• Bulletin of the Korean Chemical Society
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• v.27 no.4
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• pp.475-476
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• 2006

• Applied Chemistry for Engineering
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• v.27 no.3
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• pp.313-318
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• 2016

In this study, an amorphous silica was functionalized with aminosilane, N-[(3-trimethoxysilyl)propyl]ethylenediamine (2NS) and the late transition metal catalysts including ($(DME)NiBr_2$ and $PdCl_2$(COD)) were subsequently immobilized on the functionalized amorphous silica for norbornene polymerization. Effects of the polymerization temperature, polymerization time, Al/Ni molar ratio, and type of co-catalyst on norbornene polymerization were investigated. Unsupported late transition metal catalysts did not show any activities for norbornene polymerization. However, the $SiO_2$/2NS/Ni catayst with MAO system, with increasing polymerization temperature, increased the polymerization activity and decreased the molecular weight of the polynorbornene (PNB). Furthermore, the catalyst when increasing polymerization temperature caused the decrease in both the polymerization activity and molecular weight of PNB. This confirmed that the stability of $SiO_2$/2NS/Ni at a high temperature was greater than that of $SiO_2$/2NS/Pd. Also the longer polymerization time resulted in the higher conversion of norbornene for both catalysts. When the Al : Ni molar ratio was 1000 : 1, the highest activity (15.3 kg-PNB/($({\mu}mol-Ni^*hr$)) but lowest molecular weight ($M_n$ = 124,000 g/mol) of PNB were achieved. Also $SiO_2$/2NS/Ni catalyst with borate/TEAL resulted in diminishing the polymerization activity and molecular weight of PNB with increasing the polymerization temperature.

• Bulletin of the Korean Chemical Society
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• v.27 no.7
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• pp.1031-1037
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• 2006

New nickel complexes containing novel tetradentate ligands, 4,5-substituted-1,2-bis(pyridine-2-carboxamide)-benzene ligands but lacking alkyl or halide ligands in the coordination sphere have been prepared. They were activated with MMAO (modified methylaluminoxane) to be proven as efficient catalysts for the polymerization of norbornene. Both electron-donating and -withdrawing substituents on the benzene ring and polar solvents enhance the catalytic activity for olefin polymerization. Improvement in thermal stability of the complexes was observed. Some of these complexes were crystallographically determined to have square planar geometry. A plausible mechanism involving dissociation of ligands is proposed.

• Polymer(Korea)
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• v.39 no.3
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• pp.487-492
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• 2015

The effects of chemical structure of alkyl groups of norbornene carboxylic alkyl esters(methyl, octyl, 4-chlorobenzyl) and endo/exo ratios of norbornene monomers on activity of palladium catalyst and polymerization behavior were investigated. Norbornene ester monomers were synthesized from the reaction of 5-norborene-2-carboxylic acid and various alcohols. Polymerization catalyst, di-${\mu}$-chloro-bis(-methoxybicyclo[2,2,1]-hept-2-ene)palladium(II) (DCBMP), was synthesized according to the literature procedure and silver hexafluoroantimonate ($AgSbF_6$) was used as a conjugate anion source. Gel permeation chromatography (GPC), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) were the principal techniques for polymer characterization and $^1H$ NMR spectroscopy was used for chemical structures determination of monomers and polymers. For all of the norbonene alkyl esters GPC data showed that when the amounts of endo isomers exceeded those of exo isomers decreased molecular weight polymers were obtained probably due to the decreased catalyst activity. Polymerizations were conducted by varying the monomer/catalyst mole ratios (100:1, 200:1, 300:1). When 300:1 monomer/catalyst ratio was employed it was possible to synthesize high molecular weight ($M_n=27500g/mol$), film forming polymer from exo-norbornene carboxylic acid octyl ester.

• Bulletin of the Korean Chemical Society
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• v.34 no.9
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• pp.2720-2724
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• 2013

Polynorbornenes prepared by vinyl addition pathway are known to have some desirable characteristics for wider application but they have some critical drawbacks such as brittleness, poor solubility and adhesion. In order to improve these drawbacks, extensive research for the successful homo- and copolymerization of polar functionalized norbornene with olefin has been carried out. Even though considerable advance has been achieved in the polymerization of polar functionalized monomers, successful catalytic systems for the homopolymerization of polar functionalized norbornene are rare. In this study, a novel successful catalytic system for the polymerization of polar functionalized norborene is proposed. This system employs Pd ${\beta}$-diketiminate/borate cocatalyst in water/organic mixed solvents and it is unique due to introduction of water as a component of solvents. Polymers obtained in this study show high Mw with narrow PDI. Effects of several reaction parameters to the polymer activity and properties are investigated and optimal catalytic system are proposed.

• Bulletin of the Korean Chemical Society
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• v.32 no.6
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• pp.1884-1890
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• 2011

A series of Ni(II) and Pd(II) complexes bearing N4-type tetradentate ligands, [Ni($X^1X^2$-6-$Me_2bpb$) 1] and [Pd($X^1X^2$-6-$Me_2bpb$) 2]; 6-$Me_2bpb$ = N,N'-(o-phenylene)bis(6-methylpyridine-2-carboxamidate), $X^1$ = Cl, H, or $CH_3$, $X^2$ = $NO_2$, Cl, F, H, $CH_3$, or $OCH_3$) were designed, synthesized, and characterized to investigate electronic and steric effects of ligand on the norbornene polymerization catalysts. Using modified methylaluminoxanes as an activator, the complexes exhibited high catalytic activities for the polymerization of norbornene and the nickel complexes exhibited better catalytic activity the palladium complexes. Ni complex 1a with $NO_2$ group on the benzene ring showed the highest catalytic activity of $4.9{\times}10^6$ g of PNBEs/$mol_{Ni}{\cdot}h$ and molecular weight of $15.28{\times}10^5$ g/mol with PDI < 2.30. Complexes with electron-withdrawing groups are more thermally stable (> 100 $^{\circ}C$), and tend to afford higher polymerization productivities than the ones having electron-donating groups. Amorphous polynorbornenes were obtained with good solubility in halogenated aromatic solvents. A vinyl addition mechanism has been proposed for the catalytic polymerization.

