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Polymers, Volume 7, Issue 8 (August 2015) – 13 articles

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1680 KiB  
Article
Controllable Direct-Writing of Serpentine Micro/Nano Structures via Low Voltage Electrospinning
by Feiyu Fang, Xin Chen, Zefeng Du, Ziming Zhu, Xindu Chen, Han Wang and Peixuan Wu
Polymers 2015, 7(8), 1577-1586; https://doi.org/10.3390/polym7081471 - 24 Aug 2015
Cited by 21 | Viewed by 7053
Abstract
Micro/nanofibers prepared by direct-writing using an electrospinning (ES) technique have drawn more attention recently owing to their intriguing physical properties and great potential as building blocks for micro/nanoscale devices. In this work, a wavy direct-writing (WDW) process was developed to directly write serpentine [...] Read more.
Micro/nanofibers prepared by direct-writing using an electrospinning (ES) technique have drawn more attention recently owing to their intriguing physical properties and great potential as building blocks for micro/nanoscale devices. In this work, a wavy direct-writing (WDW) process was developed to directly write serpentine micro/nano structures suitable for the fabrication of micro devices. This fabrication ability will realize the application of electrospun-nanofiber-based wiring of structural and functional components in microelectronics, MEMS, sensor, and micro optoelectronics devices, and, especially, paves the way for the application of electrospinning in printing serpentine interconnector of large-area organic stretchable electronics. Full article
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1927 KiB  
Article
Study on the Mechanical Properties of Stay Cable HDPE Sheathing Fatigue in Dynamic Bridge Environments
by Danhui Dan, Limin Sun, Yanheng Guo and Wei Cheng
Polymers 2015, 7(8), 1564-1576; https://doi.org/10.3390/polym7081470 - 20 Aug 2015
Cited by 11 | Viewed by 6764
Abstract
As the main force-bearing component of a cable-stayed bridge, a durable stay cable is paramount to the safety and durability of the entire bridge. High-density polyethylene (HDPE) sheathing is the main protective component of a stay cable and is the key to insuring [...] Read more.
As the main force-bearing component of a cable-stayed bridge, a durable stay cable is paramount to the safety and durability of the entire bridge. High-density polyethylene (HDPE) sheathing is the main protective component of a stay cable and is the key to insuring cable durability. To address the issue of HDPE sheathing fracture on service, strain level data for in-service, HDPE bridge cable sheathing was used in this study as the basis for HDPE material aging and fatigue testing. A fatigue yield phenomenon with a yield platform on the hysteresis curve of the fatigue cycles is observed by the fatigue test. The parameters to describe this phenomenon are proposed and defined in this paper. A preliminary examination of the relationship between these parameters and the factors, such as the number of cycles, the strain amplitude, and strain rate, are presented. Based on the results obtained, it is suggested that the condition of fatigue yield of HDPE sheathing be defined as the fatigue durability limit state for the purposes of durability design, assessment, and protection of cable-stayed bridges. Full article
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2559 KiB  
Article
Effect of Meltable Triazine-DOPO Additive on Rheological, Mechanical, and Flammability Properties of PA6
by Irina Butnaru, María P. Fernández-Ronco, Justyna Czech-Polak, Maciej Heneczkowski, Maria Bruma and Sabyasachi Gaan
Polymers 2015, 7(8), 1541-1563; https://doi.org/10.3390/polym7081469 - 17 Aug 2015
Cited by 52 | Viewed by 9789
Abstract
Through a straightforward approach, a new meltable, halogen-free, nitrogen-phosphorus-based flame retardant (FR), 6-(2-(4,6-diamino-1,3,5-triazin-2-yl)ethyl) dibenzo[c,e][1,2]oxaphosphinine 6-oxide (DTE-DOPO) was synthesized and incorporated in polyamide 6 (PA6). It was proved that a very low phosphorus content of 1.46 wt% for DTE-DOPO additive [...] Read more.
