Boroxine based dynamic thermosetting polymers

Patent metadata

Field	Value
Publication number	US-11370889-B2
Application number	US-201916416148-A
Country	US
Kind code	B2
Filing date	May 17, 2019
Priority date	May 18, 2018
Publication date	Jun 28, 2022
Grant date	Jun 28, 2022

Abstract

The disclosure provides for dynamic thermosetting polymers comprising boroxine crosslinks that exhibit unusual mechanical behavior by being strong, highly malleable, recyclable and fully reprocessable. The disclosure further provides methods of making the thermosetting polymers and applications thereof.

First claim

What is claimed is:

1. A dynamic thermosetting polymer comprising:
a plurality of boroxine crosslinks having the structure of:

 formed from monomers comprising the structure of Formula IV(a), Formula IV(b), Formula IV(c), Formula IV(d), Formula IV(e), Formula IV(f), Formula IV(g), Formula IV(h) and/or Formula IV(i):

wherein,
X 1 is selected from optionally substituted (C 3 -C 24 )-alkylene, optionally substituted (C 3 -C 24 )-hetero-alkylene, optionally substituted (C 3 -C 24 )-alkenylene, optionally substituted (C 3-12 )-hetero-alkenylene, optionally substituted (C 3-12 )-alkynylene, optionally substituted (C 3 -C 12 )-hetero-alkynylene, optionally substituted (C 5 -C 12 )-cycloalkylene, optionally substituted (C 5 -C 12 )-cycloalkenylene, and optionally substituted heterocyclylidene;
X 7 is selected from optionally substituted (C 3 -C 24 )-alkylene, optionally substituted (C 3 -C 24 )-hetero-alkylene, optionally substituted (C 3 -C 24 )-alkenylene, optionally substituted (C 3-12 )-hetero-alkenylene, optionally substituted (C 3-12 )-alkynylene, optionally substituted (C 3 -C 12 )-hetero-alkynylene, optionally substituted (C 5 -C 12 )-cycloalkylene, optionally substituted (C 5 -C 12 )-cycloalkenylene, and optionally substituted heterocyclylidene; and
R 1 -R 15 are independently selected from the group consisting of H, D, aryl, heterocyclyl, (C 1 -C 6 )-alkyl, (C 1 -C 6 )-hetero-alkyl, (C 2 -C 6 )-alkenyl, (C 2-6 )-hetero-alkenyl, (C 2-6 )-alkynyl, (C 2 -C 6 )-hetero-alkynyl, ether, ester, halo, hydroxyl, boronic acid, boronic ester, carboxyl, carboxylate, aldehyde, ketone, haloformyl, carboxamide, amine, azide, isonitrile, nitroso, nitro, thiol, sulfinyl, and sulfo;
optionally, the dynamic thermosetting polymer is also formed from one or more comonomers;
optionally, the dynamic thermosetting polymer further comprises one or more plasticizers;
wherein the dynamic thermosetting polymer is malleable, can be recycled back to monomers, and/or is capable of being reprocessed.

2. The dynamic thermosetting polymer of claim 1 , wherein the plurality of boroxine crosslinks having the structure of

are formed from monomers comprising the structure of Formula V(a), Formula V(b), or Formula V(c):

wherein,
R 1 , R 2 , R 4 , R 5 , and R 6 -R 9 are independently selected from the group consisting of H, D, aryl, heterocyclyl, (C 1 -C 24 )-alkyl, (C 1 -C 24 )-heteroalkyl, (C 2 -C 24 )-alkenyl, (C 2-24 )-heteroalkenyl, (C 2-24 )-alkynyl, (C 2 -C 24 )-heteroalkynyl, (C 3 -C 24 )-cycloalkyl, (C 4 -C 24 )-cycloalkenyl, ester, halo, hydroxyl, ketone, carboxyl, carboxylate, aldehyde, boronic acid, boronic ester, haloformyl, ether, carboxamide, amine, azide, isonitrile, nitroso, nitro, thiol, sulfinyl, and sulfo;
R 16 -R 23 are independently selected from the group consisting of H, D, halo, (C 1 -C 4 )alkyl, hydroxyl, and amine;
m is an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 13, 14, 15, 16, 17, 18, 19, or 20; and
n is an integer selected from 3, 4, 5, 6, 7, 8, 9, 10, 12, 13, 14, 15, 16, 17, 18, 19, or 20.

