环氧树脂/聚砜共混体系相结构的调控研究——环氧预聚物分子量的影响

研究了不同分子量的环氧预聚物对双酚A型双官能团环氧树脂 /聚砜 (PSF) /固化剂 (二氨基二苯基砜 ,DDS)体系相分离结构的影响 .通过红外光谱 (FTIR)和动态热机械分析 (TMA)对反应转化率、玻璃化温度以及固化温度的关系的研究 ,表明环氧预聚物分子量较小时 ,凝胶点和玻璃化是影响相结构的关键因素 ;环氧分子量较大时 ,环氧扩链后粘度的变化则成为抑制相分离的重要因素 .电子显微镜 (SEM)结果表明改变环氧预聚物分子量可以达到调控相结构的目的 ,随着预聚物分子量的增大 ,体系的微区尺寸减小 .     

糠醛缩胺型高分子-稀土发光配合物的制备及发光特性

通过三步大分子反应法,制备了糠醛缩苯胺型席夫碱功能聚砜和糠醛缩环己胺型席夫碱功能化聚砜。首先,通过傅克烷基化反应在聚砜(PSF)侧链键合氯甲基,制备氯甲基化聚砜CMPSF;以制备的氯甲基化聚砜为亲电试剂,与糠醛(FF)发生傅克烷基化反应,制备侧链键合有糠醛基团的功能化聚砜PSF-FF;使糠醛的醛基分别与苯胺(AN)和环己胺(CA)的氨基发生席夫碱反应,制备糠醛缩苯胺型席夫碱功能聚砜PSF-FA和糠醛缩环己胺型席夫碱功能化聚砜PSF-FC。用红外光谱(FTIR)和核磁共振氢谱(IHNMR)表征功能化聚砜的结构。在此基础上,以这两种功能化聚砜为大分子配体,分别与Eu(Ⅲ)离子和Tb(Ⅲ)离子进行配位,制备了二元配合物PSF-(FA)3-Eu(Ⅲ)、PSF-(FA)3-Tb(Ⅲ)和PSF-(FC)3-Eu(Ⅲ)、PSF-(FC)3-Tb(Ⅲ),初步探索了配合物的光致发光性能。重点研究了制备糠醛缩胺型功能化聚砜PSF-FA和PSF-FC的反应,考察分析了主要因素对CMPSF与FF之间傅克烷基化反应(属亲电取代反应)的影响规律。结果表明,对于该傅克烷基化反应,N,N-二甲基乙酰胺因极性较强为适宜的溶剂,反应适宜的温度为70℃。二元配合物PSF-(FA)3-Eu(Ⅲ)发射Eu(Ⅲ)离子特征荧光(红光),即大分子配体PSF-FA可敏化Eu(Ⅲ)离子的荧光发射,而PSF-(FA)_3-Tb(Ⅲ)无明显的荧光效果,大分子配体PSF-FA的三重态能级与Eu(Ⅲ)离子共振能级比较匹配;配合物PSF-(FC)3-Tb(Ⅲ)发射Tb(Ⅲ)离子的特征荧光(绿光),即大分子配体PSF-FC可敏化Tb(Ⅲ)离子的荧光发射,而PSF-(FA)_3-Eu(Ⅲ)无明显的荧光效果,大分子配体PSF-FC的三重态能级与Tb(Ⅲ)离子共振能级比较匹配。     