• Bulletin of the Korean Chemical Society
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• v.30 no.3
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• pp.636-646
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• 2009

A series of the noble palladium complexes containing $\beta$-ketoiminate ligands with internal bases, [Pd(${\eta}^3$-allyl)($\beta$- ketoiminate)], [Pd(Me)($PPh_3$)($\beta$-ketoiminate)] and [Pd(Me)($\beta$-ketoiminate)], have been successfully prepared. Crystallographically determined structures showed that these complexes are distorted square planar and pendant bases of the $\beta$-ketoiminate ligands fail to coordinate to the metal in the first two classes of complexes while bases do coordinate in the 3rd class complexes. These complexes are active towards norbornene polymerization on activation with $H(OEt_2)_2BAr^'_4$ (Ar' = 3,5-bistrifluoromethylphenyl) and modified methylalumioxane (MMAO). MMAO is more efficient for the activation for polymerization. Generally, the polymerization activity increases with the following order; [Pd(allyl)($\beta$-ketoiminate)] < [Pd(Me)($PPh_3$)($\beta$-ketoiminate)] < [Pd(Me)($\beta$-ketoiminate)].

• Bulletin of the Korean Chemical Society
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• v.32 no.spc8
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• pp.3074-3080
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• 2011

We synthesized three novel poly(norbornene bisimide)s by ring opening metathesis polymerization (ROMP) and subsequent hydrogenation. Their thermal, mechanical and optical properties were investigated with TGA, DMA, UV-Vis spectrometer, and optical reflectometer. The new polymers showed high glass transition temperatures over $260^{\circ}C$ and good thermal stability with 5% wt-loss temperature higher than $390^{\circ}C$. When solvent casted, they yielded optically transparent and dimensionally stable films with a relatively low coefficient of thermal expansion of about 50 ppm $K^{-1}$. Therefore, the bisimide moieties substantially enhanced thermal and dimensional stabilities, as compared with normal ROMP-prepared polynorbornene films. Though the water uptake was increased to 0.6 wt-%, this water uptake is still considerably lower than that for polyethersulfones (1.4 wt-%) or polyimides (2.0 wt-%). Hence, the new poly(norbornene bisimide)s may become attractive candidates for flexible substrates of optoelectronic devices such as displays and photovoltaic solar cells.

• Polymer(Korea)
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• v.28 no.3
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• pp.245-252
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• 2004

We synthesized the vinyl addition-type polynorbomene copolymers using two monomers [5-hexyl-2-norbornene (HNB) and 5-methyleste-2-norbornene(MES-NB)] by means of a cationic ${\eta}^3$-allyl palladium catalyst system{[(${\eta}^3$-allyl)palladium(tricyclohexylphosphine) trifluoroacetate] and [lithium tetrakis(pentafluorophenyl) borate ${\cdot}$2.5 etherate]}. The molecular weights and yields of copolynorbomenes polymerized in various conditions were measured to investigate an optimum polymerization conditions to obtain highly ester-functionalized polynorbomenes. As a Pd catalyst content increased, the molecular weights (Mw) of polymers decreased while polymer yields increased. Also, as a Li cocatalyst content increased, the Mw’s and yields of polymers increased at the same time. The Mw’s of copolymers were also controlled by chain transfer agents such as 1-hexone, 1-octene and 1-decene, and we found that longer 1-decene and 1-octene were more efficient to reduce the Mw’s of polynorbornenes than 1-hexene. On the other hand, the content of chain transfer agents did not give influence significantly on polymer yields. From the $^1$H-NMR and GPC analysis of HNB/MES-NB(feed ratio of 40/60 mol%) copolymer, we found that this copolymer had an about 25 mol% of ester portion and a high molecular weight of 270,000.

• Macromolecular Research
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• v.14 no.4
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• pp.424-429
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• 2006

The synthesis of a series of poly(POSS-NBE-b-MTD) copolymers was successfully accomplished, taking advantage of sequential, ring-opening, metathesis block copolymerization using $RuCl_2(=CHPh)(PCy_3)_2$ catalyst. By using cyclopentyl-POSS-norbornene (POSS-NBE) monomer as the first block in the block copolymer, living poly(POSS-NBE) with controlled molecular weight and narrow molecular weight distribution was produced. Then, poly(POSS-NBE-b-MTD) copolymers were successfully prepared, in which sequential monomer addition of methyltetracyclododecene (MTD) to the living poly(POSS-NBE) chain ends was utilized to achieve quantitative crossover efficiency. Characterization by $^1H$ NMR spectroscopy and GPC confirmed the high definition and structural integrity of the poly(PO$S-NBE-b-MTD) copolymers. Thermal properties-and morphologies of the POSS-containing block copolymer nanocomposites were also investigated by using thermogravimetric analysis (TGA), transmission electron microscopy (TEM), and wide-angle X-ray scattering (WAXS).