Evaluation of polymethacrylic ionomer as compatibilizers for MCPA6/clay composites

The compatibilization effects provided by polymethacrylic ionomer (PMMA ionomer) on monomer‐casting polyamide6 (MCPA6)/clay (pristine sodium montmorillonite) composites were studied in this work. The PMMA ionomer used in this study was sodium polymethacrylate ionomer (PMMA Na⁺‐ionomer), which is a copolymer of methyl methacrylate and sodium methacrylate, prepared using emulsion polymerization. MCPA6/clay/PMMA Na⁺‐ionomer composites were prepared by in situ anionic ring‐opening polymerization (AROP) of ε‐caprolactam (CLA). X‐ray diffraction (XRD) and transmission electron microscopy (TEM) plus rheological measurement were used to characterize those composites. The results indicated that PMMA Na⁺‐ionomer is a good compatibilizer for this system. With increasing PMMA Na⁺‐ionomer content, a better dispersion of clay layers was successfully achieved in the MCPA6 matrix. Furthermore, differential scanning calorimetry (DSC) and XRD results indicated that well dispersed silicate layers limit the mobility of the MCPA6 molecule chains to crystallize, reduce the degree crystalline, and favor the formation of the γ‐crystalline form of the MCPA6 matrix. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of monomer‐casting polyamide 6/polymethacrylic ionomer blends

Monomer‐casting polyamide 6 (MCPA6)/polymethacrylic ionomer blends were synthesized by the in situ anionic ring‐opening polymerization of ?‐caprolactam. The polymethacrylic ionomer used in this study was a copolymer of methyl methacrylate and sodium or zinc methacrylate. Because the polymethacrylic ionomer strongly interacted with polyamide 6 (PA6) chains, it influenced the alignment of the polyamide chains. The change in the degree of the order of hydrogen bonding in MCPA6 caused by the addition of the polymethacrylic ionomer was studied with Fourier transform infrared. The change in the interaction between PA6 chains was studied with rheological measurements. The influence of the polymethacrylic ionomer on the crystallization behavior of MCPA6 was also studied with differential scanning calorimetry. The isothermal crystallization and subsequent melting behavior were investigated at the designated temperature. The commonly used Avrami equation was used to fit the primary stage of the isothermal crystallization. The Avrami exponent (n) values were evaluated to be 2 < n < 3 for the neat MCPA6 and MCPA6/polymethacrylic ionomer blends. The polymethacrylic ionomer, acting as a stumbling‐block agent in the blends, decelerated the crystallization rate with the half‐time of crystallization increasing. The polymethacrylic ionomer made the molecular chains of MCPA6 more difficult to crystallize during the isothermal crystallization process. More less perfect crystals formed in the MCPA6/polymethacrylic ionomer blends because of the interaction between the MCPA6 molecular chains and polymethacrylic ionomer. The crystallinity of the blends was depressed by the addition of the polymethacrylic ionomer. The thermal stability was also studied with thermogravimetric analysis. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Morphology and thermal behavior of MCPA6/SAN blends prepared by anionic ring‐opening polymerization of ϵ‐caprolactam

In this article, a series of blends of monomer casting polyamide 6 and styrene‐co‐acrylonitrile (MCPA6/SAN) were prepared by in situ anionic ring‐opening polymerization of ?‐caprolactam. Their morphology and thermal behaviors were investigated by means of scanning electron microscope, differential scanning calorimeter, and wide‐angle X‐ray diffraction (WAXD), respectively. The SAN phase had much finer domain in MCPA6/SAN than that in the PA6/SAN blends prepared by melt blending of PA6 and SAN. All the melting and crystallization parameters of MCPA6/SAN blends decreased gradually with the increase of SAN content, while the melting temperature was almost unchanged. These results were due to the hydrolysis reaction of SAN that occurred during the anionic polymerization of ?‐caprolactam. In addition, WAXD results showed that only α crystal forms existed in the MCPA6/SAN blends. In addition, the mechanical property of MCPA6 was improved obviously by incorporating a certain amount of SAN. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1357–1363, 2006     

