Enhanced flame retardancy of unsaturated polyester resin composites containing ammonium polyphosphate and metal oxides

Three metal oxides (MOs) (Fe₂O₃, Sb₂O₃, Al₂O₃) were incorporated into blends of unsaturated polyester resin (UPR)/ammonium polyphosphate (APP) composites with the aim of studying and comparing their synergistic effect on flame retardancy with APP. The UPR-APP/MOs composites were prepared, then the thermal stability and flame-retardant properties of the UPR composites were evaluated by thermogravimetric analysis (TGA), limiting oxygen index (LOI), vertical burning test (UL-94), and cone calorimetry test (CCT). Besides, residues after CCT were characterized by scanning electron microscopy and laser Raman spectroscopy. The LOI values of the UPR composites with 0.5 wt% MOs increased to around 40%. However, the CCT results indicated that the incorporation of Sb₂O₃ brought an increase in the total heat release. Moreover, these three MOs had different effects on the process of thermal degradation of UPR composites from the TGA results. Based on the above results, Al₂O₃ provided a best promotion on flame retardancy among three MOs.     

Flame retarded epoxy resins by adding layered silicate in combination with the conventional protection‐layer‐building flame retardants melamine borate and ammonium polyphosphate

The pyrolysis and flammability of phosphonium‐modified layered silicate epoxy resin nanocomposites (EP/LS) were evaluated when LS was combined with two flame retardants, melamine borate (MB) and ammonium polyphosphate (APP), that also act via a surface protection layer. Thermogravimetry (TG), TG coupled with Fourier Transform Spectroscopy (TG‐FTIR), oxygen index (LOI), UL 94 burning chamber (UL 94) and cone calorimeter were used. The glassy coating because of 10 wt % MB during combustion showed effects in the cone calorimeter test similar to nanodispersed LS, and somewhat better flame retardancy in flammability tests, such as LOI and UL 94. Adding APP to EP resulted in intumescent systems. The fire retardancy was particularly convincing when 15 wt % APP was used, especially for low external heat flux, and thus, also in flammability tests like LOI and UL 94. V0 classification is achieved when 15 wt % APP is used in EP. The flame retardancy efficiency of the protection layers formed does not increase linearly with the MB and APP concentrations used. The combination of LS with MB or APP shows antagonism; thus the performance of the combination of LS with MB or APP, respectively, was disappointing. No optimization of the carbonaceous‐inorganic surface layer occurred for LS‐MB. Combining LS with APP inhibited the intumescence, most probably through an increase in viscosity clearly above the value needed for intumescent behavior. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

New ecological polyester resins with reduced flammability and smoke evolution capacity

Smoke evolution in a smoke chamber 750 × 750 × 1000 ± 5 mm (Polish Standard PN‐91/K‐02501 equivalent to UIC 561‐OR 1991) was studied in, and the oxygen index flammability test (Polish Standard PN‐76/C‐89020) was carried out for, glass‐reinforced polyester (GRP) laminates obtained with unsaturated polyester (UP) resins containing chlorine and bromine in the chain. In these studies, the effect on these properties of such additives as ZnSnO₃ (ZS), ZnSn(OH)₆ (ZHS), Al(OH)₃, or Mg(OH)₂ and Sb₂O₃ in up to 30 mass % was determined. The most efficient ignition and smoke‐evolution retarder from among the investigated compounds were ZS and ZHS, and an essential reduction in smoke evolution was also observed with Sb₂O₃. GRP laminates with these additives meet the fire safety recommendations concerning smoke evolution for materials used in transportation and in the building industry. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 379–382, 1999     

Experimental investigation of the suppression effects of ammonium polyphosphate on explosion characteristics of unsaturated polyester resin dust

The suppression effects of Ammonium Polyphosphate (APP) with different mass fractions on the maximum explosion pressure (P_max), the explosibility index (K_st), the minimum ignition energy (MIE) and the minimum ignition temperature (MIT) of unsaturated polyester resin (UPR) dust were studied. Results indicated that the explosion severity and the ignition sensitivity of UPR dust decreased gradually when the mass fractions of APP increased. There existed a minimum inerting concentration (MIC), and the explosion of UPR dust could be suppressed completely by 60 wt% APP. Moreover, APP had a great inhibiting effect on the MIE of UPR dust cloud. The calculated MIE of UPR dust cloud increased from 10 mJ to 998 mJ when the mass fractions of APP increased to 30 wt%. Furthermore, the MIT of UPR dust cloud increased with the increase of the mass fractions of APP. When the mass fraction of APP increased to 80 wt%, the MIT increased by 290°C. The suppression mechanism of APP was studied according to thermogravimetry (TG) and differential scanning calorimetry (DSC) tests. Thermal analysis results showed that the addition of APP could increase the thermal stability of UPR. The suppression mechanism was reflected on the consumption of H and OH radicals.     

