苯乙烯/马来酸酐和苯乙烯/甲基丙烯酸二甲氨基乙酯二元体系在聚四氟乙烯多孔膜上的γ辐射接枝

在氮气的氛围下用γ辐照的方法在聚四氟乙烯多孔膜上接枝苯乙烯 马来酸酐、苯乙烯 甲基丙烯酸二甲氨基乙酯二元单体 .并且研究了剂量、剂量率、溶液中单体的浓度和二元单体的摩尔比等条件对接枝率的影响 .探讨了两种单体的竞聚率对接枝率、接枝膜的组成及性能的影响 .结果表明 ,苯乙烯 马来酸酐二元体系对接枝率有协同效应 ,苯乙烯 甲基丙烯酸二甲氨基乙脂二元体系对接枝率表现为加合效应 .制备的二元接枝的聚四氟乙烯多孔膜可以进一步磺化来制备用于质子交换膜燃料电池的质子交换膜 .     

醋酸乙烯酯在硅橡胶上的辐射接枝研究

研究了不同溶剂中的醋酸乙烯酯在硅橡胶上的辐射接技状况及接枝后硅橡胶表面结构情况．结果表明：（１）在硅橡胶－乙酸乙酯－醋酸乙烯酯体系中，接枝有自加速效应；（２）适量加入对苯二酚，接枝诱导期延长，接枝速率下降，凝胶效应消失，辐射接技经验关联式为ＲＰ＝０．２７×［Ｄ］（－０．５６０）×［Ｉ］（０．４９０）×［Ｃ］（０．９２０），接核反应为扩散控制反应；（３）不同的溶剂对硅橡胶接枝有不同的影响，如甲醇发生敏化作用，提高接枝速率，而苯发生惰化作用，降低接枝速率；（４）在合适的甲醇和苯配比时，接枝反应几乎恒速进行，用扫描电镜（ＳＥＭ）观察断面，接枝区比较均一，出现微相分离．     

马来酸酐-苯乙烯多组分单体熔融接枝聚丙烯的机理研究

用单螺杆挤出机研究了马来酸酐（ＭＡＨ）－苯乙烯（Ｓｔ）对聚丙烯（ＰＰ）的多组分单体自由基熔融接枝体系。研究结果表明,用Ｓｔ作共单体能够显著提高ＭＡＨ的接枝率。讨论了Ｓｔ用量、引发剂用量对接枝反应的影响。发现当两种单种物质的量比约为１：１时,接枝物的接枝率最高,熔体流动速率（ＭＦＲ）也最大,通过对反应机理的探讨,认为Ｓｔ和ＭＡＨ的相互作用或反应在接枝反应中起到了重要的作用,在自由基的作用下,Ｓｔ与Ｍ     

多官能团单体对马来酸酐接枝聚丙烯流变行为的影响

研究了多官能团辅助单体偏苯三酸三丙烯酯(TATM)对马来酸酐接枝聚丙烯的熔体流动速率(MFR)和流变行为的影响.当以不含抗氧剂的聚丙烯粉料为原料时,TATM的加入对稳定接枝产物MFR的效果并不理想.但将聚丙烯粉料添加抗氧剂并造粒后,TATM的加入则可有效稳定体系的MFR,各种流变曲线显示出接枝产物的熔体弹性明显提高,说明有枝化或交联结构出现.针对PP粉料和粒料间接枝产物流变行为存在的重大差异,结合熔体自由基接枝反应的机理进行了解释.TATM能够起到稳定MFR的效果是由于其提高了接枝物的熔体弹性,从而抵消了聚丙烯熔体接枝反应中所不可避免的β断链所造成的剪切黏度下降.聚丙烯粉料和粒料中抗氧剂的差异对聚丙烯的加工降解有严重影响,造成了TATM在不同聚丙烯体系中效果的差异.     

