A novel rate‐accelerating additive for atom transfer radical polymerization of styrene

Zhuang, Jia-ming; Lin, Rui; Huang, Jianying; Jiayan, Chu; Xurong, Lin; Yutai, Luo; Yousi, Zou

doi:10.1002/pola.22217

Cited by 15 publications

(7 citation statements)

References 22 publications

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“…The apparent polymerization rate constant deduced from the kinetic plot for ATRP of styrene shown in Figure 2 is 0.42 × 10 ‐4 s −1 . This rate fell within the range of reaction rates (ranging from 0.18 × 10 −4 to 1.6 × 10 −4 s −1 ), reported by other researchers under various ATRP polymerization conditions 45, 47, 48…”

Section: Resultssupporting

confidence: 86%

Statistical fluorinated copolymers from heterogeneous atom transfer radical copolymerization of styrene and 2,2,2‐trifluoroethyl methacrylate with similar reactivity ratios

Zhang

et al. 2013

J. Polym. Sci. A Polym. Chem.

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Fluorinated copolymers with statistical structure of azeotropic or gradient composition were prepared from heterogeneous atom transfer radical copolymerizations of styrene (S) and 2,2,2-trifluoroethyl methacrylate (T). The polymerization kinetic studies show that while the propagation rate constant of S increased with a decreasing S content in the comonomer feed ratio, the propagation rate of T decreased with decreases of the S content in the comonomer feed ratio. The polymerization rate and controllability of the heterogeneous ATRP of S and T were regulated by the solubility of Cu(II)/ligand in the reaction mixture, based on a mechanistic analysis and solubility tests of the Cu(II)/ligand system in the reaction media. The reactivity ratios of S and T were 0.22 and 0.35, as evaluated from kinetic analysis of monomer conversions higher than 35%. These statistical polymers self-assembled in T to form giant vesicles GVs) with broad diameter distribution in the range of 1-10 lm. Unlike the methods normally used to prepare gradient copolymers by spontaneous controlling with feeding model or batch polymerization of comonomers with obvious differences in the reactivity ratio, in this contribution, we report a novel synthetic strategy for preparing gradient copolymers can also be prepared from both monomers with very similar reactivity ratio.

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Section: Resultssupporting

confidence: 86%

Statistical fluorinated copolymers from heterogeneous atom transfer radical copolymerization of styrene and 2,2,2‐trifluoroethyl methacrylate with similar reactivity ratios

Zhang

et al. 2013

J. Polym. Sci. A Polym. Chem.

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“…investigated. Previously reported by Yousi and co-workers,[42] the addition of a catalytic amount of MN during ATRP of styrene (optimal molar ratio of MN/initiator 4/1) led to a remarkable rate enhancement while maintaining a low polydispersity value. Thus, G1bis was polymerized under the same conditions as for entry 5, but in presence of MN (MN/initiator 4/1, entry 10).…”

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confidence: 72%

Preparation of multi-allylic dendronized polymers via atom-transfer radical polymerization

Schwartz

Moingeon

Roeser

et al. 2019

European Polymer Journal

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Atom-transfer radical polymerization (ATRP) was investigated to polymerize a styrene monomer carrying carbosilane dendrons with 6 terminal allyl branches. Polymers with a monomodal molar mass distribution and low polydispersity have been produced, while by comparison the free-radical polymerization technique led to chain transfer early in the polymerization. Steric effect brought by the dendrons result in a slow polymerization rate, leading to an apparent saturation of the degree of polymerization. By pushing up the polymerization conditions (eg. increase of temperature or concentration), interchain couplings started to take place, most likely from reactions at the allyl branches. These results are very similar to the ones previously reported for the anionic polymerization of this same multiallylic dendronized monomer.

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“…51 To establish an interconnected microporous layer, the NaOH concentration and the time of reaction were dramatically reduced with respect to the previous works. 52,53 Its pore size ranges between 50 and 200 nm, and it is uniformly spread on the entire surface, as shown in Figure 1b. The layer consists of pillared and coneshaped structures, making the surface hydrophilic with a contact angle of 25 ± 9°(see the inset of Figure 1b).…”

Section: Resultsmentioning

confidence: 99%

Novel Alkali Activation of Titanium Substrates To Grow Thick and Covalently Bound PMMA Layers

Reggente

Masson

Dollinger

et al. 2018

ACS Appl. Mater. Interfaces

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Titanium (Ti) is the most widely used metal in biomedical applications because of its biocompatibility; however, the significant difference in the mechanical properties between Ti and the surrounding tissues results in stress shielding which is detrimental for load-bearing tissues. In the current study, to attenuate the stress shielding effect, a new processing route was developed. It aimed at growing thick poly(methyl methacrylate) (PMMA) layers grafted on Ti substrates to incorporate a polymer component on Ti implants. However, the currently available methods do not allow the development of thick polymeric layers, reducing significantly their potential uses. The proposed route consists of an alkali activation of Ti substrates followed by a surface-initiated atom transfer radical polymerization using a phosphonic acid derivative as a coupling agent and a polymerization initiator and malononitrile as a polymerization activator. The average thickness of the grown PMMA layers is approximately 1.9 μm. The Ti activation-performed in a NaOH solution-leads to a porous sodium titanate interlayer with a hierarchical structure and an open microporosity. It promotes the covalent grafting reaction because of high hydroxyl groups' content and enables establishing a further mechanical interlocking between the growing PMMA layer and the Ti substrate. As a result, the produced graduated structure possesses high Ti/PMMA adhesion strength (∼260 MPa). Moreover, the PMMA layer is (i) thicker compared to those obtained with the previously reported techniques (∼1.9 μm), (ii) stable in a simulated body fluid solution, and (iii) biocompatible. This strategy opens new opportunities toward hybrid prosthesis with adjustable mechanical properties with respect to host bone properties for personalized medicines.

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A novel rate‐accelerating additive for atom transfer radical polymerization of styrene

Cited by 15 publications

References 22 publications

Statistical fluorinated copolymers from heterogeneous atom transfer radical copolymerization of styrene and 2,2,2‐trifluoroethyl methacrylate with similar reactivity ratios

Statistical fluorinated copolymers from heterogeneous atom transfer radical copolymerization of styrene and 2,2,2‐trifluoroethyl methacrylate with similar reactivity ratios

Preparation of multi-allylic dendronized polymers via atom-transfer radical polymerization

Novel Alkali Activation of Titanium Substrates To Grow Thick and Covalently Bound PMMA Layers

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