Effects of temperature on the weathering of engineering thermoplastics

We have determined the activation energies (E_a) of yellowing and gloss loss for a large number of engineering thermoplastics and blends under accelerated weathering conditions. The E_a often depend on the property measured and exposure conditions, although they vary over a fairly small range. Under the CIRA/sodalime-filtered xenon arc conditions most likely to be representative of outdoor exposure, the E_a for gloss loss was ≤5 kcal/mol for all samples tested. The E_a for yellowing was also ≤5 kcal/mol except for SAN and ABS. Evidently the color bodies formed from photo-oxidation of SAN are more sensitive to temperature. A reaction with an E_a of 5 kcal/mol will increase its rate by about 33% for each 10 °C increase in temperature near room temperature. Temperature is an important, but not overwhelming, variable in the weathering of most engineering thermoplastics.     

Studies on the blends of cardanol-based epoxidized novolac resin and CTPB

Cardanol-based novolac-type phenolic resins were synthesized with different mole ratios of cardanol-to-formaldehyde, viz., 1:0.6, 1:0.7, and 1:0.8. These novolac resins were epoxidized with molar excess of epichlorohydrin at 120 °C in basic medium. The epoxidized novolac resins were, separately, blended with different weight ratios of carboxyl-terminated polybutadiene liquid rubber ranging between 0-25 wt% with an interval of 5 wt%. All the blends were cured at 150 °C with 40 wt% polyamide. The formation of various products during the curing of blend samples has been studied by Fourier-transform infra-red spectroscopic analysis. The tensile strength and elongation-at-break of the cured samples increased up to 15 wt% in the blend and decreased thereafter. This blend sample was also found to be most thermally stable system. The blend morphology, studied by scanning electron microscopy analysis, was finally correlated with the structural and property changes in the blends.     

Accelerated weathering of unbleached and bleached Kraft wood fibre reinforced polypropylene composites

In this paper, combined moisture/ultraviolet (UV) weathering performance of unbleached and bleached Kraft wood fibre reinforced polypropylene (PP) composites was studied. Composites containing 40 wt% fibre with 3 wt% of a maleated polypropylene (MAPP) coupling agent were fabricated using extrusion followed by injection moulding. Composite mechanical properties were evaluated, before and after accelerated weathering for 1000 h, by tensile and impact testing. Differential scanning calorimetry (DSC), X-ray diffraction (XRD), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM) were also carried out to assess the changes occurring during accelerated weathering. Bleached fibre composites initially showed higher tensile and impact strengths, as well as higher thermal stability and greater crystallinity. During accelerated weathering, both unbleached and bleached fibre composites reduced tensile strength (TS) and Young's modulus (YM), with the extent of the reduction found to be similar for both unbleached and bleached fibre composites. Evidence supported that the reduction of TS and YM was due to PP chain scission, degradation of lignin and reduced fibre-matrix interfacial bonding.     

Photooxidative behaviour of polyethylene/polyamide-6 blends

The photochemical behaviour of several polyethylene/polyamide-6 blends was studied under conditions of artificial accelerated weathering. Particular attention was paid to five different compositions ranging from pure polyethylene to pure polyamide with blends of PE/PA-6 of various compositions: 75/25, 50/50 and 25/75 wt/wt%. Analysis by infrared spectroscopy of the chemical modifications caused by photooxidation showed that exposing the polyethylene/polyamide-6 blends to UV-light irradiation led to the formation of oxidation photoproducts in both polymer phases. In agreement with both the mechanical and spectroscopic analyses, the photooxidation rate of the blends was observed to be much higher than that of the homopolymers. The results given in this paper suggest that photooxidation of the PE/PA blends starts in the polyamide phase and that the subsequent photooxidation of the polyethylene phase may be initiated by the radicals coming from the oxidation of PA.     

Preparation and application of porous calcium fluoride—a novel fluorinating reagent and support of catalyst

A novel material, porous calcium fluoride (PCF) with more than 60 m²/g surface area, was prepared by the reaction of soda lime (SL) with anhydrous hydrogen fluoride (AHF), and its application as a fluorinating reagent and support of catalyst was investigated.     

