Preparation and characterization of molecular photoresists: Crosslinkable positive and water developable negative tones

The development of a water‐developable negative photoresist from β‐CD using an acid‐catalyzed chemical amplification method is investigated here. Tertiary butoxyl protected β‐cyclodextrin (t‐BOC‐CD) is also synthesized and used to prepare a positive photoresist. Glutaraldehyde is added as a crosslinking agent for both positive and negative photoresists. Deprotection of t‐BOC‐CD is accelerated by a photo‐induced acid. In the presence of glutaraldehyde and acid, both the deprotected t‐BOC‐CD and β‐cyclodextrin are crosslinked. The introduction of a t‐butoxyl group into the β‐CD molecule and the addition of glutaraldehyde into the β‐CD molecules are both found to decrease the crystallinity of the molecules, improving the resist film properties. The etching resistance of both positive and negative photoresist films is improved by the crosslinking method. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Water‐dispersible porous polyisoprene‐block‐poly(acrylic acid) microspheres

Two polyisoprene‐block‐poly(tert‐butyl acrylate) (PI‐b‐PtBA) samples and a poly(tert‐butyl acrylate) (PtBA) homopolymer (hPtBA) were prepared by anionic polymerization and characterized by light scattering, size exclusion chromatography, and NMR. The tert‐butyl groups were removed from one of the diblocks to yield amphiphilic polyisoprene‐block‐poly(acrylic acid) (PI‐b‐PAA). PI‐b‐PAA was then used as the surfactant to disperse dichloromethane containing PI‐b‐PtBA and hPtBA at different weight ratios as oil droplets in water. Solid microspheres containing segregated polyisoprene (PI) and PtBA/hPtBA domains were obtained after dichloromethane evaporation. Permanent microspheres were obtained after PI domain crosslinking with sulfur monochloride. Porous microspheres were produced after the hydrolysis of PtBA and the extraction of the homopoly(acrylic acid) chains. The shape and connectivity of the poly(acrylic acid)‐lined pores were tuned by changes in the PtBA/hPtBA content in the precursor microspheres. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2785–2793, 2003     

Study of water sorption in rubbers by acoustic microscopy

Acoustic microscopy has been used to examine changes during water swelling at the surface of a rubber previously treated with an acrylic monomer. Surface modification was carried out with acrylic acid either in aqueous solution or in the vapour phase, and a photografting reaction was achieved with an aqueous solution of acrylic acid in the presence of a photo‐initiator. Water sorption induces modifications of the mechanical properties, transforming a rigid polymer into a soft material. Therefore, the acoustic impedance of the material decreases during the swelling process and the evolution of acoustic reflection coefficient is followed. The potential of ultrasonic measurements as an in situ and non‐destructive dynamic analysis technique is demonstrated. Mapping of grafted and ungrafted areas on a rubber surface is obtained with acoustic microscopy. © 2000 Society of Chemical Industry     

Design and preparation of poly(aryl ether ketone)/phosphotungstic acid hybrid films with low dielectric constant

A material with low dielectric constant was produced using nanoparticle phosphotungstic acid (PWA) modified by the silane coupling agent γ‐aminopropyltriethoxysilane (KH‐550) dispersed in a poly(aryl ether ketone) containing (3‐trifluoromethyl) phenyl side groups (FPEEK) matrix synthesized with (3‐trifluoromethyl) phenyl hydroquinone (3FHQ) and 4,4′‐difluorobenzophenone. The material was fabricated using solution‐blending. Moreover, the dielectric, thermal, and mechanical properties of this material were characterized using a precision impedance analyzer, thermal gravimetric analyzer, and universal tester, respectively. The results indicate that modified PWA (m‐PWA)/FPEEK composites show obvious improvement in the dielectric properties compared to unmodified PWA (p‐PWA)/FPEEK composites. This should be attributed to the good dispersion and compatibility of m‐PWA in FPEEK, as proven by scanning electron microscope and wide‐angle X‐ray diffraction. Besides, m‐PWA/FPEEK composites also exhibited the relatively good thermal and mechanical properties. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Lewis acid–base property of P(VDF‐co‐HFP) measured by inverse gas chromatography

