Ultradrawing properties of ultrahigh‐molecular‐weight polyethylene/attapulgite fibers

An investigation of the influence of the contents of original and modified attapulgite (ATP) on the ultradrawing properties of ultrahigh‐molecular‐weight polyethylene (UHMWPE)/ATP (FA_x) and UHMWPE/modified ATP (FA_mx) as‐prepared fibers is reported. Similar to what is found for the orientation factor values, the achievable draw ratios (D_ra) of the FA_x and FA_mx as‐prepared fibers approach a maximum value as the original ATP and/or modified ATP contents reach their corresponding optimum values. The maximum D_ra value obtained for FA_mx as‐prepared fiber specimens is significantly higher than that for FA_x as‐prepared fiber specimens prepared at the optimum original ATP content. Similar to what is found for the orientation factors and achievable drawing properties, the tensile strength (σ_f) and initial modulus (E) of both drawn F₂A_x and F₂A_mx fiber series specimens with a fixed draw ratio reach maximum values as the original and/or modified ATP contents approach the optimum values, respectively. The σ_f and E values of the F₂A_mx fiber specimens are always significantly higher than those of the corresponding F₂A_x fiber specimens prepared at the same draw ratios and ATP contents but without being modified. To understand the interesting ultradrawing, orientation and tensile properties of FA_x and FA_mx fiber specimens, Fourier transform infrared spectral, specific surface area, transmission electron microscopic and elemental analyses of the original and modified ATPs were performed. Copyright © 2012 Society of Chemical Industry     

Ultradrawing and ultimate tensile properties of ultrahigh molecular weight polyethylene composite fibers filled with functionalized nanoalumina fillers

Ultradrawing and ultimate tensile properties of ultrahigh molecular weight polyethylene (UHMWPE) composite fibers were successfully improved by the addition of nanoalumina (NAL), acid treated nanoalumina (ATNAL), and/or functionalized nanoalumina (FNAL). As evidenced by FTIR and TEM analyses, maleic anhydride grafted polyethylene (PE_g‐MAH) molecules were successfully grafted onto ATNAL fillers. The specific surface areas of FNAL fillers reached a maximal value at 516 m²/g, as they were modified using an optimal weight ratio of PE_g‐MAH to ATNAL at 8. Achievable draw ratio (D_ra) values of UHMWPE/NAL (F₁₀₀A_y), UHMWPE/ATNAL (F₁₀₀A_x%‐8‐y) and/or UHMWPE/FNAL (F₁₀₀A_x%‐8FPE^z_y) as‐prepared fibers approached a maximal value as NAL, ATNAL, and/or FNAL contents reached an optimal value at 0.1, 0.1, and 0.075 phr, respectively. The maximal D_ra values of F₁₀₀A_x%‐8FPE^z_0.075 as‐prepared fiber specimens were significantly higher than those of F₁₀₀A_0.1 and F₁₀₀A_x%‐8‐0.1 as‐prepared fiber specimens. In which, the maximal D_ra values obtained for F₁₀₀A_x%‐8FPE^z_0.075 as‐prepared fibers reached another maximal value as FNAL fillers were modified using an optimal weight ratio of PE_g‐MAH to ATNAL at 8. The ultimate tensile strength value of F₁₀₀A_2%‐8FPE⁸_0.075 drawn fiber reached 6.4 GPa, which was about 2.4 times of that of the UHMWPE drawn fibers prepared at the same optimal UHMWPE concentration and drawing condition. POLYM. ENG. SCI., 55:2205–2214, 2015. © 2015 Society of Plastics Engineers     

Ultradrawing properties of ultra‐high molecular weight polyethylene/functionalized carbon nanotube fibers