The effect of nanoclay and MWNT on fire‐retardency and mechanical properties of unsaturated polyester resins

The influence of nanomaterials such as Multi‐Walled Carbon NanoTubes (MWNT) and organoclay (Cloisite 30B) on the physical and mechanical properties of thermoset matrix such as Unsaturated Polyester (UP) resins is investigated. Although styrene containing UP resins have a wide spread application in industry, lack of information exists regarding the behavior of MWNT/organoclay/polyester ternary nanocomposite systems. The main aim of this research was first to evaluate the effect of nanofiller on the flammability of UP resins and, second, to characterize their mechanical properties such as toughness and their tensile strength. The rheological studies showed shear thinning for samples of UP resins containing MWNT and Cloisite 30B. The cone calorimetry measurement was used to evaluate the flame‐retardency, the gas emission of the nanocomposite and whether or not this system can be designated as a nanocomposite. This was understood in the test by the peak heat release rate being lowered and shifted to shorter times. Furthermore, the tensile and impact properties of samples were evaluated. The obtained results indicated that nanofiller particles caused both increase and decrease in the impact and tensile strength. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

2步法合成双环戊二烯型不饱和聚酯树脂

采用2步法合成了原子灰用双环戊二烯(DCPD)型不饱和聚酯树脂,研究了原料用量对树脂性能影响,当n(顺酐)∶n(工业DCPD)∶n(精制DCPD)∶n(二元醇)=2.0∶0.7∶0.5∶1.75时,树脂性能稳定,原子灰综合性能如气干性、耐热性、打磨性、刮涂性、柔韧性等良好。     

不饱和聚酯树脂产品质量存在的问题及其建议

概述了不饱和聚酯树脂的分类及应用;提出了国内不饱和聚酯树脂产品质量存在的问题及其建议.     

Photo‐fabricated unsaturated polyester resin composites reinforced by kenaf fibers,synthesis and characterization

New bio‐fiber composites (UPRC) cured by ultraviolet radiation were produced using kenaf fiber as reinforcing agent and unsaturated polyester resins as matrix in the presence of styrene and IRGACURE 1800 as photoinitiator. Unsaturated polyester resins based on palm oil were prepared from various ratios of monoglyceride (MG)/maleic anhydride (MA) by the interaction of the corresponding MG monomer, with different equivalents of MA, in the presence of 2‐methylimidazole as catalyst. The various characteristics of the obtained bio‐fiber composites, including mechanical, gel content, water absorption and thickness swelling test, thermal analysis, were determined and the data were discussed. Bio‐fiber composite with MG: MA ratio (1 : 4 eq./eq.) showed better mechanical properties (tensile, flexural, and impact strength) than other formulations. Gel content increased as the amount of MA was increased up to the MG: MA ratio was 1 : 4 (eq./eq.) then slightly decreased at the higher ratio formulation. Bio‐fiber composite (UPRC_c) was considered the best prepared bio‐fiber composite which contained higher degree double bond, cross‐linking and thermal stability. Moreover, morphological study of selected examples of the formed bio‐fiber composites was also carried out and showed the evidence of the enhancement of the compatibility between fiber and polymer matrix. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

不饱和聚酯型人造大理石的力学性能

简述了不饱和聚酯(UPR)型人造大理石的制备工艺。研究了质量比为4∶1的Al(OH)3/Ca(OH)2复合填料用量对不饱和聚酯型人造大理石力学性能的影响,对制得的人造大理石的耐腐蚀性进行了测试,采用光学显微镜观察了试样腐蚀前后的表面形貌。结果表明,在复合填料与UPR质量比为1.86∶1时,弯曲强度、压缩强度达到最大,分别为55.88 MPa和96.04 MPa。甲苯对人造石的腐蚀作用最大,氢氧化钠次之,硫酸腐蚀作用较小,腐蚀介质主要对不饱和树脂聚合物产生腐蚀,从而导致人造石力学性能降低。     

Ultraviolet‐curing behavior and mechanical properties of a polyester acrylate resin

