二苯酮-可聚合胺引发1,6-己二醇二丙烯酸酯的光聚合研究

以UV-Vis分光光度计法和Photo-DSC法分别研究了合成的3种可聚合胺类助引发剂DMPDA、EGDPM、EGMPM与二苯甲酮(BP)组成的引发体系的光化学初级过程及引发1,6-己二醇二丙烯酸酯(HDDA)的紫外光聚合动力学.考察了助引发剂胺的含量对BP的光化学初级过程和对引发HDDA光聚合动力学的影响,以及光强和温度对聚合动力学的影响.结果表明,随着胺含量的增加,BP的光化学初级反应速率增加,从而使体系的聚合反应速率增加.随着温度和光强的增加,单体最终转化率、最大反应速率增大,达到最大反应速率所需的时间减小.     

二芳酮-可聚合胺紫外光引发1,6-己二醇二丙烯酸酯聚合的动力学研究

用Photo-DSC(光差热扫描)研究了一种可聚合胺助引发剂乙二醇-3-吗啡啉丙酸酯甲基丙烯酸酯(EGMPM)分别与二苯甲酮(BP)、4-(4-甲苯硫基苯基)苯基甲酮(BMS)、4-氯二苯甲酮(CBP)、4-氯甲基二苯甲酮(CMBP)、4-羟甲基二苯甲酮(HMBP)等二芳酮组成的光引发体系引发以1,6-己二醇二丙烯酸酯(HDDA)为单体的紫外光聚合动力学.考察二芳酮质量分数、聚合温度、光照强度对其光聚合动力学影响,并评价其引发效果;同时计算出了EGMPM/BP引发HDDA聚合体系的活化能.结果表明,二芳酮的质量分数增加时,反应达到最大反应速率的时间减少,单体的转化率也相应增加,单体聚合速率相应增大;相同质量分数(0.1%)的不同二芳酮,BMS体系达到最大反应速率的时间最短,单体转化率也最高;随着温度和光强的增加,单体最终转化率、最大反应速率增大,达到最大反应速率所需的时间减少.     

反应型受阻胺-4-丙烯酰胺基-2,2,6,6-四甲基哌啶(AATP)熔融本体光聚合反应动力学研究

合成了反应型受阻胺4-丙烯酰胺基-2,2,6,6-四甲基哌啶(AATP),用FTIR、¹H-NMR和元素分析对其结构和组成进行了综合表征.以AATP为聚合单体,利用光-DSC技术研究了AATP熔融本体光聚合反应动力学.结果表明:AATP光聚合的诱导时间随引发剂浓度和辐照光强增加而缩短,光聚合速率随温度的升高而减小;在聚合初期,AATP光聚合速率分别与引发剂浓度和辐照光强的平方根呈较好的线性增长关系.并用稳态和非稳态相结合的光-DSC方法测定了AATP光聚合过程的动力学参数:链增长速率常数k_p=2.22-7.96×10²L/mol·s、链终止速率常数k_t=0.08-2.67×10⁴L/mol·s、表观活化能为E_p-E_t/2=-7.70-13.36kJ/mol、指前因子A_p/A_t^0.5=0.076-0.333(L/mol·s)0.5,k_p和k_t在聚合初期均随单体转化率的提高而增大,但kt增加的幅度远大于k_p.     

2,2′-二邻甲氧基苯基-4,4′,5,5′-四苯基-1,2′-二咪唑复合光引发体系的光聚合动力学研究

本文研究了对2,2′-二邻甲氧基苯基-4,4′,5,5′-四苯基-1,2′-二咪唑(BMOIM)复合光引发体系引发聚合动力学过程.采用紫外光谱仪对引发剂、供氢体、增感剂在紫外区的吸收谱图进行了表征.利用实时红外光谱仪对复合光引发体系引发聚合动力学过程进行实时监测,考察了不同光强、引发剂浓度以及不同官能度单体对反应速率及最终双键转化率的影响.结果表明,在引发剂浓度为0.6%(质量分数)时,20s内双键转换率达到96%,随着引发剂浓度的提高,聚合速率增大.聚合速率以及最终双键转化率随着光强增大而增大;双官能团单体的最终双键转化率比三官能团单体的最终双键转化率要高.     

