环状单体与乙烯基单体的杂化共聚
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摘要
本文研究了在膦腈碱(t-BuP4)催化下各种环状单体和乙烯基单体的杂化共聚,发现己内酯、丙交酯或环碳酸酯与丙烯酸酯或甲基丙烯酸酯能够进行杂化共聚,但环硅氧烷与乙烯基单体、丙烯腈与内酯不能杂化共聚.研究表明,单体与活性中心的匹配决定了杂化共聚能否进行.
In this work, we report the hybrid copolymerization of various cyclic and vinyl monomers on the catalysis of t-BuP 4 . Our studies demonstrate that (1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino) phophorany- lidenamino]-2 5, 5-catenadi(phosphazene) (t-BuP 4 ) can catalyze the hybrid copolymerization of caprolactone (CL), lactide (LA) or cyclic carbonate ester with acrylate or methyl acrylate. However, the polymerization of cyclosiloxane with vinyl monomers yields the two corresponding homopolymers, and the polymerization of lactone with acrylonitrile (AN) produces only polyacrylonitrile. Clearly, the matching of activity between monomers and active center determines the hybrid copolymerization.
In this work, we report the hybrid copolymerization of various cyclic and vinyl monomers on the catalysis of t-BuP 4 . Our studies demonstrate that (1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino) phophorany- lidenamino]-2 5, 5-catenadi(phosphazene) (t-BuP 4 ) can catalyze the hybrid copolymerization of caprolactone (CL), lactide (LA) or cyclic carbonate ester with acrylate or methyl acrylate. However, the polymerization of cyclosiloxane with vinyl monomers yields the two corresponding homopolymers, and the polymerization of lactone with acrylonitrile (AN) produces only polyacrylonitrile. Clearly, the matching of activity between monomers and active center determines the hybrid copolymerization.
引文
1Yang HJ,Xu JB,Pispas S,Zhang GZ.Hybrid copolymerization ofε-caprolactone and methyl methacrylate.Macromolecules,2012,45:3312–3317
2Dove AP.Organic catalysis for ring-opening polymerization.ACS Macro Lett,2012,1:1409–1412
3Takiguchi T,Sakurai M,Kishi T,Ichimura J,Iizuka Y.Preparation of hexaphenylcyclotrisiloxane by the reaction of hexaphenyldichlorosilane with zinc oxide.J Org Chem,1960,25:310–311
4Matsuo J,Aoki K,Sanda F,Endo T.Substituent effect on the anionic equilibrium polymerization of six-membered cyclic carbonates.Macromolecules,1998,31:4432–4438
5Schmalz H,Lanzend rfer MG,Abetz V,Müller AHE.Anionic polymerization of ethylene oxide in the presence of the phosphazene base Bu t P4–kinetic investigations using in-situ FT-NIR spectroscopy and MALDI-TOF MS.Macromol Chem Phy,2003,204:1056–1071
6Schappacher M,Fur N,Guillaume SM.Poly(methyl methacrylate)-poly(caprolactone)AB and ABA block copolymers by combined ring-opening polymerization and atom transfer radical polymerization.Macromolecules,2007,40:8887–8896
7Rokicki G.Aliphatic cyclic carbonates and spiroorthocarbonates as monomers.Prog Polym Sci,2000,25:259–342
8Ajiro H,Takahashi Y,Akashi M.Thermosensitive biodegradable homopolymer of trimethylene carbonate derivative at body temperature.Macromolecules,2012,45:2668–2674
9Paulasaari JK,Weber WP.Synthesis of hyperbranched polysiloxanes by base-catalyzed proton-transfer polymerization.Comparison of hyperbranched polymer microstructure and properties to those of linear analogues prepared by cationic or anionic ring-opening polymerization.Macromolecules,2000,33:2005–2010
2Dove AP.Organic catalysis for ring-opening polymerization.ACS Macro Lett,2012,1:1409–1412
3Takiguchi T,Sakurai M,Kishi T,Ichimura J,Iizuka Y.Preparation of hexaphenylcyclotrisiloxane by the reaction of hexaphenyldichlorosilane with zinc oxide.J Org Chem,1960,25:310–311
4Matsuo J,Aoki K,Sanda F,Endo T.Substituent effect on the anionic equilibrium polymerization of six-membered cyclic carbonates.Macromolecules,1998,31:4432–4438
5Schmalz H,Lanzend rfer MG,Abetz V,Müller AHE.Anionic polymerization of ethylene oxide in the presence of the phosphazene base Bu t P4–kinetic investigations using in-situ FT-NIR spectroscopy and MALDI-TOF MS.Macromol Chem Phy,2003,204:1056–1071
6Schappacher M,Fur N,Guillaume SM.Poly(methyl methacrylate)-poly(caprolactone)AB and ABA block copolymers by combined ring-opening polymerization and atom transfer radical polymerization.Macromolecules,2007,40:8887–8896
7Rokicki G.Aliphatic cyclic carbonates and spiroorthocarbonates as monomers.Prog Polym Sci,2000,25:259–342
8Ajiro H,Takahashi Y,Akashi M.Thermosensitive biodegradable homopolymer of trimethylene carbonate derivative at body temperature.Macromolecules,2012,45:2668–2674
9Paulasaari JK,Weber WP.Synthesis of hyperbranched polysiloxanes by base-catalyzed proton-transfer polymerization.Comparison of hyperbranched polymer microstructure and properties to those of linear analogues prepared by cationic or anionic ring-opening polymerization.Macromolecules,2000,33:2005–2010