Reactive functionalization of carbon-carbon backbone polymers and related compositions

Patent metadata

Field	Value
Publication number	US-2024132651-A1
Application number	US-202218278200-A
Country	US
Kind code	A1
Filing date	Feb 22, 2022
Priority date	Feb 22, 2021
Publication date	Apr 25, 2024
Grant date	—

Abstract

The disclosure relates to the functionalization of a carbon-carbon backbone (CCB) polymer using a (cyclic) grafting agent, an initiator, and optionally a reversible radical trapping agent. The grafting agent and/or initiator can be particularly selected in terms of their surface energy and/or half-life, respectively, to limit or control undesirable effects associated with reactive melt-processing, such as excessive crosslinking, chain scission, or grafting agent homopolymerization, as well as to improve or control desirable effects associated with reactive melt-processing, such as improved relative graft uniformity or homogeneity on the CCB polymer. In some cases, the grafting agent can further include a functional group to impart some additional or new chemical or physical property to the CCB polymer. In some cases, the reactively melt-processed mixture includes two or more different polymers that are compatibilized via the grafting agent.

First claim

1 . A method for functionalizing a carbon-carbon backbone (CCB) polymer, the method comprising:
reactive melt-processing a mixture comprising (i) a carbon-carbon backbone (CCB) polymer, (ii) a grafting agent selected from the group consisting of unsaturated cyclic anhydrides, unsaturated cyclic imides, ring-opened analogs thereof, and combinations thereof, (iii) an initiator, and (iv) optionally a reversible radical trapping agent, thereby forming a functionalized CCB polymer comprising the CCB polymer and the grafting agent; wherein at least one of conditions (A), (B), and (C) apply: (A) the grafting agent has a surface energy relative to that of the CCB polymer in a ratio in a range from 0.02 to 2.0; (B) a ratio of a half-life of the initiator relative to a residence time for the reactive melt-processing is in a range of 0.2 to 5.0; or (C) the radical trapping agent is present in the reactively melt-processed mixture.

2 .- 35 . (canceled)

36 . A method for forming a carbon-carbon backbone (CCB) compatibilizer copolymer, the method comprising:
(1) reactive melt-processing (i) a first carbon-carbon backbone (CCB) polymer, (ii) a first grafting agent selected from the group consisting of unsaturated cyclic anhydrides, unsaturated cyclic imides, ring-opened analogs thereof, and combinations thereof, (iii) a first initiator, and (iv) optionally a first reversible radical trapping agent, thereby forming a first functionalized CCB polymer comprising the first CCB polymer and the first grafting agent; wherein at least one of conditions (A1), (B1), and (C1) apply:
(A1) the first grafting agent has a surface energy relative to that of the first CCB polymer in a ratio in a range from 0.02 to 2.0;
(B1) a ratio of a half-life of the first initiator relative to a residence time for the reactive melt-processing is in a range of 0.2 to 5.0; or
(C1) the first radical trapping agent is present;
(2) reactive melt-processing (i) a second polymer, (ii) a second grafting agent selected from the group consisting of unsaturated cyclic anhydrides, unsaturated cyclic imides, ring-opened analogs thereof, and combinations thereof, (iii) a second initiator, and (iv) optionally a second reversible radical trapping agent, thereby forming a second functionalized polymer comprising the second polymer and the second grafting agent; wherein at least one of conditions (A2), (B2), and (C2) apply:
(A2) the second grafting agent has a surface energy relative to that of the second polymer in a ratio in a range from 0.02 to 2.0;
(B2) a ratio of a half-life of the second initiator relative to a residence time for the reactive melt-processing is in a range of 0.2 to 5.0; or
(C2) the second radical trapping agent is present; and
(3) reactive melt-processing the first functionalized CCB polymer and the second functionalized polymer, thereby forming a CCB compatibilizer copolymer comprising the first CCB polymer and the second polymer joined via the first grafting agent and the second grafting agent.