浇铸尼龙6/ABS聚合物合金的研究

将丁二烯组分含量不同的丙烯腈-丁二烯-苯乙烯(ABS)加入到单体己内酰胺中,通过阴离子聚合制备浇铸尼龙6(MCPA6)/ABS聚合物合金。采用傅立叶红外光谱、扫描电子显微镜、热重分析以及力学性能测试,研究了ABS的加入对浇铸尼龙6的微观结构、热性能以及力学性能影响。结果表明:ABS通过腈基在己内酰胺的阴离子聚合过程中发生共聚合反应,生成的ABS/MCPA6共聚物对合金两相起到增容作用;合金两相之间相容性随ABS中丁二烯含量的降低有所提高;热稳定性随丁二烯含量的减少而提高,但较MCPA6均有所降低。ABS的加入提高了合金的韧性,其中MCPA6/ABS749S(质量比90/10)较MCPA6缺口冲击强度提高39.73%,但硬度有所下降。     

Synthesis of well‐defined poly(methyl methacrylate) nanoparticles by reverse atom transfer radical polymerization in a microemulsion

Well‐defined poly(methyl methacrylate) (PMMA) with an α‐isobutyronitrile group and an ω‐bromine atom as the end groups was synthesized by the microemulsion polymerization of methyl methacrylate (MMA) at 70°C with a 2,2′‐azobisisobutyronitrile/CuBr₂/2,2′‐bipyridine system. The conversion of the polymerization reached 81.9%. The viscosity‐average molecular weight of PMMA was high (380,000), and the polydispersity index was 1.58. The polymerization of MMA exhibited some controlled radical polymerization characteristics. The mechanism of controlled polymerization was studied. The presence of hydrogen and bromine atoms as end groups of the obtained PMMA was determined by ¹H‐NMR spectroscopy. The shape and size of the final polymer particles were analyzed by scanning probe microscopy, and the diameters of the obtained particles were usually in the range of 60–100 nm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3670–3676, 2006     

Synthesis and properties of homogeneously dispersed polyamide 6/MWNTs nanocomposites via simultaneous in situ anionic ring‐opening polymerization and compatibilization

Toluene 2, 4‐diisocyanate (TDI) functionalized multiwalled carbon nanotubes (MWNTs‐NCO) were used to prepare monomer casting polyamide 6 (MCPA6)/MWNTs nanocomposites via in situ anionic ring‐opening polymerization (AROP). Isocyanate groups of MWNTs‐NCO could serve as AROP activators of ?‐caprolactam (CL) in the in situ polymerization. Fourier transform infrared (FTIR) showed that a graft copolymer of PA6 and MWNTs was formed in the in situ polymerization. MWNTs‐PA6 covalent bonds of the graft copolymer constituted a strong type of interfacial interaction in the nanocomposites and increased the compatibility of MWNTs and MCPA6 matrix. The nanocomposites were characterized for the morphology, mechanical, crystallization, and thermal properties through field emission transmission electron microscopy (FETEM), tensile testing, differential scanning calorimeter (DSC), and thermogravimetric analysis (TGA). FETEM analysis showed that MWNTs were homogeneously dispersed in MCPA6 matrix. The initial tensile strengths and tensile modulus of the nanocomposite with 1.5 wt % loading of MWNTs were enhanced by about 16 and 13%, respectively, compared with the corresponding values for neat MCPA6. DSC analysis indicated that the crystallization temperature of the nanocomposites was increased by 8°C by adding 1.5 wt % MWNTs compared with pure MCPA6. Besides, it was found that the thermal stability of MCPA6 was improved by the addition of the MWNTs. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

A novel approach to the preparation of thermoplastic polyurethane elastomer and polyamide 6 blends by in situ anionic ring‐opening polymerization of ε‐caprolactam

