Related Experiment Video
Updated: Jun 25, 2026
08:12
Depolymerizable Olefinic Polymers Based on Fused-Ring Cyclooctene Monomers
Published on: December 16, 2022
Synthesis of copolymers by alternating ROMP (AROMP)
Airong Song1, Kathlyn A Parker, Nicole S Sampson
1Department of Chemistry, Stony Brook University, Stony Brook, New York 11794-3400, USA.
Journal of the American Chemical Society
|March 12, 2009
Summary
Researchers achieved alternating polymerization of cyclobutene esters and cyclohexene derivatives using a ruthenium precatalyst. This method yields heteropolymers with controlled alternating backbones and functionalities, offering a new route for polymer synthesis.
Area of Science:
- Polymer Chemistry
- Organometallic Chemistry
- Materials Science
Background:
- Controlled synthesis of polymers with alternating structures is crucial for advanced materials.
- Ring-opening metathesis polymerization (ROMP) offers versatile routes to complex polymer architectures.
- Developing efficient catalysts for selective alternating copolymerization remains a challenge.
Purpose of the Study:
- To describe the alternating polymerization of cyclobutene 1-carboxylic esters and cyclohexene derivatives.
- To introduce a specific ruthenium precatalyst for this transformation.
- To demonstrate the synthesis of (AB)(n) heteropolymers with alternating backbones and functionalities.
Main Methods:
- Utilizing a ruthenium carbene precatalyst, specifically [(H(2)IMes)(3-Br-pyr)(2)Cl(2)Ru=CHPh].
- Employing cyclobutene 1-carboxylic esters and cyclohexene derivatives as monomers.
- Investigating the reaction conditions to achieve alternating copolymerization.
Main Results:
- The reaction is synthetically accessible and proceeds with high efficiency.
- The process yields (AB)(n) heteropolymers with a precisely alternating backbone structure.
- Alternating functionality is achieved due to monomer-specific polymerization behavior.
Conclusions:
- The described method provides a reliable route to synthesize well-defined alternating heteropolymers.
- Regiocontrol is achieved through the inherent inability of monomers to homopolymerize and favorable cross-polymerization kinetics.
- This advancement expands the toolkit for creating functional polymers with tailored properties.
Related Concept Videos
01:16Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)
Ring-opening metathesis polymerization or ROMP involves strained cycloalkenes as starting materials. The mechanism of ROMP proceeds by reacting cycloalkene with Grubbs catalyst to give metallacyclobutane intermediate which undergoes a ring-opening reaction to form new carbene. The new carbene reacts with another molecule of cycloalkene. Repetition of these steps leads to the formation of an unsaturated open-chain polymer product. All these steps are reversible, however, relieving the ring...
01:24Characteristics and Nomenclature of Copolymers
Copolymers are the products obtained from the polymerization of multiple monomer species. So, in a polymer chain itself, there can be multiple repeating units that come from different monomers. The process of synthesizing a polymer from different monomer species is called copolymerization. When two monomers are involved, the polymer is known as a bipolymer. Polymers with three and four monomers are termed terpolymers and quaterpolymers, respectively. Figure 1 depicts the copolymerization of...
01:13Olefin Metathesis Polymerization: Overview
Recently, the development of olefin metathesis polymerization advanced the field of polymer synthesis. Simply put, the reorganization of substituents on their double bonds between two olefins in the presence of a catalyst is known as the olefin metathesis reaction. The use of metathesis reaction for polymer synthesis is called olefin metathesis polymerization.
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists of a...
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists of a...
01:03Step-Growth Polymerization: Overview
Step-growth or condensation polymerization is a stepwise reaction of bi or multifunctional monomers to form long-chain polymers. As all the monomers are reactive, most of the monomers are consumed at the early stages of the reaction to form small chains of reactive oligomers, which then combine to form long polymer chains in the late stages. Hence, the reaction has to proceed for a long time to achieve high molecular weight polymers.
Many natural and synthetic polymers are produced by...
Many natural and synthetic polymers are produced by...
02:34Polymers
The word polymer is derived from the Greek words “poly” which means “many” and “mer” which means “parts”. Polymers are long chains of molecules composed of repeating units of smaller molecules, known as monomers. They either occur naturally, such as DNA and proteins, or can be constructed synthetically, like plastics. They have varied structural characteristics, such as linear chains, branched chains, or complex networks, that contribute to the properties that they exhibit. Additionally,...
02:34Polymers
The word polymer is derived from the Greek words “poly” which means “many” and “mer” which means “parts”. Polymers are long chains of molecules composed of repeating units of smaller molecules, known as monomers. They either occur naturally, such as DNA and proteins, or can be constructed synthetically, like plastics. They have varied structural characteristics, such as linear chains, branched chains, or complex networks, that contribute to the properties that they exhibit. Additionally,...