Environmentally degradable LLDPE/esterified styrene-maleic anhydride (ESMA) blends

LLDPE was blended with esterified styrene-maleic anhydride (ESMA) to improve the environmental degradation characteristics of LLDPE. ESMA was synthesized by esterifying styrene maleic anhydride (SMA) with n-decanol. LLDPE was blended with ESMA (EDP blends) and SMA separately in a single screw extruder by melt mixing. Composition of ESMA was varied from 20 to 40 wt% in the blends. LLDPE grafted with glycidyl methacrylate (LLDPE-g-GMA) was used as compatibilizer to improve the compatibility. Scanning electron photomicrograph (SEM) of cryofractured impact specimens showed significant reduction in domain size and uniform distribution of ESMA in LLDPE matrix in presence of compatibilizer in 70/30 blends. Environmental degradability was assessed by subjecting the films to soil burial test and exposure to buffer solution of different pH. Environmental degradation was followed by measuring the periodic change in weight of the blend samples. Films were exposed to accelerated and natural weathering and photodegradation was assessed by noting the embrittlement time of the film. Films of compatibilized blends fragmented at a faster rate than the films of uncompatibilized blend. Carbonyl index of films subjected to natural weathering was also found to be higher than that for the virgin LLDPE films.     

The epoxy–polycarbonate blends cured with aliphatic amine—I. Mechanism and kinetics

Reaction mechanism of the PC–epoxy blends cured by aliphatic amine has been investigated by varying PC contents in the blends. The transamidation reaction tends to convert nearly all the carbonates into N-aliphatic aromatic carbamates even at ambient temperature before normal curing. The remaining amine proceeds the normal curing with epoxy at a higher temperature (80°C). For the PC–epoxy/aliphatic amine blend containing 6 wt % PC, the yielded N-aliphatic aromatic carbamate further reacts with amine to produce the urea structure. The urea undergoes substitution reaction with the hydroxyl formed from the normal curing to give the N-aliphatic aliphatic carbamate. For the blend containing 12 wt % PC, the N-aliphatic aromatic carbamate converts into the N-aliphatic aliphatic carbamate via two different routes. For the blend containing lower molecular weight of the aliphatic amine, the N-aliphatic aromatic carbamate reacts with hydroxyl to form the N-aliphatic aliphatic carbamate directly. For the blend containing higher molecular weight of aliphatic amine, the N-aliphatic aromatic carbamate decomposes into the aliphatic isocyanate accelerated by the presence of the residual oxirane. The isocyanate formed then reacts with hydroxyl to yield the N-aliphatic aliphatic carbamate. The activation energy (E_a) and preexponential factor (A) of the PC–epoxy/POPDA blends decrease with the increase of the PC content. Kinetic study by thermal analysis by the method of autocatalyzed model is able to correctly predict oxirane conversion vs. time relationship for the neat epoxy/aliphatic amine and the PC–epoxy/aromatic amine systems because the dominant reaction is the normal curing reaction between amine and oxirane. The model fails to predict the PC–epoxy/aliphatic amine system because the system is complicated by several other reactions besides the normal curing reaction. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2169–2181, 1997     

Effect of fluorine functional groups on surface and mechanical interfacial properties of epoxy resins

To improve the surface and mechanical interfacial properties of epoxy resins, fluorine-containing epoxy resin (FEP) was prepared and blended with a commercially available tetrafunctional epoxy resin (TGDDM). As a result, when the fluorine content increased, the total surface energy of TGDDM/FEP blends was gradually decreased, while the water repellency of the blends was increased. The glass transition temperature and thermal stability factors of the blends showed maximum values at 20-40 wt% FEP compared with neat TGDDM epoxy resins. And the mechanical interfacial properties of the blend specimens were significantly increased with increasing the FEP content, which could be attributed to the intermacromolecular interactions in the cured TGDDM/FEP blends. These results indicate that the water repellency and toughness improvements have been achieved without significantly deterioration of the thermal properties in the TGDDM/FEP blends.     