Poly (vinylidene fluoride‐co‐hexafluoropropylene) P(VDF‐co‐HFP) is an excellent material for polymer electrolytes of lithium ion battery. To enhance the lithium ion transference number, some metal oxides were often embedded into P(VDF‐co‐HFP). The promising mechanism for the increase in lithium ionic conductivity was Lewis acid‐base theory. In this experiment, the Lewis acid–base properties of P(VDF‐co‐HFP) were measured by inverse gas chromatography (IGC). The Lewis acid constant K_a of P(VDF‐co‐HFP) is 0.254, and the base constant K_b is 1.199. Compared with other polymers characterized by IGC, P(VDF‐co‐HFP) is the strongest Lewis basic polymers. Except aluminum ion, lithium ion is the strongest Lewis acidic ion according to their η value of Lewis acids. Therefore, a strong Lewis acid–base interaction will exist between lithium ion and P(VDF‐co‐HFP). This will restrict the transference of lithium ion in P(VDF‐co‐HFP). To enhance the lithium ion transference by blending other metal ions into P(VDF‐co‐HFP), it is suggested that the preferential ions should be Al³⁺, Mg²⁺, Na⁺, and Ca²⁺ because these metal ions have relative large η values. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Lewis Acids as Highly Efficient Catalysts for the Decarboxylative Esterification of Carboxylic Acids with Dialkyl Dicarbonates

Mild Lewis acids such as Mg(ClO₄)₂ show a new level of catalytic activity for the decarboxylative esterification of carboxylic acids with commercially available dialkyl dicarbonates. In the presence of as little as one mol % Mg(ClO₄)₂ catalyst, carboxylic acids can thus easily and near quantitatively be protected at room temperature, e.g., as methyl, benzyl, or t‐butyl esters. Only volatile by‐products are released so that the purification of the products is particularly easy. Many sensitive functionalities are tolerated, including even phenol esters, or free hydroxy and BOC groups.     

Flexible /PET/batio3/ layer–layer composite film with enhanced dielectric properties fabricated by highly loaded /batio3/ coating with acrylic resin as binder

Flexible layer–layer poly(ethylene phthalate) (PET)/BaTiO₃ composite films with enhanced dielectric permittivity were fabricated by spin coating method, consisting of PET substrate film layer and modified BaTiO₃/acrylic resin hybrid coating layer. The thickness of coating layer was less than 3 μm (about 2% of PET film thickness), and therefore, the PET/barium titanate (BT) composite films remained flexible even at high volume fraction of BaTiO₃ fillers. The volume contents of BaTiO₃ were varied from 0 to 80%, and the solid contents of BaTiO₃/acrylic resin were in the range of 51.8–72.9%. Scanning electron microscopy showed strong interaction of finely dispersed BaTiO₃ particles with acrylic resin. Morphological profile also displayed uniform coating layer of modified BaTiO₃/acrylic resin and its strong adhesion with PET film. The dielectric constant of the PET/BaTiO₃ composite films increased by about 26% at 60 vol % BaTiO₃ loading when compared with the pristine PET film, whereas the dielectric loss decreased slightly. In addition, PET‐grafted poly(hydroxylethyl methacrylate) brushes were used as substrate to introduce covalent bonding with the coating layer. Further enhancement of dielectric constant and reduction of dielectric loss were realized when compared with the composite films with bare PET substrate. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42508.     

