Ideality of pressure‐sensitive paint. II. Effect of annealing on the temperature dependence of the luminescence

This article reports the effect of annealing on a pressure‐sensitive paint (PSP) consisting of platinum tetra(pentafluorophenyl)porphine (PtTFPP) in a fluoroacrylic polymer called FIB (Puklin, E.; Carlson, W. B.; Gouin, S.; Costin, C.; Green, E.; Ponomarev, S.; Tanji, H.; Gouterman, M. J Appl Polym Sci 2000, 77, 2795). Samples annealed at 150°C, 75°C, annealed by a heat gun, and dried at room temperature are compared to nonannealed samples. Temperature dependences of luminescence intensity and lifetime are studied as a function and pressure and temperature and fit with Arrhenius and Stern–Volmer equations. We find that heating above T_g is more important than drying at room temperature in lowering the temperature dependence and obtaining ideal PSP, ideal meaning independent effect of pressure and temperature on luminescence properties of the paint. Ideality is achieved by lowering the activation energy for oxygen diffusion, presumably by relaxation of the polymer network. It is shown that ideal behavior occurs only over a limited temperature region. This range is more useful for PtTFPP in FIB than for ruthenium bathophenanthroline in polydimethylsiloxane (PDMS), another common PSP formulation. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2805–2814, 2000     

Effect of molecular weight of poly(N‐isopropyl acrylamide) temperature‐sensitive flocculants on dewatering

The influence of molecular weight (MW) and dose of Poly(N‐isopropyl acrylamide) (PNIPAM) (temperature‐sensitive flocculant) on sedimentation rate, sediment density, and supernatant clarity of silica suspensions was investigated. The addition of PNIPAM resulted in rapid sedimentation (T > critical solution temperature, CST) and low sediment moisture (T < CST). Higher MW polymers resulted in more effective flocculation and sediment consolidation. At 10 ppm, PNIPAM (3.6 million Da) produced 20 m/h settling rate and 48 vol % solids sediment density, whereas 0.23 million Da polymer produced 0.1 m/h settling rate. PNIPAM produces effective flocculation and consolidation by cycling the interparticle interactions between repulsion and attraction as temperature is cycled around the CST. The change in temperature produces a hydrophilic/hydrophobic transition of the polymer, influencing adsorption onto the surface and the inter‐particle forces. Conventional polyacrylamide flocculants (not influenced by temperature), cannot be used to produce both rapid sedimentation and dense sediments. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

UV curable pressure‐sensitive adhesives for fabricating semiconductors. I. Development of easily peelable dicing tapes

In order to develop easily peelable dicing tapes from diced wafers, UV curing of various pressure‐sensitive adhesives (PSAs) was studied. After UV irradiation, the adhesive strength of a PSA composition including a diacrylourethane oligomer (UDA) decreased drastically compared with other compositions. Because of network formation via UV irradiation, this composition had a greater volume contraction that might yield microvoids at the interface between the adhesive and the wafer, resulting in the loose adhesion. Its storage modulus increased up to about 1000 times that before UV curing, which was due to the crosslinking of the UDA component. It was suggested that the increased crosslinking density and the high internal coagulant energy of the UDA backbone structure caused a remarkable decrease of the adhesive strength. Furthermore, it was ascertained that the UV‐irradiated UDA adhesives left few residual deposits on the wafer released from the tape. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 436–441, 2003     

Amphiphilic linear–hyperbranched polymer poly(ethylene glycol)–branched polyethylenimine–poly(ϵ‐caprolactone): synthesis,self‐assembly and application as stabilizer of platinum nanoparticles