侧链键合水杨醛型双齿席夫碱配基的功能化聚砜的合成及其稀土离子配合物的光致发光性能

通过氯甲基化聚砜(CMPSF)与4-羟基水杨醛(HSA)的亲核取代反应,将水杨醛(SA)基团键合在聚砜侧链,制得改性聚砜PSF-SA;再经PSF-SA的醛基分别与苯胺(AN)和环己胺(CA)发生席夫碱反应,获得了两种侧链键合了水杨醛型双齿席夫碱配基的功能化聚砜PSF-SAN和PSF-SCA,产物的结构由红外光谱和核磁共振氢谱表征。以两种功能化聚砜为大分子配体,与Tb(Ⅲ)离子及Eu(Ⅲ)离子分别配位,制得了二元高分子-稀土配合物,初步探索了配合物的光致发光性能。本文重点研究了功能化聚砜PSF-SAN和PSFSCA的制备反应,考察与分析了主要因素对CMPSF与HSA之间亲核取代反应的影响规律。结果表明,对于该亲核取代反应,适宜的溶剂为极性较强的N,N-二甲基乙酰胺,80℃为适宜的反应温度。大分子配体PSFSAN对Eu(Ⅲ)离子的荧光发射产生强烈的敏化作用,配合物PSF-(SAN)_3-Eu(Ⅲ)发射红光;大分子配体PSF-SCA对Tb(Ⅲ)离子的荧光发射也产生敏化作用,配合物PSF-(SCA)_3-Tb(Ⅲ)发射绿光。     

含羧基嵌段的离聚体的合成及其性能研究

合成了羧基有序分布和羧基无序分布的两类光固化水性聚氨酯丙烯酸酯 (PUA)的离聚物 ,研究了其光固化反应动力学 ,并测定其预聚物分散液的性能和固化膜的性能。     

双酚A聚砜链对对苯二酚聚砜链结晶性能的影响

本文报导了双酚A聚砜(B)与对苯二酚聚砜(H)两组份含量不同的嵌段共聚物的X射线衍射结果,B链的加入,使共聚物的结晶性能被破坏,B/H为0.48(摩尔比)时,所得共聚物已呈现出完全非晶相结构的特征.由IGC及DSC实验测定,表明这两种聚砜链是相容的.     

侧链结构对侧链型磺化聚砜质子交换膜性能的影响

以双酚A型聚砜(PS)为基础,与自制的1,4-二氯甲氧基丁烷反应制备氯甲基化聚砜(CPS),接着与2-萘酚-6,8-二磺酸钾(NSK)进行亲核取代反应制备萘磺酸型侧链磺化聚砜(PS-NS)。采用溶液浇注法制备相应的质子交换膜(PEMs),结合前期研究的脂肪磺酸型侧链磺化聚砜(PS-ES)和苯磺酸型侧链磺化聚砜(PS-BS) PEMs,考察侧链结构对PEMs的吸水率、吸水溶胀率和尺寸稳定性的影响关系。结果表明,与主链型芳香聚合物PEMs相比,3种侧链型磺化聚砜PEMs由于亲水基团远离疏水主链,能够形成类似于Nafion膜的相分离结构,在高吸水率下保持更好的尺寸稳定性;在相同的离子交换膜容量(IEC)下,PS-ES、PS-BS和PS-NS膜随着侧链刚性苯环数目的增加,侧链的运动能力减弱,导致PEMs的尺寸稳定性增加,相应的质子传导率减小; PS-ES膜在25℃和85℃的质子传导率分别达到0. 072和0. 141 S/cm,PS-NS在25℃和85℃的尺寸溶胀性仅为21. 8%和51. 5%,性能与商业化的Nafion115膜十分接近。     

一类高折射率光固化有机硅树脂的性能研究

光固化有机硅材料兼具光固化的高效、能耗低和环保以及有机硅树脂优异的耐温、耐候性和电绝缘性能,因此,在LED等电子器件封装方面受到广泛关注.本文研究了自制的3种含丙烯酸酯基团的光固化苯基有机硅预聚物KDS-10、KMDS-03和KMS-03的光固化特性、光学性能和热稳定性能.结果表明,这些有机硅预聚物的折光指数随苯环含量的增加而增高,苯环含量从22.3%到37.7%,折光指数相应从1.496到1.542;3种预聚物与多种丙烯酸酯相容性好,用双官能的TPGDA作稀释剂,固化反应速率最快,丙烯酸酯基团的转化率也最高;光引发剂TPO引发的光固化反应速率和转化率均最高;高折射率有机硅预聚物KDS-10光固化后的薄膜具有优异的光学性能,在550 nm处的透过率为92.54%;玻璃化转变温度约为-17.41℃,起始分解温度为385℃.     