Copper phthalocyanine oligomer grafted acrylic elastomer nanocomposites with high dielectric constants

For many applications of dielectric elastomer (DE) actuators, it is desirable to endow the DE with a high dielectric constant (ε), high breakdown field, and good flexibility. In this study, a high‐ε nanocomposite acrylic elastomer (ACM)‐g‐copper phthalocyanine (CuPc) was fabricated, in which the CuPc oligomer was grafted onto the backbone of ACM. This grafted composite exhibited several benefits over the physically blended one. Transmission electron microscopy micrographs indicated that the size of the grafted CuPc was in the range 15–30 nm, which was more than 25 times smaller than that of the simply blended one. At room temperature, ε of ACM‐g‐CuPc (with 15 wt % CuPc) reached 303 at 100 Hz. The remarkable enhancement in the dielectric response could be attributed to the greatly strengthened exchange coupling effect and the Maxwell–Wagner–Sillars polarization mechanism. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 39975.     

Exploring the Combined Effect of Electron Beam and Conductive Carbon Black on the Mechanical,Dynamic Mechanical,Thermal, and Electrical Properties of Ethylene Acrylic Elastomer

The electron beam-crosslinked and conductive carbon black-reinforced ethylene acrylic elastomer composites have been developed for various applications. The inter-connectivity of conductive carbon black agglomerates are clearly observed from the high-resolution transmission electron photo micrographs. The tensile strength of the composites has remarkably increased with increasing conductive carbon black loading up to 350 radiation dose. The dielectric permittivity (?′) and AC conductivity (σ_ac) increase with an increase in conductive carbon black loading. The electron magnetic shielding interference of the developed composites has been measured using X-band frequency range, and the electron magnetic shielding interference increases with an increase in conductive carbon black loading.     

Effect of temperature,solvent, Lewis acid and additives on the polymerization of tert‐butyl vinyl ether using Lewis acid‐induced N‐methyleneamines as cationic initiators

N‐Methyleneamines, formed by treating 1,3,5‐trimethylhexahydro‐1,3,5‐triazines with Lewis acids, have been shown to be capable initiators in the cationic polymerization of tert‐butyl vinyl ether, yielding polymers with amine functionality at the chain ends. Previous work was limited to titanium(IV) chloride (TiCl₄) as the Lewis acid in dichloromethane solvent at 0 °C (with resulting polymers possessing relatively broad polydispersity index (PDI) values near 2), while this contribution details the effect of reaction parameters on the polymeric products; specifically, the role of temperature, solvent, Lewis acid and additives. Ultimately, performing the polymerization at ?78 °C in dichloromethane with TiCl₄ as the Lewis acid and tetra‐n‐butylammonium chloride (nBu₄NCl) as the additive afforded the best control over the system, with polymers formed possessing low PDI values (<1.2). Dramatic changes in number‐average molecular weight and PDI were observed in polymers formed by initiating systems of Lewis acid‐induced N‐methyleneamines, with temperature, solvent, Lewis acid and additives all playing a role. By varying single parameters, optimization of the system was achieved. Copyright © 2009 Society of Chemical Industry     

Approach to the fabrication of acrylic elastomer nanocomposites with high dielectric constants

Dielectric elastomers (DEs) are a type of electroactive polymer that can deform in an electric field. The possession of a high dielectric constant is critical for DEs if they are to be suitable materials for the application of actuators. A novel elastomeric nanocomposite (ACE‐g‐CuPc) was fabricated by copper phthalocyanine oligomer (CuPc) grafting directly onto an acrylic elastomer (ACE) backbone. Compared with other synthetic methods, esterification has several advantages; these include fewer impurities and a simpler synthetic route. Transmission electron microscopy showed that the size of the CuPc particles of the ACE‐g‐CuPc was in the range 15–30 nm; this range was significantly smaller than that of ACE/CuPc (500 nm). The results of thermogravimetric analysis show that the thermal stability of the grafting composite was higher than that of the blending composite. At 100 Hz, the dielectric constant of the grafting composite (with 11 wt % CuPc) reached 173 at room temperature. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43904.     

