Flame Retardancy and Kinetic Behavior of Ammonium Polyphosphate–Treated Unsaturated Polyester/Phenolic Interpenetrating Polymer Network

In this study, the flammability and kinetic behavior of flame retardant unsaturated polyester (UP)/phenolic resin were investigated. The flame retardant ammonium polyphosphate (APP) was used in this research to improve the flame resistance of a UP/phenolic resin interpenetrating polymer network (IPN). The flame resistance of UP improved from none to V-0 classification by adding phenolic resin and APP. Kinetic behavior study of UP, UP/phenolic, and APP-filled UP/phenolic IPN was carried out by the Borchardt and Daniels method. The results indicated that modification of flammable UP resin markedly improved the total heat release volume of UP and the flame retardancy of the IPN network structure was also enhanced.     

Preparation of phosphorus‐containing phenolic resin and its application in epoxy resin as a curing agent and flame retardant

For the sake of improving the flame retardancy of epoxy resin (EP), a novel phosphorus‐containing phenolic resin (PPR) synthesized in our group instead of conventional phenolic resin (PR) was used to cure EP in the present research. The curing processes and the corresponding crosslinking structure and mechanical performance were investigated by differential scanning calorimeter and dynamic mechanical thermal analysis. Because of the introduction of flame‐retarding elements including P and Si, PPR exhibited higher charring capacity in the condensed phase, which is helpful to construct a char layer of higher quality. Correspondingly, PPR‐cured EP displayed remarkably improved flame retardance as compared to conventional PR‐cured EP through the related evaluations including limiting oxygen index, vertical burning test, and microscale combustion colorimeter. As a multifunction agent, it is believable that PPR possesses potential commercial value to prepare flame‐retardant EP with high performance.     

Influence of water content on failure of phenolic composites in fire

This paper evaluates the structural performance of flame resistant phenolic matrix composites exposed to fire. Experimental fire tests were performed on a glass-phenolic composite under combined static loading and one-sided radiant heating. The reduction to the tension and compression failure strengths of the phenolic composite was measured in these tests for heat flux conditions ranging from 10 kW/m² (∼225 °C) to 75 kW/m² (∼700 °C). It was discovered that the failure strengths of the phenolic composite decreased rapidly in the event of fire, particularly under compressive loading when failure occurred more rapidly than under tensile loading. The phenolic composite, despite having high flame resistance, loses strength more rapidly and fails sooner than a more flammable vinyl ester composite. The study shows that greater flammability resistance does not necessarily result in better structural performance in fire. The poor structural performance of the phenolic composite was due to explosive delamination damage and cracking caused by vaporisation of water in the matrix phase. It is shown that removing water from phenolic composites by natural or artificial ageing reduces the incidence of delamination cracking and thereby improves the materials' structural performance in fire. It is concluded that phenolic composites do not provide good structural performance in fire, even though they have low flame and smoke properties. However, reducing the water content in the matrix phase below about 10% can greatly improve the structural performance of phenolic composites during fire.     

Flame‐retardant and mechanical properties of phenolic foams toughened with polyethylene glycol phosphates

Three kinds of polyethylene glycol phosphates (PEGPs) toughening agents were synthesized by esterification of phosphorus pentoxide (P₂O₅) with polyethylene glycol and characterized by Fourier transform infrared spectra and ³¹P nuclear magnetic resonance. A series of lightweight phenolic foams toughened with different loadings of PEGPs were prepared. Optical microscopy results show that the addition of PEGPs with small molecular weight PEG improves the structural homogeneity of phenolic foams obviously. The flame retardancy of toughened phenolic foams was evaluated by using UL 94, limiting oxygen index, and cone calorimeter. The results indicate that the incorporation of PEGPs not only increases the toughness of phenolic foams but also improves their flame retardancy. Moreover, the thermal stability of PEGPs and the toughened foams was investigated by thermogravimetric analysis. Copyright © 2013 John Wiley & Sons, Ltd.     

