hydride or an alkyl group from M to form a weakly coordinating anion;
wherein:
M is Co or Fe;
each X is an anion;
n is 1, 2 or 3 so that the total number of negative charges on said anion or anions is equal to the oxidation sate of a Fe or Co atom present in (II);
R 1 , R 2 and R 3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;
R 4 and R 5 are each independently hydrogen, hydrocarbyl, an inert functional group, or substituted hydrocarbyl;
R 6 and R 7 are aryl or substituted aryl;
R 20 is alkyl; and
R 21 is alkyl
2 . A polymerization process, comprising contacting, at a temperature of about −100° C. to about +200° C., a Co[II], Co[III], Fe[II] or Fe[III] complex of a tridentate ligand of the formula
with one or both of ethylene and propylene, and an α-olefin of the formula H 2 C═CHR 21 , wherein:
R 1 , R 2 and R 3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;
R 4 and R 5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl;
R 6 and R 7 are aryl or substituted aryl; and
R 21 is alkyl;
and provided that a Co[II], Co[III], Fe[II] or Fe[III] atom also has bonded to it an empty coordination site or a ligand that may be displaced by said ethylene, and a ligand that may add to said ethylene.
3 . The process as recited in claim 1 or 2 wherein ethylene is present and propylene is not present.
4 . The process as recited in claim 2 wherein:
R 6 is
R 8 and R 13 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group;
R 9 , R 10 , R 11 , R 14 , R 15 and R 16 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group;
R 12 and R 17 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group;
and provided that any two of R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 that are vicinal to one another, taken together may form a ring.
5 . The process as recited in claim 4 wherein:
R 1 , R 2 and R 3 are hydrogen;
R 9 , R 10 , R 11 , R 14 , R 15 and R 16 is each independently halogen, alkyl containing 1 to 6 carbon atoms, or hydrogen;
R 8 and R 13 is each independently halogen, phenyl or alkyl containing 1 to 6 carbon atoms;
R 12 and R 17 is each independently halogen, phenyl, hydrogen, or alkyl containing 1 to 6 carbon atoms; and
R 4 and R 5 are each independently hydrogen or alkyl containing 1 to 6 carbon atoms.
6 . The process as recited in claim 5 wherein R 4 and R 5 are each hydrogen or methyl.
7 . The process as recited in claim 5 wherein X is chloride, bromide or tetrafluoroborate.
8 . The process as recited in claim 5 wherein said neutral Lewis acid is an alkyl aluminum compound.
9 . The process as recited in claim 8 wherein said alkyl aluminum compound is polymethylaluminoxane.
10 . The process as recited in claim 5 wherein said temperature is about −50° C. to about 100° C.
11 . The process as recited in claim 1 wherein M is Fe.
12 . The process as recited in claim 2 wherein said complex is an Fe[II] or Fe[III] complex.
13 . The process as recited in claim 1 , 2 , 11 or 12 wherein R 21 is n-alkyl.
14 . A polymerization process, comprising, contacting, at a temperature of about −100° C. to about +200° C., one or both of ethylene and propylene, an α-olefin of the formula H 2 C═CHR 21 , and a compound of the formula
wherein:
M is Co or Fe;
R 1 , R 2 and R 3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;
R 4 and R 5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl;
R 6 and R 7 are aryl or substituted aryl;
R 21 is alkyl;
T 1 is hydride or alkyl or any other anionic ligand into which ethylene or an α-olefin can insert;
Y is a neutral ligand capable of being displaced by ethylene or a vacant coordination site;
Q is a relatively non-coordinating anion;
P is a divalent polyolefin group; and
T 2 is an end group.
15 . The process as recited in claim 14 wherein ethylene is present and propylene is not present.
16 . The process as recited in claim 15 wherein said compound is (VII).
17 . The process as recited in claim 15 wherein said compound is (IX).
18 . The process as recited in claim 15 wherein said compound is (XII).
19 . The process as recited in claim 15 wherein:
R 8 and R 13 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group;
R 9 , R 10 , R 11 , R 14 , R 15 and R 16 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group;
R 12 and R 17 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group;
and provided that any two of R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 that are vicinal to one another, taken together may form a ring.
20 . The process as recited in claim 15 wherein said temperature is about −50° C. to about 100° C.
21 . The process as recited in claim 15 wherein M is Fe.
22 . The process as recited in claim 15 or 21 wherein R 21 is n-alkyl.
23 . A copolymer of ethylene and a one or more olefins of the formula H 2 C═CHR 21 wherein said copolymer has methyl branches and —R 21 branches, and wherein the total of said branches indicate an incorporation of H 2 C═CHR 21 of at least 0.5 mole percent.
24 . The copolymer as recited in claim 23 wherein said incorporation is at least 1 mole percent.
25 . The copolymer as recited in claim 23 or 24 wherein each of said methyl branches is attached to a carbon atom, and an —R 21 group is also attached to said carbon atom.
26 . The copolymer as recited in claim 23 or 24 wherein R 21 is n-alkyl.
27 . The copolymer as recited in claim 25 wherein R 21 is n-alkyl.
28 . The process as recited in claim 1 , 2 or 14 wherein said compound or complex is supported on a substrate.Join the waitlist — get patent alerts
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