[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。     

过硫酸铵-亚硫酸氢钠引发活化淀粉与丙烯酰胺反相乳液聚合动力学研究

以过硫酸铵-亚硫酸氢钠作为氧化还原引发剂,研究了经球磨活化的淀粉与丙烯酰胺在反相乳液体系中的接枝共聚反应动力学,分别考察了反应温度、引发剂浓度、淀粉浓度、单体浓度、乳化剂用量对接枝速率的影响.结果表明,在实验考察范围内的动力学关系式为:Rp∝[(NH4)2S2O4)]0.571[NaHSO3]0.571[St]0.59...     

焦磷酸络锰三价离子引发淀粉-丙烯酰胺的接枝共聚合

将带有极性基团的乙烯类单体通过化学接枝到淀粉或纤维素之类的天然多糖上,可作为絮凝剂、脱除剂和粘接剂^[1～3],近来已发展为高吸水性材料和石油分离剂^[4]。用Ce⁴⁺引发乙烯类单体接枝到淀粉和纤维素类已有报道^[5]。Rayonier用Mn³⁺的焦磷酸盐络合物引发接枝乙烯类单体至纤维素及其衍生物上^[6];Cenita等用Mn³⁺引发MMA、AN接枝淀粉^[7]。本文以焦磷酸络锰离子(Mn³⁺)作引发剂、丙烯酰胺(AM)为单体、淀粉为接枝基体进行接枝共聚,这一工作目前在国内外尚未见报道。     

丙烯酸与淀粉微波固相接枝共聚反应研究

自由基共聚是淀粉接枝共聚的主要形式,常用的方法有化学引发和Co60辐射引发等。目前这些方法多数都必须在通氮除氧的条件下进行,而且多数体系因含水或溶剂需干燥、洗涤等后处理,使成本增加[1]。固相接枝共聚反应目前报导不多[2]。本文研究了微波辐射下丙烯酸与玉米淀粉的固相接枝共聚反应并得到了比较满意的结果。目前这方面的研究国内外尚未见报导。1　实验部分1.1　原料与仪器玉米淀粉,市售,一级,使用前在真空烘箱中干燥至恒重;丙烯酸(AA),化学纯,使用前经减压蒸馏精制;引发剂过硫酸铵(APS)、过氧化二苯甲酰(BPO),均为化学纯,经重结晶…     

三价锰离子引发烯类单体在聚乙烯醇上接枝聚合的研究

<正> 无论是淀粉;纤维素,还是聚乙烯醇(PVA)的接枝反应,Ce(Ⅳ)被认为是一个十分有效的引发剂,已有较详尽的研究。与Ce(Ⅳ)相类似,Mn(Ⅲ)也可以和一些高聚物组成氧化还原引发体系,由此产生自由基,引发烯类单体在高分子主干上进行接枝聚合。Ranby等人,以焦磷酸络合的三价锰离子引发烯类单体在纤维素和淀粉的接枝反应中,获得了高效的接枝产物。有用这种引发体系在淀粉上接枝丙烯腈获得吸水276     

丙烯酸甲酯在炭黑表面的接枝聚合及水解

在炭黑表面接枝聚合物 ,可提高其在相应介质中的分散性[1] .乙酰丙酮合锰可以有效地引发羊毛、纤维素、淀粉等天然高分子的接枝聚合 [2～ 4 ] ,季君晖 [5]将其与羟甲基化炭黑组成引发体系 ,引发了甲基丙烯酸甲酯、丙烯酸丁酯、苯乙烯等单体在炭黑表面进行接枝聚合 .但该体系难以引发水溶性的单体 ,因此得到的接枝炭黑只能用于油性体系 .目前制备亲水性接枝炭黑大多采用 Ce4 +/羟甲基化炭黑引发体系 ,该体系对 O2 特别敏感 ,反应条件相当苛刻 .本文采用乙酰丙酮合锰与羟甲基化炭黑组成引发体系 ,引发丙烯酸甲酯在炭黑表面的接枝聚合 .在 Na…     

