光敏树脂及其紫外光固化涂料发展新动向

按紫外光固化涂料形态分类,并着重从光敏树脂方面综述了近年来紫外光固化涂料及其光敏研究及开发的新动向。在开发油性紫外光固化涂料新品种、提高其综合性能、拓宽应用领域的同时,研究开发水性紫外光固化涂料、紫外光固化粉沫涂料是目前紫外光固化涂料的重要发展趋向:在完善线形光敏齐聚物的同时,研究水溶性光敏齐聚物、树枝形和超支化结构聚合物体系又成为紫外光固化涂料用树脂研究的新热点。     

Polynitroalcohols obtained through nitro aldol reaction between nitro oligomers and C1‐C2‐aldehydes

Polynitroalcohols (PNA) were obtained by A_N‐reaction of nitro oligomers from ground waste rubbers (NO‐GWR) with C₁‐C₂‐aldehydes in presence of organic bases triethanolamine, triethylamine and cyclopropylamine. The A_N‐reaction was studied at temperatures from 30 to 50°C, time 4 h, and NO‐GWR : aldehyde = 1 : 0.5/2.0 mass ratios in the solution. PNA were characterized by elemental analyses, such as ¹H NMR spectra, IR spectroscopy—baseline method with internal standard and thermal analyses. The quantitative functional composition of PNA (%NO₂, %C?O, and %OH groups) was proved to be similar to the composition of PNA obtained from model butadiene–styrene nitro oligomer (BSNO). It was concluded that NO‐GWR could replace NO based on elastomers in nitro aldol reaction with formaldehyde and acetaldehyde. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3241–3250, 2006     

异氰酸酯改性光敏水性环氧丙烯酸酯的合成

以双酚A型环氧树脂与丙烯酸反应合成了具有羟基侧基的环氧丙烯酸酯，再用甲苯二异氰酸酯与内烯酸-β-羟乙酯的半加成物对上述环氧丙烯酸酯树脂进行接枝改性，再用酸酐引入羧基，经胺中和后，水性化．可得较为稳定的自乳化光敏树脂水分散体系。通过化学测试和IR解析．确定了合成条件、合成终点及产物结构，并以此为基料配成紫外光固化涂料，所得涂层性能优异。     

Different effects of tri(acryloyloxyethyl) phosphate on the thermal degradation of photopolymerized epoxy acrylate and polyurethane acrylate films

Tri(acryloyloxyethyl) phosphate (TAEP) was blended in different ratios with epoxy acrylate EB600 and polyurethane acrylate EB270 to obtain a series of UV curable flame retardant resins. The thermal degradation mechanisms of their cured films in air were studied by thermogravimetric analysis, in situ Fourier‐transform infrared spectroscopy, and direct pyrolysis/mass spectrometry measurements. The results showed that the phosphate group in TAEP first degraded to form poly(phosphoric acid) before the degradation of EB600. Then, the formed poly(phosphoric acid) effectively promoted the conversion of EB600 to form char, which prevented the sample from further burning. However, urethane group in EB270 degraded simultaneously with phosphate group in TAEP, leading to not effectively increase the conversion of EB270 to char during the thermal degradation. It was thus found that the addition of TAEP more effectively improved the thermal stability, flame retardance, and the char yield during combustion of EB600 than those of EB270. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3130–3137, 2006     

酚醛树脂为原料制备双电层电容器用电极材料的工艺研究

以酚醛树脂为原料，NaOH为活化剂制取双电层电容器用高比表面积活性炭电极材料，考察了炭化温度、活化温度、活化剂用量、活化时间等工艺参数对活性炭比电容的影响。实验结果表明，在炭化温度为600℃，活化温度为900℃，碱炭比为4，活化时间为1h的工艺条件下，制得的高比表面积活性炭比电容可达58．8F／g，用它组装成的电容器具有良好的充放电性能和循环性能，既能在大电流下快速充放电也能在小电流下缓慢充放电，但存在微孔所占比例较高引起的分散电容效应，这是大电流下放电容量有所下降的主要原因。     

Cycling of lithium/metal oxide cells using composite electrolytes containing fumed silicas

The effect on cycle capacity is reported of cathode material (metal oxide, carbon, and current collector) in lithium/metal oxide cells cycled with fumed silica-based composite electrolytes. Three types of electrolytes are compared: filler-free electrolyte consisting of methyl-terminated poly(ethylene glycol) oligomer (PEGdm, M_w=250)+lithium bis(trifluromethylsufonyl)imide (LiTFSI) (Li:O=1:20), and two composite systems of the above baseline liquid electrolyte containing 10-wt% A200 (hydrophilic fumed silica) or R805 (hydrophobic fumed silica with octyl surface group). The composite electrolytes are solid-like gels. Three cathode active materials (LiCoO₂, V₆O₁₃, and Li_xMnO₂), four conducting carbons (graphite Timrex® SFG 15, SFG 44, carbon black Vulcan XC72R, and Ketjenblack EC-600JD), and three current collector materials (Al, Ni, and carbon fiber) were studied. Cells with composite electrolytes show higher capacity, reduced capacity fade, and less cell polarization than those with filler-free electrolyte. Among the three active materials studied, V₆O₁₃ cathodes deliver the highest capacity and Li_xMnO₂ cathodes render the best capacity retention. Discharge capacity of Li/LiCoO₂ cells is affected greatly by cathode carbon type, and the capacity decreases in the order of Ketjenblack>SFG 15>SFG 44>Vulcan. Current collector material also plays a significant role in cell cycling performance. Lithium/vanadium oxide (V₆O₁₃) cells deliver increased capacity using Ni foil and carbon fiber current collectors in comparison to an Al foil current collector.     

