Thermal and photo-degradation of unstabilized ABS

Thermal- and photo-stabilities of unstabilized acrylonitrile-butadiene-styrene terpolymer, ABS, have been investigated by i.r. spectroscopy. Degradation of ABS samples is initiated by attack on the polybutadiene (PB) component; oxidation products containing hydroxyl and carbonyl groups are produced. The effect of prior thermal processing is to introduce into the polymer hydroperoxides arising from oxidative destruction of PB-unsaturation; these hydroperoxides act as catalysts during subsequent u.v. irradiation. The insolubility of degraded samples of ABS is associated with the formation of cross-linked structures and occurs mainly in the PB segment. It is concluded that the degradation characteristics of ABS are essentially those of the polybutadiene component.     

异山梨醇型聚碳酸酯与ABS树脂共混体系的结构与性能研究

采用异山梨醇型聚碳酸酯(DB),与掺混型ABS熔融共混制备了具有不同聚丁二烯(PB)含量和丙烯腈(AN)含量的DB/掺混型ABS合金,并在考察掺混型ABS特征对合金结构与性能的影响的基础上,分别使用同种掺混型ABS以及各种商品化ABS树脂,比较了DB/ABS合金和双酚A型聚碳酸酯/ABS合金的性能及其变化规律.结果表明,对DB/掺混型ABS(70/30)合金而言,PB含量变化对于合金拉伸性能的影响明显大于AN含量变化所带来的影响,在PB含量为6.3 wt%条件下,各不同AN含量的合金体系均有最好的性能表现.PB含量和AN含量变化对合金分散相形态的影响与力学拉伸性能变化特征一致.DB/ABS合金体系均具有良好的热稳定性与热力学相容性,受AN含量和PB含量变化的影响较小,合金玻璃化转变温度与DB非常接近.以双酚A型聚碳酸酯为基础的聚碳酸酯(PC)/ABS合金及以异山梨醇型聚碳酸酯为基础的DB/ABS合金,在拉伸性能变化上均表现出完全相同的规律,且无论是采用掺混型ABS还是采用商品化ABS的体系,PC/ABS与DB/ABS合金在拉伸性能所反映出的规律也是基本一致的.     

Mechanism study on char formation of zinc acetylacetonate on ABS resin

The mechanism of char formation effect of zinc acetylacetonate(Zn(acac)2) on acrylonitrile-butadiene-styrene copolymer(ABS) was studied. Thermal gravimetric analysis(TGA) was used to study the mass loss and char yield of ABS composites. In situ temperature-dependent Fourier transform infrared spectroscopy(FTIR) was used to characterize the chemical change during thermal decomposition. Roman spectroscopy and scanning electron microscopy(SEM) were applied to characterize the structure and morphology of the char after combustion. Results showed that the presence of Zn(acac)2 not only slowed down thermal decomposition of the ABS composites, but also increased the charred residue. A more compact and denser char layer with higher graphitization degree was formed for ABS composites with Zn(acac)2. To study the char formation mechanism of Zn(acac)2 on ABS, thermal decomposition was analyzed for the composites of Zn(acac)2 with PB, PS and SAN, respectively. Also, the chemical structure change was investigated for Zn(acac)2 during thermal decomposition. Based on these results, it was deduced that the increase of char yield of ABS composites was probably attributed to the interaction between the units of acrylonitrile in ABS and zinc acetate, produced during the thermal decomposition of Zn(acac)2. A proposed mechanism for crosslinking and the subsequent char formation was presented.     

Effects of polybutadiene-g-SAN impact modifiers on the morphology and mechanical behaviors of ABS blends

A series of PB-g-SAN impact modifiers with different ratio of PB to SAN ranging from 20.6/79.4 to 91.9/8.1 were synthesized by seeded emulsion polymerization. ABS blends were prepared by blending these PB-g-SAN impact modifiers and SAN resin. The rubber concentration of these ABS blends was kept at a constant value of 15 wt%. The influences of different impact modifier on the mechanical behavior and morphology of ABS blends have been investigated. The dynamic mechanical analysis on ABS blends shows that T_g of the rubbery phase shifts to a lower temperature, (tan δ)_max of the rubbery phase increases and then decreases with the increase of PB concentration in PB-g-SAN impact modifier. A uniform dispersion of rubber particles in the matrix can be observed when PB/SAN ratio in PB-g-SAN impact modifier is in the range from 20.6/79.4 to 71.7/28.3. When it exceeds 71.7/28.3, an agglomeration of rubber particles occurs. The mechanical tests indicate that the ABS blend, in which PB/SAN ratio in the impact modifier is 71.7/28.3, has the maximum impact strength and yield strength.     

