Morphologies of an Amphiphilic Diblock Copolymer of Poly (Ethylene Oxide)-b-Polystyrene and Its Blends with Poly (2,6-Dimethyl-1,4-Oxide)

Systems containing block copolymers are of great interest due to the ability of copolymers to self-assemble into a variety of structured, ordered, or partially ordered morphologies. A fascinating morphology of two-dimensional arrays of hexagonal-like holes was observed for the first time in the diblock copolymer of poly (ethylene oxide)-b-polystyrene (PEO-b-PS) by transmission electron microscopy (TEM). The blends of PEO-b-PS with poly (2,6-dimethyl-1,4-phenylene oxide) (PPO) were obtained by solution blending, and the morphologies of PEO nano-dispersed particles in PPO/PS matrix were observed by atomic force microscopy (AFM) and TEM. Using the film forming technique on water/air interface, the core-shell morphology with PEO as shells was obtained in PEO-b-PS/PPO blends. Thus, three different morphologies were obtained by controlling preparation conditions. Especially, PEO-b-PS self-organized into the hexagonal-like holes patterns was first found to our knowledge.     

Emulsifying properties,of block copolymers. Oil-water emulsions and microemulsions

The emulsifying effect of poly(styrene-b-ethylene oxide) block copolymers (Cop PS-PEO) has been studied for the toluene-water system as a function of the molecular characteristics of the copolymer (composition, molecular weight, and structure). To demonstrate the surfactive properties of Cop PS-PEO, we determined the interfacial tension γ_i for the toluene-water system in the presence of these block copolymers. For oil/water (O/W) and water/oil (W/O) emulsions, prepared in the presence of Cop PS-PEO, we determined the phase inversion point, the particle size of the dispersed phase, the stability and the viscosity as a function of the PEO content, the molecular weight, and the structure of the block copolymers. It appeared that the best results for the emulsification are obtained with Cop PS-PEO having molecular weights less than 100, 000. Stable O/W emulsions of small particle size are preferentially prepared with di- or triblock copolymers having a PEO content of 60-80 percent. In contrast, stable W/O emulsions are obtained with diblock copolymers having a PS content of 60-80 percent. The difference in behavior between diand triblock copolymers also showed the importance of the chain conformation at the toluene-water interface. As an extension, we have shown that microemulsions can be obtained with such polymeric surfactants. Isopropanol and butylamine appeared to be efficient cosurfactants for the system water/toluene/Cop PS-PEO.     

Morphology of polystyrene/polystyrene-block-poly(methyl methacrylate)/poly(methyl methacrylate) composite particles

Polystyrene/polystyrene-block-poly(methyl methacrylate)/poly(methyl methacrylate) (PS/PS-b-PMMA/PMMA) composite particles were prepared by releasing toluene from PS/PS-b-PMMA/PMMA/toluene droplets dispersed in a sodium dodecyl sulfate aqueous solution. The morphology of the composite particles was affected by release rate of toluene, the molecular weight of PS-b-PMMA, droplet size, and polymer composition. ‘Onion-like’ multilayered composite particles were prepared from toluene droplets of PS-b-PMMA and of PS/PS-b-PMMA/PMMA, in which the weights of PS and PMMA were the same. The layer thicknesses of the latter multilayered composite particles increased with an increase in the amount of the homopolymers. PS-b-PMMA/PS composite particles had a sea-islands structure, in which PMMA domains were dispersed in a PS matrix. On the other hand, PS-b-PMMA/PMMA composite particles had a cylinder-like structure consisting of a PMMA matrix and PS domains.     

Nonaqueous emulsion copolymerization of ethyl methacrylate/lauryl methacrylate in propylene glycol. II. Adsorption of poly(ethylene oxide)–polystyrene–poly(ethylene oxide) triblock copolymer on latex particles

