Synergistic effect of hindered amine light stabilizers/ultraviolet absorbers on the plasticized PVC during photo-irradiation

Two kinds of piperidine derivatives including a low-molecular weight (Wt. 481, T770) and a high-molecular weight (Wt. 2000–3100, C944) hindered amine light stabilizers (HALS) are added singly or with ultraviolet absorbers (UVA) in combination to plasticized poly(vinyl chloride) (PVC) samples. Digital photos, color changes, attenuated total refection-Fourier transform infrared spectra (ATR-FTIR), and mechanical properties are obtained to investigate the photostable effect of the light stabilizers on the plasticized PVC after artificial aging. PVC samples with HALS perform well at the first 400 h of irradiation in color change, FTIR, and mechanical properties, but at the last 400 h the photostability decreases. Besides, C944 performs better than T770, because C944 is a high-molecular weight UV stabilizer and has good extraction resistance. Plasticized PVC samples with UVA resist discoloring and photooxidation from the photo-irradiation. Excellent synergism is observed between the combination of HALS and UVA. PVC with HALS/UVA performs better than PVC with HALS and PVC with UVA in color differences, FTIR, and mechanical properties. The synergism is due to the different stages of functions between HALS and UVA. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of the combination of a benzotriazole‐type ultraviolet absorber with thermal stabilizers on the photodegradation of poly(vinyl chloride)

The effect of the combination of a benzotriazole type of UV absorber (UV326) with different types of thermal stabilizers, including an organic calcium complex and an organotin mercaptide, on the photodegradation of poly(vinyl chloride) (PVC) was investigated by color difference measurements, UV‐vis spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and viscosity‐average molecular weight (M_η) determinations. Films of PVC containing 0.5 phr of UV326, with or without 2 phr of thermal stabilizer, were prepared by solution casting and subjected to accelerated UV weathering under xenon light with an irradiance of 0.51 W/(m² nm) at 65°C. The results revealed that both UV326 and the mixture of UV326 with the organic calcium complex displayed good performance in inhibiting the photodehydrochlorination and photooxidation of PVC. In contrast, the combination of UV326 and the methyltin mercaptide remarkably accelerated the discoloration of PVC when the irradiation time increased from 300 to 400 h because of the UV sensitivity of the organotin. However, carbonyl index data indicated that a hydrogen abstraction reaction did not take place between UV326 and the methyltin mercaptide, so that the photooxidation of the PVC film was prevented effectively during the whole period of exposure, a result which may be attributed to the strong steric hindrance effect of the tert‐butyl group at the 3‐position of the phenyl ring in UV326. The changes of M_η were in good accordance with the results obtained from other characterizations. J. VINYL ADDIT. TECHNOL., 2010. © 2010 Society of Plastics Engineers     

Influence of UV absorber on photodegradation processes of poly(vinyl chloride) with different average degrees of polymerization

The influence of UV absorber (Chimassorb81) on the photodegradation mechanism of different average degrees of polymerization (DP ) of poly (vinyl chloride) (PVC) with UV‐irradiation time was investigated by viscosity‐average molecular weight determination, UV‐vis spectroscopy, FTIR, contact angle measurement, and scanning electron microscopy (SEM). The PVC films with different DP (1000 and 3000), which contained 0.3 or 0.5 phr Chimassorb81, were prepared by solution casting. It was carried out by exposing specimens to xenon‐arc light source with a spectral irradiance of 0.68 W/(m² nm) at 63°C. It is found that the Chimassorb81 is efficient photostabilizer for PVC with different DP . Although the Chimassorb81 delays the photodegradation of PVC, it does not influence the photodegradation mechanisms of PVC with different DP . The main photodegradation reaction for the lower DP of PVC is dehydrochlorination in the initial stage of UV‐irradiation, and then the crosslinking and chain scission reactions occurred after long irradiation. However, the main reaction of the higher DP of PVC is not dehydrochlorination but crosslinking and chain scission in the initial stage of UV‐irradiation. The results of carbonyl index, C? Cl index, contact angle measurement, and SEM also show that the photostability of Chimassorb81 is more effective for the higher DP of PVC, especially in the presence of higher concentration of Chimassorb81. POLYM. ENG. SCI., 47:1480–1490, 2007. © 2007 Society of Plastics Engineers     