Ultraviolet (UV) curing technology has been widely used in many applications because it has several distinct advantages compared to solvent‐based processes or thermal‐curing technology. The effects of photoinitiator types and their contents as well as reactive diluent types and their contents on the UV‐curing behavior and mechanical properties of a UV‐curable polyester acrylate resin were investigated in this study. Three photoinitiators, Irgacure 184, Darocur 1173, and benzophenone, were used in this study. Hexanediol diacrylate, tripropylene glycol diacrylate, and trimethylol propane triacrylate were used as reactive diluents to modify the properties of the acrylate resin. The change of chemical structure during UV curing was monitored by FTIR. A universal testing machine was used to measure the tensile properties of various UV‐cured acrylate films of different compositions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3921–3928, 2004     

Unsaturated polyester resin via chemical recycling of off‐grade poly(ethylene terephthalate)

BACKGROUND: The chemical recycling of poly(ethylene terephthalate) (PET), e.g. bottles and fibre wastes, has been studied for many years. Among several methods proposed for chemical recycling of waste PET, glycolysis makes it possible to employ very low amounts of reactants and lower temperatures and pressures compared with critical methanol and thermal degradation. Furthermore, unlike hydrolysis under acidic or basic conditions, glycolysis does not cause any problems related to corrosion and pollution. RESULTS: PET from off‐grades of industrial manufacture was depolymerized using excess glycol. The effects of the reaction time, volume of glycol and catalyst concentrations on the yield of the glycolysis products were investigated. A reaction time of 3 h, weight ratio (catalyst to PET) of 0.25 wt% and PET to ethylene glycol molar ratio of 1:5 were determined as suitable conditions for depolymerization. Then, the reaction of polyesterification of maleic anhydride (MA) and glycolysed products of PET was successfully performed at 160 and 190 °C for 8 h. CONCLUSION: Differential scanning calorimetry and vapour pressure osmometry results for the product of the glycolysis reactions, under suitable condition, confirmed the structure of the desired product. This sample underwent reaction with MA to produce unsaturated polyester resin (UPR). The results of Fourier transform infrared and NMR spectroscopy confirmed that the UPR had been synthesized successfully. This is the first direct report on the glycolysis reaction of off‐grade products of petrochemical companies in order to regenerate raw materials or other secondary value‐added products. Copyright © 2009 Society of Chemical Industry     

Development of fire‐retarded materials—Interpretation of cone calorimeter data

There is little consensus within the fire science community on interpretation of cone calorimeter data, but there is a significant need to screen new flammability modified materials using the cone calorimeter. This article is the result of several discussions aiming to provide guidance in the use and interpretation of cone calorimetry for those directly involved with such measurements. This guidance is essentially empirical, and is not intended to replace the comprehensive scientific studies that already exist. The guidance discusses the fire scenario with respect to applied heat flux, length scale, temperature, ventilation, anaerobic pyrolysis and set‐up represented by the cone calorimeter. The fire properties measured in the cone calorimeter are discussed, including heat release rate and its peak, the mass loss and char yield, effective heat of combustion and combustion efficiency, time to ignition and CO and smoke production together with deduced quantities such as FIGRA and MARHE. Special comments are made on the use of the cone calorimeter relating to sample thickness, textiles, foams and intumescent materials, and the distance of the cone heater from the sample surface. Finally, the relationship between cone calorimetry data and other tests is discussed. Copyright © 2007 John Wiley & Sons, Ltd.     

Behavior of nonazeotropic compositions of a styrene–unsaturated polyester resin analyzed through FTIR spectroscopy and dynamic mechanical thermal analysis

Styrene is one of the comonomers most frequently used in the curing of unsaturated polyester resins. The use of nonazeotropic compositions leads to the formation of networks, in which the styrene–polyester ratio varies significantly during curing, as shown through FTIR spectroscopy. Dynamic mechanical thermal analysis (DMTA) showed how the variation in the styrene content affects the network structure that is formed. The results showed a decrease in network density in the systems in which the azeotropic composition was not used. The styrene content is therefore a factor that governs the curing process, in addition to the ultimate properties of the cured resins. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3618–3625, 2003     

Morphology development and mechanical properties of unsaturated polyester resin containing nanodiamonds