The adsorption behavior of various poly(ethylene oxide)–polystyrene–poly(ethylene oxide) (PEO‐PS‐PEO) triblock copolymer (TBC) s on acrylic latex particles in propylene glycol was studied. The composition of the PEO‐PS‐PEO triblock polymers varied from 41 to 106 in each PEO block length and from 18 to 41 in the PS block length. The location of the PEO‐PS‐PEO TBC was determined by analyzing for the physically adsorbed amount on the latex surface, the anchored mount on the surface, the entrapped amount inside the particle, and the “free” PEO‐PS‐PEO TBCs in the propylene glycol. A contour graph technique was applied to analyze the experimental data, which showed that a minimum existed for the physically adsorbed portion at a PS block length of about 30 units. When the PS block length was less than 30 units, the adsorption decreased with increasing PS block length, indicating rearrangement of mixed PEO brush and adsorbed PS block. When the PS block was greater than 30 units, the adsorption increased with increasing block length because of the poor solvency of the PS block in the propylene glycol medium, resulting in a collapse of the PS chain. Considering the binding energy between the PS block and the latex particle surface, which governs adsorption, it was hypothesized that a lower block length limit exists, below which no adsorption takes place. The solubility of the PS block in propylene glycol guides the important upper block length limit. The anchored fraction of the block copolymer increased continuously with increasing PS block length in the entire region investigated. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1963–1975, 2001     

Use of poly(styrene)-block-poly(ethyleneoxide) as emulsifier in emulsion polymerization

Summary Poly(styrene)-block-poly(ethyleneoxide), abbreviated as (PS-b-PEO) were used as emulsifiers in emulsion polymerization of styrene and methyl methacrylate. The block copolymers had a poly(styrene) block with M_n=1000 g/mol and a poly(ethyleneoxide) block with M_n=1000, 3000 or 5000 g/mol, respectively. Stable dispersions were obtained when the PEO block molecular weight was higher than 1000 g/mol. Also the amphiphilic properties of the copolymers depended on the PEO chain length. Block copolymer micelles with hydrodynamic radii between 11 and 17nm were observed. Emulsion polymerization was performed at different block copolymer concentration at 60 and 80°C. Particle size varied between 50 and 300nm and decreased with increasing copolymer concentration. The particle size was larger at higher temperature, but the size distribution was narrower. Polymerization of methyl methacrylate gave smaller particles when compared to styrene. The dispersions were very stable towards high electrolyte concentration, but flocculation occurred at elevated temperatures. Both observations indicate that the dispersions are sterically stabilized.     

Morphology rearrangement of PEO and PG blocks of amphiphilic copolymer particles in solution affected by FeCl<Subscript>3</Subscript>/acidified water addition

The present contribution describes the preparation of nanosized aggregates by dissolving diblock copolymers consisting of hydrophobic polystyrene (PS) with randomly distributed short diene (D) moieties and hydrophilic polyether (polyethylene oxide (PEO) or polyglycidol (PG)) blocks in selective solvents. Inducing structural and/or size changes of the aggregates by addition of FeCl₃/acidified H₂O to the system is experimented. Dynamic light scattering (DLS) and size exclusion chromatography (SEC) measurements reveal resizing of the particles whilst adding FeCl₃/acidified H₂O. Further the structure and size of P(SD-EO/G) block copolymer corе-shell particles are determined by Diffusion Ordered NMR Spectroscopy (DOSY) which indicates a partial reversal of the core-shell structure upon the addition of FeCl₃/acidified H₂O. Transmission electron microscopy provides a more detailed insight on the morphology, shape and size distribution of the aggregates. For comparison, the change in the particle size under identical conditions for species of preliminary stabilized core-shell morphology is monitored as well.     

Preparation and characterization of polystyrene–poly(ethylene oxide) amphiphilic block copolymers via atom transfer radical polymerization: Potential application as paper coating materials