Photodegradation of polybenzimidazole/polyvinyl chloride composites and polybenzimidazole: Density functional theory and experimental study

In this study, density functional theory (DFT) and experimental study were conducted to investigate the photodegradation of PVC composites. The results indicate that chain crosslinking, chain scission, dehydrochlorination, and photooxidation are suppressed, while the tensile strength retention of PVC composite reaches a maximum with the incorporation of polybenzimidazole (PBI) and polyacrylic acid modified carbon black. The allyl group can obviously reduce Gibb's free energy (∆G) of PVC in attack by triplet state oxygen (³O₂), and photooxidation of PVC is accelerated in the presence of PBI due to the photogeneration of singlet state oxygen (¹O₂). Photodegradation of PBI was also studied by UV–vis spectroscopy and matrix-assisted laser desorption ionization time-of-flight mass spectroscopy, while the possible photodegradation pathways of PBI were proposed. The disappearance of UV-absorption of PBI in PVC matrix after 600 h UV-weathering is probably related to the byproducts and molecular properties.     

Different photodegradation processes of PVC with different average degrees of polymerization

The influence of ultraviolet (UV)‐irradiation on the photodegradation mechanism of different average degrees of polymerization (DP ) of poly(vinyl) chloride (PVC) with UV‐irradiation time was investigated by viscosity‐average molecular weight determination, UV‐vis spectroscopy, Fourier transform infrared (FTIR), thermogravimetric analysis (TGA), contact angle measurement, and scanning electron microscopy (SEM). PVC films with different DP (800, 1000, 1300, 3000) were prepared by solution casting. It was carried out exposing specimens to a xenon‐arc light source with a spectral irradiance of 0.68 W/(m² ·nm) at 63°C. It was found that the photodegradation mechanism of the lower DP of PVC (DP = 1000) was different from the higher DP of PVC (DP = 3000). This was because the lower DP of PVC was a homopolymer, while the higher DP of PVC was often produced by copolymerizing with a certain quantity of crosslinking agent (e.g., DAP and DAM). UV‐vis and FTIR spectroscopy studies provided some results concerning the structure of the irradiated PVC, and the carbonyl index and C? Cl index were induced to study the process of PVC photodegradation with different DP . TGA showed that the degradation temperatures of different weight loss increased with the irradiation time. The surface morphology of the irradiated polymer films with different DP was observed by contact angle measurement and SEM. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Online monitoring of the influence of the chemical structure of hindered amines on the hydrolysis of polycarbonate in a polycarbonate/poly(acrylonitrile–butadiene–styrene) blend by ultraviolet–visible spectroscopy

Without stabilization, polycarbonate (PC)/poly(acrylonitrile–butadiene–styrene) (ABS) blends are susceptible to a loss of mechanical properties after a few days of exposure to weathering conditions. ABS can be stabilized against terrestrial light by the use of hindered amines in combination with a UV absorber; such hindered amines cannot be used when PC is present in the polymer blend. The hydrolysis of PC is accelerated when a small amount of a hindered amine light stabilizer (HALS) is incorporated into the resin and is exposed to elevated temperatures. In this study, three different HALSs (Tinuvin 123, Tinuvin 770, and Tinuvin 765, Ciba, Basel, Switzerland) were used as UV stabilizers for PC/ABS blends, and their effects on the PC phase were observed with online ultraviolet–visible spectroscopy on extruded flat films. These stabilizers were compounded with the blends in a corotating twin‐screw extruder at 240°C. The molecular weight of the compounded samples was determined by gel permeation chromatography. The extent of degradation induced by the HALSs on the PC phase was found to be a function of its chemical structure. Tinuvin 123 with an amino ether functional group enhanced degradation in comparison with Tinuvin 770 and Tinuvin 765. Tinuvin 770, a secondary amine, was apt to be more reactive than Tinuvin 765, a tertiary amine, because less steric hindrance was experienced by the former. Accelerated aging of the compounded samples was performed. Decreased degradation was observed for the samples containing hindered amines; however, the HALSs alone were not effective in protecting the PC/ABS blends against harmful UV light. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of the combination of a benzophenone‐type ultraviolet absorber with thermal stabilizers on the photodegradation of poly(vinyl chloride)