工程塑料近二十年进展

叙述了通用工程塑料、特种工程塑料、聚烯烃复合材料及合金和ABS过去二十年进展,重点讨论了工程塑料单体新技术及新单体/新聚合物、聚合物增韧核——壳结构理论、纳米复合材料、反应器合金、长纤维增强热塑性塑料(LFT)、工程塑料回收及产业动态。     

Reproducibility of Florida weathering data

We have investigated the consistency and reproducibility of Florida outdoor weathering data for aromatic engineering thermoplastics. Weather and broadband (295–385 nm) UV dose data for the 14-year period from 1989 to 2002 show that considerable variability is expected for exposures with duration < 1 year, but that standard deviations for UV exposure and temperature are approximately 7% of the mean at 1 year and <5% at 2 years and greater. Only rainfall shows significant long-term variability. Weathering data on pigmented aromatic engineering thermoplastics were consistent with these expectations. Overall trends and rates of color and gloss shifts were generally reproduced for samples exposed at different times. Color shift data were generally reproducible within a ΔE of 2 and 60° gloss loss within 10 units for samples beginning exposure 6 months apart. However, very large differences in absolute values for properties can occur for data taken near periods of rapid change, especially for gloss loss. Surprisingly, considering the data as a function of broadband UV dose rather than exposure time did not seem to reduce scatter. This emphasizes the problem of comparing results between data sets for exposure times < 1 year. We conclude that Florida data do provide a useful benchmark when rates and general trends are compared, but not for absolute values at arbitrary times.     

An investigation of glasses for capillary chromatography

An investigation was conducted of various glasses, other than soda lime or borosilicate, for use in glass capillary gas chromatography. The work has uncovered some unique chromatographic qualities in the use of potash soda lead and fused silica glasses as materials for making glass capillary columns. The fused silica proved to be an ideal material for capillary column construction, being inherently more inert than glass containing metal oxides. It has been shown that through the use of thin wall capillary tubing of high flexibility many of the mechanical problems associated with glass capillary columns, such as fragility and column straightening, can be avoided.     

Meltable phenylethynyl-capped oligoimide resins derived from 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene and 3,4′-oxydianiline

A series of meltable oligoimide resins with controlled molecular weights by reactive phenylethynyl endcapping groups have been prepared by the thermal polycondensation of 3,3′,4,4′-biphenyltetracarboxylic dianhydride (s-BPDA) with the aromatic diamine mixtures consisting of different mole ratios of 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene (1,4,4-6FAPB) and 3,4′-oxydianiline (3,4′-ODA) in the presence of 4-phenylethynylphthalic anhydride (PEPA) as molecular weight-controlling and reactive endcapping reagent. Experimental results indicated that the molecular weight-controlled oligoimide resins were mixtures containing a series of biphenylethynyl-endcapped oligoimides with different chemical structures and different molecular weights. The typical oligoimide resins could be melted at temperatures of 300 °C to yield stable molten fluid with melt viscosity of 13.4 Pa s, which was suitable for melt processing. The molten oligoimide resins could be further polymer chain extended and crosslinked by thermal curing of the reactive phenylethynyl groups to give strong and tough thermosetted polyimides. Thus, the oligoimide resin with calculated molecular weight of 2500 exhibited not only good meltability with low melt viscosity, but also high melt stability and fluidability at temperatures of <300 °C. After thermal curing, the obtained thermosetted polyimide showed high glass transition temperature (>316 °C, DMA), excellent thermal stability with initial thermal decomposition temperature of 588 °C and good mechanical properties with flexural strength of 159.1 MPa, flexural moduli of 3.3 GPa, tensile strength of 94.7 MPa and elongation at breakage of 9.0%.     

