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US 9,284,387 B2Granted
Hydroamination of aldehyde-containing macromonomers
AssigneeExxonMobil Chemical Patents Inc.
InventorsDonna J. Crowther, Man Kit Ng, Patrick Brant, Hong Cheng
Life of this patent
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Abstract
This invention relates to a polyolefin composition comprising one or more of the following formulae: wherein the PO is the residual portion of a vinyl terminated macromonomer (VTM) having had a terminal unsaturated carbon of an allylic chain and a vinyl carbon adjacent to the terminal unsaturated carbon; R1 is a hydrogen atom, an aryl group, or an alkyl group, wherein the aryl group or alkyl group can include one or more heteroatoms, an alkyl or aryl amino group, a polyalkylamino group; wherein the VTM is a vinyl terminated macromonomer.
Claims12
A polyolefin composition comprising one or more of the following formulae:
- wherein the PO is the residual portion of a vinyl terminated macromonomer (VTM) having had a terminal unsaturated carbon of an allylic chain and a vinyl carbon adjacent to the terminal unsaturated carbon;
- R1 is a hydrogen atom, an aryl group, or an alkyl group, wherein the aryl group or alkyl group can include one or more heteroatoms, an alkyl or aryl amino group, a polyalkylamino group;
- wherein the VTM is one or more of:
- (i) a vinyl terminated polymer having at least 5% allyl chain ends;
- (ii) a vinyl terminated polymer having an Mn of at least 160 g/mol (measured by 1H NMR) comprising of one or more C4 to C40 higher olefin derived units, where the higher olefin polymer comprises substantially no propylene derived units;
- and wherein the higher olefin polymer has at least 5% allyl chain ends;
- (iii) a copolymer having an Mn of 300 g/mol or more (measured by 1H NMR) comprising (a) from 20 mol % to 99.9 mol % of at least one C5 to C40 higher olefin derived units, and (b) from 0.1 mol % to 80 mol % of propylene derived units, wherein the higher olefin copolymer has at least 40% allyl chain ends;
- (iv) a copolymer having an Mn of 300 g/mol or more (measured by 1H NMR), and comprises (a) from 80 mol % to 99.9 mol % of at least one C4 olefin derived unit, (b) from 0.1 mol % to 20 mol % of propylene derived units;
- and wherein the vinyl terminated macromonomer has at least 40% allyl chain ends relative to total unsaturation;
- (v) a co-oligomer having an Mn of 300 g/mol to 30,000 g/mol (measured by 1H NMR) comprising 10 mol % to 90 mol % propylene derived units and 10 mol % to 90 mol % of ethylene derived units, wherein the co-oligomer has at least X % allyl chain ends (relative to total unsaturations), where:
- 1) X=(−0.94*(mol % ethylene incorporated) +100), when 10 mol % to 60 mol % ethylene derived units are present in the co-oligomer, 2) X=45, when greater than 60 mol % and less than 70 mol % ethylene derived units are present in the co-oligomer, and 3) X=(1.83*(mol % ethylene incorporated) −83), when 70 mol % to 90 mol % ethylene derived units are present in the co-oligomer;
- (vi) a propylene co-oligomer, comprising more than 90 mol % propylene derived units and less than 10 mol % ethylene derived units;
- wherein the co-oligomer has:
- at least 93% allyl chain ends, a number average molecular weight (Mn) of 500 g/mol to 20,000 g/mol, an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.35:1.0, less than 100 ppm aluminum, and/or less than 250 regio defects per 10,000 monomer units;
- (vii) a propylene co-oligomer, comprising:
- at least 50 mol % propylene derived units and from 10 mol % to 50 mol % ethylene derived units, wherein the co-oligomer has:
- at least 90% allyl chain ends, an Mn of 150 g/mol to 20,000 g/mol, and an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.2:1.0, wherein monomers having four or more carbon atoms are present at from 0 mol % to 3 mol %;
- (viii) a propylene co-oligomer, comprising:
- at least 50 mol % propylene derived units, from 0.1 mol % to 45 mol % ethylene derived units, and from 0.1 mol % to 5 mol % C4 to C12 olefin derived units, wherein the co-oligomer has:
- at least 90% allyl chain ends, an Mn of 150 g/mol to 10,000 g/mol, and an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.35:1.0;
- (ix) a propylene co-oligomer, comprising:
- at least 50 mol % propylene derived units, from 0.1 mol % to 45 mol % ethylene derived units, and from 0.1 mol % to 5 mol % diene derived units, wherein the co-oligomer has:
- at least 90% allyl chain ends, an Mn of 150 g/mol to 10,000 g/mol, and an isobutyl chain end to allylic vinyl group ratio of 0.7:1 to 1.35:1.0;
- (x) a homo-oligomer, comprising propylene, wherein the homo-oligomer has:
- at least 93% allyl chain ends, an Mn of 500 g/mol to 70,000 g/mol, an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.2:1.0, and less than 1400 ppm aluminum;
- (xi) vinyl terminated polyethylene having:
- (a) at least 60% allyl chain ends;
- (b) a molecular weight distribution of less than or equal to 4.0;
- (c) a g′(vis) of greater than 0.95;
- and (d) an Mn (1H NMR) of at least 20,000 g/mol;
- and
- (xii) vinyl terminated polyethylene having:
- (a) at least 50% allyl chain ends;
- (b) a molecular weight distribution of less than or equal to 4.0;
- (c) a g′(vis) of 0.95 or less;
- (d) an Mn (1H NMR) of at least 7,000 g/mol;
- and (e) a Mn (GPC)/Mn (1H NMR) in the range of from 0.8 to 1.2.
34 more elements
A polyolefin composition comprising one or more of the following formulae:
- wherein the PO is the residual portion of a vinyl terminated macromonomer (VTM) having had a terminal unsaturated carbon of an allylic chain and a vinyl carbon adjacent to the terminal unsaturated carbon;
- R1 is a hydrogen atom, an aryl group, or an alkyl group, wherein the aryl group or alkyl group can include one or more heteroatoms, an alkyl or aryl amino group, a polyalkylamino group;
- wherein the VTM is one or more of:
- (i) a vinyl terminated polymer having at least 5% allyl chain ends;
- (ii) a vinyl terminated polymer having an Mn of at least 160 g/mol (measured by 1H NMR) comprising of one or more C4 to C40 higher olefin derived units, where the higher olefin polymer comprises substantially no propylene derived units;
- and wherein the higher olefin polymer has at least 5% allyl chain ends;
- (iii) a copolymer having an Mn of 300 g/mol or more (measured by 1H NMR) comprising (a) from 20 mol % to 99.9 mol % of at least one C5 to C40 higher olefin derived units, and (b) from 0.1 mol % to 80 mol % of propylene derived units, wherein the higher olefin copolymer has at least 40% allyl chain ends;
- (iv) a copolymer having an Mn of 300 g/mol or more (measured by 1H NMR), and comprises (a) from 80 mol % to 99.9 mol % of at least one C4 olefin derived unit, (b) from 0.1 mol % to 20 mol % of propylene derived units;
- and wherein the vinyl terminated macromonomer has at least 40% allyl chain ends relative to total unsaturation;
- (v) a co-oligomer having an Mn of 300 g/mol to 30,000 g/mol (measured by 1H NMR) comprising 10 mol % to 90 mol % propylene derived units and 10 mol % to 90 mol % of ethylene derived units, wherein the co-oligomer has at least X % allyl chain ends (relative to total unsaturations), where:
- 1) X=(−0.94*(mol % ethylene incorporated)+100), when 10 mol % to 60 mol % ethylene derived units are present in the co-oligomer, 2) X=45, when greater than 60 mol % and less than 70 mol % ethylene derived units are present in the co-oligomer, and 3) X=(1.83* (mol % ethylene incorporated) −83), when 70 mol % to 90 mol % ethylene derived units are present in the co-oligomer;
- (vi) a propylene co-oligomer, comprising more than 90 mol % propylene derived units and less than 10 mol % ethylene derived units;
- wherein the co-oligomer has:
- at least 93% allyl chain ends, a number average molecular weight (Mn) of 500 g/mol to 20,000 g/mol, an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.35:1.0, less than 100 ppm aluminum, and/or less than 250 regio defects per 10,000 monomer units;
- (vii) a propylene co-oligomer, comprising:
- at least 50 mol % propylene derived units and from 10 mol % to 50 mol % ethylene derived units, wherein the co-oligomer has:
- at least 90 % allyl chain ends, an Mn of 150 g/mol to 20,000 g/mol, and an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.2:1.0, wherein monomers having four or more carbon atoms are present at from 0 mol % to 3 mol %;
- (viii) a propylene co-oligomer, comprising:
- at least 50 mol % propylene derived units, from 0.1 mol % to 45 mol % ethylene derived units, and from 0.1 mol % to 5 mol % C4 to C12 olefin derived units, wherein the co-oligomer has:
- at least 90 % allyl chain ends, an Mn of 150 g/mol to 10,000 g/mol, and an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.35:1.0;
- (ix) a propylene co-oligomer, comprising:
- at least 50 mol % propylene derived units, from 0.1 mol % to 45 mol % ethylene derived units, and from 0.1 mol % to 5 mol % diene derived units, wherein the co-oligomer has:
- at least 90 %allyl chain ends, an Mn of 150 g/mol to 10,000 g/mol, and an isobutyl chain end to allylic vinyl group ratio of 0.7:1 to 1.35:1.0;
- (x) a homo-oligomer, comprising propylene, wherein the homo-oligomer has:
- at least 93 % allyl chain ends, an Mn of 500 g/mol to 70,000 g/mol, an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.2:1.0, and less than 1400 ppm aluminum;
- (xi) vinyl terminated polyethylene having:
- (a) at least 60% allyl chain ends;
- (b) a molecular weight distribution of less than or equal to 4.0;
- (c) a g′(vis) of greater than 0.95;
- and (d) an Mn (1H NMR) of at least 20,000 g/mol;
- and
- (xii) vinyl terminated polyethylene having:
- (a) at least 50% allyl chain ends;
- (b) a molecular weight distribution of less than or equal to 4.0;
- (c) a g′(vis) of 0.95 or less;
- (d) an Mn (1H NMR) of at least 7,000 g/mol;
- and (e) a Mn (GPC)/Mn (1H NMR) in the range of from 0.8 to 1.2.
34 more elements
A polyolefin composition comprising one or more of the following formulae:
- wherein the P1O and PO2, each independently, are residual portions of vinyl terminated macromonomer (VTMs) having had a terminal unsaturated carbon of an allylic chain and a vinyl carbon adjacent to the terminal unsaturated carbon;
- R1 and R2, each independently, are one of a hydrogen atom, an aryl group, or an alkyl group, wherein the aryl group or alkyl group can include one or more heteroatoms, an alkyl or aryl amino group, a polyalkylamino group or —CH2CH2P1O, —CH2CH2PO2, —CH2—CH—(CH3)—P1O, or —CH2—CH—(CH3)—PO2;
- X is an alkylidene group or an arylene group, wherein one or more carbon atoms can include one or more heteroatoms;
- wherein each VTM is one or more of:
- (i) a vinyl terminated polymer having at least 5% allyl chain ends;
- (ii) a vinyl terminated polymer having an Mn of at least 160 g/mol (measured by 1H NMR) comprising of one or more C4 to C40 higher olefin derived units, where the higher olefin polymer comprises substantially no propylene derived units;
- and wherein the higher olefin polymer has at least 5% allyl chain ends;