Through a straightforward approach, a new meltable, halogen-free, nitrogen-phosphorus-based flame retardant (FR), 6-(2-(4,6-diamino-1,3,5-triazin-2-yl)ethyl) dibenzo[c,e][1,2]oxaphosphinine 6-oxide (DTE-DOPO) was synthesized and incorporated in polyamide 6 (PA6). It was proved that a very low phosphorus content of 1.46 wt% for DTE-DOPO additive improved the flame retardancy of PA6, leading to a non-flammable material. The performance of the new additive was compared to that of the commercially-available Exolit® OP 1230. The PA6 formulations were evaluated by measuring the rheological, mechanical, and flammability behavior. Using compounding by melt extrusion, 17 wt% additives was introduced into PA6 matrix and the corresponding formulations were characterized. The results evidenced a higher homogeneity of DTE-DOPO with PA6, a high thermal stability with a catalyzing decomposition effect on PA6 caused by the presence of the new developed FR, enhanced elasticity for the PA6/DTE-DOPO formulation and a V0 rating for both formulations. Thermal and fire analysis indicated a primary gas-phase activity, combined with a complete suppression of the self-sustained burning for the PA6/DTE-DOPO formulation. Full article
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4710 KiB  
Article
Thermal Oxidation of Polyolefins by Mild Pro-Oxidant Additives Based on Iron Carboxylates and Lipophilic Amines: Degradability in the Absence of Light and Effect on the Adhesion to Paperboard
by Tuan-Anh Nguyen, Øyvind Weiby Gregersen and Ferdinand Männle
Polymers 2015, 7(8), 1522-1540; https://doi.org/10.3390/polym7081468 - 17 Aug 2015
Cited by 15 | Viewed by 8831
Abstract
Marine and inland pollution by non-degradable plastic bags and other plastic articles is a topic of great concern. Natural degradation processes based on oxidation of plastic pollutants could possibly contribute to limit the extent of pollution. Thermal degradation of polyolefins in the absence [...] Read more.
Marine and inland pollution by non-degradable plastic bags and other plastic articles is a topic of great concern. Natural degradation processes based on oxidation of plastic pollutants could possibly contribute to limit the extent of pollution. Thermal degradation of polyolefins in the absence of light by non-polluting pro-oxidants has not been presented before. In this study, we show that two amines, stearyl amine and [(3-(11-aminoundecanoyl) amino) propane-1-] silsesquioxane (amino-POSS) in combination with ferric stearate (FeSt3) tremendously accelerate the thermal oxidation of polyolefins compared with reference samples. Both amines and FeSt3 are to a large extent based on renewable resources. Polyethylene and polypropylene samples containing less than 100 ppm of iron and 1% of amine were extremely brittle after 10 days in a circulation oven in the absence of light. No significant degradation could be seen with samples containing iron but no amine. In a different application, the initial oxidation of polyethylene can be used in order to increase its adhesion to cardboard. Excellent adhesion between polyethylene and cardboard is important for liquid packaging based on renewable resources. Amino-POSS has been chosen for food packaging applications due to its expected lower leakage from polyethylene (PE) compared with stearyl amine. Film samples of PE/amino-POSS/FeSt3 blends were partly oxidized in a circulation oven. The oxidation was documented by increased carbonyl index (CI) and melt flow index (MFI). The limited extent of oxidation has been proved by unchanged tensile strength and only moderate changes in elongation at break when compared to reference polyethylene films containing no FeSt3 or amino-POSS. The PE/amino-POSS/FeSt3 blends were compression moulded to paperboard. The adhesion of non-aged blends to paperboard decreased with increasing amino-POSS content which is in good compliance with an earlier reported lubricant effect of high amounts of POSS in PE. Thermal ageing of PE/amino-POSS/FeSt3 films prior to coating however led to a significant increase in adhesion. Improved physical interlocking due to increased MFI and interaction between C=O of the blends and OH of paperboard can explain the adhesion improvement. The films were not brittle after thermal ageing, which makes their use in industrial packaging feasible. A mechanism explaining the role of amines during thermal oxidation of polyolefins in the presence of iron is proposed. Full article
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1202 KiB  
Article
Effect of Molar Mass and Water Solubility of Incorporated Molecules on the Degradation Profile of the Triblock Copolymer Delivery System
by Mayura Oak, Rhishikesh Mandke, Sushant Lakkadwala, Lindsey Lipp and Jagdish Singh
Polymers 2015, 7(8), 1510-1521; https://doi.org/10.3390/polym7081467 - 14 Aug 2015
Cited by 10 | Viewed by 5844
Abstract
The purpose of this study was to investigate the effects of size and type of incorporated model molecules on the polymer degradation and release profile from thermosensitive triblock copolymer based controlled delivery systems. In vitro release of the incorporated molecules demonstrated slow release [...] Read more.