Systemic investigation of the influence of the plain and functionalized carbon nanotube (CNT) contents on the ultradrawing properties of ultrahigh molecular weight polyethylene/carbon nanotubes (UHMWPE/CNTs, FC_y) and UHMWPE/functionalized CNTs (FC_fx‐y) as‐prepared fibers are reported. In a way similar to those found for the orientation factor values, the achievable draw ratios (D_ra) of the FC_y and FC_fx‐y as‐prepared fibers approached a maximum value as their CNT and/or functionalized CNT contents reached their corresponding optimum values. The maximum D_ra values obtained for FC_fx‐0.001 as‐prepared fiber specimens prepared at varying maleic anhydride grafted polyethylene (PE_‐g‐MAH)/modified CNTs weight ratios were significantly higher that of the FC_0.0015 as‐prepared fiber specimen prepared at the optimum plain CNT content. Tensile property analysis further suggested that excellent orientation and tensile properties of the drawn FC_y and FC_fx‐y fibers can be obtained by ultradrawing the fibers prepared at their optimum plain CNT and/or functionalized CNT contents. To understand the interesting orientation, ultradrawing and tensile properties of FC_y and FC_fx‐y fiber specimens, FTIR, specific surface area, and SEM morphology analysis of the plain and functionalized CNTs were performed in this study. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers     

Ultrahigh molecular weight polyethylene fibers prepared using conical dies with varying dimensions

Dimensions of conical dies were found to have a significant influence on thermal, morphological, orientation, ultradrawing, and dynamic mechanical properties of the as‐prepared and/or drawn ultrahigh molecular weight polyethylene (UHMWPE) fiber specimens prepared in this study. Many demarcated “micro‐fibrils” were found paralleling to fiber direction of the as‐prepared UHMWPE fiber specimens. The percentage crystallinity, melting temperatures, orientation factor (f_o) and achievable draw ratio (D_ra) values of each as‐prepared UHMWPE fiber specimen prepared at a fixed length of outlet land reach a maximum value, as the entry angles of the conical die approach the optimum value at 75°. The maximum f_o and D_ra values obtained for each F₂₀^75‐y as‐prepared fiber series specimens prepared using the optimum entry angle reach another maximum value as their length of outlet land approach the optimum value of 6.5 mm. The ultimate tensile strengths and moduli of the drawn UHMWPE fibers prepared at the optimum entry angle and length of outlet land are significantly higher than those of fibers prepared at other conditions but stretched to the same draw ratio. Possible reasons accounting for the above interesting properties were discussed in this study. POLYM. ENG. SCI., 2013. © 2013 Society of Plastics Engineers     

Drawing and ultimate tenacity properties of polyamide 6/attapulgite composite fibers

The drawing and ultimate tenacity properties of the Polyamide 6 (PA6)/Attapulgite (ATP) composite fiber specimens prepared at varying modified ATP (mATP) contents and drawing condition were systematically investigated. As evidenced by Fourier transform infrared (FTIR) and morphological analysis, demarcated translucent resins were found firmly attached on the surfaces of ATP nanofibers. The specific surface areas of the mATP specimens reached a maximum value at 381 m²/g as the weight ratios of silane coupling agents to ATP nanofibers reached an optimum value at 1.0. The percentage crystallinity and melt shear viscosity values measured at varying shear rates of PA6_x(mATP)_y specimens increased consistently as their mATP contents increased. In contrast, melting temperatures of PA6_x(mATP)_y specimens reduced slightly as their mATP contents increased. At a fixed drawing temperature and rate, the achievable draw ratio (D_ra) values of PA6_x(mATP)_y as‐spun fiber specimens approach a maximum value, as their mATP contents are close to the 0.2 wt % optimum value. The maximum D_ra values obtained for PA6_99.8(mATP)_0.2 as‐spun fiber specimens reached another maximum, when their drawing temperatures and rates approached the optimum values at 120°C and 50 mm/min, respectively. At a fixed draw ratio, the tenacity values of PA6_x(mATP)_y drawn fiber specimens drawn at the optimum drawing temperature and rate reached a maximum value, as their mATP contents approached the 0.2 wt % optimum value. Possible reasons accounting for the interesting morphological, specific surface area, drawing, orientation, and ultimate tenacity properties found for the PA6_x(mATP)_y fiber specimens are proposed. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Drawing and tensile properties of polyamide 6/calcium chloride composite fibers

