官能化乙丙橡胶的制备和表征

用２,５－二甲基－２,５－二叔丁基过氧基己烷为引发剂,甲基丙烯酸环氧丙酯（ＧＭＡ）、马来酸酐（ＭＡＨ）和丙烯酸（ＡＡ）为接枝单体,对三元乙丙橡胶（ＥＰＤＭ）和二元乙丙橡胶（ＥＰＲ）进行熔融接枝,接枝产物用ＦＴＩＲ、１３Ｃ－ＮＭＲ等进行了表征,并用化学滴定方法对接枝率进行了测定。实验结果表明,影响接枝率和凝胶质量分数的主要因素为乙丙橡胶的化学结构、引发剂和单体的用量、反应时间及温度等。接枝单体反应活性大小依次为ＧＭＡ,ＡＡ,ＭＡＨ。     

GMA／HEMA／NVP三元共聚物的合成及性能研究

以ＥＧＭＥ为溶剂，ＡＩＢＮ为引发剂合成ＧＭＡ／ＨＥＭＡ／ＮＶＰ三元共聚物。将它涂覆在聚酯ＰＣ片上进行升温固化，测试涂层的防雾性能，并对其表面进行ＡＴＲ红光谱分析。     

增容剂对聚对苯二甲酸丁二酯／热塑性聚酰胺弹性体合金热性能？…

８０份聚对苯二甲酸丁二酯（ＰＢＴ）和２０份热塑性聚酰胺弹性体（ＴＰＡＥ）分别与９各含有环氧基（－ＧＭＡ）或无水马来酸酐基（－ＭＡＨ）或酯基的增容剂及它们的复合物进行熔融共混,得到ＰＢＴ／ＴＰＡＥ／增容剂合金。用动态粘弹性温度曲线、ＤＳＣ曲线、扫描电镜观察表明,含－ＧＭＡ或－ＭＡＨ或两者共存的增容剂能使ＰＢＴ与ＴＰＡＥ间的相互作用增强,使ＴＰＡＥ在ＰＢＴ中的分散更加均匀,但对软化温度影响很小。     

增容剂对聚对苯二甲酸丁二酯/ 热塑性聚酰胺弹性体合金热性能和分散形态的影响

８０份聚对苯二甲酸丁二酯（ＰＢＴ）和２０份热塑性聚酰胺弹性体（ＴＰＡＥ）分别与９种含有环氧基（—ＧＭＡ）或无水马来酸酐基（—ＭＡＨ）或酯基的增容剂及它们的复合物进行熔融共混,得到ＰＢＴ／ＴＰＡＥ／增容剂合金。用动态粘弹性温度曲线、ＤＳＣ曲线、扫描电镜观察表明,含—ＧＭＡ或—ＭＡＨ或两者共存的增容剂能使ＰＢＴ与ＴＰＡＥ间的相互作用增强,使ＴＰＡＥ在ＰＢＴ中的分散更加均匀,但对软化温度影响很小。     

马来酸酐功能化NR的研究概况

综述了马来酸酐功能化NR的研究成果。马来酸酐功能化NR的途径有溶液法和固相力学法。在溶液中，马来酸酐在自由基引发剂存在下通过取代α-亚甲基的氢原子结合到NR上；采用无引发剂存在的固相力学法时．部分双键发生异构化。傅立叶转换红外光谱、核磁共振、凝胶渗透色谱和化学滴定等方法可定性或定量地表征反应的发生。马来酸酐功能化NR已成功用于废旧橡胶的再利用，并在提高聚合物基复合材料界面相容性方面有着广泛的应用前景。     

乙酸乙烯酯嵌段共聚物的合成研究

以ＡＩＢＮ为引发剂，用ＣＣｌ４调节乙酸乙烯酯聚合制备了带三氯甲基端基的ＰＶＡｃ大分子引发剂（ＰＶＡｃ－ＣＣｌ３）。以ＣｕＣｌ－ｂｐｙ为催化剂，用ＰＶＡｃ－ＣＣｌ３引发Ｓｔ，ＭＭＡ和ＢＭＡ等单体的ＡＴＲＰ聚合，得到了一系列相对分子质量可控、相对分子质量分布较窄的ＰＶＡｃ嵌段共聚物。     