Blends of thermoplastic polyether‐based urethane elastomer (TPEU) and monomer casting polyamide 6 (MCPA6) were prepared using ε‐caprolactam as reactive solvent, with caprolactam sodium as a catalyst in the presence of TPEU, with TPEU content varying from 2.5% to 10% by weight. In situ anionic ring‐opening polymerization and in situ compatibilization to prepare TPEU/MCPA6 blends were carried out in one step. The TPEU chains, which underwent thermal dissociation in amine solvents to bear isocyanate groups, acted as macroactivator to initiate MCPA6 chain growth from the TPEU chains and form graft copolymers of TPEU‐co‐MCPA6 to improve compatibility between TPEU and MCPA6. The structure and thermal properties were characterized by means of Fourier transform infrared spectroscopy, ¹H‐NMR spectroscopy, differential scanning calorimetry and scanning electron microscopy. Copyright © 2006 Society of Chemical Industry     

Synthesis,characterization, and photochromic properties of PMMA functionalized with 4,4′‐diacryloyloxyazobenzene

Attempts to introduce the azo chromophore into poly(methyl methacrylate) (PMMA) molecular chains were made in search for a new approach to obtain functionalized‐PMMA (f‐PMMA) with high glass transition temperature and an adequate azo content. A novel functionalized monomer, 4,4′‐diacryloyloxyazobenzene (DAOAB), was synthesized and used as grafting agent in the polymerization of methyl methacrylate. ¹H‐NMR spectrum, FTIR spectrum, elemental analysis, and MDSC measurement confirmed that the proposed structure of DAOAB was synthesized successfully. Furthermore, the thermal properties and photochromic behavior of f‐PMMA samples were also analyzed by DSC, TGA, and UV–visible spectroscopy. The results have shown that f‐PMMA exhibited a better photochromic behavior and considerably improved thermal properties than pure PMMA. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1061–1068, 2002     

Synthesis and properties of poly(methyl methacrylate)/clay nanocomposites using natural montmorillonite and synthetic Fe‐montmorillonite by emulsion polymerization

In this article, Fe‐montmorillonite (Fe‐MMT) was synthesized by hydrothermal method. For the first time, Fe‐MMT was modified by cetyltrimethyl ammonium bromide (CTAB), and poly(methyl methacrylate)(PMMA)/Fe‐MMT nanocomposites were synthesized by emulsion polymerization. Then poly(methyl methacrylate)(PMMA)/natural montmorillonite (Na‐MMT) and PMMA/Fe‐MMT nanocomposites were compared by Fourier transform infrared (FTIR) spectra, X‐ray diffraction (XRD) patterns, transmission electron microscopy (TEM), and thermal gravimetric analysis (TGA). By XRD and TEM, it was found out that the morphology of PMMA/Fe‐MMT nanocomposites was different from that of the PMMA/Fe‐MMT nanocomposites when the content of two types of clay was same in the PMMA matrix. It was possible that the presence of iron may lead to some radical trapping, which enhances intragallery polymerization to be developed to improve layer dispersion in PMMA/Fe‐MMT systems. In TGA curves, the thermal stability and residue at 600°C of PMMA/Fe‐MMT nanocomposites were higher than those of PMMA/Na‐MMT nanocomposites. Those dissimilarities were probably caused by structural Fe ion in the lattice of Fe‐MMT. POLYM. COMPOS., 27:49–54, 2006. © 2005 Society of Plastics Engineers     

Synthesis and characterization of microencapsulated sodium phosphate dodecahydrate

Microcapsules loaded with sodium phosphate dodecahydrate (DSP) were prepared according to the solvent evaporation method. The microencapsulated phase‐change materials (MEPCMs) possessed methyl methacrylate crosslinked with ethyl acrylate generated poly(methyl methacrylate) (PMMA) as the coating polymer. The influences of the polymerization time, polymerization temperature, and organic solvent types on the performances of the MEPCMs were studied in this report. The results indicate that the polymerization time and temperature had barely any effect on the size but a significant effect on the surface morphology of the microphase‐change materials. The solubility of the shell material varied in different organic solvents, and this to different phase‐transition enthalpies. In addition, DSP could be encapsulated well by PMMA, and the as‐prepared MEPCMs were equipped with a good morphology and a small particle size. When toluene and acetone were used as organic solvents, the MEPCMs had an interesting energy storage capacity of 142.9 J/g at 51.51°C, and this made them suitable for different applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1516–1523, 2013     

