低聚端羟基聚硅氧烷接枝增韧酚醛树脂的制备及性能

由低聚羟基封端聚硅氧烷（HO-PDM）与甲醛和苯酚的接枝反应制备了增韧改性酚醛树脂,用FT-IR对改性酚醛树脂的结构进行表征,用电子万能试验机测试了改性前后酚醛树脂的力学性能,用热重分析仪测试改性酚醛树脂的热稳定性。 测得改性酚醛树脂的断裂伸长率、冲击强度、抗拉强度分别为2.8%、2.875 kJ/m2和23.2 MPa;树脂失重20%的温度为431.28 ℃,峰值温度为441.8 ℃,800 ℃的残重率为51.02%。     

高残炭硼酚醛树脂的制备

酚醛树脂(PF)因其具有良好的耐热性能和机械性能而被广泛应用。但其耐热性能已经满足不了现代航空航天技术的需求,研究发现,采用硼酸对酚醛树脂进行改性,可以制得具有优良耐高温性能的硼酚醛树脂(BPF)。采用硼酸酯法合成硼酚醛树脂,n(苯酚)∶n(甲醛)=1∶1.5时耐热性最佳。热分析结果表明,合成的BPF在1000℃条件下的残炭率为78%,其耐热性能明显优于传统的酚醛树脂。同时讨论了不同硼酸含量对BPF耐热性能的影响,当n(硼酸)∶n(苯酚)0.33∶1时,残炭率趋于稳定。此外,利用差示扫描量热仪(DSC)方法确定BPF预固化温度为160℃,后固化温度为220℃。     

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.     

Thermal and mechanical characterization of high performance epoxy systems with extended cure times

Five epoxy resins of different chemistry and functionality were cured with DDS (4,4-diaminodiphenyl sulfone) using 2, 8 and 14 h curecycles. Both Differential Scanning Calorimetry (DSC) and Thermomechanical Analysis (TMA) were used to characterize reaction behavior and cured properties of the resin systems. In addition, static mechanical tests and density measurements were integrated with the thermal characterization methods to correlate resin properties with process time. Flexural three-point bending experiments showed that the resins tended to have higher yield stress and toughness values at extended cure times. The improved mechanical properties could be attributed to the full development of the epoxy molecular structure, in the form of cross-linked networks and molecular rearrangement. These results suggest that extended cure times or high temperature post-curing may be required to obtain the resin's ultimate mechanical properties for high performance composites.The authors would like to thank Dr. Andri Filippov of Shell Development Company for his interest in this work. Financial assistance and material support for this research were provided by Shell Development Company while instrument support was provided by TA Instruments through project support to the Polymeric Composites Laboratory of the University of Washington.     

含氧化叔胺侧基的水溶性酚醛树脂的合成与成像性能

本实验通过一锅、两步法制备改性酚醛树脂.首先利用环氧酚醛树脂F-44与二甲胺反应,得到叔胺化酚醛树脂,叔胺化树脂被双氧水氧化后得到最终目标产物,即含强极性氧化叔胺基团的酚醛树脂.实验表明,该新型树脂易溶于水和一些强极性溶剂,如四氢呋喃、乙二醇独甲醚和N,N-二甲基甲酰胺等.在热的作用下,树脂能够分解并失去水溶性,但仍可溶于一些有机溶剂.由该树脂与830 nm激光增感染料匹配使用,树脂体系对红外光敏感,并能够通过中性水显影得到较为清晰的阴图型图像,表明该树脂有望用于免化学处理热敏激光成像领域.     

Synthesis and characterization of carborane bisphenol resol phenolic resins with ultrahigh char yield

Two carborane-containing resol phenolic resins(P1 and P2) with high boron content were synthesized via the reaction of carborane bisphenols(1 and 2) with formaldehyde in the presence of alkaline. HRMS results indicate that P1 is mainly composed of hydroxymethylated o-carborane bisphenols, the Mw of which was restrained around 500 due to the strong steric hindrance of o-carborane bisphenol. In contrast, the molecular weight of P2 was well regulated under various reaction conditions. The obtained resins were characterized with spectroscopic techniques including FTIR, 1H-NMR, 13C-NMR, and 11B-NMR, which gave satisfactory results. TGA studies show that P2 shows char yield of 88.9% and 92.9% at 900 ?C under nitrogen and air respectively. The imported carborane cage endows phenolic resin with ultrahigh char yield. Particularly, the char yield of the obtained carborane-containing phenolic resin under air is higher than that under nitrogen. FTIR and XRD confirm that the carborane cage could react with oxygen to form B2O3 at elevated temperatures, which postpones the thermal decomposition of phenolic resin and accounts for the high char yield.     

