Fluoroalkyl End-capped Cooligomers Research Articles

Preparation and properties of novel cross-linked fluoroalkyl end-capped cooligomeric nanoparticles possessing double decker-type aromatic silsesquioxane segments as core units

Cross-linked fluoroalkyl end-capped cooligomers possessing double decker-type aromatic silsesquioxane segments as core units [RF-(Ar-SiSQ) x -(Co-M) y -RF] were prepared under mild conditions by the cooligomerizations of fluoroalkanoyl peroxide with the corresponding aromatic silsesquioxane possessing bifunctional vinyl groups (Ar-SiSQ) and comonomers (Co-M) such as acryloylmorpholine (ACMO), N,N-dimethylacrylamide (DMAA) and N-(1,1-dimethyl-3-oxobutyl)acrylamide (DOBAA). Interestingly, these cross-linked fluorinated cooligomers thus obtained were found to form the nanometer size-controlled nanoparticles with a good dispersibility in a variety of solvents including fluorinated aliphatic solvents. These fluorinated cooligomeric nanoparticles were demonstrated to have red-shifted fluorescent emissions related to the presence of aromatic silsesquioxane segments, compared with that of parent aromatic silsesquioxane, indicating that each aromatic moiety in these nanoparticles can interact effectively with each other through the π–π stacking between the aromatic moieties to afford the red-shifted fluorescent emissions. These fluorinated nanoparticles were also applied to the surface modification of poly(methyl methacrylate) (PMMA) to exhibit not only a good oleophobicity imparted by fluorine but also a fluorescent emission behavior related to aromatic silsesquioxane segments in nanoparticles on the modified PMMA surface. More interestingly, cross-linked RF-(Ar-SiSQ) x -(DOBAA) y -RF cooligomeric nanoparticles interacted with fluorescein to give the corresponding fluorinated cooligomeric particles/fluorescein nanocomposites in methanol. These fluorinated fluorescein nanocomposites were found to afford an extraordinarily enhanced light absorption (λ max = 441 nm), compared with that of fluoroalkyl end-capped DOBAA oligomer [RF-(DOBAA) n -RF] possessing no aromatic silsesquioxane segments.

Synthesis and applications of fluoroalkyl end-capped cooligomers having fullerene and mixed fullerenes in the main chain

Fluoroalkanoyl peroxides reacted with FULLERENES [fullerene (C60) and commercially available fullerenes (Nanom MixTR and Nanom BlackTR)] and radical polymerizable comonomers such as acrylic acid, N,N-dimethylacrylamide, N-(1,1-dimethyl-3-oxobutyl)acrylamide, and acryloylmorpholine to afford fluoroalkyl end-capped cooligomers having FULLERENES in the main chain under very mild conditions. Fluoroalkyl end-capped Nanom Mix and Nanom Black cooligomers thus obtained were found to exhibit a similar solubility to that of the corresponding fluoroalkyl end-capped cooligomers having fullerene in the main chain. These fluorinated FULLERENES cooligomers were found to form the nanometer size-controlled self-assembled cooligomeric aggregates in aqueous solutions. These fluoroalkyl end-capped FULLERENES cooligomers were more effective for solubilizing fullerene, Nanom Mix and Nanom Black into water, compared to those of the corresponding fluoroalkyl end-capped homooligomers having no FULLERENES in the main chain. Fluoroalkyl end-capped fullerene- and Nanom Mix-acrylic acid cooligomers were found to exhibit fluorescence spectra related to fullerene and Nanom Mix in cooligomers, respectively, in aqueous solutions. Additionally, these fluorinated fullerene- and Nanom Mix-acrylic acid cooligomers were able to increase chemiluminescence intensity related to luminol, effectively, compared to the corresponding fluorinated acrylic acid homooligomers.

