Stabilizations of molecular structures and mechanical properties of PVC and wood/PVC composites by Tinuvin and TiO2 stabilizers

Three different UV stabilizers, 2‐(2H‐benzotriazol‐2‐yl)‐4,6‐ditertpentylphenol (Tinuvin XT833), 2‐(2H‐benzotriazol‐2‐yl)‐p‐cresol (Tinuvin P), or rutile–titanium dioxide (TiO₂) were incorporated into poly(vinyl chloride) (PVC) and wood/PVC (WPVC) composite, and mechanical and physical properties and photostabilities were monitored. The polyene and carbonyl sequences of PVC increased with UV weathering time and with presence of wood flour. The yellowness index increased because of polyene and carbonyl productions, whereas the brightness increased because of the photobleaching of lignin in wood. The photostabilities of PVC and WPVC could be improved through the use of UV stabilizers. Tinuvin P was recommended in this work as the most effective stabilizer for PVC and WPVC composites. The stabilization effect was interfered by presence of wood particles. The mechanical property changes corresponded well to the structural changes under UV for neat PVC. For WPVC composites, the presence of wood particles played more significant effect on the mechanical properties during UV aging than the UV stabilizer. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Grafting polymerization of 2‐[3‐(2h‐benzotriazol‐2‐yl)‐4‐hydroxyphenyl]ethyl methacrylate on vinyltriethoxysilane‐treated cotton for the preparation of ultraviolet‐protective fabrics

Vinyltriethoxysilane was used to modify the surface of cotton to provide polymerizable vinyl groups on the fiber surface. An ultraviolet‐absorbing monomer, 2‐[3‐(2H‐benzotriazol‐2‐yl)‐4‐hydroxyphenyl]ethyl methacrylate, was polymerized on the vinyltriethoxysilane‐treated fabric to prepare ultraviolet‐protective cotton. The effects of the amounts of the solvent, silane coupling agent, and 2‐[3‐(2H‐benzotriazol‐2‐yl)‐4‐hydroxyphenyl]ethyl methacrylate on the surface morphology and ultraviolet‐protection factor of the treated cotton fabric were investigated. With a suitable process, poly{2‐[3‐(2H‐benzotriazol‐2‐yl)‐4‐hydroxyphenyl]ethyl methacrylate} was successfully coated onto the fabric, and it significantly reduced ultraviolet transmission through the fabric, resulting in a cotton fabric with excellent ultraviolet‐protection properties. The use of a silane coupling agent helped to ensure a polymer coating with good uniformity and good resistance to washing. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Transparent,Lightweight, and High Strength Polyethylene Films by a Scalable Continuous Extrusion and Solid‐State Drawing Process

The continuous production of transparent high strength ultra‐drawn high‐density polyethylene films or tapes is explored using a cast film extrusion and solid‐state drawing line. Two methodologies are explored to achieve such high strength transparent polyethylene films; i) the use of suitable additives like 2‐(2H‐benzotriazol‐2‐yl)‐4,6‐ditertpentylphenol (BZT) and ii) solid‐state drawing at an optimal temperature of 105 °C (without additives). Both methodologies result in highly oriented films of high transparency (≈91%) in the far field. Maximum attainable modulus (≈33 GPa) and tensile strength (≈900 MPa) of both types of solid‐state drawn films are similar and are an order of magnitude higher than traditional transparent plastics such as polycarbonate (PC) and poly(methyl methacrylate). Special emphasis is devoted to the effect of draw down and pre‐orientation in the as‐extruded films prior to solid‐state drawing. It is shown that pre‐orientation is beneficial in improving mechanical properties of the films at equal draw ratios. However, pre‐orientation lowers the maximum attainable draw ratio and as such the ultimate modulus and tensile strength of the films. Potential applications of these high strength transparent flexible films lie in composite laminates, automotive or aircraft glazing, high impact windows, safety glass, and displays.     

