Synthesis of norbornene derivatives and their polymers via ROMP of norbornene derivatives

2020 ◽  
Vol 32 (6) ◽  
pp. 729-737
Author(s):  
Haoyang Yu ◽  
Shaohui Lin ◽  
Daniel Sun ◽  
Qinmin Pan

Dicyclopentadiene (DCPD) is a by-product resulting from the ethylene industry, which is high yield and underused in China. A technical route of producing valuable products—norbornene derivatives and their polymers from DCPD—was proposed and studied in this research. 5-Norbornene-2,3-dicarboxylic anhydride, a downstream product of DCPD, was employed as starting material to synthesize norbornene derivatives. Norbornene derivatives, 5-norbornene-2,3-dicarboxylic acid dimethyl ester and 5-norbornene-2,3-dicarboxylic acid diphenylethyl esters, as well as their polymers have broad application prospects in many areas. Ring-opening metathesis polymerization was employed as the polymerization process, and the polymers/copolymers of norbornene derivatives were obtained successfully. The polymerization process of norbornene derivatives was investigated in detail, from which the method for controlling molecular weights and decomposition temperatures of norbornene derivatives copolymers were developed. Till now, the route of generating valuable norbornene derivatives from DCPD was completed finally.

2021 ◽  
Author(s):  
Taichi Sotani ◽  
Toshiko Mizokuro ◽  
Tatsuo Yajima ◽  
Hiromitsu Sogawa ◽  
Fumio Sanda

Ring-opening metathesis polymerization (ROMP) of norbornene derivatives is useful for preparing thermally stable and transparent polymeric materials with good moldability. This study deals with ROMP of norbornene monomer 1 bearing...


2021 ◽  
Author(s):  
Janis V. Musso ◽  
Mathis Benedikter ◽  
Paul Gebel ◽  
Vincent Gramm ◽  
Dongren Wang ◽  
...  

Cationic W alkylidene N-heterocyclic carbene complexes allow for the stereospecific ring-opening metathesis polymerization of norbornenes with high trans-iso- and high cis-syndiospecificity, respectively.


2006 ◽  
Vol 78 (10) ◽  
pp. 1877-1887 ◽  
Author(s):  
Christian Manfred Frech ◽  
Olivier Blacque ◽  
Heinz Berke

The treatment of benzene solutions of the cations [Re(NO)2(PR3)2][BArF4] (R = Cy and R = iPr; [BArF4] = tetrakis{3,5-bis(trifluoromethyl)phenyl}borate) with phenyldiazomethane afforded the moderately stable cationic rhenium(I) benzylidene dinitrosyl bis(trialkyl) phosphine complexes as [BArF4]- salts in good yields. The cationic rhenium dinitrosyl bisphosphine complexes catalyze the ring-opening metathesis polymerization (ROMP) of highly strained nonfunctionalized cyclic olefins to give polymers with relatively high polydispersity indices, high molecular weights, and Z configurations of the double bonds in the polymer chain backbones of over 80 %. The benzylidene derivatives are almost inactive in ROMP catalysis with norbornene and in olefin metathesis. NMR experiments gave first hints for the initial formation of carbene complexes when [Re(NO)2(PR3)2][BArF4] was treated with norbornene. The carbene formation is initiated by an unique reaction sequence where the cleavage of the strained olefinic bond starts with phosphine migration forming a cyclic ylid carbene complex. The [2+2] addition of a norbornene molecule to the Re=C bond leads to the rhenacyclobutane complex, which is expected to be converted into an iminate complex by attack of the ylid function onto one of the NNO atoms followed by Wittig-type phosphine oxide elimination. The formation of phosphine oxide was confirmed by NMR spectroscopy. This species is thought to drive the ROMP metathesis with alternating rhenacyclobutane formations and cycloreversions. The proposed mechanism is supported by density functional theory (DFT) calculations.


Author(s):  
Olubummo Adekunle ◽  
Susanne Tanner ◽  
Wolfgang H Binder

We report on the block copolymerization of two structurally different norbornene monomers (±)-endo,exo-bicyclo[2.2.1]-hept-5-ene-2,3-dicarboxylic acid dimethylester (7), and (±)-endo,exo-bicyclo[2.2.1]-hept-5-ene-2,3-dicarboxylic acid bis(1-oxyl-2,2,6,6-tetramethyl-piperidin-4-yl) ester (9) using ruthenium based Grubbs’ type initiators [(PCy3)2Cl2Ru(benzylidene)] G1 (PCy3 = tricyclohexylphosphine), [(H2IMes)(PCy3)Cl2Ru(benzylidene)] G2 (H2IMes = 1,3-bis(mesityl)-2-imidazolidinylidene), [(H2IMes)(py)2Cl2Ru(benzylidene)] G3 (py = pyridine or 3-bromopyridine) and Umicore type initiators [(PCy3)2Cl2Ru(3-phenylinden-1-ylidene)] U1 (PCy3 = tricyclohexylphosphine), [(H2IMes)(PCy3)Cl2Ru(3-phenylinden-1-ylidene)] U2 (H2IMes = 1,3-bis(mesityl)-2-imidazolidinylidene), [(H2IMes)(py)Cl2Ru(3-phenylinden-1-ylidene)] U3 (py = pyridine or 3-bromopyridine) via ring opening polymerization (ROMP). The crossover reaction and the polymerization kinetics were investigated using matrix assisted laser desorption ionization mass spectroscopy (MALDI-TOF) and nuclear magnetic resonance (NMR), respectively. MALDI showed that there was a complete crossover reaction after the addition of 25 equivalents of the second monomer. NMR investigation showed that U3 gave a faster rate of polymerization in comparison to U1. The synthesis of block copolymers with molecular weights up to M n = 31 000 g/mol with low polydispersities (M w/M n = 1.2) is reported.


2001 ◽  
Vol 704 ◽  
Author(s):  
James H. Wynne ◽  
Christopher T. Lloyd ◽  
Steven E. Bullock ◽  
Robert F. Cozzens

AbstractWe report the synthesis of a series of highly functional metal chelated silyl- and tert-butyl-protected 2, 3-diaminomethyl norbornene derivatives. Subsequent alterations to the previously synthesized norbornene adducts afford many other derivatives containing such functionalities as alkyl, cyano, esters, and ethers. These derivatives are then subjected to ring-opening metathesis polymerization (ROMP) employing a ruthenium homogeneous catalyst to afford phase separated block polymers. The block polymers formed serve as unique templates for the formation of size controlled metal nanoclusters having a narrow dispersion. These metal nanoclusters containing diblock polymers are evaluated as unique electrical and optical materials.


2018 ◽  
Vol 9 (42) ◽  
pp. 5179-5189 ◽  
Author(s):  
Chang-Geun Chae ◽  
Yong-Guen Yu ◽  
Ho-Bin Seo ◽  
Myung-Jin Kim ◽  
Mallela Y. L. N. Kishore ◽  
...  

Rod-like POSS-containing polynorbornenes with high molecular weights were synthesized using ROMP with molecular and kinetic control.


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