Thermoresponsive Characteristics of Fluoroalkyl End-Capped Co-oligomers in Aqueous Solutions and on the Poly(methyl methacrylate) Film Surface

Fluoroalkyl end-capped N-(1,1-dimethyl-3-oxobutyl)acrylamide--acryloylmorpholine co-oligomers were prepared by the co-oligomerizations of fluoroalkanoyl peroxides with the corresponding monomers. These fluorinated co-oligomers exhibited a lower critical solution temperature (LCST) characteristic in aqueous solutions. Of particular interest, a steep time dependence of contact angle values for dodecane was observed from 40 to 60 degrees C to decrease their values, effectively, on the modified PMMA [poly(methyl methacrylate)] film surface treated with fluorinated co-oligomer possessing the LCST: 36 degrees C (in water), although such a steep time dependence was not observed from 20 to 30 degrees C.

Synthesis and application of novel fluoroalkyl end-capped cooligomers having adamantane as a pendant group

Fluoroalkyl end-capped cooligomers having adamantane as a pendant group [RF-(Ad-HAc)x–(Co-M)y-RF] were prepared by the reactions of fluoroalkanoyl peroxide with 3-hydroxy-1-adamantylacrylate (Ad-HAc) and comonomers (Co-M) such as acrylic acid (ACA), N,N-dimethylacrylamide (DMAA), and acryloylmorpholine (ACMO) under mild conditions. Thermogravimetric analyses (TGA) showed that thermal stability of RF-(Ad-HAc)x–(Co-M)y-RF was superior to that of the corresponding fluoroalkyl end-capped cooligomers having adamantane in the main chains [RF-(Ad)x–(Co-M)y-RF] and the fluoroalkyl end-capped homooligomers possessing no adamantyl segments [RF-(M)n-RF]. It is interesting to note that fluoroalkyl end-capped Ad-Hac–DMAA cooligomer [RF-(Ad-HAc)x–(DMAA)y-RF] was found to form the nanometer size-controlled cooligomeric aggregates which consist of around 16 fluorinated cooligomeric molecules in methanol/water mixed solvents. Furthermore, these fluorinated cooligomeric aggregate could occupy around 320 ADMDD [5-(2-adamantylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione] molecules as guest molecules per aggregate core, although ADMDD could not be encapsulated into the RF-(Ad)x–(Co-M)y-RF cooligomeric and RF-(M)n-RF homooligomeric aggregate cores under similar conditions.

Solubilization of fullerene into ionic liquids by the use of fluoroalkyl end‐capped oligomers

AbstractFluoroalkyl end‐capped oligomers were solubilized into a variety of ionic liquids such as N‐methylpyrazolium tetrafluoroborate, 3‐methylpyrazolium tetrafluoroborate and 1‐butyl‐3‐methylimidazolium hexafluorophosphate, and these fluorinated oligomers were able to reduce the surface tension of these ionic liquids. Interestingly, these fluorinated oligomers were able to solubilize fullerene into ionic liquids effectively. Fluoroalkyl end‐capped fullerene co‐oligomers, which were prepared by the oligomerizations of fluoroalkanoyl peroxides with radical polymerizable monomers such as acryloylmorpholine in the presence of fullerene, were more effective in solubilizing fullerene into ionic liquids compared to the corresponding fluoroalkyl end‐capped homo‐oligomers possessing no fullerene units. Fluoroalkyl end‐capped fullerene co‐oligomers/fullerene/ionic liquid complexes thus obtained were applied to the arrangements of fullerenes above the poly(methyl methacrylate) (PMMA) surface, and the higher fluorescent intensity of fullerene was obtained in the modified PMMA surface, although the reverse side of this modified film surface afforded an extremely weak fluorescent intensity. Copyright © 2005 John Wiley & Sons, Ltd.