Synthesis of telechelic anthraquinone‐functionalized polybutadiene via ROMP and study of its photo‐oxidation and UV crosslinking behaviors

Telechelic anthraquinone‐functionalized polybutadiene (AQ‐PB‐AQ) was synthesized by ring opening metathesis polymerization to achieve homogeneous dispersion of AQ groups in the polymer matrix. It was observed that the AQ end groups act as a sensitizing group resulting in photo‐induced crosslinking and oxidation reaction at the olefin groups in the PB. The process was confirmed by comparing the polymer's mass loss and Fourier transform infrared (FTIR) spectra with those of telechelic diacetoxy‐functionalized PB (AcO‐PB‐OAc) which did not show any difference before and after ultraviolet irradiation. Homogeneity of the AQ groups in PB matrix results in rapid crosslinking of PB in a short period of time (<4 min) while a simple blend of AQ methyl ester in AcO‐PB‐OAc matrix did not show such behavior. Photo‐oxidative reaction has concurrently occurred during the crosslinking reaction. Generation of  OH,  OOH, and carbonyl groups in the matrix during the photo‐oxidation was verified by FTIR, elemental analysis, and water contact angle measurements. A plausible mechanism for the process was proposed in which the photo‐sensitized AQ groups abstract hydrogen from the PB chain to yield reactive radical species, initiating oxidative crosslinking, and degradation of PB or reduction of AQ to hydroanthraquinone species. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1249–1258     

Effect of dissolution-based recycling on the degradation and the mechanical properties of acrylonitrile-butadiene-styrene copolymer

A dissolution-based recycling technique for acrylonitrile-butadiene-styrene copolymer (ABS) is proposed, and the effects of repeated recycling cycles are studied measuring changes in chemical structure, melt viscosity, and tensile and impact properties. Acetone as solvent, 0.25 g/ml concentration, room temperature and 40 min for dissolution have been found to be the most reliable recycling parameters. FTIR, DSC and MFI results have shown that the dissolution-based recycling itself does not degrade the ABS. However, TGA analysis suggests that during the dissolution some stabilizers are probably eliminated, and consequently degradation takes place in the following injection moulding step. Darkening of recycled ABS is attributed to the butadiene degradation, pointed out by FTIR results. Otherwise, the chemical structure of the SAN matrix has not been modified, but its molecular weight has been reduced. The modulus of elasticity is not affected even after four recycling cycles. However, yield stress and impact strength decrease after the first recycling cycle, and remain constant in the following steps.     

Rheological and mechanical properties of ABS plastics prepared by bulk polymerization

A series of ABS plastics prepared by bulk polymerization was studied. The test samples contained almost equal amounts of PB but mostly differed in the molecular mass of a styrene-acrylonitrile copolymer. It was shown that the molecular mass of the copolymer strongly affects the rheological and mechanical properties of ABS plastics. An increase in molecular mass leads to a rise not only in the non-Newtonian viscosity of plastics but also in their yield point, storage modulus under periodic steady-state shear flow in the low-frequency plateau region, and impact strength. Quantitative correlations between these rheological and mechanical characteristics of the copolymers and their M _w values were established. As opposed to homophase polymer systems, a marked increase in the shear stress has no effect on viscosity in relation to the molecular mass of ABS plastics. In the case of melts, the influence of the M _w of the styrene-acrylonitrile copolymer on the rheological behavior of ABS plastics is apparently related to a change in the interaction of PB particles with the copolymer that controls the structural framework of the system. The relationship between the impact strength of the copolymer and its M _W may be explained by the fact that the latter parameter influences orientational effects in crazes that arise during steady-state shear flow of ABS plastics in the solid state.     

Changes in the microstructure and morphology of high-impact polystyrene subjected to multiple processing and thermo-oxidative degradation

Multiple processing and thermo-oxidation have been employed to simulate the degradative processes to which high-impact polystyrene (HIPS) is subjected during processing, service life, and mechanical recycling. A curve-fitting procedure has been proposed for the analysis of the individual bands corresponding to polybutadiene microstructure resulting from Raman spectroscopy. The analysis of the glass transition relaxations associated with the polybutadiene (PB) and polystyrene (PS) phases has been performed according to the free-volume theory. Both reprocessing and thermo-oxidative degradation are responsible for complex physical and chemical effects on the microstructure and morphology of PB and polystyrene PS phases, which ultimately affect the macroscopic performance of HIPS. Multiple processing affects PB microstructure and the free-volume parameter associated with the PS phase. Physical ageing of the PS phase predominates for shorter exposure to thermo-oxidation; after prolonged exposure, however, the chemical effects on the PB phase become significant and strongly influence the overall structure.     