Pyrolytic hydrolysis of polycarbonate in the presence of earth-alkali oxides and hydroxides

The rise in the use of polycarbonate (PC) calls for the development of after-use treatments. In this work, we describe a process for obtaining bisphenol A (BPA), phenol and isopropenyl phenol (IPP) from PC by hydrolysis at temperatures between 300 and 500 °C. The experiments were carried out in a steam atmosphere in the presence of MgO, CaO, Mg(OH)₂ or Ca(OH)₂ as catalysts, respectively. The results were compared with the hydrolysis of PC in the absence of any catalysts. All of these catalysts accelerated the hydrolysis of PC drastically, with MgO and Mg(OH)₂ being more effective than their Ca counterparts. The differences between oxides and hydroxides were negligible indicating the same mechanism for both, oxides and hydroxides. BPA was the main product at 300 °C, with a yield of 78% obtained in the presence of MgO. At 500 °C, BPA was mainly degraded to phenol and isopropenyl phenol (IPP). It can be shown that a combined process involving PC hydrolysis at 300 °C and BPA fission at 500 °C leads to high yields of phenol and IPP and the drastic decrease of residue.     

The synthesis,characterization, and weathering behavior of polycarbonates derived from 3,3′-dihydroxydiphenyl ether

Previous studies of the photodegradation of bisphenol A polycarbonate (BPA PC) indicate that both alkyl side chain and ring oxidation play significant roles. In order to determine the relative importance of these two pathways in the photoyellowing that accompanies photodegradation, side chain free polycarbonates based on 3,3′-dihydroxydiphenyl ether were synthesized and tested. Both accelerated weathering experiments using a QUV test apparatus and outdoor weathering indicated that these polymers photoyellowed faster than BPA PC. This suggests that ring oxidation is an important source of photoyellowing of aromatic polycarbonates.     

Pyrolysis mass spectrometry analysis of polycarbonate/poly(methyl methacrylate)/poly(vinyl acetate) ternary blends

Direct insertion probe pyrolysis mass spectrometry (DIP-MS) analyses of polycarbonate/poly(methyl methacrylate)/poly(vinyl acetate), (PC/PMMA/PVAc), ternary blends have been performed. The PC/PMMA/PVAc ternary blends were obtained by coalescing from their common γ-cyclodextrin-inclusion compounds (CD-ICs), through the removal of the γ-CD host (coalesced blend), and by a co-precipitation method (physical blend). The coalesced ternary blend showed different thermal behaviors compared to the co-precipitated physical blend. The stability of PC chains decreased due to the reactions of CH₃COOH formed by deacetylation of PVAc above 300 °C, for both coalesced and physical blends. This process was more effective for the physical blend most likely due to the enhanced diffusion of CH₃COOH into the amorphous PC domains, where it can further react producing low molecular weight PC fragments bearing methyl carbonate chain ends. The decrease in thermal stability of PC chains was less significant for the coalesced ternary blend indicating that the diffusion of CH₃COOH was either somewhat limited or competed with intermolecular reactions between PMMA and PC and between PMMA and PVAc, which were detected and were associated with their close proximity in the intimately mixed coalesced PC/PMMA/PVAc ternary blend.     

Quality assurance of recycled engineering plastics using blend technology

The automotive, electrical and electronic sectors account for over 12% of all plastics consumed. A large fraction of these polymers are engineering plastics representing a value considerably higher than that of commodity thermoplastics; hence, mechanical recycling including upgrading efforts appears economically attractive. This paper shows some methods of upgrading the property profile of ABS from dismantled automobiles using polymer blend technology. The results for blends of ABS with PC or PA are reported. The aim of blending of the waste materials is twofold: to reduce the number of plastic materials to be recycled in car dismantling plants, and to improve properties of the ABS scrap, which is the main engineering plastic in the waste stream from automobiles.     

Glow wire ignition temperature (GWIT) and comparative tracking index (CTI) of glass fibre filled engineering polymers, blends and flame retarded formulations

Engineering thermoplastic polymers such as polyamides, polycarbonates, semi-crystalline aromatic polyesters and their blends are widely used as insulating materials in electrical and electronic appliances. Flame retardants are often employed in the formulation of these materials, since good performance in terms of ignition and tracking resistance, evaluated by Glow Wire Tests (GWIT) and Comparative Tracking Index (CTI) are required in these applications. In this paper, a comparative evaluation of GWIT and CTI performances has been simultaneously performed for a wide set of glass fibre filled materials chosen among engineering thermoplastics and their blends. Some flame retarded formulations have been also tested, in order to screen the effects of various additives. Useful indications have been obtained on the effect of each polymer and additives on GWIT and CTI properties. In addition, interesting synergies have been observed, especially by blending polyesters and polyamides. Thermogravimetric measurements of char yields have been successfully related with CTI behaviour. The presence of additives changes the structure of the carbonaceous residue, hence the conductivity of the tracks. Neat polycarbonate passed the GWIT test but not CTI, while poly(butylene terephthalate) showed the best balance of GWIT and CTI performance among the pure resins tested. Blending polycarbonate with polyester did not improve significantly GWIT performance, but had a negative effect on tracking resistance. Polyesters/polyamide blends were dominated by polyester in GWIT, but they showed synergistic effects in CTI.     