超临界CO2协助多单体接枝改性聚丙烯

利用超临界CO2作为溶胀剂和携带剂,使小分子单体马来酸酐和苯乙烯单体(MAH与St)及引发剂过氧化苯甲酰(BPO)插嵌进入聚丙烯(PP)基质中,然后在100℃条件下反应4 h得到接枝产物。研究了不同超临界CO2条件及引发剂浓度对接枝率的影响,固定超临界流体压力,改变温度,42℃为最佳温度,接枝率达到2.2%;固定温度,改变压力,10 MPa为最佳条件,接枝率为2.3%。对样品的FT-IR和SEM分析表明,共单体确实接枝到了PP分子链上,而DSC分析表明,随着接枝率的提高,材料的熔点(Tm)及表观结晶度(Ca)下降。这可能是接枝破坏了PP链结构的规整性,同时扩大了分子链间的距离所致。     

St存在下MAH熔融接枝PP机理的探讨

在哈克转矩流变仪和双螺杆挤出机中,对苯乙烯（St）存在下马来酸酐（MAH）熔融接枝聚丙烯（PP）进行了研究.实验表明：St的加入不仅可显著提高MAH的接枝率,而且可减少PP的降解;当St和MAH的摩尔比为1时,MAH接枝率最大.通过反应机理分析得出：没有St时,MAH主要以单分子形式在PP降解之后接枝到PP上;而在St存在下,St与MAH以交替接枝的形式或者配合物（CTC）形式在PP降解之前接枝到PP上,形成St和MAH交替聚合的长链.后者使MAH的接枝率增加,同时增大了PP的交联,减小了PP的降解.     

马来酸酐-苯乙烯熔融接枝聚丙烯的影响因素及其性能研究

用单螺杆挤出机制备了马来酸酐 (MAH) 苯乙烯 (St)对聚丙烯 (PP)的多组分单体自由基熔融接枝体系 .研究证实了当两种单体物质的量比约为 1∶1时 ,接枝物的接枝率最高 ,而熔体流动速率 (MFR)最大 .对反应体系影响因素的研究表明单体用量和引发剂用量对不同单体用量比的系列接枝物的接枝率会产生不同的影响 ;另外 ,单体用量增加 ,接枝物的MFR减小 ,过氧化二异丙苯 (DCP)用量增加 ,接枝物的MFR增加 .对多单体熔融接枝聚丙烯PP g (MAH co St)的力学性能研究发现 ,选用合适的单体用量比、单体用量和DCP用量时 ,所制备的接枝物可具有与纯PP相当或更佳的力学性能     

PVDF基两性离子交换树脂的辐射合成及性能

以聚偏氟乙烯(PVDF)树脂为基材,采用共辐射接枝方法,在PVDF树脂上接枝苯乙烯(St)/甲基丙烯酸二甲氨基乙酯(DMAEMA)二元单体,随后对接枝产物进行磺化和质子化反应引入磺酸基和叔氨基正离子得到了一种新型的PVDF基两性离子交换树脂.红外光谱、X射线光电子能谱(XPS)、热重和扫描电镜(SEM)分析证明了辐射引发接枝共聚及功能化反应的成功进行.接枝反应条件如溶剂、剂量和二元单体浓度对接枝率(GY)有明显的影响.随着接枝率的增加,功能树脂的离子交换容量随之增大,但接枝链St与DMAEMA的摩尔比不变,其阳离子及阴离子交换容量最大分别可达2.16 mmol/g,1.06 mmol/g.     

辐射接枝技术在吸附材料制备中的应用

辐射接枝技术已成为高分子材料改性的重要方法之一.和传统化学接枝方法相比,辐射接枝技术具有操作简单,易于控制,不限制基材和单体等优点,近年来已被广泛应用于吸附材料的制备.采用辐射接枝技术制备的吸附材料,其功能团主要分布在基材表面,具有单体用量少,成本低,吸附脱附速度快,功能团利用率高,选择性好的特点.本文综述了近年来辐射接枝技术在制备选择性吸附材料方面的最新研究进展,包括对重金属、放射性核素、半金属、非金属、稀土元素、贵金属和染料等不同污染物吸附材料的合成及其应用,并对辐射接枝技术在制备吸附材料中的研究方向进行了展望.     

