Atom transfer radical polymerisation in emulsion

Chambard, Grégory; Man, Pap Patrick de; Klumperman, Bert

doi:10.1002/1521-3900(200002)150:1<45::aid-masy45>3.0.co;2-z

Cited by 51 publications

(48 citation statements)

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“…This decrease may be due to the presence of peroxides, despite thorough purification, or due to coordination to the catalyst, as THF has stronger coordinating capabilities than toluene and butyl acetate. Similar observations have been made for ATRP polymerizations, where a whole range of polar compounds such as 2-propanol [41] and water [42,43] have been found to enhance polymerization rate.…”

Section: Purified Solventsupporting

confidence: 81%

Solvent Effects, Diffusion Control and Mechanistic Aspects of Catalytic Chain Transfer Polymerization

Pierik¹,

Vollmerhaus²,

Herk³

2003

Macro Chemistry & Physics

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In the catalytic chain transfer polymerization of methyl methacrylate, butyl methacrylate and 2‐ethylhexyl methacrylate in toluene, it was found that the chain transfer constants (CT) were independent of solvent concentration and therefore of solution viscosity, and did not differ from the bulk polymerization values. For a diffusion controlled system, theoretical calculations predict an increase in CT when the solution viscosity is lowered. This points at a non‐diffusion controlled catalytic chain transfer step. These results were obtained when the solvent was thoroughly purified using a Grubbs‐type set‐up, whereas a large reduction in CT was found in unpurified solvent. Similar results were obtained for butyl acetate. Therefore it is concluded that the decrease of CT in non‐purified solvents is not related to the solvent itself, but to solvent impurities. Further we found that methyl methacrylate ended radicals do not covalently bind to the cobalt complex, in contrast to styrene and acrylate ended radicals.Chain transfer constant for the CCT polymerization of 2‐ethylhexyl methacrylate in toluene, and predictions for diffusion controlled systems.magnified imageChain transfer constant for the CCT polymerization of 2‐ethylhexyl methacrylate in toluene, and predictions for diffusion controlled systems.

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Section: Purified Solventsupporting

confidence: 81%

Solvent Effects, Diffusion Control and Mechanistic Aspects of Catalytic Chain Transfer Polymerization

Pierik¹,

Vollmerhaus²,

Herk³

2003

Macro Chemistry & Physics

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“…It is demonstrated that every ligand which can successfully work in bulk or solution ATRP, essentially can not be success in aqueous dispersed media. Only hydrophobic ligands which can form complex with transition metal and are soluble in polymerization loci (organic phase) such as bis(2-pyridylmethyl)octadecylamine (BPMODA), 4,4′-dinonyl-2,2′-bipyridine (dNbpy) and terpyridines are useful in this media [15,40]. Although Brij98 is a common and popular surfactant in aqueous dispersed media, Simms et al demonstrated that Brij98 as a non-ionic surfactant can not effectively stabilize the miniemulsion system at high temperatures.…”

Section: Resultsmentioning

confidence: 99%

Encapsulation of organomodified montmorillonite with PMMA via in situ SR&NI ATRP in miniemulsion

et al. 2012

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Encapsulation of organomodified montmorillonite within poly (methyl methacrylate) via in situ atom transfer radical polymerization with simultaneous reverse and normal initiation system (SR&NI ATRP) was successfully performed. Miniemulsion polymerization technique has been employed for its abundant advantages to encapsulate inorganic materials. Successful SR&NI ATRP was carried out using 4,4′-dinonyl-2,2′-bipyridine (dNbPy) as a hydrophobic ligand and cetyltrimethylammonium bromide (CTAB) as an effective cationic surfactant at high temperatures. Homogeneous distribution of droplets and particles with sizes in the range of around 170 nm was evaluated by dynamic light scattering (DLS) analysis. Final monomer conversion and molecular weight were determined by gravimetry and size exclusion chromatography (SEC) respectively. By increasing nanoclay content, conversion and molecular weight of nanocomposites decreased. Meanwhile, an increase in PDI values was also observed. X-ray diffraction (XRD) analysis results display organoclay layers disordered and delaminated in the polymer matrix. Thermal stability improvement of all the nanocomposites in comparison with the neat polymer was revealed by thermogravimetric analysis (TGA). Homogeneous distribution of spherical particles with sizes in the range of 170 nm was demonstrated by scanning electron microscopy (SEM) images. These results are complied with the DLS results. Transmission electron microscopy (TEM) image display a dispersion of partially exfoliated clay stacks in the matrix of PMNM 2.

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“…[11][12][13][14][15] The effects of polar solvents on the activation reaction was widely investigated by Matyjaszewski et al [23] , Chamhard et al [24] , and Haddleton et al [25] with acrylate and/or methacrylates. Water acts as a competitive co-ligand for copper species and favors the formation of Cu(II)Cl 2 , which moves the equilibrium of RX þ Cu(I)X/ L $ R .…”

Section: Use Of Water As An Accelerator For Polymerization Ratementioning

confidence: 99%

Atom Transfer Radical Block Copolymerization of 2‐(N,N‐Dimethylamino)ethyl Methacrylate and 2‐Hydroxyethyl Methacrylate

Jin

Shen

Zhu

2003

Macro Materials & Eng

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Block copolymerization of 2‐(N,N‐dimethylamino)ethyl methacrylate (DMAEMA) with 2‐hydroxyethyl methacrylate (HEMA) via atom transfer radical polymerization (ATRP) was studied in methanol using a macroinitiator method and a “one‐pot” sequential addition method. The polymerization sequence of the two monomers strongly affected the block copolymer formation. When DMAEMA was used as the first monomer, both methods produced block copolymer samples containing significant amounts of DMAEMA homopolymer chains, because of the elimination of active halogen chain‐ends during the preparation of polyDMAEMA. Well‐controlled block copolymers with various block lengths were obtained via the macroinitiator method when polyHEMA was used as macroinitiator to initiate the polymerization of DMAEMA. The sequential addition method, in which HEMA was polymerized first with 90% conversion and DMAEMA was subsequently added, also yielded controlled block copolymers when the polymerization was carried out at room temperature with the DMAEMA conversion below 60%. Increasing the temperature to 60 °C promoted the copolymerization rate but the reaction suffered from gel formation. The addition of water to the system accelerated the polymerization rate, but led to the loss of the system livingness.Gel permeation chromatograms of poly(HEMA‐b‐DMAEMA). The samples were prepared in methanol at room temperature with different block molecular weights using the macroinitiator method.magnified imageGel permeation chromatograms of poly(HEMA‐b‐DMAEMA). The samples were prepared in methanol at room temperature with different block molecular weights using the macroinitiator method.

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Atom transfer radical polymerisation in emulsion

Cited by 51 publications

References 0 publications

Solvent Effects, Diffusion Control and Mechanistic Aspects of Catalytic Chain Transfer Polymerization

Solvent Effects, Diffusion Control and Mechanistic Aspects of Catalytic Chain Transfer Polymerization

Encapsulation of organomodified montmorillonite with PMMA via in situ SR&NI ATRP in miniemulsion

Atom Transfer Radical Block Copolymerization of 2‐(N,N‐Dimethylamino)ethyl Methacrylate and 2‐Hydroxyethyl Methacrylate

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