Polyolefin degradation
Marzieh Alidadi-Shamsabadi; Shirin Shokoohi; Mahnaz Shahzamani; Homa Abbasian-Peykani
Abstract
In this work, the photo-aging behavior of high impact polystyrene (HIPS), polystyrene/ethylene propylene diene monomer (PS/EPDM) binary blends, and compatibilized polystyrene/ethylene propylene diene monomer/ polyamide 6 (PS/EPDM/PA6) ternary blends was studied and compared together. Photo-degradation ...
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In this work, the photo-aging behavior of high impact polystyrene (HIPS), polystyrene/ethylene propylene diene monomer (PS/EPDM) binary blends, and compatibilized polystyrene/ethylene propylene diene monomer/ polyamide 6 (PS/EPDM/PA6) ternary blends was studied and compared together. Photo-degradation of polymer blends faces considerable challenges, because a polymer blend is a compound of multiple components with particular interactions and its components may function as degrading or stabilizing agents. Photo-aging generally can cause changes in the color and mechanical properties of polymer compounds. Attenuated total reflection Fourier transform spectroscopy (ATR-FTIR) was conducted to study the chemical interactions between components in the prepared samples. The morphological structure of blends was studied by using scanning electron microscopy (SEM). The impact and tensile strength of the samples were measured and compared after exposure to UV radiation. To study the changes in the appearance, the yellowness index values of the samples were followed at different periods of exposure to UV irradiation. The post-radiation results showed similar mechanical performance of ternary and binary blends with the retention of mechanical properties close to each other. The impact strength and elongation-at-break for the HIPS sample were greatly reduced compared to the blends, showing their retention by 8.46 and 7.86%, respectively. The ultimate tensile strength retention in each sample is between 70 and 82% and there is no significant difference between them. The final yellowness index of HIPS was measured to be 1.6 and 1.2 times higher than that of the binary and ternary blends, respectively.
Polyolefin degradation
Sara Zarei; Gholam-Reza Nejabat; Mohammad-Mahdi Mortazavi; Soheyl KhajehPour-Tadavani
Abstract
Varying amounts of an amorphous poly(1-hexene) (PH, Mv 1.7×106 Da) were added to an LLDPE matrix containing 3% w/w Addiflex oxo-biodegradable additive (HES-W) and extruded and converted into films. Then the effect of presence of PH was investigated on microstructure, thermal and tensile behavior ...
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Varying amounts of an amorphous poly(1-hexene) (PH, Mv 1.7×106 Da) were added to an LLDPE matrix containing 3% w/w Addiflex oxo-biodegradable additive (HES-W) and extruded and converted into films. Then the effect of presence of PH was investigated on microstructure, thermal and tensile behavior of polymer films before and after 6 weeks of ultra violet irradiation (UVR). Due to UVR, viscosity average molecular weight (Mv) of the sample without PH decreased from 9.6×104 to 4.6×103 Da and for the sample containing 3% w/w PH from 11.3×104 to 3.0×104 Da, also carbonyl index (CI) of the sample without PH increased from 0 to 28.7 while for the sample containing 3% w/w PH increased from 1.8 to 30.4. Moreover, differential scanning calorimetry (DSC) showed that crystallinity of the sample without PH increased from 34.4% to 36.9% and from 28.7% to 32.1% for the sample containing 3% w/w PH. Thermal gravimetric analysis (TGA) showed lower decomposition temperature for the samples containing PH. The elongation-at-break decreased from 723.0% to 88% for the sample without PH and from 410% to 10% for the sample containing PH. Atomic force microscopy (AFM) indicated smoother surfaces for samples containing 3% w/w PH before and after UVR. Although, the aforementioned results showed that the presence of limited amounts of PH in the LLDPE matrix deteriorated thermal and mechanical properties of the matrix, it hindered the oxo-biodegradablity of the matrix by opposing assimilation process perhaps due to high Mv and/or gelation.
Polyolefin degradation
Soheyl Khajehpour-Tadavani; Gholam-Reza Nejabat; Mohammad-Mahdi Mortazavi
Abstract
Crystallinities of high-density polyethylene (HDPE) films containing various amounts of an oxo-biodegradable additive (HES-W) were investigated immediately after preparation and 6 weeks after ultraviolet (UV) irradiation (λ=254 nm). HDPE granules were mixed with oxo-biodegradable masterbatch in ...
