Fluorine Enrichment Research Articles

Synthesis of core‐shell fluoroacrylate copolymer latex via emulsion polymerization and its application in ink‐jet ink

AbstractCore‐shell fluoroacrylate copolymer latex was synthesized via semicontinuous seed emulsion polymerization, in which ethyl acrylate was utilized to prepare core, and methyl methacrylate, butyl acrylate, methacrylate acid, and hexafluorobutyl methacrylate were employed to constitute the shell. So the yielded latex particles had the soft core and hard shell. Multifunction and low viscosity of the latex had been applied as the binder of latex inks. The ζ potential showed that the latex particles had high thermodynamic stability. The latex and latex inks exhibited viscosity plateau of Newtonian fluid behaviors. Rheological tests revealed that viscous behaviors dominated in the latex and latex inks. However, there was some interaction among the latex and pigment particles. The hydrophobicity of the cast films of the latex increased with the amount of the fluoroacrylate monomer. Fluorine tended to migrate to the interface between the cast film and air. Therefore, the hydrophobicity was derived from the fluorine enrichment phenomena on the top side of the cast films. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Synthesis and characterization of core–shell polysilsesquioxane-poly(styrene-butyl acrylate-fluorinated acrylate) hybrid latex particles

Core–shell polysilsesquioxane-poly(styrene-butyl acrylate-fluorinated acrylate) [PSQ–P(St-BA-FA)] hybrid latex particles were successfully prepared by seeded emulsion polymerization with polymethacryloxypropylsilsesquioxane (PSQ) synthesized by the hydrolysis and polycondensation of (3-methacryloxypropyl)trimethoxysilane (MAPTS) in the presence of emulsifiers as seeds. The chemical composition and core–shell morphology of the resultant hybrid particles were investigated by Fourier transform infrared (FTIR) spectroscopy and transmission electron microscopy (TEM), respectively. TEM and dynamic light scattering (DLS) analysis indicated that the core–shell hybrid particles were uniform and possessed narrow size distributions. The surface properties of the latex films produced from the core–shell hybrid particles were also investigated by contact angle (CA) analysis and X-ray photoelectron spectroscopy (XPS) analysis. The results proved the enrichment of fluorine on the film surface, and the latex films had high contact angles and low surface free energies. Optical measurements indicated that the incorporation of fluorinated acrylate onto PSQ particles can effectively reduce light reflectivity of the obtained transparent hybrid latex film. Atom force microscopy (AFM) characterization showed that the obtained hybrid latex film had a smooth surface. Additionally, thermogravimetric analysis (TGA) indicated that the PSQ–P(St-BA-FA) hybrid latex film had better thermal stability than the poly(styrene-butyl acrylate) [P(St-BA)] latex film.

Surface self-segregation, wettability, and adsorption behavior of core–shell and pentablock fluorosilicone acrylate copolymers

The surfaces of films cast from core–shell fluorosilicone acrylate copolymer (BA/MMA/DFHM and BA/MMA/DFHM/MPTMS/D4) latexes and linear pentablock fluorosilicone acrylate copolymer (PDMS-b-(PMMA-b-PDFHM)2) solutions are intensively investigated and compared by XPS, DCA, AFM, and QCM-D measurements. It is found that the molecular structures and in-solution aggregate structures of these well-defined copolymers have a dramatic influence on the surface structure formation, surface wetting, and adsorption behavior. The PDMS-b-(PMMA-b-PDFHM)2 film cast from chloroform solution with high concentration of low-density unimers is able to perform as strong surface self-segregation of fluorine-containing groups as core–shell copolymer latex films. The BA/MMA/DFHM/MPTMS/D4 in the core–shell latex particles exhibits the less pronounced surface self-segregation of silicon-containing groups than PDMS-b-(PMMA-b-PDFHM)2 due to the occurrence of cross-linking reactions between polysiloxane chains. Indeed, such reactions induce the formation of silica network within the film material, which immobilizes tightly the fluorinated groups on the film surface and thus endows the film with higher surface structural stability for water compared to PDMS-b-(PMMA-b-PDFHM)2 film with similar surface fluorine concentration and even higher silicon concentration. Still, the PDMS-b-(PMMA-b-PDFHM)2 film definitely demonstrates higher advancing and receding contact angles for water than BA/MMA/DFHM/MPTMS/D4 latex film in the case of synergism between surface enrichment of fluorine and silicon.

