Effect of additives on the initial stage of emulsion polymerization of styrene (St) using poly(vinyl alcohol) as a protective colloid

Suzuki, Atsushi; Matsuda, Yuichi; Masuda, Tetsuro; Kikuchi, Kenji; Okaya, Takuji

doi:10.1007/s00396-006-1550-3

Cited by 10 publications

(6 citation statements)

References 11 publications

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“…This mechanism was in accordance with the fundamentals of methods to improve the stability of PVA/MMA emulsions, such as modifying PVA with a thiol-terminated group [6,23,24] or the addition of alcohol such as methanol [10][11][12], which repressed the grafting reaction through chain transfer and allowed more PVA molecules to distribute on the surfaces. Moreover, it was understandable that the mini-emulsion polymerization of MMA monomers stabilized by PVA could carry out smoothly because the PVA molecules all located on the O/W interfaces and there existed no problem of inside grafting [13,14].…”

Section: Factors Influencing Colloidal Stability Of the Final Emulsionssupporting

confidence: 55%

“…Some assumed this arose from the poor grafting ability of conjugated monomers such as acrylates and methacrylates [4][5][6], while excessive grafting of the soluble polymers was believed to be the influencing factor by others [7,8]. Relevant results have been reported that quite a large quantity of PVA was grafted in the polymerizations of n-butyl acrylate and methyl methacrylate monomers [9,10] and it was feasible to get stable emulsions by suppression of grafting [10][11][12][13][14], but the reason for the unstability of relevant colloids was not given and still indistinct.…”

Section: Introductionmentioning

confidence: 98%

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Comparison of the different emulsion polymerization routes between acrylic and vinyl acetate monomers using poly(vinyl alcohol) as the sole stabilizer

Lin

Xia

2012

Colloid Polym Sci

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The emulsion polymerization of acrylic and vinyl acetate monomers using poly(vinyl alcohol) (PVA) as protective colloid has been studied for a long time, whereas rare reports ranged over the lateral comparison of the two systems and the reason for the unstability of the PVA/MMA polymerization system was still indistinct. Here in this paper, a collection of experiments of methyl methacrylate (MMA) and vinyl acetate (VAc) were performed respectively with varied amount of PVA as the sole stabilizer. The grafting extent of the polymerisate was characterized through the fraction and FTIR and it was found that the grafted amount of PVA was even larger in the PVA/MMA copolymers than PVA/VAc copolymers, so the grafted mode of PVA was considered. Based on the kinetics, the slower initiation rate of sulfate radical towards MMA was found to be responsible for the unstability of corresponding colloids accompanied with the relatively quicker hydrogen abstraction of radical to PVA, which resulted in "layer-by-layer" grafting structure inside and the particle surface-grafting density was lowered thereof. This was proved with TEM and static contact angle measurements and a pseudohomopolymer model was employed to describe the relationship of colloidal stability and the PVA density on surfaces.

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Section: Factors Influencing Colloidal Stability Of the Final Emulsionssupporting

confidence: 55%

Section: Introductionmentioning

confidence: 98%

Comparison of the different emulsion polymerization routes between acrylic and vinyl acetate monomers using poly(vinyl alcohol) as the sole stabilizer

Lin

Xia

2012

Colloid Polym Sci

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“…In a controlled emulsion polymerization, block copolymer micelles as latexes are obtained because the polymerization progresses from the polymer chain end of the shell. When a hydrophilic/amphiphilic polymer prepared by conventional polymerization is used, core–shell particles as latexes are formed by physical adsorption via hydrogen bonding and/or by chemical grafting via hydrogen abstraction. , For example, poly(vinyl alcohol) (PVA) has been widely and industrially used as a steric stabilizer, i.e., a protective colloid, for commercial core–shell particles. − Since PVA does not typically form micelles and does not act as a surfactant, this polymerization is classified as a surfactant-free emulsion polymerization. However, coagulation often occurs owing to the lack of mechanical stability resulting from extensive grafting of PVA .…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Various Poly(2-hydroxyethyl vinyl ether)-Stabilized Latex Particles via Surfactant-Free Emulsion Polymerization in Water