Poly(methyl methacrylate)/POSS hybrid networks by type II photoinitiated free radical polymerization

A new strategy for organic–inorganic hybrid networks is presented through in‐situ Type II photoinitiated polymerization of methyl methacrylate with diethanolamino‐functionalized polyhedral oligomeric silsesquioxanes (POSS‐DEA). The diethanolamino groups are simply incorporated onto POSS nanoparticles by nucleophilic ring‐opening reaction of commercially available epoxycyclohexyl POSS and diethanol amine. The photoinitiated polymerization of methyl methacrylate in the presence of benzophenone as photosensitizer and POSS‐DEA as hydrogen donor leads to poly(methyl methacrylate) (PMMA)/POSS hybrid networks under UV light irradiation. The morphology and thermal properties of hybrid networks are investigated by using Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and transmission electron microscopy. The morphology results confirm that POSS cages are homogeneously distributed in PMMA matrix at the molecular levels, whereas the thermal analyses shows that the obtained hybrid networks have higher glass transition temperatures and better thermal stabilities compared to parent PMMA homopolymer. POLYM. COMPOS., 35:1614–1620, 2014. © 2013 Society of Plastics Engineers     

Preparation,morphology, and mechanical properties of elastomers based on α,ω‐dihydroxy‐polydimethylsiloxane/poly(methyl methacrylate) blends

α,ω‐Dihydroxy‐polydimethylsiloxane (PDMS)/poly(methyl methacrylate) (PMMA) blends were prepared by the radical polymerization of methyl methacrylate in the presence of PDMS, with benzoyl peroxide as the initiator. The PDMS/PMMA blends obtained by this method were a series of stable, white gums, which were vulcanized into elastomers at room temperature with methyl triethoxysilicane (MTES). The MTES dosage was much larger than the amount necessary for end‐linking the hydroxy‐terminated chains of PDMS, with the excess being hydrolyzed into crosslinked networks, which were similar to SiO₂ and acted as fillers. Investigations were carried out on the elastomeric materials by extraction measurements, swelling measurements, and scanning electron microscopy. The extraction data showed that at each composition, the sol fraction was less than expected. The extracted materials were further studied with swelling measurements, which revealed that the material obtained from an elastomer with a higher PMMA content had an apparently larger equilibrium swelling degree. Scanning electron microscopy demonstrated that the elastomer system had a microphase‐separated structure consisting of PMMA domains within a continuous PDMS matrix. Moreover, the mechanical properties of the elastomeric materials were studied in detail. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1547–1553, 2006     

Structural characterization,thermal properties,and density functional theory studies of PMMA‐maghemite hybrid material

Maghemite (γ‐Fe₂O₃)‐poly(methyl methacrylate) (PMMA) nanocomposites were prepared by grafting 3‐(trimethoxy‐silyl) propyl methacrylate on the surface of maghemite nanoparticles, this process being followed by methyl methacrylate radical polymerization. Three different hybrids with 0.1, 0.5, and 2.5 wt% of maghemite nanoparticles were studied. The results indicate that these nanocomposites consist of a homogeneous PMMA matrix in which maghemite nanoparticles with a bimodal size distribution are embedded. The existence of covalent bonding between silane monomers and atoms on the maghemite surface was evidenced. AFM images showed a clear increase in surface roughness for increasing maghemite content. The thermal stability of PMMA‐maghemite nanocomposites is higher than that of pure PMMA and increases for increasing maghemite content. The results of our theoretical studies indicate that the electron density in the maghemite nanoparticle is not homogenous, the low electron density volumes being supposed to be radical trappers during PMMA decomposition, thus acting as a thermal stabilizer. POLYM. COMPOS., 51–60, 2016. © 2014 Society of Plastics Engineers     

Preparation and characterization of thermoplastic polyurethane elastomer and polyamide 6 blends by in situ anionic ring‐opening polymerization of ϵ‐caprolactam