Amphiphilic linear–hyperbranched polymer poly(ethylene glycol)–branched polyethylenimine–poly(?‐caprolactone) (PEG‐PEI‐PCL) was synthesized by progressively conjugating PEG (one chain) and PCL (multi‐chains) to PEI (hyperbranched architecture) with a yield of 87%. PEG‐PEI‐PCL forms nano‐sized uniform spherical micelles by self‐assembly in water. The micelles had an average diameter of 56 nm determined using dynamic light scattering and 35 nm observed from transmission electron microscopy images. PEG‐PEI‐PCL was used as a stabilizer of platinum nanoparticles (PtNPs) for the first time. The particle diameter of PEG‐PEI‐PCL‐stabilized PtNPs was 7.8 ± 1.4 nm. Amphiphilic (hydrophilic–hydrophilic–hydrophobic) and hyperbranched (linear–hyperbranched–grafted) structures enabled PtNPs to effectively stabilize and disperse in liquid‐phase synthesis. The highly disperse PtNPs in PEG‐PEI‐PCL micelles improved the catalytic activity for the reduction of 4‐nitrophenol with a catalytic yield of near 100%. © 2016 Society of Chemical Industry     

Effect of the stress relaxation property of acrylic pressure‐sensitive adhesive on light‐leakage phenomenon of polarizer in liquid crystal display

The acrylic pressure‐sensitive adhesive systems with the different stress relaxation abilities are prepared by varying the curing agent from 0.3% to 3.0% and the effect of the stress relaxation ability of pressure‐sensitive adhesive system on the durability of LCD polarizer was investigated. The stress relaxation ability of the crosslinked pressure‐sensitive adhesive systems was measured by transient tensile test and dynamic viscoelastic test. And the durability was evaluated by the light‐leakage test of polarizer coated with the pressure‐sensitive adhesive after it was aged under the condition of 60°C and the relative humidity of 95% for 72 h. It was observed that the stress relaxation ability of pressure‐sensitive system is decreased with the crosslinking density, as intended. And the pressure‐sensitive adhesive with the lower stress relaxation ability exhibited the lower light‐leakage and consequently the higher durability than the other PSA systems. This observation is obviously contradictory to the previous design strategy of PSA system and the reason for this observation was discussed briefly. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Effect of polymer matrix on the performance of pressure‐sensitive paint comprising 5,10,15,20‐tetrakis(pentafluorophenyl)porphinato platinum(II) and poly(1,1,1,3,3,3‐hexafluoroisopropyl‐co‐tert‐butyl methacrylates)

Copolymers of 1,1,1,3,3,3‐hexafluoroisopropyl methacrylate (HFIPM) and tert‐butyl methacrylate (TBM) were prepared by conventional radical copolymerization as a novel binders for pressure‐sensitive paints (PSP). The monomer reactivity ratios r_HFIPM and r_TBM were determined as 0.45 and 0.67, respectively. The glass transition temperature of the copolymers increased from 77 to 126°C with increasing mole fraction of TBM units in the copolymer. The PSP were formed by combining the resulting copolymers and 5,10,15,20‐tetrakis(pentafluorophenyl)porphinato platinum(II). The pressure and temperature sensitivities of the PSPs were measured at air pressures ranging from 5 to 120 kPa and at temperatures ranging from 0 to 60°C. Modified Stern–Volmer plots indicated slight increases in the pressure sensitivity, but significant decrease in the temperature sensitivity as the mole fraction of HFIPM units increased in the copolymer. Applying a theoretical model to our calibration data, we inferred that luminescence quenching is primarily responsible for increasing the temperature sensitivity in the resulting copolymers. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43316.     

Flow‐injection polymer analysis of ethylene propylene diene monomer elastomers. I

A rapid, flow‐injection polymer analysis (FIPA) method for the solution characterization of EPDM elastomers, with a wide range of ethylene comonomer content, was developed. Solutions of the polymer were introduced into a flowing mobile phase which was monitored by an array of three detectors: a right‐angle laser light‐scattering unit, a differential refractive index detector, and a differential pressure viscometer. To adequately characterize a wide range of comonomer composition, it was found that a nominal temperature of 90°C and a solvent (e.g., 1,2,4‐trichlorobenzene) capable of high‐temperature sample dissolution was needed for the analysis. Polymer association or aggregation was observed in cyclohexane at lower analysis temperatures. With an analysis time of a few minutes, information on molecular weight, molecular size, and comonomer composition can be obtained directly. Information regarding polydispersity and properties such as melt viscosity may be obtained indirectly or through correlation to other, independent property measurements. The data were also compared to a high‐temperature GPC analysis method already in use. The combination of rapid analysis time and measurement of fundamental molecular properties suggests the usefulness of the instrumentation and method to plant process control. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2178–2189, 2002     

