Thermal degradation kinetics and mechanisms of PMEPP and MEPP/MMA copolymer

In this study, 2-methacryloxyethyl phenyl phosphate (MEPP), a phosphorus-containing flame retardant, was synthesised via the esterification of phenyl dichlorophosphate (PDCP) with 2-hydroxyethyl ethylene methacrylate (HEMA), followed by hydrolysis. A two-stage bulk polymerisation process prepared MEPP/methyl methacrylate (MEPP/MMA) copolymers containing various amounts of MEPP. The condensed-phase and volatized products produced at various temperatures during the thermal degradation of MEPP/MMA copolymer were monitored by Fourier transform infrared (FT-IR) spectroscopy and thermogravimetric analysis with Fourier transform infrared spectroscopy (TGA/FT-IR). Finally, we propose the possible mechanisms for the thermal degradation of MEPP/MMA copolymer according to the analytical results of the condensed-phase and volatilized products.     

Review Article: Recycling of Polystyrene

Recycling of polystyrene can be done by mechanical, chemical, and thermal methods. High impact polystyrene is a promising material for mechanical recycling since its properties are not extremely affected even after multiple processing of upto nine cycles. Production of liquid products and gaseous products are highly dependent on the reaction condition. The catalysts used are highly selective for the production of liquid as well as gaseous products. In this article we have reviewed the various types of methods followed so far for recycling of polystyrene.     

Effect of Thermal Aging on the Optical Properties of ABS Plastics

Poly(acrylonitrile/butadiene/styrene) (ABS) is a two-phase material consisting of elastomer particles in a glassy polymer matric of styrene and acrylonitrile (SAN) [1]. The photooxidation of ABS was the subject of several studies [2, 3]. It was suggested that several processes will take place during photooxidation. These changes include the formation of hydroperoxide [4], chain breakage of the polystyrene, and the oxidation of the polymer as it was monitored by IR spectroscopy [4–6]. Also photooxidation affect the polybutadiene in ABS and oxidizes it, which results in the formation of hydroperoxide. There are no data available on the thermal degradation of ABS. In a previous study the thermal aging of recycled high-impact polystyrene was studied using UV-vis spectroscopy [7]. It was found that this method provided very useful information about the degradation of several industrial polymers [8–12]. In this paper thermal degradation of ABS is investigated by UV-vis and IR spectroscopy.     

Thermal degradation of polystyrene in different environments

Several aspects of the thermal degradation of polystyrene are highlighted in this communication. The factors involved in determining the ratio of volatile to tar fraction products in the degradation of the pure polymer are examined, leading to the conclusion that the initial melt viscosity plays an important role in determining the balance between intra- and intermolecular transfer. The effect on the degradation of polystyrene of the presence of a second polymer is discussed. For polystyrene-polybutadiene and polystyrene-polyisoprene blends, stabilisation is observed, which is attributed to radical scavenging. The thermal degradation behaviour of polystyrene in the presence of oxygen has been investigated, with and without an antioxidant additive. Products have been characterised for oxidative conditions and the kinetics of degradation have been studied.     

Thermal and photochemical degradation of PPO/HIPS blends

In general, polymer blends show a degradation behavior different from a simple combination of the individual components, making any forecast difficult without experiments. Interactions between polymers can sensibilize or stabilize the blend against degradation. In this work, the thermal and photooxidative degradation of blends of poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) and high impact polystyrene (HIPS) have been studied under accelerated conditions. The extent of degradation was accompanied by infrared spectroscopy (FTIR) and Raman spectroscopy (FT‐Raman) and impact resistance and strain–stress testing followed its influence on the macroscopic properties of the blends. The results showed that HIPS and the blend containing 60 wt % of PPO are more susceptible to thermal and photochemical degradation, while the blends containing 40 and 50 wt % of PPO are more stable. Infrared and Raman spectroscopic analyses showed that the degradation of HIPS and its blends is caused not only by degradation of the polybutadiene phase. Effects of interactions, such as exchange of energy in excited state between the PPO and PS components of the polymeric matrix may also be responsible for the degradation and loss of mechanical properties of the PPO/HIPS blends. The chemical degradation directly affects the mechanical properties of the samples with photodegradation being more harmful than the thermal degradation at 75°C. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Effect of Thermal Aging on the Optical Properties of ABS Plastics

Poly(acrylonitrile/butadiene/styrene, ABS) is a two-phase material consisting of elastomer particles in a glassy polymer matrix of styrene and acrylonitrile (SAN) [1]. The photo-oxidation of ABS has been the subject of several studies [2, 3]. It was suggested that several processes will take place during photo-oxidation. These changes include the formation of hydroperoxide [4], chain breakage of the polystyrene, and the oxidation of the polymer as it was monitored by IR spectroscopy [4–6]. Also, photooxidation affects the polybutadiene in ABS and oxidizes it, which results in the formation of hydroperoxide. No data are available on the thermal degradation of ABS. In a previous study the thermal aging of recycled high-impact polystyrene was studied using UV-Vis spectroscopy [7]. It was found that this method provides very useful information about the degradation of several industrial polymers [8–12]. In the work reported in this paper, thermal degradation of ABS was followed by UV-Vis and IR spectroscopy.     