The purpose of this study was to investigate the effects of size and type of incorporated model molecules on the polymer degradation and release profile from thermosensitive triblock copolymer based controlled delivery systems. In vitro release of the incorporated molecules demonstrated slow release for risperidone (molecular weight (Mw) = 410.48 Da; partition coefficient (Ko/w) = 3.49), while bovine serum albumin (BSA) (Mw = ~66,400 Da; Ko/w = 0.007) and insulin (Mw = 5808 Da; Ko/w = 0.02) showed initial burst release followed by controlled release. The proton NMR, Gel Permeation Chromatography, and Cryo-SEM studies suggest that the size and partition coefficient of incorporated molecules influence the pore size, polymer degradation, and their release. In spite of using a similar polymer delivery system the polymer degradation rate and drug release notably differ for these model molecules. Therefore, size and oil-water partition coefficient are important factors for designing the controlled release formulation of therapeutics from triblock copolymer based delivery systems. Full article
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2434 KiB  
Article
Roughening Conjugated Polymer Surface for Enhancing the Charge Collection Efficiency of Sequentially Deposited Polymer/Fullerene Photovoltaics
by Yoonhee Jang, Ji-Won Seo, Jeesoo Seok, Jung-Yong Lee and Kyungkon Kim
Polymers 2015, 7(8), 1497-1509; https://doi.org/10.3390/polym7081466 - 13 Aug 2015
Cited by 11 | Viewed by 6449
Abstract
A method that enables the formation of a rough nano-scale surface for conjugated polymers is developed through the utilization of a polymer chain ordering agent (OA). 1-Chloronaphthalene (1-CN) is used as the OA for the poly(3-hexylthiophene-2,5-diyl) (P3HT) layer. The addition of 1-CN to [...] Read more.
A method that enables the formation of a rough nano-scale surface for conjugated polymers is developed through the utilization of a polymer chain ordering agent (OA). 1-Chloronaphthalene (1-CN) is used as the OA for the poly(3-hexylthiophene-2,5-diyl) (P3HT) layer. The addition of 1-CN to the P3HT solution improves the chain ordering of the P3HT during the film formation process and increases the surface roughness of the P3HT film compared to the film prepared without 1-CN. The roughened surface of the P3HT film is utilized to construct a P3HT/fullerene bilayer organic photovoltaic (OPV) by sequential solution deposition (SqSD) without thermal annealing process. The power conversion efficiency (PCE) of the SqSD-processed OPV utilizing roughened P3HT layer is 25% higher than that utilizing a plain P3HT layer. It is revealed that the roughened surface of the P3HT increases the heterojunction area at the P3HT/fullerene interface and this resulted in improved internal charge collection efficiency, as well as light absorption efficiency. This method proposes a novel way to improve the PCE of the SqSD-processed OPV, which can be applied for OPV utilizing low band gap polymers. In addition, this method allows for the reassessment of polymers, which have shown insufficient performance in the BSD process. Full article
(This article belongs to the Special Issue Organic Photovoltaics)
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9208 KiB  
Article
Disposal Options of Bamboo Fabric-Reinforced Poly(Lactic) Acid Composites for Sustainable Packaging: Biodegradability and Recyclability
by M.R. Nurul Fazita, Krishnan Jayaraman, Debes Bhattacharyya, Md. Sohrab Hossain, M.K. Mohamad Haafiz and Abdul Khalil H.P.S.
Polymers 2015, 7(8), 1476-1496; https://doi.org/10.3390/polym7081465 - 13 Aug 2015
Cited by 44 | Viewed by 10751
Abstract
The present study was conducted to determine the recyclability and biodegradability of bamboo fabric-reinforced poly(lactic) acid (BF-PLA) composites for sustainable packaging. BF-PLA composite was recycled through the granulation, extrusion, pelletization and injection processes. Subsequently, mechanical properties (tensile, flexural and impact strength), thermal stability [...] Read more.