Synergistic effect of red phosphorus, novolac and melamine ternary combination on flame retardancy of poly(oxymethylene)

New flame retardant system for poly(oxymethylene) (POM) has been studied. The combination of red phosphorus with novolac and melamine was found to act as an effective flame retardant of POM. The base POM exhibited very low limiting oxygen index (LOI) value of 15.3, while the flame retarded POM gave remarkably high LOI value of 37.5 and UL94 V-1 ranking without dripping at 0.8 mm thickness. The results of cone calorimetry, thermogravimetry and FTIR analysis suggested that the flame retarding mechanism is the intumescent char formation in the condensed phase. Novolac having a phenolic hydroxyl group is miscible with POM, and in the flaming process, red phosphorus yields phosphine and its acidic product such as phosphoric acid due to hydrolysis and oxidation reactions. In addition, all of novolac, melamine and phosphine are able to readily react with formaldehyde generated from POM during burning to give the reinforced and cross-linked char network through the polyaddition and polycondensation reactions. Therefore, the red phosphorus/novolac/melamine ternary combination system could synergistically promote the high flame retardancy of POM without the flaming drips.     

Glass capillary SCOT columns by a single-step coating method

A single-step coating method for the preparation of glass capillary SCOT columns is described. It is reproducible and less time-consuming than the well-known two-step coating procedures. Other methods attempted are discussed briefly. Both the flame ionization and electron capture detectors could be used in conjunction with temperature programming. The separations achieved with an “activity mixture”, phenols and phenolic acids, illustrate the resolution obtained. The columns are suitable for quantitative determinations and a comparison is made with a conventional packed column.     

Preparation and mechanism of polyurethane prepolymer and boric acid co‐modified phenolic foam composite: Mechanical properties,thermal stability,and flame retardant properties

In this work, a new kind of co‐modified phenolic foam was synthesized with polyurethane prepolymer (PUP) and H₃BO₃ by a simple preparation method. Firstly, in order to determine the optimal amount of PUP, the effects of different PUP additions on the mechanical properties, foam microstructure, and pulverization rate of phenolic foam were investigated. Then H₃BO₃ was added to toughened phenolic foam, in order to reduce its fire hazard. The results showed that the mechanical properties of the PFPUP8 phenolic foam composite were the best when the PUP content was 8 wt%. It had a small and regular cell structure, and its pulverization ratio was reduced by 80% compared with that of pristine phenolic foam. Meanwhile, the flame retardant properties of PFPUP8 were improved in different degrees with an increase in the amount of H₃BO₃. Particularly, when the addition of H₃BO₃ was 10 wt%, the peak heat release rate, the total heat release, and the total smoke release values of PFPUP10B were decreased by 35.4%, 42.4%, and 45.2%, respectively, compared with those of PFPUP8. The value of the limit oxygen index was increased by 33.1%. Besides, the addition of H₃BO₃ had no adverse effect on the mechanical properties and pulverization ratio of PFPUP8. In addition, the specific mechanisms of toughening, flame retardant, and smoke suppression are also discussed in this paper on the basis of an investigation into the thermal properties of the toughened flame retardant foam composites by thermogravimetric analysis in N₂ atmosphere.     

Preparation and characterization of phenolic foams with eco-friendly halogen-free flame retardant

The high solid resol phenolic resin was prepared via step polymerization of formaldehyde, paraformaldehyde, and phenol using sodium hydroxide and calcium oxide as catalysts, and employed to prepare the phenolic foams (PFs) by the introduction of retardant additives including eco-friendly halogen-free flame retardants (ammonium polyphosphate), char-forming agents (pentaerythritol), and synergists (zinc oxide, molybdenum trioxide, cuprous chloride, and stannous chloride). The effects of these additives on flame retardancy, heat resistance, and fire properties of flame-retardant composite phenolic foams (FRCPFs) were evaluated by limiting oxygen index (LOI) tests, thermogravimetric analyzer, and cone calorimeter tests. It was found that the flame retardan significantly increased the LOIs of FRCPFs. Compared with PF, heat release rate, total heat release, effective heat of combustion, production or yield of carbon monoxide (COP or COY), and Oxygen consumption (O₂C) of FRCPFs all remarkably decreased. However specific extinction area and total smoke release significantly increased, which agreed with the gas-phase mechanism of the flame-retardant system. The results indicate that FRCPFs have excellent fire-retardant performance and less smoke release. APP/PER/ZnO is shown to be better flame-retardant system for PFs.     