Thermodynamic study of a pressure‐temperature phase diagram for poly(N‐isopropylacrylamide) gels

The volume change, ΔV_h,_, accompanying the hydrophobic hydration associated with the volume phase transition in Poly(N‐isopropylacrylamide) gels was measured by a simple method. The hydration accompanies a negative ΔV_h′?2.5 cm³/mol. The P‐T phase diagram, the coexistence curve, for the gels was determined from the swelling ratio‐pressure curves up to 350 MPa for various constant temperatures. The contour of the coexistence curve is shaped like an ellipsoid on the P‐T plain, which is a feature peculiar to the reversible pressure‐temperature denaturation of a protein. The thermodynamic analysis of the Clausius–Clapeyron relation for the measured ΔV_h elucidates that the obtained coexistence curve represents the phase boundary between thermodynamic different phases like the two phases, native and denatured, of a protein and gives the transition enthalpy, ΔH, 5.2kJ/mol by estimate, which well coincides with the transition heat measured by a calorimetric method. Considering the volume‐dependent free energy, Δv_mi · P, for the mixing free energy of the gel, we can fit the calculated curve to the measured swelling ratio‐pressure curve of PNIPA gels. The value of Δv_mi changes the sign from negative to positive above around 100MPa. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 405–412, 2005     

Resultant synergism in the shear resistance of acrylic pressure‐sensitive adhesives prepared by emulsion polymerization of n‐butyl acrylate/2‐ethyl hexyl acrylate/acrylic acid

Acrylic emulsion pressure‐sensitive adhesives (PSAs) were synthesized by the copolymerization of n‐butyl acrylate with various levels of 2‐ethyl hexyl acrylate (2EHA) and a small constant amount of acrylic acid. The effect of varying the n‐butyl acrylate/2EHA monomer composition on the kinetic behavior of the polymerization and the characteristics of the copolymers prepared in a batch process were investigated. The results showed that increasing the amount of 2EHA in the monomer caused the polymerization rate and the glass‐transition temperature of the acrylic copolymers to decrease. Increasing the amount of 2EHA caused the gel content of the copolymers to decrease, reaching a minimum at 50 wt %; thereafter, the gel content increased at higher 2EHA levels. For the acrylic emulsion, the peel‐fracture energy of the PSAs decreased as the amount of 2EHA in the monomer was increased up to 50 wt %. At higher 2EHA levels, the peel‐fracture energy was relatively constant. Interestingly, a synergistic effect of increased shear resistance at 25 wt % 2EHA was observed without a significant trade‐off in terms of the peel and tack properties. This behavior was attributed to a good interconnection between the microgels and the free polymer chains inside the contacting particles in the adhesive film. Cooperation between various levels of 2EHA in the copolymer structure simultaneously changed the crosslink molecular weight (M_c) of the microgels and the entanglement molecular weight (M_e) of the free chains in the adhesive network morphology. The adhesive performance of the PSAs was found to be correlated with their M_c/M_e values as the 2EHA proportion was varied. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation of poly(divinylbenzene‐co‐N‐isopropylacrylamide) microspheres and their hydrogen‐bonding assembly behavior for raspberry‐like core‐corona polymer composite

