Anionic synthesis of aromatic amide and carboxyl functionalized polymers. Chain-end functionalization of poly(styryl)lithium withN,N-diisopropyl-4-(1-phenylethenyl)benzamide

Summers, Gabriel J.; Quirk, Roderic P.

doi:10.1002/(sici)1099-0518(199806)36:8<1233::aid-pola5>3.0.co;2-0

Cited by 26 publications

(17 citation statements)

References 12 publications

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“…When the LiCl : DBTMGLi molar ratio is greater than one, a 1 : 1 complex is formed with a fast exchange rate. 13 C Relaxation times also indicate a dimeric aggregation for this complex, in full agreement with an MNDO (modified neglect of differential overlap) calculation. Living PtBMA oligomers also form a 1 : 1 complex with LiCl.…”

Section: Analysis Of the Active Site Structuresupporting

confidence: 78%

“…For these reasons, living poly(tert-butyl-methacrylate) (PtBMA), stable at 0°C, and its dimeric model, di-tert-butyl 2-lithio-2,4,4'-trimethylglutarate (DBTMGLi), have been recently studied [31,32]. The last monomer units of PtBMA have also been selectively labeled by 13 C) of both the dimeric model and the growing chains has been conducted in the absence and presence of μ-and μ/σ-type ligands [33,34], the main conclusions of which are as follows:…”

Section: Analysis Of the Active Site Structurementioning

confidence: 99%

“…At a time when the recently discovered controlled radical polymerization [2*] is viewed as a much less demanding process, anionic polymerization still remains an important method, well-suited to kinetic studies [3*], the synthesis of polymers of predictable molecular weight (MW) with a narrow molecular weight distribution (MWD), tailoring of block copolymers [4,5*,6-9], design of nonlinear molecular architectures [10**, 11] and telechelic polymers [12][13][14][15][16][17], and stereoregular polymerization [18,19]. Major progress in mechanistic studies and macromolecular engineering reported in the past year(s) is to be found in the very challenging field of the anionic polymerization of (meth)acrylic monomers.…”

Section: Introductionmentioning

confidence: 99%

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Recent developments in anionic polymerization

Jérôme

Tong

1998

Current Opinion in Solid State and Materials Science

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The past year witnessed very significant advances in the living anionic polymerization of (meth)acrylate monomers, particularly in hydrocarbons at or below 0°C. Block polymerization of alkyl methacrylates with primary alkyl acrylates, although somewhat improved, remains a challenge. Anionic polymerization of styrene, diene and its derivatives was carried out with the aim of synthesizing functional polymers and block copolymers of various architectures. There has been a trend towards combining different living techniques in order to design polymers of unique architectures and properties. AbbreviationsDBTMGLi di-tert-butyl 2-lithio-2,4,4'-trimethylglutarate

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Section: Analysis Of the Active Site Structuresupporting

confidence: 78%

Section: Analysis Of the Active Site Structurementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Recent developments in anionic polymerization

Jérôme

Tong

1998

Current Opinion in Solid State and Materials Science

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“…The synthesis of amine chain end‐functionalized polymers by living anionic polymerization methods is well documented in the literature 21–25. In particular, the general, quantitative, living functionalization method,21, 26, 27 which is based on the addition reactions of simple and polymeric organolithium compounds to 1,1‐diphenylethylene derivatives functionalized with the hydroxyl, carboxyl, amide, primary, and tertiary amine groups in the protected or free form provides the most efficient method for the functionalized polymers because (1) these addition reactions are simple and quantitative and (2) only monoaddition reactions have been reported because of steric factors; that is, no oligomerization of the 1,1‐diphenylethylene unit occurs.…”

