对羟基苯甲酸对HDPE结晶行为及力学性能的影响

采用DSC研究了对羟基苯甲酸(HBA)对高密度聚乙烯(HDPE)非等温结晶行为的影响。分析了HBA的引入对HDPE的结晶行为、晶片厚度分布、结晶度以及力学性能的影响。结果表明，当HBA用量为HDPE的0．5％-1．0％时可以促进HDPE的结晶，从而加快HDPE的结晶速度，提高HDPE的结晶度，降低片晶的平均厚度及其分布，并提高其力学性能。     

2-(4-苯甲酰基-3-羟基苯氧基)丙烯酸乙酯的合成研究

以2，4-二羟基二苯甲酮为原料，经醚化、酯化反应合成有机中间体2-（4-苯甲酰基-3-羟基苯氧基）丙烯酸乙酯；并对其反应的工艺条件进行研究。研究结果表明：反应温度、催化剂的用量和聚合物抑制剂对收率有明显的影响。由此得出反应的适宜条件是：反应温度为150℃；催化剂用量为1．2g；使用聚合物抑制剂收率可达80．5％。     

一种双端丙烯酸酯类液晶单体的合成

以对羟基苯甲酸、脱氧熊果苷、丙烯酰氯和甲基丙烯酰氯为原料,通过醚化、酯化、加氢、酯化、脱保护和酯化反应制备了双端丙烯酸酯类液晶单体4-甲基丙烯酰氧基苯甲酸-4'-丙烯酰氧基苯酚酯,其液相含量> 99%,总收率为38%。目标化合物经气相-质谱和红外光谱进行了结构鉴定。     

连续玻纤增强HDPE复合材料的结晶动力学

采用差示扫描量热(DSC)法分析了不同降温速率下高密度聚乙烯(HDPE)和连续玻纤(GF)增强HDPE复合材料的非等温结晶和熔融行为。使用莫志深法对HDPE和HDPE/GF复合材料的非等温结晶动力学进行研究,得出莫氏方程可以描述其非等温结晶动力学过程。并且采用偏光显微镜(POM)观察结晶形态。结果显示:降温速率越大,聚合物结晶峰越宽、聚合物开始结晶时的温度越低、结晶峰温度越低。GF起到异相成核的作用,使得HDPE/GF复合材料的成核速率高于纯HDPE,但由于纤维对晶体生长具有一定的阻碍作用,使其结晶焓较低。通过熔融曲线分析发现,降温速率和GF的加入对HDPE及HDPE/GF复合材料熔融温度和熔融峰温度的影响并不显著。采用莫志深法的研究结果与由动力学参数得出的结论相一致,HDPE/GF复合材料比HDPE更易结晶。POM等温结晶观察结果表明,HDPE/GF复合材料比HDPE的结晶速率更快,这与DSC和莫志深方程结果一致。     

4,4’-双(4-羟基苯甲氧基)-3,3’,5,5’-四甲基联苯二缩水甘油醚的合成与表征

以对羟基苯甲酸、3-溴丙烯、3,3′,5,5′-四甲基联苯二酚等为原料,通过间氯代过氧化苯甲酸氧化法合成4,4′-双(4-羟基苯甲氧基)3,3′,5,5′-四甲基联苯二缩水甘油醚,化合物结构用FT-IR和~1HNMR进行了表征。并对氢氧化钠用量,缚酸剂,氧化反应温度和时间的选择进行了讨论。     

β晶聚丙烯非等温结晶动力学的研究

利用差示扫描量热法（DSC）研究了聚丙烯在加入稀土类β晶成核剂前后形成的α晶聚丙烯和β晶聚丙烯的非等温结晶行为，发现该成核剂能诱导生成高含量β晶型，当其含量为0．1％（质量分数，下同）时，β晶型含量大于90％。采用Jeziorny法和莫志深法对DSC数据进行处理后发现，该成核剂的加入虽然降低了结晶速率，但使结晶温度得到大幅度提高，是一种有效的成核剂。     

