Effect of resin composition on curing kinetic of nanoclay-reinforced unsaturated polyester resins

Curing behavior of two resins of different unsaturated polyesters [FARAPOL 101 (UF) and Bushpol 81715 (UB)] containing 3 wt % organically modified clay (OMC), catalyzed with methyl ethyl ketone peroxide as initiator and promoted by cobalt naphtenate accelerator was investigated by dynamic differential scanning calorimetry (DSC) and gel time test methods. Chemical structures of UF and UB resins were characterized by ¹H NMR, XRD and TEM techniques were used for morphology characterization of nanocomposites. DSC results showed that after adding OMC, the redox reaction rate of UF increased less than that of UB resin. Measurements of cloud-point temperature (T _c) indicated that the miscibility of styrene/UB alkyd chains was more than that of styrene/UF alkyd chains. Therefore, the alkyd/styrene ratio inside the platelets in UB would be more than that in the platelets in UF nanocomposite. Among the three factors in redox reaction rate of UB/OMC and UF/OMC systems namely: (1) decreasing alkyd-styrene copolymerization share among platelets of OMC, (2) decreasing the activation energy, (3) decreasing the number of collisions, the first one was more effective in UF/OMC system than in UB/OMC system. Consequently, the difference between redox reaction rates of UF/OMC and neat UF was negligible compared with the corresponding difference for UB/OMC and neat UB system.     

不饱和聚酯树脂的常温固化

(续接上期)5不饱和聚酯树脂固化网络结构分析5·1不饱和聚酯树脂交联网络结构不饱和聚酯中的双键与交联剂中的双键聚合形成不溶不熔的交联网络,网络中含有2种聚合物分子链结构。网络主体由不饱和聚酯分子链的无规线团组成,苯乙烯共聚分子链穿插其中,将不饱和聚酯分子链连接和固     

不饱和聚酯树脂的常温固化

综述了不饱和聚酯树脂的固化特征、固化反应,固化机理和交联固化反应活性。介绍了4种固化反应过程、引发剂和固化反应链增长过程,同时介绍了其交联固化反应活性及影响因素。     

The effect of curing of unsaturated polyester resin on the dynamic relaxation time

The effect of hot curing of unsaturated polyester resin on the dynamic relaxation time was studied using dielectric measurements along with two dynamic mechanical measurement methods. It was found that the dynamic response during cure was a material frequency dependent property and did not depend on the measurement method. All relaxation times, measured during cure, by all three measurement methods used, converged to a single equation: τ(t)_av=at^b where t= curing time, a, b=constants. The increase of the relaxation time during cure followed the same trend as a friction factor, which was found to increase with conversion. The crosslinking density was found to increase slowly with conversion, while the relaxation time increased exponentially. These two different modes of behavior during cure explain the high resolution of dynamic measurements as a cure monitoring tool, which can easily detect small curing changes. This behavior of the relaxation time was explained by the sharp rise of activation energy due to a parallel decrease of free volume at high conversion.     

不饱和聚酯树脂固化动力学研究进展

介绍了不饱和聚酯树脂(UPR)固化反应动力学的n级反应模型和自催化模型,指前因子(A)和表观活化能(E)的求解方法:Kissinger法,Ozawa法和Friedman法以及由Crane方程或形状指数Si求解反应级数(n)的方法,综述了目前国内外DSC法研究UPR固化动力学的进展。     

A dynamic mechanical study of the curing reaction of an unsaturated polyester

The curing process of an unsaturated polyester was followed by employing the dynamic spring analysis (DSA) technique attached to the Rheovibron viscoelastometer. The storage and loss moduli and the gel times of the resin with various concentrations of initiator (methyl ethyl ketone peroxide) were determined at several temperatures. The activation energy for the curing process studied was about 40 kJ/mol. Temperature effects on films partially cured below the ultimate glassy transition temperature (T_g) were studied similarly using the tensile mode on the Rheovibron from room temperature to 120°C. Two modulus peaks were observed upon heating and these were independent of precure conditions. The lower temperature peak was the result of continued curing and the higher temperature peak was attributed to the glassy relaxation of the cured product. The DSA technique were found to be useful for characterization of the curing process and the results showed good qualitative agreement with those obtained by tensile measurements using cast films when the shapes of the curves were compared.     

The effect of resin chemistry on the curing behavior and chemorheology of unsaturated polyester resins

The effect of the structure of unsaturated polyester resin on its curing and rheological behavior during isothermal cure has been investigated, using three different grades of resin. In the investigation, the structure of the resins was determined, using nuclear magnetic resonance spectrometry (NMR), together with chemical analysis. Both a differential scanning calorimeter (DSC) and an infrared (IR) spectrometer were used to determine the curing kinetics, and a cone-and-plate rheometer was used to determine the variation of rheological properties during isothermal cure. On the basis of the experimental study, we have concluded: (1) at the same styrene-to-fumarate mole ratio, the resin having isophthalates cures slower than the one having none; (2) everything else being equal, the resin having a high styrene-to-fumarate mole ratio cures faster than the resin having a low one; (3) the higher the concentration of initiator, the faster a resin cures. It has been found that a resin that cures faster does not necessarily achieve a higher final degree of cure than one that cures slowly. We have found that a mechanistic kinetic model developed in our previous investigation is very useful for investigating the reactivity of unsaturated polyester resin, by determining the rate constant and activation energy of the propagation reaction. On the basis of rheological investigation, we have concluded that both t_η∞ determined from steady shearing flow measurement and t_{tan δ = 1} determined from oscillatory shearing flow measurement may be used as a measure of gel time.     