- (iii) a copolymer having an Mn of 300 g/mol or more (measured by 1H NMR) comprising (a)
- from 20 mol % to 99.9 mol % of at least one C5 to C40 higher olefin derived units, and (b) from 0.1 mol % to 80 mol % of propylene derived units, wherein the higher olefin copolymer has at least 40% allyl chain ends;
- (iv) a copolymer having an Mn of 300 g/mol or more (measured by 1H NMR), and comprises (a) from 80 mol % to 99.9 mol % of at least one C4 olefin derived unit, (b) from 0.1 mol % to 20 mol % of propylene derived units;
- and wherein the vinyl terminated macromonomer has at least 40% allyl chain ends relative to total unsaturation;
- (v) a co-oligomer having an Mn of 300 g/mol to 30,000 g/mol (measured by 1H NMR) comprising 10 mol % to 90 mol % propylene derived units and 10 mol % to 90 mol % of ethylene derived units, wherein the co-oligomer has at least X % allyl chain ends (relative to total unsaturations), where:
- 1) X=(−0.94*(mol % ethylene incorporated)+100), when 10 mol % to 60 mol % ethylene derived units are present in the co-oligomer, 2) X=45, when greater than 60 mol % and less than 70 mol % ethylene derived units are present in the co-oligomer, and 3) X=(1.83* (mol % ethylene incorporated) −83), when 70 mol % to 90 mol % ethylene derived units are present in the co-oligomer;
- (vi) a propylene co-oligomer, comprising more than 90 mol % propylene derived units and less than 10 mol % ethylene derived units;
- wherein the co-oligomer has:
- at least 93 % allyl chain ends, a number average molecular weight (Mn) of 500 g/mol to 20,000 g/mol, an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.35:1.0, less than 100 ppm aluminum, and/or less than 250 regio defects per 10,000 monomer units;
- (vii) a propylene co-oligomer, comprising:
- at least 50 mol % propylene derived units and from 10 mol % to 50 mol % ethylene derived units, wherein the co-oligomer has:
- at least 90 %allyl chain ends, an Mn of 150 g/mol to 20,000 g/mol, and an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.2:1.0, wherein monomers having four or more carbon atoms are present at from 0 mol % to 3 mol %;
- (viii) a propylene co-oligomer, comprising:
- at least 50 mol % propylene derived units, from 0.1 mol % to 45 mol % ethylene derived units, and from 0.1 mol % to 5 mol % C4 to C12 olefin derived units, wherein the co-oligomer has:
- at least 90 % allyl chain ends, an Mn of 150 g/mol to 10,000 g/mol, and an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.35:1.0;
- (ix) a propylene co-oligomer, comprising:
- at least 50 mol % propylene derived units, from 0.1 mol % to 45 mol % ethylene derived units, and from 0.1 mol % to 5 mol % diene derived units, wherein the co-oligomer has:
- at least 90 %allyl chain ends, an Mn of 150 g/mol to 10,000 g/mol, and an isobutyl chain end to allylic vinyl group ratio of 0.7:1 to 1.35:1.0;
- (x) a homo-oligomer, comprising propylene, wherein the homo-oligomer has:
- at least 93 % allyl chain ends, an Mn of 500 g/mol to 70,000 g/mol, an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.2:1.0, and less than 1400 ppm aluminum;
- (xi) vinyl terminated polyethylene having:
- (a) at least 60% allyl chain ends;
- (b) a molecular weight distribution of less than or equal to 4.0;
- (c) a g′(vis) of greater than 0.95;
- and (d) an Mn (1H NMR) of at least 20,000 g/mol;
- and
- (xii) vinyl terminated polyethylene having:
- (a) at least 50% allyl chain ends;
- (b) a molecular weight distribution of less than or equal to 4.0;
- (c) a g′(vis) of 0.95 or less;
- (d) an Mn (1H NMR) of at least 7,000 g/mol;
- and (e) a Mn (GPC)/Mn (1H NMR) in the range of from 0.8 to 1.2.
36 more elements
Dependencies are inferred from the claim text.