非绝热聚合波的数学模拟

对非绝热波聚合体系进行了数学模拟, 将反应器尺寸与聚合波关联, 建立了非绝热条件下蔓延聚合波波速和最大波温的数学模型; 利用所建模型计算不同引发剂浓度、 不同环境温度、 不同试管直径下淀粉接枝聚合波的波速和波温, 并与实验测定值进行了比较. 结果表明, 非绝热聚合波的数学模型对无相变体系的拟合结果令人满意, 对聚合波的发生条件及反应器尺寸的影响有很好的预见性; 另一方面, 对于存在相变及与环境有质量交换的波聚合体系, 所建模型的预测性受到了限制.     

光引发N-乙烯基吡咯烷酮在嵌段聚醚聚氨酯膜上接枝聚合的研究

本文研究了在碱性介质中,氮气氛下 N-乙烯基吡咯烷酮(N-VP)在嵌段聚醚聚氨酯(SPEU)膜上的接枝聚合。测定了接枝率与接枝液中 N-VP单体浓度、光照时间、催化剂浓度等条件的关系。测定了接枝后 SPEU 膜的吸水性,并用扫描电镜对膜表面进行了观察。对碱性介质中的接枝机理进行了初步探讨。     

低密度聚乙烯-丙烯酸气相光接枝体系反应机理的研究

研究了以二苯甲酮(BP)为光敏剂,丙烯酸在低密度聚乙烯(LDPE)膜上两步法气相光接枝聚合;从反应的基本要素出发,利用紫外光分光光度计跟踪测定了二苯甲酮在LDPE膜中的扩散情况,发现其扩散系数随BP浓度的升高而降低,约在0.8～2.0×10-12m2.s-1之间.同样方法跟踪测定了BP在不同条件下的光还原反应,结果表明:当远紫外光被滤掉后,其半衰期大大加长,氧气的存在更是加剧了这一效应;并且通过测定不同条件下气相光接枝聚合的一些基本规律,提出单体扩散为该气相光接枝聚合的控制步骤.     

三醋酸纤维素膜辐射可控接枝甲基丙烯酸缩水甘油酯及其性能

三醋酸纤维素(CTA)是一种高强度的天然高分子衍生物,对其进行表面接枝改性将扩展其在物质分离、吸附、检测等领域的广泛应用,但是化学接枝改性CTA比较困难。 本文结合辐射引发接枝和可逆加成-断裂链转移(RAFT)聚合方法,成功地在CTA膜表面可控接枝了聚甲基丙烯酸缩水甘油酯(PGMA)。 研究了吸收剂量、单体GMA质量分数和RAFT试剂含量等因素对接枝率的影响,采用傅里叶变换红外光谱仪(FT-IR)、扫描电子显微镜(SEM)和接触角技术手段对CTA膜接枝前后的结构、形貌和表面性质进行了表征。 实验结果表明,为了得到较高的接枝率,同时又保持较好的形貌,合适的条件为:吸收剂量为10~12 kGy,GMA质量分数为30%,RAFT试剂与GMA的物质的量比为1：400;在不同条件下得到的最高接枝率为41%,接枝聚合物相对分子质量分布最低为1.33。 此外,接枝PGMA后的CTA膜疏水性增加。 该工作提供了可控接枝CTA的简便方法,与传统辐射接枝相比,RAFT辅助辐射接枝反应更加可控,得到的PGMA接枝链更加均匀,有利于根据实际应用来控制接枝率和进行后续的功能修饰。     

低密度聚乙烯丙烯酸气相光接枝体系反应机理的研究

研究了以二苯甲酮 (BP)为光敏剂 ,丙烯酸在低密度聚乙烯 (LDPE)膜上两步法气相光接枝聚合 ;从反应的基本要素出发 ,利用紫外光分光光度计跟踪测定了二苯甲酮在LDPE膜中的扩散情况 ,发现其扩散系数随BP浓度的升高而降低 ,约在 0 8～ 2 0× 10 -12 m2 ·s-1之间 .同样方法跟踪测定了BP在不同条件下的光还原反应 ,结果表明 :当远紫外光被滤掉后 ,其半衰期大大加长 ,氧气的存在更是加剧了这一效应 ;并且通过测定不同条件下气相光接枝聚合的一些基本规律 ,提出单体扩散为该气相光接枝聚合的控制步骤     

等离子体引发HEMA的RAFT接枝聚合改性聚丙烯多孔膜

采用等离子体引发的可逆加成-断裂链转移(RAFT)接枝聚合法,以甲基丙烯酸羟乙酯(HEMA)为单体,对聚丙烯(PP)多孔膜表面作了亲水改性.研究了接枝聚合动力学,并以FT-IR、SEM、压汞、水通量等方法研究了改性膜的表面结构形态及孔结构.结果表明,等离子体引发的RAFT接枝聚合速率显著低于普通等离子体引发的接枝聚合速率.表面接枝率随着接枝聚合时间的延长呈线性增长趋势,同时改性膜的孔径和水通量随之减小.     