Effects of the injection‐molding temperatures and pyrolysis cycles on the butadiene phase of high‐impact polystyrene

Recycling is a thermal process in which polymers are melted to produce new products. It is possible that these thermal processes could modify their mechanical and thermal properties. Polymer degradation can be characterized with thermogravimetric analysis and differential scanning calorimetry. Recycled materials tested with these methods have shown variations in some thermal properties, such as the glass‐transition temperature and thermal degradation onset, but the sensitivity of these methods is not sufficient to investigate the changes in the characteristics of polymers when materials are exposed to moderate temperature conditions or several thermal cycles. To study these structural changes, a much more sensitive technique, such as pyrolysis–gas chromatography/mass spectrometry (Py–GC/MS), is needed. Small variations in the structure can be determined by Py–GC/MS. Each pyrolysis product can be identified by its retention time and mass spectrum with the use of reference literature. In this work, we have studied structural changes in high‐impact polystyrene as a function of the injection‐molding temperature and pyrolysis cycles. The results do not show significant changes in samples processed at different temperatures with Py–GC/MS, but the values of the pyrolysis products differ as a function of the pyrolysis cycles. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Enhancement of the high‐temperature properties of an SEBS thermoplastic elastomer by chemical modification

A procedure was developed for benzoylating the polystyrene segments in polystyrene‐b‐poly(ethylene‐co‐butene)‐b‐polystyrene (SEBS) triblock copolymers. The products were characterized by NMR spectroscopy, gel permeation chromatography, dynamic mechanical thermal analysis, and membrane osmometry. The mechanical properties of the parent and benzoylated copolymers, measured from 25 to 150°C, indicated that benzoylation increases the utility of the polymers at elevated temperatures. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1203–1210, 2002     

Recycling of polymers from plastic packaging materials using the dissolution–reprecipitation technique

In this work, results are presented on the application of the dissolution/reprecipitation technique in the recycling of polymers from waste plastic packaging materials used in food, pharmaceuticals and detergents. Initially, the type of polymer in each packaging was identified using FT-IR. Furthermore, experimental conditions of the recycling process (including type of solvent/non-solvent, initial polymer concentration and dissolution temperature) were optimized using model polymers. The dissolution/reprecipitation technique was applied in the recycling of a number of plastic materials based on polyethylene (LDPE and HDPE), polypropylene, polystyrene, poly(ethylene terephthalate) and poly(vinyl chloride). The recovery of the polymer was measured and possible structural changes during the recycling procedure were assessed by FT-IR spectroscopy. Potential recycling-based degradation of the polymer was further investigated by measuring the thermal properties (melting point, crystallinity and glass transition temperature), of the polymer before and after recycling, using DSC, their molecular properties (average molecular weight) using viscosimetry, as well as their mechanical tensile properties. High recoveries were recorded in most samples with the properties of the recycled grades not substantially different from the original materials. However, a slight degradation was observed in a few samples. It seems that this method could be beneficial in waste packaging recycling program.     

Thermal degradation and combustion of polymeric blends

The thermal stability of polymer blends was investigated by means of gas chromatography–mass spectroscopy (GC/MS) and thermal analysis. Evaluated changes in thermal stability can be attributed to blending. On the other hand, we were interested in whether blending may provide a method to control thermal stability and combustibility of polymeric materials. A new scheme of thermal degradation for polystyrene‐polydimethylsiloxane (PDMS) blend was suggested. In the case of polystyrene (PS) as a part of the blend, the products of degradation of PS diffuse through the phase boundary, which cause interaction with PDMS polymers. Apparently, PDMS acts as an inert component, slowing down the termination reaction by dilution of macroradicals formed in random scission degradation process of the PS component. On the other hand, it stabilizes the PS by means of interpolymer recombination, which leads to cross products of thermal degradation. Two of the degradation products: 2‐phenyl‐4(1′,3′,3′,5′,5′‐pentamethylcyclotrisiloxane)‐butane and 2‐phenyl‐4(1′,3′,3′,5′,5′,7′,7′‐heptamethylcyclotrisiloxane)‐butane were assigned to the products of cross‐interpolymer recombination which can accelerate the process of PDMS depolymerization by means of radical initiation of PS* fragments. The connection between a polymer thermal oxidative degradation and its combustion under diffusion flames condition was shown by using composition of polypropylene‐polypropylene‐co‐polyethylene (PP/PP‐co‐PE). In general, the solid‐phase polymer reaction can play a very important role in the reduction of polymer combustibility. It was shown that the composition of PP/PP‐co‐PE (62 : 38) has the highest induction period of autooxidation, which correlates with its combustibility. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3300–3311, 2002     