Thermal,mechanical, and morphological properties of novolac‐type phenolic resin blended with fullerenol polyurethane and linear polyurethane

Fullerenol polyurethane (C₆₀‐PU) and linear polyurethane (linear‐PU) modified phenolic resins were prepared in this study. Phenolic resin/C₆₀‐PU and phenolic resin/linear‐PU blends show good miscibility as a result of the intermolecular hydrogen bonding existing between phenolic resin and PU modifiers. DSC and thermogravimetric analysis methods were used to study the thermal properties of phenolic resin blended with different types of PUs. The intermolecular hydrogen bonding that existed between phenolic resin and C₆₀‐PU was investigated by Fourier transform infrared spectroscopy. The morphology and mechanical properties of phenolic resin/C₆₀‐PU and phenolic resin/linear‐PU blends were also investigated. The char yield of the modified phenolic resins decreased with increasing PU modifier content. Significant improvement in the toughness of the modified phenolic resins was observed. The improvements of impact strength were 27.4% for the phenolic resin/linear‐PU system and 54.3% for the phenolic resin/C₆₀‐PU system, respectively, both with 3 phr linear‐PU and C₆₀‐PU content. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2436–2443, 2001     

Using Taguchi experimental design to reveal the impact of parameters affecting the abrasion resistance of sol–gel based UV curable nanocomposite films on polycarbonate

This work aims at studying the abrasion resistance of differently formulated organic–inorganic hybrid coatings prepared by sol–gel method. The organic phase contained UV curable urethane acrylate oligomers and monomers having different functionalities. The inorganic phase was composed of tetraethyl orthosilicate (TEOS) and 3-methacryloxy propyltrimethoxy silane (MEMO). Through a Taguchi experimental design, the impact of influencing parameters such as molar ratio of precursors, hydrolysis ratio (R), post-curing temperature, post-curing time and weight percentage of inorganic to organic part were investigated. Very high transparency of hybrid coatings indicated that nano sized inorganic phase had formed. MEMO could facilitate the connection of two phases, preventing macro phase separation. However, high levels of MEMO lead to ‘defect structure’ in silica network as well as to decreased transparency and mechanical properties. The optimum condition in which highly transparent films with great abrasion resistance occurred was observed at equimolar ratio of water to alkoxide and TEOS: MEMO ratio being unity. Statistical analysis revealed that thermal post-curing was not significantly important.     

Synthesis and characterization of novel phenolic resins containing aryl‐boron backbone and their utilization in polymeric composites with improved thermal and mechanical properties

In the present study, a novel aryl‐boron‐containing phenolic resin named as PBPR has been synthesized from phenol and formaldehyde in the presence of phenylboronic acid. The chemical structure of the PBPR was confirmed by Fourier transform infrared, nuclear magnetic resonance and X‐ray photoelectron spectroscopy. The molecular weight, viscosity and curing behavior were examined to demonstrate that PBPRs have better processability than common boric acid‐modified phenolic resin. The thermal stability and fracture toughness of the cured PBPRs were greatly enhanced, where the char yield at 1000°C (nitrogen atmosphere) and the glass transition temperature reached 70.0% and 218°C, respectively. The excellent mechanical and ablative properties of the PBPR composites may have benefited from the good interfacial adhesion between the resin matrix and the reinforced fiber. The flexural strength and the linear ablative rate are 436.8 ± 5.2 MPa and 0.010 mm/sec, respectively. This study opens a new window for the preparation of high‐performance ablative composites by designing a resin matrix containing an aryl‐boron backbone. Copyright © 2013 John Wiley & Sons, Ltd.     