丙烯酸改性聚醚砜中空纤维渗透汽化膜的研究

采用自由基聚合反应制备了丙烯酸接枝改性的聚醚砜中空纤维渗透汽化膜,该膜用于醇／水分离获得了良好的效果。结果表明,通过改变聚合单体的浓度可以控制膜的接枝率,并调节膜的选择性和通量。改性膜的红外光谱和电镜分析结果表明：膜的接枝反应主要发生在中空纤维膜的内表面,膜的外表面接枝程度很低。力学性能测试表明接枝后膜的拉伸强度减弱。     

在聚砜膜表面接枝聚甲基丙烯酸及接枝膜对生物碱化合物的吸附特性

首先将聚砜(PSF)氯甲基化,制得氯甲基化聚砜(CMPSF),CMPSF流延成膜后与乙二胺(EDA)反应,制得表面键合有EDA的氨基化膜(AMPSF)。在此基础上,在水溶液体系中构建氨基-过硫酸盐表面引发体系,使甲基丙烯酸(MAA)发生接枝聚合,制得了功能接枝膜PSF-gPMAA。考察了影响膜接枝过程的主要因素,优化了接枝聚合条件。采用傅里叶红外光谱(FTIR)、光学显微镜(OM)及称重法对接枝膜PSF-g-PMAA进行了表征。最后研究了功能接枝膜对氧化苦参碱和金雀花碱两种生物碱化合物的吸附特性。结果表明,采用氨基-过硫酸盐表面引发体系,可以顺利地实施MAA在PSF膜表面的接枝聚合,接枝度随氨基化膜AMPSF表面氨基键合量的增大而增大,接枝聚合适宜的温度为50℃,溶液中适宜的过硫酸盐用量为单体质量的1.0%。在适宜的条件下可制得PMAA接枝度为4.62mg/cm2的接枝膜。凭借强静电相互作用和氢键作用的协同作用,功能接枝膜PSF-g-PMAA对生物碱化合物可产生强烈的吸附作用,在中性溶液中,对氧化苦参碱和金雀花碱的吸附容量分别可达277μg/cm2和331μg/cm2。     

电子束预辐照聚丙烯与丙烯酸的接枝共聚合

应用电子束预辐照的方法对丙烯酸与等规聚丙烯粉末的接枝共聚合进行了研究．讨论了辐照剂量、储藏时间、反应温度、Ｍｏｈｒ’ｓ 盐浓度及单体浓度等因素对接枝率的影响（ 所有的实验,辐照及接枝聚合等都是在有氧的条件下进行的） ．同时对接枝材料对金属离子的吸附性能作了初步的探讨．结果表明,接枝聚合可以在有氧的条件下顺利进行．接枝材料在离子吸附方面有较大的应用前景．     

聚全氟乙丙膜电子束引发预辐射接枝AA和SSS制备阳离子交换膜的研究

利用电子束引发预辐射接枝技术,在聚全氟乙丙烯(FEP)薄膜上接枝丙烯酸(AA)和对苯乙烯磺酸钠(SSS),制备一种含羧酸基团和磺酸基团的阳离子交换膜,详细研究了反应温度、单体总浓度、pH值变化、辐照气氛及添加剂对接枝率的影响规律,明确了实验条件与接枝率的对应关系。FTIR测试证明了接枝产物是全氟乙丙烯和丙烯酸、对苯乙烯磺酸钠的接枝共聚物。     

Graft Copolymerization of Methyl Methacrylate on Potato Starch Using Potassium Trioxalatomanganate,K3[Mn(C2O4)3], as Initiator

Graft copolymerization of methyl methacrylate on potato starch was carried out in methanol-water medium at 35°C in the dark using potassium trioxalatomanganate, K₃[Mn(C₂O₄)₃], as initiator. The effect of different methanol-water ratios (v/v), the temperature of polymerization, the initiator concentration, the monomer concentration, the starch content, and the time of polymerization were studied. Percent total conversion, % grafting, and grafting efficiency (%) under different conditions were evaluated and compared. High grafting efficiency (～80%), high % total conversion (～85%), and high % grafting (-95%) were readily obtained. The reaction mechanism for graft copolymer formation is discussed.     