反应型增容剂PS-co-GMA的合成及反应动力学的研究

以过氧化苯甲酰（ＢＰＯ）为引发剂,利用改进的本体聚合方法制备了苯乙烯—甲基丙烯酸环氧丙酯共聚物（ＰＳｃｏＧＭＡ）,用红外光谱证实了ＰＳｃｏＧＭＡ共聚物的存在,并探讨了聚合温度,聚合时间对聚合物的分子量和转化率的影响,通过以上研究确定了最佳反应条件：反应温度为７０℃,反应时间为６ｈ时,可得到性能满意的ＰＳｃｏＧＭＡ共聚物。     

甲基丙烯酸缩水甘油酯的合成

在季铵盐催化剂和对苯二酚阻剂聚剂存在下，由甲基丙烯酸甲酯（ＭＭＡ）和环氧氯丙烷合成了甲基丙烯酸缩水甘油酯（ＧＭＡ）。通过正交实验设计，得到了最佳反应条件；反应温度１００￣１０５℃，反应时间４ｈ，四丁基溴化铵（ＴＢＡＢ）催化剂的用量为１．２ｇ。ＧＭＡ的产率为８３．６％，纯度为９８％。     

絮凝—缓蚀—阴垢剂GMT—A2在循环冷却水处理中的应用研究

本文详细地研究了自行研制的多功能水处理剂ＧＭＴ－Ａ２在循环冷却水处理中的絮凝、缓蚀、阻垢效果。采用了动态摸拟实验及交流阻抗等测试方法，研究比较了ＧＭＴ－Ａ２与典型缓蚀阻垢剂ＡＴＭＰ的缓蚀、阻垢效果；并对ＧＭＴ－Ａ２的缓蚀、阻垢用途机理进行了探讨。     

低密度聚乙烯（LDPE）／马来酸酐（MAH）溶液接枝反应的研究

聚乙烯功能化不仅可改善通用聚乙烯材料的表面粘接性、染色性等，而且可做为聚烯烃材料与其他极性材料（如尼龙类材料）共混相容性的增溶剂。本工作以马来酸酐（ＭＡＨ）为接枝单体，以过氧化二苯甲酰（ＢＰＯ）为引发剂对低密度聚乙烯（ＬＤＰＥ）进行了溶液接枝功能化的研究，考察了实验条件（ＢＰＯ用量，ＭＡＨ用量，反应时间、反应温度、加料方式及反应气氛等）对产物接枝率及特性粘数的影响。     

The effect of glycidyl methacrylate and styrene comonomers on compatibility,physical-mechanical properties,and swelling behavior of SBR/NBR blends

The effect of functionalized styrene-butadiene rubber (SBR) with glycidyl methacrylate (GMA) monomers, in the presence of styrene comonomers (SBR-g-GMA-co-St) as a compatibilizer on physical-mechanical, morphological, and swelling behavior of SBR/nitrile butadiene rubber (NBR) blends were studied. It was proved that the compatibilizer made through dicumyl peroxide-induced reaction which possessed 1.5 phr GMA in addition to 1.5 phr styrene comonomers showed higher efficiency of grafting. Possible in situ reactions between SBR-g-GMA-co-St and NBR component also were evaluated with an attenuated total reflectance mode of Fourier-transform infrared spectroscopy. SBR/NBR blend containing compatibilizer with a middle value of grafting demonstrated the most reactions between components. Dynamic mechanical thermal analysis results illustrated that the presence of SBR-g-GMA-co-St caused a significant improvement in compatibility of two components. This was verified with the scanning electron microscope pictures in which a smoother surface of the sample was clear. The enhancement in microstructure led to an increase in tensile strength, elongation at break, and storage modulus. Moreover, the increase in the intermolecular cross-links and made interactions considerably affected blends' swelling behavior in both hydrocarbon solvents (carbon tetrachloride and chloroform).     

Reactive processing of polymers: Melt grafting of glycidyl methacrylate on ethylene propylene copolymer in the presence of a coagent