Hydrophilization of polypropylene films by using migratory additives

Linear and branched hydrophilic additives of various molecular weights (MWs) were extruded with polypropylene (PP) to make blend films. The surface‐modifying additives included polyethylene glycol (PEG), hydroxyl‐terminated four‐arm polyethylene oxide (PEO), and a commercial hydrophilic additive, Irgasurf HL560. Films were extruded by using a twin‐screw microcompounder at 200°C, and the resulting film thickness was 100 μm. Attenuated total reflectance (ATR)‐FTIR spectrometry and water contact angle measurements were performed on the film surfaces over time to investigate the additive migration behavior. Although ATR‐FTIR detected concentration increases for all additives in the subsurface region, there was no significant improvement in surface hydrophilicity for the PEGs and four‐arm PEOs in the same period of time as water contact angles were measured on the surfaces. Among the linear additives, low MW PEG (1 kDa) was found to migrate faster than the high MW varieties. The linear PEG and four‐arm PEO with MW higher than 2 kDa did not exhibit significant migration to the surface within a month. Irgasurf was found to change the surface wettability effectively in a relatively short time. J. VINYL ADDIT. TECHNOL., 13:57–64, 2007. © 2007 Society of Plastics Engineers.     

Synthesis of a photo‐patternable cross‐linked epoxy system containing photodegradable carbonate units for deep UV lithography

Bis(2‐(oxiran‐2‐ylmethyl)‐1,3‐dioxoisoindolin‐5‐yl) carbonate and polymers containing 9‐anthracenylmethylmethacrylate (AMMA), p‐tert‐butoxy styrene (PTBS), and methacrylic acid (MAA) monomeric units were synthesized with the aim of developing a novel photo‐patternable cross‐linked epoxy system. The oxirane groups in bis(2‐(oxiran‐2‐ylmethyl)‐1,3‐dioxoisoindolin‐5‐yl) carbonate were reacted with the carboxylic acid in the polymer to generate a cross‐linked epoxy film, and the photo degradation of the cross‐linked film was achieved through decomposition of the carbonate groups in the cross‐linked film by deep UV irradiation. Because the copolymer containing anthracene groups has relatively high reflective index and absorption at 248 nm, this cross‐linked system can be applied to patternable bottom antireflective coating materials for deep UV lithography applications. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Electropolymerization of a new 4‐(2,5‐Di‐2‐thiophen‐2‐yl‐pyrrol‐1‐yl)‐tetra substituted nickel phthalocyanine derivative

A new tetrakis 4‐(2,5‐di‐2‐thiophen‐2‐yl‐pyrrol‐1‐yl) substituted nickel phthalocyanine (NiPc‐SNS) was synthesized and characterized by elemental analysis, Fourier Transform Infrared (FT‐IR), and UV–vis spectroscopies. The electrochemical polymerization of this newly synthesized NiPc‐SNS was performed in dichloromethane (DCM)/tetrabutylammonium perchlorate (TBAP) solvent/electrolyte couple. An insoluble film was deposited on the electrode surface, both during repetitive cycling and constant potential electrolysis at 0.85 V. Resulting polymer film, P(NiPc‐SNS), was characterized utilizing UV–vis and FT‐IR spectroscopic techniques and its electrochemical behavior was investigated via cyclic voltammetry (CV). Spectroelectrochemical behavior of the polymer film on indium tin oxide (ITO) working electrode was investigated by recording the electronic absorption spectra, in situ, in monomer‐free electrolytic solution at different potentials and it is found that the P(NiPc‐SNS) film can be reversibly cycled between 0.0 and 1.1 V and exhibits electrochromic behavior; dark olive green in the neutral and dark blue in the oxidized states with a switching time of 1.98 s. Furthermore, the band gap of P(NiPc‐SNS) was calculated as 2.27 eV from the onset of π–π* transition of the conjugated backbone. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Degradation assessment of LDPE multilayer films used as a greenhouse cover: Natural and artificial aging impacts

