Hexafluoroisopropyl Acrylate Research Articles

Organocatalytic Strategy for a Formal 1,6-Conjugate Hydroxylation.

Thanks to the versatile vinylogous hexafluoro iso-propyl acrylate molecular platforms, a regio- and enantioselective sulfa-Michael reaction was achieved upon organocatalytic conditions, allowing the subsequent amidation, one-pot oxidation, and Mislow-Bravermann-Evans [2,3]-sigmatropic rearrangement along with a 1,3-chirality transfer, leading eventually to a formal asymmetric 1,6-hydroxylation sequence.

Additive-Assisted Hydrophobic Li+ -Solvated Structure for Stabilizing Dual Electrode Electrolyte Interphases through Suppressing LiPF6 Hydrolysis.

Lithium-metal batteries have attracted much attention due to their high energy density. However, the hydrolysis of LiPF6 leads to uncontrollable Li dendrites growth and fast capacity fading. Herein, a hydrophobic Li+ -solvated structure is designed by inducing the hexafluoroisopropyl acrylate into the electrolyte system. Due to the alkene groups and non-polar perfluorocarbon (-CF2 CF2 CF3 ) chain, a hydrophobic surface around Li-ion solvated aggregates can be obtained to protect the LiPF6 against the attack from trace H2 O. Moreover, the additive could also help to form an organic solid electrolyte interphase with rich polar C-F bonds, which can capture Li ions to restrain the dendrite growth. Therefore, the Li||Li symmetric cells show a stable cycling performance up to 500 h at a current density of 1 mA cm-2 . The Li||LiNi0.6 Co0.2 Mn0.2 O2 cells show good cycling stability, exhibiting a specific capacity of 111 mAh g-1 at 1 C with a capacity retention of 74 % after 200 cycles.

Additive‐Assisted Hydrophobic Li+‐Solvated Structure for Stabilizing Dual Electrode Electrolyte Interphases through Suppressing LiPF6Hydrolysis

AbstractLithium‐metal batteries have attracted much attention due to their high energy density. However, the hydrolysis of LiPF6leads to uncontrollable Li dendrites growth and fast capacity fading. Herein, a hydrophobic Li+‐solvated structure is designed by inducing the hexafluoroisopropyl acrylate into the electrolyte system. Due to the alkene groups and non‐polar perfluorocarbon (−CF2CF2CF3) chain, a hydrophobic surface around Li‐ion solvated aggregates can be obtained to protect the LiPF6against the attack from trace H2O. Moreover, the additive could also help to form an organic solid electrolyte interphase with rich polar C−F bonds, which can capture Li ions to restrain the dendrite growth. Therefore, the Li||Li symmetric cells show a stable cycling performance up to 500 h at a current density of 1 mA cm−2. The Li||LiNi0.6Co0.2Mn0.2O2cells show good cycling stability, exhibiting a specific capacity of 111 mAh g−1at 1 C with a capacity retention of 74 % after 200 cycles.

Preparation of Functional Alternating Polymer Brushes and Their Orthogonal Surface Modification through Microcontact Printing.

This paper reports microcontact printing (μCP) to immobilize an alkoxyamine initiator (regulator) on glass and silicon substrates and subsequent surface-initiated alternating nitroxide-mediated copolymerization (siNMP) of hexafluoroisopropyl acrylate (HFIPA) and 7-octenylvinyl ether (OVE). The resulting patterned polymer brushes are analyzed by using atomic force microscopy (AFM). In addition, site-specific post-functionalization of the alternating polymer brushes by applying two orthogonal surface reactions is achieved with thiols and amines through μCP. The versatility of this post-polymerization modification approach is demonstrated by site-selective immobilization of small organic molecules, fluorophores, and ligands providing a binary bioactive surface. The successful side-by-side orthogonal immobilization is verified by using X-ray photoelectron spectroscopy (XPS) and fluorescence microscopy.

Alternating copolymerization by nitroxide-mediated polymerization and subsequent orthogonal functionalization.

A novel method for the preparation of functionalized alternating copolymers is presented. Nitroxide-mediated polymerization of hexafluoroisopropyl acrylate with 7-octenyl vinyl ether provides the corresponding alternating polymer, which can be chemically modified using two orthogonal polymer-analogous reactions. A thiol-ene click reaction followed by amidation provides dual-functionalized alternating copolymers. The potential of this method is illustrated by the preparation of a small library (15 examples) of functionalized alternating copolymers.

A rational approach to activated polyacrylates and polymethacrylates by using a combination of model reactions and SET-LRP of hexafluoroisopropyl acrylate and methacrylate

A new class of activated polyacrylates was elaborated by a combination of model reactions and SET-LRP of hexafluoroisopropyl acrylate and methacrylate.