Section: Introductionmentioning

confidence: 99%

Tertiary amine‐functionalized polymers by atom transfer radical polymerization

Summers

Ndawuni

Summers

2001

J. Polym. Sci. A Polym. Chem.

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The quantitative synthesis of tertiary amine‐functionalized polymers by atom transfer radical polymerization is reported. Tertiary amine‐functionalized polystyrene was prepared with the adduct of 1‐(bromoethyl)benzene with 1‐(4‐dimethyl‐aminophenyl)‐1‐phenylethylene as an initiator in the atom transfer radical polymerization of styrene in the presence of a copper (I) bromide/2,2′‐bipyridyl catalyst system. The polymerization proceeded via a controlled free‐radical polymerization process to afford quantitative yields of the corresponding tertiary amine‐functionalized polystyrene with predictable number‐average molecular weights (1600–4400), narrow molecular weight distributions (1.09–1.31), and an initiator efficiency of 0.95. The polymerization process was monitored by gas chromatographic analysis. The tertiary amine‐functionalized polymers were characterized by thin‐layer chromatography, size exclusion chromatography, potentiometry, and spectroscopy. All experimental evidence was consistent with quantitative functionalization via the 1,1‐diphenylethylene derivative. Polymerization kinetic measurements showed that the polymerization reaction followed first‐order‐rate kinetics with respect to monomer consumption and that the number‐average molecular weight increased linearly with monomer conversion. © 2001 John Wiley & Sons, Inc. J Polym Sci A Part A: Polym Chem 39: 2058–2067, 2001

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“…The addition reaction of polymeric organolithium compounds with 1,1‐diphenylethylene and its derivatives is an integral component of many recently developed procedures for the synthesis of well‐defined, chain‐end functionalized polymers, block copolymers, macromonomers, as well as heteroarm and regular star‐branched polymers 1–7. For example, a general functionalization methodology has been developed based on the addition of polymeric organolithium compounds with substituted 1,1‐diphenylethylenes as shown in Scheme , where X and Y represent functional groups 1,5,8–17…”

Section: Introductionmentioning

confidence: 99%

Adducts of Polymeric Organolithiums with 1,1‐Diphenylethylene. Rates of Formation and Crossover to Styrene and Diene Monomers

Quirk

Lee

2003

Macro Chemistry & Physics

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The addition reactions of 1,1‐diphenylethylene (DPE) to polymeric organolithium (PLi) compounds and the crossover reactions of the resulting polymeric 1,1‐diphenylalkyllithiums with styrene, isoprene and butadiene monomers have been investigated and optimized. The addition of poly(styryl)lithium (PSLi) to one unit of DPE at 25 °C is complete in 6 and 8 h in benzene and cyclohexane, respectively. After 3 d at 25 °C, the extent of end‐capping with DPE was only 9% for poly(butadienyl)lithium and 15% for poly(isoprenyl)lithium. Addition of THF ([THF]/[PLi] = 15–40) promotes quantitative addition of poly(dienyl)lithiums to DPE within 1–4 hours at 25 °C. Crossover reactions of polymeric 1,1‐diphenylalkyllithiums (growth out) to styrene monomers are slow relative to crossover reactions to diene monomers. Crossover to diene monomers is complete within approximately 2 min at 25 °C and leads to well‐defined, narrow molecular weight distribution block copolymers ($\overline M _{\rm w} /\overline M _{\rm n}$ = 1.01 with $\overline M _{\rm n}$ (out, calc) > 2 900 g · mol−1). Crossover to styrene monomers requires 12 h and leads to broad molecular weight distributions ($\overline M _{\rm w} /\overline M _{\rm n}$ > 1.1) and inefficient crossover if $\overline M _{\rm n}$ (out; calc) < 7 000 g · mol−1 and the chain end concentration is ≤ 10−3 M. Crossover to the styrene monomer is favored by low temperatures (5 °C), high chain end concentrations, and higher molecular weights of the growing block. magnified image

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Anionic synthesis of aromatic amide and carboxyl functionalized polymers. Chain-end functionalization of poly(styryl)lithium withN,N-diisopropyl-4-(1-phenylethenyl)benzamide

Cited by 26 publications

References 12 publications

Recent developments in anionic polymerization

Recent developments in anionic polymerization

Tertiary amine‐functionalized polymers by atom transfer radical polymerization

Adducts of Polymeric Organolithiums with 1,1‐Diphenylethylene. Rates of Formation and Crossover to Styrene and Diene Monomers

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