两亲性超支化聚砜胺对染料的可逆高装载

采用戊酰氯、壬酰氯和棕榈酰氯对超支化聚砜胺(HPSA)进行封端,合成了3种不同烷基末端的两亲性核壳型超支化聚砜胺,并将其用于小分子装载.发现它们对刚果红(CR)、甲基橙(MO)、虎红(RB)等水溶性染料具有很强的装载能力,且对同种染料的封装载荷随着末端亲油性烷基链的增长而增大.对于末端为棕榈酰基的HPSA-PC,平均每个大分子可以捕捉CR和MO分子的数目分别高达41.8和19.4个,远高于已报道的树枝状聚合物和超支化聚合物对这些染料的封装载荷.这主要是聚砜胺内核的高度亲水性及其与亲油性烷基外壳的极性差所致.与已报道的聚合物不同,两亲性超支化聚砜胺装载的染料用纯水洗涤可以释放出来.这种高装载性能和可逆性赋予超支化聚砜胺在药物释放、分子识别和分离以及纳米催化剂和纳米涂料等领域具有广阔的应用前景.     

具有高效长侧链的芘磺酸型磺化聚砜阳离子交换膜的性能

以双酚A型聚砜和无致癌毒性的溴甲基化试剂1,4-二溴丁烷为原料,通过烷基化反应在聚砜分子上引入可交换溴原子制备溴代聚砜(BPSF),将BPSF与8-羟基-1,3,6-芘三磺酸钠(TS)试剂通过亲核取代反应制备一种磺酸基团远离聚合物主链的芘磺酸型磺化聚砜(PS-TS).采用溶液流延法制备PS-TS阳离子交换膜,通过控制亲...     

以氯代酰氯为试剂的聚砜膜材料的付-克酰基化反应

采用氯乙酰氯和氯丁酰氯两种ω-氯代酰氯化试剂,在Lewis酸催化剂存在下,于室温下分别对聚砜（PSF）材料实施了Friedel-Crafts酰基化反应,制备了氯代酰基化（CA）聚砜材料CAPSF。用FT-IR、1H-NMR与佛尔哈德分析法表征了该产物的化学结构与组成。结果表明：在室温（25°C）下,以CH2Cl2为溶剂...     

Determination of the glass transition temperature of latex films: Comparison of various methods

The glass transition temperature (T_g) for two latices with different styrene/butadiene compositions was determined by the thermal SPM probe resonance frequency method. The results were compared with the T_g values obtained by differential scanning calorimetry (DSC), dynamical mechanical analysis (DMA), process rheometer (PR) and thermo-mechanical analyzer (TMA) measurements. The T_g values detected by the thermal SPM method agreed well with the T_g values obtained by DSC and calculated by the Fox–Flory equation. DMA, on the other hand, showed a significantly higher T_g value for both latices than those obtained from theoretical calculations, the thermal SPM method and DSC. The T_g obtained from the PR curve was slightly higher for the latex with a low styrene content, whereas good agreement was obtained with the thermal SPM data for the latex with a high styrene content. The glass transition temperature determined by TMA agreed fairly well with the thermal SPM data for the latex with the low styrene content, whilst the value of T_g for the second latex was much less than those obtained by the other methods. The thermal SPM method detects changes in thermal behavior (thermal diffusivity, heat capacity) during heating of the latex films rather than changes in the mechanical properties. Information about the sample history could be seen in the thermal SPM curves, which was further associated with the degree of latex film formation, especially when the roughness of the films was taken into consideration.     

