Synergetic Effect of Monomer Functional Group Coordination in Catalytic Insertion Polymerization

Area of Science:

• Polymer Chemistry
• Organometallic Catalysis

Background:

• Copolymerization of functionalized dienes with butadiene is crucial for developing advanced materials.
• Stereoregular polymer synthesis requires precise control over monomer incorporation.
• Nickel-based catalysts offer potential for controlled polymerization.

Purpose of the Study:

• To investigate the efficient copolymerization of PhS- and PhNH-functionalized dienes with butadiene.
• To understand the influence of linker length on polymerization rates and comonomer incorporation.
• To elucidate the mechanism of enhanced comonomer binding and incorporation.

Main Methods:

• Copolymerization of functionalized dienes (PhS-x-BD, x=3-7) with butadiene using [(mesitylene)Ni(allyl)][BArF4] (Ni-1).
• Analysis of polymerization rates and comonomer incorporation ratios.
• Investigation of the role of functional group binding to the active catalytic site.

Main Results:

• Efficient synthesis of stereoregular copolymers was achieved.
• Polymerization rates and comonomer incorporation were highly dependent on the linker length.
• Specific linker lengths resulted in high comonomer reactivity ratios.
• Favorable binding of the functional group to the active site enhanced comonomer incorporation.

Conclusions:

• [(Mesitylene)Ni(allyl)][BArF4] (Ni-1) is an effective catalyst for stereoregular copolymerization.
• Linker length is a critical parameter for controlling comonomer incorporation in functionalized diene-butadiene copolymers.
• Functional group coordination to the nickel active site plays a key role in enhancing comonomer uptake.