PYROLYSIS OF WASTE POLYSTYRENE IN HEAVY OIL

Waste plastics are an environmental problem because of recycling limitations and their resistance to natural decomposition. This research investigates the thermal degradation (pyrolysis) of waste polystyrene in heavy oil as a tertiary recycling method. Kinetic parameters for pyrolysis were obtained, and distillate products from the reaction were characterized by gas chromatography/mass spectroscopy. Four types of heavy oil were used to find which would be most suitable in this process. Complete pyrolysis of polystyrene occurred at temperatures lower than those reported in the literature.     

Thermal degradation of polymers. part IV. Vacuum pyrolysis of poly(m-aminostyrene). The residue and the fraction volatile at pyrolysis temperature involatile at room temperature

The effect of the extent of degradation of poly(m–aminostyrene) on the quantity and composition of the residue and the effect of pyrolysis temperature on the fraction volatile at pyrolysis temperature are discussed. The behavior of poly(m–aminostyrene) is compared to that of polystyrene; a significant difference has been found for the behavior of the residue from poly(m–aminostyrene), which is ascribed to a crosslinking reaction involving the amino substituent. Mechanisms to acount for the observed products of degradation have been suggested and are discussed. Relative thermal stability studies have also been made and compared with results from polystyrene.     

The degradation of polystyrene during extrusion

An investigation was made of the magnitude and mechanism of shear degradation of a narrow distribution, high molecular weight (M_w = 670,000) polystyrene. An Instron rheometer was used to perform the extrusion at temperatures from 164° to 250°C. The change in molecular weight distribution was studied by gel permeation chromatography. The maximum shear stress employed was 5.83 kg/cm². It was found that degradation could be induced at high stress at temperatures of 50°C lower than degradation of polystyrene would occur exclusively due to thermal forces. An activation energy for the degradation, calculated at constant shear rate, was +20.2 kcal/mole. The direction and magnitude of this value are consistent with degradation induced through a mechanical reduced activation for thermal degradation.     

吡啶基官能化SBS热塑性弹性体热老化研究

采用动态力学分析(DMA)法和红外光谱(FT-IR)法,研究了不同老化条件下SBSVP(吡啶基官能化苯乙烯-丁二烯-苯乙烯嵌段共聚物)的热老化行为。结果表明:SBSVP在无氧热老化过程中,其降解反应与交联反应并存,并发生动态变化;低于160℃时以降解反应为主,超过160℃时交联反应占优势,聚合物交联密度变化是导致材料储能模量及玻璃化转变温度发生相应变化的主要原因;SBSVP热老化后,其分子链中的C=C键含量降低,说明老化主要发生在PB链段;SBSVP在热老化过程中,老化温度对其影响程度大于老化时间。     

Dehydrohalogenation during pyrolysis of brominated flame retardant containing high impact polystyrene (HIPS-Br) mixed with polyvinylchloride (PVC)

Dehydrohalogenation during pyrolysis of brominated flame retardant containing polystyrene (brominated high impact polystyrene (HIPS-Br)) mixed with polyvinylchloride (PVC) was carried out in a laboratory scale batch process. Thermal and catalytic degradation of HIPS-Br mixed with PVC on carbon composite of iron oxide (TR-00301) catalyst was investigated. The thermal degradation of waste plastics (HIPS-Br/PVC) yielded liquid products with 55,000 ppm bromine and 4300 ppm chlorine content in oil. Catalytic degradation (4 g; TR-00301) of HIPS-Br/PVC waste plastics at 430 °C produced halogen-free clean oil, which can be used as a fuel oil or chemical feedstock. The main liquid products during catalytic degradation were benzene, toluene, styrene, ethyl benzene, α-methyl styrene, butyl benzene, 1,2-dimethyl benzene etc. The average carbon number of the liquid products produced during catalytic degradation (9.3) of waste plastics was less than that of the thermal degradation (10.4) and the density of liquid products was found to be lower during the catalytic degradation than the thermal degradation. The possibility of a single step catalytic process for the conversion of halogenated waste plastics into fuel oil with the simultaneous removal of chlorine and bromine content from the oil was demonstrated.     

