Pentafluorophenyl Methacrylate Research Articles

Improvement of the physical properties of poly(methyl methacrylate) by copolymerization with pentafluorophenyl methacrylate

AbstractCopolymers of methyl methacrylate (MMA) and pentafluorophenyl methacrylate (PFPMA) of various compositions were prepared with a free‐radical initiator. When PFPMA was included in the copolymers, the glass‐transition temperatures increased and showed a positive deviation from the Gordon–Taylor equation. A copolymer containing 20 wt % PFPMA exhibited almost zero orientational birefringence, and the photoelastic birefringence became zero when the copolymer contained 13 wt % PFPMA. When 20 wt % PFPMA was incorporated into the MMA copolymer, its water absorption decreased to 0.4 wt % versus 1.8 wt % for poly(methyl methacrylate) (PMMA) under the same condition. The flammability of the PFPMA/MMA copolymer was reduced in comparison with that of the MMA homopolymer. The refractive indices of the PFPMA/MMA copolymers were very close to that of PMMA, and the transmittances of the copolymers were slightly better than that of PMMA. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007

Initiated Chemical Vapor Deposition of a Surface‐Modifiable Copolymer for Covalent Attachment and Patterning of Nucleophilic Ligands

AbstractMany novel areas of biological investigation require the patterned immobilization of bioactive ligands. In this work, easily modified thin films of poly[(pentafluorophenyl methacrylate) (PFM)‐co‐(ethylene glycol diacrylate) (EGDA)]are synthesized by initiated chemical vapor deposition (iCVD). PFM possesses a pentafluorophenyl ester side chain moiety, which is an excellent leaving group for the attachment of nucleophilic ligands by a single reaction step, while the EGDA functions as a crosslinking agent. Patterned surface modification through microcontact printing of fluorescently labeled amines that remain immobilized after repeated solvent rinses is demonstrated. Bulk modification of the copolymer with aminoethoxyethanol, which results in a ≈20° reduction in the observed contact angle with water, is also shown.magnified image

Property modification of poly(methyl methacrylate) through copolymerization with fluorinated aryl methacrylate monomers

AbstractCopolymers of methyl methacrylate (MMA) with 2,3,5,6‐tetrafluorophenyl methacrylate (TFPMA), pentafluorophenyl methacrylate (PFPMA), and 4‐trifluoromethyl‐2,3,5,6‐tetrafluorophenyl methacrylate (TFMPMA) were investigated. All the three systems showed a random copolymerization character. The composition, glass transition temperature (Tg), and refractive index of the copolymers obtained were studied. Tgs of TFPMA/MMA and PFPMA/MMA copolymers were found to deviate positively from the Gordon–Taylor equation. However, Tgs of TFMPMA/MMA copolymers were well fit with the Gordon–Taylor equation. These results indicated the existence of interaction between MMA and either TFPMA or PFPMA units in copolymers. This interaction resulted in the enhancement of the Tg of MMA polymers through the copolymerization with TFPMA and PFPMA. The refractive index and the light transmittance of copolymers were close to those of PMMA. Copyright © 2007 John Wiley & Sons, Ltd.

Surface Reactivity of Pulsed-Plasma Polymerized Pentafluorophenyl Methacrylate (PFM) toward Amines and Proteins in Solution

Pulsed-plasma polymerization has been used to deposit ultrathin layers of pentafluorophenyl methacrylate by using low duty cycles and low power input. The monomer structure can be retained such that the chemical reactivity of the active ester group could be studied using the reaction with a simple amine. The film properties in aqueous phosphate buffer have been investigated using Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and real time surface plasmon resonance spectroscopy. The films react readily with diaminohexane and immunoglobulin (IgG), yet the reactivity shows a dependence on the extent of hydrolysis of the ester group.