Poly(ethylene oxide) (PEO) monochloro macroinitiators or PEO telechelic macroinitiators (Cl‐PEO‐Cl) were prepared from monohydroxyfunctional or dihydroxyfunctional PEO and 2‐chloro propionyl chloride. These macroinitiators were applied to the atom transfer radical polymerization of styrene (S). The polymerization was carried out in bulk at 140°C and catalyzed by Copper(I) chloride (CuCl) in the presence of 2,2′‐bipyridine (bipy) ligand (CuCl/bipy). The amphiphilic copolymers were either A‐B diblock or A‐B‐A triblock type, where A block is polystyrene (PS) and B block is PEO. The living nature of the polymerizations leads to block copolymers with narrow molecular weight distribution (1.072 < M_w/M_n < 1.392) for most of the macroinitiators synthesized. The macroinitiator itself and the corresponding block copolymers were characterized by FTIR, ¹H NMR, and SEC analysis. By adjusting the content of the PEO blocks it was possible to prepare water‐soluble/dispersible block copolymers. The obtained block copolymers were used to control paper surface characteristics by surface treatment with small amount of chemicals. The printability of the treated paper was evaluated with polarity factors, liquid absorption measurements, and felt pen tests. The adsorption of such copolymers at the solid/liquid interface is relevant to the wetting and spreading of liquids on hydrophobic/hydrophilic surfaces. From our study, it is observed that the chain length of the hydrophilic block and the amount of hydrophobic block play an important role in modification of the paper surface. Among all of block copolymers synthesized, the PS‐b‐PEO‐b‐PS containing 10 wt % PS was found to retard water absorption considerably. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4304–4313, 2006     

Associative properties of perfluorooctyl end‐functionalized polystyrene–poly(ethylene oxide) diblock copolymers

The synthesis of 2,2,3,3‐tetrahydro‐perfluoroundecanoyl end‐functionalized polystyrene–poly(ethylene oxide) block (PS‐block‐PEO‐R_F) copolymers and their matching PS‐block‐PEO diblock copolymers was carried out by sequential anionic polymerization. Viscometry and ¹⁹F NMR studies show that the PS‐block‐PEO copolymers, in contrast to their matching PS‐block‐PEO‐R_F copolymers, exhibit a micellar rather than the associative behavior seen for the latter. However, the presence of an excess of fluorinated acid, used for end‐functionalization, produces a reduction of the associative behavior above the overlap concentration, with the fluorinated acid acting like a surfactant. A competition may also occur between PS—and R_F—mediated micellization. Copyright © 2004 Society of Chemical Industry     

Nonaqueous poly(methyl methacrylate) dispersions: radical dispersion polymerization in the presence of AB block copolymers of polystyrene and poly(dimethyl siloxane)

Well defined AB block copolymers of polystyrene (PS) and poly(dimethyl siloxane) (PDMS) have been prepared with PS molecular weights in the range 8 800 to 43 600 and PDMS molecular weights in the range 2 400 to 48 000. Provided the PS and PDMS molecular weights have a ratio within the range 0.5 to 4.0, these block copolymers stabilize particles of poly(methyl methacrylate) in n-alkanes. The particle size over the range 0.1 to 0.5 μm may be varied by performing dispersion polymerizations of methyl methacrylate as a function of monomer content of the seed stage and as a function of the concentration, molecular weight and composition of the block copolymer. From silicon analyses of the poly(methyl methacrylate) particles, values of the surface area stabilized per PDMS chain were established. The results indicate complete surface coverage of the particles.     

Thermoreversible gelation of biodegradable polyester (PHBV) in toluene

In present paper we investigate thermoreversible gelation of biodegradable polyester poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) in toluene. Hot PHBV solutions became transparent gels after cooling to room temperature. This physical gelation process was followed by light scattering and viscosity measurements for solutions of different PHBV concentrations. It has been found that gelation temperature increases with increasing polymer concentration in toluene. PHBV films have been prepared by gelation process followed by solvent removal on solid substrates. It has been demonstrated that PHBV concentration in the solution influences the surface morphology of obtained films. Homogeneous PHBV films with increased surface roughness can be obtained by means of developed technique. Hydrolytic degradation studies indicate that surface morphology of obtained PHBV layers changes considerably with degradation time.     

The effect of the architecture and concentration of styrene–butadiene compatibilizers on the morphology of polystyrene/low‐density polyethylene blends

