双亲性无规共聚物自组装胶束结构及其乳化性能

以不同交联度、溶胀程度的双亲无规共聚物聚[(苯乙烯-alt-马来酸酐)-co-(7-对乙烯基苄氧基-4-甲基香豆素-alt-马来酸酐)](PSMVM)胶束作为聚合物胶束乳化剂稳定甲苯/水体系, 重点研究光交联度对胶束结构及其乳化性能的影响. 结果表明, 胶束交联度、溶胀度和荷电性对胶束结构及乳化性能有较大影响.     

具有分子间氢键的刚性长侧链液晶高分子的合成

主链液晶高分子材料力学性能的各向异性,限制了其作为结构材料的应用和发展^[1].含马来酸酐共聚物(如与乙烯、异丁烯、十八碳烯、苯乙烯和氯乙烯等交替、无规结构共聚物,其中马来酸酐质量分数为5%～50%)是一种耐热性和加工性优良的树脂.     

苯乙烯/马来酸酐共聚物修饰碳纳米管的研究

利用羟基碳纳米管上的羟基与马来酸酐之间的简单反应, 在碳纳米管上引入双键, 进一步引发苯乙烯聚合, 在碳纳米管表面接枝苯乙烯马来酸酐共聚物, 同时采用羟基碳纳米管与苯乙烯马来酸酐共聚物直接反应也在碳纳米管的表面引入了苯乙烯马来酸酐共聚物. 经IR, Raman, TG和TEM测定, 证明了碳纳米管与苯乙烯马来酸酐共聚物之间为化学键连接关系.     

P(MMA-co-MAh)-g-mPEG的合成及环境敏感性

采用偶合接枝法在甲基丙烯酸甲酯(MMA)和马来酸酐(MAh)无规共聚物上接枝不同含量的聚乙二醇单甲醚(mPEG), 合成具有pH敏感和温度敏感的两亲接枝共聚物P(MMA-co-MAh)-g-mPEG, 并对其进行了红外光谱和核磁共振波谱表征. 通过紫外-可见分光光度计测量了接枝共聚物水溶液的透光率, 结果表明, 接枝聚合物的水溶液呈现低临界溶解温度(LCST), 其LCST值对环境pH值和无机盐等因素敏感, 并可通过控制亲水侧链含量来调节.     

马来酸酐—苯乙烯本体自由基聚合反应

在杷来酸酐－苯乙烯本体聚合反应过程中，于７０℃和低引发剂浓度（０．５９－１．８×１０＾－３ｍｏｌ／Ｌ条件下，共聚物组成与单体的配比无关，生成无规共聚物；在高引发剂浓度（２×１０＾－２ｍｏｌ／Ｌ），随马来酸酐单体含量的增加，趋向生成１：１交替共聚物，温度的提高可以使生砀共聚物结构向１：１组成移动，当温度超过１４０℃时将生成无规共聚物，在本体聚合反应体系中，存在共聚反应和苯乙烯的均聚反应，而且随着的提     

聚(苯乙烯-alt-马来酸酐)-b-聚苯乙烯亲水/亲油嵌段共聚物在溶液中的聚集行为研究

采用RAFT方法合成了由马来酸酐／苯乙烯和苯乙烯组成的交替序列两嵌段共聚物P(MAn-alt-St)-b-PSt。将其中的马来酸酐用PEO进行水解,得到了支化的亲水亲油两嵌段共聚物。通过H—NMR和IR对共聚物的结构组成进行表征。以二甲基氨基黄酮化舍物为荧光探针,测定了形成共聚物胶束的临界浓度(CMC)。用TEM和SEM现察不同酸碱条件下所得纳米材料形貌,并对其形成机制进行了讨论。     

原位聚合法制备厌氧胶固化引发剂微胶囊

采用原位聚合法制备了以脲醛树脂为壁材、过氧化苯甲酰为芯材的厌氧胶固化引发剂微胶囊。研究了乳化剂聚丙烯酸钠、十二烷基苯磺酸钠、阿拉伯树胶、苯乙烯-马来酸酐共聚物的单独使用及阿拉伯树胶与苯乙烯-马来酸酐共聚物的复配组合和其它工艺条件对微胶囊制备的影响;运用FT-IR、TG和SEM等测试技术对微胶囊进行了表征。结果表明,以苯乙烯-马来酸酐共聚物和阿拉伯树胶作为复合乳化剂,反应终点pH值为1.5左右,反应温度70℃,反应时间4 h,搅拌速率1 000 r/m in,可制得分散适中、形貌较好、粒径约为100μm的微胶囊。以实验制备的微胶囊配制成可预涂厌氧胶胶液,性能可以达到国外公司同类产品的技术指标。     