A Bifunctional β‐Isocupreidine Derivative as Catalyst for the Enantioselective Morita–Baylis–Hillman Reaction and a Mechanistic Rationale for Enantioselectivity

AbstractStarting from β‐isocupreidine (β‐ICD), a series of difunctional catalysts were synthesized to ascertain their usefulness in the asymmetric Morita–Baylis–Hillman (MBH) reaction. The trichloroacetylcarbamate derivative was found to give the (R)‐MBH adducts in excellent optical purities (90–99 % ee) and moderate to good yields (43–83 %), in some cases, better than β‐ICD. A number of acrylates were also tested and 2,6‐dimethyl‐4‐nitrophenyl acrylate was identified as a suitable alternative to the popular hexafluoroisopropyl acrylate, with both the β‐ICD and trichloroacetylcarbamate derivatives. The mechanism of the rate‐ and selectivity‐determining step was ascertained by means of experimental observations and a computational investigation aimed at clarifying the transition state structures is reported. These studies have clarified the reasons for the effectiveness of these structurally related catalysts in the asymmetric MBH reaction between acrylates and aldehydes.

β‐Isocupreidine—Hexafluoroisopropyl Acrylate Method for Asymmetric Baylis—Hillman Reactions.

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β-Isocupreidine–hexafluoroisopropyl acrylate method for asymmetric Baylis–Hillman reactions

Key features of the β-isocupreidine (β-ICD)-catalyzed asymmetric Baylis–Hillman reaction of aldehydes with 1,1,1,3,3,3-hexafluoroisopropyl acrylate (HFIPA) are presented. In addition, an improved method using azeotropically dried β-ICD is described.

Copolymers from oligosiloxane methacrylates as a plasticizer-free membrane matrix for ion-selective sensors

Cross-linked copolymers have been prepared by free-radical photoinitiated polymerization of dimethacryloxypropyl oligodimethylsiloxane with monomethacryloxypropyl oligodimethylsiloxane and the polar comonomers cyanomethyl methacrylate, cyanoethyl methacrylate, trifluoroethyl methacrylate and hexafluoroisopropyl acrylate, respectively, for use as a plasticizer-free membrane matrix for ion-selective sensors. The polymerization course in dependence on the composition of the monomer mixture and on the presence of ionophore and ion conducting salt as well as chloroform as solvating agent was studied by means of differential scanning calorimetry. The resulting copolymer membranes were characterized concerning the content of residual C C double bonds and sol as well as their thermo-mechanical and electroanalytical properties. The thermal and mechanical properties of these copolymer membranes exhibiting a heterogeneous network structure are adjustable in a wide range by variation of the ratio of the monomers used. In comparison with the most widely used poly(vinyl chloride) based membranes containing a plasticizer, the K + and Ca 2+ selective sensor membranes based on the new copolymers exhibit analogous or even better electro-analytical properties and above all, a distinctly longer lifetime.

Influence of partial matrix fluorination on morphology and performance of HPDLC transmission gratings

The morphology and the electro-optical performance characteristics were investigated in holographic polymer-dispersed liquid crystal (HPDLC) transmission gratings with partially fluorinated polymer matrices. HPDLC transmission gratings were prepared using standard UV curable monomer mixtures along with mono-functional fluorinated acrylate monomers and a nematic liquid crystal, TL203. Partial fluorination of the host polymer matrices by incorporating hexafluoroisopropyl acrylate (HFIPA) or trifluoroethyl acrylate (TFEA) in the standard formulation has been found to influence the morphological and the electro-optical properties of the resulting HPDLC transmission gratings. Significant decrease in switching voltages and higher relaxation times were observed in fluorinated HPDLCs. Conversely, an addition of methyl acrylate (MA), a non-fluorinated monomer with a similar structure in the standard formulation, resulted in an increase in the switching voltage and produced no significant change in the relaxation time in the HPDLC gratings. Presence of fluorine atoms at the polymer-liquid crystal (LC) interface not only decreased the surface anchoring strength but also influenced the orientation of LC droplet directors.

Tailoring Transparency of Imageable Fluoropolymers at 157 nm by Incorporation of Hexafluoroisopropyl Alcohol to Photoresist Backbones

Hexafluoroisopropyl alcohol-functionalized acrylic and styrenic monomers, such as 2-[4-(2-hydroxyhexafluoro isopropyl)cyclohexane]hexafluoroisopropyl acrylate (2), 2-[4-(2,2,2-trifluoro-1-methoxy-methoxy-1-trifluoromethylethyl)cyclohexane]hexafluoroisopropyl acrylate (3), and 2-[4-(2,2,2-trifluoro-1-ethoxymethoxy-1-trifluoromethylethyl)]styrene (4), were synthesized, and their (co)polymers were studied as photoresist platforms for 157 nm lithography. It was found that these (co)polymers are unusually transparent at 157 nm, and absorbances of poly(2) and poly(2-co-4) were determined to be 1.93 and 2.38 μm-1, respectively. Results indicated that both electron-withdrawing effects and bulkiness of CF3 groups play important roles in tailoring the absorbance of chromophores. Lithographic studies were carried out with poly(2)-based resists using 157 and 248 nm steppers, and it was demonstrated that, after selective modification, it is possible to use conventional resist backbones, such as acrylic or styrenic pol...

