IP Library › Granted Patent US 12,365,752
Granted Patent B2
US 12,365,752 · App. 18/746,848 · Granted Jul 22, 2025

Functional oligomers and functional polymers including hydroxylated polymers and conjugates thereof and uses thereof

Inventors: Jeremiah A. Johnson (Boston, MA); Wenxu Zhang (Belmont, MA); Peyton Shieh (Cambridge, MA); Keith Husted (Boston, MA)
Assignee: Massachusetts Institute of Technology
C08F232/08C07D321/12C08F8/12C08F234/02
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Quick Facts
Patent No.
US 12,365,752
App. No.
18/746,848
Granted
Jul 22, 2025
Kind
B2
Abstract

The present disclosure describes functional oligomers or functional polymers. The functional oligomers or functional polymers may contain functional groups, e.g., —OH and/or —CHO. The functional oligomers or functional polymers may be obtained from hydrolyzing certain copolymers and may be soluble in commercially available solvents. The copolymers may be thermosetting polymers. The functional oligomers and functional polymers may be useful for recycling thermosetting polymers and may be useful as starting materials for preparing additional oligomers or polymers.

Claims (102)

1. A method of preparing a hydroxylated polymer comprising hydrolyzing a copolymer prepared by a method comprising polymerizing in the presence of a metathesis catalyst:

i) one or more instances of a first monomer, wherein each instance of the first monomer is independently of the formula:

or salt thereof, wherein:

each instance of

 is Ring B, wherein each instance of Ring B is independently a substituted or unsubstituted, monocyclic carbocyclic ring, substituted or unsubstituted, monocyclic heterocyclic ring, substituted or unsubstituted, monocyclic aryl ring, or substituted or unsubstituted, monocyclic heteroaryl ring;

each instance of Z is independently C(R P ) 2 or O;

each instance of R P is independently hydrogen, halogen, or substituted or unsubstituted, C 1-6 alkyl; and

each instance of is independently a single bond or double bond; and

ii) one or more instances of a second monomer, wherein each instance of the second monomer is of Formula (B):

or a salt thereof; wherein:

each instance of Y is independently O or C(R Q ) 2 ;

each instance of R Q is independently hydrogen, halogen, or substituted or unsubstituted, C 1-6 alkyl;

each instance of R K is independently hydrogen, halogen, substituted or unsubstituted, C 1-10 alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or —OR N ;

each instance of R N is independently hydrogen, substituted or unsubstituted acyl, substituted or unsubstituted, C 1-10 alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or an oxygen protecting group;

each instance of j is independently 1, 2, or 3; and

each instance of k is independently 0, 1, 2, or 3;

wherein any two instances of the first monomer are the same as or different from each other, and any two instances of the second monomer are the same as or different from each other; and

wherein the step of hydrolyzing the copolymer comprises hydrolyzing one or more instances of the —O—Si bonds of the copolymer to form —OH.

2. A method of preparing a functional oligomer or functional polymer comprising hydrolyzing a copolymer prepared by a method comprising polymerizing in the presence of a metathesis catalyst:

i) one or more instances of a first monomer, wherein each instance of the first monomer is of the formula:

or salt thereof;

ii) one or more instances of a second monomer, wherein each instance of the second monomer is of the formula:

or a salt thereof; and

iii) optionally one or more instances of a third monomer;

wherein:

each instance of Z is independently a single bond, C(R P ) 2 , or O;

each instance of R P is independently hydrogen, halogen, or substituted or unsubstituted, C 1-6 alkyl;

each instance of is independently a single or double bond;

each instance of R H is independently hydrogen, halogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, —OR a , —OCN, —OC(═O)R a , —OC(═S)R a , —OC(═O)OR a , —OC(═O)N(R a ) 2 , —OS(═O)R a , —OS(═O)OR a , —OS(═O)N(R a ) 2 , —OS(═O) 2 R a , —OS(═O) 2 OR a , —OS(═O) 2 N(R a ) 2 , —OSi(R a ) 3 , —OSi(R a ) 2 (OR a ), —OSi(R a )(OR a ) 2 , —OSi(OR a ) 3 , oxo, —N(R a ) 2 , —N═C(R a ) 2 , ═NR a , —NC, —NCO, —N 3 , —NO 2 , —NR a C(═O)R a , —NR a C(═O)OR a , —NR a C(═O)N(R a ) 2 , —NR a S(═O)R a , —NR a S(═O)OR a , —NR a S(═O)N(R a ) 2 , —NR a S(═O) 2 R a , —NR a S(═O) 2 OR a , —NR a S(═O) 2 N(R a ) 2 , —SR a , —SCN, —S(═O)R a , —S(═O)OR a , —S(═O)N(R a ) 2 , —S(═O) 2 R a , —S(═O) 2 OR a , —S(═O) 2 N(R a ) 2 , —SeR a , halogen, —CN, —C(═NR a )R a , —C(═NR a )OR a , —C(═NR a )N(R a ) 2 , —C(═O)R a , —C(═O)OR a , —C(═O)SR a , —C(═S)OR a , or —C(═O)N(R a ) 2 ;