Glass fiber reinforced composites of phenolic–urea–epoxy resin blends

The present work aims to modify conventional epoxy resin by blending with four different phenolic–urea oligomers. These oligomers are similar to phenolic–urea resin matrix and simultaneously function as amino curing agent for epoxy matrix. In this context, phenolic–urea oligomers were prepared respectively by polycondensation reaction of four phenols namely phenol, m-cresol, resorcinol and 1,5-dihydroxy naphthalene, respectively with formaldehyde and urea in presence of acid catalyst. The resulting oligomers were characterized by elemental analysis, spectral studies (IR & NMR), number average molecular weight $(\overline{M}n)$ estimated by non-aqueous conductometric titration and thermal stability by thermogravimetric analysis (TGA). Each of these oligomers was used in resin matrix as a blending component for the modification of commercial epoxy resin for fabricating glass fiber reinforced laminates. Finally these laminates were evaluated for their synergetic thermal stability, mechanical properties and chemical resistance to different reagents.     

Thermal behaviour of teflon/phenolic liners in self-lubricating bearings

The gun system of the M1 series tank rides on a pair of self-aligning spherical bearings that allows the elevation and depression of the cannon. Because these bearings are encapsulated within the rotor housing, periodic lubrication or maintenance is impossible. To overcome this problem self-lubricating bearings were incorporated into the system. There are two basic liner designs, molded and fabric. Molded liners are produced by applying a formulation of teflon and typically asbestos into a phenolic resin, which is applied to the bearing surface, then cured. Fabric liners utilize a woven fabric bonded to the bearing surface, then teflon which is mixed into phenolic resin is applied to the bearing surface and cured. Initial studies of the existing bearing liner were completed to determine the liner composition and establish a baseline or standard to compare thermal and mechanical properties with potential vendors. DSC revealed an average teflon content of 39.53%, which varied significantly throughout the liner. TG analysis showed an asbestos concentration of 12.22%. The remainder of the liner was phenolic resin. Physical testing of the bearing from ?20 to 120?C under normal loading conditions demonstrated excellent thermal stability with little wear. Bearings from each vendor were tested and compared to the standard properties of the baseline bearing. Some properties were difficult to compare or insignificant due to the design differences between molded and fabric liners. The testing program resulted in the qualification of two bearings, which met or exceeded the established standards. Both of these bearings were designed with fabric liners.     

Strain-induced post-curing of acrylate networks

The mechanical properties and network structure of photocurable polymers are strongly dependent on processing conditions. Here it is reported that highly crosslinked acrylate systems undergo unexpected additional post-curing during DMTA measurements, resulting in an increase in glass-transition temperature (T_g). A detailed study of the conditions under which this increase in T_g takes place unequivocally shows that a small (0.1%) oscillatory strain applied above T_g is responsible for additional cross-linking reactions. The effect of strain-induced post-curing is confirmed by applying post-curing treatments under oscillatory shear strain in rheological tests. Different acrylate systems were characterized and the results show that the strain induced post-curing depends on the network structure of the polymer. In polymer networks with an initial high crosslink density the effect is pronounced while in polymers with an initial lower crosslink density no shift in T_g is observed.     

The effect of basecoat pigmentation on mechanical properties of an automotive basecoat/clearcoat system during weathering

The aim of this study is to elucidate the effect of basecoat pigmentation on mechanical aspects of an automotive basecoat/clearcoat (BC/CC) system during artificial weathering exposures. A silver basecoat as the most reflective and a black basecoat as the most absorptive basecoat were selected. These two extreme behaviored basecoats were chosen with hopes that other basecoats would behave somewhere between the silver and the black extremes. The structural and mechanical properties of the coatings were investigated after various weathering exposure times (0, 150, 300, 450, 600 h). Dynamic mechanical thermal analysis (DMTA) was carried out to study variations in structure and basic characteristics of the system such as cross-linking density and T_g during weathering. In order to investigate variations in mechanical properties of the system, nano indentation, nano scratch, and tensile tests were also utilized.It was found that although both silver and black systems experienced post-curing reactions (dominant at earlier stages of weathering) and degradation reactions (dominant at later stages of weathering), but basecoat pigmentation affected the post-curing and degradation reaction rates of the BC/CC system, leading to variations in mechanical properties. It was concluded that post-curing occurred to a greater extent in the black pigmented system whilst in the silver pigmented system weathering degradation was much more sever.     