Interaction of poly(methyl methacrylate) and manganese chloride

The thermal degradation of poly(methyl methacrylate) (PMMA), in the presence of manganese chloride has been studied by sealed tube reactions and thermogravimetric analysis coupled to FT-IR spectroscopy. From sealed tube reactions it was found that the degree of mixing of the MnCl₂ and PMMA has an important effect on monomer formation. In systems where the two components are simply poured together, the amount of monomer is about half that observed for the thermolysis of PMMA alone; when the two components are thoroughly mixed by dissolution in solvent, the monomer yield fails to zero. The TGA–FT-IR experiment on solvent mixed material does show the presence of monomer. In sealed tubes, monomer may not escape and must repolymerize, while in the TGA experiment the monomer is swept out before reaction may occur. Monomer production also commences at temperatures lower than those for degradation of PMMA alone. It is apparent that manganese chloride catalyzes both the degradation of polymer to monomer and the reoligomerization of this monomer. The gases that are produced include CO, CO₂, CH₃Cl, HCl, and CH₄. A mechanism is proposed to account for all of these products and a manganese ionomer is the final product of the reaction.     

The characterization of organic modified clay and clay‐filled PMMA nanocomposite

Recently, polymer–clay hybrid materials have received considerable attention from both a fundamental research and application point of view. 1 - 3 This organic–inorganic hybrid, which contains a nanoscale dispersion of the layered silicates, is a material with greatly improved physical and mechanical characteristics. These nanocomposites are synthesized through in situ polymerization or direct intercalation of the organically modified layered silicate (OLS) into the polymer matrix. Thus, understanding the relationship between the molecular structure and the thermal stability (decomposition temperature, rate, and the degradation products) of the OLS is critical. In this study, modern thermal analysis techniques combined with infrared spectroscopy and mass spectrometry (TGA‐FTIR‐MS) were used to obtain information on the thermal stability and degradation products of organic modified clay. Furthermore, the thermal and mechanical properties of clay‐filled PMMA nanocomposites were determined by using TGA and DSC. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1702–1710, 2002     

Environmental degradation of some polymer blends. Blends of polystyrene with acrylonitrile butadiene styrene,poly(vinyl chloride), and polybutadiene and blends of polybutadiene with poly(vinyl chloride)

One class of polymer/additive which has become increasingly important is polymer blends. In this study the ultimate tensile strength, elongation at break, and the modulus of acrylonitrile–butadiene–styrene, poly(vinyl chloride), polybutadiene and polystyrene and their blends have been studied over an entire binary composition range. We have correlated these mechanical properties to their degradation behavior under natural and accelerated weathering by measurement of various indices during thermal and natural weathering. It was found that during natural weathering the presence of polystyrene in acrylonitrile–butadiene–styrene (ABS) improved the weatherability of ABS; the converse was true when the blends were heated in an air oven at 100°C. It was also found that the weatherability of PB was improved in the presence of polystyrene and large improvement in the rigidity was observed. Similarly, from a measurement of carbonyl index, it was found that PVC has a stabilizing effect on PB. In many cases, the 50:50 composition of the polymers gave the best compromise of good mechanical properties, heat stability, and outdoor weathering. The mechanisms of possible interactions between the degrading polymers are discussed.     

Enhancement of the high‐temperature utility of a polystyrene‐b‐poly(ethylene‐co‐butylene)‐b‐polystyrene block copolymer by friedel–crafts naphthoylation

A procedure was developed for the Friedel–Crafts naphthoylation of the polystyrene segments of a polystyrene‐b‐poly(ethylene‐co‐butene)‐b‐polystyrene (SEBS) triblock copolymer. It was possible to obtain up to 72% 1‐naphthoylation or 100% 2‐naphthoylation of the polystyrene segments in the copolymer. Naphthoylation could also be accomplished using trifluoromethanesulfonic acid as a catalyst. The naphthoylated products were characterized by ¹H‐NMR spectroscopy, size‐exclusion chromatography, and dynamic mechanical thermal analysis. The mechanical properties of the original and naphthoylated polymers were measured from 25 to 125°C. The results obtained indicate that naphthoylation enhances the tensile properties of the polymers at elevated temperatures. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1289–1295, 2003     

Effects of ultrahigh speed twin screw extrusion on the thermal and mechanical degradation of polystyrene

This article characterizes a novel twin screw extrusion (TSE) process with the capability of rotating at speeds up to 4500 rpm. The resulting extreme high shear rate is expected to result in molecular weight changes due to thermomechanical degradation of the polymeric materials being extruded, polystyrene (PS) in this case. In order to differentiate between mechanical and thermal factors affecting degradation of PS running at ultrahigh speeds and also to evaluate the relative importance of the two mechanisms, PS has been extruded at different screw speeds and different barrel temperatures with corresponding melt temperatures. Viscosity measurements and size exclusion chromatography measurements show the extent of degradation due to mechanical stress as a result of high screw rotational speeds. Furthermore, through analyzing the kinetics of PS depolymerization, the reaction rate and hypothetical apparent temperatures at each screw speed have been calculated. All results support the idea that the mechanical shear stress can be considered as the controlling factor of polymer degradation in ultrahigh speed TSE. POLYM. ENG. SCI., 56:743–751, 2016. © 2016 Society of Plastics Engineers