Synthesis and characterization of the novel block copolymer poly(ε‐caprolactone)‐<i>b</i>‐poly(4‐vinyl pyridine) by the combination of coordination and controlled free‐radical polymerizations

Li, Zhongyu; Lu, Gang; Huang, Junlian

doi:10.1002/app.20999

Cited by 11 publications

(26 citation statements)

References 19 publications

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“…However, it was supposed that some unreacted Ti(OPr) 4 and excess HO-TEMPO still remained in the mixture.…”

Section: Synthesis Of Ti(o-tempo)mentioning

confidence: 98%

“…4-Hydroxyl-2,2,6,6-tetramethylpiperidinyloxy (HO-TEMPO), benzoyl peroxide (BPO), and Ti(OPr) 4 (from Aldrich) were used without further purification.…”

Section: Experimental Section Materialsmentioning

confidence: 99%

“…HO-TEMPO (1.0 g, 5.81 mmol) and Ti(OPr) 4 (0.413 g, 1.45 mmol) were added in a 50-mL round-ground flask with a magnetic stirrer. The flask was placed in a preheated oil bath at 758C and after 10 min, the vacuum was adjusted at about 80-100 mbar.…”

Section: Synthesis Of Ti(o-tempo)mentioning

confidence: 99%

“…The multifunctional initiator Ti(O-TEMPO) 4 was obtained by Ti(OPr) 4 alcoholysis with HO-TEMPO according to the reaction of Scheme 1.…”

Section: Synthesis Of Ti(o-tempo)mentioning

confidence: 99%

“…Alcoholysis of Ti(OPr) 4 by 4-hydroxy 2,2,6,6 tetramethyl piperidinyl-1-oxyl (HO-TEMPO) gave a bifunctional initiator Ti(O-TEMPO) 4 . Poly e-caprolactone prepolymer end-capped with the nitroxide group was first prepared by ring opening polymerization of e-caprolactone with this initiator at high conversion.…”

mentioning

confidence: 99%

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Study of a new titanium dual initiator for the synthesis of poly(ε‐caprolactone)‐b‐polystyrene block copolymers by the combination of coordination and nitroxide mediated polymerizations

Li¹,

Jeanmaire²,

Zerroukhi³

2007

J of Applied Polymer Sci

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ABSTRACT:Poly e-caprolactone-polystyrene blockcopolymers (PCL-b-PSt) were synthesized using a modified titanium catalyst as the dual initiator. Alcoholysis of Ti(OPr) 4 by 4-hydroxy 2,2,6,6 tetramethyl piperidinyl-1-oxyl (HO-TEMPO) gave a bifunctional initiator Ti(O-TEMPO) 4 . Poly e-caprolactone prepolymer end-capped with the nitroxide group was first prepared by ring opening polymerization of e-caprolactone with this initiator at high conversion. The nitroxide-end-capped structure and molar mass (M n ) of the polymers were demonstrated by typical UV absorption band. This analytical technique indicates a near-quantitative nitroxide functionality and a M n in good agreement with size exclusion chromatography (SEC) ones. This polyester prepolymer was used to further initiate the radical polymerization with styrene and reach the block copolymers (PCL-b-PSt). All the prepolymers and block copolymers were characterized by SEC and NMR spectroscopy. Additionally, the preparation of star polymers bearing two kinds of arms (PCL and PSt) was envisaged and a preliminary result was given.

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“…However, it was supposed that some unreacted Ti(OPr) 4 and excess HO-TEMPO still remained in the mixture.…”

Section: Synthesis Of Ti(o-tempo)mentioning

confidence: 98%

“…4-Hydroxyl-2,2,6,6-tetramethylpiperidinyloxy (HO-TEMPO), benzoyl peroxide (BPO), and Ti(OPr) 4 (from Aldrich) were used without further purification.…”

Section: Experimental Section Materialsmentioning

confidence: 99%

Section: Synthesis Of Ti(o-tempo)mentioning

confidence: 99%

“…The multifunctional initiator Ti(O-TEMPO) 4 was obtained by Ti(OPr) 4 alcoholysis with HO-TEMPO according to the reaction of Scheme 1.…”

Section: Synthesis Of Ti(o-tempo)mentioning

confidence: 99%

mentioning

confidence: 99%

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Study of a new titanium dual initiator for the synthesis of poly(ε‐caprolactone)‐b‐polystyrene block copolymers by the combination of coordination and nitroxide mediated polymerizations

