FANG Jianghua, HU Minjie, ZHOU Guoquan, YANG Jianping, GAO Haoqi. COPOLYMERIZATION OF NORBORNENE AND METHYL ACRYLATE CATALYZED BY
Fe(acac)3-Al(i-Bu)3. [J]. Acta Polymerica Sinica (6):631-634(2008)
DOI:
FANG Jianghua, HU Minjie, ZHOU Guoquan, YANG Jianping, GAO Haoqi. COPOLYMERIZATION OF NORBORNENE AND METHYL ACRYLATE CATALYZED BY
Fe(acac)3-Al(i-Bu)3. [J]. Acta Polymerica Sinica (6):631-634(2008) DOI: 10.3724/SP.J.1105.2008.00631.
COPOLYMERIZATION OF NORBORNENE AND METHYL ACRYLATE CATALYZED BY
Fe(acac)3-Al(i-Bu)3
The copolymerization of norbornene (NB) with methyl acrylate (MA) in the presence of iron (Ⅲ) acetylacetonate [Fe(acac)3] associated with a triisobutylaluminum [Al(i-Bu)3] catalyst system was investigated.The polymerization was carried out under dry nitrogen in toluene in a glass flask equipped with a rubber septum.For preparing the catalyst system Fe(acac)3 was first dissolved in the reaction solvent
and Al(i-Bu)3 was then added. The monomers were first dissolved in the reaction solvent
and the catalyst was introduced to initiate the polymerization. After a given reaction time
the polymerization mixture was poured into a large amount of methanol containing a few percent of hydrochloric acid to precipitate the polymer. The liquid phase was filtered
and the recovered polymer was dried in vacuo. The characteristics of copolymerization of norbornene and methyl acrylate by Fe(acac)3- Al(i-Bu)3 were studied. T he copolymers were characterized by FTIR
13C-NMR
GPC and elementary analysis. Copolymers with NB content of 12.3 mol%
19.5 mol% and 26.0 mol%
respectively were prepared. The molecular weight of the copolymers was in the range of 0.52×10.5~1.05×10.5
and its distribution index Mw/Mn was in the range of 2.25~2.67. They both decreased with increasing the molar ratio of NB/MA. The copolymerization can be performed in the solvents such as aromatic hydrocarbons. The third composition could exert influence on the copolymerization. The yield of copolymers with a third composition like carbon tetrachloride or 1
4-dioxane and triphenylphosphine was higher than that of copolymers without the third composition. However
the addition of 1
10-phenanthroline or 8-hydroxy quinoline and α
α′-dipyridine decreased the yield. The copolymerization could be obtained at room temperatures
however
increasing reaction temperature caused an increase of the copolymer yield. The yield of copolymer was also changed with the change of Al/Fe molar ratio
and the suitable Al/Fe molar ratio was 25. The copolymer can form porous membrane on cover glass automatically with pore size of 7~15 μm during evaporation of THF from the copolymer solution at room temperature.