Free‐radical grafting of acrylic acid onto isotactic polypropylene using styrene as a comonomer in supercritical carbon dioxide

Free‐radical grafting of acrylic acid (AAc) onto isotactic polypropylene (iPP) using styrene (St) as a comonomer in supercritical carbon dioxide (SCCO₂) medium was studied. The effects of temperature and pressure of reaction on functionalization degree (grafting degree of AAc) of the products were analyzed. The increase of reaction temperature increases the diffusion of monomers and radicals in the disperse reaction system of SCCO₂. In addition, the increase of temperature accelerates the decomposition rate of 2,2′‐azobisisobutyronitrile (AIBN), thus promoting grafting reaction. It was also observed that functionalization degree of the products decreases with the increase of pressure of SCCO₂ in the range of experiment. The effects of comonomer St on the functionalization degree of the products were investigated. The AAc graft degree of the resulting polymer was drastically higher in the present of St. It reached a maximum when the mass ratio of St and AAc was about 0.7 : 1. Because AAc is not sufficiently reactive toward iPP macroradicals, it would be helpful to use a second monomer that can react with them much faster than AAc. St preferentially reacts with the iPP macroradicals to form more stable styrene macroradicals, which then copolymerize with AAc to form branches. The highest functionalization degree was obtained when the AIBN was 0.75 wt %. When the initiator was used excessively, the functionalization degree decreased because of severe chain degradation of the iPP backbone. The morphologies of pure iPP and grafted iPP are different under the polarizing optical microscope. The diameter of the pure iPP spherulites is 20–38 μ and that of the grafted iPP spherulites is reduced with the increase of the functionalization degree of the products. This is proposed to be because the polar grafts formed during the reaction would have a tendency to associate in the hydrophobic PP environment. This might preserve some of the local crystalline order that existed during the reaction in the swollen iPP phase. It can be proven by a DSC cooling investigation that the crystallization temperature increased as the functionalization degree increased. This is proposed to be because the side‐chain of grafting polymer helps to bring about the heterogeneous nucleation in grafting polymer. Therefore, a large number of nuclei can emerge to a lesser supercooling degree. It can be also proven that the percent crystallization decreased as the functionalization degree increased, probably due to the grafted branches, which disrupted the regularity of the chain structure and increased the spacing between the chains. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2203–2210, 2004     

固载型杂多酸催化剂研究进展

介绍了固载型杂多酸的制备、表征及其表面作用机理。着重综述了近年来活性炭、SiO2、TiO2、MCM 41分子筛、γ Al2O3、TiO2 Al2O3、阳离子交换树脂、惰性膜、USY 1、ZrO2 SO2 4和TiO2 WO3等各种固载型杂多酸催化剂在国内外的研究和应用情况,并展望了未来的研究方向。     

N-氧化烟酸的合成

以烟酸为原料，在冰醋酸溶液中，用双氧水氧化合成N-氧化烟酸。实验发现在合成中加入一种共沸剂，可以降低反应的回流温度，同时，也可将反应生成的水不断带走，使转化率增大，并且具有合成工艺简单，溶剂可以重复使用，无三废等特点。适宜的反应条件为：烟酸：双氧水：冰醋酸的摩尔比为1：1.5:3，共沸剂A或B的用量为30ml，反应时间为5h，收率92.0%。     

草酸二乙酯水解宏观动力学研究

在65～80℃对草酸二乙酯水解生成草酸的反应宏观动力学进行了研究,得到的草酸二乙酯水解反应速率方程可表示为rc=dcc/dt=kc0.5acc1-kc1.5c k=2.117×105exp(-3.479×104/RT) k=5.273×102exp(-1.398×104/RT) 并用实验数据对模型进行了检验.     

陶瓷原料中SiO_2的钼酸银沉淀法测定

通过实验,发现络合滴定用的指示剂——偶氮胂—Ⅲ,可用作本测定中的沉淀滴定指示剂。根据标准 AgNO_3溶液同 MoO_4~(2-)的定量反应,计算出以硅钼黄 Hg[Si(Mo_2O_7)_6]形式存在的MoO_4~(2-)量,再据以算出硅酸盐中 SiO_2的含量。     

Synthesis of fatty hydroxamic acids catalyzed by the lipase ofMucor miehei

Biotechnological synthesis of a new class of amphiphilic molecules—fatty hydroxamic acids—was carried out using the lipase ofMucor miehei by reacting hydroxyl amine with the fatty acids in their free or methyl ester form. Concurrently with enzymatic synthesis, chemical synthesis of hydroxamic fatty acids has also been developed by adapting methods that already existed for water-soluble acids. Different parameters were studied to determine the optimum operating conditions: temperature, molar ratio of reagents, quantity of biocatalyst and length of reaction. A general method, whatever the type of fatty acids used, is described.     

马来海松酸及其衍生物的研究与应用进展

马来海松酸及其衍生物在造纸、微生物、油墨、涂料、橡胶、杀菌、医药等领域具有重要的用途。本文对马来海松酸的制备、马来海松酸衍生物的研究与应用进展进行了综述,并对马来海松酸及其衍生物的研究及应用前景进行了展望。     

2-氨基-5-甲基苯甲酸合成工艺的改进

对甲苯胺与水合氯醛、盐酸羟胺反应制得异亚硝基乙酰对甲苯胺,于浓硫酸中脱水成环得到5-甲基靛红,然后在碱性条件下以双氧水为氧化介质合成2-氨基-5-甲基苯甲酸。通过正交实验得到了一、二步反应的较佳工艺条件,三步反应总收率以对甲苯胺计算达61.7%。通过FTIR和1HNMR对最终产品进行了表征。     

耐热丙烯酸酯胶粘剂的研制

选用甲基丙烯酸甲酯预聚物作为主体树脂,通过交联剂种类及含量对胶粘剂拉伸剪切强度和应力-溶剂银纹性能影响的研究,研制出一种耐热性能满足使用要求的丙烯酸酯胶粘剂。试验结果表明,适量的交联剂有利于提高胶粘剂的耐温性能,但交联剂加入量过大对胶粘剂起到增塑作用,反而不利于胶粘剂高温性能的改善。高分子材料由于吸收和扩散的速度较慢,不易使有机玻璃产生银纹,提高胶粘剂中高分子材料的含量,有利于胶粘剂应力-溶剂银纹性能的提高。     

辐照法制全硫化聚丙烯/丙烯酸酯热塑性弹性体

用辐照法制备了全硫化聚丙烯，丙烯酸酯热塑性弹性体．对其物理机械性能、耐热油性进行了测试。结果表明，所制备的热塑性弹性体的性能优于动态硫化法。橡胶质量分数为30％、40％时，拉伸强度分别达到10．9MPa、13．6MPa，断裂伸长率分别为132％、157％；在10HD℃的油中浸泡70h。体积变化率只有28％。采用透射电子显微镜和扫描电子显微镜研究了所制备弹性体的微观形态，弹性体中橡胶粒子小、分散均匀；辐照后橡胶粒子与聚丙烯界面之间的作用力得到加强。