The effect of the combination of a UV absorber (Chimassorb 81) with different types of thermal stabilizers, including an organic calcium complex and an organotin mercaptide, on the photodegradation of poly(vinyl chloride) (PVC) was investigated by color difference measurements, UV–Vis spectroscopy, Fourier‐transform infrared spectroscopy, thermogravimetric (TG) analysis, and viscosity‐average molecular weight determination. Films of PVC containing 0.5 phr of Chimassorb 81, with and without 2 phr of a thermal stabilizer, were prepared by solution casting. Then the accelerated UV weathering of the films was carried out under xenon light with an irradiance of 0.51 W/(m² · nm) at 65°C. The results showed that both Chimassorb 81 and the mixture of Chimassorb 81 with the organic calcium complex showed good behavior in inhibiting the photodehydrochlorination and photooxidation of PVC. In contrast, the combination of Chimassorb 81 and methyltin mercaptide significantly accelerated initial color development during the final 200 h of exposure because of the UV sensitivity of the organotin. Moreover, when Chimassorb 81 and the methyltin mercaptide were used together to stabilize PVC films, the expected antioxidant effect of the mixture was not observed, in contrast to the behavior found with other stabilized systems, perhaps because the Chimassorb 81 had been depleted by the methyltin mercaptide during the UV irradiation. The TG analysis revealed that ultraviolet irradiation had caused severe destruction of the PVC chains. However, addition of Chimassorb 81 or the combination of Chimassorb 81 with the organic calcium complex effectively prevented the destruction, as was demonstrated by changes in the activation energies for thermal degradation. J. VINYL ADDIT. TECHNOL., 2010. © 2010 Society of Plastics Engineers     

Effect of relatively nontoxic thermal stabilizers on photodegradation of poly(vinyl chloride)

The influence of relatively nontoxic thermal stabilizers including different types of organic calcium complex (Ca/Zn system of liquid stabilizers) and organotin on photodegradation of poly(vinyl chloride) (PVC) was investigated by color difference measurement, viscosity‐average molecular weight determination, UV–vis spectroscopy, Fourier transform infrared (FTIR), and thermogravimetric (TG) analysis. PVC films containing relatively nontoxic thermal stabilizers were prepared by solution casting and then exposed to xenon‐arc light source with the irradiance of 0.51 W/(m²·nm) at 65°C. Two major chain processes, photodehydrochlorination and photo‐oxidation, occur simultaneously during photodegradation of PVC. It has been confirmed by both color difference and UV–vis spectra that during the former 300 h of irradiation, organic calcium complex stabilizers retard photodehydrochlorination as well as initial color development of PVC films while organotin stabilizers remarkably accelerate photodehydrochlorination after 100 h. Relative carbonyl index (RCI) is first introduced to the analysis of FTIR results, which implies that organotin has a better ability to inhibit photo‐oxidation than organic calcium complex and ensures longer stabilization time. The antioxidation of mercaptan organotin has been observed because it is an effective decomposer of peroxides and hydroperoxides. TG analysis reveals that some unstable structures generated due to the irradiation of ultraviolet can easily split away off from PVC macromolecular backbones under relatively low temperature. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Effects of ultraviolet absorbers on the ultraviolet degradation of rice‐hull/high‐density polyethylene composites

