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US 12,365,752 B2Granted
Functional oligomers and functional polymers including hydroxylated polymers and conjugates thereof and uses thereof
AssigneeMassachusetts Institute of Technology
InventorsJeremiah A. Johnson, Wenxu Zhang, Peyton Shieh, Keith Husted
Life of this patent
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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.
Claims7
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(RP)2 or O;
- each instance of RP is independently hydrogen, halogen, or substituted or unsubstituted, C1-6 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(RQ)2;
- each instance of RQ is independently hydrogen, halogen, or substituted or unsubstituted, C1-6 alkyl;
- each instance of RK is independently hydrogen, halogen, substituted or unsubstituted, C1-10 alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or —ORN;
- each instance of RN is independently hydrogen, substituted or unsubstituted acyl, substituted or unsubstituted, C1-10 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.
19 more elements
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(RP)2, or O;
- each instance of RP is independently hydrogen, halogen, or substituted or unsubstituted, C1-6 alkyl;
- each instance of is independently a single or double bond;
- each instance of RH 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, —ORa, —OCN, —OC(═O)Ra, —OC(═S)Ra, —OC(═O)ORa, —OC(═O)N(Ra)2, —OS(═O)Ra, —OS(═O)ORa, —OS(═O)N(Ra)2, —OS(═O)2Ra, —OS(═O)2ORa, —OS(═O)2N(Ra)2, —OSi(Ra)3, —OSi(Ra)2(ORa), —OSi(Ra)(ORa)2, —OSi(ORa)3, oxo, —N(Ra)2, —N═C(Ra)2, ═NRa, —NC, —NCO, —N3, —NO2, —NRaC(═O)Ra, —NRaC(═O)ORa, —NRaC(═O)N(Ra)2, —NRaS(═O)Ra, —NRaS(═O)ORa, —NRaS(═O)N(Ra)2, —NRaS(═O)2Ra, —NRaS(═O)2ORa, —NRaS(═O)2N(Ra)2, —SRa, —SCN, —S(═O)Ra, —S(═O)ORa, —S(═O)N(Ra)2, —S(═O)2Ra, —S(═O)2ORa, —S(═O)2N(Ra)2, —SeRa, halogen, —CN, —C(═NRa)Ra, —C(═NRa)ORa, —C(═NRa)N(Ra)2, —C(═O)Ra, —C(═O)ORa, —C(═O)SRa, —C(═S)ORa, or —C(═O)N(Ra)2;
- or the two instances of RH 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 Ra 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 Ra are joined to form substituted or unsubstituted heterocyclyl or substituted or unsubstituted heteroaryl;
- Y is O or C(RQ)2;
- each instance of RQ is independently hydrogen, halogen, or substituted or unsubstituted, C1-6 alkyl;
- each instance of RK is independently hydrogen, halogen, substituted or unsubstituted, C1-10 alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or —ORN;
- each instance of RN is independently hydrogen, substituted or unsubstituted acyl, substituted or unsubstituted, C1-10 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.
25 more elements
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(RP)2, or O;
- each instance of RP is independently hydrogen, halogen, or substituted or unsubstituted, C1-6 alkyl;
- each instance of is independently a single or double bond;
- each instance of RH 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, —ORa, —OCN, —OC(═O)Ra, —OC(═S)Ra, —OC(═O)ORa, —OC(═O)N(Ra)2, —OS(═O)Ra, —OS(═O)ORa, —OS(═O)N(Ra)2, —OS(═O)2Ra, —OS(═O)2ORa, —OS(═O)2N(Ra)2, —OSi(Ra)3, —OSi(Ra)2(ORa), —OSi(Ra)(ORa)2, —OSi(ORa)3, oxo, —N(Ra)2, —N═C(Ra)2, ═NRa, —NC, —NCO, —N3, —NO2, —NRaC(═O)Ra, —NRaC(═O)ORa, —NRaC(═O)N(Ra)2, —NRaS(═O)Ra, —NRaS(═O)ORa, —NRaS(═O)N(Ra)2, —NRaS(═O)2Ra, —NRaS(═O)2ORa, —NRaS(═O)2N(Ra)2, —SRa, —SCN, —S(═O)Ra, —S(═O)ORa, —S(═O)N(Ra)2, —S(═O)2Ra, —S(═O)2ORa, —S(═O)2N(Ra)2, —SeRa, halogen, —CN, —C(═NRa)Ra, —C(═NRa)ORa, —C(═NRa)N(Ra)2, —C(═O)Ra, —C(═O)ORa, —C(═O)SRa, —C(═S)ORa, or —C(═O)N(Ra)2;
- or the two instances of RH 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 Ra 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 Ra are joined to form substituted or unsubstituted heterocyclyl or substituted or unsubstituted heteroaryl;
- each instance of RS is independently hydrogen or —ORa;
- each instance of w is independently 0, 1, 2, 3, or 4;
- each instance of RT 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
18 more elements
A compound of Formula (B1):
- or a salt thereof;
- wherein:
- Y is O or C(RQ)2;
- each instance of RQ is independently hydrogen, halogen, or substituted or unsubstituted, C1-6 alkyl;
- each instance of RK is independently hydrogen, halogen, substituted or unsubstituted, C1-10 alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or —ORN;
- each instance of RN is independently hydrogen, substituted or unsubstituted acyl, substituted or unsubstituted, C1-10 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:
7 more elements
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(RP)2 or O;
- each instance of RP is independently hydrogen, halogen, or substituted or unsubstituted, C1-6 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(RQ)2;
- each instance of RQ is independently hydrogen, halogen, or substituted or unsubstituted, C1-6 alkyl;
- each instance of RK is independently hydrogen, halogen, substituted or unsubstituted, C1-10 alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or —ORN;
- each instance of RN is independently hydrogen, substituted or unsubstituted acyl, substituted or unsubstituted, C1-10 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.
19 more elements
Dependencies are inferred from the claim text.