or the two instances of R H of one or more instances of

 are joined with the intervening carbon atoms to independently form a substituted or unsubstituted, monocyclic carbocyclic ring, substituted or unsubstituted, monocyclic heterocyclic ring, substituted or unsubstituted, monocyclic aryl ring, or substituted or unsubstituted, monocyclic heteroaryl ring;

each instance of R a is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted, monocyclic carbocyclyl, substituted or unsubstituted, monocyclic heterocyclyl, substituted or unsubstituted, monocyclic aryl, substituted or unsubstituted, monocyclic heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom, or two instances of R a are joined to form substituted or unsubstituted heterocyclyl or substituted or unsubstituted heteroaryl;

Y is O or C(R Q ) 2 ;

each instance of R Q is independently hydrogen, halogen, or substituted or unsubstituted, C 1-6 alkyl;

each instance of R K is independently hydrogen, halogen, substituted or unsubstituted, C 1-10 alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or —OR N ;

each instance of R N is independently hydrogen, substituted or unsubstituted acyl, substituted or unsubstituted, C 1-10 alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or an oxygen protecting group;

j is 1, 2, or 3; and

k is 0, 1, 2, or 3; and

iii) optionally one or more instances of a third monomer;

wherein any two instances of the first monomer are the same as or different from each other, any two instances of the second monomer are the same as or different from each other, any two instances of the third monomer are the same as or different from each other, and each instance of the first monomer, the second monomer, and the third monomer if present, is different from each other;

wherein the step of hydrolyzing the copolymer comprises hydrolyzing one or more instances of the —O—Si bonds of the copolymer to form —OH;

any two instances of the first monomer are the same as or different from each other, any two instances of the second monomer are the same as or different from each other, any two instances of the third monomer are the same as or different from each other, and each instance of the first monomer, the second monomer, and the third monomer if present, is different from each other; and

wherein the step of hydrolyzing the copolymer comprises hydrolyzing one or more instances of the —O—Si bonds of the copolymer to form —OH.

3. A method of preparing a functional oligomer or functional polymer comprising hydrolyzing a copolymer prepared by a method comprising polymerizing in the presence of a metathesis catalyst:

i) one or more instances of a first monomer, wherein each instance of the first monomer is of the formula:

or salt thereof;

ii) one or more instances of a second monomer, wherein each instance of the second monomer is of the formula:

or a salt thereof; and

iii) optionally one or more instances of a third monomer;

wherein:

each instance of Z is independently a single bond, C(R P ) 2 , or O;

each instance of R P is independently hydrogen, halogen, or substituted or unsubstituted, C 1-6 alkyl;

each instance of is independently a single or double bond;

each instance of R H is independently hydrogen, halogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, —OR a , —OCN, —OC(═O)R a , —OC(═S)R a , —OC(═O)OR a , —OC(═O)N(R a ) 2 , —OS(═O)R a , —OS(═O)OR a , —OS(═O)N(R a ) 2 , —OS(═O) 2 R a , —OS(═O) 2 OR a , —OS(═O) 2 N(R a ) 2 , —OSi(R a ) 3 , —OSi(R a ) 2 (OR a ), —OSi(R a )(OR a ) 2 , —OSi(OR a ) 3 , oxo, —N(R a ) 2 , —N═C(R a ) 2 , ═NR a , —NC, —NCO, —N 3 , —NO 2 , —NR a C(═O)R a , —NR a C(═O)OR a , —NR a C(═O)N(R a ) 2 , —NR a S(═O)R a , —NR a S(═O)OR a , —NR a S(═O)N(R a ) 2 , —NR a S(═O) 2 R a , —NR a S(═O) 2 OR a , —NR a S(═O) 2 N(R a ) 2 , —SR a , —SCN, —S(═O)R a , —S(═O)OR a , —S(═O)N(R a ) 2 , —S(═O) 2 R a , —S(═O) 2 OR a , —S(═O) 2 N(R a ) 2 , —SeR a , halogen, —CN, —C(═NR a )R a , —C(═NR a )OR a , —C(═NR a )N(R a ) 2 , —C(═O)R a , —C(═O)OR a , —C(═O)SR a , —C(═S)OR a , or —C(═O)N(R a ) 2 ;

or the two instances of R H of one or more instances of

 are joined with the intervening carbon atoms to independently form a substituted or unsubstituted, monocyclic carbocyclic ring, substituted or unsubstituted, monocyclic heterocyclic ring, substituted or unsubstituted, monocyclic aryl ring, or substituted or unsubstituted, monocyclic heteroaryl ring;