This article focuses on the assessment and understanding of the mechanism of natural and artificial aging processes of a triple‐layer film made of low‐density polyethylene (LDPE) used as greenhouse cover. The film material contains color dye and ultraviolet–A (UV–A) and infrared (IR) stabilizers and antioxidant. The combined effect of temperature variations and UV–A radiations, of the natural and artificial aging, on the physical properties (free surface energy and yellow color measurements), mechanical behavior (tensile tests), thermal stability (TGA and DSC analysis), and structural stability (FTIR analysis) was investigated. The natural aging was conducted on a greenhouse, located in northern Algeria, over a period of 7 months. However, the artificial aging was performed at four different agricultural greenhouse simulating conditions of temperature and UV–A radiation (namely, at 40°C, 40°C with UV–A, 50°C, and 50°C with UV–A) for periods of aging up to 5486 h (7.6 months). The results revealed that, the maximum loss of the yellow color additives occurs at 2981 h under the natural aging process and at 2440, 1096, 1340, and 121 h under the four artificial aging conditions, respectively. There was an observed increase in the films free surface energy and a significant degradation in the mechanical properties with aging time. This can be correlated with the film material structural changes. The natural aging of the film in North Africa is almost equivalent to artificial aging at 40°C. The concurrent effect of temperature and UV–A radiations induced polymer chains scission leading to faster degradation in the film material and consequently a reduction in its durability and service lifetime. The results show also that the measured parameters are directly related to the limit of use criterion for evaluating the lifespan of agricultural greenhouse LDPE covers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Ionic mechanisms in pulse irradiated poly(vinyl chloride) system containing stabilizing additives

The pulse radiolysis studies of poly(vinyl chloride), PVC, film containing stabilizers i.e., Tinuvin P, Irgastab PVC 11, and Irganox 1076 have been carried out with the main aim of investigating ionic reactions in these systems. The evidences are presented concerning the formation of ionic transients in model solvents i.e. 2‐propanol and sec‐butyl chloride as well as in PVC film. In PVC‐stabilizer system under consideration the additives can contribute to the positive charge transfer processes whereas Tinuvin P, in addition may scavenge effectively electrons (the rate constant for e^?_solv scavenging in 2‐propanol equals 5.9 × 10⁹ mol^?1 dm³ s^?1) influencing the negative charge scavenging by PVC matrix itself and the HCl formation during the radiolysis of PVC. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Structurally bound stabilizers: Melt grafting of UV stabilizers onto polypropylene,polyethylene, and polystyrene

Monomeric ultraviolet stabilizers, 2-hydroxy-4-methacryloyloxy benzophenone and 2-hydroxy-4-acryloyloxy benzophenone were synthesized by a modified process. These reactive UV stabilizers were grafted onto the backbone of polypropylene (PP), low-density polyethylene (LDPE), and polystyrene (PS) by melt processing in the mixer of Brabender Plasticorder. An infrared spectroscopic method was standardized for the quantitative determination of the extent grafting of these additives on the polymer backbone. Grafting of both the additives occurred in the order PS > LDPE > PP. Methacryloxy derivative of benzophenone was found to be more reactive towards the polymers studied than the acryloxy derivative.     

Diffusion of amine stabilizers in vulcanized natural rubber compositions used in tires

The diffusion of amine stabilizers in vulcanized natural rubber formulations used in tires was investigated. Experiments were undertaken using a “sandwich” system composed of a sample disk containing the additive (source disk) between two external disks of nonadditivated rubber (reception disks). Diffusion coefficients (D) were calculated from the experimental migration curves following the Boltzman–Matano model. Theoretical diffusion curves for the additives were obtained according to the limited extension source in an infinite medium. Experimental data showed reasonable fitting with the theoretical curves, suggesting that D does not depend on the additive concentration. Thermooxidative stability data for the vulcanized rubber containing the additives showed no correlation to the diffusion process. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 670–676, 2000     

Photostabilizing efficiency of ultraviolet light stabilizers for rigid poly(vinyl chloride) against photo‐oxidation