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Crystallinities of high-density polyethylene (HDPE) films containing various amounts of an oxo-biodegradable additive (HES-W) were investigated immediately after preparation and 6 weeks after ultraviolet (UV) irradiation (λ=254 nm). HDPE granules were mixed with oxo-biodegradable masterbatch in a twin-screw extruder and the extrudates were converted into films with thicknesses of 35±5 micrometers. The films were exposed to UV light for 6 weeks. Crystallinities of the films are investigated by X-ray diffraction spectroscopy (XRD) and differential scanning calorimetry (DSC). The XRD results show that upon UV exposure, the crystallinities of the films enhance. The DSC thermograms have confirmed the XRD results and also show a decrease in melting points of the samples after UV exposure. Further investigations on viscosity average molecular weights (Mv) of the samples show that their Mv decrease sharply after UV exposure. Scanning electron microscopy (SEM) shows clear cracks on the samples surfaces after 6 weeks exposure to UV irradiation. Investigating the functionalities of the polymers through Fourier transform infrared spectroscopy (FTIR) show the emergence of carbonyl peaks after UV irradiation so that the carbonyl index of the samples increases. It is concluded that maximum oxo-biodegradation enhancement of the HDPE film samples can be achieved by using a specific amount of the oxo-compound (3 wt%); furthermore the crystallinities of the samples show considerable enhancement after UV exposure which can be due to better packing ability of low molecular weight chains along with probable dipole-dipole attractions between the carbonyl groups on different newly formed short polar chains.
Polyolefin degradation
Abbas Kebritchi; Mehdi Nekoomanesh; Fereidoun Mohammadi; Hossein Khonakdar; Udo Wagenknecht
Abstract
In this work, the effect of hexyl branch content on thermal behavior of a fractionated ethylene/1-octene copolymer with emphasis on high temperatures was investigated. The ethylene/1-octene copolymer was carefully fractionated to different fractions with homogenous hexyl branch (HB) content by preparative ...
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In this work, the effect of hexyl branch content on thermal behavior of a fractionated ethylene/1-octene copolymer with emphasis on high temperatures was investigated. The ethylene/1-octene copolymer was carefully fractionated to different fractions with homogenous hexyl branch (HB) content by preparative temperature rising elution fractionation (P-TREF) method. The P-TREF fractions were thermally analyzed via differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and evolved gas analysis (EGA). The P-TREF profile showed a short chain branch distribution (SCBD) of around 1.24. A linear relationship between P-TREF elution temperature (ET) and methylene sequence length (MSL) was presented. The DSC curves exhibited a monolithically increase in melting temperature (Tm) as well as crystallization temperature (Tc) by decreasing short chain branch (SCB) content. The calculated values of lamellae thickness suggested a linear function of SCB content and Tm. The TGA studies of P-TREF fractions depicted a two-stage thermal degradation behavior: pre-degradation and main degradation stages. Tmax for both pre-degradation and main degradation stages was increased for fractions with less hexyl branch content. As an interesting point the pre-degradation stage was found more intensified for more linear fractions. The concentration of main products was found to be affected by the content of hexyl branches using Py-GC-MS.
Polyolefin degradation
Zaher Tamri; Ali Vaziri Yazdi; Mehdi Nekoomanesh Haghighi; Mehrdad Seifali Abbas-Abadi; Amir Heidarinasab
Abstract
Pyrolysis of high impact polystyrene (HIPS) waste has been investigated under different process parameters, such as temperature, heating rate and types of zeolitic catalysts to produce valuable liquid products. Liquid, gas and coke as products of pyrolysis and aromatic, naphthene, olefin and paraffin ...
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Pyrolysis of high impact polystyrene (HIPS) waste has been investigated under different process parameters, such as temperature, heating rate and types of zeolitic catalysts to produce valuable liquid products. Liquid, gas and coke as products of pyrolysis and aromatic, naphthene, olefin and paraffin as liquid components were obtained and their molecular weight distributions were studied with changing the process parameters in a stirred reactor. Aromatic-rich hydrocarbons within the gasoline range were the main pyrolysis products. Type of zeolitic catalysts, temperature and heating rate had significant effects on the products quality and quantity. Non-isothermal mass losses of high impact polystyrene were measured using a thermo-gravimetric analyzer (TGA) at heating rates of 5, 15, 30, 45 and 90°C min-1 until the furnace wall temperature reached 600°C. The DTG (differential thermal gravimetric) curves showed that heating rate had no obvious effect on the degradation trends in the studied range, and by increasing heating rate, the activation energies were decreased obviously from 222.5 to183.6 kJ mol-1.
Polyolefin degradation
Milad Fonouni; Reza Yegani; Sattar Anarjani; Akram Tavakoli
Abstract
An essential characteristic for high performance inherently hydrophobic membranes such as microporous high density polyethylene (HDPE) membranes is to have a hydrophilic surface. In this project, wet chemical functionalization as a facile and effective method was developed to give a hydrophilic property ...
