Efficient method of synthesizing linear oligomers and application to frontal ring-opening metathesis polymerization

A method for preparing chain-terminated oligomers, comprising:

• adding an amount of a phosphite ester and an amount of a catalyst to an amount of a functionalized cycloalkene and an amount of a chain transfer agent to provide a mixture;
• and
• heating the mixture to produce the chain-terminated oligomers as a majority product;
• wherein the chain transfer agent is a monosubstituted olefin;
• wherein a degree of polymerization of the oligomers is controlled by a molar ratio of the amount of the functionalized cycloalkene to the amount of the chain transfer agent,
• wherein the oligomers comprise an oligomer of formula (I):
• wherein R is a straight-chain, branched, or cyclic (C1-C20)alkyl group, or an aryl, heteroaryl, or heterocyclic group, optionally substituted with a boronate ester group, a hydroxy group, an epoxy group, an ester group, or an amide group;
• wherein each R1 is independently hydrogen, a straight-chain, branched, or cyclic (C1-C20)alkyl group or (C1-C20)alkenyl group;
• wherein represents an optional double bond, provided that when a double bond is present, the R1 at one end of the double bond is not hydrogen;
• and
• wherein one or both R1 groups of one monomer of the oligomer of formula (I) are the same or different than one or both R1 groups of an adjacent monomer.

A method of preparing chain-terminated oligomers of formula (Ia), comprising:

• adding an amount of a phosphite ester of formula P(OR3)3 and an amount of a catalyst to an amount of dicyclopentadiene and an amount of a chain transfer agent to provide a mixture;
• and
• heating the mixture to produce the chain-terminated oligomers of formula (Ia) as a majority product;
• wherein R is a straight-chain, branched, or cyclic (C1-C20)alkyl group, or an aryl, heteroaryl, or heterocyclic group, optionally substituted with a boronate ester group, a hydroxy group, an epoxy group, an ester group, or an amide group;
• wherein R3 are all simultaneously or each independently methyl, ethyl, n-butyl, tert-butyl, or phenyl;
• wherein the chain transfer agent is a monosubstituted olefin of formula (II):
• wherein R2 is a straight-chain, branched, or cyclic (C1-C20)alkyl group or (C1-C20)alkoxy group, or an aryl, heteroaryl, or heterocyclic group, the (C1-C20)alkyl group, (C1-C20)alkoxy group, aryl, heteroaryl, or heterocyclic group optionally substituted with a halogen atom, a hydroxy group, a boronate ester group, an epoxy group, an ester group, or an amide group;
• and
• wherein a degree of polymerization of the chain-terminated oligomers of formula (Ia) is controlled by a molar ratio of the amount of dicyclopentadiene to the amount of the chain transfer agent.

A composition, comprising dicyclopentadiene and oligomers of formula (I):

• wherein the oligomers of formula (I) are in an amount of from about 20 weight % to about 80 weight % based on a combined 100 weight % of the oligomers of formula (I) and the dicyclopentadiene;
• wherein a number-average degree of polymerization of the oligomers of formula (I) is from 3 to 30;
• wherein R is a straight-chain, branched, or cyclic (C1-C20)alkyl group, or an aryl, heteroaryl, or heterocyclic group, optionally substituted with a boronate ester group, a hydroxy group, an epoxy group, an ester group, or an amide group;
• wherein each R1 may independently be hydrogen, a straight-chain, branched, or cyclic (C1-C20)alkyl group or (C1-C20)alkenyl group;
• wherein represents an optional double bond, provided that when a double bond is present, the R1 at one end of the double bond is not hydrogen;
• and
• wherein one or both R1 groups of one monomer of the oligomers of formula (I) are the same as, or different than, one or both R1 groups of an adjacent monomer.