Tack properties of pressure‐sensitive adhesives

Relevant experiments are essential to clearly understand the role of various molecular (chemical structure, surface energy, composition), experimental (contact time, contact pressure, temperature) or topological (sample roughness and thickness) parameters, on the tack properties of pressure sensitive adhesives (PSA). The “mechano‐optical tack tester” (MOTT) is a novel device that we have developed to provide accurate measurements of both the contact area and the tack strength. The MOTT is designed to apply controlled contact pressures by mean of a quartz prism probe, for determined contact times, onto the surface of PSA samples. The probe is then pulled up at controlled rates while the tearing force (tack strength) and the contact area are plotted versus time. The tack energy is then calculated. Using the MOTT, the influence of various parameters (contact pressure, contact area, sample thickness, …) on the tack properties of PSA samples has been studied. The main result lies in the strong dependence of the tack energy on the sample thickness. This points out that the release energy is close to the interface rather than in the bulk of the PSA films, and is a function of the contact area. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1201–1208, 2000     

Investigation of shear failure mechanisms of pressure‐sensitive adhesives

We report new experiments investigating the failure mechanisms in shear, of thin layers of acrylic pressure‐sensitive adhesives (PSA). We have developed a novel experimental device able to shear a soft adhesive layer confined between a rigid hemispherical lens and a rigid glass substrate. Using the resources of in situ contact visualization, the nonhomogeneous deformation of the layer and the shear failure processes were observed optically. Depending on the rheological properties of the adhesive, ratios of the contact radius over the layer thickness of 10–30 were achieved, mimicking well the contact conditions encountered in a thin adhesive layer within a joint. When the adhesive was weakly crosslinked, we observed a fluid‐like behavior and could measure a reasonable value for the viscosity of the PSA, implying that flow can occur in the layer and failure will occur by creep. On the other hand, for a more crosslinked adhesive, closer to what is used in applications, a stick‐slip peeling behavior was observed, which involves a coupling between peeling mechanisms at the leading edge of the contact and interfacial slippage. Such a process suggests a failure by fracture rather than by creep. Interestingly, the peeling mechanisms and the associated stress levels change significantly when the layer becomes as thin as 20 μm, implying a fracture process that is controlled by a critical energy release rate in shear G_IIc rather than by a critical shear stress causing failure of the interfacial bonds. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3316–3330, 2005     

Acrylic acid level and adhesive performance and peel master‐curves of acrylic pressure‐sensitive adhesives

Three series of pressure‐sensitive adhesives were prepared with constant glass‐transition temperature, using emulsion polymerization. The monomers chosen were butyl acrylate, 2‐ethylhexyl acrylate (EHA), methyl methacrylate (MMA), and acrylic acid (AA). Within each polymer series, the proportion of AA monomer was held constant for each polymer preparation but acrylic ester monomer levels were varied. Adhesion performance was assessed by measurement of loop tack, static shear resistance, and through the construction of peel master‐curves. Peel master‐curves were generated through peel tests conducted over a range of temperatures and peel rates and through application of the time–temperature superposition principle. Bulk effects dominated by polymer zero shear viscosity change as AA and EHA levels were varied were attributed to the observed effect on static shear resistance and the horizontal displacements of peel master‐curves. Static shear resistance was found to strongly correlate with log(a_C), a parameter introduced to horizontally shift peel master‐curves to form a superposed, “super master‐curve”. An interfacial interaction was proposed to account for deviations observed when loop tack was correlated with log(a_C). Surface rearrangements via hydrogen bonding with the test substrate were suggested as responsible for the interfacial interaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1237–1252, 2006     