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An essential characteristic for high performance inherently hydrophobic membranes such as microporous high density polyethylene (HDPE) membranes is to have a hydrophilic surface. In this project, wet chemical functionalization as a facile and effective method was developed to give a hydrophilic property to HDPE membranes using polar functional groups. KClO3, K2Cr2O7 and KMnO4 were selected as oxidizing agents. The optimum concentrations and treatment time intervals were determined for each oxidizing agent. Water contact angle and pure water flux measurements were conducted to evaluate the surface hydrophilicity and membrane performance, respectively. The results showed that among different oxidizing agents, 1wt% K2Cr2O7 solution with 60 min immersion time had the highest impact on the pure water flux. The percentage of re-construction phenomenon was about 4.70%, 21.94% and 32.6% for the HDPE membranes treated by KClO3, K2Cr2O7 and KMnO4, respectively. In addition, the attenuated total reflectance spectra-Fourier transform infrared spectroscopy (ATR-FTIR) results confirmed the presence of hydroxyl groups (O–H peak appeared at 3418.78 cm−1) in the membrane modified by KClO3. Bovine serum albumin (BSA) filtration experiments revealed that the total fouling ratio (TFR) and irreversible fouling ratio (IFR) decreased from 88.10% and 42.60% for pristine membrane to 65%, 68% and 72%and 26.60%, 29.30% and 35% for the modified membranes treated by KClO3, K2Cr2O7 and KMnO4, respectively. The results indicated that incorporation of hydrophilic functional groups on the surface of HDPE membranes improved the fouling resistance behavior.
Polyolefin degradation
Nikoo Karami; Reza Jahanmardi
Abstract
The present work is aimed to find a new and efficient type of antioxidants for polypropylene. Hence, effects of 3,3-bis(4-hydroxy-2-methyl-5-propan-2-ylphenyl)-2-benzofuran-1-one, generally known as thymolphthalein, on thermo-oxidative stability of polypropylene in solid and melt states were evaluated ...
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The present work is aimed to find a new and efficient type of antioxidants for polypropylene. Hence, effects of 3,3-bis(4-hydroxy-2-methyl-5-propan-2-ylphenyl)-2-benzofuran-1-one, generally known as thymolphthalein, on thermo-oxidative stability of polypropylene in solid and melt states were evaluated and compared with those of SONGNOX 1010, an efficient commercially used antioxidant for the polymer. Oven ageing experiments followed by Fourier transform infrared (FTIR) spectroscopy showed that thymolphthalein increased thermo-oxidative stability of the polymer outstandingly in the solid state and its stabilization efficiency was comparable to that of SONGNOX 1010. In addition, measurements of oxidative induction time (OIT) and oxidation onset temperature (OOT) revealed that thymolphthalein improved thermo-oxidative stability of the polymer in the melt state significantly. It was also observed that thymolphthalein did not interfere with the stabilization action of SONGNOX 1010 in the polymer neither in melt nor in solid state. On the basis of the obtained results, a probable mechanism for the stabilization action of thymolphthalein in the polymer is proposed.
Polyolefin degradation
Larissa Stieven Montagna; Ana Paula Testa Pezzin; Maria Madalena Forte; Ruth Marlene Santana
Abstract
In abiotic degradation the action of light radiation is one of the most important parameters, because polymers undergo degradation due to the action of light (natural or artificial). The aim of this study was to investigate the degradation rate for samples of polypropylene (PP) modified with an organic ...
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In abiotic degradation the action of light radiation is one of the most important parameters, because polymers undergo degradation due to the action of light (natural or artificial). The aim of this study was to investigate the degradation rate for samples of polypropylene (PP) modified with an organic pro-degradant submitted to ageing in a natural environment and to accelerated ageing test. The degradation behavior of the samples exposed to the ageing processes was evaluated through changes in the degree of crystallinity (Xc ), surface morphology (Scanning Electron Microscopy) and molecular weight. The results indicated that for the modified polypropylene samples natural ageing led to a 42.3% reduction in the molecular weight and the surface morphology showed evidence of erosion. In the accelerated ageing process the UV radiation was stronger, which led to a 94.3% increase in the degree of crystallinity and micro-voids were present on the surface of the modified polypropylene.
Polyolefin degradation
Larissa Montagna; Andre Luis Catto; Maria Madalena Forte; Ruth Marlene Santana
Abstract
In this study, PP films were modified with an organic pro-degradant in different concentrations (1, 2 and 3 wt.%), exposed in the first step of degradation to natural ageing for 100 days followed by biodegradation in simulated soil in the respirometric test for 100 days. At the end of the combined degradation ...
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In this study, PP films were modified with an organic pro-degradant in different concentrations (1, 2 and 3 wt.%), exposed in the first step of degradation to natural ageing for 100 days followed by biodegradation in simulated soil in the respirometric test for 100 days. At the end of the combined degradation process the PP samples were characterized according to their morphological and physical properties and the CO2 generated during the biodegradation in soil was monitored. The CO2 production by the PP films modified with the organic pro-degradant was proportional to the oxidation rate and weight loss of the samples. The reduction in the average viscosimetric molecular weight could be attributed to chain scission due to the weathering conditions to which the samples were exposed (natural ageing followed by biodegradation in soil). Scanning electron microscopy (SEM) of the PP films revealed surface deterioration of the films with the organic pro-degradant after the combined degradation process.