The effect of styrene–butadiene block copolymers (SB) with varying number of blocks and length of styrene blocks on the morphology, rheology, and impact strength of 4/1 polystyrene/low‐density polyethylene (PS/LDPE) blends was studied. The scanning and transmission electron microscopy and X‐ray scattering were used for determination of the size of LDPE particles and the localization and structure of SB copolymers in blends. It is shown that the dependence of the LDPE particle size on the amount of added SB and localization of SB copolymers in blends is predominantly controlled by the length of their styrene blocks. It follows from thermodynamic considerations that the reason is the difference in composition asymmetry between SB with short and long styrene blocks. Coalescence of particles of SB having short styrene blocks at the surface of LDPE droplets and movement of SB with long styrene blocks to the PS–LDPE interface were observed during annealing of PS/LDPE/SB blends. Pronounced migration of SB copolymer during annealing shows that their localizations in blends in steady state on long steady mixing and at thermodynamic equilibrium are different. The values of tensile impact strength of PS/LDPE/SB blends correlate well with the size of LDPE particles and the amount of SB at the interface. Viscosity of PS/LDPE/SB depends on molecular structure of SB copolymers by a manner different from that of tensile impact strength. The results of this study and literature data lead to the conclusion that the compatibilization efficiency of SB copolymers for a certain polystyrene‐polyolefin pair is a function of not only molecular parameters of SB but also of the polystyrene/polyolefin ratio, the amount of SB in a blend, and mixing and processing conditions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2803–2816, 2006     

Nanodroplet formation and exclusive homogenously nucleated crystallization in confined electrospun immiscible polymer blend fibers of polystyrene and poly(ethylene oxide)

By utilizing electrospun blend fibers of polystyrene (PS) and poly(ethylene oxide) (PEO) with diameters in sub-microns, nanodroplets of the minor component (PEO) were obtained by annealing the blend fibers above the glass transition temperature (T_g) of the matrix polymer (PS), as a result of the Rayleigh-Plateau instability in the melt. However, direct thermal annealing of the PS/PEO blend fibers led to poor Rayleigh breakup of the PEO fibers in the PS matrix, and fractionated crystallization with both homogeneous and heterogeneous nucleation was observed, probably due to a broad size distribution of PEO particles. On the contrary, after confining the PS/PEO blend fibers with a high T_g polymer, poly(4-tert-butyl styrene) (P4tBS, T_g ∼ 143 °C), well-defined Rayleigh breakup of the PEO fiber was achieved by annealing the P4tBS-coated PS/PEO blend fibers at 150 °C. Consequently, exclusive homogeneously nucleated PEO crystallization was observed at −20 °C. This report could provide a universal method to achieve nano-sized droplets for the study of nanoconfinement effect by utilizing electrospun immiscible polymer blend fibers without addition of any compabitilizers.     

Compatibilization of PA6/PPO blend with carboxylated poly(styrene) compounds

PA6/PPO 70/30 blends were reactively compatibilized using carboxylated polystyrene (PS) and poly(styrene‐block‐4‐methylstyrene) with various degrees of carboxylation. The high carboxylation of PS (up to about 50%) caused a decrease of dispersed PPO dimensions with a simultaneous deterioration of properties, especially of toughness and elongation. The best mechanical behavior was found for PS with 1% degree of carboxylation and for neat PS. On the other hand, degrees of carboxylation higher than 50% caused an increase in particle size. This was most significant for block copolymers, where a marked change in size and shape occurred, from spherical particles of about 1 μm in size to large, elongated particles about 50 μm long or a similar rough cocontinuous structure. The deteriorated mechanical behavior is tentatively explained by unsuitable properties of the reactively formed compatibilizer and thus of the interface. The enhanced rigidity of highly carboxylated poly(4‐methylstyrene) chains (and its product of grafting with PA6), causing its decreased emulsification ability together with the expected rigid interface, which probably suppresses breakup of the PPO phase, may be responsible for the increase of the dispersed PPO dimensions found. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2273–2280, 2001     

Nonaqueous emulsion copolymerization of ethyl methacrylate/lauryl methacrylate in propylene glycol. I. Evaluation of stabilizing efficiency for PEO‐PS‐PEO triblock copolymers

Sixteen poly(ethylene oxide)–polystyrene–poly(ethylene oxide) (PEO‐PS‐PEO) triblock copolymers were synthesized by anionic polymerization. They were characterized by gel permeation chromatography and proton NMR. The molecular weight of these 16 PEO‐PS‐PEO triblock copolymers ranged from 5100 to 13,300. The polystyrene (PS) block length was between 13 and 41. The PEO block length was between 41 and 106. The polydispersity index for these PEO‐PS‐PEO triblock copolymers were 1.05 ± 0.02. When using these stabilizers in the emulsion copolymerization of ethyl methacrylate and lauryl methacylate in propylene glycol, only a narrow window of stability was observed. Stable latexes were formed only when the molecular weights of the PEO blocks were within the range of 5300–7700 and the molecular weights of the PS blocks were 2000–4000. The stabilizer ability for these triblock copolymers was correlated with their molecular weight and conformation in propylene glycol. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1951–1962, 2001     