The influence of calcium chloride (CaCl₂) contents on the drawing and tensile properties of polyamide 6 (PA6)/CaCl₂ composite fibers prepared at varying drawing temperatures were investigated. At any fixed drawing temperature, the achievable draw ratio (D_ra) values of PA6_x(CaCl₂)_y as-spun fiber specimens approach a maximum value, as their CaCl₂ contents are close to the 3 wt% optimum value. The maximum D_ra values obtained for PA6_x(CaCl₂)_y as-spun fiber specimens prepared at the optimum CaCl₂ content reach another maximum as their drawing temperatures approach the optimum drawing temperature at 120 °C. The initial modulus, tensile strength and birefringence values of the PA6 and PA6_x(CaCl₂)_y fiber specimens were found to improve consistently with D_ra or with drawing temperatures when they were stretched to a fixed D_ra. Similar to those found for their achievable drawing properties, the ultimate initial modulus, tensile strength and birefringence values of PA6_x(CaCl₂)_y fiber specimens approach a maximum value, as their CaCl₂ contents and drawing temperatures approach the 3 wt% and 120 °C optimum values, respectively. Experiments including thermal, FTIR, melt shear viscosity and wide angle X-ray diffraction experiments were performed on the PA6_x(CaCl₂)_y resin and/or fiber specimens to clarify the possible reasons accounting for the interesting drawing, tensile and birefringence properties found for the PA6_x(CaCl₂)_y fiber specimens.     

Drawing and ultimate tensile properties of nylon 6/nylon 6 clay composite fibers

This study systematically investigated the drawing and ultimate tenacity properties of the Nylon 6 (NY6)/nylon 6 clay (NYC) composite fiber specimens prepared at varying NYC contents and drawing temperatures. The achievable draw ratio (D_ra) values of NY6_x(NYC)_y as‐spun fiber specimens initially increase in conjunction with NYC content, and then approach a maximum value, as their NYC contents and drawing temperature approach the 0.5 wt% and 120°C, respectively. The percentage crystallinity (X_c) values of NY6_x(NYC)_y as‐spun fiber specimens increased significantly, as their NYC contents increased from 0 to 2 wt%. As revealed by high power wide angle X‐ray diffraction analysis, α form NY6 crystals grew at the expense of γ form NY6 crystals originally present in NY6_x(NYC)_y as‐spun fiber specimens as their draw ratios increased. The ultimate modulus, tenacity, and orientation factor values of NY6_x(NYC)_y fiber specimens approach a maximum value, as their NYC contents and drawing temperatures approach the 0.5 wt% and 120°C optimum values, respectively. The thermal and melt shear viscosity experiments were performed on NY6_x(NYC)_y resins and/or fiber specimens to determine the optimum NYC content and possible deformation mechanisms accounting for the interesting drawing, orientation, and ultimate tenacity properties found above. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Drawing and ultimate tensile properties of modified polyamide 6 fibers

The drawing and ultimate tensile properties of the modified PA 6 (MPA) fiber specimens prepared at varying drawing temperature were systematically investigated, wherein the MPA resins were prepared by reactive extrusion of PA 6 with the compatibilizer precursor (CP). At any fixed drawing temperature, the achievable draw ratio (D_ra) values of MPA as‐spun fiber specimens increase initially with increasing CP contents, and then approach a maximum value, as their CP contents are close to the 5 wt% optimum value. The maximum D_ra values obtained for MPA as‐spun fiber specimens prepared at the optimum CP content reach another maximum as their drawing temperatures approach the optimum drawing temperature at 120°C. The tensile and birefringence values of PA 6 and MPA fiber specimens improve consistently as their draw ratios increase. Similar to those found for their achievable drawing properties, the ultimate tensile and birefringence values of MPA fiber specimens approach a maximum value, as their CP contents and drawing temperatures approach the 5 wt% and 120°C optimum values, respectively. Investigations including Fourier transform infrared, melt shear viscosity, gel content, thermal and wide angle X‐ray diffraction experiments were performed on the MPA resin and/or fiber specimens to clarify the optimum CP content and possible deformation mechanisms accounting for the interesting drawing, birefringence, and ultimate tensile properties found for the MPA fiber specimens prepared in this study. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Ultradrawing properties of ultrahigh‐molecular weight polyethylene/functionalized carbon nanotube fibers and transmittance properties of their gel solutions