Fabrication of Bioactive Surfaces by Plasma Polymerization Techniques Using a Novel Acrylate‐Derived Monomer

AbstractSummary: Material coating of surfaces can enhance receptivity for cells and biological compounds. Existing plasma coating technologies and possible materials are limited. A new polymer from pentafluorophenyl methacrylate (PFM) monomer was synthesized, and was plasma enhanced chemical vapor deposited on silicon wafers. The optimal plasma polymerization parameters for the PFM monomer and its copolymerization with the cross‐linking agents 1,7‐octadiene and 1,4‐butanediol divinyl ether co‐monomers were established. All the resulting polymer coatings leave the labile pentafluorophenyl group on the surface, enabling a rapid reaction with an amino‐terminated biotin ligand and allowing layer‐by‐layer self‐assembly of biotin‐streptavidin. In addition, the deposited polymer layers showed an extremely flat morphology with a nanoscale average roughness. This approach provides an easy means of obtaining functionalized surfaces which can enhance and control the biocompatibility of bulk materials. Merging the versatility of plasma polymerization processes, via simple monomers and reaction conditions, with biological platforms that enable target of cell adhesion brings us closer to the ultimate goal of controlling cell function through structured surfaces for their application in tissue engineering.Schematic representation of a functionalized surface obtained by plasma polymerization of the PFM monomer, showing labile pentafluorophenyl groups on the surface.magnified imageSchematic representation of a functionalized surface obtained by plasma polymerization of the PFM monomer, showing labile pentafluorophenyl groups on the surface.

RAFT Polymerization of Pentafluorophenyl Methacrylate: Preparation of Reactive Linear Diblock Copolymers

AbstractSummary: Reversible addition fragmentation chain transfer (RAFT) polymerization of pentafluorophenyl methacrylate (PFMA) was carried out in the presence of cumyldithiobenzoate and 4‐cyano‐4‐((thiobenzoyl)sulfanyl)pentanoic acid, respectively. These chain transfer agents with 2,2′‐azoisobutyronitrile (AIBN) as initiator yielded the active ester polymer poly(PFMA) with $\overline M _{\rm n}$ up to 17 000 g · mol−1 and low polydispersity index ($\overline M _{\rm w} /\overline M _{\rm n}$ < 1.2). Kinetic analysis using 19F NMR spectroscopy and gel permeation chromatography (GPC) measurements showed controlled polymerization behavior for both chain transfer agents. Successful preparation of linear diblock copolymers consisting of an active ester block and methyl methacrylate, N‐acryloylmorpholine, or N,N‐diethylacrylamide, respectively, could be demonstrated. These polymers could easily react with amines in a polymer analogous reaction to form multifunctional polymers. magnified image

Comparative evaluation of poly(pentafluoroaryl methacrylate)s and their non-fluorinated analogues as positive-working electron-beam resists

In order to rationalise the effects of fluorination on the performance of positive-working electron-beam resists based on methacrylate polymers, poly(pentafluorophenyl methacrylate) and poly(pentafluorobenzyl methacrylate) and their non-fluorinated analogues have been synthesized, and their electron-beam sensitivities and oxygen plasma etch rates determined for comparison with the corresponding parameters for alkyl methacrylate and fluoroalkyl methacrylate polymers reported in the literature. The fluoroaryl polymers were found to have enhanced dry-etch resistances, and in the case of poly(pentafluorophenyl methacrylate), to display a higher lithographic sensitivity than its parent non-fluorinated polymer. The plasma resistances and the lithographic sensitivities of thee materials are considered, respectively, in terms of the potential for nucleophilic degradation of the ester side-groups, and of the thermochemistry of the available pathways for radiation-induced decomposition.

Etude par DSC de la polymerisation en masse des methacrylates de methyle et de pentafluorophenyle

The bulk polymerizations of methyl methacrylate and pentafluorophenyl methacrylate (MAPF) have been studied by different scanning calorimetry, using 2,2-azobis(2-methylpropionitrile) (AIBN) and bis(4-tertiobutylcyclohexyl) peroxydicarbonate as initiators. Overall rates of polymerization are compared for the two monomers with AIBN, and for MAPF with both initiators. The heats of polymerization in the 50–90 range are found to be close to 50 kJ · mol −1.