Preparation of core–shell particles by dispersion polymerization with a poly(ethylene oxide) macroazoinitiator

A macroazoinitiator (MAI) containing a poly(ethylene oxide) (PEO) block was used with a methyl methacrylate monomer to prepare polymer particles in ethanol/H₂O solutions. The effects of the monomer/MAI ratio (RMI) and H₂O content in the solutions on the molecular weight, particle diameters, and chemical structure of the resulting polymer particles were investigated. The reaction mixtures showed three kinds of states, which were milky colloid solutions, macrogels and/or precipitations, and clear solutions. The colloid solutions were obtained in the solutions with an H₂O content of about 50–90 vol % and a RMI of 20–400. In the colloid solutions, core–shell nanospheres consisting of PEO shells and poly(methyl methacrylate) (PMMA) cores were predominantly obtained. In the specific conditions close to the area of gel and/or precipitation formation, particles connected about 0.5–5 μm in length were obtained. Multiblock copolymers nanospheres tended to be obtained with lower RMIs, and PMMA‐PEO‐PMMA tri‐bloc and/or PMMA‐PEO di‐block copolymer nanospheres were obtained with higher RMIs. The solubility of the monomer and the generated polymer in solutions may have affected the polymerization development and the state of the products. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Morphology and mechanical properties of polypropylene/polystyrene blends compatibilized with styrene–butadiene block copolymers

The effect of molecular structure of styrene–butadiene block (SB) copolymers on the morphology, tensile properties, impact strength, and microhardness of polypropylene/polystyrene (PP/PS) (80/20) blends was studied. The addition of SB copolymers substantially reduces the size of dispersed PS particles formed at mixing. The distribution of SB copolymers between the interface and bulk phases is controlled by the length of styrene blocks in SB, but a decrease in the size of PS particles at mixing correlates with total molecular weight of SB copolymers. For a substantial part of compatibilized blends, PS particles aggregate rapidly during compression molding and form honeycomb‐like particles split by SB partitions, which persist at further annealing. Aggregation of PS particles continues slowly at further annealing. Blends containing PS particles with well‐developed honeycomb structure show lower yield stress, higher plasticity, and lower tensile impact strength than the blends having PS particles with simple or undeveloped honeycomb structure. Microhardness of PP/PS blends is additive and of PP/PS/SB blends is lower than the additive due to the effect of SB copolymers on crystalline structure of PP matrix. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Poly(styrene-graft-ethylene oxide) as a compatibilizer in polystyrene/polyamide blends

Polystyrene (PS) blends containing a dispersed phase of either polyamide-6 (PA-6) or polyamide-12 (PA-12) were compatibilized by additions of 1, 3, or 5 wt % poly(styrene-graft-ethylene oxide). The graft copolymers were found to have a stabilizing effect on the domain sizes. Weight average radii of PA-6 domains in compression molded samples were reduced by a factor of 5 with 3 wt % graft copolymer added. The corresponding size reduction for PA-12 domains was by a factor of 3. Also, the domain sizes were more uniformly distributed in blends containing the graft copolymers. Thermal analysis of the blends revealed that compatibilization retarded the PA crystallization, with some PA crystallizing at the PS glass transition. This retarded crystallization is explained as a result of the domain size reduction and by the presence of graft copolymer at the interface. The graft copolymers had a toughening effect on the blends and the impact strength of a PS/PA-12 blend was improved by 65% by adding 3 wt % of graft copolymer. Binary blends of the PA and poly(ethylene oxide) (PEO) were investigated in a separate study to verify miscibility of the graft copolymer side chains and the PA. Hydrogen bonding between PA-6 and PEO was confirmed by IR spectroscopy and partial miscibility was indicated by melting point depressions. © 1995 John Wiley & Sons, Inc.     

