Functionalized polydicyclopentadiene polymer

Patent metadata

Field	Value
Publication number	US-10344110-B2
Application number	US-201815999209-A
Country	US
Kind code	B2
Filing date	Aug 17, 2018
Priority date	Feb 19, 2016
Publication date	Jul 9, 2019
Grant date	Jul 9, 2019

Abstract

Disclosed herein are embodiments of methods for making and using functionalized forms of polydicyclopentadiene polymers. The disclosed polymers and methods enable a greater range of uses than the unmodified polydicyclopentadiene, which is currently used industrially. In addition, the presence of the functional groups contemplated by the disclosed compounds and formulae allow for the control of the polymer surface energy, and also enables the use of reversible chemical crosslinks, which permits recycling of the material.

First claim

We claim:

1. A method, comprising:
reacting cyclopentadiene with a substituted cyclopentadiene compound, or a salt thereof, to form a multicyclic compound having a structure satisfying Formula A and/or Formula B

wherein the substituted cyclopentadiene compound has a structure satisfying a formula

and
wherein X is an electron-withdrawing group or radical-stabilizing group.

2. The method of claim 1 , wherein the salt of the substituted cyclopentadiene compound has a structure satisfying a formula

wherein M is a metal counterion or non-metal counterion, and wherein reacting occurs under acidic conditions.

3. The method of claim 2 , wherein M is an alkali metal, an alkaline earth metal, or a tetra-substituted ammonium species and X is selected from an ester (CO 2 R), an acid (CO 2 H), an amide (—CONRR′), a ketone (—COR), an aldehyde (—COH), a nitrile (—CN), a nitro group (—NO 2 ), a trifluoromethyl group (—CF 3 ), an alkoxy group (—OR), a phosphine oxide, or a sulfur-containing species; wherein R and R′ independently are selected from H, aliphatic, aryl, heteroaliphatic, heteroaryl, or combinations thereof; —(CH 2 ) y OH; —(CH 2 ) y SH; or —(CH 2 ) y NR a R b , where y is an integer between 0 and 10 and R a and R b independently are selected from H, aliphatic, aryl, heteroaliphatic, heteroaryl, or combinations thereof.

4. The method of claim 1 , further comprising performing an olefin metathesis reaction on the multicyclic compound.

5. The method of claim 1 , wherein a conjugate addition is used to remove isomers of Formula A from isomers of Formula B.

6. A polymer made from:
(i) polymerizing the multicyclic compound having a structure satisfying Formula A and/or Formula B

wherein X is an electron-withdrawing group or radical-stabilizing group; or
(ii) polymerizing a mixture of multicyclic compounds, wherein the mixture of multicyclic compounds comprises a mixture of regioisomeric compounds having structures satisfying formulas

wherein X is an electron-withdrawing group or radical-stabilizing group; or
(iii) polymerizing a pre-crosslinked monomer having a structure satisfying a formula

or a combination thereof; wherein G is a linking group or a cleavable linking group.

7. The polymer of claim 6 , wherein X is selected from an ester (—CO 2 R), an acid (—CO 2 H), an amide (—CONRR′), a ketone (—COR), an aldehyde (—COH), a nitrile (—CN), a nitro group (—NO 2 ), a trifluoromethyl group (—CF 3 ), an alkoxy group (—OR), a phosphine oxide, or a sulfur-containing species; wherein R and R′ independently are selected from H, aliphatic, aryl, heteroaliphatic, heteroaryl, or combinations thereof; —(CH 2 ) y OH; —(CH 2 ) y SH; or —(CH 2 ) y NR a R b , where y is an integer between 0 and 10 and R a and R b independently are selected from H, aliphatic, aryl, heteroaliphatic, heteroaryl, or combinations thereof.

8. The polymer of claim 6 , wherein the linking group is selected from an ester, an amide, an alkyl group, an aromatic group, a heteroaromatic group, an olefin, an alkyne, an ether, a silyl ether, an alkyl silane, a disulfide, a cyclic group, or a combination thereof; and the cleavable linking group is selected from a linking group capable of being cleaved under radical conditions, oxidative conditions, enzymatic conditions, electromagnetic radiation conditions, reductive conditions, acidic conditions, basic conditions, or metal-catalyzed conditions.

9. A polymer, comprising at least one subunit having a structure satisfying one or more of the following formulas:

wherein
X is an electron-withdrawing group or radical-stabilizing group; and
a bold line of the crosslinked form comprises a primary molecular crosslink, which can further comprise one or more functional groups or polymer subunits.

10. The polymer of claim 9 , wherein X is selected from an ester (—CO 2 R), an acid (—CO 2 H), an amide (—CONRR′), a ketone (—COR), an aldehyde (—COH), a nitrile (—CN), a nitro group (—NO 2 ), a trifluoromethyl group (—CF 3 ), an alkoxy group (—OR), a phosphine oxide, or a sulfur-containing species; wherein R and R′ independently are selected from H, aliphatic, aryl, heteroaliphatic, heteroaryl, or combinations thereof; —(CH 2 ) y OH; —(CH 2 ) y SH; or —(CH 2 ) y NR a R b , where y is an integer between 0 and 10 and R a and R b independently are selected from H, aliphatic, aryl, heteroaliphatic, heteroaryl, or combinations thereof.

11. The polymer of claim 9 , wherein the polymer is a linear polymer having a structure satisfying a formula

wherein
each of G and G′ independently is selected from an end-capping group; and
n is any integer value greater than 10.

12. The polymer of claim 11 , wherein the end-capping group is selected from
CH 2 , —CH(aryl), —CH(aliphatic), —CH(heteroaliphatic), or —CH(heteroaryl).

13. A polymer, comprising one or more molecular crosslinks and having a structure satisfying a formula selected from:

wherein
one or more bold lines of the formula independently comprises a primary molecular crosslink, which can further comprise one or more functional groups or polymer subunits;
A is a heteroatom or heteroatom-containing group;
B is a linking group;
Z is an integer between 0 and 10; and
X is an electron-withdrawing group or radical-stabilizing group.

14. The polymer of claim 13 , wherein the heteroatom is O or S and the heteroatom group is NH or NR, wherein R is alkyl, aromatic, heteroaromatic, or a combination thereof.

15. The polymer of claim 13 , wherein the linking group is selected from an alkyl group, aromatic group, a heteroaromatic group, or a combination thereof.

16. A method, comprising:
forming a polymer by combining (i) a photoredox mediator compound or a catalyst comprising ruthenium (Ru), molybdenum (Mo), tungsten (W), titanium (Ti), tantalum (Ta), or a combination thereof; and (ii) a compound having a structure satisfying a formula

or a combination thereof; wherein X is an electron-withdrawing group or radical-stabilizing group.

17. The method of claim 16 , further comprising exposing the polymer to a chemical process or physical process that converts a functional group of the polymer.

18. The method of claim 17 , wherein the chemical process is selected from an esterification reaction, a hydrolysis reaction, a condensation reaction, a metal-mediated coupling, a decarboxylation reaction, a photochemical reaction, an addition of a nucl

Assignees

• Uvic Ind Partnerships Inc

Inventors

• Wulff Jeremy E
• Chen Jun
• Moffitt Matthew G
• Burns Fraser P
• Cuthbert Tyler J
• Liu Chang
• Li Tong

Classifications

• C08F8/28

  Condensation with aldehydes or ketones · CPC title

• C08F4/40

  Redox systems · CPC title

• C09B69/10 Primary

  Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds · CPC title

• C07C2603/68

  Dicyclopentadienes; Hydrogenated dicyclopentadienes · CPC title

• C08F8/12

  Hydrolysis · CPC title