Termination of Living Anionic Polymerizations Using Chlorosilane Derivatives: A General Synthetic Methodology for the Synthesis of End-Functionalized Polymers

Peters, M. A.; Belu, A. M.; Linton, Richard W.; Dupray, Laurence M.; Meyer, Thomas J.; DeSimone, Joseph M.

doi:10.1021/ja00117a008

Cited by 102 publications

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“…These reactions therefore provide another possible procedure to the synthesis of end-functionalized polymers. DeSimone and coworkers synthesized end-functionalized polystyrenes and polyisoprenes with either hydroxy or amino group by reacting the corresponding living polymers with chlorosilanes containing the protected functionalities 15 and 16 [26]. Perfluoroalkyl (Rf)-terminated polystyrenes were also obtained by the reactions with perfluorodimethylchlorosilanes [27].…”

Section: Synthesis Of End-functionalized Polymers With Use Of Functiomentioning

confidence: 99%

Recent advance in syntheses and applications of well-defined end-functionalized polymers by means of anionic living polymerization

Hirao¹,

Hayashi

1999

Acta Polym.

112

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Section: Synthesis Of End-functionalized Polymers With Use Of Functiomentioning

confidence: 99%

Recent advance in syntheses and applications of well-defined end-functionalized polymers by means of anionic living polymerization

Hirao¹,

Hayashi

1999

Acta Polym.

112

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“…Polymeric amines are expected for functional materials such as polyelectrolytes, 5 polymeric chelating reagents, 6 and polymer catalysts. 7 If the BOC group can be removed from the polymer obtained in this work, a novel optically active polymeric amine may be obtained.…”

Section: Cleavage Of Boc Group From the Polymermentioning

confidence: 99%

Synthesis and reactions of a poly(methacrylate) from an optically active amino alcohol

Sanda

Koyama

Endō

1998

J. Polym. Sci. A Polym. Chem.

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Synthesis and radical polymerization of a novel optically active methacrylate, (S)–2–tert–butoxycarbonylamino–3–phenylpropyl methacrylate (MA–F–BOC), were examined. MA–F–BOC was synthesized from methacrylic acid and N–protected (L)–phenylalaninol. Radical polymerization of MA–F–BOC quantitatively afforded the corresponding polymethacrylate with a relatively high molecular weight. Radical copolymerizations of MA–F–BOC were carried out with styrene and acrylamide to afford the copolymers. Radical polymerization of MA–F–BOC in the presence of n–butanethiol afforded the oligomers, whose degrees of polymerizations were 3.3–8.0. The BOC group was completely cloven with HBr to afford the corresponding optically active polymeric amine quantitatively. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 1981–1986, 1998

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“…These authors claimed that reactions of 1 and polystyryl-and polyisopropenyllithium produce aliphatic primary amine end-functionalized polymers with 95+% degrees of amination. In addition, DeSimone and co-workers 20 developed a chlorosilane derivative, [N,N-bis(trimethylsilyl)amino]butylchlorodimethylsilane, and Schlaad and co-workers 21 developed a slightly different terminating reagent, 1-(chlorodimethyldilyl)-3-[N,N-bis(trimethylsilyl)amino]propane, for synthesis of primary amine functionalized polymers.…”

Section: Introductionmentioning

confidence: 99%

Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry Characterization of Primary Amine End-Functionalized Polystyrene and Poly(methyl methacrylate) Synthesized by Living Anionic Polymerization Techniques

Σακελλαρίου

Mays

2007

Macromolecules

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The reaction of living anionic polymers with 2,2,5,5-tetramethyl-1-(3-bromopropyl)-1-aza-2,5-disilacyclopentane (1) was investigated using coupled thin layer chromatography and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Structures of byproducts as well as the major product were determined. The anionic initiator having a protected primary amine functional group, 2,2,5,5-tetramethyl-1-(3-lithiopropyl)-1-aza-2,5-disilacyclopentane (2), was synthesized using all-glass high-vacuum techniques, which allows the long-term stability of this initiator to be maintained. The use of 2 in the preparation of well-defined aliphatic primary amine R-end-functionalized polystyrene and poly(methyl methacrylate) was investigated. Primary amino R-end-functionalized poly(methyl methacrylate) can be obtained near-quantitatively by reacting 2 with 1,1-diphenylethylene in tetrahydrofuran at room temperature prior to polymerizing methyl methacrylate at -78°C. When 2 is used to initiate styrene at room temperature in benzene, an additive such as N,N,N′,N′-tetramethylethylenediamine is necessary to activate the polymerization. However, although the resulting polymers have narrow molecular weight distributions and well-controlled molecular weights, our mass spectra data suggest that the yield of primary amine R-end-functionalized polystyrene from these syntheses is very low. The majority of the products are methyl R-end-functionalized polystyrene.

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Termination of Living Anionic Polymerizations Using Chlorosilane Derivatives: A General Synthetic Methodology for the Synthesis of End-Functionalized Polymers

Cited by 102 publications

References 0 publications

Recent advance in syntheses and applications of well-defined end-functionalized polymers by means of anionic living polymerization

Recent advance in syntheses and applications of well-defined end-functionalized polymers by means of anionic living polymerization

Synthesis and reactions of a poly(methacrylate) from an optically active amino alcohol

Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry Characterization of Primary Amine End-Functionalized Polystyrene and Poly(methyl methacrylate) Synthesized by Living Anionic Polymerization Techniques

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