阳离子共聚物的反相悬浮聚合

采用反相悬浮聚合方法合成颗粒状的阳离子型高分子絮凝剂。选用丙烯酰胺(Am)和氯化[N,N,N-三甲基乙醇丙烯酸酯]盐(AQ)两种单体,研究反应体系的特征及影响分子量的基本因素,诸如温度、单体浓度、引发剂浓度、分散剂浓度、水相和油相的体积比(Vw/Vo)对分子量的影响。为了选择出最佳原料比,本文对两种单体的原料比进行了研究。实验中还发现亚硫酸钠是一种优良的缩短反应诱导期、加速反应进程的试剂。     

Synthesis and biodegradation of poly(γ-butyrolactone-co-l-lactide)

Biodegradable polyesters were synthesized by ring-opening copolymerization of -butyrolactone (BL) and its derivatives withl-lactide (LLA). Although tetraphenyl tin was the main catalyst used, other organometallic catalysts were used as well.¹H and¹³C NMR spectra showed that poly(BL-co-LLA)s were statistical and that their number-average molecular weights were as high as 7×10⁴. The maximum BL content obtained from copolymerization BL/LLA was around 17%. TheT _m andT _g values of the copolymers showed a gradual depression with an increase in BL content. NoT _m was obtained for the copolymers containing more than 13 mol% BL. The biodegradability of the copolyesters was evaluated by enzymatic hydrolysis and nonenzymatic hydrolysis tests. The enzymatic hydrolysis was carried out at 37°C for 24 h using lipases fromRhizopus arrhizus andR. delemar. Hydrolyses by both lipases showed that an increase in BL content of the copolymer resulted in enhanced biodegradability. Nonenzymatic accelerated hydrolysis of copolymers at 70°C was found to increase proportionally to their exposure time. The hydrolysis rate of these copolymers was considerably faster than that of PLLA. The higher hydrolyzability was recorded for the BL-rich copolymers. The copolymerization of -methyl--butyrolactone (MBL) or -ethyl--butyrolactone (EBL) with LLA resulted in relatively LA-rich copolymers.     

Dyes adsorption using a synthetic carboxymethyl cellulose-acrylic acid adsorbent

Removal of noxious dyes is gaining public and technological attention. Herein grafting polymerization was employed to produce a novel adsorbent using acrylic acid and carboxymethyl cellulose for dye removal. Scanning electron microscopy and Fourier-transform infrared spectroscopy verified the adsorbent formed under optimized reaction conditions. The removal ratio of adsorbent to Methyl Orange, Disperse Blue 2BLN and malachite green chloride reached to 84.2%, 79.6% and 99.9%, respectively. The greater agreement between the calculated and experimental results suggested that pseudo second-order kinetic model better represents the kinetic adsorption data. Equilibrium adsorptions of dyes were better explained by the Temkin isotherm. The results implied that this new cellulose-based absorbent had the universaiity for removal of dyes through the chemical adsorption mechanism.     

金属氧化物降解六氯苯的活性比较及催化机理研究

以氧化铝(α-Al_2O_3、γ-Al_2O_3)、氧化钙(CaO)、过渡金属氧化物(Mn O_2、α-Fe_2O_3、γ-Fe_2O_3、Ni_2O_3、CuO)为催化剂,考察了催化剂种类、添加比例等因素对六氯苯(Hexachlorobenzene,HCB)降解效果和产物组分的影响.结果表明,催化效果随催化剂添加比例的提高显著增加.在反应温度为350℃,反应时间1 h,金属氧化物添加比例为100∶1的条件下,碱土金属氧化物CaO及过渡金属氧化物中的α-Fe_2O_3和Ni_2O_3降解活性较好,这3种氧化物对HCB的降解率分别达到65.5%、100.0%和100.0%,脱氯率D_1分别为54.4%、81.9%和77.5%.HCB降解有机产物分析结果显示,8种金属氧化物与HCB样品反应产物中均存在低氯代苯,在α-Fe_2O_3和Ni_2O_3的催化作用下有2~4氯代低氯苯检出,说明在降解过程中存在明显的逐级脱氯/加氢反应;与CaO反应后的产物中低氯代苯较少,经拉曼光谱定性分析,有无序碳的检出,说明除了脱氯/加氢还存在脱氯缩合反应.     

Novel Polymeric Materials from Biological Oils

A variety of novel polymeric materials ranging from elastomers to tough, rigid plastics have been prepared by the cationic copolymerization of regular soybean oil, low-saturation soybean oil, or conjugated low-saturation soybean oil with various alkene commonomers. Using appropriate compositions and reaction conditions, 70–100% of the soybean oil is covalently incorporated into the cross-linked polymer networks, contributing significantly to cross-linking during copolymerization. The resulting thermosets exhibit thermophysical and mechanical properties that are competitive with those of their petroleum-based counterparts. In addition, good damping and shape memory properties have been obtained by controlling the degree of cross-linking and the rigidity of the polymer backbone. New materials with similar characteristics have also been produced from other biological oils, including tung, and fish oils using the same technique. The new, more valuable properties of these bioplastics suggest numerous promising applications of these novel polymeric materials.     