The influences of the dispersion level of carbon nanotubes (CNTs) and functionalized CNTs on the transmittance properties of ultrahigh‐molecular weight polyethylene (UHMWPE) gel solutions and on ultradrawing properties of their as‐prepared fibers are reported. The transmittance properties suggest that the dispersion level of functionalized CNTs in UHMWPE/functionalized CNTs gel solution is significantly better than plain CNTs in UHMWPE/CNTs gel solutions. The orientation factors, achievable draw ratios, tensile strength (σ_f), and modulus (E) values of UHMWPE/CNTs (F_xC_y) and UHMWPE/functionalized CNTs (F_xC_f‐y) as‐prepared fiber specimens reached a maximum value as their CNT and functionalized CNT contents approached optimum contents at 0.00015 and 0.0001 wt%, respectively. The σ_f and E values of both F_xC_0.0012 and F_xC_f‐0.001 series fiber specimens prepared at their optimum CNT and functionalized CNT contents reached another maximum as their UHMWPE approached optimum UHMWPE concentration of 1.7 wt%. Possible reasons accounting for these interesting properties are proposed. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Ultradrawing properties of ultrahigh‐ molecular‐weight polyethylene/carbon nanotube fibers prepared at various formation temperatures

The influence of formation temperature on the ultradrawing properties of ultrahigh‐molecular‐weight polyethylene/carbon nanotube (UHMWPE/CNT) fiber specimens is investigated. Gel solutions of UHMWPE/CNT with various CNT contents were gel‐spun at the optimum concentration and temperature but were cooled at varying formation temperatures in order to improve the ultradrawing and tensile properties of the UHMWPE/CNT composite fibers. The achievable draw ratio (D_ra) values of UHMWPE/CNT as‐prepared fibers reach a maximum when they are prepared with the optimum CNT content and formation temperature. The D_ra value of UHMWPE/CNT as‐prepared fibers produced using the optimum CNT content and formation temperature is about 33% higher than that of UHMWPE as‐prepared fibers produced using the optimum concentration and formation temperature. The percentage crystallinity (W_c) and melting temperature (T_m) of UHMWPE/CNT as‐prepared fiber specimens increase significantly as the formation temperature increases. In contrast, W_c increases but T_m decreases significantly as the CNT content increases. Dynamic mechanical analysis of UHMWPE and UHMWPE/CNT fiber specimens exhibits particularly high α‐transition and low β‐transition, wherein the peak temperatures of α‐transition and β‐transition increase dramatically as the formation temperature increases and/or CNT content decreases. In order to understand these interesting drawing, thermal and dynamic mechanical properties of the UHMWPE and UHMWPE/CNT as‐prepared fiber specimens, birefringence, morphological and tensile studies of as‐prepared and drawn fibers were carried out. Possible mechanisms accounting for these interesting properties are proposed. Copyright © 2010 Society of Chemical Industry     

Synthesis and properties of polystyrene‐g‐mSiO2 filled polypropylene nanocomposites

Hydrophobically modified nanosilica was prepared from tetraethoxysilane (TEOS) and γ‐methacryloxypropyltrimethoxysilane (MPS) by a two step sol‐gel process. The polystyrene‐grafted‐modified nanosilica (PS‐g‐mSiO₂) hybrid particles were prepared by grafting polystyrene onto the resulting hydrophobically modified nanosilica by dispersion polymerization. The hybrid nanoparticles were subsequently used as the filler to fabricate polypropyrene (PP) nanocomposites. The crystallization kinetics, crystal morphology and crystallization phase component of PS‐g‐mSiO₂/PP nanocomposite were studied using a differential scanning calorimeter (DSC), polarizing optical microscopy (POM) and X‐ray diffraction (XRD). Crystallization half life (t_1/2) decreased, while the Arami exponent (n) of PS‐g‐mSiO₂/PP nanocomposite increased compared with that of virgin PP. A rheological study allowed the unambiguous characterization of the dispersibility of nanosilicas in PS‐g‐mSiO₂/PP nanocomposite. The storage modulus, melt viscosity and the elongation to break of the PS‐g‐mSiO₂/PP nanocomposite were found to be strongly dependent on the grafting of PS on nanosilicas. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Study on structure and properties of SSBR/SiO2 co‐coagulated rubber and SSBR filled with nanosilica composites