Enhanced surface segregation of poly(methyl methacrylate) end-capped with 2-perfluorooctylethyl methacrylate by introduction of a second block

New fluorinated copolymers of poly(methyl methacrylate)- b-poly(butyl methacrylate) or poly( n-octadecyl methacrylate) end-capped with 2-perfluorooctylethyl methacrylate (PMMA x - b-PBMA y - ec-PFMA z or PMMA x - b-PODMA y - ec-PFMA z ) were synthesized by living atom transfer radical polymerization. Thin films made of PMMA 230- b-PODMA y - ec-PFMA 1 were characterized by differential scanning calorimetry, angle-resolved X-ray photoelectron spectroscopy and X-ray diffraction. These films were found to exhibit robust surface segregation of the end groups. Furthermore, the fluorine enrichment factor at the film surface was found to increase linearly with increasing degree of polymerization of poly( n-octadecyl methacrylate) and its increasing fusion enthalpy in the second block, which enhances the segregation of the fluorinated moieties.

Surface modification of polyvinylidene fluoride- co-hexafluoropropylene (PVDF–HFP) hollow fiber membrane for membrane gas absorption

The outer surface of polyvinylidene- co-hexafluoropropylene (PVDF–HFP) asymmetric microporous hollow fiber membrane prepared by phase inversion process was activated by 10 wt.% of NaOH solution, and subsequently modified with the mixture solution of α,ω-triethoxysilane terminated perfluoropolyether or Fluorolink ®S 10 (FS10) and tetraethoxysilane (TEOS) in order to enhance the hydrophobicity of the membrane. The chemical and physical changes of the membranes were investigated by attenuated total reflection infrared spectroscopy FTIR-ATR and scanning electron microscope (SEM). The characteristics of the modified membrane were examined in terms of liquid entry pressure of water (LEPw), pore size and pore size distribution, contact angle and mechanical properties. The modified fibers were also used in the membrane contactor system to evaluate their performance for CO 2 absorption. FTIR-ATR result showed the enrichment of fluorine and ethoxysilane on the modified PVDF–HFP membranes leading to higher LEPw and contact angle than those of the unmodified membrane by 36% and 33%, respectively. The contact angle increased from 95.5° to 127.8°. Compared to the unmodified PVDF–HFP hollow fiber, the cross-sectional morphology and mechanical properties of the modified membrane changed insignificantly, while the membrane mean pore size was reduced from 32.7 nm to 25.2 nm. The CO 2 physical absorption performance of the modified fibers was better than the unmodified fibers. The membrane mass transfer coefficients of the unmodified and modified PVDF–HFP hollow fiber were 5.69 × 10 −5 and 7.56 × 10 −5 m/s, respectively, indicating that the modified membranes have good potential for application in the gas absorption process.

Synthesis and properties of cationic polyurethane-fluorinated acrylic hybrid latexes by emulsifier-free emulsion polymerization and the solvent-free method

A series of cationic polyurethane-fluorinated acrylic hybrid latex (PUFA) have been synthesized by solvent-free method. In the method, vinyl monomers acted as dilution agent and the polyurethane (PU) having quaternary ammonium groups acted as macromolecular emulsifier without using any other solvent and surfactant. The structure and properties of PUFA were characterized by Fourier transform infrared spectroscopy (FT-IR), F19 nuclear magnetic resonance (F19 NMR), particle size distribution (PSD) analysis, transmission electron microscopy (TEM), contact angle (CA), surface free energy analysis, scanning electron microscope (SEM) equipped with energy dispersive X-ray spectrometry (EDS), and thermogravimetric (TG) analysis. The FT-IR, F19 NMR, and EDS confirmed that the FA monomer had been introduced into the chain of the PUFA hybrid polymer. The PSD analysis indicated the particles of PUFA were smaller than corresponding pure PU dispersion and narrower in particle size distribution. The CA and surface free energy analysis proved the PUFA hybrid latex film with fluorine possessed higher contact angle and lower surface free energy in contrast with the film without fluorine. The FPUA films exhibited good surface property which could be enhanced at higher annealing temperature. The EDS of PUFA confirmed the fluorine enrichment on the surface of PUFA. TG analysis suggested the PUFA hybrid latex film had a better thermal stability than pure PU.

