Atom transfer radical polymerization (ATRP) of styrene and methyl methacrylate with α,α-dichlorotoluene as initiator; a kinetic study

Neumann, Andreas; Keul, Helmut; Höcker, Hartwig

doi:10.1002/1521-3935(20000601)201:9<980::aid-macp980>3.0.co;2-k

Cited by 23 publications

(15 citation statements)

References 14 publications

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“…In Equation (1)- (21), C is the catalyst in its lower oxidation state, CX is the catalyst in its higher oxidation state, M is the monomer, DD is a chain with two dormant ends, DR is a chain with a dormant end and a free radical end, RR is a chain with two free radical ends, PP is a chain with two dead ends, PD is a chain with a dormant end and a dead end, PR is a chain with a free radical end and a dead end, and r is the chain length.…”

Section: Model Developmentmentioning

confidence: 99%

“…We will show that some of these effects would be hard to be predicted without a fundamental polymerization model. In the second part, we use the experimental data reported in the literature [21,22,27] to validate the model. A common difficulty in this type of modeling is the lack of reliable kinetic parameters for free radical polymerization.…”

Section: Model Parametersmentioning

confidence: 99%

“…Hocker and group [21] used a,a-dichlorotoluene (DCT) as bifunctional initiator for styrene polymerization in butyl acetate. Copper chloride and bipyridine were used as the catalyst and the ligand, respectively.…”

Section: Solution Polymerization Of Styrenementioning

confidence: 99%

“…Even though the literature describing the chemistry of ATRP with bifunctional initiators is rich, [21][22][23][24][25][26][27] to our knowledge no mathematical models have been published for ATRP with bifunctional initiators.…”

Section: Introductionmentioning

confidence: 99%

“…In the present paper, we compare our model predictions with experimental results available in the literature. [21,22,27] To our knowledge, this is the first time a fundamental polymerization kinetic model is used to fit and predict experimental ATRP results using bifunctional initiators.…”

Section: Introductionmentioning

confidence: 99%

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Modeling of Atom Transfer Radical Polymerization with Bifunctional Initiators: Diffusion Effects and Case Studies

Al‐Harthi

Soares

Simon

2006

Macro Chemistry & Physics

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Summary: A mathematical model for atom transfer radical polymerization (ATRP) with bifunctional initiators was developed. The model was validated with three case studies in bulk and solution polymerization. We used only polymer yield data to estimate some of the model parameters, while others were obtained from the literature. The model fits the polymer yield data and also predicts weight‐average molecular weights and polydispersities very well. The free volume theory was also incorporated to the model to study the effect of diffusion‐controlled reactions. The adjustable parameters in the free volume theory for the termination, propagation, activation, and deactivation reactions were varied to show the effect on monomer conversion, polymer chain length, and polydispersity. The model shows that diffusion‐limited termination reactions produce polymer with smaller polydispersities, while diffusion‐limited propagation reactions have the opposite effect. Both models, considering and neglecting diffusion effects on the kinetic rate constants, were compared with experimental data. Even though the model predictions for monomer conversion, number‐average molecular weight, and polydispersity are good in both cases, the simulations indicate that diffusion‐controlled reactions can be ignored for the cases studied in the three case studies described in this paper.Comparison between model predictions and experimental data for BA polymerization of number‐average molecular weight in bulk at 90 °C.magnified imageComparison between model predictions and experimental data for BA polymerization of number‐average molecular weight in bulk at 90 °C.

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Section: Model Developmentmentioning

confidence: 99%

Section: Model Parametersmentioning

confidence: 99%

Section: Solution Polymerization Of Styrenementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Modeling of Atom Transfer Radical Polymerization with Bifunctional Initiators: Diffusion Effects and Case Studies

Al‐Harthi

Soares

Simon

2006

Macro Chemistry & Physics

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Chemical modification of polyaniline by N‐grafting of polystyrene synthesized via ATRP

Gheybi

Abbasian

Moghaddam

et al. 2007

J of Applied Polymer Sci

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The N-substituted polyaniline (PANi) was synthesized by incorporation of bromine-terminated polystyrene (PS-Br) onto the emeraldine form of polyaniline. End brominated polystyrene was synthesized by atom transfer radical polymerization (ATRP) technique and then deprotonated polyaniline was reacted with PS-Br to prepare PS-grafted PANi (PS-g-PANi) copolymer through Ngrafting reaction. The degree of N-grafting can be controlled by adjusting the molar feed ratio of PS-Br to the number of repeat units of PANi. The microstructure and compositions of the PS-g-PANi copolymers with different degrees of N-substitution were characterized by FT-IR, elemental analysis, differential scanning calorimetry (DSC), and scanning electron microscopy (SEM). The cyclicvoltammetry shows that the electroactivity of N-substituted PANi is strongly dependent on the degree of N-grafting. The solubility of PS-g-PANi copolymers in common organic solvents such as tetrahydrofuran and chloroform was improved by increasing the degree of N-grafting, and also the samples are partially soluble in xylene.

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MALDI‐TOF Analysis of Halogen Telechelic Poly(methyl methacrylate)s and Poly(methyl acrylate)s Prepared by Atom Transfer Radical Polymerization (ATRP) or Single Electron Transfer‐Living Radical Polymerization (SET‐LRP)

Couthouis

Keul

Möller

2015

Macro Chemistry & Physics

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Poly(methyl methacrylate)s (PMMA)s and poly(methyl acrylate)s (PMA)s are prepared by atom transfer radical polymerization (ATRP) or single electron transfer-living radical polymerization (SET-LRP) using methyl dichloroacetate (MDCA) and ethyl dibromoacetate (EDBA) as bifunctional initiators. The chain-end functionality is determined by MALDI-TOF mass spectrometry. The target PMMA ( M n = 2000 g mol −1 ) and PMA ( M n = 2000 g mol −1 ) samples obtained by ATRP of MMA and MA with MDCA as initiator have 12 and 81 mol% bis -chloro end groups, respectively; those prepared by SET-LRP have 57 and 100 mol% bis -chloro end groups, respectively. The PMMAs obtained by ATRP or SET-LRP with EDBA have no bromine end groups.

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Atom transfer radical polymerization (ATRP) of styrene and methyl methacrylate with α,α-dichlorotoluene as initiator; a kinetic study

Cited by 23 publications

References 14 publications

Modeling of Atom Transfer Radical Polymerization with Bifunctional Initiators: Diffusion Effects and Case Studies

Modeling of Atom Transfer Radical Polymerization with Bifunctional Initiators: Diffusion Effects and Case Studies

Chemical modification of polyaniline by N‐grafting of polystyrene synthesized via ATRP

MALDI‐TOF Analysis of Halogen Telechelic Poly(methyl methacrylate)s and Poly(methyl acrylate)s Prepared by Atom Transfer Radical Polymerization (ATRP) or Single Electron Transfer‐Living Radical Polymerization (SET‐LRP)

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