Viscoelasticity and tack of poly(vinyl pyrrolidone)–poly(ethylene glycol) blends

The adhesive properties of blends of high molecular weight poly(vinyl pyrrolidone) (PVP) and low molecular weight poly(ethylene glycol) (PEG) were systematically investigated with a probe test and correlated with their viscoelastic properties. The material parameters that were varied were the PEG content (31–41 wt %) and the hydration rate. The 36% PEG showed the best balance of properties for a pressure‐sensitive adhesive. At low debonding rates, the debonding took place through the formation of a fibrillar structure, whereas at high debonding rates, the debonding was brittle. This transition was attributed to the breakage and reformation of hydrogen bonds between PVP units and OH groups on PEG during the large strain of the polymer chains in elongation. This transition was observed, albeit shifted in frequency, for all three compositions, and the characteristic relaxation times of the hydrogen‐bonded network were estimated. A comparison between the tack properties of the adhesives and their linear viscoelastic properties showed a very strong decoupling between the small‐strain and large‐strain properties of the adhesive, which was indicative of a pronounced deviation from rubber elasticity in the behavior of the blends. This deviation, also seen during tensile tests, was attributed to the peculiar phase behavior of the blends. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2395–2409, 2002     

Effect of chemical structure of acrylic pressure‐sensitive adhesives for polarizing film on light leakage phenomenon in TFT‐LCDs

Increasing image quality in thin‐film transistor liquid crystal displays (TFT‐LCD) is a recognized challenge for electronic companies and specialists working in this area. One of the main problems in TFT‐LCDs is a phenomenon called “light leakage”, affecting black–white contrast and color brightness. It occurs because of a heat‐induced shrinkage and disorientation of the polarizing film of TFT‐LCD, which controls the intensity of the light from the backlight unit. Improvement of the light leakage can be achieved through using a pressure‐sensitive adhesive (PSA) used for assembling the polarizing film onto the TFT‐LCD panel. In this paper, eight acrylic/methacrylic monomers with high glass transition temperature (Tg) were employed for synthesis of the polymers for the adhesive. Effect of structure, Tg, and elasticity modulus of the synthesized polymers on the light leakage was investigated simultaneously for 2.5‐ and 7.0‐in. size samples. We demonstrated that the light leakage can be minimized through two different mechanisms—high stress relaxation of the polymers with low Tg and low modulus and high shrinkage resistance of the polymers with high Tg and high modulus. The results of this work indicate a possibility to develop a universal PSA for polarizing film in TFT‐LCDs of different sizes that will have a positive effect on manufacturing productivity and lowering prices of digital devices. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis of poly(isobutyl‐co‐2,2,2‐trifluoroethyl methacrylate) with 5,10,15,20‐tetraphenylporphinato platinum(II) moiety as an oxygen‐sensing dye for pressure‐sensitive paint

Pressure‐sensitive paint (PSP), which consists of luminescent molecules embedded in an oxygen‐permeable polymer, has been developed for use in wind‐tunnel experiments. To improve the PSP technique, a novel luminescent methacrylate monomer, 5‐[4‐(2‐methacryloyloxyethoxycarbonyl)phenyl]‐10,15,20‐triphenylporphinato platinum(II), was synthesized and copolymerized with isobutyl methacrylate and 2,2,2‐trifluoroethyl methacrylate to produce a dye‐pendant copolymer ( 2 ). The introduction of 5,10,15,20‐tetraphenylporphinato platinum(II) (PtTPP) dye into 2 was confirmed by ultraviolet–visible spectroscopy and extended X‐ray absorption fine structure measurements. The extent of PtTPP dye incorporation in 2 was proportional to the molar fraction of the PtTPP‐pendant methacrylate monomer in the feed. The oxygen‐sensing property of 2 was compared with that of a PSP consisting of PtTPP dye embedded in poly(isobutyl‐co‐2,2,2‐trifluoroethyl methacrylate). Although the simple mixture of PtTPP and poly(isobutyl‐co‐2,2,2‐trifluoroethyl methacrylate) showed a marked deviation from a single Stern–Volmer relation, novel copolymer 2 gave a highly linear Stern–Volmer plot. This was unequivocal evidence of dye conjugation on the oxygen‐sensing polymer film. © 2005Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2997–3006, 2005     