Effects of plastic additives on depolymerization of polycarbonate in sub-critical water

The effects of plastic additives on depolymerization of polycarbonate (PC) in sub-critical water were examined. Depolymerization of PC with two additives was carried out in an autoclave at temperatures from 533 to 613 K for reaction times ranging from 15 to 60 min. The additives used were a flame retardant (decabromodiphenyl ether, DBDPO) and a plasticizer (di-n-octyl phthalate, DnOP). The main products of PC depolymerization in the presence or absence of the additives were bisphenol A (BPA) and phenol, which were identified by Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and gas chromatography mass spectrometry (GC-MS), and quantified by gas chromatography (GC). The addition of DBDPO accelerated the hydrolysis of PC while the addition of DnOP had the opposite effect, and both additives reduced the yield of BPA. The activation energy for PC depolymerization in sub-critical water was found to be lower with DBDPO additive than with DnOP.     

Preparation of monodispersed vinylpyridine–divinylbenzene porous copolymer resins and their application to high-performance liquid chromatographic separation of aromatic amines

For the separation of aromatic amines, two types of monodispersed porous polymer resins were prepared by the copolymerization of 2-vinylpyridine and 4-vinylpyridine with divinylbenzene in the presence of template silica gel particles (particle size 5 μm), followed by dissolution of the template silica gel in an alkaline solution. The transmission electron micrographs and the scanning electron micrograph revealed that these templated polymer resins have a spherical morphology with a good monodispersity and porous structure. Using these monodispersed polymer resins, the high-performance liquid chromatographic separation of aromatic amines in the mobile phases of pHs 2.0, 2.9, 4.1, 7.2 and 11.7 were carried out. The 2-vinylpyridine–divinylbenzene copolymer resins showed slightly stronger retentions for aromatic amines than the 4-vinylpyridine–divinylbenzene copolymer resins. Under acidic conditions (around pH 2.0), aniline and the toluidines showed no retention on these copolymer resins due to the repulsion between the cationic forms of these amines and pyridinium cations in the stationary phase, whereas less basic aromatic amines or non-basic acetanilide showed slight retentions. Above pH 4.1, the separation of aromatic amines with these polymer resins showed a typical reversed-phase mode separation. Therefore, the separation patterns of aromatic amines are effectively tunable by changing the pH value of the mobile phases. A good separation of eight aromatic amines was achieved at pH 2.9 using the 2-vinylpyridine–divinylbenzene copolymer resins.     

Study on flame-retardant mechanism of polycarbonate containing sulfonate-silsesquioxane-fluoro retardants by TGA and FTIR

The flame retardancy of bisphenol A polycarbonate (PC) containing potassium diphenylsulfone sulfonate (KSS), poly(aminopropyl/phenylsilsesquioxane) (PAPSQ) and poly(vinylidenefluoride) (PVDF) was measured by limited oxygen index (LOI) and examined according to UL94. A high LOI and UL94 V-0 rating for 1.6 mm thickness samples were obtained by a combined use of equivalent KSS, PAPSQ and PVDF at 0.1-0.3 wt% loading, respectively. The improvement in flame retardancy of PC compositions arose from the synergistic interaction of three additives. Thermogravimetric analysis (TGA) indicated that the combination decreased the activation energy (E) of PC degradation and elevated the thermal degradation rate of PC to ensure the formation of an insulating carbon layer. FTIR analysis showed that the LOI char of PC containing the three additives took on a highly cross-linking aromatic ester and ether structure.