Narrowdisperse poly(divinylbenzene‐co‐N‐isopropylacrylamide) (poly(DVB‐co‐NIPAM)) functional microspheres with the diameter in the range of 630 nm and 2.58 μm were prepared by distillation–precipitation polymerization in neat acetonitrile in the absence of any stabilizer. The effect of N‐isopropylacrylamide (NIPAM) ratio in the comonomer feed on the morphology of the resultant polymer particles was investigated in detail with divinylbenzene (DVB) as crosslinker and 2,2′‐azobisisobutyronitrile (AIBN) as initiator. The monodisperse poly(DVB‐co‐NIPAM) microspheres with NIPAM fraction of 20 wt % were selected for the preparation of raspberry‐like core‐corona polymer composite by the hydrogen‐bonding self‐assembly heterocoagulation with poly(ethyleneglycol dimethacrylate‐co‐acrylic acid) [poly(EGDMA‐co‐AA)] nanospheres. Both of the functional poly(DVB‐co‐NIPAM) microspheres and the core‐corona particles were characterized with scanning electron microscopy (SEM), Fourier transform infrared spectra (FTIR), and elemental analysis (EA). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1350–1357, 2007     

UV curable pressure‐sensitive adhesives for fabricating semiconductors. II. The effect of functionality of acrylate monomers on the adhesive properties

In an attempt to control the adhesive properties of acrylic copolymer‐based pressure‐sensitive adhesives, a series of multifunctional acrylate monomers were added and UV cured. The adhesive compound with a difunctional monomer had increased peel strength after UV curing. On the other hand, the compound with a tri‐ or more functional (polyfunctional) monomer had markedly decreased strength after UV curing. Those adhesives containing any polyfunctional monomer also showed much higher storage modulus than an adhesive containing a difunctional monomer. The greater volume contraction of UV‐cured polyfunctional monomer suggested microvoids at the interface between the adhesive layer and the adherent, resulting in poor strength. Estimated values of the peel strength of UV‐cured adhesives according to the theoretical equations proved that the strength is approximately inversely proportional to the elastic moduli. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2889–2895, 2004     

Direct polymer reaction of poly(styrene‐co‐maleic anhydride): Polymeric imidization

Using direct polymer reaction of poly(styrene‐co‐maleic anhydride) (SMA), a synthesis of copolymer of styrene and N‐aryl succinimide (SMI) has been investigated. SMI copolymers were synthesized from SMA copolymers by a concerted two‐step reaction, which consisted of the condensation reaction (step 1) of SMA with aromatic amine to prepare a precursor, succinamic acid, for imide formation and the cyclodehydration reaction (step 2) of succinamic acid. In this article, the application of Searle's preparation method of N‐aryl or N‐alkyl maleimide to the direct polymer reaction for SMI was attempted. Compared with synthesis of monomeric imides, the imide formation in polymeric condition appeared to be a little more sensitive to the reaction condition. The optimum condition for maximum conversion was examined in terms of time, temperature, and the amount of reactants. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1187–1196, 1999     

Uses of electron‐beam irradiation to prepare pH‐ and temperature‐sensitive hydrogels from reactive poly(vinyl alcohol) grafts

Thermosensitive poly(vinyl alcohol)‐graft‐(maleic anhydride), PVA‐MA, and poly(vinyl alcohol)‐graft‐(N‐isopropylacrylamide maleic anhydride) (PVA‐MA‐NIPAAm) copolymers containing carboxyl groups were prepared using electron beam irradiation at dose 80 kGy. The swelling ratios of the cross‐linked gels were measured at various temperatures. The LCST values were measured using DSC technique. The temperature dependence of the swelling ratios of the cross‐linked copolymers and terpolymers were measured at different temperatures. The swelling ratios of copolymers increased with increasing temperature up to 25–38°C, then decreased. The swelling behavior of both copolymers and terpolymers was referred to formation of hydrogen bonds between amide group of NIPAAm moieties and carboxyl group in MA moieties and to hydrophobic interaction due to methyl groups of NIPAAm. The swelling behaviors of these gels were analyzed in buffer solution at various pH. Swelling ratios of all gels were relatively high and they showed reasonable sensitive to pH. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

pH‐ and temperature‐sensitive in vitro release of salicylic acid through poly(vinyl alcohol‐g‐acrylamide) membranes