Kinetics study of thermal decomposition of epoxy resins containing flame retardant components

Hyperbranched polyphosphate ester (HPPE) and phenolic melamine (PM) were blended in different ratios with a commercial epoxy resin to obtain a series of flame retardant resins. The thermal decomposition mechanism of their cured products in air was studied by thermogravimetric analysis and in situ Fourier-transform infrared spectroscopy. The degradation behaviours of epoxy resins containing various flame retardant components were found to be greatly changed. The incorporation of phosphorus and nitrogen compounds improved the thermal stability at elevated temperature. The kinetics of thermal decomposition was evaluated by Kissinger method, Flynn-Wall-Ozawa method and Horowitz-Metzger method. The results showed that the activation energy at lower degree of the degradation decreased by the incorporation of flame retardant components, while increased at higher degree of the degradation.     

光固化阻燃单体、树脂合成及其阻燃机理研究

本文综述了过去十余年间中国科技大学施文芳教授研究组在光固化阻燃技术领域的工作成果，主要包括活性单体、稀释剂、光固化树脂配方等体系，品类有磷酸酯类单体、含磷丙烯酸酯、超支化丙烯酸酯树脂、膦酸酯类单体和树脂、丙烯酸化环状磷腈、甲基丙烯酸化三聚氰胺、含磷环氧单体等十余种。同时介绍了这些配方体系的合成、性能和应用方法，以及对其热降解、阻燃性能评价和阻燃机理的研究。     

Physical and mechanical characterization of near-zero shrinkage polybenzoxazines

A new class of phenolic-like thermosetting resins has been developed that is based on the ring-opening polymerization of a benzoxazine precursor. These new materials were developed to combine the thermal properties and flame retardance of phenolics with the mechanical performance and molecular design flexibility of advanced epoxy systems. The polybenzoxazines overcome many of the traditional shortcomings of conventional novolak and resoletype phenolic resins, while retaining their benefits. The physical and mechanical properties of these new polybenzoxazines are investigated and are shown to compare very favorably with those of conventional phenolic and epoxy resins. The ring-opening polymerization of these new materials occurs with either near-zero shrinkage or even a slight expansion upon cure. Dynamic mechanical analysis reveals that these candidates for composite applications possess high moduli and glass transition temperatures, but low crosslink densities. Long-term immersion studies indicate that these materials have a low rate of water absorption and low saturation content. Impact, tensile, and flexural properties are also studied. Results of the dielectric analysis on these polybenzoxazines demonstrate the suitability of these materials for electrical applications. © 1996 John Wiley & Sons, Inc.     

高性能聚苯并(噁)嗪树脂

聚苯并噁嗪树脂作为一种新型酚醛树脂,不仅具有优异的耐热性和阻燃性,而且克服了传统酚醛树脂在成形固化过程中释放小分子的缺点,在制备高性能材料方面已引起研究者的广泛关注。本文综述了近年来国内外为制备高性能化聚苯并噁嗪树脂所作的一些研究工作,包括从主链或侧链中引入苯环等刚性官能团、在主链或侧链中引入可聚合官能团、与另一种高分子形成共混或共聚物以及与其他材料复合形成复合材料等,并对该树脂材料的工业开发前景、国内外研究现状以及发展趋势进行了分析。     

Beer Digestions for Metal Determination by Atomic Spectrometry and Residual Organic Matter