The photostabilizing efficiency of different light stabilizers in poly(vinyl chloride) (PVC) was investigated by discoloration, ultraviolet (UV) reflection experiment, Fourier transform infrared spectrum (FTIR), and scanning electron microscopy (SEM). The results show that the addition of light stabilizers can slow down discoloration of PVC. The UV reflection results verify that this change is due to the distribution of light stabilizers on irradiated surfaces, which can absorb (such as organic stabilizers) or reflect (such as titanium dioxide) UV light differently. The order of stabilizers that can slower the extent of discoloration is titanium dioxide (TiO₂) > Tinuvin 234 (U4) > XT 833 (H2), U4 > Tinuvin 531 (U3) > Chimassorb 944 (H1), phenyl salicylate (U1). FTIR results show that the carbonyl group of pure PVC, TiO₂, and H1‐doped PVC increases significantly, indicating that the photo‐oxidation reactions of these irradiated samples are relatively serious. The SEM results show that the surface damages of PVC doped with U2, U4, and H2 are somehow slighter, with only small holes or cavities on the surface, whereas the surfaces of pure PVC and H1‐doped PVC are full of big and deep holes and some holes or cavities of 10 μm are detected. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Photo-oxidation of polypropylene films. VI. Possible UV-stabilization mechanisms

The effects of the chemical nature, concentration, stability, and location of various additives on the ultraviolet stability of polypropylene are discussed. It is shown that effective stabilizers of thin films do not depend on UV absorption for their protective action, whereas some relatively inefficient additives operate solely as UV screeners. Adequate UV protection was observed when small amounts (～0.01 wt-%) of effective stabilizers were concentrated in or on the surfaces of commercial films, and the remaining bulk of the film contained only a very low concentration (～0.01 wt-%) of uniformly blended additive. Previous attempts at demonstrating energy-transfer stabilization of the polymer are discussed with reference to the present data; it is concluded that effective polypropylene stabilizers probably operate by a combination of chromophore quenching, radical scavenging, and hydroperoxide decomposition.     

Degradation behavior of polyoxymethylene: Influence of different stabilizer packages

Stabilizer effects of two types (homopolymer and copolymer) of commercially available polyoxymethylenes containing two different stabilizer packages under various aging conditions have been studied by the application of thermogravimetric analysis coupled with mass spectrometry. Increasing yellowness during thermooxidative aging has been observed. Investigations of the melt volume rate have proved that the UV‐stabilized materials exhibit a higher increase in the melt volume rate after oven aging, which is caused by reactions of the additives, than the solely heat‐stabilized materials. The thermogravimetric analysis/mass spectrometry investigations have proved broad synergy effects between the heat‐ and UV‐stabilizer systems. The formation of chains with thermally stable end groups or of cyclic products proceeds during aging, particularly in the presence of UV stabilizers. This formation might be the result of intermolecular transacetalization reactions. The degradation behavior of UV‐irradiated homopolymer and copolymer samples has also been investigated. Oven storage and weathering cause comparable shifts in the derivative thermogravimetry traces, so similar damage reactions can be suggested. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Fundamental studies on solvent dyeing with tetrachloroethylene. III. Effect of water added to the solvent dyebath on the diffusion of disperse dyes in poly(ethylene terephthalate)

The diffusion and adsorption of disperse dyes on poly(ethylene terephthalate) (PET) from the tetrachloroethylene (TCE) dyebath were investigated by the method of cylindrical film roll when water was added to the TCE dyebath. The diffusion coefficients of three disperse dyes were increased with an increase in the addition of water to the TCE dyebath, and that of C.I. Disperse Violet 8 showed a peak. The solubilities of water in TCE in the absence and presence of disperse dye were measured at 90°C by Karl Fischer titration. The solubilities in TCE were 0.040 in the absence of dye and 0.041–0.045 g H₂O/100 g TCE in the presence of disperse dye. In the presence of Violet 8, the solubilities showed a peak with increasing addition of water. The effect of water addition on the diffusion coefficients was attributed to the dissolution of water in the TCE dyebath. The water dissolved in TCE brought about an additional swelling of PET swollen previously by TCE. No marked influence on the surface concentration of dye was observed by the water addition to TCE.     

