Effect of ligand spacer on silica gel supported atom transfer radical polymerization of methyl methacrylate

被引:75
作者
Shen, YQ [1 ]
Zhu, SP [1 ]
Pelton, R [1 ]
机构
[1] McMaster Univ, Dept Chem Engn, Hamilton, ON L8S 4L7, Canada
关键词
D O I
10.1021/ma001699w
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
Silica gels grafted with tetraethyldiethylenetriamine (TEDETA) and di(2-picolyl)amine (DiPA) via poly(ethylene glycol) (PEG) spacers of different chain lengths were synthesized and used as CuBr support for the atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA). The spacer length strongly affected the polymerization rate and polymer molecular weight control. Catalyzed by CuBr immobilized on the silica gel, the MMA polymerization rate increased with spacer length in the order of PEG(1) < PEG(10) < PEG(3) (the subscript is the number of the EG units). Copper bromide supported via three-unit PEG (SG-PEG(3)-TEDETA and SG-PEG(3)-DiPA) controlled the MMA polymerization best, producing PMMA with controlled molecular weights (initiator efficiency ca. 75%) and low polydispersities (M-w/M-n similar to 1.2-1.4). The recycled catalysts had activities similar to the fresh ones at the late stage of polymerization with improved initiator efficiencies. The PMMA-block-poly(2-(NN-dimethylamino)ethyl methacrylate) with well-controlled molecular weight and low polydispersity was also synthesized by this support system.
引用
收藏
页码:5812 / 5818
页数:7
相关论文
共 36 条
[1]   Copper(I) mediated living radical polymerisation in an ionic liquid [J].
Carmichael, AJ ;
Haddleton, DM ;
Bon, SAF ;
Seddon, KR .
CHEMICAL COMMUNICATIONS, 2000, (14) :1237-1238
[2]   Controlled radical polymerization of methacrylic monomers in the presence of a bis(ortho-chelated) arylnickel(II) complex and different activated alkyl halides [J].
Granel, C ;
Dubois, P ;
Jerome, R ;
Teyssie, P .
MACROMOLECULES, 1996, 29 (27) :8576-8582
[3]   Atom transfer radical polymerization of methyl methacrylate initiated by alkyl bromide and 2-pyridinecarbaldehyde imine copper(I) complexes [J].
Haddleton, DM ;
Jasieczek, CB ;
Hannon, MJ ;
Shooter, AJ .
MACROMOLECULES, 1997, 30 (07) :2190-2193
[4]   Atom transfer polymerisation of methyl methacrylate mediated by solid supported copper catalysts [J].
Haddleton, DM ;
Kukulj, D ;
Radigue, AP .
CHEMICAL COMMUNICATIONS, 1999, (01) :99-100
[5]   3-aminopropyl silica supported living radical polymerization of methyl methacrylate: Dichlorotris(triphenylphosphine)ruthenium(II) mediated atom transfer polymerization [J].
Haddleton, DM ;
Duncalf, DJ ;
Kukulj, D ;
Radigue, AP .
MACROMOLECULES, 1999, 32 (15) :4769-4775
[6]   Monohydroxy terminally functionalised poly(methyl methacrylate) from atom transfer radical polymerisation [J].
Haddleton, DM ;
Waterson, C ;
Derrick, PJ ;
Jasieczek, CB ;
Shooter, AJ .
CHEMICAL COMMUNICATIONS, 1997, (07) :683-684
[7]   Copper(I)-mediated living radical polymerization under fluorous biphasic conditions [J].
Haddleton, DM ;
Jackson, SG ;
Bon, SAF .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (07) :1542-1543
[8]   Copper(I) bromide/N-(n-octyl)-2-pyridylmethanimine-mediated living-radical polymerization of methyl methacrylate using carbosilane dendritic initiators [J].
Hovestad, NJ ;
van Koten, G ;
Bon, SAF ;
Haddleton, DM .
MACROMOLECULES, 2000, 33 (11) :4048-4052
[9]   Controlled synthesis of polymer brushes by "Living" free radical polymerization techniques [J].
Husseman, M ;
Malmström, EE ;
McNamara, M ;
Mate, M ;
Mecerreyes, D ;
Benoit, DG ;
Hedrick, JL ;
Mansky, P ;
Huang, E ;
Russell, TP ;
Hawker, CJ .
MACROMOLECULES, 1999, 32 (05) :1424-1431
[10]   The effect of molecular architecture on the thermotropic behavior of poly[11-(4′-cyanophenyl-4"-phenoxy)undecyl acrylate] and its relation to polydispersity [J].
Kasko, AM ;
Heintz, AM ;
Pugh, C .
MACROMOLECULES, 1998, 31 (02) :256-271