Radical Polymerization of Vinyl Monomers by Hydrophilic Macromolecules. II. Uncatalyzed Polymerization in the Presence of Copper(II) Ions

Imoto, Minoru; Ouchi, Tatsuro

doi:10.1080/07366578308079444

Cited by 13 publications

(1 citation statement)

References 77 publications

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“…Combining these interfacial factors, it may be helpful to further understand the mechanism of emulsion polymerization. In fact, the interface has been suggested to be the locus of initial reaction for the thermally initiated emulsion polymerization. , Therefore, the role of reaction in the interface of monomer/ aqueous phase should be evaluated in all the mechanistic study of emulsion polymerization, though the thickness of interface is just on the order of tens molecular size…”

Section: Introductionmentioning

confidence: 99%

Mechanism of Soap-Free Emulsion Polymerization of Styrene and 4-Vinylpyridine: Characteristics of Reaction in the Monomer Phase, Aqueous Phase, and Their Interface

et al. 2001

Macromolecules

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The characteristics of reactions in the monomer phase, aqueous phase, and the interface of monomer/aqueous phase of soap-free emulsion polymerization of 4-vinylpyridine (4VP) and styrene (St) system were evaluated by using the different types of initiators, addition of organic solvents, and changes of agitation rate. The oil-soluble initiators 2,2′-azobis(2,4-dimethylvaleronitrile) (ADVN), benzoyl peroxide (BPO), and 2,2′-azobis(isobutyronitrile) (AIBN), the organic water-soluble initiator, 2,2′-azobis(2amidinopropane) dihydrochloride (V50), and the inorganic water-soluble initiator, potassium persulfate (KPS), were used. 1 H NMR and scanning electronic microscopy (SEM) were employed for the characterizations. As a result, the mechanism of interfacial particle formation was supported. Namely, the minimonomer droplets were generated by the disturbance in the interface of monomer/aqueous phase due to the agitation. The minimonomer droplets were stabilized by the adsorption of surface-active oligomer generated by the reactions in both the aqueous phase and the interface. The monomer transfer from the bulk monomer phase to the growing particles was via the coalescence of minimonomer droplets with particles. The role of reaction in the aqueous phase was proposed to just provide the surface-active oligomer for the stabilization of particles. The rapid reaction in the aqueous phase due to the high concentration of hydrophilic monomer produced longer hydrophilic chains and led to the coagulation of particles by a bridging-coagulation effect. On the basis of this mechanism, the coagulum-free stable latices with high monomer conversion were prepared by using KPS and AIBN and, theoretically, can be prepared by using any type of initiators at a high level of solid content and feed ratio of hydrophilic monomer.

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Section: Introductionmentioning

confidence: 99%

Mechanism of Soap-Free Emulsion Polymerization of Styrene and 4-Vinylpyridine: Characteristics of Reaction in the Monomer Phase, Aqueous Phase, and Their Interface

et al. 2001

Macromolecules

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Morphological studies in thermally initiated emulsion (co)polymerization without conventional initiators

Du¹,

Ma²,

Ni³

et al. 2002

J of Applied Polymer Sci

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Poly(methyl methacrylate-co-styrene) composite latices were prepared by thermally initiated seed emulsion (co)polymerization of styrene (ST), methyl methacrylate (MMA), or ST and MMA employing a PST or PMMA seed in the absence of conventional initiators. The changes of particle morphology, observed by transmission electron microscopy (TEM), were investigated by varying seed particle component, the weight ratio of monomer to seed polymer, monomer composition, and employing preswelling of the seed particles. The size distribution of polymer particles obtained from thermally initiated emulsion (co)polymerization was improved by employing the seed process. Hemisphere-like, sandwich-like, core-shell, and inverted core-shell particle morphologies were observed depending upon the polymerization conditions. The preswelling of seed particles did not affect the morphology of final particles. The particle morphologies, obtained from the thermal process, were compared with those obtained from conventional seed emulsion polymerization. The incorporation of an initiator fragment SO 4 Ϫ to polymer chain ends seemed to allow the PST chains to gain some hydrophilicity. From the observation of particle morphology, the hydrophilicity of involved polymers were in the following order: PMMA with ionic (OSO 4 Ϫ ) chain ends Ͼ PMMA with no ionic ends Ͼ PST with ionic ends Ͼ 60% MMA P(MMA-co-ST) with no polar ends Ͼ 40% MMA P(MMA-co-ST) with no polar ends Ͼ PST with no polar ends.

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Synthesis of high solid latices by thermally initiated emulsion polymerization

Du¹,

Ma²,

Nagai³

et al. 2002

J of Applied Polymer Sci

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Radical Polymerization of Vinyl Monomers by Hydrophilic Macromolecules. II. Uncatalyzed Polymerization in the Presence of Copper(II) Ions

Cited by 13 publications

References 77 publications

Mechanism of Soap-Free Emulsion Polymerization of Styrene and 4-Vinylpyridine: Characteristics of Reaction in the Monomer Phase, Aqueous Phase, and Their Interface

Mechanism of Soap-Free Emulsion Polymerization of Styrene and 4-Vinylpyridine: Characteristics of Reaction in the Monomer Phase, Aqueous Phase, and Their Interface

Morphological studies in thermally initiated emulsion (co)polymerization without conventional initiators

Synthesis of high solid latices by thermally initiated emulsion polymerization

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