Adjustably stable adhesive compositions for medical and non-medical uses, and recycling

Patent metadata

Field	Value
Publication number	US-12152174-B2
Application number	US-202418635583-A
Country	US
Kind code	B2
Filing date	Apr 15, 2024
Priority date	Apr 13, 2023
Publication date	Nov 26, 2024
Grant date	Nov 26, 2024

Abstract

Adhesive compositions for medical and non-medical uses are provided. The adhesive compositions can include cyclic disulfide monomers, oligomers of reactions between the cyclic disulfides, polymers of the cyclic disulfides, solid articles formed formed from the polymers, and any combination thereof. Methods of making, using, and recycling the adhesive compositions are provided, including use of the adhesive compositions on a variety of substrates that include biological tissue; biomaterials, including synthetics and natural such as bone, wood, and cellulosics; metals and alloys; polymers, plastics, and rubbers; ceramics; composites; and, any combination of these materials. The adhesives can adhere to substrates in a variety of environmental conditions that include ambient atmospheric conditions, wet conditions that include adhering materials underwater, and in a wide variety of temperatures and pressures, such as those temperatures and pressures found in medical environments, including in living tissue, as well as many residential, commercial, industrial, and manufacturing environments.

First claim

We claim:

1. An adhesive composition, comprising
a plurality of substituted 1,2-dithiolane monomers, the substituted 1,2-dithiolane monomers functional to polymerize through a ring-opening reaction to form a polydisulfide polymer having
a first active thiol end and a second active thiol end; and,
a plurality of repeating units having a substituted dithioalkyl structure from the ring opening reaction as follows

wherein,
n is 3;
each R i and R k is independently selected from the group consisting of H; alkyl, cycloalkyl, alkenyl, alkynyl, and aryl groups, each of the groups having from 1-8 carbons; hydroxylated alkyl, cycloalkyl, alkenyl, alkynyl, and aryl groups, each of the groups having from 1-8 carbons; and, carboxylated alkyl, cycloalkyl, alkenyl, alkynyl, and aryl groups, each of the groups having from 1-8 carbons; wherein, i and k are integers, and at least one R i or R k in each repeating unit includes a carbonyl functionality;
and,
m is an integer selected to match a desired molecular weight of the polymer;

and,
a plurality of stabilizer molecules configured to stabilize the first active thiol end of the polymer, the plurality of stabilizer molecules being the substituted cyclic disulfide molecules derivatized to include a functional group that forms a first labile bond with the first active thiol end, the first labile bond selected from the group consisting of a thioester bond, a thiocarbamate bond, and a thioether bond;
wherein, the repeating units and the stabilizer molecules are the same, or substantially the same, chemical moieties following a depolymerization of the polymer.

2. The adhesive composition of claim 1 , further including a plurality of terminator molecules for forming a labile bond with the second active thiol group, the plurality of terminator molecules selected from the group consisting of R′OH, R′CO 2 H, and R′SH, and R′ is selected from the group consisting of alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, and aryl groups, each of the groups having from 1-8 carbons; and, the second labile bond is selected from the group consisting of thioethers, thioesters, and disulfides.

3. The adhesive composition of claim 1 , further including a plurality of terminator molecules for forming a labile bond with the second active thiol group, the plurality of terminator molecules selected from the group consisting of alkanols having from 1-8 carbons, alkanoic acids having from 1-8 carbons, and alkylthiols having from 1-8 carbons, and the second labile bond is selected from the group consisting of thioethers, thioesters, and disulfides.

4. The adhesive composition of claim 1 , further including a plurality of terminator molecules for forming a labile bond with the second active thiol group, the plurality of terminator molecules selected from the group consisting of ethanol, and a substituted 1,2-dithiolane with a hydroxyl functionality.

5. The adhesive composition of claim 1 , wherein:
the repeating unit is a substituted 1,3-dithiopropyl structure as follows

wherein,
m is an integer;
R i includes R 1 , R 2 , and R 3 ; and,
each R k is H;

and,
each stabilizer molecule includes the substituted 1,3-dithiopropyl structure.