低相对分子质量苯乙烯-马来酸酐交替共聚物的合成

将引发剂偶氮二异丁腈(AIBN)、共聚单体苯乙烯(St)和马来酸酐(MA)溶解于甲苯中,采用沉淀聚合法合成苯乙烯-马来酸酐共聚物(SMA).分别研究了反应温度、引发剂用量、反应时间、单体配比和单体浓度对聚合物得率和酸酐含量的影响.采用正交实验确定最优反应条件为:单体浓度20%,单体物质的量比为1∶1,引发剂用量为0.60%,反应温度为86℃,反应时间2h,产物得率为86.86%,酸酐含量为50.28%.并利用傅里叶变换红外光谱(FTIR)、核磁共振碳谱(~(13)C NMR)、凝胶渗透色谱(GPC)和热分析法分别研究聚合物的分子结构、相对分子质量及相对分子质量分布和热稳定性.结果表明产物是苯乙烯-马来酸酐交替共聚物,相对分子质量分布较窄,具有良好的热稳定性.     

氢化苯乙烯-丁二烯-苯乙烯嵌段共聚物及其马来酸酐接枝共聚物增韧聚对苯二甲酸乙醇酯共混材料的辐射效应

采用双螺杆熔融共混的方法制备了含三羟甲基丙烷三丙烯酸酯(TMPTA)的聚对苯二甲酸乙二酯/氢化苯乙烯-丁二烯-苯乙烯嵌段共聚物（PET/SEBS）和聚对苯二甲酸乙二酯/马来酸酐接枝氢化苯乙烯-丁二烯-苯乙烯嵌段共聚物（PET/SEBS-g-MAH）共混材料,并在Co-60源中对其进行辐照。 通过对共混材料的力学性能、相态结构测和凝胶含量分析,对比研究了辐射对以上2种共混材料结构及性能的影响。 扫描电子显镜观察和凝胶含量分析结果表明,在适量TMPTA存在时,辐射有效地改善了PET/SEBS体系的相容性。 冲击强度的变化证实了这种增容效应,当SEBS的质量分数为20%、TMPTA质量分数为1%,经50 kGy辐照后,冲击强度达到17.3 kJ/m2。 当在SEBS分子链上引入马来酸酐官能团,辐照后,体系的相态结构变化并不明显,冲击强度最大值仅为11.5 kJ/m2,明显低于不含马来酸酐官能团的体系。     

磺化苯乙烯-马来酸酐共聚物

磺化苯乙烯-马来酸酐共聚物是由苯乙烯-马来酸酐共聚物直接磺化并中和成钠盐制备。由于它分子中含有很多磺酸及羧酸负离子,因此,是一很好的阴离子聚电解质,被广泛用于泥浆稀释剂、水泥添加剂和皮革鞣剂等。     

Synthesis of uniform anatase TiO2 nanoparticles by gel-sol method. 4. Shape control

Uniform anatase-type TiO(2) nanoparticles of different shapes have been formed by phase transformation of a Ti(OH)(4) gel matrix in the presence of shape controllers. For example, triethanolamine (TEOA) was found to change the morphology of TiO(2) particles from cuboidal to ellipsoidal at pH above 11. The shape control can be explained in terms of the specific adsorption of TEOA onto the crystal planes parallel to the c-axis of the tetragonal system in the alkaline range, as supported by the observation of preferential adsorption of TEOA onto the crystal planes parallel to the c-axis at pH 11.5 and by the pH dependence of the adsorption onto ellipsoidal particles. Diethylenetriamine (DETA) also modified the particle shape to ellipsoidal above pH 9.5 and the aspect ratio was much higher than with TEOA. The mechanism of the shape control could be explained in the same way as with TEOA, since analogous specific adsorption was observed with DETA as well. Similar shape control to yield ellipsoidal particles of a high aspect ratio was also achieved with other primary amines, such as ethylenediamine (ED), trimethylenediamine (TMD), and triethylenetetramine (TETA). However, secondary amines, such as diethylamine, and tertiary amines, such as trimethylamine and triethylamine, acted as a complexing agent of Ti(IV) ions to promote the growth of ellipsoidal particles of a low aspect ratio, rather than a shape controller to produce ellipsoids of a high aspect ratio. Sodium oleate and sodium stearate were found to modify the particle shape from round-cornered cubes to sharp-edged cubes. The mechanism was explained in terms of the reduction of the specific surface energies of the [001] and [100] planes of the tetragonal crystal system by the preferential adsorption of oleate or stearate ion onto these planes, based on the adsorption experiment using ellipsoidal and cubic particles.     