The present study was conducted to determine the recyclability and biodegradability of bamboo fabric-reinforced poly(lactic) acid (BF-PLA) composites for sustainable packaging. BF-PLA composite was recycled through the granulation, extrusion, pelletization and injection processes. Subsequently, mechanical properties (tensile, flexural and impact strength), thermal stability and the morphological appearance of recycled BF-PLA composites were determined and compared to BF-PLA composite (initial materials) and virgin PLA. It was observed that the BF-PLA composites had the adequate mechanical rigidity and thermal stability to be recycled and reused. Moreover, the biodegradability of BF-PLA composite was evaluated in controlled and real composting conditions, and the rate of biodegradability of BF-PLA composites was compared to the virgin PLA. Morphological and thermal characteristics of the biodegradable BF-PLA and virgin PLA were obtained by using environment scanning electron microscopy (ESEM) and differential scanning calorimetry (DSC), respectively. The first order decay rate was found to be 0.0278 and 0.0151 day−1 in a controlled composting condition and 0.0008 and 0.0009 day−1 in real composting conditions for virgin PLA and BF-PLA composite, respectively. Results indicate that the reinforcement of bamboo fabric in PLA matrix minimizes the degradation rate of BF-PLA composite. Thus, BF-PLA composite has the potential to be used in product packaging for providing sustainable packaging. Full article
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2734 KiB  
Article
Synthesis of Antibacterial Silver–Poly(ɛ-caprolactone)-Methacrylic Acid Graft Copolymer Nanofibers and Their Evaluation as Potential Wound Dressing
by Mohammed A. Al-Omair
Polymers 2015, 7(8), 1464-1475; https://doi.org/10.3390/polym7081464 - 12 Aug 2015
Cited by 18 | Viewed by 5266
Abstract
Electrospun polycaprolacyone/polymethacrylic acid graft copolymer nanofibers (PCL/MAA) containing silver nanoparticles (AgNPs) were synthesized for effective wound disinfection. Surface morphology, AgNPs content, water uptake of electrospun PCL/MAA graft copolymer nanofibers without and with AgNPs, and levels of AgNPs leaching from the nanofibers in water [...] Read more.
Electrospun polycaprolacyone/polymethacrylic acid graft copolymer nanofibers (PCL/MAA) containing silver nanoparticles (AgNPs) were synthesized for effective wound disinfection. Surface morphology, AgNPs content, water uptake of electrospun PCL/MAA graft copolymer nanofibers without and with AgNPs, and levels of AgNPs leaching from the nanofibers in water as well as antimicrobial efficacy were studied. Scanning electron microscope images revealed that AgNPs dispersed well in PCL/MAA copolymer nanofibers with mean fiber diameters in the range of 200–579 nm and the fiber uniformity and diameter were not affected by the AgNPs. TEM images showed that AgNPs are present in/on the electrospun PCL/MAA graft copolymer nanofibers. The diameter of the electrospun nanofibers containing AgNPs was in the range of 200–579 nm, however, the diameter of AgNPs was within the range of 20–50 nm and AgNPs were observed to be spherical in shape. The PCL/MAA copolymer nanofibers showed a good hydrophilic property and the nanofibers containing AgNPs had excellent antimicrobial activity against the Gram-negative bacteria Escherichia coli and Pseudomonas aeruginosa, and against the Gram-positive bacteria Bacillus thuringiensis and Staphylococcus aureus, with a clear inhibition zone with a diameter between 22 and 53 mm. Moreover, electrospun PCL/MAA copolymer nanofibers sustained the release of AgNPs into water over 72 h. Full article
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5541 KiB  
Article
Preparation and Characterization of Polyvinylidene Fluoride/Graphene Superhydrophobic Fibrous Films
by Rasoul Moradi, Javad Karimi-Sabet, Mojtaba Shariaty-Niassar and Mohammad A. Koochaki
Polymers 2015, 7(8), 1444-1463; https://doi.org/10.3390/polym7081444 - 06 Aug 2015
Cited by 116 | Viewed by 11121
Abstract
A new strategy to induce superhydrophobicity via introducing hierarchical structure into the polyvinylidene fluoride (PVDF) film was explored in this study. For this purpose nanofibrous composite films were prepared by electrospinning of PVDF and PVDF/graphene blend solution as the main precursors to produce [...] Read more.