In this study, acrylamide (AAm) was grafted onto poly(vinyl alcohol) (PVA) in solution with UV radiation, and membranes were prepared from the graft copolymer (PVA‐g‐AAm) for transdermal release of salicylic acid (SA) at in vitro conditions. Permeation studies were carried out using a Franz‐type diffusion cell. Release characteristics of SA through PVA and PVA‐g‐AAm membranes were studied using 2.0 mg/mL SA solutions. Effects of the presence of AAm in the copolymer, pH of donor and acceptor solution, and concentration of SA and temperature on the release of SA were investigated. Permeation of SA through the membranes was found to be pH‐dependent, and increase in pH generally increased the release percentage of SA, and the presence of AAm in the membrane positively affected the permeation. The effect of concentrations of SA on the permeation was also searched using saturated solution of SA, and permeated amount of SA was found to be less than in the case of unsaturated SA solution. Studies showed that the release of SA from PVA‐g‐AAm membranes was temperature‐sensitive and increase in temperature increased the permeation rate. 82.76% (w/w) SA was released at the end of 24 h at (39 ± 1)°C, and the overall activation energy for the permeation of SA through PVA‐g‐AAm membranes was found to be 19.65 kJ/mol. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and performance study on P(St‐MMA)‐SiO2 doped P(VDF‐HFP) based composite polymer electrolyte

The organic–inorganic hybrid material poly(styrene‐methyl methacrylate)‐silica (P(St‐MMA )‐SiO₂) was successfully prepared by in situ polymerization confirmed by Fourier transform infrared spectroscopy and was employed to fabricate poly(vinylidene fluoride‐hexafluoropropylene) (P(VDF‐HFP )) based composite polymer electrolyte (CPE ) membrane. Desirable CPEs can be obtained by immersing the CPE membranes into 1.0 mol L^?1 LiPF₆‐EC /DMC /EMC (LiPF₆ ethylene carbonate + dimethyl carbonate + ethylmethyl carbonate) liquid electrolyte for about 0.5 h for activation. The corresponding physicochemical properties were characterized by SEM , XRD , electrochemical impedance spectroscopy and charge–discharge cycle testing measurements. The results indicate that the as‐prepared CPEs have excellent properties when the mass ratio of the hybrid P(St‐MMA )‐SiO ₂ particles to polymer matrix P(VDF‐HFP ) reaches 1:10, at which point the SEM analyses show that the as‐prepared P(St‐MMA )‐SiO ₂ particles are uniformly dispersed in the membrane and the CPE membrane presents a homogeneous surface with abundant interconnected micropores. The XRD results show that there may exist interaction forces between the P(St‐MMA )‐SiO ₂ particles and the polymer matrix, which can obviously decrease the crystallinity of the composite membrane. Moreover, the ionic conductivity at room temperature and the electrochemical working window of the CPE membrane can reach 3.146 mS cm^?1 and 4.7 V, respectively. The assembled LiCoO₂/CPE /Li coin cell with the CPE presents excellent charge–discharge and C ‐rate performance, which indicates that P(St‐MMA )‐SiO ₂ hybrid material is a promising additive for the P(VDF‐HFP ) based CPE of the lithium ion battery. © 2016 Society of Chemical Industry     

Triphase catalysis: Hydroxylation of cyclo‐octane by NaOCl catalyzed by coordinatively bound manganese(III) porphyrin to nitrogen‐based polymer supports

The anionic manganese (III) porphyrin was immobilized onto crosslinked poly(benzylpicoline‐co‐styrene) resin through coordinate linkage. The immobilized metalloporphyrin was employed as a heterogeneous catalyst for the hydroxylation of cyclo‐octane by NaOCl. The observed reaction rates depend on experimental parameters such as stirring speed, substrate amount, temperature, and catalyst amount. The influence of different polymer‐based axial ligands, particle size, and percent crosslinking of the polymer support was also discussed. The imidazole‐based polymer supports show higher rate constant values than the pyridine‐based supports. The catalyst shows significant decrease in catalytic activity on recycling. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 104–111, 2000     

Synthesis and characterization of pH‐ and temperature‐sensitive silk sericin/poly(N‐isopropylacrylamide) interpenetrating polymer networks