乙烯基单体在炭黑表面上的接枝聚合

讨论了分别在铈离子体系，正丁基锂体系，过渡金属离子乙酰丙酮铜（Ⅱ）以及焦磷酸络锰（Ⅲ）体系的作用下，炭黑与乙烯基单体的接枝聚合．研究了引发剂浓度、单体浓度、反应时间对接枝聚合反应的影响．利用ＦＴ ＩＲ分析确证了炭黑表面的接枝反应，利用ＴＥＭ表征了接枝炭黑的形态．结果表明，在所研究的多种炭黑表面接枝聚合体系中，正丁基锂体系的接枝率最高，可达２００％．而各种氧化还原体素的接枝率只能达到３０％左右．表面接枝后的炭黑在介质中的分散稳定性明显改善．     

Styrene-assisted melt free radical grafting of glycidyl methacrylate onto polypropylene

The free radical grafting reactivity of glycidyl methacrylate (GMA) onto polypropylene (PP) in the molten state is low. This article shows that adding styrene as a second monomer (or comonomer) increases both the rate and yield of GMA grafting and reduces PP chain scission. The proposed mechanism is that when St is added to the PP/GMA/peroxide grafting system, St reacts first with PP macroradicals to form stable styryl macroradicals. These latter then react (or copolymerize) with GMA to form GMA grafted PP. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1053–1063, 1998     

Graft Copolymerization on to Cellulose Using Binary Mixture of Monomers

The graft copolymerization of acrylonitrile (AN) and ethyl acrylate (EA) comonomers onto cellulose has been carried out using ceric ammonium nitrate (CAN) as an initiator in the presence of nitric acid at 35±0.1°C. The addition of ethyl acrylate as comonomer has shown a significant effect on overall and individual graft copolymerization of acrylonitrile on cellulose. The graft yield (%G_Y) and other grafting parameters viz. true grafting (%G_T), graft conversion (%C_G), cellulose number (Ng) and frequency of grafting (G_F) were evaluated on varying the concentration of comonomers from 6.0–30.0×10^?1 mol dm^?3 and ceric (IV) ions concentration from 2.5–25×10^?3 mol dm^?3 at constant feed composition (f_AN 0.6) and constant concentration of nitric acid (7.5×10^?2 mol dm^?3) in the reaction mixture. The graft yield (%G_Y) and other grafting parameters were optimal at 15×10^?1 mol dm^?3 concentration of comonomers and at 10×10^?3 mol dm^?3 concentration of ceric ammonium nitrate. The graft yield (%G_Y) and composition of grafted chains (F_AN) was optimal at a feed composition (f_AN) of 0.6. The energy of activation (Ea) for graft copolymerization has been found to be 16 kJ mol^?1. The molecular weight (Mw) and molecular weight distribution (Mw/Mn) of grafted chains was determined by GPC and found to be optimum at 15×10^?1 mol dm^?3 concentration of comonomer in the reaction mixture. The composition of grafted chains (F_AN) determined by IR method was used to calculate the reactivity ratios of monomers, which has been found to be 0.62 (r₁) and 1.52 (r₂), respectively for acrylonitrile (AN) and ethyl acrylate (EA) monomers used for graft copolymerization. The energy of activation for decomposition of cellulose and grafted cellulose was determining by using different models based on constant and different rate (β) of heating. Considering experimental observations, the reaction steps for graft copolymerization were proposed.     

