Mn^3＋引发淀粉与丙烯腈接枝共聚物的研究

用过渡金属离子或其配合物引发淀粉的接枝共聚是一个饶有兴趣的课题。Ce~(4 )离子引发淀粉与烯类单体的接枝共聚已有广泛报道。Mehrotra等用稳定的[Mn(H_2P_2O_7)_3]~(3-)引发淀粉与烯类单体的接枝共聚取得了满意的结果。本文报道用电镜,x-射线衍射和热重分析等方法对这一接枝共聚物的形态、结构和热稳定性的研究结果。     

高锰酸钾引发丙烯腈与木质纤维素接枝共聚的研究

研究了用高锰酸钾引发羟丙基马尾松磨石磨木浆粕与丙烯腈的接技共聚反应。得出,木质素对接技反应的影响可能主要来源于它的酚型结构单元。用羟丙基醚化木质素的酚羟基后接枝反应可顺利进行。X-射线衍射结果显示,接技共聚反应有可能渗透到纤维素晶区内部,随接技量的提高,反应具有一定的消晶作用。     

木薯淀粉与丙烯酸接枝共聚制备淀粉增稠剂

用过硫酸盐 (过硫酸纳、钾或胺盐 )氧化法使木薯淀粉与丙烯酸接枝共聚。探索到最佳反应温度 55℃ ,反应时间 3h ,单体用量 3.1 2 5mol/L ,引发剂浓度 3.5mmol/L ,接枝百分率可达 70 %以上。产品用作淀粉糊的增稠起到明显的效果     

吸水性淀粉－丙烯腈接枝共聚物的一步合成

以硝酸铈铵为引发剂，在几种水－有机溶剂体系中一步合成了吸水性淀粉－丙烯腈接枝共聚物。其中所含的ＰＡＮ均聚物比水作溶剂时的多。在水－正丁醇溶液（Ｖ／Ｖ＝１∶３）中，ＰＡＮ的接枝效率为８３％，淀粉的接枝效率为７２％，产品的吸水倍数为８２０ｇ／ｇ。     

红外光谱法测定干酪素与丙烯腈接枝共聚物的组成

以干酪素vc-o的特征吸收峰(1244cm^-1)和丙烯腈vcmN的特征吸收峰(2244cm^-1)为测定波长,利用二者的吸光度比值与干酪素和丙烯腈接枝共聚物中丙烯腈的百分含量呈线性的关系,建立了利用红外光谱测定干酪素与丙烯腈接枝共聚物组成的方法,线性范围为22％～54％,相关系数r=0．9911,相对标准偏差(RSD)为1．50％。该法简便、快速,有良好的稳定性。     

丙烯腈在聚丙烯上接枝共聚

丙烯腈在聚丙烯上非均相接枝共聚，得杨梅形氰基树脂。研究了接枝共聚条件对单体转化率和接枝率的影响。表观聚合速度可表示为，碰撞频率因子和聚合活化能分别是1．36×1011s-1和99．2kJ．mol-1。从光学显微镜观察到改性树脂在水中接枝连束的分布状态。丙烯腈和二乙烯基苯在聚丙烯上接校共聚，再经二甲苯率取，得笼形氰基树脂。二乙烯基苯在单体中的相对含量对树脂的溶胀性能和笼孔尺寸有很大的影响，制取功能材料时应予适当调节。扫描电镜照片展示了笼形树脂的笼腔和网络结构形态。     

海藻酸钙凝胶小球与丙烯腈的接枝共聚改性

海藻酸钙水凝胶由天然多糖海藻酸钠与二价钙离子交联形成,具有良好的生物相容,性在药物控制释放等领域得到了广泛的应用。但海藻酸钙水凝胶在大气和电解质溶液中的稳定性较差,常采用与壳聚糖等聚电解质形成复合物的方法加以改善。我们曾利用化学法将醋酸乙烯酯接枝到海藻酸钙     

腐植酸与丙烯腈接枝共聚的研究

研究了低pH水溶液中丙烯腈与煤腐植酸的接枝共聚反应。以K_2S_2O_8-Fe(Ⅱ)和K_2S_2O_8-AH_2(抗坏血酸)引发体系效果最佳;各种来源的腐植酸的接枝度差别不大,均大于75％,部分接枝物在强碱下降解。     

[Mn(H_2P_2O_7)_3]~(3-)引发淀粉与丙烯腈接枝聚合反应的动力学研究

以[Mn(H_2P_2O_7)_3]~(3-)为引发剂,研究了丙烯腈与玉米淀粉的接枝共聚反应。由实验结果求出了反应速率与引发剂浓度、单体浓度、淀粉浓度和反应温度的关系,推导并验证了接枝反应动力学模型,探讨了反应机理,求得了接枝反应活化能。     