木质素磺酸镁接枝丙烯酰胺的影响因素

天然高分子化合物木质素是木材水解工业和造纸工业的副产物。早期人们在研究纤维素同甲基丙烯酸甲酯、丙烯腈的接枝反应中时发现了木质素的接枝反应活性[1],Meisterh和Patil[2]则实现了将—CONH2接枝于木质素的设想,雷中方[3]等研究了木质素同具有较好吸附能力的—CONH2的接枝改性,并讨论了改性产物的水处理性能,他们所用的木质素是采用酸析法从碱法草浆黑液中提取的。本文以酸法制浆的红液 木素磺酸镁为原料,合成了木质素 丙烯酸胺接枝共聚物,并对接枝聚合过程中的引发体系、引发剂浓度、反应温度、木素与单体用量比、固液比等影…     

高锰酸钾—硫脲体系引发丙烯酸接枝共聚尼龙的研究

研究了以高锰酸钾和硫脲组成的氧化还原引发体系,在水介质中,引发丙烯酸接枝共聚尼龙的共聚反应。考察了丙烯酸浓度、引发剂浓度及温度等因素对接枝共聚反应的影响。红外光谱分析和Ｘ射线衍射图谱证明了接枝反应的存在及对聚合物结晶度的影响。     

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。     

纤维素与苯乙烯-丙烯腈共聚用单体的接枝共聚

研究了以高锰酸钾为引发剂,苯乙烯-丙烯腈共聚用单体与纤维素的接枝共聚。讨论了影响接枝共聚反应的一些参数,反应规律和接枝共聚物的结构及性质。实验表明,在以水为介质的反应体系中,接枝共聚反应可顺利进行。     

丙烯酸β-羟丙酯与聚氯乙烯膜的紫外光接枝改性

采用液相接枝方法 ,在紫外线辐照下 ,合成了一系列丙烯酸 β-羟丙酯 (β -HPAT) /聚氯乙烯接枝膜。讨论了引发剂浓度、单体浓度、光照时间、光照强度对接枝率的影响。结果表明 ,引发剂浓度为 6 .5 1× 10 -3 mol/L ,单体浓度 2 .0mol/L ,光照时间为 2 .0h ,且光照强度越强时 ,接枝率最大。接枝膜的结构特征通过FT -IR光谱进行了确证 ,最后 ,对接枝膜进行TGA分析 ,结果表明聚氯乙烯经过表面改性后 ,表面极性增大 ,热稳定性大大提高。     

Grafting Vinyl Monomers onto Silk Fibers. XIII. Graft Copolymerization of Methyl Methacrylate onto Silk Using Fe3+−Cysteine Redox System

The graft copolymerization of methyl methacrylate onto silk fibers initiated by the ferric chloride-eysteine redox system has been investigated in aqueous medium. The rate of grafting was calculated by varying the concentrations of monomer, initiator, acidity of the medium, cysteine, and temperature. The percentage of grafting increases with an increase of Fe³⁺ concentration up to 2,5 × 10^?3 mol/L and thereafter it decreases. The graft yield increases steadily upon increasing the monomer concentration. The graft yield also increases with increasing cysteine concentration up to 0.5 × 10^?3 mol/L and then decreases. The effect of the perchloric acid concentration, temperature, solvents, and certain neutral salts on graft yield has also been investigated and a suitable reaction scheme has been proposed.     

米根霉细胞壁结构性多糖与丙烯酸接枝共聚反应研究

化学改性天然高分子絮凝剂是利用天然高分子物质进行化学改性而成的。与人工合成的有机高分子絮凝剂相比,它具有选择性大、无毒、价廉、易降解等优点,因此将会有广阔的应用前景,近几年,将乙烯基单体接枝到生物高分子上的工作引起了人们的兴趣,这种天然高分子与合成高分子的结合有可能得到理想的性能,获得新的材料：如生物降解塑料、絮凝剂、离子交换剂等,目前这方面的研究主要中在纤维素、淀粉和壳聚糖的接枝共聚上。     

Grafting Vinyl Monomers onto Wool Fibers. VII. Graft Copolymerization of Methyl Methacrylate onto Wool Using Peroxydiphosphate-Thiourea Redox System

Graft copolymerization of methyl methacrylate onto wool was investigated in aqueous solution using the potassium peroxy-diphosphate-thiourea redox system as the initiator. The rate of grafting was determined by varying the monomer, peroxydi-phosphate ion, temperature, and solvent. The graft yield increases with increasing peroxydiphosphate ion up to 80 × 10^?-⁴ mol/L, and with further increase of peroxydiphosphate ion the graft yield decreases. The graft yield increases with increasing monomer concentration. The percentage of grafting decreases with increasing thiourea concentration. The rate of grafting increases with an increase of temperature. The effect of acid and water-soluble solvent and certain salts on graft yield has been investigated and a suitable rate expression has been derived.     