Fat-simulating and accelerating solvents for polyolefins and MWD of solvent extracts of polyethylenes

Migration kinetics of straight-chain oligomers and antioxidants from several polyolefins at different temperatures into various solvents have been studied by radioactive tracer techniques. Anhydrous ethanol appears to be a well suited food-oil or liquid-fat simulant for extracting different types of migrants from polyolefins. Pure and mixed triglycerides are also good oil or fat simulants, but the triglycerides offer no simpler analytical procedures than the use of oil or fat themselves. n-Octanol may also be considered as a reasonable oil or fat simulant; however, its action depends somewhat on the choice of migrants. The accelerating action of n-heptane over that of oil or simulants is quantitatively demonstrated. The accelerating effects are greater for migration systems with lower diffusion coefficients. The diffusion coefficients for migration into n-heptane are about 20 times greater than the diffusion coefficients into ethanol or oil for otherwise identical migration systems yielding diffusion coefficients of about 10^?7 cm²s^?1 into oil or ethanol. For systems yielding diffusion coefficients into oil or ethanol of about 10^?12 cm²s^?1, the corresponding diffusion coefficients into n-heptane are about 1000 times greater. The molecular weight distributions (MWDs) of the n-heptane and ethanol extracts of polyolefins have been analysed. n-Heptane can not only accelerate the migration of the individual migrant but also remove oligomer species that are slightly soluble or present at low levels in the oil or simulant extracts.     

微波固化环氧树脂／氨基二苯醚树脂的耐热性能研究

以二苯醚树脂(DPO)为原料，合成了一类新型耐高温树脂一氨基二苯醚树脂(ANDPO)，用作双酚A环氧树脂(EP)的固化剂，以提高环氧树脂的耐热性。采用微波技术固化EP／ANDPO体系。通过FTIR定量研究了EP／ANDPO体系的反应程度，利用差示扫描量热法(DSC)和热重分析法(TG)研究了固化体系的耐热性能，并与热固化进行了比较。结果表明：微波固化显著提高了体系的固化速度和热性能。体系转化率为95％时，400W的微波只需10min即可完成固化，而热固化需要在150℃固化240min。微波固化产物的Tg、表观分解温度TA、温度指数Tzg分别为172．6℃、322℃和200℃。而热固化产品的Tg、TA、Tzg分别为163．5℃、306℃和189℃。两种固化方式所得产品的TA、Tzg均高于目前所用的芳香族胺类固化剂，显著提高了环氧树脂的耐热性能。     

Thermal cure monitoring of phenolic resole resins based on in situ fluorescence technique

The thermal curing reaction of two phenolic resole resins is monitored using the fluorescence technique. The intrinsic fluorescence can be used as an indicator for cure monitoring for the first resole. As the thermal curing proceeds, the intrinsic fluorescence intensity of the resole resin decreases and exhibits a few nanometers of redshift. The fluorescence intensity of the emission maxima is correlated with the conversion measured by differential scanning spectroscopy. A linear correlation is found at three different temperatures. The intrinsic fluorescence cannot always be used for monitoring the curing process of phenolic resole resins. Thus, three intramolecular charge transfer compounds and two organic donor–π‐acceptor salts are selected and applied for the cure monitoring of the second phenolic resole resin. As the curing reaction proceeds, the fluorescence emission spectra of the probes exhibit a blue spectral shift and the intensity changes because of environmental changes. An intensity ratio method is applied in which the ratios of the low‐ to high‐intensity changes in the emission bands are used to determine the degree of the curing process. There is a smooth correlation between the intensity ratio method and the degree of cure. The method enables one to follow the changes in the polymer structure at low and intermediate degrees of the curing process (below 70%) and obtain comparable results from different types of probes during the same curing process. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1773–1780, 2002     

Oligomer-Rich Fraction from Polydisperse Sample of Poly(bis(β-phenoxyethoxy)phosphazene)

Poly[bis(-phenoxyethoxy)phosphazene] [PBPEP] had been shown in our previous paper to be a very useful polymer for investigating the crystallization mechanism of polymers, as the crystallization rate of PBPEP is extraordinarily small when isothermally crystallized from the melt. The crystallization of the low molecular weight oligomers of PBPEP was first studied in comparison to the high molecular weight polymers. The oligomer-rich fraction was obtained by fractionation of the as-polymerized sample, which had a broad molecular weight distribution. The fractions thus obtained were characterized by solution viscometry and size exclusion chromatography. The melting temperature and the growth rate of the spherulite from the melt were investigated by differential scanning calorimetry and optical microscopy. The growth rate was one or two orders of magnitude smaller in the oligomer-rich fraction than in the other high molecular weight fractions. A collapsed spherulite appeared in the oligomer-rich fraction at high crystallization temperatures. It is speculated that in the oligomer-rich fraction there is an excess free energy due to defects in the crystal phase. This defect is considerably larger in the oligomer-rich fraction than in the other fractions because a large quantity of short length chains is present.