Characterization of nano‐organized multilayers constituted by successive inorganic (gold) and organic (alkylthiols) layers

Nanostructured multilayers constituted by alternate metallic (gold) and organic (alkyldithiol) layers, and grafted onto glass or silicon substrates are prepared and analysed. Such complex layers could be of interest as a new type of surfaces but also as localized dissipative zones particularly in the field of adhesion science. The formation and the structure of these model systems are examined using a number of techniques such as atomic force microscopy (AFM), wetting analysis (contact angles), X‐ray photoelectron spectroscopy (XPS) and conductivity measurements. It is shown that, in terms of electrical conductivity, gold layers exhibit a percolation transition from an insulating granular structure to a conductive worm‐like structure at a threshold thickness of about 5 nm. XPS (and wettability) analyses clearly indicate that the fractional coverage of the gold surface is about 30% with alkyldithiol and that these molecules are either grafted in a stand‐up position or in the form of a loop. Moreover, a partial electrical connection between two successive gold layers is observed, confirming that the confined organic layer of alkyldithiol between them is too loosely organized to play the role of an insulating barrier. Copyright © 2007 John Wiley & Sons, Ltd.     

Radical polymerization of trifluoromethyl‐substituted methyl methacrylates and their application for use in pressure‐sensitive paint

Three CF₃‐substituted methyl methacrylates (MMAs), 2,2,2‐trifluoroethyl methacrylate (TFEMA), 1,1,1,3,3,3‐hexafluoroisopropyl methacrylate (HFIPMA) and nonafluoro‐tert‐butyl methacrylate (NFTBMA), were polymerized by conventional radical polymerization to give oxygen‐permeable polymers for application in pressure‐sensitive paint (PSP). The radical copolymerizations of styrene with TFEMA, HFIPMA, or NFTBMA were carried out to examine the effect of CF₃ groups on the polymerizability. The e values increased in the order of MMA (0.40) < TFEMA (0.76) < HFIPMA (1.19) < NFTBMA (1.31). The homopolymers of TFEMA, HFIPMA and NFTBMA (PTFEMA, PHFIPMA, and PNFTBM, respectively) were examined as polymers for use in PSP using 5,10,15,20‐tetrakis(pentafluorophenyl)porphinato platinum(II) (PtTFPP). The PSP consisting of PNFTBMA and PtTFPP exerted very high pressure sensitivity and very low temperature sensitivity. In the absence of oxygen, the temperature sensitivity decreased in the order of PTFEMA > PHFIPMA > PNFTBMA = PMMA, which corresponds to the order of glass transition temperatures (T_g). However, the activation energies of the overall process of the luminescence quenching by oxygen were found to be 16.8 (PMMA), 13.0 (PTFEMA), 6.8 (PHFIPMA), and 4.3 kJ mol^?1 (PNFTBMA). Therefore, the low temperature sensitivity of PNFTBMA was attributed to its high degree of substitution with CF₃ groups and to its relatively high T_g value. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 963–972     

High‐pressure‐synthesis of poly(isopropenyl alcohol) and its biocompatibilities

Free radical polymerization under ambient conditions gives very low‐molecular weight homopolymer of isopropenyl acetate (IPAc). On the other hand, poly (isopropenyl acetate) (PIPAc) with a weight average molecular weight over 10⁴ was found to be synthesized by high‐pressure (1 GPa) radical polymerization. Poly(isopropenyl alcohol) (PIPOH) was then derived from PIPAc by saponification. The structure and properties of PIPAc and PIPOH were investigated using X‐ray diffraction, thermal analyses, X‐ray photoelectron spectroscopy, and dynamic contact angles. Though PIPOH is insoluble in water, the surface free energy (55 mJ/m²) was comparable with that of poly(vinyl alcohol). To utilize the peculiar combination of “aqueous insolubileity and high hydrophilicity” of PIPOH, biocompatibilities of PIPOH surface was investigated. The PIPOH surface was found to show high repellencies to albumin adsorption, whole thrombogenesis, and cell adhesion. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 754–761, 2009     