Many standard and official sample digestion procedures for trace metal determination are carried out in open vessels on hot plates. A new procedure for the determination of trace metals by flame atomic absorption spectrometry or inductively coupled plasmaatomic emission spectrometry in beer samples was developed to be performed in closed reactors assisted by microwaves. The results are compared with the ones obtained by other procedures by means of the analysis of the variance. The differences between the procedures are attributed to residual organic matter. Voltammetry, absorption molecular spectrophotometry and high pressure liquid chromatography with a photodiode array detector are used to study the nature of these residues. Nitrobenzoic acids, phenolic acids and other organic compounds are often present after digestion. The results obtained are related to the precision in metal determination by atomic spectrometry. The need for elaboration of certified reference materials for trace metals in beer is suggested.     

Extraction of phenolic compounds from environmental water samples using oil-in-water emulsions

A fast, sensitive and simple oil-in-water emulsion (OWE) method was developed for extraction of four phenolic pollutants in environmental water samples followed by gas chromatography and flame ionization detection. In this method, the density of a binary organic solvent (one heavier and one lighter than the sample) was balanced with the density of the sample solution. A stable emulsion was formed at room temperature under vigorous stirring using a Teflon-coated magnetic stirring bar. After addition of 10 µL of the heavier organic solvent and centrifugation, phase separation occurred. The influence of several important parameters on the extraction efficiency of phenolic compounds was evaluated. Under optimized experimental conditions, the calibration graphs were linear in the concentration range 0.025–20 mg L^?1 with coefficients of determination more than 0.9994. The limits of detection and quantification were in the range 19.2–76.0 and 64.1–251.0 μg L^?1, respectively. Intra-day and inter-day precisions were less than 5.0 %. The procedure was used for the determination of phenolic compounds in spiked water samples with good results. Recoveries range from 96.5 to 103.0%, and relative standard deviations are <2.5% (for n?=?3).     

Chromatographic Techniques for the Determination of Free Phenol in Foundry Resins

Phenol is a toxic compound present in a wide variety of foundry resins. Its quantification is important for the characterization of the resins as well as for the evaluation of free contaminants present in foundry wastes. Two chromatographic methods, liquid chromatography with ultraviolet detection (LC-UV) and gas chromatography with flame ionization detection (GC-FID), for the analysis of free phenol in several foundry resins, after a simple extraction procedure (30 min), were developed. Both chromatographic methods were suitable for the determination of phenol in the studied furanic and phenolic resins, showing good selectivity, accuracy (recovery 99–100%; relative deviations <5%), and precision (coefficients of variation <6%). The used ASTM reference method was only found to be useful in the analysis of phenolic resins, while the LC and GC methods were applicable for all the studied resins. The developed methods reduce the time of analysis from 3.5 hours to about 30 min and can readily be used in routine quality control laboratories.     

Phenolic resin/polyhedral oligomeric silsesquioxane (POSS) composites: Mechanical,ablative, thermal,and flame retardant properties

Three different polyhedral oligomeric silsesquioxanes (POSS), trisilanolphenyl polyhedral oligomeric silsesquioxane (T‐POSS), octaaminophenyl polyhedral oligomeric silsesquioxanes (OAPS), and octaphenyl polyhedral oligomeric silsesquioxanes (OPS) were incorporated into phenolic resin (PR), respectively; PR/POSS composites were successfully prepared, and the properties of PR/POSS composites were studied. The limiting oxygen index (LOI), cone calorimeter, and thermal gravimetric analysis (TGA) were used for the estimation of flame retardancy and thermal stability. Oxyacetylene flame test and flexural strength test were used to study the ablative and mechanical properties of the PR/POSS composites. The results indicated that T‐POSS was more effective in improving the flame retardancy of PR than OAPS or OPS. Meanwhile, compared with pure PR, the second line ablation rates of PR/4% T‐POSS, PR/4% OAPS, and PR/4% OPS were significantly reduced by 53.3%, 61.9%, and 40.0%, respectively. In addition, the thermal stability and flexural strength of PR/4% T‐POSS were significantly higher than that of all other PR composites.     