37 . The method of claim 36 , wherein:
the first grafting agent and the second grafting agent are monofunctional grafting agents; the first functionalized CCB polymer and the second functionalized polymer are reactively melt-processed with a coupling agent; and the CCB compatibilizer copolymer comprises coupling agent links between the first CCB polymer and the second polymer.

38 . The method of claim 36 , comprising: performing steps (1), (2), and (3) in a single melt-processing apparatus.

39 . The method of claim 36 , comprising: performing steps (1), (2), and (3) in two or more melt-processing apparatus.

40 . The method of claim 36 , wherein:
the second polymer is selected from the group consisting of high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), polypropylene (PP), polystyrene (PS), polyethylene terephthalate (PET), polylactic acid (PLA), polyamides, and combinations thereof; and the second polymer is different from the CCB polymer.

41 . The method of claim 36 , wherein the second polymer comprises a second CCB polymer different from the first CCB polymer.

42 . A method for compatibilizing a polymer blend, the method comprising:
forming a CCB compatibilizer copolymer according to the method of claim 36 ; and melt-blending a mixture comprising a first polymer, a second polymer, and the CCB compatibilizer copolymer, thereby forming a compatibilized polymer blend; wherein the first polymer and the second polymer correspond to segments of the CCB compatibilizer copolymer.

43 . The method of claim 42 , wherein:
the CCB compatibilizer copolymer is present in an amount in a range of 0.1 wt. % to 10 wt. % relative to the compatibilized polymer blend; the first polymer is present in an amount in a range of 2 wt. % to 95 wt. % relative to the compatibilized polymer blend; and the second polymer is present in an amount in a range of 2 wt. % to 95 wt. % relative to the compatibilized polymer blend.

44 . The method of claim 42 , wherein the first polymer and the second polymer are from a recycled polymer stream.

45 . A method for compatibilizing a polymer blend, the method comprising:
providing a CCB compatibilizer copolymer formed according to the method of claim 36 ; and melt-blending a mixture comprising a first polymer, a second polymer, and the CCB compatibilizer copolymer, thereby forming a compatibilized polymer blend; wherein the first polymer and the second polymer correspond to segments of the CCB compatibilizer copolymer.

46 . The method of claim 45 , wherein:
the CCB compatibilizer copolymer is present in an amount in a range of 0.1 wt. % to 10 wt. % relative to the compatibilized polymer blend; the first polymer is present in an amount in a range of 2 wt. % to 95 wt. % relative to the compatibilized polymer blend; and the second polymer is present in an amount in a range of 2 wt. % to 95 wt. % relative to the compatibilized polymer blend.

47 .- 52 . (canceled)

53 . A functionalized carbon-carbon backbone (CCB) polymer comprising:
a free-radical-initiated reaction product between a (i) a carbon-carbon backbone (CCB) polymer and (ii) a grafting agent selected from the group consisting of unsaturated cyclic anhydrides, unsaturated cyclic imides, ring-opened analogs thereof, and combinations thereof.

54 . A carbon-carbon backbone (CCB) compatibilizer copolymer comprising:
a free-radical-initiated reaction product between a (i) a carbon-carbon backbone (CCB) polymer, (ii) a further polymer, and (iii) a grafting agent selected from the group consisting of unsaturated cyclic anhydrides, unsaturated cyclic imides, ring-opened analogs thereof, and combinations thereof; wherein the CCB compatibilizer copolymer comprises the CCB polymer and the further polymer joined via the grafting agent.

Assignees

• Univ Michigan State

Inventors

• Rabnawaz Muhammad
• Naveed Muhammad

Classifications

• C08F299/00 Primary

  Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers · CPC title

• C08F255/023

  On to modified polymers, e.g. chlorinated polymers · CPC title

• C08L23/06

  Polyethylene · CPC title

• C08F2438/02

  Stable Free Radical Polymerisation [SFRP]; Nitroxide Mediated Polymerisation [NMP] for, e.g. using 2,2,6,6-tetramethylpiperidine-1-oxyl [TEMPO] · CPC title

• C08L2205/025

  containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure · CPC title