Decomposition of 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane and its use in polymerization of styrene and methyl methacrylate

Wang, Sheng; Shan, Guorong; Huang, Zhiming; Wang, Zhixue; Pan, Zu-Ren

doi:10.1016/j.polymer.2005.08.016

Cited by 10 publications

(10 citation statements)

References 15 publications

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“…Further polymerization studies concluded that DEKTP could be also used to initiate St polymerization and act as a multi‐functional initiator yielding polymers with large molecular weights at higher polymerization rates than those obtained when a typical mono‐functional initiator is employed …”

Section: Introductionmentioning

confidence: 99%

Thermal decomposition of diethyl ketone triperoxide in methyl methacrylate: Theoretical and experimental study of the initial solvation state and its influence on the polymerization process

Rodríguez¹,

Enríquez-Medrano²,

Grande

et al. 2015

J of Applied Polymer Sci

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The decomposition rate constant (kd) of diethyl ketone triperoxide (DEKTP, 3,3,6,6,9,9‐hexaethyl‐1,2,4,5,7,8‐hexaoxacyclononane) in methyl methacrylate (MMA) was determined by the kinetic study of its thermal decomposition at temperatures from 110 to 140°C. The calculated kd for DEKTP in MMA was 2.4 times lower (at 130°C) compared with that previously determined and reported in styrene (St). Density functional theory (DFT) calculations demonstrated that the decomposition of DEKTP molecule in MMA required higher interaction energy than in St, thus explaining its lower kd value. Bulk polymerization kinetics of MMA using DEKTP as the initiator revealed the presence of an induction period, in contrast with St polymerization, providing clear evidence of the solvation state influence at early polymerization stages. This work provides mechanistic insights into the interactions among the multi‐functional cyclic peroxide DEKTP and vinyl monomers; St and MMA, and their influence on the polymerization kinetics. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 42905.

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Section: Introductionmentioning

confidence: 99%

Thermal decomposition of diethyl ketone triperoxide in methyl methacrylate: Theoretical and experimental study of the initial solvation state and its influence on the polymerization process

Rodríguez¹,

Enríquez-Medrano²,

Grande

et al. 2015

J of Applied Polymer Sci

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“…The 1 H NMR spectra of SiO 2 -g-PS and cleaved PS are illuminated in Figures 5 and 6, respectively. In Figure 5, the chemical shifts range from 6.0 to 7.4 ppm are reasonably assigned to the proton in the PS chains, and the chemical shifts of -CH-as well as -CH 2 -in PS repeating unit were found at δ = 1.8 and 1.4, respectively [26] . The chemical shifts of δ =2.3 and 1.25 are reasonably attributed to the -CH 3 (Figure 5, b) in TDI and -CH 3 ( Figure 5, d) in 2-bromoisobutyl bromide, respectively.…”

Section: Preparation Of Silica-based Atrp Macroinitiatormentioning

confidence: 79%

Preparation of well-defined polystyrene/silica hybrid nanoparticles by ATRP

2008

Sci. China Ser. B-Chem.

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Immobilization of the atom transfer radical polymerization (ATRP) macroinitiators at the silica nanoparticle surfaces was achieved through surface modification with excess toluene-2,4-diisocynate (TDI), after which the residual isocyanate groups were converted into ATRP macroinitiators. Structurally well-defined polystyrene chains were grown from the nanoparticle surfaces to yield individual particles composed of a silica core and a well-defined, densely grafted outer polystyrene by ATRP, which was initiated by the as-synthesized silica-based macroinitiator. FTIR, NMR and gel permeation chromatography (GPC) were used to characterize the polystyrene/silica hybrid particles.

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“…Since the second half of the 1980 s, several experimental studies and mathematical models regarding the use of multifunctional free radical initiators have been reported, mostly related to the production of poly(styrene) (PS), poly(methyl methacrylate) (PMMA), poly(vinyl acetate) (PVAc), and styrene/methacrylate copolymers . In most cases, polymerizations have been performed in bulk or solution processes.…”

Section: Introductionmentioning

confidence: 99%

“…The main factor that has prevented the widespread use of bifunctional initiators in vinyl chloride polymerization processes is the low rate of thermal decomposition of most commercially available initiators at the feasible PVC process temperatures (40–60 °C). The vast majority of commercial multifunctional peroxides are used at reaction temperatures above 90 °C . The lack of further studies regarding the use of multifunctional initiators in vinyl chloride free radical polymerizations is very intriguing, since the available results highlighted the potential benefits of using multifunctional initiators in PVC processes.…”

Section: Introductionmentioning

confidence: 99%

Mathematical Modeling of Molecular Weight Distributions in Vinyl Chloride Suspension Polymerizations Performed with a Bifunctional Initiator through Probability Generating Functions

Castor

Sarmoria

Asteasuain

et al. 2014

Macro Theory & Simulations

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This paper presents a mathematical model to describe the evolution of the molecular weight distribution (MWD) in vinyl chloride (VCM) free‐radical suspension polymerizations performed with a bifunctional initiator, 1,3‐di(2‐neodecanoylperoxyisopropyl) (DIPND). The model yields, as a function of time, the mass balances for the distinct phases, the monomer conversion, the number‐ and mass‐average molecular weights and the complete MWD of both the growing and dead polymer chains. In order to describe the MWD, the model uses probability generating functions (pgf) to transform the mass balance equations into a reduced and finite set of model equations. As shown throughout many examples, the MWD's of the final polymer resin is little sensitive to the presence of the linear symmetrical bifunctional initiator.

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Decomposition of 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane and its use in polymerization of styrene and methyl methacrylate

Cited by 10 publications

References 15 publications

Thermal decomposition of diethyl ketone triperoxide in methyl methacrylate: Theoretical and experimental study of the initial solvation state and its influence on the polymerization process

Thermal decomposition of diethyl ketone triperoxide in methyl methacrylate: Theoretical and experimental study of the initial solvation state and its influence on the polymerization process

Preparation of well-defined polystyrene/silica hybrid nanoparticles by ATRP

Mathematical Modeling of Molecular Weight Distributions in Vinyl Chloride Suspension Polymerizations Performed with a Bifunctional Initiator through Probability Generating Functions

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