New Strategies for High Resolution Photoresists.

2-[4-(2-hydroxyhexafluoro isopropyl)cyclohexane]hexafluoroisopropyl acrylate (AF) was prepared as a key monomer for 157nm photoresist platforms. In order to balance transparency with other desirable traits such as etch resistance, new strategies for high resolution photoresists were developed and are discussed. (1) The α-trifluoromethyl group was introduced on the polymer backbone and the resulting polymer showed unexpectedly high transparency at 157nm (A=1.6μm-1) despite a carbonyl group in all the monomers. A new 157nm transparent monomer that will provide a solubility switch necessary for base solubility was designed. (2) p-t-Butoxy-tetrafluorostyrene was copolymerized with AF. The high acidity of p-hydroxy-tetrafluorostyrene allowed us to increase the content of the monomer in the system to produce a novel polymer that is highly transparent at 157nm (A=2.1μm-1). The polymer showed good 248nm lithographic performances. (3) Introduction of fluorine on the polymer backbone was carried out. Due to a lower electron density of the vinyl groups with fluorine, these vinyl monomers can be copolymerized with electron-rich vinyl monomers such as norbornene using radical initiators. 2-Methyl-2-adamantyl trifluoroacrylate (MAdTFA) was synthesized. An alternating copolymer with a norbornene derivative was found to have high Tg and gave clear images using 248nm imaging.

Rejuvenation of 248nm Resist Backbones for 157nm Lithography.

Fluorocarbinol-based acrylic and styrenic monomers, such as 2-[4-(2-hydroxyhexafluoro isopropyl)cyclohexane]hexafluoroisopropyl acrylate (1) 2-[4-(2, 2, 2-trifluoro-1-methoxy-methoxy-1-trifluoromethylethyl)cyclohexane]hexafluoroisopropyl acrylate (2), and 2-[4-(2, 2, 2-trifluoro-1-ethoxymethoxy-1-trifluoromethylethyl)]styrene (3), were synthesized and their (co)polymers were studied as photoresist platforms for 157nm lithography. It was found that these (co)polymers are unusually transparent at 157nm, and absorbances of poly(1) and poly(1-co-3) were determined to be 1.93 and 2.38μm-1, respectively. It was also found that further improvement in transparency is possible by adding transparency enhancers to the resist platform. Lithographic studies were carried out with poly(1)- and poly(3)-based resists using 157 and 248nm steppers, and it was proven that, after selective modification, it is possible to use conventional resist backbones, such as acrylic or styrenic, in the design of single-layer resists for 157nm lithography.

The effect of fluorine-substituted acrylate monomers on the electro-optical and morphological properties of polymer dispersed liquid crystals

The effects of fluorinated acrylate monomers on the electro-optical and morphological properties of polymer dispersed liquid crystal (PDLC) films are reported. The partial fluorination of host polymer matrices resulted in improved optical properties and better defined morphologies. An enhancement in contrast ratio was observed for fluorinated systems containing trifluoroethyl acrylate (TFEA) and hexafluoroisopropyl acrylate (HFIPA). Conversely, the incorporation of methyl acrylate (MA), a chemically similar non-fluorinated acrylate, resulted in no appreciable change in contrast ratio and an increase in relaxation time. Scanning electron microscopy morphological studies were conducted to understand further the influence of fluorinated monomers in PDLC systems.

含ふっ素ビニルモノマーのアニオン重合 ＩＩＩ アクリル酸ヘキサフルオロイソプロピル，メタクリル酸ヘキサフルオロイソプロピルのアニオン重合反応性

含ふっ素ビニルモノマーのアニオン重合 ＩＩＩ アクリル酸ヘキサフルオロイソプロピル，メタクリル酸ヘキサフルオロイソプロピルのアニオン重合反応性

Textile properties of cotton cellulose graft copolymers and terpolymers

AbstractCotton cellulose graft copolymers and terpolymers were prepared by radiation initiated processes. Monomers copolymerized with irradiated cellulose from solutions of methanol‐water were: methacrylic acid (MAA), methacrylonitrile (MAN), and hexafluoroisopropyl acrylate (6FIPA). Cotton cellulose, immersed in solutions of N‐vinyl carbazole (NVC) in 1,2‐dichloroethane, was irradiated to form a copolymer. Terpolymers prepared were; cellulose‐poly(MAA)‐poly(MAN), cellulose‐poly(MAA)‐poly(6FIPA), and cellulose‐poly(MAN)‐poly(6FIPA). Textile properties of the cotton fabric copolymers and terpolymers determined included: flex and flat abrasion resistance, breaking strength, and water repellency. The properties of the cellulose copolymers and terpolymers were related to chemical structures of the monomers used and the glass transition temperatures of their homopolymers.