6. The adhesive composition of claim 5 , wherein:
the repeating unit is a substituted 1,3-dithiopropyl structure as follows

wherein,
m is an integer;
R 1 is a pentanoic acid group, and R 2 and R 3 are each H;

and,
each stabilizer molecule includes the substituted 1,3-dithiopropyl structure, wherein R 1 is a pentanoic acid group, and R 2 and R 3 are each H.

7. The adhesive composition of claim 5 , further including a plurality of terminator molecules selected from the group consisting of ethanol and a substituted 1,2-dithiolane with a hydroxyl functionality, the terminator molecules functioning to form a second labile bond with the second active thiol end of the polymer to further stabilize the polymer.

8. The adhesive composition of claim 5 , wherein:
the repeating unit has a substituted 1,3-dithiopropyl structure

wherein,
m is an integer;
R 1 and R 3 are H, and R 2 is a carboxylic acid group;

and,
each stabilizer molecule includes the substituted 1,3-dithiopropyl structure, wherein R 1 and R 3 are H and R 2 is a carboxylic acid group.

9. A stabilized and recyclable polydisulfide polymer, comprising:
a plurality of substituted 1,2-dithiolane monomers, the substituted 1,2-dithiolane monomers functional to polymerize through a ring-opening reaction to form a polydisulfide polymer having
a first active thiol end and a second active thiol end; and,
a plurality of repeating units having a substituted dithioalkyl structure from the ring opening reaction as follows

wherein,
n is 3;
each R i and R k is independently selected from the group consisting of H; alkyl, cycloalkyl, alkenyl, alkynyl, and aryl groups, each of the groups having from 1-8 carbons; hydroxylated alkyl, cycloalkyl, alkenyl, alkynyl, and aryl groups, each of the groups having from 1-8 carbons; and, carboxylated alkyl, cycloalkyl, alkenyl, alkynyl, and aryl groups, each of the groups having from 1-8 carbons; wherein, i and k are integers, and at least one R i or R k in each repeating unit includes a carbonyl functionality;
and,

m is an integer selected to match a desired molecular weight of the polymer;

and,
a plurality of stabilizer molecules configured to stabilize the first active thiol end of the polymer, the plurality of stabilizer molecules being the substituted cyclic disulfide molecules derivatized to include a functional group that forms a first labile bond with the first active end, the first labile bond selected from the group consisting of a thioester bond, a thiocarbamate bond, and a thioester bond;
wherein, the repeating units and the stabilizer molecules are the same, or substantially the same, chemical moieties following a degradation of the polymer during a recycling of the polymer.

10. The stabilized and recyclable polydisulfide polymer of claim 9 , further including a plurality of terminator molecules for forming a labile bond with the second active thiol group, the plurality of terminator molecules selected from the group consisting of R′OH, R′CO 2 H, and R′SH, and R′ is selected from the group consisting of alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, and aryl groups, each of the groups having from 1-8 carbons; and, the second labile bond is selected from the group consisting of thioethers, thioesters, and disulfides.

11. The stabilized and recyclable polydisulfide polymer of claim 9 , further including a plurality of terminator molecules for forming a labile bond with the second active thiol group, the plurality of terminator molecules selected from the group consisting of alkanols having from 1-8 carbons, alkanoic acids having from 1-8 carbons,

Assignees

• Univ California

Inventors

• Messersmith Phillip B
• Pal Subhajit
• Defrates Kelsey G
• Shin Jisoo

Classifications

• C08G75/06

  from cyclic thioethers · CPC title

• C09D181/02

  Polythioethers; Polythioether-ethers · CPC title

• C09J181/02

  Polythioethers; Polythioether-ethers · CPC title

• C08G75/02

  Polythioethers · CPC title

• C08L81/02

  Polythioethers; Polythioether-ethers · CPC title