Synthesis of PMMA and PMMA block copolymers at elevated temperatures by phosphor ylide-mediated polymerizations

Dimov, D. K.; Warner, William N.; Hogen‐Esch, Thieo E.; Juengling, Stephan; Warzelhan, Volker

doi:10.1002/1521-3900(200007)157:1<171::aid-masy171>3.0.co;2-1

Cited by 12 publications

(17 citation statements)

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“…The same effect was calculated for the TPP, triphenylmethanide system containing the sterically crowded triphenylmethanide anion (Table , no. 5, Δ E = −20.9 kJ/mol at the B3LYP/TZV(P)//BP86/SV(P) level), which is in agreement with the fast initiation of MMA polymerization by this initiator 9a…”

Section: Resultssupporting

confidence: 83%

“…3, Δ E = 76.2 kJ/mol for n = 1 and 11.0 kJ/mol for n = 2 at the B3LYP/TZV(P)//BP86/SV(P) level) are much higher than those for the TPP systems. This agrees with the fact that the MMA polymerization in the presence of the NTP + counterion is by orders of magnitude slower than with TPP + . 9b,c …”

Section: Resultssupporting

confidence: 79%

“…The DFT calculations carried out in the present study qualitatively agree with the experimental findings , on the relative reactivities of metal-free initiators containing different cations of phosphonium type. It is shown that the isomerization of ylides to ion pairs may be rather endothermic in the initiation step, in qualitative agreement with induction periods observed during metal-free anionic MMA polymerization with phosphonium counterions 10a.…”

Section: Discussionsupporting

confidence: 84%

“…Later it was shown that the structure of the phosphorus-containing cation has a tremendous effect on the apparent reactivity of the chain end. Thus, (1-naphthyl)triphenylphosphonium (NPP + ) counterions lead to an extremely slow polymerization (half-lives of hours in boiling THF), 9b,c whereas the bis(triphenylphosphoranylidene)ammonium (PNP + ) gives faster polymerizations than TPP + 10c. This was explained by the higher stability of the NPP ylide and the lower one of the PNP ylide, as compared to the TPP ylide.…”

Section: Introductionmentioning

confidence: 99%

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Quantum-Chemical Study of Structure and Activity of Chain Ends in Metal-Free Anionic Polymerization of Methacrylates

Weiß¹,

Steiger²,

Jüngling³

et al. 2003

Macromolecules

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Kinetic and NMR studies of the anionic polymerization of methyl methacrylate using tetraphenylphosphonium and other phosphorus-containing, metal-free counterions indicated an equilibrium between an active ion pair and a corresponding ylide as a dormant species. We present density functional theory (DFT) calculations of the energy difference between the ion pair and the ylide for the ester enolate of methyl isobutyrate with various counterions which support this view. It is possible to establish a correlation based on the calculated energy difference between the ylide and the ion pair and the apparent activity of the chain end. The ylide formed after the first polymerization step is extremely stable compared to the ion pair, whereas after addition of one molecule of methyl methacrylate, the ylide of the dimer is destabilized through steric interactions and the polymerization can proceed much faster. This explains the observation of a pronounced induction period when using the ester enolate of methyl isobutyrate as an initiator.

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Section: Resultssupporting

confidence: 83%

Section: Resultssupporting

confidence: 79%

Section: Discussionsupporting

confidence: 84%

Section: Introductionmentioning

confidence: 99%

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Quantum-Chemical Study of Structure and Activity of Chain Ends in Metal-Free Anionic Polymerization of Methacrylates

Weiß¹,

Steiger²,

Jüngling³

et al. 2003

Macromolecules

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“…Reetz et al first synthesized poly(n-butyl acrylate) with narrow molecular weight distributions (MWD = 1.11) in a different solvent using tetrabutylammonium salts of thiolates as metal-free anionic initiators (29). Subsequently, several research groups also have made considerable efforts carry out the metal-free anionic polymerization of alkyl (meth)acrylates in the presence of tetraphenylphosphonium and other cations, which produced high molecular weight with narrow molecular weight distributions (30)(31)(32)(33). The synthesis of poly[alkyl (meth)acrylates] at room temperature or higher temperature was successful, in spite of metal-free anionic polymerization; as far as we know, there is no report on how to synthesize the fluoroacrylic polymers via this method.…”

Section: Introductionmentioning

confidence: 99%

Controlled Synthesis, Characterization and Application of Novel Functional Fluorinated Polymer By Metal-Free Anionic Polymerization

Yan

Liu

Sun

et al. 2012

Journal of Macromolecular Science, Part A

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A well-defined block polymer, di-n-butyl ester terminated poly (2,2,3,4,4,, was synthesized by the metal-free anionic polymerization. The tetrabutylammonium salt of di-n-butyl malonate was served as functional carbanionic initiator for the anionic polymerization of 2,2,3,4,4,4-hexafluorobutyl methacrylate in a controlled 'living' manner for the first time at ambient temperature. The chemical structure of this product was characterized by FT-IR, 1 H-NMR, and 13 C-NMR. Gel permeation chromatography (GPC) results showed that the molecular weight of BTHFMA ranged from 1025 to 6582 and the molecular weight distributions were fairly narrow (Mw/Mn = 1.12-1.16). By blending the poly(methyl methacrylate-co-butyl acrylate) [P(MMAco-BA)] with BTHFMA, we minimized the amount of the BTHFMA used while achieving a hydrophobic surface. The surface properties and compositions of the [P(MMA-co-BA)]/BTHFMA blend films were studied by contact angle and X-ray photoelectron spectroscopy (XPS). The results demonstrated that the 5 wt% blends of BTHFMA could obviously increase hydrophobic ability of the blend with a high water contact angle (98.2 o ) and low surface energy (24.2mN/m). XPS results indicated the fluorine mass content of the surface of the 5 wt% blend was up to 26.6%, which suggested BTHFMA enriched on the surface of the blend.

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Metal Enolates in Polymer Science and Technology

Lecomte

Jérôme

2010

Patai's Chemistry of Functional Groups

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Synthesis of metal enolato complexes 223 José Vicente 6. Coordination chemistry of metal enolato complexes 313 José Vicente 7. Metal enolates as synthons in organic chemistry 355 Daniel Stolz and Uli Kazmaier 8. Acid-base properties of enols and enolates 411 Jason Eames 9. Redox chemistry and electrochemistry of metal enolates 461 Guido Pampaloni and Piero Zanello 10. Catalysis using β-diketonato metal complexes

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Synthesis of PMMA and PMMA block copolymers at elevated temperatures by phosphor ylide-mediated polymerizations

Cited by 12 publications

References 0 publications

Quantum-Chemical Study of Structure and Activity of Chain Ends in Metal-Free Anionic Polymerization of Methacrylates

Quantum-Chemical Study of Structure and Activity of Chain Ends in Metal-Free Anionic Polymerization of Methacrylates

Controlled Synthesis, Characterization and Application of Novel Functional Fluorinated Polymer By Metal-Free Anionic Polymerization

Metal Enolates in Polymer Science and Technology

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