EFFECT OF SELECTIVE SOLVENTS FOR B BLOCK ON SURFACE SEGREGATION OF FLUORINE-CONTAINING ABC TRIBLOCK COPOLYMERS

Novel ABC triblock copolymers of poly(methyl methacrylate)-b-poly(n-butyl methacrylate)(or n-octadecyl methacrylate)-b-poly(2-perfluorooctylethyl methacrylate)(PMMA230-b-PBMA12(or PODMA12)-b-PFMAn) were synthesized by atom transfer radical polymerization(ATRP).The effect of selective solvents on surface structure of the triblock copolymers film was investigated by X-ray photoelectron spectroscopy(XPS),X-ray diffraction(XRD) and dynamic light scattering(DLS).The higher surface enrichment of fluorinated moieties in PMMA230-b-PBMA12-b-PFMA1 was found as the film was cast by cyclohexanone solution,compared to the film cast by toluene solution.When the length of PFMA units was about 4,the ratio of fluorine to carbon was nearly the same.As for PMMA230-b-PODMA12-b-PFMAn,the fluorinated moieties can segregate more easily on the surface as the film was cast with toluene solution,compared to the film cast from cyclohexanone solution.The reason could be attributed to the difference in compatibility between solvent and the middle block in triblock copolymers,which would affect the stability of triblock copolymers micelle in various solutions.When the solvent was the good solubility for the middle block chain,there were unstable and loose packed micellar aggregates in solution.The unstable micelle of the triblock copolymer in solution was in favor of fluorine segregation on the surface during film-formation.During film formation,the perfluoroalkyl side chains can easily segregate to the surface and be packed in a well-ordered manner,resulting in enhanced surface enrichment of fluorine element.The results suggest that copolymer solution properties,may play an important role in structure formation on the solid surface,in addition to for the molecular chain structures of copolymers.

Novel cationic polyurethane-fluorinated acrylic hybrid latexes: Synthesis, characterization and properties

The cationic polyurethane-fluorinated acrylic (PUFA) hybrid latexes were obtained from double bond-end capped polyurethane macromonomer having quaternary ammonium groups with perfluoroalkyl acrylate (FA) by radical copolymerization. Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) confirmed that the FA monomer had been introduced into the chain of the PUFA hybrid polymer. Particle size distribution (PSD) analysis showed that the particle size of PUFA increased with the increase of the FA content. TEM indicated that the PUFA hybrid possessed core–shell structure. The analysis of the contact angles (CAs), XPS and atomic force microscopy (AFM) had shown that there was a remarkable enrichment of fluorine on the film–air interface, which was more evident when the PUFA hybrid film annealed at higher temperature. At the same time, the influences of the soft segment molecular weight, the N-methyldiethanolamine (MDEA) content and the FA content on other properties such as the surface tension of the PUFA latexes, the surface free energy of the PUFA films and the thermal properties were studied. The results showed that the MDEA content had contrary influence on latex's and film's surface properties. Thermal stabilization usually brought by fluorine was not observed in our investigated systems.

Partially fluorinated polymer networks: Surface and tribological properties

Functionalization of epoxy-based networks by the preferential surface enrichment of perfluorinated tails to achieve hydrophobic surface is described. Two series of crosslinked fluorinated epoxy-based materials containing variable fluorine contents (from 0 to 5 wt % F) were prepared using formulations based on partially fluorinated diamine, epoxy monomer and a curing agent. The epoxy monomer was based on diglycidyl ether of bisphenol A (DGEBA) while the curing agents were either propyleneoxide diamine (JEFFAMINE) or 4,4′-methylenebis(3-chloro 2,6-diethylaniline) (MCDEA). The selected fluorinated epoxies (FE) were: 2,2,3,3,4,4,5,5,6,6,7,7,8,9,9,9-hexadecafluoro-8-trifluoromethyl nonyloxirane (FED3) and 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluoro nonyloxirane (FES3). The influence on surface properties of the architecture of FE, and the molecular structure of the unit building blocks was analyzed and discussed. It was found that both series showed high hydrophobicity and oleophobicity, independently of the crosslink density, bulk composition, and curing conditions. XPS measurements showed a surface composition much richer in fluorinated segments than expected from bulk composition. Fluorine enrichment was also manifested at the polymer/aluminium interface for JEFFAMINE-based networks. This observation is discussed in terms of the molecular weight dependence of surface tension and configurational entropy of the thermosetting matrix. At least for the range of this study, while increasing the amount of fluorine incorporated in both network series, dynamic friction is reduced due to surface migration of fluorine species during polymerization