3. The dynamic thermosetting polymer of claim 2 , wherein the plurality of boroxine crosslinks having the structure of:

are formed from monomers comprising the structure of:

4. The dynamic thermosetting polymer of claim 1 , wherein the dynamic thermosetting polymer is also formed from one or more comonomers having the structure of Formula I and/or Formula II:

wherein,
Ar is selected from aryl, aromatic heterocycle, or an aromatic mixed ring system, wherein each of the foregoing groups comprise one or more substituents, and wherein at least one substituent is a boronic acid group; and
R is selected from aryl, heterocyclyl, (C 1 -C 24 )-alkyl, (C 1 -C 24 )-heteroalkyl, (C 1 -C 24 )-alkenyl, (C 1-12 )-heteroalkenyl, (C 2-12 )-alkynyl, (C 2 -C 12 )-heteroalkynyl, (C 3 -C 12 )-cycloalkyl, (C 4 -C 12 )-cycloalkenyl, (C 1 -C 24 )-ester, mixed ring system, or any combination of the foregoing groups, wherein each of the foregoing groups comprise one or more substituents, wherein at least one substituent is a boronic acid group.

5. The dynamic thermosetting polymer of claim 4 , wherein the one or more comonomers have the structure of Formula IV:

wherein,
R 1 -R 5 are independently selected from the group consisting of H, D, aryl, heterocyclyl, (C 1 -C 24 )-alkyl, (C 1 -C 24 )-heteroalkyl, (C 2 -C 24 )-alkenyl, (C 2-24 )-heteroalkenyl, (C 2-24 )-alkynyl, (C 2 -C 24 )-heteroalkynyl, (C 3 -C 24 )-cycloalkyl, (C 4 -C 24 )-cycloalkenyl, (C 1 -C 24 )-ester, halo, hydroxyl, boronic acid, boronic ester, ketone, carboxyl, carboxylate, aldehyde, haloformyl, ether, carboxamide, amine, azide, azo, isonitrile, nitroso, nitro, nitrosooxy, thiol, sulfinyl, and sulfo,
wherein at least one of R 1 to R 5 is an aryl, (C 1 -C 24 )-alkyl, a (C 1 -C 24 )-heteroalkyl, a (C 1 -C 24 )-alkenyl, a (C 1-12 )-heteroalkenyl, a (C 2-12 )-alkynyl, a (C 2 -C 12 )-heteroalkynyl, a (C 3 -C 12 )-cycloalkyl, a (C 4 -C 12 )-cycloalkenyl, a heterocyclyl, and a (C 1 -C 24 )-ester, wherein for each of the foregoing groups the groups comprise one or more substituents, wherein at least one substituent is a boronic acid group.

6. The dynamic thermosetting polymer of claim 1 , wherein the dynamic thermosetting polymer is formed from boronic acid-containing polymers that are prepared by incorporating or linking monomers that comprise boronic acid functional groups with monomers or comonomers that do not comprise boronic functional groups by using a step-growth polymerization method, a chain-growth polymerization method, a ring-opening polymerization method, and an olefin metathesis polymerization method.

7. The dynamic thermosetting polymer of claim 1 , wherein the dynamic thermosetting polymer is formed from boronic acid-containing polymers that are made by functionalizing polymers made using step-growth polymerization method, a chain-growth polymerization method, a ring-opening polymerization method, and an olefin metathesis polymerization method, with boronic acid groups.

8. The dynamic thermosetting polymer of claim 1 , wherein the dynamic thermosetting polymer further comprises a plasticizer selected from the group consisting of Bis(2-ethylhexyl) phthalate, Bis(2-propylheptyl) phthalate, Diisononyl phthalate, Di-n-butyl phthalate, Butyl benzyl phthalate, Diisodecyl phthalate, Dioctyl phthalate, Diisooctyl phthalate, Diethyl phthalate, Diisobutyl phthalate, Di-n-hexyl phthalate, Trimethyl trimellitate, Tri-(2-ethylhexyl) trimellitate, Tri-(n-octyl,n-decyl) trimellitate, Tri-(heptyl,nonyl) trimellitate, n-octyl trimellitate, Bis(2-ethylhexyl)adipate, Dimethyl adipate, Monomethyl adipate, Dioctyl adipate, Dibutyl sebacate, Dibutyl maleate, Diisobutyl maleate, dioctyl terephthalate, 1,2-Cyclohexane dicarboxylic acid diisononyl ester, Alkyl sulp

Assignees

• Univ California

Inventors

• Guan Zhibin
• Ogden William

Classifications

• C08G79/08 Primary

  a linkage containing boron · CPC title

• C09D185/04

  containing boron · CPC title

• C08K5/3432

  Six-membered rings · CPC title

• C09J185/04

  containing boron · CPC title