Synthesis of Recyclable Tire Additives via Equilibrium Ring-Opening Metathesis Polymerization

Linear trans-polypentenamers are highly desired materials among synthetic tire additives due to their comparable physical properties to natural rubber. trans-Polypentenamer can be prepared by equilibrium ring-opening metathesis polymerization (ROMP) using well-defined ruthenium catalyst systems. This unique feature of the equilibrium polymerization reaction opens a way for the synthesis of durable, environmentally benign elastomers where polymers including synthetic tire additives can be synthesized and readily recycled using the same transition metal catalyst system. The addition of silica fillers significantly improves the physical properties of the composite materials in comparison to the use of polymeric material. It is also known that the structural effects and the polymer–filler surface interaction are of prime importance. Herein, we report on the synthesis of silica filler compatible recyclable polypentenamer copolymers via equilibrium ROMP of cyclopentene 1 and 4-(triethoxy)siloxy cyclopentene 11....

[1]  Jean L. Leblanc,et al.  Rubber–filler interactions and rheological properties in filled compounds , 2002 .

[2]  J. Gillham,et al.  Thermomechanical behavior of uncrosslinked 1,5-polypentenamers , 1974 .

[3]  D. Richter,et al.  Filled elastomers: polymer chain and filler characterization by a SANS–SAXS approach , 2002 .

[4]  R. Grubbs,et al.  Synthesis of Well-Defined Poly((vinyl alcohol)2-alt-methylene) via Ring-Opening Metathesis Polymerization , 2002 .

[5]  A. J. Amass,et al.  Anionic graft copolymerization of ethylene-propylene terpolymers , 1972 .

[6]  K. Sanui,et al.  Hydroformylation of a Polypentenamer and Preparation of Derivatives Therefrom , 1974 .

[7]  V. Kranz,et al.  Polymerisationsenthalpie der ringöffnenden polymerisation von cyclopenten (CPE) zu trans‐polypentenamer (TPR) , 1972 .

[8]  M. Teodorescu,et al.  Ring-opening polymerization of cycloolefin induced by tungsten porphyrinates , 1994 .

[9]  G. Black,et al.  Living Ring‐Opening Olefin Metathesis Polymerization , 2008 .

[10]  A. Medalia.  Carbon black. Physics, chemistry and elastomer reinforcement , 1977 .

[11]  R. Grubbs,et al.  Ruthenium catalyzed equilibrium ring-opening metathesis polymerization of cyclopentene , 2013 .

[12]  J. P. Harrity,et al.  A Recyclable Ru-Based Metathesis Catalyst , 1999 .

[13]  Hassan S. Bazzi,et al.  Synthesis of Polypentenamer and Poly(Vinyl Alcohol) with a Phase‐Separable Polyisobutylene‐Supported Second‐Generation Hoveyda–Grubbs Catalyst , 2016 .

[14]  G. Bazan,et al.  Evaluation of cyclopentene-based chain-transfer agents for living ring-opening metathesis polymerization , 1989 .

[15]  Bielawski,et al.  Highly Efficient Ring-Opening Metathesis Polymerization (ROMP) Using New Ruthenium Catalysts Containing N-Heterocyclic Carbene Ligands C.B. is grateful to the National Science Foundation for a pre-doctoral fellowship. The authors thank Dr. Matthias Scholl for providing catalysts 4 a and 4 c. , 2000, Angewandte Chemie.

[16]  R. Grubbs.  Living Ring-Opening Olefin Metathesis Polymerization , 2012 .

[17]  G. Natta,et al.  Stereospecific Homopolymerization of Cyclopentene , 1964 .

[18]  M. B. Bever,et al.  Concise encyclopedia of composite materials , 1989 .

[19]  E. A. Ofstead,et al.  Equilibrium ring‐opening polymerization of mono‐ and multicyclic unsaturated monomers , 1972 .

[20]  L. Bronstein,et al.  Nanostructured Inorganic−Organic Composites as a Basis for Solid Polymer Electrolytes with Enhanced Properties , 2001 .

[21]  Lionel Delaude,et al.  Synthesis and evaluation of new RuCl2(p-cymene)(ER2R′) and (η1:η6-phosphinoarene)RuCl2 complexes as ring-opening metathesis polymerization catalysts , 2000 .

[22]  Hassan S. Bazzi,et al.  One-Pot Synthesis of Poly(vinyl alcohol) (PVA) Copolymers via Ruthenium Catalyzed Equilibrium Ring-Opening Metathesis Polymerization of Hydroxyl Functionalized Cyclopentene , 2014 .

[23]  R. Grubbs,et al.  Synthesis and activity of a new generation of ruthenium-based olefin metathesis catalysts coordinated with 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene ligands. , 1999, Organic letters.

[24]  R. Register,et al.  Synthesis of narrow-distribution polycyclopentene using a ruthenium ring-opening metathesis initiator , 2008 .

[25]  J. Donnet,et al.  Reinforcement of Elastomers by Silica , 1977 .

[26]  Robert H. Grubbs,et al.  A Versatile Precursor for the Synthesis of New Ruthenium Olefin Metathesis Catalysts , 2001 .

[27]  H. Tucker,et al.  Structure and properties of polypentenamer , 1975 .