Preparation and surface properties of core‐shell polyacrylate latex containing fluorine and silicon in the shell

AbstractThe core‐shell polyacrylate latex particles containing fluorine and silicon in the shell were successfully synthesized by a seed emulsion polymerization, using methyl methacrylate (MMA) and butyl acrylate (BA) as main monomers, dodecafluoroheptyl methacrylate (DFMA), and γ‐(methacryloxy) propyltrimethoxy silane (KH‐570) as functional monomers. The influence of the amount of fluorine and silicon monomers on the emulsion polymerization process and the surface properties of the latex films were discussed, and the surface free energy of latex films were estimated using two different theoretical models. The emulsion and its films were characterized by particle size distribution (PSD) analysis, transmission electron microscopy (TEM), Fourier transform infrared spectrum (FTIR), nuclear magnetic resonance (1H‐NMR and 19F‐NMR) spectrometry, contact angle (CA) and X‐ray photoelectron spectroscopy (XPS), differential scanning calorimetry (DSC), and thermogravimetry (TG) analysis. The results indicate that the average particle size of the latex particles is about 160 nm and the PSD is narrow, the synthesized latex particles exist with core‐shell structure, and a gradient distribution of fluorine and silicon exist in the latex films. In addition, both the hydrophobicity and thermal stability of the latex films are greatly improved because of the enrichment of fluorine and silicon at the film‐air interface, and the surface free energy is as low as 15.4 mN/m, which is comparable to that of polytetrafluoroethylene (PTFE). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Properties of clear polyurethane films modified with a fluoropolymer emulsion

An emulsion of a fluoroethylene vinyl ether polyol, Lumiflon FE-4400, was incorporated into clearcoats of two-part water-based military polyurethane topcoats. This additive was mixed with the aqueous dispersion polyol component. The polyol component was then mixed with the isocyanate component with a high speed disperser to properly mix the reactants. Films were prepared by drawing down the dispersion onto glass substrates using a 4-mil stainless steel Bird applicator. After drying at ambient conditions the films were removed from the glass for analysis. As measured using X-ray photoelectron spectroscopy, Lumiflon FE-4400 segregated to the surface providing significant fluorine enrichment at the air interface, as high as 90 times the bulk concentration. Although increasing the concentration of Lumiflon FE-4400 increased the surface concentration, the ratio of surface concentration to the bulk concentration decreased. As expected, water contact angle increased approximately in a linear fashion with the surface fluorine concentration. At 1–5 wt% added Lumiflon FE-4400, the physical and mechanical properties were not significantly affected. However, addition of Lumiflon FE-4400 at or above 10% of polyol fraction significantly reduced the glass transition temperature, modulus, crosslink density, strength, toughness and weathering resistance. Phase contrast microscopy showed that the morphology of these films went from being uniform to having distinct aggregates that increased in size and number as fluorinated polyol fraction increased, likely explaining the reduction in film properties. Accelerated weathering of pigmented coatings was also performed. Although fluorinated resins typically improve weathering resistance of coatings, in this study, increasing the Lumiflon FE-4400 content decreased the weathering resistance as a result of the ethoxylation of the fluorinated additive necessary to produce an aqueous fluoropolymer emulsion.

Influence of fluorinated acids bonding on surface properties of crosslinked epoxy-based polymers

Two series of crosslinked fluorinated epoxy-based materials containing variable fluorine contents (from 0 to 6 wt.% F) were prepared using formulations based on a fluorinated acid (FA), epoxy monomer and a diamine. The epoxy monomer was based on diglycidyl ether of bisphenol A (DGEBA) while the curing agent was propyleneoxide diamine (Jeffamine D-230). The selected FA were: 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptanoic acid (FA1), perfluoro-heptanoic acid (FA2), and perfluoro-nonanoic acid (FA3). One of the series synthesized, FA–DGEBA/Jeffamine, is characterized by covalent attachment of the FA to the polymer by an ester bond. The other series, FA–Jeffamine/DGEBA, is characterized by ionic interaction between FA and polymer chains. The influence on thermal and surface properties of the architecture and chain-length of FA, and the nature of the linkage between FA and network precursors, was analyzed and discussed. It was found that both series showed high oleophobicity, but depending on the linkage between the fluorinated acid and the network, it was possible to develop hydrophobic or hydrophilic materials. The fluorine enrichment with the perfluoroalkyl substitutions was proved by XPS. By this technique it was possible also to analyze the concentration of ammonium groups at the surface.