Surface hardness and transparency of poly(methyl methacrylate)‐silica coat film derived from perhydropolysilazane

To prepare hard and transparent poly (methyl methacrylate)‐silica coat film on glass or polycarbonate substrates, poly(methyl methacrylate‐co‐2‐hydroxyethyl methacrylate) random copolymers and perhydropolysilazane (PHPS) were blended in solution. Then the solution was cast on the substrates. The grafting of PHPS onto 2‐hydroxyethyl methacrylate unit was analyzed by ¹H NMR spectroscopy. Surface hardness and transparency of the coat film were measured by nano‐indentation method and UV‐Vis spectroscopy, respectively. Surface hardness of coat film depended on the volume fraction of silica in the coat film, and reached 2.7 GPa when the volume fraction of silica was 76.4%. Transparency of the coat films prepared with PHPS was almost 100%, indicating that the coat film prepared with PHPS was highly transparent not only on glass substrate but also on the polycarbonate substrate. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

2‐oxo‐tetrahydrofuran‐3‐yl 9H‐carbazole‐9‐carbodithioate mediated reversible addition‐fragmentation chain transfer (RAFT) polymerization

The 2‐oxo‐tetrahydrofuran‐3‐yl 9H‐carbazole‐9‐carbodithioate (OTCC) mediated reversible addition‐fragmentation chain transfer (RAFT) polymerizations of styrene and methyl acrylate were investigated. The results showed that OTCC was an effective RAFT agent for the polymerizations of styrene and methyl acrylate. The polymerizations exhibited “living”/controlled characters. The resulting carbazole and 2‐oxo‐tetrahydrofuran‐3‐yl groups end‐labeled polymer exhibited stronger fluorescence in N, N‐dimethyl formamide, compared with those of OTCC under the same conditions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Novel poly(3,4‐dialkoxythiophene)s carrying 1,3,4‐oxadiazolyl‐biphenyl moieties: synthesis and nonlinear optical studies

Two new donor–acceptor types of polymer, poly{2‐(biphenyl‐4‐yl)‐5‐[3,4‐dialkoxy‐5‐(1,3,4‐oxadiazol‐2‐yl)thiophen‐2‐yl]‐1,3,4‐oxadiazole}s, were synthesized starting from 2,2′‐sulfanediyldiacetic acid and diethyl ethanedioate through multi‐step reactions. The polymerization was carried out via the polyhydrazide precursor route. The optical and charge‐transporting properties of the polymers were investigated using UV‐visible and fluorescence emission spectroscopic and cyclic voltammetric studies. The polymers showed bluish‐green fluorescence in solutions. The electrochemical band gaps of the polymers were determined to be 2.16 and 2.22 eV. The nonlinear optical properties of the polymers were investigated at 532 nm using the single‐beam Z‐scan technique with nanosecond laser pulses. The polymers showed strong optical limiting behaviour due to effective three‐photon absorption. The values of the three‐photon absorption coefficients for the polymers were found to be 9 × 10^?24 and 17 × 10^?24 m³ W^?2, which are comparable to those of good optical limiting materials. Copyright © 2010 Society of Chemical Industry     

Synthesis and characterization of titanium dioxide optical films by sol–gel processes

The main purpose of this study is to synthesize the front panel of monitor with a high refractive index optical film. Our experiment uses titanium dioxide nanoparticles mixed with methyl methacrylate (MMA), 2‐hydroxyethyl methacrylate (2‐HEMA), and tri(ethylene glycol) dimethacrylate (TEGDMA) of the wet type and economical sol–gel production process. Our product has a superior mechanical, thermal, and optical properties was demonstrated by Fourier transform infrared spectrum (FTIR), differential scanning calorimeter (DSC), thermogravimetric analysis (TGA), UV/visible spectrum, and Spectro Ellipsometer. In addition, we found the surface of the two series of thin film with the organic and inorganic high refractive index (TiO₂) mixed materials, has high transmittance for visible light above 90%, refractive index <1.65 and the hardness test 6H. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2271–2280, 2007     

Synthesis and characterization of light‐absorbing cyclopentadithiophene‐based donor–acceptor copolymers

