Macrocyclic poly(akane)s and poly(alkane-co-alkene)s

Patent metadata

Field	Value
Publication number	US-11807694-B2
Application number	US-201816648159-A
Country	US
Kind code	B2
Filing date	Aug 24, 2018
Priority date	Sep 22, 2017
Publication date	Nov 7, 2023
Grant date	Nov 7, 2023

Abstract

Macrocyclic polyalkene homopolymers and copolymers can be formed and converted to macrocyclic polyalkanes or macrocyclic poly(alkane-co-alkene) upon hydrogenation or, when the macrocyclic polyalkene is reacted with an alkene in the presence of an olefin metathesis catalyst, to a macrocyclic poly(alkane-co-alkene) comprising vicinal —C(═CR2)—'s. Upon hydrogenation of a macrocyclic poly(alkane-co-alkene) comprising vicinal —C(═CR2)-'s, macrocyclic poly(alkane)s or poly(alkane-co-alkene)s with isolated —C(═CR2)- groups can be provided, depending on the degree of hydrogenation. The poly(alkane-co-alkene)s with isolated —C(═CR2)- units can be used to form poly(macrocyclic poly(alkane-co-alkene))s, poly(macrocyclic poly(alkane))s, and/or bi-, tri-, and/or multi-macrocyclic poly(alkane-co-alkene)s or bi-, tri-, and/or multi-macrocyclic poly(alkane)s.

First claim

What is claimed is:

1. A macrocyclic polyalkene copolymer, comprising a conjugated polyalkene having no chain ends and in the form of a macrocycle, comprising at least two different repeating units have the structure —RC═CR— where R is independently: H; a substituted or unsubstituted C 1 to C 30 alkyl, provided that when all R are an unsubstituted C 1 to C 30 alkyl, at least one R is not a C 4 , C 6 , C 7 , or C 13 alkyl; substituted or unsubstituted C 3 to C 30 alkenyl having one or more alkene bonds where a plurality of alkene bonds can be non-conjugated, conjugated, or a mixture thereof; or where two R groups are combined as a C 8 -C 30 cycloalkene where the alkylene portion of the cycloalkene is substituted or unsubstituted and/or interrupted one or more times with O, NR′, C(O), C(O)O, and/or C(O)NR″, where R′ and/or R″, when present are each independently H, C 1-30 alkyl, or C 3 to C 30 alkenyl.

2. The macrocyclic polyalkene copolymer according to claim 1 , having a structure of:

wherein R and R′ in the structure are each independently an R as defined in claim 1 , and each of n, x, and y is independently an integer of 1 to 100, or optionally, wherein each of n, x, and y is independently an integer of 1 to 50, or each of n, x, and y is independently an integer of 1 to 25.

3. The macrocyclic polyalkene copolymer according to claim 1 , wherein each R is independently: H; a substituted or unsubstituted C 1 to C 30 alkyl; or a substituted or unsubstituted C 3 to C 30 alkenyl, or optionally, wherein each R is independently H or a substituted or unsubstituted C 1-3 , C 5 , C 8-12 , or C 14-30 alkyl.

4. A macrocyclic polyalkane or macrocyclic poly(alkane-co-alkene), comprising alkane repeating units have the structure —RHC—CHR— and, optionally, alkene repeating units have the structure —RC═CR— or —C(═CR 2 )—, where, if present, the R of the —RC═CR— alkene repeating units are the same as the R units of at least one of the alkane repeating units, and where R is independently: H; a substituted or unsubstituted C 1 to C 30 alkyl, or, when absent an alkene repeating unit or comprising exclusively one unsubstituted alkane repeating units or a copolymer with —H 2 C—CH 2 — repeating units, R is C 1-3 , C 5 , C 8-12 , or C 14-30 , substituted or unsubstituted C 3 to C 30 alkenyl having one or more alkene bonds where a plurality of alkene bonds can be non-conjugated, conjugated, or a mixture thereof; or where two R groups are combined as a C 8 -C 30 cycloalkane and/or cycloalkene where the alkylene portion of the cycloalkane and/or alkene is substituted or unsubstituted and/or interrupted one or more times with O, NR′, C(O), C(O)O, and/or C(O)NR″, where R′ and/or R″, when present, are each independently H, C 1-30 alkyl, C 3 to C 30 alkenyl.

5. The macrocyclic polyalkane or macrocyclic poly(alkane-co-alkene) according to claim 4 , having a structure of

wherein R and R′ in the structure are each independently an R as defined in claim 4 , and each of n, x, and y is an integer of 1 to 100, or optionally, wherein each of n, x, and y is independently an integer of 1 to 50, or each of n, x, and y is independently an integer of 1 to 25.