The effect of the addition of a low profile additive on the curing shrinkage of an unsaturated polyester resin

Composites made of glass fibers and unsaturated polyester resins are widely applied for various products. The failure processes of such composites are insufficiently understood. Fracture of the resin often initiates bulk composite fracture. Residual stresses occur during the curing of the resin due to the resin volumetric shrinkage. These unfavorable stresses may enhance resin fracture. Moreover, resin shrinkage may decrease the surface quality of the product. The addition of Low Profile Additives (LPA) to the resin may decrease or even remove these problems. The shrinkage behavior of unsaturated polyester resin with varying amounts of LPA is investigated in this work. The emphasis is on the development of curing shrinkage occurring after the gel point of the resin and on accompanying shirnkage stresses. These stresses can be reduced and even reversed by the addition of LPA.     

不饱和聚酯树脂BPO/DMA/MHPT固化体系的研究

采用引发剂过氧化苯甲酰(BPO)和复合促进剂N,N-二甲基苯胺(DMA)/N-甲基-N-2-羟乙基对甲苯胺(MHPT)组成的固化体系,室温条件下对不饱和聚酯树脂(UPR)进行固化,研究了BPO用量为5.0%、促进剂总量为4.0%时改变DMA与MHPT配比对UPR凝胶时间、固化速度及原子灰的凝胶时间、表干时间、附着力的影响,得出了MHPT和DMA的适宜质量比为1.5:2.5,可使UPR在固化过程中有较长的施工期、后期快速固化,且原子灰有适宜的表干时间和良好的附着力。     

Glycidyl amine adducts as accelerators for the curing of unsaturated polyester resin

The behavior of the adducts of aromatic amines with epoxide compounds as accelerators in curing of an unsaturated polyester resin was studied. To determine their usefulness, the gelation times, peak exotherm temperatures, and chromatographic and gravimetric analyses of the products extracted from the cured resin samples were investigated. The effectiveness of the adducts was compared with that for N,N-dimethylaniline. © 1997 John Wiley & Sons, Inc. J Appl Polm Sci 65:1525–1531, 1997     

A nonisothermal differential scanning calorimetry study of the curing kinetics of an unsaturated polyester system

Nonisothermal differential scanning calorimetry (DSC) measurements were used to estimate the kinetic parameters for the curing reaction of a commercial unsaturated polyester resin. The reaction rate expression was derived from a mechanistic kinetic model based on the concept of free radical polymerization, accounting also for the diffusion controlled reaction. The total heat of reaction was evaluated in experiments run at very low scan speeds and using high amount of initiator. The kinetic parameters were found to show no dependency on the heating rate nor on the initiator concentration. Dynamic DSC measurements provide reliable kinetic data over a broad range of temperatures that is mostly significant for process simulations.     

Effect of particulates and fiber reinforcements on the curing behavior of unsaturated polyester resin

The effect of particulates and reinforcement on the curing behavior of unsaturated polyester resin was investigated. Also investigated was the effect of surface treatment of particulates on the curing behavior of unsaturated polyester resin. We have found that (1) an increase in the surface area, by either increasing the loading of particulates for a fixed particle size or decreasing the size of particulates for a fixed loading of particulates, enhanced the rate of cure, and (2) the treatment of glass beads with γ-methacryloxy propyltrimethoxy silane enhanced the rate of cure of unsaturated polyester resin.     

二茂铁甲酸封端不饱和聚酯的固化及热性能研究

以乙二醇、反丁烯二酸为原料合成的不饱和聚酯作为主链,二茂铁甲酸(FCA)作为封端剂,合成了含二茂铁基的不饱和聚酯(RFc),采用红外光谱对产物结构进行了表征。采用DSC及TGA研究了不同二茂铁甲酸含量对不饱和聚酯树脂固化性能和热稳定性的影响。结果表明,随着二茂铁甲酸含量的增加,RFc树脂固化反应活性减弱,热稳定性下降。其最高放热峰温度在171～173℃,且具有比较宽的加工温度范围(152～195℃),符合模塑料固化工艺要求。树脂的耐热性较好,初始热分解温度约为340℃,N2气氛下600℃残炭率可达19.76%。     

不饱和聚酯/复合引发体系非等温固化动力学研究

采用非等温DSC法研究了不饱和聚酯/复合引发体系在不同升温速率下的固化行为,通过T-Φ外推法确定了该体系的凝胶温度、固化温度和后固化温度分别为102.7℃,124.0℃和196.5℃。通过Kissinger和Crane方程对DSC数据进行处理,获得了固化反应的表观活化能E=116.88 kJ/mol,碰撞因子A=7.35×1014,反应级数n=0.945,并由此得到了该体系的固化动力学方程。     