Fluorinated/siloxane copolymer blends for fouling release: chemical characterisation and biological evaluation with algae and barnacles

Fouling-release coatings were prepared from blends of a fluorinated/siloxane copolymer with a poly(dimethyl siloxane) (PDMS) matrix in order to couple the low modulus character of PDMS with the low surface tension typical for fluorinated polymers. The content of the surface-active copolymer was varied in the blend over a broad range (0.15–10 wt % with respect to PDMS). X-ray photoelectron spectroscopy depth profiling analyses were performed on the coatings to establish the distribution of specific chemical constituents throughout the coatings, and proved enrichment in fluorine of the outermost layers of the coating surface. Addition of the fluorinated/siloxane copolymer to the PDMS matrix resulted in a concentration-dependent decrease in settlement of barnacle, Balanus amphitrite, cyprids. The release of young plants of Ulva, a soft fouling species, and young barnacles showed that adhesion strength on the fluorinated/siloxane copolymer was significantly lower than the siloxane control. However, differences in adhesion strength were not directly correlated with the concentration of copolymer in the blends.

Fundamental investigations of the effect of the linkage group on the behavior of hydrophilic–hydrophobic poly(arylene ether sulfone) multiblock copolymers for proton exchange membrane fuel cells

A growing number of alternative proton exchange membrane (PEM) research efforts involve multiblock copolymer chemistries, but little emphasis is placed on the methods used to couple the oligomers. Fluorinated linkage groups can help increase block efficiency during coupling, but their effect on a PEM is not well known. The choice of linkage type, hexafluorobenzene (HFB) vs. decafluorobiphenyl (DFBP), appears to have small but observable influences on multiblock copolymers with disulfonated and unsulfonated poly(arylene ether sulfone) oligomers. DFBP linkages promote greater phase separation than HFB linkages, resulting in increased stiffness, decreased ductility, and increased proton conductivity at low humidities. DFBP linkages also promote more surface enrichment of fluorine, causing changes in surface morphology and slightly increased water desorption, but determining the impact on actual fuel cell performance requires further research.

Effect of polytetrafluoroethylene gradient-distribution on the hydrophobic and tribological properties of polyphenylene sulfide composite coating

PTFE/PPS composite coating was prepared on stainless steel block by spraying and curing at high temperature. The hydrophobic properties and tribological performances of the coatings were measured with CA-A contact angle meter and evaluated on a ring-on-block wear tester, respectively. Moreover, the worn surfaces of the PPS composite coating and the transfer films formed on the surface of the counterpart ring were investigated by SEM and optical microscope (OM), respectively. FTIR and XPS analyses were performed to detect the element gradient-distribution and chemical changes of the PTFE/PPS composite coating. It was concluded that during the curing process, PTFE macromolecule chain shifted gradually from coating interior to the surface, resulting in fluorine (F) enrichment on the top surface. The gradient distribution of fluorine led to the possession of both good hydrophobic property and strong adhesive strength of the PTFE/PPS composite coatings. XPS analyses indicated that the high shear force led to decomposition and oxidation of the element of S in the PTFE/PPS coating; and the generated active S reacted tribochemically with counterface Fe, atmospheric O and H 2O to form FeSO 4 or Fe 2(SO 4) 3.

Synthesis, characterization and properties of a novel fluorinated polyurethane

A novel fluorinated polyurethane (FPU) was prepared by fluorinated polyether glycol (PTMG- g-HFP) as a soft segment, 1,6-hexamethylene diisocyanate (HDI) or toluene diisocyanate (TDI) as a hard segment and 1,4-butanodiol (BDO) as a chain extender. Fourier transform infrared spectroscopy (FTIR), 1H NMR, 13C NMR and gel permeation chromatography (GPC) were used to characterize the structure of the fluorinated polyurethane. The thermal stabilities of the fluorinated polyurethane and the corresponding hydrogenated polyurethane were studied by thermogravimetric analysis (TGA). X-ray photoelectron spectroscopy (XPS) analysis at two different sampling depths for the fluorinated polyurethane was used to investigate the surface compositions of FPU. And the mechanical properties of the fluorinated polyurethane and the corresponding hydrogenated polyurethane were also measured. Chemical resistance of polyurethane films was estimated through spot tests with different solvents. The results showed that FPU had high thermal stability, strain-hardening property and good chemical resistance. The XPS measurements showed the fluorine enrichment on the surface of FPU.

