Fully and partially backbone-degradable polymers via low temperature ring-opening metathesis polymerization (romp)

Patent metadata

Field	Value
Publication number	US-2023303776-A1
Application number	US-202118012001-A
Country	US
Kind code	A1
Filing date	Jul 1, 2021
Priority date	Jul 2, 2020
Publication date	Sep 28, 2023
Grant date	—

Abstract

Aspects disclosed herein include fully or partially degradable polymers, liquid formulations comprising such polymers, methods for treating or managing a condition in a subject using such polymers, methods for using such polymers, and methods of synthesizing such polymers. Aspects disclosed herein also include monomers suitable for forming a partially or fully degradable polymer and methods for forming such monomers.

First claim

We claim:

1 . A fully or partially degradable polymer comprising:
a plurality of first repeating units; wherein each first repeating unit is characterized by formula FX1A;

wherein:
each of E 1 and E 2 is independently NR 6 , O, or OR 7 ;
each of R 1 -R 5 is independently a hydrogen, a halogen, a methyl group, or any combination of these;
each of R 6 and R 7 is independently hydrogen, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted phenyl group, or any combination of these; and
each of m and n is independently 1 or 2.

2 . The polymer of claim 1 , wherein each first repeating unit is chemically degradable in the presence of an acid.

3 . The polymer of any one of the preceding claims , wherein each first repeating unit comprises a ROMP-polymerized monomer group.

4 . The polymer of any one of the preceding claims , wherein the entire polymer is characterized by a total degree of polymerization selected from the range of 2 to 10,000.

5 . The polymer of any one of the preceding claims comprising at least 4 of the first repeating units.

6 . The polymer of any one of the preceding claims being a homopolymer, wherein each repeating unit of said homopolymer is independently the first repeating unit.

7 . The polymer of any one of the preceding claims , wherein:
each of E 1 and E 2 is independently NH, each of R 1 -R 5 is independently a hydrogen, m is 1, and n is 1; or each of E 1 and E 2 is independently NH, each of R 1 -R 5 is independently a hydrogen, m is 1, and n is 2; or each of E 1 and E 2 is independently N(CH 3 ), each of R 1 -R 5 is independently a hydrogen, m is 1, and n is 2; or each of E 1 and E 2 is independently N(CH 3 ), each of R 1 -R 5 is independently a hydrogen, m is 1, and n is 1; or each of E 1 and E 2 is independently N(C 2 H 6 ), each of R 1 -R 5 is independently a hydrogen, m is 1, and n is 2; or each of E 1 and E 2 is independently N(C 2 H 6 ), each of R 1 -R 5 is independently a hydrogen, m is 1, and n is 1; or each of E 1 and E 2 is independently NH, each of R 1 -R 5 is independently a hydrogen, m is 2, and n is 2; or each of E 1 and E 2 is independently NH, each of R 1 -R 5 is independently a hydrogen, m is 1, and n is 2; or each of E 1 and E 2 is independently N(CH 3 ), each of R 1 -R 5 is independently a hydrogen, m is 2, and n is 2; or each of E 1 and E 2 is independently N(CH 3 ), each of R 1 -R 5 is independently a hydrogen, m is 1, and n is 2; or each of E 1 and E 2 is independently N(C 2 H 6 ), each of R 1 -R 5 is independently a hydrogen, m is 2, and n is 2; or each of E 1 and E 2 is independently N(C 2 H 6 ), each of R 1 -R 5 is independently a hydrogen, m is 1, and n is 2; or each of E 1 and E 2 is independently NR 6 , each R 6 is independently —(CH 2 )—(phenyl), each of R 1 -R 5 is independently a hydrogen, m is 1, and n is 1; or E 1 or E 2 is N(CH 3 ) and the other of E 1 or E 2 is O, each of R1-R 5 is independently a hydrogen, m is 1, and n is 1; or E 1 or E 2 is N(CH 3 ) and the other of E 1 or E 2 is O(CH 3 ), each of R1-R 5 is independently a hydrogen, m is 1, and n is 1; or E 1 or E 2 is N(C 2 H 6 ) and the other of E 1 or E 2 is O(C 2 H 6 ), each of R 1 -R 5 is independently a hydrogen, m is 1, and n is 1.