RP-3替代燃料自点火燃烧机理构建及动力学模拟

通过对RP-3 航空煤油成分的分析, 以及对8 组替代模型的对比实验, 选取了73.0%(质量分数)正十二烷, 14.7% 1,3,5-三甲基环己烷, 12.3%正丙基苯作为RP-3 航空煤油的替代模型. 使用本课题组自主研发的机理自动生成程序ReaxGen, 构建了RP-3 替代燃料的高温燃烧详细机理, 用该机理模拟了激波管点火延时, 并与实验数据进行比较. 用物质产率分析和近似轨迹优化算法(ATOA)简化方法简化了详细机理. 最后对燃烧机理在不同化学计量比及压力条件下的点火延时做了敏感度分析, 考察了燃烧机理在不同化学计量比下关键反应的异同. 结果表明, 该替代模型的燃烧机理能很好地描述RP-3煤油的高温点火特性.     

四氧化三铁纳米粒子表面接枝聚L-谷氨酸苄酯多孔微载体的构建和性能

在氨基化改性的四氧化三铁(Fe₃O₄)纳米粒子表面引发N-羧酸酐L-谷氨酸苄酯(BLG-NCA)开环聚合, 制得四氧化三铁/聚L-谷氨酸苄酯(PBLG)复合材料(Fe₃O₄-g-PBLG). 改变单体和引发剂比例可以调控Fe₃O₄-g-PBLG的接枝率, 采用热失重分析(TGA)测得实际接枝率分别为66.36%, 79.66%和89.52%. 通过双乳液挥发法制备磁性Fe₃O₄-g-PBLG多孔微载体, 其中接枝率为89.52%的微载体密度为1.034 g/mL, 孔隙率为92.57%, 粒径为200~300 μm, 孔径为40~50 μm, 保水率为370%~400%. 同时Fe₃O₄-g-PBLG微载体具有超顺磁性, 在外加磁场作用下可排布成任意形状, 对治疗复杂结构的骨缺损具有显著优势. 因此Fe₃O₄-g-PBLG多孔微载体在骨组织工程领域具有潜在应用价值.     

Influence of Monomer and Initiator Concentrations on the Simultaneous Grafting of Several Monomers onto Insoluble Collagen

Simultaneous grafting of 2-hydroxyethyl methacrylate and methyl methacrylate (3:1 and 3:2 mole ratios) onto insoluble collagen with ceric ammonium nitrate as initiator was attempted with a view to optimizing conditions for the preparation of hydrogels. The influence of monomer and initiator concentrations on the grafting reactions was investigated. The grafting results are discussed in the light of grafting efficiency and percentage of grafting. They were found to be lower when the 3:1 mole ratio of monomers was used.     

1-烯丙基-3-甲基咪唑离子液体单体与丙烯腈共聚行为的研究

以1-烯丙基-3-甲基咪唑盐酸盐([AMIM]Cl)作为离子液体单体,偶氮二异丁腈作为引发剂,二甲基亚砜为溶剂,实现了与丙烯腈(AN)在不同反应条件下的自由基共聚合.研究了AN/[AMIM]Cl二元共聚合的动力学,得到了相应的竞聚率数据(rAN=8.11,r[AMIM]Cl=0).用1H-NMR、GPC、DSC、TGA等手段对共聚物进行了表征.通过对AN/[AMIM]Cl二元共聚及AN/IA/[AMIM]Cl三元共聚的研究发现,[AMIM]Cl在与丙烯腈共聚时具有双重作用,一部分离子单体进入到共聚物的分子链中调节其亲水性及可纺性,剩下的大部分留在纺丝液中可显著降低纺丝液的黏度,从而使高分子量高固含量纺丝液的纺制成为可能,有望得到高性能的碳纤维原丝.     

Solvent effect on grafting polymerization of NIPAAm onto cotton cellulose via γ-preirradiation method

Grafting polymerization of N-isopropylacrylamide (NIPAAm) onto cotton cellulose preirradiated in air by ⁶⁰Co-γ-rays was accomplished in mixed solvents of water and alcohols or acetone. The grafting yields changed with different ratios of water and organic solvents. In the system of solvents comprised of water and methanol, the Trommsdorff effect appeared in the curve of the grafting yields vs. the concentrations of the monomer. In the same system, the dependence of the grafting yield of NIPAAm on the grafting temperature was different from that of acrylamide (AAm). The relation between the grafting yields of the samples and their crystallinities measured by X-ray diffraction could be regarded as a proof of the ‘third-phase’ conception.     