Synthesis,characterization, and drug release behaviors of a novel thermo‐sensitive poly(N‐acryloylglycinates)

In this study, a novel thermo‐sensitive poly(N‐acryloylglycinates) was prepared in order to get a potential drug release carrier. The corresponding monomers and the polymers were characterized with Fourier‐transform infrared (FTIR) and ¹H NMR. The thermo‐sensitivity of the poly(N‐acryloylglycinates) was evaluated by measuring their lower critical solution temperatures (LCST) in water, inorganic salt solution, and different pH solutions. The results indicated that poly(N‐acryloylglycine methyl ester) (NAGME) and poly(N‐acryloylglycine ethyl ester) (NAGEE) exhibit a reversible thermo‐sensibility in their aqueous solutions at 61.5 and 12.5°C, respectively. However, no thermo‐sensitive behavior of poly(N‐acryloylglycine propyl ester) (NAGPE) was found due to its over hydrophobicity. The swelling studies on hydrogels were carried out at different temperatures, in different pH, and inorganic salt solutions. The hydrogels showed a remarkable phase transition at about 35°C with changing temperature. The release rate of caffeine from the thermo‐sensitive hydrogel was apparently decreased as the crosslinker content increased and temperature decreased. Seventy five percent caffeine from the polymeric hydrogel with 5% NMBA (N, N‐methylenebis(acrylamide)) was released at room temperature within 240 min, whereas 95.4% caffeine diffused into the medium at 37°C. Copyright © 2009 John Wiley & Sons, Ltd.     

Self‐Assembled,Thermosensitive PCL‐g‐P(NIPAAm‐co‐HEMA) Micelles for Drug Delivery

Summary: A novel thermosensitive amphiphilic copolymer (PCL‐g‐P(NIPAAm‐co‐HEMA)) comprised of hydrophobic PCL segments and hydrophilic P(NIPAAm‐co‐HEMA) segments was designed and synthesized. The structure of the copolymer was characterized by FT‐IR, ¹H NMR and GPC analysis. The copolymer may self‐assemble into micelles in water and the resulting micelles demonstrated temperature sensitivity with a lower critical solution temperature (LCST) of 33 °C. The critical micellar concentration (CMC) obtained from surface tension measurements and the fluorescence method was around 30 mg · L⁻¹. Transmission electron microscopy (TEM) showed that the micelles exhibit a nanospheric morphology within a narrow size range of 150–160 nm. A cytotoxicity study showed that the PCL‐g‐P(NIPAAm‐co‐HEMA) copolymer exhibits good biocompatibility. The controlled drug release of the resulting micelles was investigated and it was found that micelles loaded with prednisone acetate showed improved drug release behavior due to the special micellar structure.

Self‐assembly of the PCL‐g‐P(NIPAAm‐co‐HEMA) copolymers.     

A pH‐sensitive water‐soluble N‐carboxyethyl chitosan/poly(hydroxyethyl methacrylate) hydrogel as a potential drug sustained release matrix prepared by photopolymerization technique

Biocompatible pH‐sensitive semi‐interpenetration polymeric network hydrogels (semi‐IPN) based on water‐soluble N‐carboxyethyl chitosan (CECS) and 2‐hydroxyethyl methacrylate (HEMA) were synthesized by the photopolymerization technique. pH‐sensitivity, cytotoxicity, morphology, mechanical property, and water state of hydrogel were investigated by a swelling test, methylthiazolydiphenyl‐tetrazolium bromide (MTT) assay, scanning electron microscopy (SEM), universal testing machine, and differential scanning calorimetry (DSC), respectively. The drug release studies were carried out using 5‐Flurouracil as the model drug. The results indicated that the hydrogels were sensitive to pH of the medium and its wet state had good mechanical properties. The results of cytotoxicity and prolonged drug release characteristics revealed the suitability of the hydrogels as drug delivery matrices. The release kinetics was evaluated by fitting the experimental data to standard release equations, and the best fit was obtained with the Higuchi model of the hydrogel. Copyright © 2008 John Wiley & Sons, Ltd.     