Glycidyl methacrylate (GMA) was grafted on ethylene–propylene copolymer during melt processing with peroxide initiation in the presence and absence of a more reactive comonomer (coagent), trimethylolpropane triacrylate (Tris). The characteristics of the grafting systems in terms of the grafting reaction yield and the nature and extent of the competing side reactions were examined. The homopolymers of GMA (Poly‐GMA) and Tris (Poly‐Tris) and the GMA‐Tris copolymer (GMA‐co‐Tris) were synthesized and characterized. In the absence of the coagent, high levels of poly‐GMA, which constituted the major competing reaction, was formed, giving rise to low GMA grafting levels. Further, this grafting system resulted in a high extent of gel formation and polymer crosslinking due to the high levels of peroxide needed to achieve optimum GMA grafting and a consequent large drop in the melt index (increased viscosity) of the polymer. In the presence of the coagent, however, the grafting system required much lower peroxide concentration, by almost an order of magnitude, to achieve the optimum grafting yield. The coagent‐containing GMA‐grafting system has also resulted in a drastic reduction in the extent of all competing reactions, and in particular, the GMA homopolymerization, leading to improved GMA grafting efficiency with no detectable gel or crosslinking. The mechanisms of the grafting reactions, in the presence and absence of Tris, are proposed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1401–1415, 2001     

Reconsideration on the mechanism of free-radical melt grafting of glycidyl methacrylate on polyolefin

The styrene (St) assisted melt grafting of glycidyl methacrylate (GMA) on polyolefin was carried out by Haake mixer, and the grafting mechanism was investigated and reconsidered. It was revealed that there is equilibrium of grafting of GMA and depolymerization of grafted PGMA chains in the GMA/polyolefin grafting process, which was affected by both of the temperature and GMA concentration. It was found that the depolymerization of PGMA grafted on polyolefin occurred at the temperature above ceiling temperature of PGMA and dominated the grafting process before the addition of styrene monomer, which induced the decrease in grafting ratio of GMA. Adding styrene as co-monomer could promote the equilibrium moving forward to form the St-GMA chains so that the grafting ratio was greatly improved. It is proved that either controlling the reacting temperature below the ceiling temperature or changing the feeding order of styrene and GMA is effective to attain high grafting ratio of GMA on polyolefin.     

Melt free-radical grafting of glycidyl methacrylate onto polypropylene

This paper concerns free-radical grafting of glycidyl methacrylate (GMA) onto polypropylene (PP) in the molten state carried out in a batch mixer. This free-radical grafting proceeds very rapidly as it goes to completion within two to three minutes at 200°C. The grafting yield of GMA alone is low and it is greatly enhanced upon addition of styrene as a second monomer with a reduced chain degradation of PP. Homopolymer and copolymer of GMA formed during grafting were quantified. It is suggested that in the presence of styrene, the dominating grafting mechanism is that styrene reacts with the PP macroradicals to form more stable styryl macroradicals which then react with GMA to form GMA-grafted PP. The rate of this reaction is much greater than that between the PP macroradicals and GMA. Unlike grafting of mixtures of maleic anhydride and styrene, which is dictated primarily by formation of a charge transfer complex, free-radical grafting of GMA in the presence of styrene follows a random copolymerization process.     

复合引发剂引发GMA熔融接枝聚1-丁烯

采用复合引发剂用Haake流变仪研究了甲基丙烯酸缩水甘油酯(GMA)-苯乙烯(St)多组分单体熔融接枝高全同聚1-丁烯(iPB)。用傅里叶变换红外光谱对接枝物进行了分析,并分别考察了复合引发剂比例、GMA用量、引发剂总用量和St用量对接枝的影响。结果表明:在复合引发剂引发下,GMA和iPB可熔融接枝,接枝率最高可达1.74%;St作为共单体可明显提高GMA的接枝率和接枝效率,当n(St)/n(GMA)为1.5时,接枝率为单独使用GMA时的2.3倍。     

N-vinyl pyrrolidone-assisted free radical functionalization of glycidyl methacrylate onto styrene-b-(ethylene-co-butylene)-b-styrene

N-vinyl pyrrolidone (NVP)-assisted free radical functionalization of glycidyl methacrylate (GMA) onto styrene-b-(ethylene-co-butylene)-b-styrene (SEBS) was investigated to attempt to overcome the low grafting reactivity of GMA and the low efficiency of the styrene (St)-assisted functionalization method. By using the optimal amount of NVP, the degree of GMA grafting was increased by at least 7.5 and 2.5-fold when compared to GMA alone and the St-assisted grafting procedure, respectively. Also, no apparent cross-linking or degradation reactions of SEBS were observed. It was proposed that NVP reacted first with SEBS macroradicals, and then the resulting NVP-macroradicals copolymerized with GMA to produce high degrees of grafting of both GMA and NVP onto SEBS.     