SYNTHESIS AND APPLICATIONS OF NOVEL FLUOROALKYL END-CAPPED OLIGOMERS CONTAINING 3,5-DIMETHYL-4-HYDROXYBENZYL AND 3-(2H-BENZOTRIAZOL-2-yl)-4-HYDROXYPHENYL SEGMENTS

New fluoroalkyl end-capped co-oligomers containing 3,5-dimethyl-4-hydroxybenzyl segments [RF‒(DMHB)x‒(DMAA)y–RF] were prepared by the reactions of fluoroalkanoyl peroxides with N-(3,5-dimethyl-4-hydroxybenzyl)methacrylamide [DMHB] and N,N-dimethylacrylamide (DMAA). Similarly, fluoroalkyl end-capped homo- and co-oligomers containing 3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl segments [RF–(BTRI)x–(Co–M)y–RF] were prepared by the reactions of fluoroalkanoyl peroxides with 2-[3–(2H‒benzotriazol–2–yl)–4–hydroxyphenyl]ethyl methacrylate [BTRI] and co-monomers [Co–M] such as acrylic acid (ACA), DMAA, and acryloylmorpholine (ACMO). The fluoroalkyl end-capped DMHB and BTRI co-oligomers thus obtained were soluble not only in water but also in common organic solvents. In addition, these fluorinated co-oligomers were able to reduce the surface tension of 0.1 N NaOH solutions quite effectively to around 20 mN/mlevels, although the corresponding non-fluorinated co-oligomers were not effective in reducing the surface tension of 0.1 N NaOH solutions. A modified polystyrene film surface treated with these fluoroalkyl end-capped DMHB and BTRI co-oligomers was found to exhibit a good oleophobicity imparted by fluorine with an excellent hydrophilicity. XPS analyses showed that end-capped fluoroalkyl groups in RF-(BTRI)n-RF homo-oligomer were arranged regularly above the modified polystyrene surface. Of particular interest, it was demonstrated that the self-assembled molecular aggregates formed by RF-(DMHB)x-(DMAA)y-RF co-oligomers could interact strongly with 7,7,8,8-tetracyanoquinodimethane (TCNQ) as a guest molecule to form a host–guest intermolecular complex, though such a host–guest interaction was not observed in the corresponding non-fluorinated DMHB co-oligomer.

Synthesis and antibacterial activity of novel fluoroalkyl end-capped cooligomers containing dimethyl(octyl)ammonium segments

New fluoroalkyl end-capped cooligomers containing dimethyl(octyl)ammonium segments were prepared by the reactions of fluoroalkanoyl peroxides with 2-(acryloxyethyl)dimethyl(octyl)ammonium chloride (AEMOAC) and comonomers such as N, N-dimethylacrylamide, acrylic acid, and acryloylmorpholine (ACMO). These fluorinated AEMOAC cooligomers thus obtained were in general soluble not only in water but also in organic solvents such as methanol, ethanol, THF, chloroform, DMSO, and DMF. Especially, fluoroalkylated AEMOAC–ACMO cooligomers were readily soluble in these solvents, and were able to reduce the surface tension of water quite effectively with a clear breakpoint resembling a critical micelle concentration, the same as for low-molecular weight fluorinated surfactants. Furthermore, the modified poly(methyl methacrylate) (PMMA) surface treated with these fluorinated AEMOAC–ACMO cooligomers was shown to have a strong hydrophilicity with a good oil repellency. In particular interest, the modified PMMA surface with these cooligomers was clarified to exhibit a high antibacterial activity. Therefore, these new partially fluoroalkylated AEMOAC cooligomers are applicable to new functional materials possessing not only the surface antibacterial activity but also the surface active property imparted by fluorine.

Synthesis of fluoroalkyl end-capped co-oligomers containing 8-hydroxyquinolyl segments and application to oligomer-catalyzed solvolysis reactions

New fluoroalkyl end-capped co-oligomers containing 8-hydroxyquinolyl segments were prepared by the reactions of fluoroalkyl end-capped co-oligomers bearing isocyanato groups. The solvolysis of p-nitrophenyl propaonate (PNP) in the presence of these fluorinated co-oligomers and the corresponding  co-oligomers was investigated in 3:1 (v/v) aqueous methanol buffer solution (0.05 M phosphate, pH 9.2) at 30°C. A large rate enhancement was observed in the presence of the fluorinated co-oligomers for the solvolysis of PNP as compared with the corresponding non-fluorinated co-oligomers. Therefore, these fluoroalkyl end-capped co-oligomers are of particular interest as new fluorinated biomimetic systems for enzyme catalysts.