The blends of thermoplastic polyether‐based urethane elastomer (TPEU) and monomer casting polyamide 6 (MCPA6) were prepared using ε‐caprolactam (CL) as a reactive solvent, and CL sodium as a catalyst at various TPEU contents (2.5–15 phr by weight). In situ anionic ring‐opening polymerization and in situ compatibilization of TPEU/MCPA6 blends were realized in one step. The dissociated TPEU chains acted as macroactivator to initiate MCPA6 chain growth from the TPEU chains. The formed block copolymers (TPEU‐co‐MCPA6), which have been confirmed by Fourier transform infrared spectroscopy and ¹H‐NMR analysis, improved the compatibility between TPEU and MCPA6. In addition, both differential scanning calorimetry and dynamic mechanical analysis studies revealed that the crystallinity temperature, melting temperature, the degree of crystallization, and the glass‐transition temperature of MCPA6 component remarkably shifted to a low temperature with increasing TPEU content. Mechanical properties demonstrated that the impact strength and the elongation‐at‐break of the blends significantly increased with the content of TPEU, whereas a progressive decrease occurred in tensile strength, flexural strength, and flexural modulus. WAXD spectra showed that only α‐form crystal of PA6 component existed in the TPEU/MCPA6 blends. Furthermore, scanning electron microscopes (SEM) of the cryo‐fractured surfaces confirmed a substantially improved compatibility, and reflected a seemly single‐phase morphology. POLYM. ENG. SCI., 46: 1196–1203, 2006. © 2006 Society of Plastics Engineers     

Effect of talc/MMA in situ polymerization on mechanical properties of PVC‐matrix composites

In this study, polymethyl methacrylate (PMMA)‐coated talc was produced by the in situ polymerization of methyl methacrylate on the talc surface. The polymerization reaction was performed by both batch and semicontinuous emulsion processes. The polymerization kinetics, particle size and distribution, grafting efficiency, and coated‐talc morphology were systematically investigated. It was found that the talc particles have no effect on the polymerization of PMMA. The PMMA produced was found to cover the talc surface well. However, only a small amount can be grafted onto the talc. The size distribution of talc particles treated by semicontinuous emulsion polymerization is more uniform than by batch polymerization. The treated talc was subsequently used as filler in a poly(vinyl chloride) (PVC) matrix, and mechanical properties of the PMMA‐coated‐talc/PVC composites were studied. Morphological structure of PVC‐matrix composites revealed that the PMMA coating on talc improved the dispersion of talc in the PVC matrix and enhanced the interfacial adhesion between the talc and PVC. The mechanical properties of the composites, especially the impact strength, were found to be improved. There appears to be a critical covering thickness of PMMA on the talc surface for optimum toughening. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2105–2112, 2001     

Influence of chemical functionalization of carbon nanotubes on their dispersibility in alkyl methacrylate polymer matrix

Nanocomposites based on poly(methyl methacrylate) (PMMA) and poly(methyl methacrylate‐co‐octadecyl methacrylate) (M/O) matrices and four different types of multiwall carbon nanotubes: pristine, oxidized (MWCNT–COOH), methyl ester (MWCNT–COOCH₃), and dodecyl ester (MWCNT–COOC₁₂H₂₅) functionalized, were prepared in situ by radical (co)polymerization. The effectiveness of preparation of nanocomposites regarding dispersion and distribution of various MWCNT in polymer matrices was sized by Scanning electron microscopy. In case of PMMA matrix, the best dispersion and distribution were accomplished for MWCNT–COOCH₃ due to their chemical resemblance with polymer matrix. After the introduction of 10 mol % of octadecyl methacrylate in polymer matrix a fairly good dispersion and distribution of MWCNT–COOCH₃ were retained. The addition of 1 wt % of MWCNTs caused a significant reduction in the degree of polymerization of the PMMA matrix. But at the same time, the present MWCNTs increased storage modulus of PMMA nanocomposites except for dodecyl ester functionalized MWCNT. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46113.     