Morphological evolution of multistage polymer particles in the alkali post-treatment

Multistage carboxyl-containing polymer latex particles were synthesized by multistep emulsion copolymerization using methyl methacrylate (MMA), butyl acrylate (BA), methacrylic acid (MAA), ethylene glycol dimethacrylate (EGDMA) and styrene (St) as raw materials, and the latex particles with diverse morphologies including multihollow, hollow and “bowl-like” were obtained by post-treating the multistage latex particles under alkali condition. The morphological evolution of the particles in the alkali post-treatment process was characterized with electron microscopy, and effects of alkali treatment conditions including treatment temperature, time as well as initial pH on particle morphology were investigated. Results indicated that the alkali treatment temperature and initial pH were the key parameters to control the morphology of the treated particles. When the alkali treatment temperature was below 60 °C or the initial pH was lower than 8.5, the particle morphology was almost unchanged no matter how long the treatment time was prolonged. The multihollow and hollow particles could be formed as alkali treatment temperature exceeded 60 °C in the range of initial pH from 8.8 to 9.5. While the latex particles with “bowl-like” morphology were observed when the multistage latex was alkali treated at 90 °C for 3 h with initial pH 9.8. Furthermore, extending alkali treatment time was beneficial to get the swelling equilibrium of the latex particles.     

Influence of PSSS additive and temperature on morphology and phase structures of calcium oxalate

Calcium oxalate (CaOx) particles with different morphologies and phase structures were prepared by a facile precipitation reaction of sodium oxalate with calcium chloride in the absence and presence of poly(sodium 4-styrene-sulfonate) (PSSS) at different temperatures. The as-prepared products were characterized with scanning electron microscopy and X-ray diffraction. The influence of experimental conditions including pH, temperature, and concentration of PSSS and CaC2O4 on the morphologies and phase structures of the prepared calcium oxalate particles were investigated. It was found that variations in the concentration of PSSS and CaC2O4, temperature, and pH significantly influenced the crystal structure, morphology, and particle size of the samples. Various crystal morphologies of calcium oxalate, such as plate, leaf-shaped, bipyramid, and cylinder could be fabricated, depending on the experimental conditions. Higher PSSS concentration and reaction temperature favored the formation of metastable calcium oxalate dihydrate (COD) crystals and stable calcium oxalate monohydrate (COM), respectively. Especially, cylinder-shaped CaC2O4 particles were obtained at 80 degrees C in the presence of PSSS for the first time. This research may provide new insight into understanding and potentially regulating the formation of kidney stones and the control of morphology and phase structures of calcium oxalate particles.     

A systematic morphosynthesis of barium sulfate in the presence of phosphonate inhibitor

A systematic study of the influence of various experimental parameters on the morphology and size of BaSO4 crystals after crystallization from water in the presence of diethylenetriamine penta (methylphosphonic acid) (DETPMP) was presented. Depending on the experimental conditions, there are various crystal morphologies including flowers, ellipsoids, spheres, or conjoined spheres. The results indicated that the experimental parameters, such as the concentration of the inhibitor, the pH of solution, the aging of the particle growth, and the ratio [Ba2+]/[SO4(2-)], are important for the morphology and size of BaSO4. The morphogenesis of BaSO4 is controlled by the chelation of DETPMP with Ba2+ at the nucleation and the surface adsorption inhibition of crystal growth.     

CuO／ZrO_2超细粒子催化剂的制备和物性结构表征Ⅰ．水凝胶pH值的影响

用乙醇超临界流体干燥法制备了ＣｕＯ／ＺｒＯ２超细粒子催化剂，考察了制备过程中水凝胶ｐＨ值对催化剂物性参数如比表面积、孔结构和晶相等的影响，并与干凝胶进行了对比．结果表明，ｐＨ值在６．５～１０．０范围内对晶相影响不大，但对物性结构的影响较大，比表面积和孔体积很快增大，孔形由椭圆形转变为均一的圆柱形，最可几孔径减小，微孔增多；与干凝胶相比，气凝胶表现出高比表面积和多孔结构的特点．ｐＨ＝１０．０时，气凝胶型催化剂的物性参数最佳     

pH- and Dopant-Dependent CdMoO(4):Mn Nanocrystals: Luminescence and Magnetic Properties

CdMoO(4):Mn nanocrystals with a tetragonal crystal structure were prepared by aqueous coprecipitation method at a low temperature of 2 °C under different pH values. The size of the CdMoO(4):Mn nanocrystals of spherical morphology increases with the Mn dopant concentration from 35 to 55 nm for pH = 4. The morphology could be tuned from nanocrystals to microstructures consisting of smaller nanoparticles by the Mn concentration when the pH value of the precursor was increased to 8. The thermal stability of the luminescence and magnetic properties of the Mn-doped samples also depend on the pH and the doping level. The effects of the pH and dopant on the luminescence and magnetic properties, including magnetic susceptibility and electron paramagnetic resonance, were investigated. This approach contributes to better understanding of aqueous chemistry methods to control the growth of nanocrystals.     