A new strategy to induce superhydrophobicity via introducing hierarchical structure into the polyvinylidene fluoride (PVDF) film was explored in this study. For this purpose nanofibrous composite films were prepared by electrospinning of PVDF and PVDF/graphene blend solution as the main precursors to produce a net-like structure. Various spectroscopy and microscopy methods in combination with crystallographic and wettability tests were used to evaluate the characteristics of the synthesized films. Mechanical properties have been studied using a universal stress-strain test. The results show that the properties of the PVDF nanofibrous film are improved by compositing with graphene. The incorporation of graphene flakes into the fibrous polymer matrix changes the morphology, enhances the surface roughness, and improves the hydrophobicity by inducing a morphological hierarchy. Superhydrophobicity with the water contact angle of about 160° can be achieved for the PVDF/graphene electrospun nanocomposite film in comparison to PVDF pristine film. Full article
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3022 KiB  
Article
Stable Poly(methacrylic acid) Brush Decorated Silica Nano-Particles by ARGET ATRP for Bioconjugation
by Marcello Iacono and Andreas Heise
Polymers 2015, 7(8), 1427-1443; https://doi.org/10.3390/polym7081427 - 06 Aug 2015
Cited by 12 | Viewed by 8083
Abstract
The synthesis of polymer brush decorated silica nano-particles is demonstrated by activator regeneration by electron transfer atom transfer radical polymerization (ARGET ATRP) grafting of poly(tert-butyl methacrylate). ATRP initiator decorated silica nano-particles were obtained using a novel trimethylsiloxane derivatised ATRP initiator obtained [...] Read more.
The synthesis of polymer brush decorated silica nano-particles is demonstrated by activator regeneration by electron transfer atom transfer radical polymerization (ARGET ATRP) grafting of poly(tert-butyl methacrylate). ATRP initiator decorated silica nano-particles were obtained using a novel trimethylsiloxane derivatised ATRP initiator obtained by click chemistry. Comparison of de-grafted polymers with polymer obtained from a sacrificial initiator demonstrated good agreement up to 55% monomer conversion. Subsequent mild deprotection of the tert-butyl ester groups using phosphoric acid yielded highly colloidal and pH stable hydrophilic nano-particles comprising approximately 50% methacrylic acid groups. The successful bio-conjugation was achieved by immobilization of Horseradish Peroxidase to the polymer brush decorated nano-particles and the enzyme activity demonstrated in a conversion of o-phenylene diamine dihydrochloride assay. Full article
(This article belongs to the Collection Silicon-Containing Polymeric Materials)
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1777 KiB  
Article
Interdiffusion and Spinodal Decomposition in Electrically Conducting Polymer Blends
by Antti Takala, Päivi Takala, Jukka Seppälä and Kalle Levon
Polymers 2015, 7(8), 1410-1426; https://doi.org/10.3390/polym7081410 - 04 Aug 2015
Cited by 2 | Viewed by 5618
Abstract
The impact of phase morphology in electrically conducting polymer composites has become essential for the efficiency of the various functional applications, in which the continuity of the electroactive paths in multicomponent systems is essential. For instance in bulk heterojunction organic solar cells, where [...] Read more.