Polyolefin degradation
Mehrdad Seifali Abbas-Abadi; Mehdi Nekoomanesh Haghighi; Armando G. McDonald; Hamid Yeganeh
Abstract
Pyrolysis of low density polyethylene (LDPE) by equilibrium fluid catalytic cracking (FCC) was studied in a stirred reactor under different process parameters. In this work, the effect of process parameters such as degradation temperature (420-510°C), catalyst/polymer ratio (0-60%), carrier gas type ...
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Pyrolysis of low density polyethylene (LDPE) by equilibrium fluid catalytic cracking (FCC) was studied in a stirred reactor under different process parameters. In this work, the effect of process parameters such as degradation temperature (420-510°C), catalyst/polymer ratio (0-60%), carrier gas type (H2, N2, ethylene, propylene, Ar and He), residence time and agitator speed (0-300 rpm) on the condensate yield (liquid, gas and coke) and product composition were considered. Reaction products were determined by GC analysis and shown to contain naphthenes (cycloalkanes), paraffins (alkanes), olefins (alkenes) and aromatics. Higher temperature and more catalyst amount enhanced LDPE cracking. The maximum “fuel like” condensed product yield was attained at 450°C and 10% catalyst, respectively and gaseous products increased with increases in temperature. Hydrogen as a reactive carrier gas increased the condensed and paraffinic product yield. Appropriate heat transfer (by stirring) increased the catalyst efficiency in a stirred reactor.
Polyolefin degradation
Abbas Kebritchi; Mehdi Nekoomanesh; Fereidoon Mohammadi; Hossein Ali Khonakdar
Abstract
In this work, the role of comonomer content of 1-hexene-medium density polyethylene (MDPE) copolymer, synthesized using Phillips catalyst, on thermal behavior parameters such as: crystallization, melting temperature and thermal degradation was investigated in detail. The copolymer was fractionated to ...
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In this work, the role of comonomer content of 1-hexene-medium density polyethylene (MDPE) copolymer, synthesized using Phillips catalyst, on thermal behavior parameters such as: crystallization, melting temperature and thermal degradation was investigated in detail. The copolymer was fractionated to homogenous short-chain branching (SCB) fractions by "preparative temperature rising elution fractionation" (P-TREF) method and then it was subjected to thermal analyses. A broad chemical composition distribution (CCD) in terms of SCB content and molecular weight (Mw) was observed by P-TREF and gel permeation chromatography (GPC), respectively. Based on P-TREF results, a parabolic relationship between methylene sequence length (MSL) and elution temperature (ET) was presented. Differential scanning calorimetry (DSC) showed distinct, well-defined melting peaks over a 22 °C temperature range for SCB contents of about 3-12 (br/1000 C). The variations in physical characteristics such as melting temperature (Tm), crystallinity (Xc), crystallization temperature (Tc) and lamellae thickness (Lc) against SCB content were correlated. Thermogravimetric analysis (TGA) suggested linear relationships between the temperature at maximum degradation rate (Tmax) as well as the degradation initiation temperature (T5%) versus SCB content. Moreover, the TGA curves exhibited distinct differences at both initiation and propagation stages of thermal degradation at dissimilar comonomer contents.
Catalysis
Maria Marques; Renato Oliveira; Rafael Araujo; Bruno Amantes
Abstract
A fourth-generation Ziegler-Natta catalyst was prepared to synthesize polypropylene (PP), which was stabilized by in situpolymerization employing lignin as antioxidant. The antioxidant properties of lignin were compared with those of the commercial antioxidant Irganox 1010. The presence of lignin in ...
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A fourth-generation Ziegler-Natta catalyst was prepared to synthesize polypropylene (PP), which was stabilized by in situpolymerization employing lignin as antioxidant. The antioxidant properties of lignin were compared with those of the commercial antioxidant Irganox 1010. The presence of lignin in the reaction medium slightly decreased the catalytic activity of the reaction. The isotacticity index (I.I.) of PP synthesized with lignin (PP-lig) was not affected by the presence of the additive in the reaction medium. The thermal properties, characterized by differential scanning calorimetry, showed slightly decreased degree of crystallinity (Xc), but the melting temperature (Tm) and crystallization temperature (Tc) were not affected when compared with the neat polymer. Lignin showed good activity as a stabilizer by thermogravimetry. The initial temperature of degradation (Tonset) increased when compared to the pure PP and PP stabilized with the commercial antioxidant. The lower carbonyl index of the PP, evaluated by infrared spectroscopy (FTIR) after thermo-oxidative treatment, also revealed the stabilizing action of lignin.