Synthesis and characterization of fluorinated polyurethane with fluorine-containing pendent groups

A novel fluorinated polyurethane (FPU) with fluorine-containing pendent groups was prepared by using fluorinated polyether glycol (PTMG- g-HFP) as a soft segment, 1,6-hexamethylene diisocyanate (HDI) or toluene diisocyanate (TDI) as a hard segment and 1,4-butanodiol (BDO) as a chain extender. FTIR, 1H NMR, 13C NMR and GPC were used to characterize the structure of the fluorinated polyurethane. Thermal stabilities of the fluorinated polyurethane and the corresponding hydrogenated polyurethane were studied by TGA. XPS analysis at two different sampling depths for the fluorinated polyurethane was used to investigate the surface compositions of FPU. The results showed the fluorine enrichment on the surface of FPU.

Synthesis and characterization of hybrid fluoro‐emulsion based on silica/copolymer composite particles

AbstractBACKGROUND: To create a hydrophobic surface, a commonly used two‐step process is the formation of a rough surface and its subsequent modification with materials of low surface energy. Here, a new method for making a hydrophobic surface is proposed using emulsion copolymerization with a low‐surface‐energy fluoropolymer in the presence of a high percentage of silica particles creating a well‐spread roughness.RESULTS: Irregular core–shell structural composite particles such as of snowman shape and sandwich shape were obtained and characterized. The hydrophobicity and chemical structure of the hybrid film were investigated. It was found that strong inter‐ and intramolecular chemical bonding in the composite film may improve the properties of the hybrid film. Enrichment of fluorine on the film surface and well‐distributed roughness due to the silica particles covered by the fluoropolymer contribute to the increased hydrophobicity of the film. The water contact angle on the film increased from 106 ± 2° to 135 ± 2°.CONCLUSION: The stable core–shell hybrid latex synthesized in this work will be of use in preparing high‐performance hydrophobic aqueous coatings. Copyright © 2008 Society of Chemical Industry

Effect of Hyperbranched Surface-Migrating Additives on the Electrospinning Behavior of Poly(methyl methacrylate)

Poly(methyl methacrylate) (PMMA) was electrospun in the presence of a low molecular weight, hyperbranched poly(ethylene imine) additive partially functionalized with perfluorinated and aliphatic end-groups (M(n) approximately 1600 g/mol). The additive exhibited surface segregation with an insignificant influence on the rheological behavior of PMMA solutions. A morphological transition from beaded electrospun fibers to uniform fibers was observed upon introduction of additive at low PMMA concentrations. XPS revealed a surface enrichment of fluorine and nitrogen, which are both present in the hyperbranched additive. Surface fluorine content depended primarily on the amount of additive in solution, and a dependency on the PMMA/additive weight ratio was not observed.

Synthesis and characterization of an epoxy based thermoset containing a fluorinated thermoplastic

AbstractA novel fluorinated thermoplastic (FT) was synthesized from diglycidyl ether of bisphenol A (DGEBA), and 3‐(trifluoromethyl)aniline. FT was found to be miscible with DGEBA as shown by the existence of a single glass transition temperature (Tg) within the whole composition range. On the basis of several experimental techniques, it was found that upon heating etherification reaction takes place between FT and DGEBA. A DGEBA‐aromatic diamine (4,4′‐methylenebis(3‐chloro 2,6‐diethylaniline) formulation was modified with the FT. The influence of FT on the epoxy‐amine kinetics was investigated. Both structural parameters, gelation, and vitrification, were found to be affected by etherification reaction between epoxy and hydroxyls groups belonging to FT. The presence of ether linkages induced system stoichiometry modification. In addition, the curing conditions influence on FT migration towards the surface was studied on samples prepared with 20 wt % of modifier. SEM–EDX analysis confirmed that modified systems exhibits notable fluorine enrichment within the uppermost 200 μm. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2781–2792, 2007