Features of living radical polymerization of vinyl monomers in homogeneous system using N,N-diethyldithiocarbamate derivatives as photoiniferters

Otsu, Takayuki; Matsunaga, Toshiaki; Doi, Tadashi

doi:10.1016/0014-3057(94)00122-7

Cited by 145 publications

(100 citation statements)

References 12 publications

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“…1). [27][28][29][30][31][32] In this article, we report the mechanical properties (thermal, tensile, and viscoelastic) of copolymers prepared by the grafting of PMMA onto NR according to a method that we recently developed, [24][25][26] that is, by methyl methacrylate (MMA) photopolymerization initiated by N,N-diethyldithiocarbamate (DEDT) groups introduced beforehand in side positions on the NR chains (Scheme 1). The introduction of DEDT initiating groups along the NR chains was achieved by the addition of sodium N,N-diethyldithiocarbamate trihydrate (DEDT-Na) onto oxirane rings previously created on the chains.…”

Section: Introductionmentioning

confidence: 99%

Physical and mechanical properties of poly(methyl methacrylate)‐grafted natural rubber synthesized by methyl methacrylate photopolymerization initiated by N,N‐diethyldithiocarbamate functions previously created on natural rubber chains

Derouet

Tran

Leblanc

2009

J of Applied Polymer Sci

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Well-defined poly(methyl methacrylate) (PMMA)-grafted natural rubbers (NRs) were prepared to study the structure-property relationships. Syntheses were achieved by the photopolymerization of methyl methacrylate initiated by N,N-diethyldithiocarbamate groups created beforehand in side positions on the NR chains. With this procedure, good control of the graft density and PMMA content could be obtained. Thermal, morphological, and mechanical properties of NR-g-PMMA copolymers were studied as a function of the NR/PMMA composition and graft density. NR-g-PMMAs containing 15-80% grafted PMMA showed characteristics of heterogeneous materials (characterized by two glass-transition temperatures, those of PMMA and NR, in differential scanning calorimetry). Under these conditions, they developed the morphology of thermoplastic elastomers with PMMA nodules dispersed in the rubber matrix when the PMMA content was near 20%; conversely, they developed the morphology of softened thermoplastics with rubber nodules dispersed in PMMA when the PMMA content was near 80%. Graft copolymers containing about 20% PMMA remained essentially rubbery, but they were already different from pure NR. On the other hand, the thermal stability of NR wash improved after the introduction of PMMA grafts onto NR chains.

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Section: Introductionmentioning

confidence: 99%

Physical and mechanical properties of poly(methyl methacrylate)‐grafted natural rubber synthesized by methyl methacrylate photopolymerization initiated by N,N‐diethyldithiocarbamate functions previously created on natural rubber chains

Derouet

Tran

Leblanc

2009

J of Applied Polymer Sci

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“…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). AA is also smaller than other monomers, thus, it is possible that the difference in conversion rates is due to the combination of two factors: differences in molecule sizes and inherited chemical reactivity of corresponding monomers [24,25]. As can be seen in Fig.…”

Section: Resultsmentioning

confidence: 94%

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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“…38 To achieve a better control of molecular weight and molecular weight distribution, and to synthesize new polymer grafts like block copolymer ones, controlled/living radical polymerization methods including nitroxide-mediated free radical polymerization (TEMPO), 18,[39][40][41][42][43][44] atom transfer radical polymerization (ATRP), and reverse ATRP 66 were developed. In the early 1980s, Otsu et al [67][68][69][70][71] described a new living-like method for the radical polymerization of vinyl monomers such as styrene and methyl methacrylate (MMA). The polymerization that proceeds under UV irradiation is initiated by dithiocarbamate compounds described as photoiniferters, which mean that they act as an initiator, transfer agent, and terminator.…”

Section: Introductionmentioning

confidence: 99%

“…75 In the present article, the purpose is to investigate the synthesis of poly(methyl methacrylate)-grafted silica (PMMA-grafted silica) microparticles by using a ''grafting from'' approach based on Otsu's work, to favor the grafting compared to the undesirable formation of homopolymers. [67][68][69][70][71] The objective was to initiate radical photopolymerization of MMA from various types of DEDT groups covalently bound to the surface of silica particles. First time, a procedure to synthesize DEDT-functionalized silica microparticles was developed starting from a precipitated Kieselgel 1 S. It consisted to use a two-step reaction: by introduction of chlorinated functions onto the surface of silica particles, followed by nucleophilic substitution of chlorines by DEDT functions via a S N 2 substitution mechanism (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Synthesis and characterization of poly(methyl methacrylate)‐grafted silica microparticles

Derouet

Thuc

2008

J of Applied Polymer Sci

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A procedure to synthesize poly(methyl methacrylate)-grafted silica microparticles was developed by using radical photopolymerization of methyl methacrylate (MMA) initiated from N,N-diethyldithiocarbamate (DEDT) groups previously bound to the silica surface (grafting ''from''). The functionalization of silica microparticles with DEDT groups was performed in two steps: introduction of chlorinated functions onto the surface of silica particles, and then nucleophilic substitution of chlorines by DEDT functions via a S N 2 mechanism. The study was performed with a Kieselgel 1 S silica which was initially chlorinated in surface, either by direct chlorination of silanols with thionyl chloride, or by using a condensation reaction between silanols and a chlorofunctional trialkoxysilane reagent, 4-(chloromethyl)phenyltrimethoxysilane and chloromethyltriethoxysilane, respectively. Three types of DEDT-functionalized silica microparticles were prepared with a good control of the reactions, and then characterized by solid-state 13 C and 29 Si CP/MAS NMR. Their ability to initiate MMA photopolymerization was studied. The kinetics of MMA photopolymerization was followed by HPLC and 1 H-NMR. Whatever the silica used the grafting progresses very slowly. On the other hand, the conversion of MMA in PMMA grafts is depending on the structure of the DEDT-functionalized Kieselgel 1 S used. Poly(methyl methacrylate)-grafted silica microparticles bearing high length grafts (DP n about 100) were synthesized.

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Features of living radical polymerization of vinyl monomers in homogeneous system using N,N-diethyldithiocarbamate derivatives as photoiniferters

Cited by 145 publications

References 12 publications

Physical and mechanical properties of poly(methyl methacrylate)‐grafted natural rubber synthesized by methyl methacrylate photopolymerization initiated by N,N‐diethyldithiocarbamate functions previously created on natural rubber chains

Physical and mechanical properties of poly(methyl methacrylate)‐grafted natural rubber synthesized by methyl methacrylate photopolymerization initiated by N,N‐diethyldithiocarbamate functions previously created on natural rubber chains

Macroradical initiated polymerisation of acrylic and methacrylic monomers

Synthesis and characterization of poly(methyl methacrylate)‐grafted silica microparticles

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