Novel latent initiator for cationic polymerization of epoxides

A novel latent initiator for cationic polymerization of epoxides, a composite catalyst containing aluminum complexes and phenol derivatives protected with tert‐butoxycarbonyl groups (tBOC), is reported. At a certain temperature, protected phenols generate the parent phenols which are coinitiators with aluminum complexes. The deprotection temperature of the tBOC group depends on the structure of the phenol moieties. Bis(p‐t‐butoxycarbonyloxyphenyl)sulfone (Ph1) generates (p‐dihydroxyphenyl)sulfone (PhH1) at around 150°C, the temperature at which the curing of epoxides is conventionally carried out. The thermally generated PhH1 and aluminum complexes initiate the curing of epoxides. Epoxy resin compositions containing these composite catalysts have a long shelf life at room temperature and are cured at around 150°C, showing that the composite catalyst has excellent latent properties. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 181–187, 2001     

Supramolecular composites of photo‐cured acrylated castor oil and fibers formed by the self‐assembly of low molecular weight organic gelators

A mixture of acrylated castor oil (ACO) with N‐carbobenzyloxy‐L ‐isoleucylaminooctadecane (CIA) or (R)‐12‐hydroxystrearic acid (HSA) containing photo‐initiators was heated to 130°C and gradually cooled to room temperature to give bio‐based gelatinous material. The photo‐curing of the gel generated a crosslinked ACO composite containing CIA or HSA. The optical micrographic and differential scanning calorimetry analyses revealed that a supramolecular fibrous network is formed for photo‐cured ACO (cACO)/CIA and that spherulitic crystals are formed for cACO/HSA. The tan δ peak temperatures measured by dynamic mechanical analysis for cACO/CIA and cACO/HSA composites were higher than that of cACO. The flexural strength and modulus of cACO/CIA composites increased with an increase of CIA content, and those values were higher than those of cACO/HSA composites. POLYM. COMPOS., 33:2001–2008, 2012. © 2012 Society of Plastics Engineers     

Enhanced properties of phthalonitrile‐terminated polyarylene ether nitriles embedded with hybrid MWCNT–boehmite nanocomposites

The main motivation of the present work was to fabricate novel multifunctional polymer‐based nanocomposites. The nanocomposites embedded with multi‐walled carbon nanotube‐boehmite (MWCNT‐boehmite) were prepared via hot pressure casting technique. The MWCNT coated with boehmite were synthesized by hydrothermal synthesis. Subsequently, as‐prepared MWCNT‐boehmite was added into the phthalonitrile‐terminated polyarylene ether nitriles (PEN‐t‐CN) matrix in order to benefit from the synergetic effect of MWCNT and boehmite. Scanning electron microscopy (SEM), transmission electron microscopy (TEM) X‐ray diffraction (XRD), and Fourier transform infrared (FTIR) were employed to confirm the existence of MWCNT‐boehmite in our article. Furthermore, the structures, fracture morphologies, thermal, mechanical and dielectric properties of the nanocomposites were investigated, respectively. SEM images indicated that the MWCNT‐boehmite was homogeneously dispersed in the polymer, which acted as an essential factor to ensure good physical properties. The TGA analysis showed that the incorporation of MWCNT‐boehmite enhanced the thermal stability of the nanocomposites with initial degradation temperature (T_id) increasing from 458 to 492°C, while that of the pure PEN‐t‐CN was 439°C. The mechanical testing proved that significant enhancement of mechanical properties has been achieved. The tensile strength of PEN‐t‐CN/MWCNT‐boehmite composites with 3 wt% MWCNT‐boehmite reached the maximum (78.33 MPa), with a 41.7 % increase compared to the pure polymer. More importantly, the unique dielectric properties were systematically discussed and the results demonstrated that dielectric properties exhibited little dependency on frequency. For the incorporation of hybrid filler, the positive impact of MWCNT‐boehmite hybrid material resulted in polymer‐based nanocomposites with enhanced physical properties. POLYM. COMPOS., 36:2193–2202, 2015. © 2014 Society of Plastics Engineers     