Melting and glass transitions in paraffinic and naphthenic oils

Naphthenic and paraffinic oils were analyzed by modulated differential scanning calorimetry (MDSC). The results showed several improvements in the analysis of thermal properties when compared with standard DSC. The glass transition temperature (T_g), the enthalpy relaxation at T_g, and the melting endotherms could be deconvoluted, and reversible melting could be identified. This allowed for an easier interpretation of the thermal properties of the oils. With MDSC, the T_gs in mineral oils were found to coincide with endothermic enthalpy relaxation, which is generally regarded as a melting endotherm with standard DSC. A decrease in heat capacity after T_g was attributed to the existence of rigid amorphous material. From Δc_p at T_g and the oil molecular weight, the number of repeat units in the oil chains was estimated at less than 20. The T_g of a hypothetical pure aromatic oil was found to be similar to that for petroleum asphaltenes, and that for a naphthenic oil of infinite molecular weight to be similar to that of petroleum resins.     

Thermotropic main chain liquid crystalline polyesters containing ferrocene and phosphate units: synthesis and characterization

A new series of liquid crystalline main chain copolyesters were prepared, having ferrocene in the mesogenic segment and a methyl phosphate group along with a methylene spacer. The even numbered methylene groups were varied from two to ten. Liquid crystalline behaviour was investigated on a hot stage optical polarized microscope. Thermal properties of the polymers were analysed by TGA and DSC, revealing that the polymers yield high char products, probably caused by the formation of phosphorus and iron oxides. The glass transition (T_g) temperatures of the polymers were found to be fairly low, the result of the incorporation of bulky phosphorus and ferrocene moieties in the chain. The phase behaviour was analysed and correlated with the structure of the polymers. The liquid crystalline textures of the polymers became more transparent with increasing spacer length. Energy minimized structures for the polymer repeating units reveal that both the ferrocene and phosphorus moieties produce more molecular entanglement, thus reducing the T_g and T_m of the polymers.     

Thermal and topographical characterization of polyester- and styrene/acrylate-based composite powders by scanning probe microscopy

The thermal properties of two conventional polyester-based toners and a chemically prepared styrene/acrylate toner with different thermal histories were studied by scanning probe microscopy (SPM) and differential scanning calorimetry (DSC). The thermal transition temperatures detected by SPM agreed with the results of the DSC measurements. The validity of SPM for detecting thermal transitions was further confirmed by studying two amorphous reference polymers with different glass transition points (T_g) and three crystalline reference polymers with different melting points (T_m). When the toner sample was heated by the SPM probe above the glass transition temperature of the toner powder (T_probe > T_g), changes occurred in the surface topography and roughness causing different levels of local sintering of the particles. A set of roughness parameters calculated from the SPM image data were used to quantify the most essential features of toner surfaces. Environmental scanning electron microscopy (ESEM) was used to study the penetration depth of heat dissipated by the SPM probe. The probe-annealing was compared with oven-annealing in order to establish the effect of thermal history on the thermal properties of the materials.     

(2,6-Diphenyl) phenyl methacrylate—2. Radical copolymerization with methyl methacrylate. The Tgs of its copolymers with an addendum on the polymerization of (2,6-diphenyl) phenyl acrylate

The radical copolymerization of (2,6-diphenyl) phenyl methacrylate (1) with methyl methacrylate in DMF with AIBN at 70°C has the reactivity ratios r₁ = 0.071 and r₂ = 1.42, from which Q₁ = 1.45 and e₁ = 1.20. The copolymers had M_ns in the range of 10,000–40,000 and T_gs ranging from 406 to 480 K from which the hypothetical T_g for poly-1 was deduced as 500 K (227°C). Unlike 1, (2,6-diphenyl) phenyl acrylate could be polymerized to oligomers with M_n of the order of 2500.     