The morphological structure, glass transition, mechanical properties, and dynamic mechanical properties of star‐shaped solution‐polymerized styrene‐butadiene rubber (SSBR) synthesized by a multifunctional organic lithium initiator and SiO₂‐SSBR composite (N‐SSBR) prepared through adding a small amount of nanosilica modified by silane coupling agent to star‐shaped SSBR synthetic solution and co‐coagulating, and their nanocomposites filled with 20 phr nanosilica were investigated, respectively. The results showed that the silica particles were well dispersed with nanosize in N‐SSBR, which glass‐transition temperature (T_g) was 2°C higher than SSBR. N‐SSBR/SiO₂ nanocomposite exhibited lower Payne effect and internal friction loss, higher mechanical properties, and its T_g was 2°C higher than SSBR/SiO₂ nanocomposite. N‐SSBR might promote the dispersion of nanosilica powder in matrix and could be applied to green tire tread materials. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Properties of polyamide 6,10/poly(vinyl alcohol) blends and impact on oxygen barrier performance

The oxygen transmission rate, average volume of free‐volume cavities (V_f) and fractional free volume (F_v) of polyamide 6,10 (PA610)/poly(vinyl alcohol) (PVA) (i.e. PA610_xPVA⁰⁵_y, PA610_xPVA⁰⁸_y and PA610_xPVA¹⁴_y) blend films reduced to minimum values when their PVA contents reached corresponding optimal values. Oxygen transmission rate, V_f and F_v values obtained for optimal PA610_xPVA^z_y blown films were reduced considerably with decreasing PVA degrees of polymerization. The oxygen transmission rate of the optimal bio‐based PA610₈₀PVA⁰⁵₂₀ blown film was only 2.4 cm³ (m²·day·atm)^?1, which is about the same as that of the most often used high‐barrier polymer, ethylene–vinyl alcohol copolymer. Experimental findings from dynamic mechanical analysis, differential scanning calorimetry, wide‐angle X‐ray diffraction and Fourier transform infrared spectroscopy of the PA610_xPVA^z_y blends indicate that PA610 and PVA in the blends are miscible to some extent at the molecular level when the PVA contents are less than or equal to the corresponding optimal values. The considerably enhanced oxygen barrier properties of the PA610_xPVA^z_y blend films with optimized compositions are attributed to the significantly reduced local free‐volume characteristics. © 2017 Society of Chemical Industry     

Ultradrawing properties of gel films of ultrahigh‐molecular‐weight polyethylene and low‐molecular‐weight polyethylene blends prepared at various formation temperatures

The ultradrawing behavior of ultrahigh‐molecular‐weight polyethylene/low‐molecular‐weight polyethylene film specimens prepared at various concentrations and formation temperatures was studied. The critical draw ratio (D_rc) of UL_?0.7 film specimens was found to depend significantly on the formation temperature used to prepare the film specimens. At any fixed drawing temperature, the D_rc values of UL_?0.7 specimens prepared at various formation temperatures increased significantly as the formation temperatures were reduced. In fact, with an optimum drawing temperature of 95°C, the D_rc values of UL_?0.7 specimens prepared at a formation temperature of 0°C reached 488, about 50% higher than that of UL_?0.7 specimens prepared at a formation temperature of 95°C. These interesting phenomena were investigated in terms of the thermal, birefringence, and tensile properties of these undrawn and drawn UL_?0.7 specimens. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3728–3738, 2003     

Fine disperse dyeable polypropylene fiber from polypropylene/polystyrene nano‐ceria blends