GRAFT COPOLYMERIZATION OF VINYL MONOMERS ONTO STARCH INITIATED BY TRANSITION METAL-THIOUREA REDOX SYSTEMS

In this paper, the capabilities of grafting acrylonitrile (AN) onto starch initiatedby Fe(III)-TU, V(V)-TU, Cr(VI)-TU, Mn(VII)-TU redox systems were compared in thepresence of sulfuric acid of different concentrations. It was shown that the grafting capabili-ty of Mn(VII)-TU is the highest in these initiating systems. Using Mn (VII-TU as initia-tor, the effects of various acids (HClO_4, H_2SO_4, HNO_3, HCl) on the graft copolymerizationof acrylonitrile onto starch were discussed, and the capabilities of graft copolymerizationof methyl methacrylate (MMA), acrylamide (AM), acrylic acid (AA) onto starch wereinvestigated. The experimental results show that the order of the influences of differentacids is HClO_4>H_2SO_4>HNO_3>HCl, and the order of grafting capabilities of differentmonomers grafted onto starch is MMA>AN>AM>AA. The structure and morphology ofgraft copolymers were studied with infrared spectroscopy and scanning electron microscopy.The size, shape and roughness of surface of the grafted starch granules are changed aftergrafting.     

铬酸引发丙烯酸正丁酯与淀粉接枝共聚反应

作为淀粉改性方法之一 ,不饱和酸及其酯与淀粉接枝共聚反应是一个较新的研究领域 ,其中以 Ce4 +离子作为引发剂的较多[1,2 ] ,也有用Mn3+-H2 SO4 体系 [3]和 Mn[( H2 P2 O7) 3]3-引发体系的[4 ] 。铬酸是一种具有强氧化性的强酸 ,虽然它单独存在时并不引发乙烯类单体的聚合 ,有报道[5] 铬酸可以引发丙烯腈与苎麻纤维素接枝共聚 ,淀粉和纤维素同属于碳水化合物。本文对铬酸引发丙烯酸正丁酯与淀粉接枝共聚反应进行了研究 ,考察了反应条件对接枝反应的影响。1　实验部分1 .1　原料可溶性淀粉 (北京奥特生物技术责任有限公司 ) ,丙烯酸正丁…     

GRAFT COPOLYMERIZATION OF METHYL ACRYLATE ONTO CHITOSAN INITIATED BY POTASSIUM DIPERIODATONICKELATE (IV)

ABSTRACT

A novel redox system, potassium diperiodatonickelate [Ni (IV)]‐chitosan, was employed to initiate the graft copolymerization of methyl acrylate (MA) onto chitosan in alkali aqueous solution. The effects of reaction variables such as monomer concentration, initiator concentration, reaction time, pH and temperature were determined. By means of a series of copolymerization, the grafting conditions were optimized. The maximum grafting percentage obtained was 404.1% when 0.3 g chitosan was copolymerized with 1.8 mL monomer at 35°C for 5 hours with [Ni (IV)]=9.4×10^?4 M and the total volume was 20 mL. Ni (IV)-chitosan system is found to be an efficient redox initiator for this graft copolymerization. A single electron transfer mechanism is proposed to explain the formation of radicals and the initiation. The grafted copolymers were characterized by IR and X-ray diffraction diagrams. The thermal stability of chitosan and chitosan-g-PMA was studied by thermogravimetric analysis (TGA).     

原位制备淀粉接枝聚乳酸

研究了淀粉与乳酸的原位接枝反应.结果表明,利用乳酸中所含的水先将淀粉糊化,然后在95℃下减压反应,可直接得到淀粉-聚乳酸接枝共聚物.研究发现,上述反应体系中可原位生成丙交酯.该丙交酯的开环聚合是淀粉发生接枝反应的主要原因.利用定量核磁共振等方法对接枝产物的微结构进行了详细的解析.     

铈盐作用下甲基丙烯酸甲酯在壳聚糖模型化合物上接枝聚合机理研究

铈盐作用下甲基丙烯酸甲酯在壳聚糖模型化合物上接枝聚合机理研究张国栋冯新德（北京大学高分子科学与工程系北京１００８７１关键词壳聚糖，接枝共聚合，硝酸铈胺，接枝机理甲壳素是自然界中产量仅次于纤维素的一种多糖，而壳聚糖是其２位碳上乙酰氨基的乙酰基部分...     

GRAFT COPOLYMERIZATION OF ACRYLAMIDE ONTO POLY(N-PARA-TOLYLACRYLAMIDE) FILMS INITIATED BY CERIC ION

Functional monomers having phenylcarbamoyl and p-tolylcarbamoyl were synthesized. Binary initiation system consisted of Ce~(4+) and these functional monomers could initiate acrylamide polymerization. It was found that acrylamide could graft copolymerize onto macromolecules having these functional monomers units. The formation of graft copolymer has been verified by its percentage of water absorption, contact angle with water, XPS and SEM photographs. The reaction mechanism was proposed and the main reactive site of graft ocpolymerization initiated by Ce~(4+) would take place predominantly at the functional pendant group.