Block emulsion polymerisation

However, in a recent publication, Shirinyan, Mnatsalianov, et al. (20) find that differences between the rates of vinyl acetate emulsion polymerisation observed with samples of similar polyvinyl alcohols manufactured by the same process In three different factories could be attributed to a condensation product of acetaldehyde derived from hydrolysis of residual vinyl acetate this gave rise to a conjugated ketone type ultra-violet spectrum and could be extracted from the polyvinyl alcohol under suitable conditions. This could be the uncontrolled factor which appears to have confounded nmuiy of the experiments reported here. Even more recently the same laboratory ( ) has reported that there Is an optimum sequence length of hydroxyl groups in the polyvinyl cdcohol-acetate block copolymer for polymerisation rate and dispersion stability. 

Tuzar and Kratochvil (23) have reported that styrene-butadiene block copolymers mlcellise in selective solvents for polystyrene and solubilise large amounts of polybutadiene homopolymer. Sinc.e the surface active grades of polyvinyl alcohol are polyvinyl alcohol-acetate block copolymers and water is a selective solvent for polyvinyl alcohol a similar effect may be expected which could affect the course of the vinyl acetate emulsion polymerisation. 

Most reports on emulsion polymerisation have been limited to commercially available surfactants which, in many cases, are relatively simple molecules such as sodium dodecyl sulphate and simple nonionic surfactants. However, studies on the effects of surfactant structure on latex formation have revealed the importance of the structure of the molecule. Block and graft copolymers (polymeric surfactants) are expected to be better stabilisers when compared to simple surfactants. The use of these polymeric surfactants in emulsion polymerisation and the stabilisation of the resulting polymer particles is discussed below. 

Most aqueous emulsion and dispersion polymerisation that have been reported are based on a few commercial products with a broad molecular weight distribution and varying block composition. The results obtained from these studies could not establish the effect that the structural features of the block copolymer would have on their stabilising ability and effectiveness in polymerisation. Fortunately, model block copolymers with well-defined structures can be synthesised, and their roles in emulsion polymerisation have been determined using model polymers and model latexes. 

A series of well-defined A-B block copolymers of polystyrene-block-polyethylene oxide (PS-PEO) were synthesised [6] and used for the emulsion polymerisation of styrene. These molecules are ideal as the polystyrene (PS) block is compatible with the PS formed, and thus it forms the best anchor chain. The PEO chain (the stabilising chain) is strongly hydrated with water molecules and extends into the aqueous phase where it forms the steric layer necessary for stabilisation. 

Boston, Mas., 23rd-27th Aug.1998, p.440-1. 012 AMPHIPHILIC BLOCK COPOLYMERS AS SURFACTANTS IN EMULSION POLYMERISATION... 

The idea of the preparation of porous polymers from high internal phase emulsions had been reported prior to the publication of the PolyHIPE patent [128]. About twenty years previously, Bartl and von Bonin [148,149] described the polymerisation of water-insoluble vinyl monomers, such as styrene and methyl methacrylate, in w/o HIPEs, stabilised by styrene-ethyleneoxide graft copolymers. In this way, HIPEs of approximately 85% internal phase volume could be prepared. On polymerisation, solid, closed-cell monolithic polymers were obtained. Similarly, Riess and coworkers [150] had described the preparation of closed-cell porous polystyrene from HIPEs of water in styrene, stabilised by poly(styrene-ethyleneoxide) block copolymer surfactants, with internal phase volumes of up to 80%. 

The poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) block copolymers were also used to gel the continuous aqueous phase. Poloxamers may be used as the secondary hydrophilic surfactant in the preparation of the w/o/w system, and the finished emulsion is then irradiated. The polymerisation reaction can be monitored by cone-and-plate viscometry. Fig. 9 shows the flow curve obtained for a water/isopropyl myristate/water emulsion as a function of the radiation dose. As the dose of y-irradiation is increased, the viscosity of the w/o/w emulsion increased up to a gel-point1. The gel-point of the emulsion is dependent on the type and concentration of poloxamer. In the example shown, prepared using a mixture of 5% (w/v) Pluronic F87 and 5% (w/v) Pluronic F88 in the external phase, the gel-point was reached at 4.2 (Fig. 9). Fig. 10 shows the changes in the properties of irradiated systems on storage. 

Block copolymers with polypeptide segments were occasionally used to stabilise oil-in-water emulsions or as emulsifiers in heterophase polymerisation processes. 

The polyners eu e pr red in eiqueous emulsions at 100-120 C and 5-7 MPa pressure with a free reKiical initiator. The polymers are prepared at high monomer conversions and display normal solution viscosity behavior. Vii lidene fluoride is much more reactive than hexafluoropropylene, and, under the polymerisation conditions, no (HFP)n blocks are formed, whereas (VF2 )n sequences are present. The nudn polymer structure, therefore, is represented by the following blocks ... 

Functional oligomers with a terminal alpha-substituted acrylate group can be synthesised by catalytic free-radical chain transfer polymerisation based on cobalt II or II chelates. The apphcations of such oligomers in the design of low molec.wt., graft and block copolymer emulsions and dispersions for waterborne, two-component PU paints are reviewed. The emulsions and dispersions are shown to have composition and molec.wt. control and to exhibit... 

Details are given of the synthesis of biodegradable graft copolymers based on a backbone of polylactic acid grafted with short blocks of polyacrylamide. Emulsion and solution polymerisations were examined. Molecular structures were determined by proton NMR and FTIR and by DSC. Cytotoxicity tests were conducted to assess their biocompatibility. Preliminary results of their potential in controlled release technologies are reported. 17 refs. 

Two main nitroxide families have been examined TEMPO (N1 in Figure 5.6) and derivatives (N2-N7) and SGI (NIO). With TEMPO, most of the results were related to styrene homopolymerisation and only a few articles reported the homopolymerisation of n-butyl acrylate (Georges et al, 2004) in addition to its copolymerisation with styrene. With SGI, the homo-, random and block copolymerisations were investigated for both styrene and -butyl acrylate monomers. Only in the case of styrene has the emulsion process been examined, and due to the difficulties encountered most authors turned their attention towards miniemulsion polymerisation. 

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