Dual‐curable fluorinated poly(methacrylate) copolymers for optical adhesives

In pursuit of photo‐curable adhesive for optical communication, dual‐curable acrylic oligomers (AOs) having alkoxy silane group, fluorine atoms and vinyl group as a pendent group were synthesized by two‐stage reactions. The isocyanate group containing oligomers were firstly synthesized via radical polymerization of acrylic monomers, and followed by urethane reaction with 2‐hydroxy ethyl methacrylate. The dual curing behaviors, e.g. thermal and photo‐cure, were studied by using photo‐differential scanning calorimetry (DSC) and real‐time IR. An optimum adhesive formulation, based on AO (15 g), epoxy acrylate (80 g), isobonyl methacrylate (17 g) and photo‐initiator (3 g), was obtained. As the content of AO was increased in the optical adhesive formulation, refractive index decreased but transmittance increased due to the increase in fluorine content. The optical transmittance at the range of 1.3 to 1.55 μm was higher than 90%. The addition of colloidal silica with the earlier mentioned formulation was helpful in decreasing crosslinking volume shrinkage and the increasing of glass fiber adhesion. The required properties for the optical adhesive, including chemical resistance and thermal resistance, dimension stability, etc. were also investigated. Copyright © 2005 John Wiley & Sons, Ltd.     

A detailed theoretical study on the excited‐state hydrogen‐bonding dynamics and the proton transfer mechanism for a novel white‐light fluorophore

In this work, density functional theory (DFT) and time‐dependent DFT (TDDFT) methods were used to investigate the excited‐state dynamics of the excited‐state hydrogen‐bonding variations and proton transfer mechanism for a novel white‐light fluorophore 2‐(4‐[dimethylamino]phenyl)‐7‐hyroxy‐6‐(3‐phenylpropanoyl)‐4H‐chromen‐4‐one ( 1 ). The methods we adopted could successfully reproduce the experimental electronic spectra, which shows the appropriateness of the theoretical level in this work. Using molecular electrostatic potential (MEP) as well as the reduced density gradient (RDG) versus the product of the sign of the second largest eigenvalue of the electron density Hessian matrix and electron density (sign[λ₂]ρ), we demonstrate that an intramolecular hydrogen bond O1–H2···O3 should be formed spontaneously in the S₀ state. By analyzing the chemical structures, infrared vibrational spectra, and hydrogen‐bonding energies, we confirm that O1–H2·O3 should be strengthened in the S₁ state, which reveals the possibility of an excited‐state intramolecular proton transfer (ESIPT) process. On investigating the excitation process, we find the S₀ → S₁ transition corresponding to the charge transfer, which provides the driving force for ESIPT. By constructing the potential energy curves, we show that the ESIPT reaction results in a dynamic equilibrium in the S₁ state between the forward and backward processes, which facilitates the emission of white light.     

Poly(acrylate/epoxy) hybrid adhesives for low‐surface‐energy plastic adhesion

The formulation, polymerization, and performance of a new class of low‐surface‐energy adhesives for plastics are described. The polymerization involves the simultaneous room‐temperature polymerization of polyoxirane monomers in an acrylic monomer phase. The polymerization of the acrylic phase and adhesion promotion to plastics are catalyzed after the decomplexation and oxidation of trialkylborane–amine complexes. The polymerization of the epoxy phase is catalyzed with a Lewis acid such as BF₃, ZnCl₂, or SnCl₄ complexed with ether or amine. This article explores the resulting adhesives as a function of the epoxy monomer functionality, concentration, solubility in the acrylic monomer, Lewis acid catalyst concentration, phase crosslinking, and postprocessing thermal history. The adhesive morphology exhibits a finely dispersed epoxy phase strongly interacting with the major acrylic phase resulting from a nucleation‐and‐growth phase‐separation mechanism. Excellent adhesion to plastics, including polyethylene, polypropylene, poly(tetrafluoroethylene), poly(ethylene terephthalate), and nylon, is achieved with a much higher thermal performance than that achievable with acrylic polymers alone. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 989–998, 2007     