可聚合型光引发剂4-丙烯酰氧基二苯甲酮的光聚合性能研究

以实时红外光谱(RT-IR)法研究了合成的4-丙烯酰氧基二苯甲酮(4-ABP)的光聚合动力学性质,考察了不同单体、不同引发剂和助引发剂浓度、不同光强对聚合性能的影响.以萃取法对比研究了4-ABP和二苯甲酮(BP)在固化膜中的的残留量.结果表明,4-ABP是一种非常有效的光引发剂.随着引发剂浓度和光强的增大,单体转化率、最大反应速率都增大,诱导期缩短.萃取实验表明4-ABP在固化膜中的残留量远低于BP.     

含氟光引发剂的合成及其性能研究

以2-羟基-4'-(2-羟乙氧基)-2-甲基苯丙酮(Irgacure 2959)和全氟辛酰氯(PFOC)为原料合成了光引发剂全氟辛酸-2-[4-(2-羟基-2-甲基丙酰)苯氧基]乙酯(2959-F),利用红外光谱(FT-IR)和核磁共振(¹⁹F NMR)对2959-F进行了结构表征;通过紫外吸收光谱测定了2959-F的紫外吸收谱;通过实时红外光谱(RT-IR)对合成的含氟光引发剂进行了光聚合反应动力学研究,考察了光强和引发剂浓度对单体的双键转化率和聚合速率影响,并研究了光引发剂2959-F的抗氧阻聚性能.结果表明:随着光强的增大,单体的双键转化率和聚合速率增加;在一定范围内,引发剂的浓度越高,双键转化率越高,聚合速率越快.2959-F具有较高的双键转化率和较快的聚合速率,并且具有较好的抗氧阻聚性.     

4-乙烯基-1-环己烯二环氧化物阳离子单体光聚合性能研究

本文用实时红外光谱研究了4-乙烯基-1-环己烯二环氧化物(TTA22)单体的光聚合性能。分别考察了光引发剂浓度、光源、光强及增感剂浓度对其光聚合性能的影响。选用3,4-环氧环己基甲酸-3′,4′-环氧环己基甲酯(TTA21)作为参照,比较了不同单体的光固化性能。结果表明,随着引发剂浓度以及光强的增加,环氧基转化率及转化速率随之增加。LED光源下单体的转化率和转化速率低于UV汞灯。对TTA22和TTA21光固化后材料的热稳定性进行分析,结果显示TTA21的热稳定性优于TTA22的。     

2,4-双(三氯甲基)-6-(4-甲氧基-1-苯乙烯基)-s-三嗪光引发剂的合成与聚合动力学研究

本研究以4-甲氧基苯甲醛和2,4-双(三氯甲基)-6-甲-基1,3,5-三嗪为原料合成了一种引发剂2,4-双(三氯甲基)-6-(4-甲氧基-1-苯乙烯基)-s-三嗪(BMT),并利用红外光谱、紫外光谱、核磁共振等手段对其结构进行表征.利用实时红外光谱研究其光聚合动力学性能,结果表明,不同引发剂浓度,不同单体和不同光强对单体双键转化率都有一定的影响.     