α-成核剂对聚丙烯结晶性能和形态的影响

用差示扫描量热仪（DSC）、广角X射线衍射（WAXD）研究了不同含量的α成核剂对聚丙烯的结晶行为和结晶形态的影响，用偏光显微镜观察了结晶尺寸大小的变化，测试了聚丙烯的力学性能，同时对聚丙烯的透光性也进行了表征。结果表明，添加少量α-成核剂提高了聚丙烯的结晶温度和结晶度，且随α-成核剂的添加，聚丙烯的球晶尺寸明显缩小，聚丙烯的拉伸强度也相应增强。当α-成核剂的质量分数为0．3％时，拉伸强度最大，薄片的透光性显著改善。     

聚丙烯／间同1，2-聚丁二烯共混物的等温结晶动力学

利用Avrami方程研究了聚丙烯（PP）及PP／间同1，2-聚T2烯（s—PB）共混物的等温结晶动力学。DSC研究表明：在相同的结晶温度下，如128℃时共混物的结晶速率为0．45min^-1，比纯PP的0．17min^-1大，s-PB起到了成核剂的作用，使共混物的结晶速率加快；共混物的Avrami指数n为2．71～323，共混物的结晶主要是以三维方式增长、异相成核。共混物的Arrhenius结晶活化能为309．35kJ·mol^-1比纯PP的338．11kJ·mol^-1低，结晶活化能的降低也证明了s-PB在共混物的结晶过程中起到了成核剂的作用并使结晶速率加快。     

2-苯基-1,3-二氧杂环-4-戊烯-乙酸甲酯的合成

以苯甲酸、3-溴丙烯和乙酸为原料,三氟化硼乙醚为催化剂合成2-苯基-1,3-二氧杂环-4-戊烯-乙酸甲酯,包括烯丙基苯甲酸酯的制备和烯丙基苯甲酸酯的环化。考察了烯丙基苯甲酸酯与乙酸的摩尔比、反应时间、温度、催化剂用量对反应的影响。结果表明,较佳的反应条件为:取0.05 mol烯丙基苯甲酸酯,n(烯丙基苯甲酸酯)∶n(乙酸)=1.0∶1.2(摩尔比),催化剂用量为5.0%,在室温(25℃)下反应10 h,所得产品的产率在87%以上。     

2-苯基-1,3-二氧杂环-4-戊烯-乙酸甲酯的合成

以苯甲酸、3-溴丙烯和乙酸为原料,三氟化硼乙醚为催化剂合成2-苯基-1,3-二氧杂环-4-戊烯-乙酸甲酯,包括烯丙基苯甲酸酯的制备和烯丙基苯甲酸酯的环化。考察了烯丙基苯甲酸酯与乙酸的摩尔比、反应时间、温度、催化剂用量对反应的影响。结果表明,较佳的反应条件为:取0.05 mol烯丙基苯甲酸酯,n(烯丙基苯甲酸酯)∶n(乙酸)=1.0∶1.2(摩尔比),催化剂用量为5.0%,在室温(25℃)下反应10 h,所得产品的产率在87%以上。     

DPL—Ⅱ结晶速度仪在高聚物中的应用

介绍了采用基于解偏振光强度方法，热平衡时间很短的ＤＰＬ－Ⅱ结晶速度仪，分别测定了ＰＥＴ、ＰＰ、ＰＥ等在不同温度下等温结晶过程及等速升温条件下的晶体熔化过程，并解析出诱导期，结晶速率，结晶过程机理，Ａｖｒａｍｉ指数，ｎ、ｋ及熔点。     

Recent advances in the monitoring,modelling and control of crystallization systems

Crystallization is one of the most important unit operations used for the separation and purification of crystalline solid products. Appropriate design and control of the crystallization process is paramount to produce crystalline products with tailor-made-properties. This paper provides an overview of selected recent developments in the modelling, monitoring and control of crystallization processes. We consider the topics discussed in this review to be enabling technologies for the development of the next generation of crystallization processes with significantly improved predictability, robustness and controllability.     

