Metallocene/methylaluminoxane-catalyzed copolymerizations of oxygen-functionalized long-chain olefins with ethylene

Abstract

Copolymerizations of ethylene with 10‐undecen‐1‐ol, 10‐undecenyl methyl ether, 10‐undecenyl trimethyl silyl ether, and 1‐undecene were performed with rac‐ethylene‐bis(1‐indenyl)zirconium dichloride as a catalyst and methylaluminoxane as a cocatalyst. All three oxygen‐functional comonomers copolymerized with ethylene, although the activity of the catalyst decreased considerably compared with the homopolymerization of ethylene. The conversions of the comonomers varied from 17 to 40%, depending on the amount of comonomer in the feed. Under the same conditions, the conversion of 1‐undecene was 50–75%. The incorporation (0.7–3.6 mol %, depending on the feed) and the effect on the activity of the catalyst were on the same level for all the functional comonomers, which indicates that trimethylsilyl or methyl groups do not act as effective protecting groups for oxygen atoms. According to NMR and Fourier transform infrared analyses, the final functional group in the copolymers of the trimethylsilyl ether comonomer was hydroxyl. In contrast, the methyl ether group remained untouched in the copolymer, which suggests that the formation of aluminum alkoxides via a reaction with a cocatalyst is not a prerequisite for comonomer incorporation. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1966–1971, 2000

Kinetic Studies of Metallocene‐Catalyzed Copolymerization of Propene with 10‐Undecene‐1‐ol Using In‐Line FTIR Spectroscopy

“…In the last years several groups have studied the copolymerization of olefins with different polar comonomers. [1,8,[13][14][15][16][17][18][19][20][21][22] Experimental Part Materials Toluene (Fluka, p.a.) was dried over sodium/ potassium and distilled prior to use.…”

Monitoring of chemical reactions during polymer synthesis by real‐time attenuated total reflection (ATR)–FTIR spectroscopy

“…This copolymerization is already described in numerous articles. [17][18][19][20] However, until recently, it was not possible to get information about the decrease of the comonomer concentration during the copolymerization. Therefore, to obtain samples of well controlled comonomer composition, the monomers should be copolymerized only to small conversions so as to minimize the error caused by conversion dependent changing comonomer/propene ratios.…”

Reactivity Comparison of ω-Alkenols and Higher 1-Alkenes in Copolymerization with Propylene Using An Isospecific Zirconocene-MMAO Catalyst

“…The copolymerization of ethylene with alkylaluminum-protected polar comonomer has been studied extensively for the synthesis of functionalized polyethylene bearing alcohol [7][8][9][10][11][12][13][14][15][16][17][18], ester [8,9,19,20], ether [10,21], and acid functionalities [8,9,11,17]. However, the copolymerization activity of almost all of these catalytic systems dropped significantly compared to the homopolymerization of ethylene.…”