Preparation of BaCrO4 particles in the presence of EDTA from aqueous solutions

BaCrO₄ particles with well-defined morphologies have been synthesized in the presence of EDTA as a crystal growth modifier from aqueous solutions. The influence of pH on the morphology of BaCrO₄ crystals with and without EDTA additive was investigated to better understand the formation mechanism. EDTA has a strong interaction with the crystal faces of BaCrO₄ and influences the final morphology of BaCrO₄ crystals. In the presence of EDTA, BaCrO₄ particles at pH?=?6 always exhibit a spindle-like morphology due to the large inhibition effect of EDTA on the BaCrO₄ crystallization. With decreasing pH, the particle morphology changes into a peanut-type at both pH?=?5 and pH?=?4 due to the relatively low inhibition and the following secondary heterogeneous nucleation and growth. The possible morphological evolution of BaCrO₄ particles is also proposed.     

Preparation of Ultrafine TATB and the Technology for Crystal Morphology Control

The ultrafine 1,3,5‐triamino‐2,4,6‐trinitrobenzene (TATB) has been prepared by using solvent and non‐solvent method, and the influencing factors in close relationship with the grain size and crystal morphology control such as categories and dosage of surfactants, volume ratio of solvent to non‐solvent have also been considered in this paper. It showed that these factors had remarkable effect on the crystal morphology, particle size and agglomeration during the crystallization process. By using 0.095% (mass percentage) ionic surfactant (S) as the additive and using spray‐drops feeding device as the dropping equipment, 1.06 g TATB raw materials have been refined into free‐running ellipsoid and spherical TATB grains with the grain size from 30 to 50 nm. By using 0.014% (mass percentage) non‐ionic surfactant (P) as the additive, spherical TATB grains with the particle diameter of 50 nm and with narrow particle‐size distribution have also been obtained. It was shown by the characterizations that the ultrafine particle of TATB had better heat resisting evenness and its 5 seconds ignition point is advanced by 7.5 K.     

以PS-b-P2VP为模板剂诱导调控聚苯胺形貌、尺寸及电化学性能

采用可逆加成-断裂链转移自由基聚合（RAFT）法合成了具有pH响应性的两亲嵌段共聚物聚苯乙烯-b-聚（2-乙烯基吡啶）（PS₁₀₁-b-P2VP₇₀），并以其胶束为"模板"，通过氧化聚合制备聚苯胺（PANI）.通过调节PS₁₀₁-b-P2VP₇₀胶束溶液的pH值，探究PANI颗粒形貌的可控调节及颗粒尺寸与PANI电化学性能之间的关系.利用凝胶渗透色谱（SEC）和核磁共振氢谱（¹H NMR）确定了PS₁₀₁-b-P2VP₇₀的分子量分布及结构；利用傅里叶变换红外光谱（FTIR）、透射电子显微镜（TEM）、粒度测试、循环伏安（CV）、计时电位（Chronopotentio-metry）及交流阻抗谱（EIS）对PANI结构、形貌和电化学性能进行了表征.结果表明"模板"法合成的PANI形貌尺寸得到了很好的控制，在pH ≤ 4时其尺寸随pH值的增加而减小；当pH=5时，模板剂中P2VP段疏水性的明显增大导致其胶束颗粒聚集为尺寸较大的聚集体，并使其诱导的PANI颗粒平均粒径显著增大；当pH=4时PANI颗粒在溶液中的平均粒径为141 nm，呈"串状"形貌且分散性最好.PANI具有快速充放电能力和良好的赝电容特性，随颗粒尺寸减小样品电化学性能增强.pH=4时样品电化学活性最好，循环伏安曲线面积最大，放电比容量最高，在电流密度为1 A/g时，其放电比容量可达1411.88 F/g，且该样品阻抗值最小.     

Size-dependent surface CO stretching frequency investigations on nanodiamond particles

In this work, the spectroscopic properties of surface functionalized nanodiamond particles are investigated via Fourier transform infrared spectroscopy. The functionalization of the nanodiamond surface was achieved chemically using strong acid treatment method. The size dependent C=O stretching frequency (between 1680 and 1820 cm(-1)) are studied for particle diameter sizes from the 5 to 500 nm range. The surface C=O stretching frequencies at approximately 1820 cm(-1), for large particle size (500 nm), down shifted to 1725 cm(-1) (5 nm) with decreasing particle sizes. We attributed the shift as a result of hydrogen bond formation between the COOH groups in the carboxylated nanodiamond surfaces. Particle size was characterized with dynamic light scattering method and surface morphology of the particles was investigated with scanning electron microscopy. The influence of pH value on C=O stretching frequency is also analyzed. This finding affords useful information for the studying of surface functionalized nanodiamonds with implications for their interaction with biomolecules.