溶液法马来酸酐接枝氯化聚丙烯的研究

采用溶液法用马来酸酐对氯化聚丙烯接枝改性。考察了反应温度、引发剂浓度、单体浓度、溶剂用量等因素对接枝率的影响，测定了反应前后氯含量的变化。采用FT-IR和DSC对产物进行了表征。     

多组分单体熔融接枝聚丙烯及其性能研究

利用单螺杆挤出机研究聚丙烯的多组分极性单体熔融接枝，从而改善和提高聚丙烯的极性。红外和熔体流动速率的结果表明，对于单组分接枝体系，在适当的反应条件下，甲基丙烯酸缩水甘油酯、甲基丙烯酸羟乙酯等极性单体均可以接枝在聚丙烯上，但同时也伴随着较严重的聚丙烯降解。而采用多组分单体接枝体系，通过加入甲基丙烯酸缩水甘油酯和苯乙烯单体，或甲基丙烯酸羟乙酯和苯乙烯单体，能够有效地控制聚丙烯的降解，大幅度提高接枝率，     

Mathematical Modeling of the Grafting of Maleic Anhydride onto Polypropylene

Summary: A kinetic model for the free radical grafting of maleic anhydride (MAH) onto polypropylene (PP) was developed. The model is able to predict the effect of MAH and initiator concentrations on the grafting degree as well as the changes in the polymer molecular weight distribution during the grafting process. Simulation results are validated by comparison with data from different sources, showing that the model is able to represent reasonably the main trends of the experimentally measured variables both in batch (internal mixer, static film) and in continuous processing (twin-screw extruder), under different conditions. Model predictions are also compared well with a Monte Carlo simulation previously presented in the literature for the same process.     

Ultrasonically Initiated Grafting of Maleic Anhydride onto Poly(propylene)

This paper presents the studies on the grafting of MAH onto PP performed in solution by means of ultrasonic initiation. The effect of sonic intensity and monomer concentration on the amount of grafted MAH was investigated. It was found that grafting reaction could be initiated by ultrasound at ambient temperatures in the absence of an initiator. The quantity of product grafted was found to be 1.35%. It has been shown that optimum conditions for grafting are reached at an ultrasonic intensity of 300 W and a MAH concentration of 30%. PP‐g‐MAH is characterized by FTIR and XRD. DSC shows that the crystallinity of PP‐g‐MAH is lower than that of pure PP.

     

聚丙烯与马来酸酐和苯乙烯在超临界CO2中的双组分接枝

聚丙烯与马来酸酐和苯乙烯在超临界CO2中的双组分接枝     

Grafting reactions of vinyl acetate onto poly[(vinyl alcohol)-co-(vinyl acetate)]

The grafting preference of vinyl acetate onto the methine carbon of poly(vinyl alcohol) (PVOH) versus the acetate group of poly(vinyl acetate) (PVAc) was determined as part of an attempt to prepare novel branched PVOH from partially hydrolyzed PVAc. The results showed long chain grafting on the acetate groups of the PVAc units rather than the methine carbons of the PVOH or PVAc units. Decreasing the monomer or initiator concentration decreased the molecular weight of the graft copolymer formed. Of the initiators studied, ammonium persulfate gave the largest increase in copolymer molecular weight. Both hydrolysis and reacetylation combined with gel permeation chromatography (GPC) and ¹³C-NMR of the fully hydrolyzed material were used to estimate the number and location of grafts. © 1996 John Wiley & Sons, Inc.     

马来酸酐接枝稀土异戊橡胶接枝率的测试方法

以马来酸酐(MAH)和稀土异戊橡胶(IR)聚合液为主要原料,采用溶液接枝改性反应制备了马来酸酐接枝稀土异戊橡胶(IR-g-MAH)。以IR-g-MAH接枝率的测试方法为研究对象,对比直接滴定法和返滴法,并进一步优化直接滴定法的测试条件。实验结果表明,直接滴定法测试的结果准确度高、重复性好,且测试过程简单。其较优的测试条件为:水解试剂为乙醇,样品用量为0.2~0.5g,KOH-乙醇标准溶液浓度为0.02~0.06mol/L。     

马来酸酐与聚烯烃接枝产物的表征

综述了马来酸酐与聚烯烃接枝产物的多种表征手段，重点分析了纯化处理，化学滴定以及红外分析方法的表征原理，应用和改进方法。