Microphase separation in poly(acrylonitrile–butadiene–styrene) (ABS) studied with paramagnetic spin probes. II. Simulation of electron spin resonance spectra

We recently presented electron spin resonance spectra of poly(acrylonitrile–butadiene–styrene) (ABS) doped with 10‐doxylnonadecane (10DND) and 5‐doxyldecane (5DD) as spin probes. The spectra were measured in three types of ABS that differed in their butadiene contents and methods of preparation. Results for the ABS polymers were evaluated by comparison with similar studies on the homopolymers polybutadiene (PB) and polystyrene (PS) and the copolymers poly(styrene‐co‐acrylonitrile) (SAN) and poly(styrene‐co‐butadiene) (SB). Only one spectral component was detected for 10DND in PB, PS, SAN, and SB. In contrast, two spectral components differing in their dynamic properties were detected in the ABS samples and were assigned to spin probes located in butadiene‐rich domains (the fast component) and SAN‐rich domains (the slow component). The presence of two spectral components was taken as an indication of microphase separation. In this study, we present details on the dynamics and microphase separation by simulating spectra of 10DND in ABS, PB, PS, and SAN. The simulations are based on a dynamic model defined by the components of the rotational diffusion tensor and the diffusion tilt angle between the symmetry axis of the rotational diffusion tensor and the direction of the nitrogen 2p_z atomic orbital. The jump diffusion model led to good agreement with experimental spectra. In this model, the spin probe has a fixed orientation for a given time and then jumps instantaneously to a new orientation. The temperature variation of the rotational correlation time in PB and PS consisted of two dynamic regimes, with different activation energies. The transition temperature at which the change in dynamics occurs (T_tr) is 380 K for PS and 205 K for PB, essentially the same as the corresponding glass‐transition temperatures measured by differential scanning calorimetry. We suggest that T_tr is a better indicator of the glass transition than the temperature at which the total spectral width is 50 G, especially for large probes. The simulation program allowed the determination of the relative intensities of the fast and slow spectral components as a function of temperature; this information was used to clarify the redistribution of the probe above the glass transition of the SAN‐rich component in ABS systems. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 424–433, 2002; DOI 10.1002/polb.10110     

Radiolysis of alkyl benzene sulfonat (ABS) in aqueous solution

Degradation of alkyl benzene sulfonate (ABS) in aerated aqueous solution irradiated with gamma radiation with doses up to 1.8 kGy were studied. The degree of degradation, pH change, the effect of pH on the degradation, COD values and the degradation products were determined. The degradation of ABS increases with the increase of doses and decreases with the increase of ABS concentration. The degradation was somewhat more efficient in slightly acidic and neutral solutions than at basic pH oxalic acid was detected by HPLC as degradation product.     

Natural and artificial weathering characteristics of stabilized acrylic–urethane paints

Depth-profiling by Fourier transform infrared (FTIR) spectroscopy, dynamic mechanical analysis (DMA), microhardness and scanning electron microscopy (SEM) observations have been used to monitor degradation chemistries in two-package acrylic–urethane coatings when exposed to different exposure conditions. Three artificial and three natural weathering protocols (QUV, ASTM D5894, ISO20340, Pipady (south of France), Bandol (south of France) and Kure Beach (USA)) were selected for this study. The same chemical events were found to occur under all conditions, particularly under natural and artificial exposures. Both loss of the amide II band at 1520 cm⁻¹ and carbonyl growth occurred but at relatively low rate owing to the presence of hindered-amine light stabilizers in the film. A less typical loss of urea biuret linkages also occurs during all exposures and results in a change in the balance between urethane and urea links across the depth of the film during weathering. The chemical degradation of the polymer matrix involves the formation of species that are readily ablated from the surface and results in loss of gloss, increase in hardness and a rougher topology. The dramatic loss of gloss observed after Pipady and Bandol exposures show that loss of gloss should not be systematically correlated to the advance in chemical degradation.     