The blend of polypropylene (PP) and atactic polystyrene (PS) hybrid with nano‐ceria (CeO₂) was prepared for fine dyeable fiber. Nano‐CeO₂ modified with stearic acid was in situ added to PS by radical suspension polymerization. The dispersion of hy‐PS with nano‐CeO₂ in the PP crystals was investigated. The rheological behavior of the blend was similar to that of PP under the testing conditions, and the blend had stable spinning and drawing processability. The fine modified PP filaments were processed from the blend and had practical mechanical properties. The dyeability of the knitting fabrics from these filaments was studied. The increased amorphous content and the interface between PP and hy‐PS allowed the dye to penetrate the fiber, and the modified PP fiber had strong affinity to dye because of the complexation between cerium and dye. These effects resulted in improving K/S value and color fastness to soaping. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Multiple-step drawing innovative ultrahigh-molecular-weight polyethylene fibers modified with bacterial cellulose and scCO2-aid

Innovative supercritical carbon dioxide (scCO₂)-assisted ultrahigh-molecular-weight-polyethylene (UHMWPE)/modified bacterial cellulose (MBC) as-spun fibers were found to display substantially lower dynamic transition temperatures than those acquired for scCO₂-assisted UHMWPE or UHMWPE/MBC as-spun fibers prepared without scCO₂-assistance or incorporation of MBC nanofibers. Multiple-step drawing methods were first-time applied to these finely ''relaxed'' scCO₂-assisted UHMWPE/MBC fibers and considerably improved their achievable draw ratios (D_ras), orientation factor (f_os), and tensile tenacities (σ_tts). The best five-step drawn scCO₂UHMWPE/MBC fiber displayed a particularly high σ_tt of 135 g d⁻¹, which was ~35, ~3.75, and ~1.7 fold of σ_tts acquired for good steel fiber and the most appropriate single-step drawn scCO₂-assisted UHMWPE and UHMWPE/MBC fibers, respectively. The particularly high D_ras, f_o, and σ_tts acquired for the best multiple-step drawn scCO₂-assisted UHMWPE/MBC fibers is ascribed to their more ''relaxed'' UHMWPE structures, thinner lamellae, and successive increased drawing temperature in the multiple-step drawing processes.     

Recoverable surface modification using dendritically fluorocarbon‐functionalized poly(methyl methacrylate)

Dendritically fluorocarbon‐functionalized poly(methyl methacrylate) (PMMA) has been explored as a robust surface‐modifying additive in PMMA blends. These functionalized materials, denoted F_xPMMA_y, where x is the number of C₈F₁₇ fluorocarbon groups per dendron connected to a PMMA chain of y kg/mol, have been synthesized by living radical polymerization. These materials adsorb efficiently to the surfaces of their blends with unfunctionalized PMMA, resulting in increased hydrophobicity and lipophobicity. Contact‐angle goniometry has indicated a substantial reduction in the surface energy toward polytetrafluoroethylene‐like surface properties in the case of pure F₄PMMA_8.6 and substantial, but incomplete fluorocarbon surface coverage at a lower F_xPMMA_y concentration. The partial coverage has been confirmed by Rutherford backscattering and, together with the weak dependence of the surface modification on the F_xPMMA_y structure, indicates incomplete equilibrium of the surface adsorption. The modified surfaces are quite durable with respect to abrasion under water but are progressively eroded when the double‐wipe test is carried out with acetone. F_xPMMA_y, dispersed in the remaining film, acts as a reservoir of spare functional groups, from which the damaged surface may be replenished, leading to the recovery of the modified surface properties. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Hybrid effect on mechanical properties of M40‐T300 carbon fiber reinforced Bisphenol A Dicyanate ester composites