不饱和聚酯树脂微波固化特性研究

探讨了UPR在微波加热作用下固化的可行性及特性规律,采用DSC及FTIR等手段对微波加热固化及传统加热树脂固化性能进行了分析,结果显示微波加热凝胶固化时间比后者快几倍至20多倍,热性能、力学性能基本相当,这表明微波加热固化UPR可行且高效。     

The effect of the chemical structure of low-profile additives on the curing behavior and chemorheology of unsaturated polyester resin

An experimental study was conducted to investigate the effect of the chemical structure of low-profile additives on the curing behavior and chemorheology of unsaturated polyester resin during isothermal cure. For the study a general-purpose unsaturated polyester resin was cured in the presence of t-butyl perbenzoate as Initiator. The curing behavior of the resin was investigated using differential scanning calorimetry (DSC). Three different thermoplastic low-profile additives were used, namely poly(vinyl acetate) (PVAc), poly(styrene-co-butadiene), which is also known as KRATON DX-1300, and dehydrochlorinated Isobutylene/isoprene copolymer, often referred to as conjugated diene butyl (CDB) rubber. Each of the these additives, about 30 weight percent, was first dissolved in styrene. The solution was then mixed with unsaturated polyester resin and CaCO₃. The CaCO₃ particles helped stabilize the emulsions consisting of resin and KRATCN, and of resin and CDB. For each resin formulation, a series of isothermal DSC runs were made at various levels of cure pressure. It was found that for all three low-profile resins investigated, the final degree of cure went through a maximum as cure pressure was increased from atmospheric to 6.21 MPa (900 psi). We have observed evidence that in the presence of an initiator generating free radicals, the unsaturated double bonds in the KRATON and CDB undergo grafting reactions with the styrene monomers and unsaturated polyester resin, increasing the glass transition temperature of KRATON and CDB, to an extent which varies with the cure conditions employed. Both steady and oscillatory shearing flow properties were determined using a cone-and-plate rheometer. The rheological measurements indicate that the resin/CaCO₃/KRATON and resin/CaCO₃/CDB systems give rise to gel times shorter than the resin/CaCO₃/PVAc system. It is concluded that both KRATON and CDB are more effective, both for enhancing the rate of cure of unsaturated polyester resin and imparting impact properties to the cured composites, than those thermoplastic low-profile additives that contain neither unsaturated double bonds nor a chemical structure that has rubber-like properties in the solid state.     

端羧基超支化聚酯改性环氧树脂固化体系研究

利用丁二酸酐对端羟基超支化聚酯(AHBP)的端基进行改性,得到新的端羧基超支化聚酯(CHBP),并将其用于环氧树脂体系的增韧。研究了CHBP用量、羧基含量对环氧树脂/甲基四氢苯酐(EP/MeTHPA)固化体系的力学性能和热性能的影响。结果表明,改性后分子末端全部带羧基的CHBP的增韧作用最好,冲击强度可达18.5kJ/m2。CHBP质量分数为15%时,固化物的冲击强度可达18.2 kJ/m2,拉伸强度64.86 MPa,玻璃化温度(Tg)从100℃提高到106℃左右,可满足增韧环氧树脂的同时不降低其耐热性的要求。     

The effect of pressure on the curing behavior of unsaturated polyester resins

The effect of pressure on the curing behavior of unsaturated polyester resin was investigated, both experimentally and theoretically. The resin used was a general-purpose unsaturated polyester resin and the initiator used was t-butyl perbenzoate. A series of isothermal runs with differential scanning calorimetry (DSC) were made at various levels of cure pressure. It was found that the rate of cure was retarded under pressure, and that the ultimate degree of cure went through a maximum at a certain pressure as the cure pressure was increased from atmospheric pressure to 6.21 MPa (900 psi). It was interpreted that pressure has two competing effects on the curing behavior of unsaturated polyester resin; one is a free volume effect that hinders the curing reaction and the other is a thermodynamic effect that favors it. Therefore, when the pressure is higher than a certain level, the free volume effect becomes predominant over the thermodynamic effect, the ultimate degree of cure diminishing as the cure pressure is increased beyond that level. Theoretical interpretation of the experimental results is given, using a mechanistic kinetic model developed in our previous publication.     

Water-containing resin based on unsaturated polyester

Unsaturated polyester resins containing water were prepared through two steps: formation of a stable W/O emulsion of polyester prepolymer and subsequent polymerization of the emulsion. In this paper, conditions for formation of the resins from the W/O type emulsion and the heat-protection properties of the resulting water-containing resins are reported. The stability of the emulsions was measured, and the results are discussed in relation to the gelation time, since the polymerization of the emulsions is required to proceed faster than their disintegration. It was found that with increasing viscosity of the emulsions their stability increases and the gelation time shortens. The above requirement is fulfilled at almost all regions of emulsifier concentration where stable W/O emulsions are formed. Water-containing unsaturated polyester resins exhibit a remarkable heat-protection effect at elevated temperatures (500 and 2500°C.) in comparison with polyester resins not containing water.