Thermal degradation of styrene-butadiene diblock copolymer: Part 2—Characteristics and mechanism of degradation of the copolymer

The degradation behaviour of the copolymer has been studied under programmed heating conditions and isothermally at 380°C and compared with the characteristics of the degradation of polystyrene (PS), polybutadiene (PB) and a 1:1 by weight blend of the homopolymers, under the same conditions. The degradation shows many similarities to that of the blend. Evolution of styrene from the PS sections is at first inhibited by early volatile products from the PB parts of the chains and is subsequently retarded by other products. The extent of these stabilisation effects is greater in the copolymer than in the blend. In consequence, greater amounts of PS and PB chain structures can persist to higher degradation temperatures than in the case of homopolymer or blend: this explains the considerably higher proportion of toluene in the volatile products and the greater extent of aromatisation of the PB chain fragments.     

Microphase separation in poly(acrylonitrile–butadiene–styrene) (ABS) studied with paramagnetic spin probes. I. Electron spin resonance spectra

Microphase separation in poly(acrylonitrile–butadiene–styrene) (ABS) was studied as a function of the butadiene content and method of preparation with electron spin resonance (ESR) spectra of nitroxide spin probes. Results for the ABS polymers were evaluated by comparison with similar studies of the homopolymers polybutadiene (PB), polystyrene (PS), and polyacrylonitrile (PAN) and the copolymers poly(styrene‐co‐acrylonitrile) (SAN) and poly(styrene‐co‐butadiene) (SB). Two spin probes were selected for this study: 10‐doxylnonadecane (10DND) and 5‐doxyldecane (5DD). The probes varied in size and were selected because their hydrocarbon backbone made them compatible with the polymers studied. The ESR spectra were measured in the temperature range 120–420 K and were analyzed in terms of line shapes, line widths, and hyperfine splitting from the ¹⁴N nucleus; the appearance of more than one spectral component was taken as an indication of microphase separation. Only one spectral component was detected for 10DND in PB, PS, and PAN and in the copolymers SAN and SB. In contrast, two spectral components differing in their dynamic properties were detected for both probes in the three types of ABS samples studied and were assigned to spin probes located in butadiene‐rich domains (the fast component) and SAN‐rich domains (the slow component). The behavior of the fast component in ABS prepared by mass polymerization suggested that the low‐T_g (glass‐transition‐temperature) phase was almost pure PB. The corresponding phase in ABS prepared by emulsion grafting also contained styrene and acrylonitrile monomers. A redistribution of the spin probes on heating occurred with heating near the T_g of the SAN phase, suggesting that the ABS polymers as prepared were not in thermodynamic equilibrium. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 415–423, 2002; DOI 10.1002/polb.10109     

Characterization and formation mechanism of the precipitates generated by irradiation of dicyclohexano-18-crown-6 aqueous solution

Dicyclohexano-18-crown-6 (DCH18C6) aqueous solution was irradiated using ⁶⁰Co source and precipitates containing yellow transparent blocks (PA) and powders (PB) were obtained. TGA analysis confirms that both PA and PB have higher thermal stability than DCH18C6. Both DSC and GPC results suggest that PA might be oligomer and PB were ultrahigh molecular weight polymers. The FTIR spectra indicate that both PA and PB have similar chemical structures containing carboxyl and hydroxyl groups. By using scavengers, it was found that the formation of PA and PB is attributed to the radiation-induced radical polymerization of DCH18C6, and ·OH radical produced by water radiolysis might be a critical species for the formation of PA and PB. These studies help to understand the radiation chemistry behavior of DCH18C6 in the reprocessing of nuclear fuel.     

Degradation of polymer mixtures. IX. Blends of polystyrene with polybutadiene

The degradation of cis-1,4-polybutadiene, polystyrene, and blends of PB and PS has been studied by thermogravimetry, thermal volatilization analysis, and differential scanning calorimetry. Volatile products have been investigated and separated by subambient TVA and characterized spectroscopically. In the degradation of the blends, there is no change in the nature of the volatile products of degradation, but the rate of degradation of the PS component is markedly reduced. The PB component is the first to break down, and during the initial period of degradation of the PB, the PS degradation is apparently inhibited. It is suggested that some of the volatile products of decomposition of PB, most notably 4-vinylcyclohexene, may diffuse into the PS phase in the blend and act as radical inhibitors.     

Activity‐Based Sensing: A Synthetic Methods Approach for Selective Molecular Imaging and Beyond

Emerging from the origins of supramolecular chemistry and the development of selective chemical receptors that rely on lock‐and‐key binding, activity‐based sensing (ABS)—which utilizes molecular reactivity rather than molecular recognition for analyte detection—has rapidly grown into a distinct field to investigate the production and regulation of chemical species that mediate biological signaling and stress pathways, particularly metal ions and small molecules. Chemical reactions exploit the diverse chemical reactivity of biological species to enable the development of selective and sensitive synthetic methods to decipher their contributions within complex living environments. The broad utility of this reaction‐driven approach facilitates application to imaging platforms ranging from fluorescence, luminescence, photoacoustic, magnetic resonance, and positron emission tomography modalities. ABS methods are also being expanded to other fields, such as drug and materials discovery.     