Ring-Opening Polymerization of Cyclic Esters onto Liquefied Biomass

Ring-opening polymerization of cyclic esters (-caprolactone, -valerolactone, and l-lactide) onto liquefied biomass (LB) was conducted to obtain the polyester-type polyol and to regulate the characteristics of LB. IR and ¹H-NMR spectra of the obtained polyol showed that the polymerization was successfully conducted in the presence of acid catalyst, which is used in liquefaction. The molecular weight (M_w), hydroxyl value, and viscosity were controllable by changing the reaction conditions. Polyester-type polyurethane foams with a wide range of properties were prepared from the obtained polyol with the appropriate combinations of foaming agents.     

Ethoxylated Soybean Polyols for Polyurethanes

Soybean polyols prepared by ring opening reactions of epoxidized soybean oil with hydrogen active compounds (water, alcohols, organic or inorganic acids, thiols, hydrogen etc.) have a low reactivity in the reaction with isocyanates because the hydroxyl groups are secondary. This paper presents a simple and convenient method to increase the reactivity of soybean polyols with secondary hydroxyl groups by ethoxylation reactions with the preservation of triglyceride ester bonds. The method uses mild reaction conditions: low alkoxylation temperature of 35–45 °C, low pressure of 0.1–0.2 MPa (15–30 p.s.i.) and a superacid as catalyst (HBF₄). The new soybean polyols have a higher reactivity toward isocyanates in polyurethane formation due to the high percentage of primary hydroxyl groups. The primary hydroxyl content was determined by the second order kinetics of polyol reaction with phenyl isocyanate.     

聚合反应时间对聚酰亚胺基碳膜结构和性能的影响研究

目的 系统研究前驱体聚合反应时间对PI膜及其碳化、石墨化后薄膜结构和性能的影响规律。方法 通过调整聚合合成聚酰胺酸(PAA)溶液过程中的反应时间,制备石墨膜前驱体聚酰亚胺(PI)原膜,将不同工艺条件下制得的PI膜进行碳化、石墨化处理,得到高导热率石墨膜。利用扫描电镜、红外光谱、拉曼光谱仪和LFA激光闪射仪对制备的PI膜、碳化膜及石墨膜的微观结构和热导率进行检测。结果 随聚合反应时间的延长,PI膜酰亚胺化程度和石墨膜的石墨化程度及导热性能先增高、后降低。反应时间为3 h时,制得的石墨膜结构致密,石墨片层取向性好,导热性能最好,热导率可达765.2 W/(m.K)。结论 PI膜前驱体聚合反应时间显著影响PI膜酰亚胺化的程度和有序度,进而影响石墨膜的定向性和导热性能。     

聚硅氯化铝混凝剂中Al(Ⅲ)水解聚合历程及铝硅作用特性研究

采用共聚与复合两种制备工艺，制备出了系列具有不同碱化度和不同Ａｌ／Ｓｉ摩尔比的聚硅氯化铝混凝剂，分析研究了ＰＡＳＣ中Ａｌ（Ⅲ）的水解－聚合历程以及聚硅酸与铝水解聚合产物的相互作用，探讨了ＰＡＳＣ溶液的酸解聚。     

包埋类脂的吸附剂制备及吸附POPs性能

用丙酮作溶剂将三油酸甘油酯分散到醋酸纤维(CA)基体中,采用悬浮聚合的方法制备出了一种兼具亲水性,又能高倍富集持久性有机污染物的球形复合吸附剂。通过对分散剂的种类及其用量、悬浮介质的种类及其用量的研究,获得了球形复合吸附剂的最佳合成路线与工艺.球形吸附剂粒径为1～2mm。通过荧光分析和电镜扫描分析,表明三油酸甘油酯已被包埋到醋酸纤维基体中,并得到了均匀分散。采用七氯、狄氏剂、异狄氏剂、灭蚁灵为代表性的持久性有机污染物(POPs)。动力学吸附实验表明,当初始浓度为1μg/L时,在快速吸附阶段,溶液中80%的氯、狄氏剂、异狄氏剂可得到有效去除,但并没有达到吸附平衡。快速吸附完后,还在持续地进行慢速吸附。而对于灭蚁灵,吸附速度远远低于其他几种POPs。实验证明了吸附速度不仅与辛醇/水系数有关,而且还与有机污染物的分子结构有关。