Development of a needle trap device packed with titanium‐based metal‐organic framework sorbent for extraction of phenolic derivatives in air

We developed a novel method of needle trap device packed with titanium‐based metal‐organic framework for the extraction of phenolic derivatives in air followed by gas chromatography‐flame ionization detector analysis. The synthetized adsorbent was packed inside a 22‐gauge spinal needle. This method was first tested at laboratory scale, and then was used for field sampling of phenolic derivatives in air. A glass chamber placed on a heater at 60°C was used to provide different concentrations of phenolic derivatives. The desorption conditions and breakthrough volume were optimized using response surface methodology. The limit of detection and limit of quantitation of the proposed method were estimated to be in the range of 0.001–0.12 and 0.003–0.62 ng/mL, respectively, indicating a high sensitivity for the suggested sampler. Storing the packed needle trap device in a refrigerator at 4?C for 60 days did not dramatically affect the storage stability. Our findings indicated that there was a high correlation coefficient (R² = 0.99) between the measurement results of this method and the NIOSH recommended method (XAD‐7 sorbent tube). Therefore, it can be concluded that the needle trap device packed with titanium‐based metal‐organic framework can be used as a efficient method for extraction of phenolic derivatives in air.     

The GLC Separation of Hydroxyl-Substituted Amines of Biological Importance Including the Catecholamines. Preparation of Derivatives for Electron Capture Detection

Abstract

The catecholamines and related biological amines have been converted to trimethylsilyl ether-amide derivatives through a two-step reaction sequence. All hydroxyl groups (phenolic and alcohol) were converted to TMSi ethers by reaction with TSIM. N-acylimidazole was added to the reaction mixture to effect the acylation of primary and secondary amines. TMSi-Ac (trimethylsilyl ether-acetyl) and TMSi-HFB (trimethylsilyl ether-heptafluorobutyryl) derivatives were studied. The HFB derivatives had excellent GLC properties. It is proposed to compare the sensitivity of detection of these and related compounds by flame ionization and by electron capture detection systems.     

Photochemical behaviour of fire-retarded polymers

The influence of a non-halogenated intumescent fire retardant on the photooxidation of polypropylene is reported. The photooxidation of polypropylene stabilised with a phenolic antioxidant and two redox antioxidants (HALS), without and with the flame retardant has been studied. The chemical modifications resulting from UV-light exposure with wavelengths above 300 nm in the presence of oxygen were followed by IR and UV-visible spectroscopies. Special attention was given to the influence of each component on the rate of oxidation of the polymeric matrix. The photooxidation of the fire-retarded polymer can be described by two independent phenomena: the photooxidation of the intumescent agent and the photooxidation of the polymer. The results obtained offer new insight in the formulation of stabilised fire-retarded PP for outdoors applications.     

Conductive polymers as new media for solid-phase extraction: isolation of chlorophenols from water sample

Three different conductive polymers, poly-N-methylaniline (PNMA), polyaniline and polydiphenylamine were synthesised and used as sorbents for the solid-phase extraction of some phenolic compounds from water. The separation and determination was, subsequently, performed by gas chromatography-electron-capture and flame ionization detection. Among these easy-made polymers, PNMA gave better recovery for the extraction of the studied analytes. The capability of the PNMA to extract other non-polar compounds such as chloro- and methylbenzene, decane, decanol, cyclohexane and cyclohexanol was also studied. The polymer showed some sort of selectivity towards aromatic compounds than aliphatic. Preconcentration of sample volumes up to 1 l at pH 2 using 120 mg of PNMA led to acceptable recoveries for phenolic compounds, except for phenol. Recovery of phenol for 100 ml of water was 72%. Limits of detection for chlorophenols when 250 ml river water was preconcentrated were between 1 and 40 ng l(-1), analyzed by GC-electron-capture detection.