In situ synthesis of polyamide 6/MWNTs nanocomposites by anionic ring opening polymerization

In situ anionic ring opening polymerization is used to prepare monomer casting polyamide 6 (MCPA6)/carbon nanotubes (CNTs) nanocomposites, whereby water is used as auxiliary dispersing agent of hydroxyl functionalized multiwalled carbon nanotubes (MWNTs‐OH) and ε‐caprolactam (CL) monomer. The MWNTs‐OH were dispersed homogenously in MCPA6 matrix when being observed through transmission electron microcopy. The well dispersed MWNTs‐OH existed at the center of many radial texture phases in MCPA6 matrix. Polarizing microscope analysis showed that these radial texture phases were MCPA6 spherulitic crystallities. Differential scanning calorimetry analysis revealed that the crystallization temperature of the MCPA6/MWNTs‐OH nanocomposites had been improved by adding only 0.2 wt % MWNTs‐OH when compared with pure MCPA6. The influence of MWNTs‐OH on the thermal stability of MCPA6 under nitrogen and air environments was also investigated by thermal gravimetric analysis (TGA). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Polymerization of methyl methacrylate with a thermal iniferter: Diethyl 2,3‐dicyano‐2,3‐di(p‐tolyl)succinate

A hexa‐substituted ethane type compound, diethyl‐2,3‐dicyano‐2,3‐di(p‐tolyl)succinate (DCDTS), was successfully synthesized and used for initiation of methyl methacrylate (MMA) polymerization. The reaction demonstrated the characteristics of a “living” polymerization; i.e., both the yield and the molecular weight of the resulting polymers increased linearly with increasing reaction time, the molecular‐weight distribution of PMMA obtained was ～1.60 and almost unaffected by the conversion, and the resultant polymer can be chain extended by adding fresh MMA. End group analysis of the resultant PMMA confirmed that DCDTS behaves as a thermal iniferter for MMA polymerization. A block copolymer was prepared from the resultant PMMA, which contains a hexa‐substituted C? C bond functional end group. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2566–2572, 2001     

Electropolymerization of p‐phenylenediamine on Pt‐electrode from aqueous acidic solution: Kinetics,mechanism, electrochemical studies,and characterization of the polymer obtained

Ar plasma‐induced graft polymerization of poly(ethylene glycol) (PEG) on Ar plasma pretreated poly(methyl methacrylate) (PMMA) surfaces was carried out to improve the antistatic properties. The surface composition and microstructure of the PEG‐grafted PMMA surfaces from plasma induction were characterized by attenuated total reflectance Fourier transfer infrared (ATR‐FTIR) spectroscopy, water contact angles (CA), and atomic force microscopy (AFM) measurements. The measurements revealed that the antistatic properties can be remarkably improved with the surface resistivity of PEG‐grafted PMMA surface decreasing significantly by 3–6 orders of magnitude, with the optimum condition for polymerization grafted onto the Ar plasma pretreated PMMA surface being 40 W for RF power and 3 min for glow discharge time. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis of PMMA‐PTHF‐PMMA and PMMA‐PTHF‐PST linear and star block copolymers

Combination of cationic, redox free radical, and thermal free radical polymerizations was performed to obtain linear and star polytetramethylene oxide (poly‐THF)‐polymethyl methacrylate (PMMA)/polystyrene (PSt) multiblock copolymers. Cationic polymerization of THF was initiated by the mixture of AgSbF₆ and bis(4,4′ bromo‐methyl benzoyl) peroxide (BBP) or bis (3,5,3′,5′ dibromomethyl benzoyl) peroxide (BDBP) at 20°C to obtain linear and star poly‐THF initiators with M_w varying from 7,500 to 59,000 Da. Poly‐THF samples with hydroxyl ends were used in the methyl methacrylate (MMA) polymerization in the presence of Ce(IV) salt at 40°C to obtain poly(THF‐b‐MMA) block copolymers containing the peroxide group in the middle. Poly(MMA‐b‐THF) linear and star block copolymers having the peroxide group in the chain were used in the polymerization of methyl methacrylate (MMA) and styrene (St) at 80°C to obtain PMMA‐b‐PTHF‐b‐PMMA and PMMA‐b‐PTHF‐b‐PSt linear and star multiblock copolymers. Polymers obtained were characterizated by GPC, FT‐IR, DSC, TGA, ¹H‐NMR, and ¹³C‐NMR techniques and the fractional precipitation method. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 219–226, 2004