In China, rice‐hull powder is widely used as a fiber component to reinforce polymers because of its ready availability and lower cost compared to wood fibers. However, an issue concerning these composites is their weathering durability. In this study, the effects of two ultraviolet absorbers (UVAs), UV‐326 and UV‐531, on the durability of rice‐hull/high‐density polyethylene (HDPE) composites were evaluated after the samples were exposed to UV‐accelerated weathering tests for up to 2000 h. All of the samples showed significant fading and color changes in exposed areas. X‐ray photoelectron spectroscopy and Fourier transform infrared spectroscopy were used to detect surface chemical changes. The results indicate that surface oxidation commenced immediately within the first 500 h of exposure for all of the samples. However, the control rice‐hull/HDPE composites underwent a greater degree of oxidation than those with the UVAs. Scanning electron microscopy revealed that the rice‐hull/HDPE composites degraded significantly upon accelerated UV aging, with dense cracking on the exposed surface. The UVAs provided effective protection for the rice‐hull/HDPE composites, and UV‐326 had a more positive effect on the color stability than UV‐531. The results reported herein serve to enhance our understanding of the efficiency of UV stabilizers in the protection of rice‐hull/HDPE composites against UV radiation, with a view toward improving their formulation. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Long-term weathering behavior of UV-curable clearcoats: Depth profiling of photooxidation,UVA, and HALS distributions

The long-term weathering performance of two UV-curable clearcoat systems was studied using in-plane microtomy in combination with infrared spectroscopy, UV spectroscopy, and ESR spectroscopy. Oxygen transport characteristics were also studied using the half-time method. The photooxidation versus depth profile was highly dependant on the presence of hindered amine light stabilizers (HALS) for both coating systems. Ultraviolet light absorbers (UVA) had little effect on the photooxidation profile. A photooxidation gradient was formed in both clearcoats due to a reduction in oxygen solubility when compared to standard thermoset clearcoats. This gradient was only seen in formulations not containing HALS. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, on October 27–29, 2004, in Chicago, IL.     

Transparent plasticised PVC film with ultraviolet and high-energy visible light shielding performance

In this paper, the ultraviolet (UV) absorbers and pigment yellow were added into the plasticised poly (vinyl chloride) (PVC) films for the purpose of improving the UV and high-energy visible light (HEV) shielding performance. The optical properties were investigated by a Ultraviolet-visible-near-infrared (UVPC) spectrophotometer and a transmission & haze meter. It was found that all the samples exhibited high transmittance and low haze. UV326 was more effective than UV531 as an UV absorber. Pigment yellow played a positive role in the optical properties. By a simple combination of 0.5?phr UV326 and 6?×?10^?3?phr pigment yellow, more than 80% optical transparency in the visible light range (400–800?nm) and 90% shielding efficiency of UV light (from 200 to 400?nm) were realised. Furthermore, the presence of pigment yellow in PVC matrix could effectively block HEV, and the average transmittance of HEV decreased with the increasing pigment yellow concentration.     

Photodegradation of multilayer films based on PET copolymers

An investigation was conducted on the effects of photodegradation of multilayer films based on PET copolymers. The films were composed by different layers with PET, PET/PEN, and PET/PEI copolymers with a total thickness of 23 μm. The films produced by coextrusion followed by a biaxial orientation in an industrial equipment were exposed to the ultraviolet radiation in the laboratory for periods of up to 600 h. The samples were investigated by FTIR‐ATR, UV/visible spectroscopy, fluorescence spectroscopy, size exclusion chromatography, mechanical properties, and scanning electron microscopy. The results showed that the photooxidation is concentrated at the surface layers and that coextruded films were more sensitive to the UV radiation effects. The deterioration in mechanical properties with exposure and the fracture behavior were shown to be consistent with the amount of degradation that occurred in the films. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