Interpenetrating polymer networks (IPNs) composed of silk sericin (SS) and poly(N‐isopropylacrylamide) (PNIPAAm) were prepared simultaneously. The properties of the resultant IPN hydrogels were characterized by differential scanning calorimetry and SEM as well as their swelling behavior at various temperatures and pH values. The single glass transition temperature (T_g) presented in the IPN thermograms indicated that SS and PNIPAAm form a miscible pair. The swollen morphology of the IPNs observed by SEM demonstrated that water channels (pores present in SEM micrographs) were distributed homogeneously through out the network membranes. The swelling ratio of the IPNs depended significantly on the composition, temperature and pH of the buffer solutions. The dynamic transport of water into the IPN membrane was analyzed based on the Fickian equation. Copyright © 2006 Society of Chemical Industry     

Rhodium(I) complex catalyst immobilized on terpolymers of N‐vinylpyrrolidinone and 1‐vinylimidazole

The hydrosilylation of cyclohexanone and acetone with triethysilane and diphenysilane catalyzed by polymer‐supported Rh(I) complex has been investigated. Two terpolymers of styrene, divinylbenzene, and 1‐vinylimidazole (S/DVB/VI) or N‐vinylpyrrolidinone (S/DVB/NVP) were used as the catalysts supports. Physical characterization of these materials has involved the measurements of the structural parameters in the dry and swollen states by DSC, the nitrogen BET adsorption method and inverse steric exclusion chromatography ISEC. From these results it can be concluded that the original polymer structure has been changed during the complex attachment giving rise to materials of higher porosity. X‐ray photoelectron spectroscopy XPS, IR, and AAS spectroscopy were used to characterization of heterogeneous complexes before and after use. The effect of the morphology of the support on the catalytic properties of the polymer‐supported Rh(I) species was tested in the hydrosilylation of ketones and correlated with the reaction mechanism. It was demonstrated that the high selectivity of homogeneous rhodium complex toward the silyl ethers can be partially reversed to the dehydrogenative silylation products by a proper choice of polymer support with favorable microporous structure. Recycling tests demonstrated high stability of the supported catalysts during prolonged use. The constant selectivity of the supported catalysts demonstrated during recycling experiments showed that they could be useful for practical application. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis,characterization, and metal complexation of poly(N‐phenylmaleimide‐co‐acrylic acid) and poly(N‐phenylmaleimide‐co‐acrylamide) as polychelatogens in aqueous solution

We carried out the free‐radical copolymerization of N‐phenylmaleimide with acrylic acid and acrylamide with an equimolar feed monomer ratio. We carried out the synthesis of the copolymers in dioxane at 70°C with benzoyl peroxide as the initiator and a total monomer concentration of 2.5M. The copolymer compositions were obtained by elemental analysis and ¹H‐NMR spectroscopy. The hydrophilic polymers were characterized by elemental analysis, Fourier transform infrared spectroscopy, ¹H‐NMR spectroscopy, and thermal analysis. Additionally, viscosimetric measurements of the copolymers were performed. Hydrophilic poly(N‐phenylmaleimide‐co‐acrylic acid) and poly(N‐phenylmaleimide‐co‐acrylamide) were used for the separation of a series of metal ions in the aqueous phase with the liquid‐phase polymer‐based retention method in the heterogeneous phase. The method is based on the retention of inorganic ions by the polymer in conjunction with membrane filtration and subsequent separation of low‐molecular‐mass species from the formed polymer/metal‐ion complex. The polymer could bind several metal ions, such as Cr(III), Co (II), Zn(II), Ni(II), Cu(II), Cd(II), and Fe(III) inorganic ions, in aqueous solution at pH values of 3, 5, and 7. The interaction of the inorganic ions with the hydrophilic polymer was determined as a function of pH and a filtration factor. Hydrophilic polymeric reagents with strong metal‐complexing properties were synthesized and used to separate those complexed from noncomplexed ions in the heterogeneous phase. The polymers exhibited a high retention capability at pH values of 5 and 7. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006