Epoxy-modified, unsaturated polyester hybrid networks

Hybrid polymer networks (HPNs) based on unsaturated polyester resin (UPR) and epoxy resins were synthesized by reactive blending. The epoxy resins used were epoxidised phenolic novolac (EPN), epoxidised cresol novolac (ECN) and diglycidyl ether of bisphenol A (DGEBA). Epoxy novolacs were prepared by glycidylation of the novolacs using epichlorohydrin. The physical, mechanical, and thermal properties of the cured blends were compared with those of the control resin. Epoxy resins show good miscibility and compatibility with the UPR resin on blending and the co-cured resin showed substantial improvement in the toughness and impact resistance. Considerable enhancement of tensile strength and toughness are noticed at very low loading of EPN. Thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC) were employed to study the thermal properties of the toughened resin. The EPN/UPR blends showed substantial improvement in thermal stability as evident from TGA and damping data. The fracture behaviour was corroborated by scanning electron microscopy (SEM). The performance of EPN is found to be superior to other epoxy resins.     

丁腈弹性纳米粒子改性酚醛树脂的研究

酚醛树脂具有优异的耐热性、电绝缘性,尺寸稳定性、成型加工性和阻燃性等,广泛地应用在涂料、胶粘剂和复合材料工业上,酚醛树脂由于含有大量苯环以及固化后形成高度交联结构,韧性很差,因此增韧是其高性能化的主要方向之一,橡胶是最广泛使用的增韧剂,几十年来发展了天然橡胶、丁腈橡胶、丁苯橡胶、液体羧基丁腈橡胶、丁吡橡胶等,壬基酚、腰果壳油、桐油、亚麻油、热塑性塑料等也是酚醛树脂有效的增韧剂。     

Dynamic mechanical properties of epoxy‐phenolic mixtures

The dynamic‐mechanical properties of different mixtures formed by an epoxy resin (DGEBA type) and a phenolic resin (resole type) cured by trietylenetetramine and/or p‐toluensulphonic acid at different concentrations have been studied by means of dynamic mechanical thermal analysis (DMTA). All samples were cured by pressing at 90 °C during 6 h. The mechanical studies were performed between ?100 to 300 °C at a heating rate of 2 °C/min. This study was also carried out for the epoxy‐TETA and phenolic‐p‐toluensulphonic acid systems. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1548–1555, 2005     

高碳含量低模量的酚醛树脂

用线型酚醛树脂与甲醛作用制得一种热固性酚醛树脂,与一般热固性酚醛树脂比较,它的碳含量较高,模量较低,热稳定性相似,可以用于制备复合材料。     

Determination of oxidation parameters by DSC for polypropylene stabilized with hydroxytyrosol (3,4-dihydroxy-phenylethanol)

Oxidation thermal parameters on samples of polypropylene (PP) stabilized with hydroxytyrosol were determined. For comparison purposes, α-tocopherol and a synthetic phenolic commercial antioxidant (Irganox 1076), were also analyzed. Oxidation induction time (OIt) and oxidation induction temperature (OIT) were determined by differential scanning calorimetry (DSC). The addition of hydroxytyrosol 0.1 mass% to PP was enough to obtain efficient stabilization during processing. Certain decrease in stabilizing properties of natural antioxidants was observed for compression moulded materials at high temperatures. However, these samples were still efficiently stabilized in comparison to the pure material. Hydroxytyrosol showed good performance as polypropylene antioxidant and it might be considered as promising alternative to the use of phenolic synthetic compounds.     

Synthesis,characterization of Mannich base oligomers used with epoxy resin for glass fibre-reinforced laminates

This article aims to modify conventional epoxy resin by blending with four different Mannich base oligomers. These oligomers are similar to phenolic resin matrix and simultaneously function as amino curing agent for epoxy matrix. In this context, Mannich base oligomers were prepared, respectively, by Mannich polycondensation reaction of four phenols namely phenol, m-cresol, resorcinol and 1,5-dihydroxy naphthalene, respectively, with formaldehyde and piperazine in presence of acid catalyst. The resulting oligomers were characterized by elemental analysis, spectral studies (IR and NMR), number average molecular mass [`(M)]_n {\bar{M}}_{\rm n} estimated by non-aqueous conductometric titration and thermal stability by thermogravimetric analysis (TG). Each of these oligomers was used in resin matrix as a blending component for the modification of commercial epoxy resin for fabricating glass fibre reinforced laminates. Finally, these laminates were evaluated for their synergetic thermal stability, mechanical properties and chemical resistance to different reagents.