受阻胺光稳定剂对PVC的光稳定作用

传统上,聚氯乙烯（ＰＶＣ）防光老化主要用于二苯甲酮类光稳定体系,一般认为在聚烯烃中应用效果较好的受阻胺光稳定剂,不适用于ＰＶＣ体系,将受阻胺光稳定剂试用于ＰＶＣ薄膜,结果表明,该光稳定剂用于ＰＶＣ中,其光,热稳定效果与二苯甲酮类紫外光稳定剂相近,为使ＰＶＣ具有防尘功能的丙烯酸酯类聚合物表面涂层,对ＰＶＣ的紫外光稳定有益。     

Influence of different types of UV absorber/UV stabilizer combination on the photodegradation of PC/ABS blend

The polycarbonate/poly(acrylonitrile butadiene styrene) blends, (PC/ABS), are mainly degraded by sunlight known as photodegradation when exposed to outdoor conditions. It is the ultraviolet (UV) radiation that is responsible for the degradation of the blend. To stabilize against the harmful UV radiation and to scavenge the radical species which arise from UV or thermally induced degradation of the PC or the ABS, UV absorbers, and UV stabilizers are used. In this article three different UV absorbers namely, Tinuvin 1577—hydroxyphenyl triazine type, Cyasorb 5411—benzotriazole type, Uvinul 3030—cyanoacrylate type, and two different UV stabilizers, Tinuvin 765—monomeric hindered amine type, Tinuvin 622—oligomeric hindered amine were compounded in different combinations with PC/ABS blend at 240°C using a twin screw extruder. Accelerated aging of the compounded sample was done by Atlas Suntest apparatus. The photodegradation studies were done using UV–vis, attenuated total reflectance Fourier transform infrared (ATR‐FTIR) spectroscopy, and Yellowing index measurement. The molecular weight of the compounded sample before aging was determined by gel permeation chromatography (GPC). It was found that samples protected with hydroxyphenyl triazine type UV absorber and oligomeric hindered amine show the best result for decreasing the degradation products, oxidation rate, and yellowing of the PC/ABS blend. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synergistic effect of hindered amine light stabilizers/ultraviolet absorbers on the polyvinyl chloride/powder nitrile rubber blends during photodegradation

The photostability of hindered amine light stabilizer (HALS) and ultraviolet absorber (UVA) on the blends of plasticized poly (vinyl chloride) (PVC) and powder nitrile rubber (NBR) has been studied with a Xenon Test Chamber. The digital photos, color differences, attenuated total refection‐Fourier transform infrared (ATR‐FTIR) spectra and mechanical properties of the blends have been determined. HALS combined with UVA effectively protects PVC/NBR blends from yellowing and restrains the decrease of elongation at break of the blends. The synergistic phenomenon is ascribed to the different photostable mechanisms of HALS and UVA at different photo aging stages. The color of PVC/NBR control sample quickly changes into yellow at the first 400 h of irradiation, due to the polyenes structures that induced by the double bonds of butadiene in NBR. From 400 to 800 h, crosslinking dominates and the amount of polyenes decreases, resulting into the decrease of color change. At the early stage of irradiation, chain‐scission of polymer takes the predominant place, and the tensile strength decreases. But during the latter stage, crosslinking takes the predominant place and the tensile strength increases slightly. HALS and UVA have a little effect on the maintaining of elongation at break of PVC/NBR blends. POLYM. ENG. SCI., 2013. © 2013 Society of Plastics Engineers     

硬脂酸铁加速LDPE膜光降解作用的研究

本文合成了硬脂酸铁(FeSt_s),用等离子体发射光谱、热分析仪、紫外光谱、红外光谱等分析手段进行了表征,研究了它对光氧化低密度聚乙烯(LDPE)薄膜羰基指数和粘均分子量的影响,并探讨了它的作用机理.结果表明:在LDPE膜中加入0.1%～0.3?St_s,即可控制可分解LDPE膜的使用寿命;羧酸铁在光解LDPE膜中的敏化活性依次递减如下:硬脂酸铁>月桂酸铁>辛酸铁;月桂酸铁和辛酸铁的光敏催化活性较低;二苯甲酮不是LDPE的有效光敏剂,能阻滞LDPE的光降解作用;高温下UV光降解LDPE膜的光降解速率高于低温下的光降解速率.     