6. The macrocyclic polyalkane or macrocyclic poly(alkane-co-alkene) according to claim 4 , wherein each R is independently: H; a substituted or unsubstituted C 1 to C 30 alkyl; or a substituted or unsubstituted C 3 to C 30 alkenyl; provided that when all R are an unsubstituted C 1 to C 30 alkyl, at least one R is not a C 4 , C 6 , C 7 , or C 13 alkyl, or optionally, wherein each R is independently H or a substituted or unsubstituted C 1-3 , C 5 , C 8-12 , or C 14-30 alkyl.

7. The macrocyclic polyalkane or macrocyclic poly(alkane-co-alkene) according to claim 4 , wherein the macrocyclic polyalkane has C 8 -C 30 cycloalkane repeating units, or optionally wherein the macrocyclic polyalkane is macrocyclic polypropylene.

8. The macrocyclic polyalkane or macrocyclic poly(alkane-co-alkene) according to claim 4 , wherein the macrocyclic poly(alkane-co-alkene) comprises vicinal —C(═CR 2 )— groups.

9. The macrocyclic polyalkane or macrocyclic poly(alkane-co-alkene) according to claim 8 , having a structure

wherein the H atoms depicted in the structure can be H or another R group as defined in claim 8 , and each of n and y is an integer of 1 to 100, or optionally, wherein each y is independently an integer of 1 to 20 and n is an integer of 1 to 50, or each y is independently an integer of 1 to 10 and n is an integer of 1 to 25, or each y is independently an integer of 1 to 5 and n is an integer of 1 to 10.

10. The macrocyclic polyalkane or macrocyclic poly(alkane-co-alkene) according to claim 4 , wherein the macrocyclic polyalkane or macrocyclic poly(alkane-co-alkene) comprises vicinal —C(CHR 2 )— groups.

11. The macrocyclic polyalkane or macrocyclic poly(alkane-co-alkene) according to claim 9 , wherein each R is independently: H; a substituted or unsubstituted C 1 to C 30 alkyl; or a substituted or unsubstituted C 3 to C 30 alkenyl, or optionally, wherein each R is independently H or a substituted or unsubstituted C 1-3 , C 5 , C 8-12 , or C 14-30 alkyl.

12. The macrocyclic polyalkane or macrocyclic poly(alkane-co-alkene) according to claim 9 , wherein the macrocyclic polyalkane has C 8 -C 30 cycloalkane repeating units in the polymer backbone.

13. The macrocyclic polyalkane or macrocyclic poly(alkane-co-alkene) according to claim 12 having a structure:

wherein each y and n are independently integers from 1 to 100, or optionally, wherein each y is independently an integer of 1 to 20 and n is an integer of 1 to 50, or each y is independently an integer of 1 to 10 and n is an integer of 1 to 25, or each y is independently an integer of 1 to 5 and n is an integer of 1 to 10.

14. The macrocyclic polyalkane or macrocyclic poly(alkane-co-alkene) according to claim 4 , further comprising C═C bridges between a plurality of macrocyclic poly(alkane-co-alkene)s to form a poly(macrocyclic poly(alkane-co-alkene)), or one or more C═C bridges between alkene repeating units of the macrocyclic poly(alkane-co-alkene)s, in the form of bi-macrocyclic, tri-macrocyclic and/or multi-macrocyclic poly(alkane-co-alkene)s.

15. A method of forming a macrocyclic polyalkane or a macrocyclic poly(alkane-co-alkene) according to claim 4 comprising:
reacting a macrocyclic polyalkene and hydrogen in the presence of a hydrogenation catalyst to form the polyalkane or poly(alkane-co-alkene); and
isolating the macrocyclic polyalkane or a macrocyclic poly(alkane-co-alkene).

16. The method of claim 15 , wherein the hydrogen is provided in an amount of at least a molar equivalent of the macrocyclic polyalkene, thereby forming a polyalkane, or the hydrogen is provided in an amount of less than a molar equivalent of the macrocyclic polyalkene, thereby forming a poly(alkane-co-alkene).

17. A method of forming a macrocyclic polyalkane or a macrocyclic poly(alkane-co-alkene) according to claim 8 comprising:
reacting a macrocyclic poly(cycloalkene) with an excess of an alkene and an olefin metathesis catalyst thereby forming a macrocyclic poly(alkane-co-

Assignees

• Univ Florida
• Univ Florida

Inventors

• Veige Adam S

Classifications

• C08F110/06 Primary

  Propene · CPC title

• C08F110/14

  Monomers containing five or more carbon atoms · CPC title

• C08F138/00

  Homopolymers of compounds having one or more carbon-to-carbon triple bonds · CPC title

• C08G61/08

  of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring · CPC title

• C08F2500/25

  Cycloolefine · CPC title