等离子体引发聚合固定金属离子亲和膜的制备及其吸附性能

引　言亲和膜分离技术综合了亲和色谱选择性高和膜过程简单、连续、易放大的特点 ,近 10年来对这类膜及其过程的研究在生化分离领域成为热点[1～ 3] .在亲和膜制备过程中 ,膜的活化大都是通过化学反应来实现的 ,工艺复杂 ,费时费力 .而等离子体引发聚合法可以直接将所需基团接枝到膜上 ,省略膜的活化过程 ,与传统的方法相比具有工艺简单、操作方便、基膜和接枝单体的选择范围广等优点 .等离子体引发聚合在膜分离领域的应用主要集中在渗透汽化膜材料的改性和制备[4 ] 、固定化酶膜的制备[5] ,而在亲和膜的制备方面报道较少 .Ｋｉｙｏｈａｒａ…     

Radiation‐induced grafting of glycidyl methacrylate onto high‐density polyethylene (HDPE) and radiation lamination of HDPE

Radiation‐induced grafting of glycidyl meth‐acrylate (GMA) onto high‐density polyethylene (HDPE) and the radiation lamination of HDPE by bulk grafting of GMA were reported. The effects of irradiation dose, monomer concentration, and atmosphere on grafting were investigated. The extent of grafting initially increased with irradiation dose and then remained almost constant. The extent of grafting was higher in 2M GMA than in 1M GMA at the same irradiation dose. The extent of grafting in nitrogen was higher than that in air. The grafted samples were characterized with FTIR spectrometry and thermogravimetric (TG) analysis. A carbonyl group was found on grafted HDPE samples, and the carbonyl index increased with the extent of grafting. TG analyses proved the existence of grafted materials on HDPE and the grafted GMA thermally decomposes at a temperature lower than that of HDPE. Strong adhesion could be obtained with radiation lamination of HDPE by bulk grafting of GMA. Benzophenone facilitates the grafting in a proper concentration range. The adhesion mechanism of the laminated samples was the entanglement of the grafted chains. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 772–779, 2005     

Free radical grafting of glycidyl methacrylate onto polypropylene in a co-rotating twin screw extruder

Free radical grafting of glycidyl methacrylate (GMA) onto molten polypropylene (PP) was studied in a co-rotating twin screw extruder. Grafting yields of GMA obtained under various experimental conditions along the screw length allowed for a good appreciation of the effects of chemical parameters (the presence of styrene and the concentrations of peroxide and monomers) and those of processing parameters (feed rate, screw speed, and specific throughput). Similar to the results obtained in a batch mixer,¹ free radical grafting of GMA carried out in the extruder in the presence or absence of styrene proceeded rapidly, as it was virtually completed half-way down stream of the extruder. Additionally, the presence of styrene as a second monomer increased the GMA grafting yield reatly with reduced PP chain degradation. The ultimate GMA grafting yield increased with increasing concentration of peroxide, 1,3-bis(tert-butylperoxyisopropyl)benzene. This similarity between the batch mixer and the extruder is related to the fact that in both cases it is the concentration of the peroxide and its half lifetime that determine the grafting rate and the ultimate grafting yield. On the othe hand, the GMA grafting yield decreased with increasing screw speed or feed rate. For a particular specific throughput (the ratio of throughput to screw speed), an increase in throughput with a concomitant increase in screw speed brought about a decrease in GMA grafting yield. It was concluded that the GMA grafting yield is affected primarily by the residence time in the zone in which free radicals are not depleted. The effects of screw speed, feed rate, and specific throughput manifest mainly through this local residence time distribution. Specific energy is not a good measure of the performance of the extruder with respect to the free radical rafting of GMA onto PP. © 1995 John Wiley & Sons, Inc.     

GMA/St双组分单体熔融接枝聚丙烯的研究

分别以甲基丙烯酸缩水甘油酯（GMA）和马来酸酐（MAH）为接枝单体，苯乙烯（St）为接枝共单体，过氧化二异丙苯（DCP）为引发剂对聚丙烯（PP）进行熔融接枝，研究了接枝单体的种类、组分配比等因素对PP的接枝率和熔体流动速率等的影响，并研究了接枝PP的力学性能和耐热变形性能。实验结果表明：作为接枝单体，GMA比MAH更具有优越性；双组分单体熔融接枝PP的接枝率和性能优于单组分单体熔融接枝；接枝PP的结晶参数受其接枝率的影响；当PP／GMA／St／DCP=100／6／3／0、3时，PP—g^-（GMA—CO—St）的接枝率最高，力学性能和耐热变形性能最好。