Effect of nanosilica on the thermal,mechanical, and dielectric properties of polyarylene ether nitriles terminated with phthalonitrile

Nanosilica/polyarylene ether nitriles terminated with phthalonitrile (SiO₂/PEN‐t‐Ph) composites were prepared by hot‐press approach. To ensure the nano‐SiO₂ can disperse uniformly, the solution casting method combined with ultrasonic dispersion technology had been taken previously. The mass fraction of nano‐SiO₂ particles was varied to investigate their effect on the thermal, mechanical, and dielectric properties of the nanocomposites. From scanning electron microscope images, it was found that the nanoSiO₂ particles were dispersed uniformly in the PEN‐t‐Ph matrix when the addition of nano‐SiO₂ was less than 16.0 wt%. However, when the mass fraction of nano‐SiO₂ increased to 20.0 wt%, the nano‐SiO₂ particles tend to self‐aggregate and form microns sized particles. Thermal studies revealed that nano‐SiO₂ particles did not weaken the thermal stabilities of the PEN‐t‐Ph matrix. Mechanical investigation manifested that the SiO₂/PEN‐t‐Ph nanocomposites with 12.0 wt% nano‐SiO₂ loading showed the best mechanical performance with tensile strength of 108.2 MPa and tensile modulus of 2107.5 Mpa, increasing by 14% and 19%, respectively as compared with the pure PEN‐t‐Ph film. Dielectric measurement showed that the dielectric constant increased from 3.70 to 4.15 when the nano‐SiO₂ particles varied from 0.0 to 20.0 wt% at 1 kHz. Therefore, such composite was a good candidate for high performance materials at elevated temperature environment. POLYM. COMPOS., 35:344–350, 2014. © 2013 Society of Plastics Engineers     

Poly(acrylic acid–sodium styrene sulfonate) organogels: Preparation,characterization, and alcohol superabsorbency

Polymeric organogels based on acrylic acid and sodium styrene sulfonate (SSS) were synthesized and characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, dynamic mechanical thermal analysis (DMTA), and rheometrical analyses. The organogels exhibited medium alcohol absorbency because of counterion binding that formed in solvents with low dielectric constants. After acid treatment, the possibility of counterion binding was decreased, and the organogels achieved superabsorbency in alcohols, for example, about 80 and 50 g/g in methanol and ethanol, respectively. The superabsorbency was also measured in higher alcohols (i.e., n‐propanol and isopropyl alcohol) and polyols (i.e., ethylene glycol, propylene glycol, 1,3‐propanediol, and glycerol). The dielectric constant, viscosity, and structural features of the alcohols were investigated as important parameters determining the alcohol superabsorbency. DMTA of dried samples showed two glass‐transition temperatures (T_g's), that is, the matrix T_g and the complex T_g, which increased with increasing SSS content. The tan δ peak intensity increased after the acid treatment. With increasing SSS, the storage modulus of the dried gel increased; whereas that of the rheometrically measured hydrated gel decreased. Tan δ decreased with increasing SSS because of enhanced counterion binding. These alcohol‐specific superabsorbing organogels are suggested as excellent candidates for the manufacture of products with high alcohol contents, such as hand sanitizers and fuel gels. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Fast‐responding bulk hydrogels with microstructure

A new method was used for the production of fast‐responding bulk hydrogels with microstructure (BHMs) with a high swelling ratio. These BHMs were synthesized first by the formation of poly(N‐isopropylacrylamide‐co‐acrylic acid) (NIPAAm–AA) microgel particles and then by the crosslinking of the particles with N‐isopropylacrylamide monomer. The polymer obtained had the desired microstructure but was bulk (monolithic), so it could be used in a variety of applications. The NIPAAm–AA microgel particles were characterized with transmission electron microscopy, and the formed BHMs were characterized with scanning electron microscopy. Compared with conventional bulk hydrogels, the BHMs had very high swelling ratios and much faster swelling rates attributable to the collaboration of the ionized microgel particles and bulk hydrogels. An increase in the microgel particles embedded in the BHMs provided faster hydrogel swelling. The number of ionic acrylic acid groups in the hydrogels affected their swelling behavior. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 169–178, 2002     