基于α-羟烷基苯酮(HAPK)可聚合大分子光引发剂的合成及其引发三丙二醇双丙烯酸酯(TPGDA)光聚合动力学的研究

以α-羟烷基苯酮(HAPK)、甲苯-2,4-二异氰酸酯(TDI)、聚乙二醇600(PEG600)和丙烯酸-β-羟乙酯(HEA)为原料,通过3步反应,合成了一种可聚合大分子光引发剂:HAPK-TDI-PEG600-TDI-HEA(HTPTH).用IR对反应过程进行了监测.通过Photo-DSC研究了HTPTH引发三丙二醇双丙烯酸酯(TPG-DA)光聚合动力学,考察了光强、引发剂浓度对TPGDA光聚合动力学的影响.结果表明,随着引发剂浓度和光强的增大,最大反应速率对应的转化率、单体最终转化率、最大反应速率都增大,达到最大反应速率所需的时间减小.     

KCD/MDEA/TA三元引发剂引发丙烯酸酯/液晶复合体系光聚合动力学

采用配有441.6 nm滤光片的光差示扫描量热仪研究了3,3'-羰基双(7-二乙胺香豆素)(KCD)/N-甲基二乙醇胺(MDEA)/2-(4-甲氧苯基)-4,6-双(三氯甲基)-1,3,5-三嗪(TA)三元引发剂引发丙烯酸酯/液晶复合体系光聚合动力学行为. 结果表明, 在KCD/MDEA复合引发剂中添加TA, 显著提高了丙烯酸酯/液晶复合体系的最大光聚合速率[R_p(max)]和单体转化率, 当TA质量分数为0.5%时, 体系的R_p(max)和单体转化率分别提高了100%和69%. 同时, 随着光照强度的增加, 该体系的R_p(max)和单体转化率呈增大的趋势, 当光强从1.5 mW/cm⁺²提高到35.2 mW/cm⁺²时, 其R_p(max)和最终单体转化率分别提高了2.5和2.8倍.     

Dispersion and reactivity of copper catalysts supported on Al2O3-ZrO2

A series of CuO/Al(2)O(3)-ZrO(2) catalysts with Cu loadings varying from 1.0 to 20 wt % were prepared and characterized by X-ray diffraction (XRD), temperature-programmed reduction (TPR), temperature-programmed desorption (TPD) of CO(2) and NH(3), electron spin resonance (ESR), and Brunauer-Emmett-Teller surface area measurements. The dispersion and metal area of copper were determined by the N(2)O decomposition method. XRD results suggest that the copper oxide is present in a highly dispersed amorphous state at copper loadings < 10 wt % and as a crystalline CuO phase at higher Cu loadings. ESR results suggest the presence of two types of copper species on the Al(2)O(3)-ZrO(2) support. TPR results suggest well-dispersed copper oxide species at low Cu loadings and crystalline copper oxide species at high Cu loadings. Well-dispersed copper oxide species were reduced more easily than large copper oxide species by H(2). The results of CO(2) TPD suggest that the basicity of the catalysts was found to increase with an increase of copper loading up to 5.0 wt % and decreases with a further increase of copper loading. The results of NH(3) TPD suggest that the acidity of the catalysts was found to decrease with an increase of copper loading up to 5.0 wt % and increases with a further increase of copper loading. The catalytic properties were evaluated for the vapor-phase dehydrogenation of cyclohexanol to cyclohexanone and correlated with the results of CO(2) TPD measurements and the dispersion of Cu on the Al(2)O(3)-ZrO(2) support.     

Aggregation of Sodium 2,4,5-(tri-n-Alkyl)-benzene Sulfonates in Aqueous Solution: Micellization and Microenvironment Characteristics Studied by Electron Paramagnetic Resonance and Steady-State Fluorescence Quenching

The aggregation behaviors and microenvironmental characteristics of five sodium tri-n-alkylbenzene sulfonates (STABS) micelles have been investigated by electron paramagnetic resonance (EPR) and steady-state fluorescence quenching (SSFQ) techniques. The results indicated that the micropolarity of STABS micelles was less sensitive to the increase of the alkyl chain length, and showed slight decrease with the increasing solution concentration. The microviscosity of STABS micelles increased with the increase of the long alkyl chain length, decreased with the increase of the short alkyl chain length, and exhibited little increase when increase the solution concentration. The salinity of added inorganic salt exhibited obvious effect on the decrease of micropolarity and increase of microviscosity of STABS. These results suggested that these different alkyl chains showed different effects on the micellization of STABS and the salinity's effect was even bigger.     

