Kinetics of the Photopolymerization of Vinyl Monomers by Bis(Isopropylxanthogen) Disulfide. Design of Block Copolymers

Niwa, Masazo; Matsumoto, Takahiro; Izumi, Hisashi

doi:10.1080/00222338708068142

Cited by 42 publications

(8 citation statements)

References 5 publications

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“…Similar results were obtained by Niwa et al who studied in detail the photo-polymerisation of vinyl monomers initiated by bis(isopropylxanthogen) disulphide (BX). The results showed that in homogeneous polymerisation acrylates have higher reactivity as compared to methacrylates, which is in accordance with our experimental results [23]. According to their functionality, the conversion of different monomers can range from 40 to 100% (conversion in the present case ranged from 35 to 77% depending on the monomer).…”

Section: Resultssupporting

confidence: 93%

“…UV irradiation was performed for 900 and 1800 s. Figure 4 shows the results of this study in terms of conversion over time. The lower initiator concentration produced lower conversion, which is in agreement with early studies by Lin [26] and Niwa et al [23]. The apparent increase in conversion rate over time might be attributed to the lower concentration of monomer in solution, which in turn leads to higher amount of UV energy reaching the IMS after some grafting time.…”

Section: Resultssupporting

confidence: 89%

See 1 more Smart Citation

Macroradical initiated polymerisation of acrylic and methacrylic monomers

Mijangos¹,

Guerreiro²,

Piletska³

et al. 2009

J of Separation Science

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An approach has been developed for the grafting of monomers onto poly(trimethylolpropane trimethacrylate) (polyTRIM) particles using 2,2-diethyl dithiocarbamic acid benzyl ester (DDCABE) as an initiator. A set of polymers was prepared with this technique over different lengths of time and the kinetics of the reaction studied experimentally. It was found that the grafting of initiator to the polymeric support followed a second order reaction, while the subsequent addition of monomers from solution into the polyTRIM macroradicals followed a first order reaction. The living nature of the iniferter modified macroradicals permits easy consecutive grafting of multiple polymeric layers, allowing straightforward functionalisation of particles. However, the effectiveness of the grafted initiator decreased with each cycle of polymerisation. This technique can be used for a wide range of applications in analytical and biochemistry.

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Section: Resultssupporting

confidence: 93%

Section: Resultssupporting

confidence: 89%

Macroradical initiated polymerisation of acrylic and methacrylic monomers

Mijangos¹,

Guerreiro²,

Piletska³

et al. 2009

J of Separation Science

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“…This work presents a strategy for preparing cation exchangers with increased surface hydrophilicity from DVB polymeric particles through attachment of thiol-terminated sulfopropyl methacrylate telomers onto epoxy groups via a grafting to scheme and subsequent acidic ring-opening hydrolysis of remaining epoxy groups into diols. The telomers were prepared by iniferter polymerization [22] using isopropyl xanthic disulfide as photoreactive iniferter [29,30]. The prepared materials were tested as ion-exchange material for protein separation.…”

Section: Introductionmentioning

confidence: 99%

A cation‐exchange material for protein separations based on grafting of thiol‐terminated sulfopropyl methacrylate telomers onto hydrophilized monodisperse divinylbenzene particles

Nordborg¹,

Limé²,

Shchukarev³

et al. 2008

J of Separation Science

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A strong cation-exchange separation material has been prepared from monodisperse divinylbenzene particles modified by a "grafting to" approach, utilizing as anchoring points epoxy groups introduced onto the surface of the particles via oxidation of residual vinyl groups. The grafted chains consisted of thiol-terminated telomers of sulfopropyl methacrylate prepared by iniferter mediated polymerization, and grafting was performed by reaction of the corresponding thiolate anion with the surface epoxy groups. Attachment through epoxy moieties that were subsequently converted into 2,3-propanediol groups increased the hydrophilicity of the polymeric particles and incubation experiments showed no signs of the proteins denaturing on the column during an extended contact time of 1 h at room temperature. The performance of the grafted material was demonstrated by the chromatographic separation of cytochrome C, lysozyme, myoglobin, and ribonuclease A, in a cation-exchange mode.

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“…Moreover, molecular weights range from 9000 (styrene) to 70 000 (methyl acrylate) and the yields are quite high after only 3 h (ca. 90%) [230,231]. In addition, the authors observed that the initial value of DPn decreases with increase in the concentration of xanthogen disulfide [TX], an observation in agreement with the following kinetic equation:…”

Section: S 49supporting

confidence: 72%

“…One of the most interesting investigations on the stepwise polymerization was performed by Niwa et al [230,231] who prepared different diblock copolymers with, very often, a high increase of molecular weight and low polydispersity indexes. As an example of precursor of diblock copolymers, they prepared telechelic 50 as follows: In this synthesis, the reactivity of monomers M decreases in the classic order: methyl acrylate > MMA >> acrylonitrile ~ vinyl acetate > Sty, and DPn values increase linearly with the monomer conversion.…”

Section: S 49mentioning

confidence: 99%

Synthesis of block copolymers by radical polymerization and telomerization

Améduri

Boutevin

Gramain

Advances in Polymer Science

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The synthesis of block copolymers, cooligomers or cotelomers performed from radical polymerization and radical telomerization is discussed. In the first part, the two main methods proposed for obtaining block copolymers by radical polymerization are reviewed. The first method concerns the use of multifunctional micro-or macroinitiators that decompose according to two processes or at two different temperatures, allowing the stepwise insertion of different base units. The second method, more recently proposed, tends to control the reactivity of the growing radicals by the use of either additional stable free radicals or organometallic compounds acting as counter radical, allowing reversible termination steps. These methods still in full development and often referred to as "living" processes, allow well defined block copolymers with narrow molecular weight distributions to be produced. The second part of the review deals with methods of preparation by radical telomerization. Besides the traditional process involving the coupling of co-functional oligomers or telomers and the bistelomerization, the dormant or living telomerization methods are also described. In this last case, the "living" character is achieved by the use of well-chosen transfer agents with specific cleavable bonds leading to reversibility of the termination step.

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Kinetics of the Photopolymerization of Vinyl Monomers by Bis(Isopropylxanthogen) Disulfide. Design of Block Copolymers

Cited by 42 publications

References 5 publications

Macroradical initiated polymerisation of acrylic and methacrylic monomers

Macroradical initiated polymerisation of acrylic and methacrylic monomers

A cation‐exchange material for protein separations based on grafting of thiol‐terminated sulfopropyl methacrylate telomers onto hydrophilized monodisperse divinylbenzene particles

Synthesis of block copolymers by radical polymerization and telomerization

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