High‐k dielectric composites of poly(2‐cyanoethyl vinyl ether) and barium titanate for flexible electronics

High‐k dielectric composite material for electronic applications was obtained by mixing a polymer with high dielectric constant, poly(2‐cyanoethyl vinyl ether) (CEPVA), and highly crystalline barium titanate (BT). Barium titanate nanoparticles of a size in the range 40–90 nm were prepared by the solvothermal method. By optimizing the reaction conditions, the formation of carbonate impurities and the agglomeration of formed nanoparticles were significantly reduced compared to state‐of‐the‐art procedures. Dielectric spectroscopy was measured in the range of 0.01 Hz to 10 MHz and showed the dielectric constant to be ?′ ～ 35–40 with only 30 vol % content of BT in the composite. Extrapolating to 100% BT nanoparticle concentration and using the Lichtenecker model, the dielectric constant ?′ = 365 ± 27 at 10 kHz was obtained. The relaxation and electrical properties were investigated in depth, and a new relaxation phenomenon was revealed. CEPVA/BT composite is considered suitable for electronic applications, in which high ?′ together with a good mechanical flexibility are required, such as organic field effect transistors. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45236.     

Effect of ethylene ionomers on the properties of crosslinked polyethylene

Most premature failure of underground crosslinked polyethylene (XLPE) cables in service, a matter of great concern, is due to aging induced by water treeing. To improve the water‐tree resistance, sodium‐neutralized poly (ethylene‐co‐acrylic acid) (EAA–Na) ionomers were blended with XLPE; the EAA–Na ionomers were prepared through the neutralization of sodium hydroxide and poly(ethylene‐co‐acrylic acid). A series of XLPE/EAA–Na ionomer blends were investigated through the measurement of the water absorption ratio, water treeing, and mechanical and dielectric testing; the results strongly suggested that EAA–Na ionomers could improve the water‐tree resistance of XLPE, and the XLPE/EAA–Na blends retained excellent mechanical properties and dielectric properties. Moreover, through the characterization of XLPE/EAA–Na blends with Fourier transform infrared spectrometry, dynamic mechanical analysis, and scanning electron microscopy, it was found that the neutralization reaction could be achieved completely; the XLPE and EAA–Na ionomers were partially compatible, so the EAA–Na ionomers could be dispersed well in the matrix with the process examined in this study. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3483–3490, 2007     

Preparation of polystyrene/poly[2‐methoxy‐5‐(2′‐ethylhexyloxy)‐p‐phenylenevinylene] fluorescent microspheres by miniemulsion polymerization

Fluorescent microspheres have great potential for use as probes in biological diagnostics. In this context, poly[2‐methoxy‐5‐(2′‐ethylhexyloxy)‐p‐phenylenevinylene] (MEH‐PPV), a conjugated polymer which has high quantum yield, controllable emitting wavelength and facile processing in manufacture, was used as a fluorescent material for the preparation of polystyrene (PS)/MEH‐PPV fluorescent microspheres via miniemulsion polymerization. We demonstrate that the emitting wavelength of the PS/MEH‐PPV fluorescent microspheres can be regulated by changing the amount of azobisisobutyronitrile initiator in the polymerization process. Using acrylic acid comonomer, poly[styrene‐co‐(acrylic acid)]/MEH‐PPV fluorescent microspheres with functional carboxyl groups were also prepared. All the microspheres were characterized using transmission electron microscopy, scanning electron microscopy, fluorescence microscopy and fluorescence spectrophotometry. The functional carboxyl groups were characterized using Fourier transform infrared spectroscopy. This work provides a novel platform for the preparation of conjugated polymer fluorescent microspheres for biological applications. © 2012 Society of Chemical Industry