Interply and intraply hybrid composites based on Bisphenol A Dicyanate ester (BADCy), high strength carbon fibers T300, and high modulus carbon fibers M40 were prepared by monofilament dip‐winding and press molding technique. The tensile, flexural, interlaminar shear properties and SEM analysis of the hybrid composites with different fiber content and fiber arrangement were investigated. The results indicated that the mechanical properties of intraply hybrid composites were mainly determined by fiber volume contents. When the ratio of fiber volume content was close to 1:1, the intraply hybrid composites possessed lowest tensile and flexural strength. The mechanical properties of interply hybrid composite mainly depended on the fiber arrangement, instead of the fiber volume contents. The hybrid composites using T300 fiber layout as outside layer possessed high flexural strength and low flexural modulus, which was close to that of T300/BADCy composites. The hybrid composites ([(M40)_x/(T300)_y]_S) using M40 fiber layout as outside layer and T300 fibers in the mid‐plane had high flexural modulus and interlaminar shear strength. POLYM. COMPOS., 2010. © 2010 Society of Plastics Engineers     

Synthesis and gelation of novel fluoroalkyl end‐capped N‐(1,1‐dimethyl‐3‐oxobutyl)acrylamide copolymers containing triol segments—Interaction of these fluorinated gels with various hydrophilic compounds

Fluoroalkyl end‐capped N‐(1,1‐dimethyl‐3‐oxobutyl)acrylamide (DOBAA) copolymers containing triol segments were prepared by the reactions of fluoroalkanoyl peroxide with the corresponding monomer and N‐tris(hydroxymethyl)methylacrylamide (NAT). These obtained fluorinated copolymers [R_F‐(DOBAA)_x‐(NAT)_y‐R_F] were found to cause gelation in water, dimethyl sulfoxide, and N,N‐dimethylformamide under the non‐crosslinked conditions, although the corresponding nonfluorinated DOBAA–NAT copolymer [‐(DOBAA)_x‐(NAT)_y‐] could cause no gelation in these solvents. This gelation is governed by the synergistic interaction of strong aggregations of end‐capped fluoroalkyl segments and intermolecular hydrogen bonding between triol segments. We also studied the uptake and release of a variety of hydrophilic compounds such as methylene blue, methyl orange, 4‐hydroxyazobenzene‐4′‐sulfonic acid sodium salt, 2,4‐dihydroxyazobenzene‐4′‐sulfonic acid sodium salt, acriflavine hydrochloride, acridine hydrochloride, lucigenin, and fluorescein by this fluorinated copolymer gel and fluoroalkyl end‐capped NAT homopolymer gel [R_F‐(NAT)_n‐RF] for comparison. It was demonstrated that the uptake and release ratios of these hydrophilic compounds by R_F‐(DOBAA)_x‐(NAT)_y‐R_F gel become generally lower than those of R_F‐(NAT)_n‐R_F gel. Interestingly, R_F‐(DOBAA)_x‐(NAT)_y‐R_F gel has no releasing power toward methylene blue, acridine hydrochloride, lucigenin, and fluorescein, although R_F‐(NAT)_n‐R_F gel has a good releasing power toward these compounds. Additionally, R_F‐(DOBAA)_x‐(NAT)_y‐R_F gel was applied to the controlled release of anticancer drugs such as methotrexate (MTX), and the releasing ratios of MTX became higher with increasing pH values (from pH 4.3 to 9.1). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88:3212–3217, 2003     

siRNA Modified with 2′‐Deoxy‐2′‐C‐methylpyrimidine Nucleosides

(2′S)‐2′‐Deoxy‐2′‐C‐methyluridine and (2′R)‐2′‐deoxy‐2′‐C‐methyluridine were incorporated in the 3′‐overhang region of the sense and antisense strands and in positions 2 and 5 of the seed region of siRNA duplexes directed against Renilla luciferase, whereas (2′S)‐2′‐deoxy‐2′‐C‐methylcytidine was incorporated in the 6‐position of the seed region of the same constructions. A dual luciferase reporter assay in transfected HeLa cells was used as a model system to measure the IC₅₀ values of 24 different modified duplexes. The best results were obtained by the substitution of one thymidine unit in the antisense 3′‐overhang region by (2′S)‐ or (2′R)‐2′‐deoxy‐2′‐C‐methyluridine, reducing IC₅₀ to half of the value observed for the natural control. The selectivity of the modified siRNA was measured, it being found that modifications in positions 5 and 6 of the seed region had a positive effect on the ON/OFF activity.