Studies of the solid-state thermal degradation of PVC. I. Autocatalysis by hydrogen chloride

The thermal degradation of virgin and HCI-treated PVC in powder form, as well as of PVC films of different thicknesses, has been studied as a function of time and temperature. The rate of dehydrochlorination was determined conductimetrically and from the polyene sequence distributions as obtained by UV spectroscopy. Increases in the rate of dehydrochlorination, ranging between 30 and 45%, were observed at all temperatures for the samples pretreated with HCI, while the corresponding activation energies were found to be lower by about 20%. For the PVC films, the rate increased with thickness, i.e., with longer residence time of evolved HCI within the sample. The results offer insight regarding the autocatalytic role of evolved HCI.     

Characterization of new hindered amine light stabilizers

New polymerizable urethane functional monomers containing hindered amine (III, III′) and their copolymers with styrene (S) and methyl methacrylate (MMA) are characterized and tested as hindered amine light stabilizers (HALS). Experimental results indicated that the monomers possess high photostabilizing effectiveness comparable to that of Tinuvin 770 and Tinuvin 765. Their copolymers with S and MMA showed lower photostabilizing effectiveness mainly due to the low hindered amine content in the copolymers. The copolymers, however, showed very high resistance to liquid extraction. UV and ESR analyses indicate that the photostabilizing mechanism of these HALS is through the scavenging action of nitroxyl radicals formed from degradation of the substrate polymer. © 1993 John Wiley & Sons, Inc.     

Improved Ultraviolet (UV) Radiation Stability of the Polypropylene (PP) Films of Woven Jumbo Bags for Outdoor Applications

Several formulations were developed with polypropylene (PP) in combination with antioxidants, calcium stearate, hindered amine light stabilizers (HALS) and ultraviolet light absorber (UVA) for making woven jumbo bags, which will be capable of carrying a load of two tons of materials in outdoor conditions. Thin films of these formulations were extruded followed by stretching to improve mechanical properties. Both stretched and un-stretched PP films were subjected to severe accelerated weathering by ultraviolet (UV) radiation for various periods and it was observed that un-stretched films reached 50% retention of tensile strength (TS) within 500 hours of exposure, while stretched films (tapes) did not reach 50% TS retention even after 10,500 hours of the exposure indicating an improved UV stability of the stretched films of PP.     

In‐line analysis of the influence of monomeric and oligomeric hindered amine on the hydrolysis of polycarbonate in a PC/ABS blend

The polycarbonate/polyacrylonitrile butadiene styrene (PC/ABS) blends lose mechanical properties when exposed to outdoor conditions. This is due to the ultraviolet (UV) induced photo‐oxidation of the PC phase and the polybutadiene portion of the ABS. It is known that ABS can be stabilised against terrestrial light by the use of hindered amine in combination with a UV absorber. However, such hindered amine cannot be used when PC is present in a multi component polymer blend. The hydrolysis of PC is accelerated when a small amount of hindered amine light stabilisers (HALS) is incorporated in the resin and is exposed to elevated temperature. In this article the effect of monomeric and oligomeric hindered amine on the hydrolysis of PC during the compounding of PC/ABS blend in a twin screw extruder at 240°C is observed by means of in‐line UV‐vis spectroscopy. Tinuvin 765 was used as monomeric hindered amine and Tinuvin 622 as oligomeric hindered amine. The molecular weight of the compounded sample was determined by gel permeation chromatography (GPC) and the rheological properties were observed using an online viscometer. It was found that the extent of hydrolysis induced by the oligomeric hindered amine is less compared to monomeric amine. It was also observed that polymeric hindered amine imparts better dispersion of the ABS phase into the polymer blend. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010