et al. 2018

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Following the recent success of the controlled radical polymerization of hydroxy-functional vinyl ethers [Macromolecules 2016[Macromolecules , 49, 1563 2017, 50, 8346], we report a surfactant-free, batch emulsion polymerization stabilized by the poly(hydroxy-functional vinyl ether)s. A series of emulsion polymerizations of various hydrophobic monomers such as vinyl acetate (VAc), methyl methacrylate (MMA), ethyl acrylate (EA), and styrene (St) were performed using poly(2-hydroxyethyl vinyl ether) (PHEVE) with hydrophilic azoinitiator, 2,2′-azobis(2-amidinopropane) dihydrochloride. In the emulsion polymerization in water using PHEVE as a steric stabilizer, the polymerization proceeded smoothly to form PHEVE-stabilized spherical particles without any coagulation. The mean particle diameter could be controlled over a size range (261 nm−ca. 1 μm) with relatively narrow size distributions by varying the synthesis parameters. Furthermore, one-pot emulsion polymerization was also conducted from HEVE to poly(vinyl acetate) (PVAc) latex particles through PHEVE. However, in the case of other analogous stabilizers such as poly(4-hydroxybutyl vinyl ether) (PHBVE) and poly(2-metoxyethyl vinyl ether) (PMOVE) as a more hydrophobic stabilizer than PHEVE, highly stable latex particles were not formed, with the exception of PMOVE-stabilized PSt latex particles (micelles). The dispersing ability of PHEVE was further confirmed by RAFT emulsion polymerization of VAc. The RAFT emulsion polymerization of VAc using PHEVE macromolecular chain transfer (macro-CTA) proceeded in water to form PHEVE-b-PVAc latex particles with 71−293 nm size depending on degree of PVAc block. However, using binary mixed PHEVE and thermoresponsive PHBVE macro-CTAs, the resulting latex particles formed small aggregate of particles at 20 °C due to the decrease in stability and hydrophilicity relative to PHEVE. All the products using PHEVE successfully prepared are core−shell particles with PHEVE shells which give high dispersion stability for hydrophobic core. Such PHEVE-stabilized particles resulted in highly ordered three-dimensional colloidal crystals owing to the interaction of their hydrophilic PHEVE surfaces.

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“…16,17 However, the utilization of PVA as the sole stabilizer in emulsion polymerization has been limited to VAc or vinyl chloride monomers, and it meets difficulties in the emulsion polymerizations of conjugate monomers such as styrene and acrylic monomers with the formation of coagulum. 18,19 A common understanding is that the PVA without well segregated hydrophilic groups and hydrophobic groups has poor stabilizing capacity for emulsion, it only generates pseudo-micelles or several chains aggregating in a pseudo-micellar structure, 20 and the stability during emulsion polymerization is strongly but intricately dependent on the grafting of PVA with highly reactive monomers initiated by specific initiator like APS. 21,22 From this point of view, the alternation of initiator or the acceleration of monomers conversion are worth attempting to remain the stability during emulsion polymerization and broaden the choice on monomer species.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of polystyrene latex via emulsion polymerization with poly(vinyl alcohol) as sole stabilizer

Lü

Liu

Luo

2017

J of Applied Polymer Sci

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Compared with low molecular surfactants, poly(vinyl alcohol) (PVA) could afford latexes with particular tackiness as an important property for various applications. However, until now, except for some highly reactive monomers, most of monomers including styrene seldom use PVA as protective colloid in emulsion polymerization. In this work, we used oil‐soluble initiator, 2,2′‐azobisisobutyronitrile, to accelerate the copolymerization of styrene and divinyl benzene in PVA protected colloids and synthesize polystyrene (PS) latex within 50 min at 70 °C successfully. The reaction system could remain stable even at the monomer‐to‐water ratio as high as 1:4, and the polymerization in pseudo‐micelles or latex particles was always dominant. The adjustment of the size of the PS latex in the range from 70 to 100 nm was facilely achieved by changing the polymerization temperature, the addition of PVA, or the monomer‐to‐water ratio. This method was also exploited to synthesize poly(styrene‐co‐methyl methacrylate) and poly(styrene‐co‐4‐chlorostyrene) latexes, indicating prospects in applications with the advantages of high capacity and broad applicability. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45111.

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Effect of additives on the initial stage of emulsion polymerization of styrene (St) using poly(vinyl alcohol) as a protective colloid

Cited by 10 publications

References 11 publications

Comparison of the different emulsion polymerization routes between acrylic and vinyl acetate monomers using poly(vinyl alcohol) as the sole stabilizer

Comparison of the different emulsion polymerization routes between acrylic and vinyl acetate monomers using poly(vinyl alcohol) as the sole stabilizer

Synthesis of Various Poly(2-hydroxyethyl vinyl ether)-Stabilized Latex Particles via Surfactant-Free Emulsion Polymerization in Water

Synthesis of polystyrene latex via emulsion polymerization with poly(vinyl alcohol) as sole stabilizer

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