Comparison of simulated and experimental fundamental ICP parameters

False-color spatial maps of experimentally determined and simulated values of electron number density (n_e), electron temperature (T_e) and heavy-particle temperature (T_g) for an argon inductively coupled plasma (ICP) in the plasma decay region (tail flame) are compared in detail. Experimental and theoretical values are in general very consistent; the difference between experiment and computation is approximately 10% for n_e and T_e and 20% for T_g in the plasma region examined. The errors in n_e and T_e are larger at the edge of the plasma, most likely because air entrainment becomes significant. This comparison provides a link between measurements and the current mathematical model and serves to partially validate both methods. Sources of error in both experiment and theory are considered and discussed.     

Miscibility and crystallinity of poly(3-hydroxybutyrate)/poly(3-hydroxybutyrate-co-3-hydroxyvalerate) blends

With the objective of developing new biodegradable materials, the miscibility and the crystallinity of blends of poly(3-hydroxybutyrate), P(3HB), and poly(3-hydroxybutyrate-co-3-hydroxyvalerate), P(3HB-co-3HV), have been studied. P(3HB) (300 kg mol⁻¹)/P(3HB-co-3HV)–10% 3HV (340 kg mol⁻¹) blends were prepared by casting in a wide range of proportions, and characterized by differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FT-IR). The experimental values for the glass transition temperatures (T_g) are in good agreement with the values provided by the Fox equation, showing that the blends are miscible. It was observed that the T_g and the melting temperature (T_m) decreases with the increase in the P(3HB-co-3HV)–10% 3HV content, while the crystallization temperature (T_c) increases. FT-IR analyses confirmed the decrease on the crystallinity of P(3HB)/P(3HB-co-3HV)–10% 3HV blends with higher copolymer contents. Bands related to the crystallinity were changed, due to the copolymer content that produced miscible and less crystalline blends.     

基于基团贡献法和分子动力学预测聚间苯二甲酰对苯二胺的玻璃化转变温度

采用基团贡献法(GC)和分子动力学法(MD)模拟了聚间苯二甲酰间苯二胺纤维(MPDI)和聚对苯二甲酰对苯二胺(PPTA)的玻璃化转变温度, 并与实验值进行了对比. 结果表明, 使用基团贡献法和分子动力学法测得的MPDI和PPTA的玻璃化转变温度与实验值接近, 说明基团贡献法和分子动力学法可以用来预测芳香族聚酰胺的玻璃化转变温度. 在此基础上, 采用GC和MD预测了聚间苯二甲酰对苯二胺(PPIA)的玻璃化转变温度. 在MD模拟中, 对密度、 比体积、 回转半径和非键相互作用随温度的变化规律进行了分析. 结果表明, 自由体积理论能较好地解释PPIA的玻璃化转变现象, 其中非键相互作用随温度的变化是玻璃化转变的本质原因. PPIA的玻璃化转变温度介于MPDI和PPTA之间, 有望成为综合性能介于两者之间的另一种高性能聚酰胺.     

Gas permeability in rubbery polyphosphazene membranes

The synthesis, characterization, and gas permeability of 10 new polyphosphazenes has been studied. Additionally, the first gas permeation data has been collected on hydrolytically unstable poly[bis-(chloro)phosphazene]. Gases used in this study include CO₂, CH₄, O₂, N₂, H₂, and Ar. CO₂ was the most permeable gas through any of the phosphazenes and a direct correlation between the T_g of the polymer and CO₂ transport was noted with permeability increasing with decreasing polymer T_g. To a lesser degree, permeability of all the other gases studied also yielded increases with decreasing polymer T_g. The trend observed for these new polymers was further supported by published data for other phosphazenes. Furthermore, permeability data for all gases were found to correlate to the gas condensability and the gas critical pressures, except for hydrogen, suggesting that the nature of the gas is also a significant factor for permeation through rubbery phosphazene membranes. Ideal separation factors () for the CO₂/H₂ and CO₂/CH₄ gas pairs were calculated. For CO₂/CH₄, no increase in was observed with decreasing T_g, however increases in were noted for the CO₂/H₂ pair.