Crystalline and spectroscopic characterization of poly(2-aminoethyl methacrylate hydrochloride) chains grafted onto poly[(R)-3-hydroxybutyric acid]

The present study is aimed to investigate the degree of crystallinity of poly(3-hydroxybutyrate) P(3HB) grafted with poly(2-aminoethyl methacrylate hydrochloride) (PAEMA) chains using WAXS, micro Raman, and FTIR spectroscopy. The samples were obtained by radiation induced graft polymerization of the monomer in the substrate using different solvents for comparison. The results of crystallinity are consistent with those obtained of lower crystallinity in grafting copolymer relative to the substrate P(3HB). The low crystallinity is directly related to the increase of the degree of grafting, meaning that although the P(3HB) amorphous region is grafted, the crystalline zone is also affected in some extent by the grafting process and the environment of the new molecule. Three different methods were surveyed to determine the variation of crystallinity degree with the grafting degree. It is shown that all methods provide linear relationships between these variables, but WAXS method was found more acceptable than the others (FTIR and Raman). A detailed characterization of the vibrational bands characteristic of amorphous and helical crystalline structure of the grafting copolymers are also highlighted.     

均匀设计法优化2-羟基-3-氰甲基-5-甲基苯乙酮的合成

以对甲基酚为起始原料，通过酰基化，Fries重排，氯甲基化和氰化合成了2－羟基－3－氰甲基－5－甲基苯乙酮，采用均匀设计对合成条件进行研究，获得了满意的收率（88．5％）。     

湿化学法合成LiNi_(1/3)Mn_(1/3)Co_(1/3)O_2及其表征(英文)

利用琥珀酸为鳌合剂的湿化学法成功合成了一系列锂离子电池正极材料LiNi1/3Mn1/3Co1/3O2,在合成过程中改变琥珀酸与金属离子摩尔比(R)并研究了这一参数对合成LiNi1/3Mn1/3Co1/3O2材料物理及电化学性质的影响.采用热重、X射线衍射、Rietveld精修、扫描电镜以及超导量子干涉仪对反应机理、材料的结构、形貌以及磁学性质进行了详细表征.得到最佳合成条件为R=1,此时LiNi1/3Mn1/3Co1/3O2的阳离子混排度最低.此外,通过Rietveld精修得到该材料阳离子混排度的结果与通过磁学方法得到的结果定量相符,如对于在R=1条件下合成的样品,Rietveld精修结果显示其阳离子混排度为1.85%,而超导量子干涉仪的测试结果为1.80%.当充放电区间为3.0-4.3V,电流密度为0.2C(1C=160mA·g-1)时,该样品的首次放电容量为161mAh·g-1,库仑效率为93.1%,经过50次循环后,容量保持率可达91.3%.     

Surface modification of polypropylene membranes by γ-ray induced graft copolymerization and their solute permeation characteristics

Porous hydrophobic polypropylene (PP) membranes were subjected to the surface modification by the γ-ray induced graft copolymerization with hydrophilic 2-hydroxyethyl methacrylate (HEMA). The structural changes and surface morphologies of the modified PP membranes were characterized by a Fourier transform infrared spectroscopy (FT-IR), elemental analysis (EA) and field emission scanning electron microscopy (FE-SEM). Peroxides produced from γ-ray irradiation were determined by a 1,1-diphenyl-2-picryl hydrazyl (DPPH) method and the surface hydrophilicities of membranes were measured by a static contact angle measurement. The contact angle of the modified membranes reduced with the degree of grafting (DG) of HEMA onto the membrane surface, and it decreased up to about half of that before modification. The permeation behaviors of all membranes were investigated by a bovine serum albumin (BSA) filtration experiment. As a result, the DG of the modified membrane increased with the reaction time. However, in the case of irradiation dosage it showed the maximum value at 20 kGy. Also, the modified membrane showed a higher solution flux, lower BSA adsorption, and the better flux recovery after cleaning than that of the unmodified membrane. Particularly, 40.6% grafted membrane showed a two-fold increase in a BSA solution flux, 62% reduction in total fouling and three-fold increase in flux recovery after chemical cleaning.