Encapsulation of drugs by lyophilized empty dipalmitoylphosphatidylcholine liposomes: effect of calcium ion

The effects of divalent cation (Ca2+) on the characteristics of dipalmitoylphosphatidylcholine (DPPC) liposomes regenerated from lyophilized empty liposomes by rehydration and warming were investigated. The results showed that the volume (ml) of internal aqueous compartment per g lipid (captured volume; Vcap) has a maximum at a certain concentration range of calcium chloride and the maximal value is more than ten times the minimal value. This phenomenon can be explained by considering that binding of Ca2+ to phosphate groups in DPPC molecules induces an increase in the distance (r) between adjacent bilayer membranes in multilamellar liposomes through electrostatic force and causes an increase in Vcap. The dynamic properties of lyophilized liposomes in the rehydration process were examined using a multilamellar vesicle model. The results of simulation suggested that a repulsive force induced between the adjacent bilayer membranes causes rearrangement of the constituent lipid molecules in a liposome followed by an increase in the distance r, a decrease in the internal lamellar number, a smaller increase in liposome size and finally a significant increase in Vcap.     

Development and evaluation of cyclodextrin complexed hydroxyapatite nanoparticles for preferential albumin adsorption

Our study focuses on the incorporation of β-CD into the HA structure, its effects on the phase of HA and the biological responses to proteins and blood cells. Hydroxyapatite (HA) containing levels of β-cyclodextrin (β-CD) of upto 0.9 wt% has been produced by co-precipitation method. The complexes were analyzed by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectroscopy, thermal gravimetric analysis (TG) and differential scanning analysis (DSC) methods. The size of the complexes as analyzed using DLS (dynamic light scattering) was between 150 nm and 350 nm. The results show that an increase in concentration of β-CD in the prepared samples that leads to an increase in hydrophobicity seems to promote an affinity for albumin adsorption. The PAGE results were substantiated by Lowry measurements and the results reveal that the H2 (containing 0.7 wt% β-CD) sample shows around 40% increase in albumin adsorption when compared to the H1 (containing 0.5 wt% β-CD) sample. The preferential adsorption of albumin has not been demonstrated in vivo. The ability to design particles that can preferentially interact with particular protein can obtain desired targeting effects. So the results indicate that HA/β-CD complexes have immense potential in targeted delivery of drugs. The in vivo potential of the developed samples was further confirmed in vitro by the results of cell aggregation and haemolytic activity.     

原子吸收法研究部分水解聚丙烯酰胺/Cr(Ⅲ)凝胶的交联密度

由 Cr( )交联部分水解聚丙烯酰胺 ( HPAM)形成的水凝胶已广泛应用于油田三次采油生产中 ,对于调整吸水剖面和提高原油采收率起到重要作用 .在 HPAM/Cr( )交联机理和交联动力学等方面的研究多采用粘度法 [1] 、紫外 -可见分光光度法 [2 ] 、流变学法[3] 、原子力显微镜 ( AFM)法 [4 ] 、粒度及其分布法 [5] 等 ,考察 HPAM/Cr( )交联反应过程 ,而对交联密度ρ的研究却少见报道 .ρ可用单位体积凝胶中参与交联反应的 Cr( )的量 ( g/cm3)来表征 ,在微观上反映了交联点的数目 ,在宏观上与凝胶的强度和脱水程度相联系 ,因而是交联体系…     

主链含己烷雌酚的聚酸酐的合成及其降解性能研究

聚酸酐是一类新型的药物控制释放载体材料,具有良好的生物相容性和表面溶蚀性能^[1].聚酸酐的降解和药物释放速率可通过改变单体结构、共聚物的组成和主链上的酸酐键密度实现.后者主要是把降解速率不同的酯键、酰(亚)胺键和磷酸酯键引入主链上.     

