Adhesive materials and methods of making and using the same

Patent metadata

Field	Value
Publication number	US-2016160097-A1
Application number	US-201414908956-A
Country	US
Kind code	A1
Filing date	Jul 30, 2014
Priority date	Jul 30, 2013
Publication date	Jun 9, 2016
Grant date	—

Abstract

A compound of formula (I): can be used as a monomer for making an underwater adhesive polymer. The compound of formula (I) can be prepared using eugenol as a starting material.

First claim

1 . A monomer for making an underwater adhesive polymer comprising a compound of formula (I):

wherein:
each of R 1 and R 2 , independently, is H, alkyl, or a protecting group;
L 1 is a linker moiety; and
M 1 is a polymerizable moiety;
provided that the compound of formula (I) is not eugenol, 3,4-dihydroxyphenylalanine or 3,4-dihydroxycinnamic acid.

2 . The monomer of claim 1 , comprising a compound of formula (II):

wherein:
each of R 1 and R 2 , independently, is H, alkyl, or a protecting group, provided that at least one is a protecting group; and
L 2 is a linker moiety including a bond, —O—, —S—, —C(O)—, —C(O)NH—, —C(S)—, —(CHR a ) n —, —[CH 2 CH(R a )O] n —, or a combination thereof;
wherein each R a , independently, is H or alkyl; and
each n, independently, is an integer from 1 to 10.

3 . The monomer of claim 1 , wherein M 1 is an organic polymerizable moiety selected from the group consisting of an acrylate group, a methacrylate group, a cyanoacrylate group, an epoxide group, an episulfide group, a styryl group, a vinyl group, and an isocyanate group.

4 . The monomer of claim 1 , wherein R 1 and R 2 are not simultaneously H.

5 . The monomer of claim 1 , wherein at least one of R 1 and R 2 is a protecting group.

6 . The monomer of claim 1 , wherein R 1 is a trialkylsilyl group and R 2 is a trialkylsilyl group.

7 . The monomer of claim 1 , wherein L 1 does not include an —NH— or an —NHR moiety; and M 1 does not include an —NH— or an —NHR moiety; wherein R is a substituent.

8 . The monomer of claim 1 , wherein the compound has the formula:

wherein X 1 is a bond, 0, or S;
L 2 is a bond, —(CHR a ) n —, —[CH 2 CH(R a )O] n +, or a combination thereof;
R 4 is H or C 1 -C 6 alkyl;
R 5 is H, C 1 -C 6 alkyl, or aryl; and
X 2 is a bond, O or S.

9 . The monomer of claim 1 , wherein the compound has the formula:

wherein R 4 is H or methyl; and X 2 is O or S.

10 . A method of making an adhesive polymer comprising polymerizing a monomer of formula (I):

wherein:
each of R 1 and R 2 , independently, is H, alkyl, or a protecting group;
L 1 is a linker moiety; and
M 1 is a polymerizable moiety;
provided that the compound of formula (I) is not eugenol, 3,4-dihydroxyphenylalanine or 3,4-dihydroxycinnamic acid;
wherein the monomer of formula (I) is optionally polymerized with one or more additional monomers.

11 . The method of claim 10 , further comprising forming the monomer of claim 10 by protecting the catechol moiety of eugenol with one or more protecting groups to form a compound of formula:

wherein each of R 1 and R 2 , independently, is H, alkyl, or a protecting group, provided that at least one of R 1 and R 2 is a protecting group; and
further modifying the protected eugenol to form a monomer of claim 10 .

12 . The method of claim 10 , wherein polymerizing includes forming a pre-polymer.

13 . The method of claim 12 , further comprising applying the pre-polymer to a substrate.

14 . The method of claim 12 , wherein polymerizing includes further polymerizing the pre-polymer.

15 . The method of claim 10 , wherein the one or more additional monomers includes a (meth)acrylate monomer, an epoxide monomer, an episulfide monomer, a styryl monomer, a vinyl monomer, or an isocyanate monomer.

16 . The method of claim 10 , further comprising deprotecting the catechol moiety.

17 . A polymer comprising a repeating unit having the formula:

wherein:
each of R 1 and R 2 , independently, is H, alkyl, or a protecting group;
X 1 is a bond, O, or S;
L 2 is a bond, —(CHR a ) n —, —[CH 2 CH(R a )O] n —, or a combination thereof;
each R a , independently, is H or alkyl;
each n, independently, is an integer from 1 to 10;
R 4 is H or C 1 -C 6 alkyl;
R 5 is H, C 1 -C 6 alkyl, or aryl; and
X 2 is a bond, O or S.

18 . The polymer of claim 17 , wherein the repeating unit has the formula:

19 . The polymer of claim 17 , further comprising a second repeating unit derived from a (meth)acrylate monomer, an epoxide monomer, an episulfide monomer, a styryl monomer, a vinyl monomer, or an isocyanate monomer.

20 . The polymer of claim 17 , wherein the polymer is a self-healing polymer.

Assignees

• Univ California

Inventors

• Waite Herbert J
• Ahn B Kollbe
• Hawker Craig J
• Suwon Jinhwa Heo
• Kang Taegon

Classifications

• C08F30/08

  containing silicon · CPC title

• C07F7/1852

  Chemistry & Metallurgy · mapped topic

• C09J143/04 Primary

  Homopolymers or copolymers of monomers containing silicon · CPC title

• C08F220/302

  and two or more oxygen atoms in the alcohol moiety · CPC title

• C09J129/02

  Homopolymers or copolymers of unsaturated alcohols (C09J129/14 takes precedence) · CPC title