8 . The polymer of any one of the preceding claims being characterized by characterized by formula FX30B, FX31B, FX32B, FX33B, FX34B, FX35B, FX36B, FX37B, FX38B, FX39B, FX40B, FX41B, or FX42B:

or

.

9 . The polymer of any one of the preceding claims being a copolymer and comprising:
a plurality of second repeating units, each second repeating unit comprising a ROMP-polymerized monomer group;
wherein at least one second repeating unit is covalently attached to a first repeating unit.

10 . The polymer of claim 9 , wherein a ratio of the degree of polymerization of all first repeating units to the degree of polymerization of the entire polymer is selected from the range of 0.15 to 0.95.

11 . The polymer of claim 9 or 10 , wherein each second repeating unit comprises the ROMP-polymerization product of a monomer comprising: a substituted or unsubstituted norbornene group, a substituted or unsubstituted dicyclopentadiene group, a substituted or unsubstituted norbornene-imide group, a substituted or unsubstituted oxanorbornene-imide group, a substituted or unsubstituted oxanorbornene group, a substituted or unsubstituted cyclooctene group, a substituted or unsubstituted 1,5-cyclooctadiene group, a substituted or unsubstituted dithiocine group, a substituted or unsubstituted dioxaphosphepine group, a substituted or unsubstituted dioxepinone group, any derivative thereof, or any combination of these.

12 . The polymer of any one of claims 9-11 , being a block copolymer, an alternating copolymer, a random copolymer, a graft copolymer, or any combination of these.

13 . The polymer of any one of claims 9-12 being characterized by formula FX3:

wherein:
each U 1 is independently the first repeating unit;
each U 2 is independently the second repeating unit;
each of u and q is independently an integer selected from the range of 2 to 10,000;
each of Q 1 and Q 2 is independently a polymer terminating group; and
the symbol “/” indicates that the units separated thereby are covalently linked randomly or in any order.

14 . The polymer of any one of claims 9-13 , wherein each second repeating unit comprises a polymer backbone group directly or indirectly covalently linked to one or more side chain moieties; wherein each second repeating unit is characterized by formula FX4:
wherein: each M is independently the polymer backbone group of one of the second repeating units and each M independently comprises a ROMP-polymerized monomer group; each Z is independently one of the one or more side chain moieties of each second repeating unit; q is an integer selected from the range of 2 to 10000; w is an integer selected from the range of 1 to 4; and the polymer backbone group of each second repeating unit is directly or indirectly covalently attached to the polymer backbone group of a different second repeating and/or to a first repeating unit.

15 . The polymer of claim 14 , wherein each second repeating unit is characterized by formula FX5:
wherein: L is a covalent linking group; each of i and w is independently an integer selected from the range of 1 to 4.

16 . The polymer of any one of claims 9-15 , wherein second repeating unit is characterized by formula FX21B, FX22B, FX23B, FX24B, FX25B, FX26B, FX27B, FX28B, FX29B, any substituted version thereof, or any combination thereof:
wherein: each of Z5 and Z6 is independently a side chain moiety or a combination of a covalent linking group and a side chain moiety.

17 . The polymer of any one of claims 9-16 , wherein each second repeating unit is characterized by formula FX6, FX7, FX8, FX9, FX10, FX11, FX12, or FX13:

Assignees

• Univ Northwestern

Inventors

• Gianneschi Nathan C
• Liang Yifei
• Sun Hao

Classifications

• C08G79/04 Primary

  Phosphorus linked to oxygen or to oxygen and carbon · CPC title

• C08L85/02

  containing phosphorus · CPC title

• C08G2261/334

  containing heteroatoms · CPC title

• C08G2261/418

  Ring opening metathesis polymerisation [ROMP] · CPC title

• C08G61/08 Primary

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