PVA碱性凝胶聚合物电解质薄膜电化学稳定性研究

应用溶解—铸膜法制备聚乙烯醇(polyvinylalcohol,PVA)碱性凝胶聚合物电解质(gelpolymerelectrolyte,GPE)薄膜.交流阻抗(EIS)测试表明,随着KOH含量的增加,该薄膜的离子电导率表现为先增大而后减小的变化趋势,当KOH含量为42%(bymass,下同)时,电导率达到最大值,为2.01×10-3S/cm.X射线衍射(XRD)结果表明,当膜中KOH含量大于20%时,晶态的PVA就逐渐转变为非晶态结构.又当KOH含量增加到一定值后,由于体系中未电离的非晶态KOH量的增多而导致离子电导率下降.循环伏安(CV)和拉曼光谱(Raman)结果表明,该薄膜具有很好的电化学稳定性,可应用于碱性二次电池.     

磺酸型阴离子聚氨酯离聚物的研究(Ⅰ)——不同离子化程度对性能的影响

合成了不同离子化程度的磺酸型阴离子聚氨酯离聚物,并通过红外光谱、示差扫描量热、动态力学、应力-应变等方法研究了它们的性能,结果表明:离子化程度不同对聚氨酯离聚物的软硬段相容性有较大的影响,引入少量离子,使软硬段相容性提高,引入大量离子时,则又使软硬段相分离程度提高,随着离子化程度的提高,材料的抗张强度、水溶性逐步提高,为控制聚氨酯材料的亲水性及制备水溶性聚氨酯提供了一种新途径。     

Thermal properties of poly(urethane-ester-siloxane)s based on hyperbranched polyester

Novel polyurethanes (PUs) were synthesized using hydroxy-terminated hyperbranched polyester (BH-20) and 4,4′-methylenediphenyl diisocyanate (MDI) as hard segments and hydroxy-terminated ethylene oxide-poly(dimethylsiloxane)-ethylene oxide triblock copolymer (PDMS-EO) as soft segment, with soft segment content ranging from 30 to 60 wt %. The PUs were synthesized by two-step solution polymerization method. The influence of the soft segment content on the structure, swelling behavior and thermal properties of PUs was investigated. According to the results obtained by swelling measurements, the increase of the hard segment content resulted in the increase of the crosslinking density of synthesized samples. DSC results showed that the glass transition temperatures increase from 36 to 65°C with increasing hard segment content. It was demonstrated using thermogravimetric analysis (TGA) that thermal stability of investigated PUs increases with increase of the soft PDMS-EO content. This was concluded from the temperatures corresponding to the 10 wt % loss, which represents the beginning of thermal degradation of samples.     

多孔聚合物微球孔结构对丙烯催化聚合性能的影响

多孔聚苯乙烯-二乙烯基苯(PS-DVB)微球具有物理化学性质稳定、比表面积大和生产成本低等优点,同时粒径大小可调,在生物医药、吸附、分离和催化剂载体等领域具有广阔应用前景。 通过引入功能单体丙烯氰(AN)、丙烯酰胺(AA)和N-乙烯基咔唑(VC)制备了3种多孔聚合物微球(PPMs),优选含氰基官能化的PPM-AN载体负载Ziegler-Natta(Z-N)催化剂催化丙烯聚合研究孔结构对催化性能的影响。 结果表明,一方面,由于存在模板效应和受限作用,聚丙烯呈微球和纳米纤维状;另一方面,PPM-AN载体负载Z-N催化剂中Ti和Mg的负载量随着载体比表面积的增大而增多。 丙烯聚合结果表明,同一压力下,由于丙烯单体受PPM-AN载体孔的限制作用,随着孔径增大,重均相对分子质量、相对分子质量分布和等规度总体趋势均是升高。