Synthesis, Structure And Catalytic Performance Of Late Transition Metal Catalysts For Copolymerization Of Functional Cycloolefin

In this paper, eleven novel late transition metal catalyst nickel (II), palladium (II) and copper (II) complexes(Cl-Cll) were synthesized and characterized in detail. All these new complexes(Cl-Cll) can act as catalyst precursors on activation with B(C6Fs)3 or MAO for the homopolymerizafion as well as copolymerization of norbornene and functional norbornene, such as 5-norbornenene-2-carboxylic-methyl ester,2-heptoxymethylene norbornene (HN),2-butyloxymethylene norbornene (BN), and TPE-CH=CH2. The microstructures and properties of the obtained polymers have been characterized and tested by means of FT-IR、1H NMR、13C NMR、WAXD、TGA and GPC techniques.Pd(II) complexes with dichelate fluorinated β-ketonaphthyliminato ligand, {CF3C(O)CHC[N(naphthyl)]-CH3}2Pd (C1), as well as monochelate fluorinated β-ketonaphthyliminatoligand,{CF3C(O)CHC[N(naphthyl)]CH3}Pd(CH3)(PPh3)(C2), were synthesized and their solid-state structures were confirmed by X-ray crystallographic analysis. Pd(II) complexes were employed as precursors to catalyze norbornene(NB) homo-and copolymerization with ester-functionalized norbornene derivative by using B(C6F5)3 as a co-catalyst. High activity up to 2.3×10 gpolymr/molPd·hfor C1/B(C6F5)3 system and 3.4×106 gpolymer/molPd≮h for C2/B(C6F5)3 system in homo-polymerization of norbornene. Moreover, the Pd (II) complexes exhibited high level of tolerance toward the ester-functionalized norbornene monomer.In comparison with Cl/B(C6Fs)3 system, C2/B(C6Fs)3 system exhibited higher activity toward the copolymerization of norbornene with 5-norbornene-2-carboxylic acid methyl ester (NB-COOCH3), and the obtained soluble vinyl-addition type copolymers with relatively high molecular weights (MWs 3.6-7.5×104g/mol) as well as narrow molecular weight distributions (1.49-2.15) depending on the variation of monomer feed ratios. The NB-COOCH3 insertion ratio in all copolymers could be controlled range from 2.8 to 21.0 mol% by tuning a content of 10-50 mol%NB-COOCH3 in the monomer feed ratios. Copolymerization kinetics study were expressed by the NB and NB-COOCH3 monomers reactivity ratios, rNB-COOCH3=0-18, rNB-1-28 were determined for Cl/B(C6Fs)3 system, and rNB-COOSH3=0.19, rNB=3.57 for C2/B(C6F5)3 system by the Kelen-Tudos method.Well defined C-C bridged constrained geometry configuration (CGC) Ni (II) complexes (C3-C7) were synthesized by coordination reaction and in situ coupling reaction in the presence of (DME)NiBr2. First proposed the synthesis method of the CGC C-C bridged nickel complexes, which can be applied to other late transition metal catalysts synthesized. At the same time, this coupling method widened the construction of C-C bond in organic synthesis. On activation with B(C6Fs)3, the Ni-based complexes showed high catalytic activities for norbornene homo-polymerization, activities reach 10 gpolymer/molNi·h. The copolymerization of 2-heptoxymethylene norbornene (HN) with norbornene by the pre-catalysts C3 and C4 was also explored in the presence of B(C65s)3. High molecular weight polymers with unimodal molecular weight distributions were obtained, indicating that the nature of the polymerization was single site. The catalytic activity, co-monomer incorporation and the properties of the resultant polymers can be controlled over a wide range by tuning the catalyst structures and reaction parameters.The copolymerization of TPE-CH=CH2 with norbornene by C4/B(C6F5)3 was obtained vinyl-addition type copolymers with AIE performance, the catalytic activity can reach 1.07×105 gpolymer/molNi·h.The structure and properties of the polymer were characterized, and their fluorescence spectra properties were studied. The polymer has the good performance of Vinyl-type polymer as well as AIE property.Three-dimensional geometry a-diimine palladium(II) and copper(II) chloride complexes, bearing 9,10-dihydro-9,10-ethanoanthracene-11,12-diimine ligands, were synthesized and sufficiently characterized by elemental and spectroscopic analysis along with X-ray diffraction analysis. The parameters of reaction conditions, the type of metals and steric effects of coordinative ligands had influences on the catalytic properties. C9 was selected as catalyst precursor for the copolymerization of norbornene (NB) with 2-butyloxymethylene norbornene (BN), which exhibited catalytic activities up to 1.1×105 gpolymer/molPd·h and produced copolymers with relatively high molecular weights. The fraction of BN in copolymer could reach up to 9.8-62.1% by controlling monomer feed ratios from 10-80%. The achieved vinyl-addition type poly(NB-co-BN) copolymers displayed high thermal stability and were soluble in CHCl3 and THF common organic solvents.