each instance of R a is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted, monocyclic carbocyclyl, substituted or unsubstituted, monocyclic heterocyclyl, substituted or unsubstituted, monocyclic aryl, substituted or unsubstituted, monocyclic heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom, or two instances of R a are joined to form substituted or unsubstituted heterocyclyl or substituted or unsubstituted heteroaryl;

each instance of R S is independently hydrogen or —OR a ;

each instance of w is independently 0, 1, 2, 3, or 4;

each instance of R T is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

any two instances of the first monomer are the same as or different from each other, any two instances of the second monomer are the same as or different from each other, any two instances of the third monomer are the same as or different from each other, and each instance of the first monomer, the second monomer, and the third monomer if present, is different from each other; and

wherein the step of hydrolyzing the copolymer comprises hydrolyzing one or more instances of

 of the copolymer to form

4. A compound of Formula (B1):

or a salt thereof; wherein:

Y is O or C(R Q ) 2 ;

each instance of R Q is independently hydrogen, halogen, or substituted or unsubstituted, C 1-6 alkyl;

each instance of R K is independently hydrogen, halogen, substituted or unsubstituted, C 1-10 alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or —OR N ;

each instance of R N is independently hydrogen, substituted or unsubstituted acyl, substituted or unsubstituted, C 1-10 alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or an oxygen protecting group;

j is 1, 2, or 3; and

k is 0, 1, 2, or 3;

provided that the compound is not of the formula:

5. A copolymer prepared by a method comprising polymerizing:

one or more instances of a first monomer;

one or more instances of a second monomer, wherein the second monomer is a compound of claim 4 , or a salt thereof; and

optionally one or more instances of a third monomer;

wherein any two instances of the first monomer are the same as or different from each other, any two instances of the second monomer are the same as or different from each other, any two instances of the third monomer are the same as or different from each other, and each instance of the first monomer, the second monomer, and the third monomer if present, is different from each other;

in the presence of a metathesis catalyst.

6. A method of preparing a copolymer of claim 5 comprising polymerizing:

one or more instances of a first monomer;

one or more instances of a second monomer, wherein the second monomer is a compound of claim 4 , or a salt thereof; and

optionally one or more instances of a third monomer;

wherein any two instances of the first monomer are the same as or different from each other, any two instances of the second monomer are the same as or different from each other, any two instances of the third monomer are the same as or different from each other, and each instance of the first monomer, the second monomer, and the third monomer if present, is different from each other;

in the presence of a metathesis catalyst.

7. A method of preparing a conjugate comprising reacting a hydroxy-reacting substance with a hydroxylated polymer, wherein the hydroxylated polymer is prepared by hydrolyzing a copolymer prepared by a method comprising polymerizing in the presence of a metathesis catalyst:

i) one or more instances of a first monomer, wherein each instance of the first monomer is independently of the formula:

or salt thereof, wherein:

each instance of

 is Ring B, wherein each instance of Ring B is independently a substituted or unsubstituted, monocyclic carbocyclic ring, substituted or unsubstituted, monocyclic heterocyclic ring, substituted or unsubstituted, monocyclic aryl ring, or substituted or unsubstituted, monocyclic heteroaryl ring;

each instance of Z is independently C(R P ) 2 or O;

each instance of R P is independently hydrogen, halogen, or substituted or unsubstituted, C 1-6 alkyl; and

each instance of is independently a single bond or double bond; and

ii) one or more instances of a second monomer, wherein each instance of the second monomer is of Formula (B):

or a salt thereof; wherein:

each instance of Y is independently O or C(R Q ) 2 ;

each instance of R Q is independently hydrogen, halogen, or substituted or unsubstituted, C 1-6 alkyl;

each instance of R K is independently hydrogen, halogen, substituted or unsubstituted, C 1-10 alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or —OR N ;

each instance of R N is independently hydrogen, substituted or unsubstituted acyl, substituted or unsubstituted, C 1-10 alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or an oxygen protecting group;

each instance of j is independently 1, 2, or 3; and

each instance of k is independently 0, 1, 2, or 3;

wherein any two instances of the first monomer are the same as or different from each other, and any two instances of the second monomer are the same as or different from each other; and

wherein the step of hydrolyzing the copolymer comprises hydrolyzing one or more instances of the —O—Si bonds of the copolymer to form —OH.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 27, 2024
From: JOHNSON, JEREMIAH A.; ZHANG, WENXU; SHIEH, PEYTON; HUSTED, KEITH
To: MASSACHUSETTS INSTITUTE OF TECHNOLOGY
Reel/Frame 068790/0595 →
Continuity (3)
Division 17022021 · Sep 15, 2020
Provisional Application 62935799 · Nov 15, 2019
Related Publication 20240425633A1 · Dec 26, 2024
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