Unsaturated polyester/styrene (UP ) resin was filled with nanodiamonds (NDs ) containing carboxyl and methacrylate functionalities using mechanical mixing. Field emission SEM exhibited a uniform dispersion of tightly bound aggregates of nanosized spherical NDs with good interfacial interaction. Rheological measurements exhibited a step increment in the shear viscosity of a UP /ND suspension at 0.6 wt% ND resembling a percolation state at this loading. Shear viscosity data supported by dynamic mechanical analysis results suggested the development of effective ND particles in which ND aggregates were covered by only polyester macromolecules. Accordingly, the morphology of UP /ND composites approached a quasi‐percolation state at 0.6 wt% in which effective ND particles were connected thoroughly, instead of direct ND ?ND contact, forming a co‐continuous polyester phase covering the ND particles. Based on such morphology, DSC and Fourier transform infrared analysis suggested the development of heterogeneous microgels in cured UP resin containing NDs which in turn governed the overall mechanical properties of the composites. © 2017 Society of Chemical Industry     

Postfire full stress–strain response of fire‐damaged concrete

This paper reports experimental data establishing the postfire full stress–strain response of fire‐affected concrete. Such data are useful in situations when redesign of fire‐damaged concrete elements is considered. Heating was carried out to various temperatures in the range 217–470°C. Cooling was carried out either by quenching or in air. The postfire strain at ultimate stress significantly increased after heating to temperatures higher than 320°C. Quenching seems to aggravate the loss in compressive strength and further increase the strain at ultimate stress. Quenching involved spraying the heated concrete with tap water for 5 min. It is evident that knowledge of maximum temperature of exposure alone is not sufficient for estimation of the postfire stress–strain relationship. Other characteristics of exposure such as method of cooling are also important in evaluating the modification in the structural behaviour of fire‐affected concrete. Copyright © 2005 John Wiley & Sons, Ltd.     

2010-2011年国际不饱和聚酯树脂工业进展

介绍了2010-2011年国际原油市场、不饱和聚酯部分项目投产及企业并购情况。综述了UPR领域的研究及应用进展,包括UPR的改性、力学性能的改进、老化机理、生物复合材料、新型不饱和聚酯复合材料及其应用。     

微胶囊化聚磷酸铵及其阻燃聚丙烯的研究进展

从聚磷酸铵（APP）的微胶囊化方法入手,以微胶囊所用囊材材料（三聚氰胺、三聚氰胺甲醛树脂、异氰酸酯聚合物、硅油以及热塑性树脂等）为主要线索,分析并讨论国内外研究微胶囊化APP所取得的成果：经三聚氰胺及三聚氰胺甲醛树脂微胶囊化后能提高APP的耐水性,并能在一定程度上提高其阻燃性能,而硅油微胶囊化后的APP具有良好的疏水性;并介绍了微胶囊化APP阻燃聚丙烯（PP）所取得的一些进展,三聚氰胺和三聚氰胺甲醛树脂微胶囊化的APP添加到PP中较一般未包覆的APP阻燃性更佳。     

Preparation and characterization of bismaleimide (N,N′‐bismaleimido‐4,4′‐diphenyl methane)–vinyl ester oligomer–modified unsaturated polyester interpenetrating matrices for advanced composites

Interpenetrating networks of varying percentages of bismaleimide (BMI) in vinyl ester oligomer (VEO) modified unsaturated polyester (UP) matrices have been developed. Vinyl ester oligomer was prepared by reacting commercially available epoxy resin GY 250 (Ciba‐Geigy) and acrylic acid, and used as a toughening agent for unsaturated polyester resin. Unsaturated polyesters modified with 10, 20, and 30 wt % vinyl ester oligomer were made. The VEO toughened unsaturated polyester matrix systems, further modified with 5, 10, and 15 wt % bismaleimide (BMI). BMI–VEO–UP matrices were characterized using differential scanning calorimetry, thermogravimetric analysis, and heat deflection temperature analysis. The matrices, in the form of castings, were characterized for their mechanical properties according to ASTM methods: tensile strength, flexural strength, and unnotched Izod impact test. Data obtained from mechanical studies and thermal characterization indicate that the introduction of VEO and BMI into unsaturated polyester resin improves thermomechanical properties according to their percentage concentration. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2502–2508, 2002     

2009-2010年国外不饱和聚酯树脂工业进展

介绍了2009-2010年国外不饱和聚酯树脂(UPR)企业的运营情况,UPR主要原料(苯乙烯、苯酐、顺酐、丙二醇)的供需状况。综述了UPR领域的研究及应用进展,包括生物基UPR复合材料的开发及新型UPR及复合材料的制备方法,UPR测试方法及力学性能的改进。