Recycling of ABS and PC from electrical and electronic waste. Effect of miscibility and previous degradation on final performance of industrial blends

The aim of this work, within the framework of polymer recycling, is to upgrade waste from electrical and electronic equipment. Blends of the two major residues were prepared via a melt blending process. These are ABS consisting of a SAN thermoplastic matrix with a dispersed elastomeric (polybutadiene rubber) component and polycarbonate (PC). The effect of partial miscibility and previous degradation levels was investigated. Mechanical characterization of ABS/PC systems was carried out to determine the optimum composition range. Previous degradation levels of the two wastes were investigated by FTIR and little degradation was found on ABS due to the presence of a polybutadiene rubber which is more sensitive to thermo-oxidative processes but no significant degradation was found on PC. Differential scanning calorimetry (DSC) tests demonstrated certain miscibility between the two components by identifying two glass transition temperatures. This partial miscibility, together with the small degradation of the elastomeric component, contributes to a low interaction promoting a decrease on mechanical performance. Scanning electron micrographs (SEM) showed the system morphology and certain lack of adherence along SAN/polybutadiene interface related to degradation of polybutadiene spheres which act as stress concentrators. The use of the equivalent box model (EBM) allowed to quantify the interaction level by determining an interaction/adherence parameter “A”, which turned to be lower than 1 and corroborated the lack of interaction.     

Thermal behaviour of binary and ternary copolymers containing acrylonitrile

Three types of acrylonitrile copolymers (acrylonitrile-styrene-butadiene copolymer (ABS¹), acrylonitrile-styrene random copolymer (SAN²) and acrylonitrile-butadiene random copolymer (BAN³) were studied by thermogravimetry (TG/DTG⁴) and by pyrolysis in a semi-batch process at 450 °C in order to find structure–thermal behaviour relationships. The overlapped thermo-oxidative degradation processes were separated and the corresponding kinetic parameters were calculated. The TG/DTG studies have evidenced that the styrene-acrylonitrile interactions stabilize the nitrile groups reacting by chain scission rather than cyclization and destabilize the styrene units. Also, the cyclization of the acrylonitrile units in ABS is favoured by interactions with the styrene and butadiene units. The pyrolysis behaviour evidenced that the styrene-acrylonitrile interactions in SAN and ABS lead to the formation of 4-phenylbutyronitrile as the most important decomposition compound. ABS shows similar composition of the degradation oil with SAN copolymer therefore in the ABS the styrene-butadiene interactions are less important than those between styrene and acrylonitrile units.     

Comparison of the Effect of an Organoclay,Triphenylphosphate, and a Mixture of Both on the Degradation and Combustion Behaviour of PC/ABS Blends

Summary: Polycarbonate Acrylonitrile-Butadiene-Styrene blends (PC/ABS) with flame retardants Triphenyl Phosphate (TPP), nanoclay and their mixtures were prepared in a twin- screw extruder. The morphological properties were characterized by X-ray diffractometry (XRD) which showed the intercalated structure of nanoclay in the matrix. Thermal stability of the samples was studied using Thermogravimetric Analysis (TGA), and the degradation kinetic parameters were determined using various methods including Kissinger, Flynn-Wall-Ozawa and Coats-Redfern methods. It was found that the sample containing both TPP and nanoclay has the highest activation energy. The activation energy order of PC/ABS blends with different flame retardant packages, obtained by Kissinger method agrees well with that obtained by Coats-Redfern. Cone calorimetry and limited oxygen index (LOI)/underwriters laboratory 94 (UL94) methods were used to investigate the fire behaviour and flammability of materials. The reduced mass loss rate (MLR), peak heat release rate (PHRR) and enhanced LOI of the composite containing mixture system confirmed a synergistic effect of TPP and nanoclay.     

Design and Synthesis of Transparent Poly （acrylonitrile-butadiene-styrene） and Relationship Between Its Phase Construction and Transparency

IntroductionABS resins have been widely applied to the field ofengineering materials because of their excellent me-chanical,electrical,physical,and chemical proper-ties.Typically,ABS resins comprise a rigid copolymermatrix-phase dispersed in a graft copol…