Li¹,

Jeanmaire²,

Zerroukhi³

2007

J of Applied Polymer Sci

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Nitroxide‐mediated synthesis of styrenic‐based segmented and tapered block copolymers using poly(lactide)‐functionalized TEMPO macromediators

Jabbar¹,

Graffe²,

Lessard³

et al. 2008

J of Applied Polymer Sci

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Poly(styrene)-poly(lactide) (PS-PLA), poly (tert-butyl styrene)-poly(lactide) (PtBuS-PLA) diblocks, and poly(tert-butyl styrene)-poly(styrene)-poly(lactide) (PtBuS-PS-PLA) segmented and tapered triblocks of controlled segment lengths were synthesized using nitroxide-mediated controlled radical polymerization. Well-defined PLA-functionalized macromediators derived from hydroxyl terminated TEMPO (PLA T ) of various molecular weights mediated polymerizations of the styrenic monomers in bulk and in dimethylformamide (DMF) solution at 120-1308C. PS-PLA and PtBuS-PLA diblocks were characterized by narrow molecular weight distributions (polydispersity index (M w /M n ) < 1.3) when using the PLA T mediator with the lowest number average molecular weight M n 5 6.1 kg/mol while broader molecular weight distributions were exhibited (M w /M n 5 1.47-1.65) when using higher molecular weight mediators (M n 5 7.4 kg/mol and 11.3 kg/mol). Segmented PtBuS-PS-PLA triblocks were initiated cleanly from PtBuS-PLA diblocks although polymerizations were very rapid with PS segments $ 5-10 kg/mol added within 3-10 min of polymerization at 1308C in 50 wt % DMF solution. Tapering from the PtBuS to the PS segment in semibatch mode at a lower temperature of 1208C and in 50 wt % DMF solution was effective in incorporating a short random segment of PtBuS-ran-PS while maintaining a relatively narrow monomodal molecular weight distribution (M w /M n % 1.5).

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One‐Pot Synthesis of Lactide–Styrene Diblock Copolymers via Catalytic Immortal Ring‐Opening Polymerization of Lactide and Nitroxide‐Mediated Polymerization of Styrene

et al. 2010

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An efficient, practical, and industrially relevant procedure for the production of polymer materials, in which a part of the oil-derived polyolefins has been replaced by a renewable, biodegradable, and biocompatible poly(lactide) block, is presented. Binary catalytic systems combining innocuous metals (yttrium, zinc, magnesium, or calcium) and bifunctional alcohols (acting as transfer agents) were developed to promote the immortal ring-opening polymerization of lactide directly in styrene. Up to 20,000 equivalents of lactide were polymerized (metal catalyst loading of 50-100 ppm) in a controlled fashion in the presence of 10-100 equivalents of a double-headed transfer agent to give as many end-functionalized poly(lactide) macromolecules that can be used eventually as macroinitiators for the controlled nitroxide-mediated polymerization of styrene. The specific use of the sterically shielded complex [BDI-iPr]Zn-N(SiMe(3))(2) ([BDI-iPr]=bis(diketiminate) ligand) allowed the efficient, catalytic, and controlled production of poly(lactide)-block-poly(styrene) materials in a one-pot, solvent-free sequential procedure, with nearly 100% atom-efficiency.

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Synthesis and characterization of the novel block copolymer poly(ε‐caprolactone)‐b‐poly(4‐vinyl pyridine) by the combination of coordination and controlled free‐radical polymerizations

Cited by 11 publications

References 19 publications

Study of a new titanium dual initiator for the synthesis of poly(ε‐caprolactone)‐b‐polystyrene block copolymers by the combination of coordination and nitroxide mediated polymerizations

Study of a new titanium dual initiator for the synthesis of poly(ε‐caprolactone)‐b‐polystyrene block copolymers by the combination of coordination and nitroxide mediated polymerizations

Nitroxide‐mediated synthesis of styrenic‐based segmented and tapered block copolymers using poly(lactide)‐functionalized TEMPO macromediators

One‐Pot Synthesis of Lactide–Styrene Diblock Copolymers via Catalytic Immortal Ring‐Opening Polymerization of Lactide and Nitroxide‐Mediated Polymerization of Styrene

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