Crystallization of alkaline protease as a means of purification process

A purification protocol of alkaline protease purification using crystallization was developed by investigating the effects of pH, temperature, initial enzyme concentration, salt (as crystal inducer) concentration, and the presence of impurity proteins. A commercial alkaline protease solution was used as a starting material and NaCl was used as a crystal inducing salt. The crude enzyme solution was first diafiltered against deionized water and then concentrated by ultrafiltration. To the enzyme concentrate appropriate amount of NaCl was added to induce the crystallization which was lasted for 24 hours, and the enzyme crystals formed were filtered and washed with deionized water before being resolubilized. Crystal habit was typical needle shape, and the reaction order of its formation was estimated to be 1.53. The crystallization was strongly influenced by initial enzyme concentration. Solubility of alkaline protease at 25°C was 24.8 mg/ml, which was about one half of that of 4°C. Enzyme recovery yield of the purification process including the crystallization step ranged 50 to 60 %. The crystallization step was shown to successfully exclude impurity proteins from their habits as evidenced by gel permeation chromatography. The optimum condition for the crystallization was: pH 9.0, 25°C temperature, ca. 53 mg/ml or higher enzyme concentration, and minimum 5 % (w/w) NaCl concentration. In summary, an enzyme purification protocol based on crystallization was established, which can be applied to obtain a higher-purity alkaline protease solution on a large scale.     

聚丙烯/蒙脱土纳米复合材料的结晶性能研究

采用差示扫描量热法研究蒙脱土(MMT)对聚丙烯(PP)等温结晶性能的影响。结果表明：加入MMT后提高了PP的结晶速率，使结晶度增大，但对PP熔点的影响不大；加入相容剂PP-g-MAH后，使有机MMT对PP的成核作用更加明显，从而提高了PP／MMT。纳米复合材料的结晶度；PP／MMT纳米复合材料的n值在3左右，其成核方式是异相成核方式。     

赤泥/聚丙烯复合材料非等温结晶动力学研究

采用DSC研究了聚丙烯(PP)及聚丙烯/赤泥复合材料的非等温结晶动力学,对所得的数据采用了Avrami方程的Jeziorny法及Mo法进行处理.结果表明:赤泥的加入提高了PP的结晶温度和结晶速率,PP的结晶活化能降低,赤泥成核活性高于改性的赤泥.在同样含量下,经钛酸酯偶联剂改性的赤泥使PP结晶温度增加,结晶活化能与赤泥/聚丙烯复合材料相比有小幅的增加.赤泥具有异相成核作用,经表面修饰的赤泥异相成核效果降低.     

Modeling Growth Rate Dispersion in Industrial Crystallizers

The phenomenon of healing appears to be a plausible explanation for the growth rate dispersion observed in many industrial crystallizers. In this paper a growth model is postulated, which describes the healing of plastically deformed attrition fragments. The rate of healing is assumed to be inversely proportional to the initial strain and to the rate of change of either the length, the area, or the volume of the crystal. The validity of the proposed model is verified by the simulation of growth of the smallest crystals (L₀) in time in a growth experiment for specific combinations of the model parameters. In addition, the applicability of the proposed model is evaluated through simulations of steady state experimental data obtained in a 75‐liter Draft Tube (DT) crystallizer. It is concluded that the proposed model is able to fit reasonably well the experimental crystal size distribution. The model predicts the existence of a ‘dead time’ during which attrition fragments with large initial strain do not grow and which may last several residence times.     

苯基膦酸盐类制备及其对聚乳酸结晶行为的影响

通过差示扫描量热仪研究成核剂对聚乳酸结晶行为的影响,成核剂主要选取苯基膦酸盐、苯基膦酸盐复配物和多酰胺类化合物,通过研究发现苯基膦酸锌及其复配物对聚乳酸结晶有较明显的促进作用,苯基膦酸锌最佳添加量为0.8%,苯基膦酸锌复配物最佳添加量为1%。