硅烷气相接枝水解交联聚丙烯

硅烷气相接枝水解交联聚丙烯;聚丙烯;气相接枝;硅烷交联     

Analysis and Characterization of Microwave Irradiation–Induced Graft Copolymerization of Methyl Methacrylate onto Delignified Grewia Optiva Fiber

Grafting of methyl methacrylate (MMA) onto delignified Grewia optiva fiber using ascorbic acid/H₂O₂ as an initiator was carried out under microwave irradiation. The effects of varying the microwave power, exposure time, and concentration of initiator and monomer of graft polymerization were studied to obtain maximum grafting percentage (26.54%). The experimental results showed that the optimal conditions for grafting were: exposure time, 10min; microwave power, 110 W; ascorbic acid concentration, 3.74mol/L × 10^?2; H₂O₂ concentration, 0.97mol/L × 10^?1; monomer concentration, 1.87mol/L × 10^?1. The graft copolymers were characterized by Fourier transform-infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), and thermogravimetric analysis (TGA).     

Ceric Ion-Initiated Grafting of Poly(Methyl Acrylate) onto Chitin

Abstract

Poly(methy1 acrylate) was grafted onto chitin in an aqueous medium by using the ceric ion as a redox initiator in the presence of 10^?4 M nitric acid and oxygen from the atmosphere. The grafting percentage turned out to be dependent on reaction temperature, time, and initiator concentration, but it was found to be independent of monomer concentration. In the course of the grafting reaction, homopolymerization of methyl acrylate occurs. The percentage of homopolymer was found to depend only on the reaction temperature. The apparent activation energy for the grafting reaction was estimated to be 11 kcal/mol. The grafted chitin is insoluble in solvents for chitin but shows enhanced swelling in some organic solvents.     

Grafting Vinyl Monomers onto Silk Fibers: Graft Copolymerization of Vinyl Monomers onto Silk Using the Vanadyl Acetylacetonate Complex

Abstract

The graft copolymerization of methyl methacrylate (MMA) onto mulberry silk fibers was studied in aqueous solution using the acetylacetonate oxovanadium (IV) complex. The rate of grafting was investigated by varying the concentration of the monomer and the complex, the acidity of the medium, the solvent composition of the reaction medium, the surfactants, and the inhibitors. The graft yield increases with increasing concentration of the initiator up to 8.75 × 10^?5 mol/L, of the monomer up to 0.5634 mol/L, and thereafter it decreases. Among the various vinyl monomers studied, MMA was found to be most suitable for grafting. Grafting increases with increasing concentration of HCIO₄ and with increasing temperature. Inhibitors like picryl chloride and hydroquinone significantly decrease the extent of grafting. Alcoholic solvents at a solvents/water ration of 10:90 seem to constitute the most favorable medium for grafting. A suitable reaction scheme has been proposed, and the activation energy calculated from the Arrhenius plots.     

Ce(Ⅳ)盐引发丙烯酰胺在聚乙烯醇微球表面接枝聚合的研究

以硫酸铈铵为引发剂,采用水溶液聚合体系,在酸性介质中实施了丙烯酰胺(AM)在聚乙烯醇交联微球(CPVA)表面的接枝聚合,制备了接枝微粒CPVA-g-PAM,重点研究了各种因素对接枝聚合的影响规律,探讨了铈盐引发接枝聚合的机理.实验结果表明,在Ce(Ⅳ)盐的氧化作用下,在含有大量羟基的CPVA微球表面会产生自由基,顺利地实现丙烯酰胺的自由基接枝聚合反应.PAM的接枝度首先取决于水介质中硫酸的浓度,接枝度随硫酸浓度的增大呈现先增大后减小的变化规律,当H+离子浓度为0.36mol/L时,PAM的接枝度最高,酸浓度对接枝度的影响反映了铈盐引发接枝聚合的微观机理.引发剂Ce4+盐的浓度过大,将会促进氧化终止过程,降低接枝度,适宜的Ce4+盐浓度为5.98×10-3mol/L.在接枝聚合过程中,单体丙烯酰胺浓度和反应温度也会对接枝聚合产生影响.在本研究所确定的适宜条件下,可制得PAM接枝度为27.13g/100g的接枝微粒CPVA-g-PAM.