Synthesis of poly(fluorinated styrene)‐block‐poly(ethylene oxide) amphiphilic copolymers via atom transfer radical polymerization: potential application as paper coating materials

BACKGROUND: The surface of a substrate which comprises a fibrous material is brought into contact with a type of amphiphilic block copolymer which comprises hydrophilic/hydrophobic polymeric blocks. These amphiphilic copolymers have been synthesized by atom transfer radical polymerization (ATRP) technique. The atom transfer radical polymerization of poly(2,3,4,5,6‐pentafluorostyrene)‐block‐poly(ethylene oxide) (PFS‐b‐PEO) copolymers (di‐ and triblock structures) with various ranges of PEO molecular weights was initiated by a PEO chloro‐telechelic macroinitiator. The polymerization, carried out in bulk and catalysed by copper(I) chloride in the presence of 2,2′‐bipyridine ligand, led to A–B–A amphiphilic triblock and A–B amphiphilic diblock structures. RESULTS: With most of the macroinitiators, the living nature of the polymerizations led to block copolymers with narrow molecular weight distributions (1.09 < M_w/M_n < 1.33) and well‐controlled molecular structures. These block copolymers turned out to be water‐soluble through adjustment of the PEO block content (>90 wt%). Of all the block copolymers synthesized, PFS‐b‐PEO(10k)‐b‐PFS containing 10 wt% PFS was found to retard water absorption considerably. CONCLUSION: The printability of paper treated with the copolymers was evaluated with contact angle measurements and felt pen tests. The adsorption of such copolymers at the solid/liquid interface is relevant to the wetting and spreading of liquids on hydrophobic/hydrophilic surfaces. Copyright © 2009 Society of Chemical Industry     

Synthesis and properties of polystyrene‐b‐poly(ethylene oxide)‐b‐polystyrene triblock copolymers

A series of well‐defined and property‐controlled polystyrene (PS)‐b‐poly(ethylene oxide) (PEO)‐b‐polystyrene (PS) triblock copolymers were synthesized by atom‐transfer radical polymerization, using 2‐bromo‐propionate‐end‐group PEO 2000 as macroinitiatators. The structure of triblock copolymers was confirmed by ¹H‐NMR and GPC. The relationship between some properties and molecular weight of copolymers was studied. It was found that glass‐transition temperature (T_g) of copolymers gradually rose and crystallinity of copolymers regularly dropped when molecular weight of copolymers increased. The copolymers showed to be amphiphilic. Stable emulsions could form in water layer of copolymer–toluene–water system and the emulsifying abilities of copolymers slightly decreased when molecular weight of copolymers increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 727–730, 2006     

Octadecyl acrylate - Methyl methacrylate block and gradient copolymers from ATRP: Comb-like stabilizers for the preparation of micro- and nano-particles of poly(methyl methacrylate) and poly(acrylonitrile) by non-aqueous dispersion polymerization

Three random and three block copolymers of methyl methacrylate (MMA) and octadecyl acrylate (ODA) were synthesized by atom transfer radical polymerization. These copolymers were assessed for their application as stabilizers in the one-step non-aqueous dispersion (NAD) polymerization of MMA and of acrylonitrile (AN) in a non-polar solvent mixture of hexane and dodecane. In all cases stable spherical micro-particle colloidal dispersions were formed with particle diameters in the range of 62-2725 nm for PMMA. Uniform monodisperse PMMA particles with standard deviations in size distributions of less than 5% were obtained in two cases demonstrating the utility of ODA:MMA copolymers as replacement preformed stabilizers in the one-step synthesis of MMA micro-spheres. Overall the block copolymer PMMA₆₄-block-PODA₃₆ gave greater control over size when varying the solvent:monomer ration than a related gradient PMMA-PODA copolymer. These copolymers were further used as stabilizers in the one-step NAD polymerization of MMA with ethylene glycol dimethacrylate (EGDMA) under similar conditions allowing for the preparation of monodisperse cross-linked PMMA particles with diameters ranging from 110 to 1700 nm. The general utility of the copolymers as stabilizers was demonstrated by the NAD polymerization of acrylonitrile (AN) in non-polar solvent mixture of hexane and dodecane giving ‘crumpled’ latex dispersions with particle diameters in the range 85-483 nm.