Fluorescent probes for monitoring the pulsed‐laser‐induced photocuring of poly(urethane acrylate)‐based adhesives

Fluorescence spectroscopy was used to study the kinetics of polymerization of acrylic adhesive formulations exposed to a 355‐nm pulsed emission from an Nd‐YAG laser. Nine fluorescent probes were used for monitoring the laser curing, showing different sensitivities. In general, the fluorescence intensity emission increased as crosslinking occurred. In addition, solvatochromic fluorescent probes showed a blueshift in their emission. A relative method was applied for the evaluation of the polymerization rates in three different acrylic systems. Special features of pulsed‐laser‐induced polymerization were treated in detail, such as the influence of the laser pulse frequency and the incident laser beam intensity. The polymerization rate slowed down as the pulse repetition rate decreased. An inhibition period due to oxygen quenching was observed, and it was highly dependent on the laser repetition rate and the nature of the photoinitiator. The effect of the laser beam intensity on the kinetics of such fast reactions was studied. In general, increasing the laser energy improved the rate of polymerization. The degree of cure improved as the polymerization rate increased as a result of faster crosslinking, rather than relaxation volume kinetics. Moreover, a saturation rate effect occurred that depended on the photoinitiator. The different behaviors of the two photoinitiators in the curing of the same acrylic formulation was explained on the basis of primary radical termination. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1227–1238, 2004     

Synthesis and Characterization of Poly(Biphenyl‐2‐yl p‐Styrenesulphonate) as Profungicide in Controlled Release Technique

A new fungicide controlled release formulation was prepared by the reaction of p‐styrenesulphonyl chloride with biphenyl‐2‐ol (Dowicide A) as fungicide. The resulting monomer containing the fungicide was polymerized with benzoyl peroxide as initiator. The monomer and the polymer were identified by spectroscopic methods, and molecular weight of the polymer was determined by GPC. Also mp, Tg and Td of the polymer were identified by DSC. The release characteristic of the polymer was studied in neutral, alkaline, and acidic media. Also, the effect of the temperature on the release of bioactive agent (Dowicide A) was investigated. The hydrolysis data showed that the release rates are strongly dependent upon the pH of the medium and the temperature.     

New pivot for investigating flame‐retarding mechanism: Quantitative analysis of zinc phosphate doped aliphatic waterborne polyurethane‐based intumescent coatings for flame‐retarding plywood

The quantitative analysis of zinc phosphate (ZnP) on the flame resistance of intumescent flame retardant coatings (IFRCs) is presented including cone calorimeter (CC) and pyrolysis kinetics, using aliphatic waterborne polyurethane (AWP) as the coating binder. The CC results show that an appropriate dosage (2 wt%) of ZnP in the AWP‐based coating constitutes an improved flame resistance, evidenced by the fire performance index increased from 0.41 to 0.71 seconds m² kW^?1, as well as the reduced fire growth index. The characterization analysis determines the dehydrated ZnP facilitates the formed amorphous char‐residue with a heat‐sink effect, leading to an increase in heat absorption, which climbs from the 253.00to 351.30 J·g^?1. Besides, the pyrolysis kinetics verifies that the 3D Jander model (n = 2) mainly governs the whole pyrolysis process of pure coatings by the modified Coats‐Redfern integral method. The ZnP‐containing coating exerts an improved E_α corresponding to 95–200°C, which climbs from 24.96 to 35.80 kJ mol^?1, leading to the formation of a continuous and compact char layer. It explores an effective quantitative analysis of the flame resistance of organic–inorganic hybrid IFRCs, deepening the flame‐retarding mechanism.