The impact of phase morphology in electrically conducting polymer composites has become essential for the efficiency of the various functional applications, in which the continuity of the electroactive paths in multicomponent systems is essential. For instance in bulk heterojunction organic solar cells, where the light-induced electron transfer through photon absorption creating excitons (electron-hole pairs), the control of diffusion of the spatially localized excitons and their dissociation at the interface and the effective collection of holes and electrons, all depend on the surface area, domain sizes, and connectivity in these organic semiconductor blends. We have used a model semiconductor polymer blend with defined miscibility to investigate the phase separation kinetics and the formation of connected pathways. Temperature jump experiments were applied from a miscible region of semiconducting poly(alkylthiophene) (PAT) blends with ethylenevinylacetate-elastomers (EVA) and the kinetics at the early stages of phase separation were evaluated in order to establish bicontinuous phase morphology via spinodal decomposition. The diffusion in the blend was followed by two methods: first during a miscible phase separating into two phases: from the measurement of the spinodal decomposition. Secondly the diffusion was measured by monitoring the interdiffusion of PAT film into the EVA film at elected temperatures and eventually compared the temperature dependent diffusion characteristics. With this first quantitative evaluation of the spinodal decomposition as well as the interdiffusion in conducting polymer blends, we show that a systematic control of the phase separation kinetics in a polymer blend with one of the components being electrically conducting polymer can be used to optimize the morphology. Full article
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2877 KiB  
Article
Synthesis of High Performance Cyclic Olefin Polymers (COPs) with Ester Group via Ring-Opening Metathesis Polymerization
by Jing Cui, Ji-Xing Yang, Yan-Guo Li and Yue-Sheng Li
Polymers 2015, 7(8), 1389-1409; https://doi.org/10.3390/polym7081389 - 04 Aug 2015
Cited by 24 | Viewed by 11909
Abstract
Novel ester group functionalized cyclic olefin polymers (COPs) with high glass transition temperature, high transparency, good mechanical performance and excellent film forming ability have been achieved in this work via efficient ring-opening metathesis copolymerization of exo-1,4,4a,9,9a,10-hexahydro-9,10(1′,2′)-benzeno-l,4-methanoanthracene (HBM) and comonomers (5-norbornene-2-yl methylacetate (NMA), [...] Read more.
Novel ester group functionalized cyclic olefin polymers (COPs) with high glass transition temperature, high transparency, good mechanical performance and excellent film forming ability have been achieved in this work via efficient ring-opening metathesis copolymerization of exo-1,4,4a,9,9a,10-hexahydro-9,10(1′,2′)-benzeno-l,4-methanoanthracene (HBM) and comonomers (5-norbornene-2-yl methylacetate (NMA), 5-norbornene-2-yl methyl 2-ethylhexanoate (NME) or 5-norbornene-2-yl methyldodecanoate (NMD)) utilizing the Grubbs first generation catalyst, Ru(CHPh)(Cl)2(PCy3)2 (Cy = cyclohexyl, G1), followed by hydrogenation of double bonds in the main chain. The fully hydrogenated copolymers were characterized by nuclear magnetic resonance, FT-IR spectroscopy analysis, gel permeation chromatography, and thermo gravimetric analysis. Differential scanning calorimetry curves showed that the glass transition temperatures (Tg) linearly decreased with the increasing of comonomers content, which was easily controlled by changing feed ratios of HBM and comonomers. Static water contact angles tests indicate that hydrophilicity of copolymers can also be modulated by changing the comonomers incorporation. Additionally, the mechanical performances of copolymers were also investigated. Full article
(This article belongs to the Special Issue Metal-Mediated Polymer Synthesis)
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1327 KiB  
Article
Transparent Heat-Resistant PMMA Copolymers for Packing Light-Emitting Diode Materials
by Shu-Ling Yeh, Chao-Yuan Zhu and Shiao-Wei Kuo
Polymers 2015, 7(8), 1379-1388; https://doi.org/10.3390/polym7081379 - 29 Jul 2015
Cited by 29 | Viewed by 7760
Abstract
Transparent and heat-resistant poly(methyl methacrylate) copolymers were synthesized by bulk polymerizing methyl methacrylate (MMA), isobornyl methacrylate (IBMA), and methacrylamide (MAA) monomers. Copolymerization was performed using a chain transfer agent to investigate the molecular weight changes of these copolymers, which exhibited advantages including a [...] Read more.
Transparent and heat-resistant poly(methyl methacrylate) copolymers were synthesized by bulk polymerizing methyl methacrylate (MMA), isobornyl methacrylate (IBMA), and methacrylamide (MAA) monomers. Copolymerization was performed using a chain transfer agent to investigate the molecular weight changes of these copolymers, which exhibited advantages including a low molecular weight distribution, excellent optical properties, high transparency, high glass transition temperature, low moisture absorption, and pellets that can be readily mass produced by using extrusion or jet injection for packing light-emitting diode materials. Full article
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