Cyclopentadithiophene and benzothiadiazole based donor–acceptor polymers are fast emerging as the most promising class of materials for organic solar cells. Here we report on a series of Cyclopentadithiophene and benzothiadiazole based conjugated polymers, namely poly[4,7‐bis(4,4‐dioctyl‐4H‐cyclopenta[2,1‐b;3,4‐b′]dithiophene‐2‐yl)benzo[1,2,5]thiadiazole] (P1), poly[4,7‐bis(4,4‐dioctyl‐4H‐cyclopenta[2,1‐b;3,4‐b′]dithiophene‐2‐yl)benzo[1,2,5]thiadiazole‐alt‐9‐(heptadecan‐9‐yl)‐2,7‐bis(4,4,5,5‐tetramethyl)‐1,3,2‐dioxaborolan‐2‐yl)‐9H‐carbazole] (P2) and poly[4,7‐bis(4,4‐dioctyl‐4H‐cyclopenta[2,1‐b;3,4‐b′]dithiophene‐2‐yl)benzo[1,2,5]thiadiazole‐alt‐5,11‐bis(2‐hexyldecyl)‐3,9‐bis(4,4,5,5‐tetramethyl)‐1,3,2‐dioxaborolan‐2‐yl)‐5,11‐dihydroindolo[3,2‐b]carbazole] (P3), with alternating donor and acceptor units and discuss their photophysical and electrochemical properties. Stille coupling of 2‐tributylstannyl‐4,4‐dioctylcyclopenta[2,1‐b:3,4‐b′]dithiophene with 4,7‐dibromobenzo[1,2,5]thiadiazole generated the alternating donor–acceptor monomer 4,7‐bis(4,4‐dioctyl‐4H‐cyclopenta[2,1‐b;3,4‐b′]dithiophene‐2‐yl)benzo[1,2,5]thiadiazole (CPDT‐BT‐CPDT). Homopolymer P1 of CPDT‐BT‐CPDT was synthesized by oxidative polymerization using FeCl₃. Copolymers P2 and P3 were synthesized by palladium‐catalysed Suzuki polycondensation. The synthesized polymers showed good solubility in common organic solvents, and UV‐visible measurements showed that the absorption maxima of the polymers lie in the range 624 to 670 nm. The energy gaps of these polymers were found to lie in the range 1.29 to 1.50 eV. Gel permeation chromatography measurements against polystyrene standards showed the number‐average molecular weight to be in the range (2.2–6.0) × 10⁴ g mol^?1. Thermogravimetric analysis showed the polymers to possess high thermal stability. A preliminary study of photodiode devices prepared using polymers P1, P2 and P3 when blended with the PC₇₁BM electron acceptor found that P2 is the optimum chemical structure for pursuing further device optimization.© 2015 Society of Chemical Industry     

Synthesis and properties of optically clear silicone resin/epoxy resin hybrids

Optically clear silicone/epoxy hybrid resins were synthesized. The silicone resin (SiR) carrying Si? H, Si? CH?CH₂ and Si? OH groups was prepared by hydrolytic condensation. The blends of SiR and diglycidyl ether of hydrogenated bisphenol A (DGEHBA) were cured through platinum‐catalyzed hydrosilylation and aluminium acetylacetonate‐catalyzed polymerization. The curing process was studied using differential scanning calorimetry and rigid‐body pendulum rheometry. It was found that the ratio of SiR to DGEHBA plays a major role in the curing process. The Si? OH groups of SiR assist polymerization of DGEHBA, and react with the epoxy resin to prevent phase separation. The cured hybrid resins are single‐phase materials with a transmittance of about 87% at 400 nm for a thickness of 3 mm using air as reference. UV resistance and thermal stability of the hybrids are largely dependent on the composition. The adhesive strength of the SiRs can be significantly improved by a small fraction of DGEHBA, with a marginal influence on UV resistance. However, increasing the epoxy proportion has a marked negative influence on thermal stability. Compounding stabilizers, especially thermal stabilizers, are essential, in particular for high epoxy content, if the hybrids are to be used for high‐brightness light‐emitting diode packaging. Copyright © 2011 Society of Chemical Industry