淀粉-丙烯酸-醋酸乙烯酯接枝共聚反应研究

以水为溶剂,过硫酸铵 亚硫酸钠为引发剂,研究了淀粉 丙烯酸 (AA) 醋酸乙烯酯 (VAc)接枝共聚反应。探讨了单体配比、引发剂用量、反应温度、反应时间等因素对反应的影响,并通过红外光谱对接枝共聚物进行了结构表征。     

淀粉接枝共聚反应的研究进展

概述近年来淀粉接枝共聚中引发体系、接枝单体、聚合方法及其应用,展望淀粉接枝共聚反应的发展趋势。     

淀粉接枝丙烯酸异辛酯-醋酸乙烯共聚反应的研究

采用乳液聚合的方法,以硝酸铈铵为引发剂,十二烷基硫酸钠为乳化剂,重点考察了淀粉与醋酸乙烯／丙烯酸异辛酯的接枝共聚反应中引发剂浓度、单体浓度、反应温度、反应时间等条件对接枝率、接枝效率以及接枝反应速率的影响,得到了较为理想的产物。结果表明,接枝率最高可达248.9％,接枝效率可达72.1％,单体转化率可达94.3％。     

玉米淀粉接枝丙烯酸共聚反应研究

对于过硫酸铵-亚硫酸氢钠组成的氧化还原引发体系下的淀粉-丙烯酸接枝共聚反应。本课题较系统地研究了引发剂浓度、单体浓度、单体中和度、反应温度和反应时间等因素对该接枝共聚反应的影响，通过物料的二次加入有效地提高了该反应的接枝效果，并对该接枝共聚物进行了红外测试表征。     

木薯淀粉与醋酸乙烯酯的接枝共聚研究

以木薯淀粉为接枝骨架,过硫酸铵为引发剂,醋酸乙烯酯(VAC)为接枝单体,进行接枝共聚。研究了单体浓度、引发剂浓度、反应时间、反应温度对淀粉醋酸乙烯酯接枝共聚反应的影响,并通过正交试验,确定了最佳反应条件。结果表明:当单体浓度为1.1mol/L、引发剂浓度为18.3×10-3mol/L,反应温度60℃、反应时间3~3.5h时,可得到高的单体转化率、接枝效率和接枝率,并用SrectrumOne红外光谱对接枝物的化学结构进行了分析。     

淀粉接枝丙烯酰胺共聚反应及共聚物的应用

本文综述了淀粉接枝丙烯酰胺共聚反应的机理，影响因素及共聚物的应用情况。     

高锰酸钾引发淀粉／丙烯腈接枝共聚反应动力学

以高锰酸钾为引发剂,研究了玉米淀粉与丙烯腈的接枝共聚反应动力学。由试验结果得出了接枝反应速度与引发剂浓度、单体浓度、淀粉浓度和反应温度间的关系,并由此关联出接枝反应速度表达式。用顺磁共振原位分析等方法分析了在接枝反应过程中锰离子价态的变化和淀粉的氧化程度,并依据试验结果对接枝反应机理进行了初步的探讨。     

淀粉接枝改性絮凝剂研究进展

对淀粉接枝絮凝剂的研究进展进行了综述。     

反相乳液法淀粉丙烯酰胺接枝共聚反应的研究

以木薯淀粉为主要原料,研究了淀粉/丙烯酰胺单体/乳化剂/油/水反相乳液体系的接枝共聚反应规律,考察了反应温度、引发剂和乳化剂浓度、淀粉单体比、油水比等因素对淀粉接枝丙烯酰胺共聚反应过程的影响,并对反应机理进行了探讨.结果显示：在本实验考察范围内引发剂浓度、单体淀粉比、反应温度影响显著;乳化剂用量和油水比对反相乳液体系的形成及稳定有重要的影响;淀粉与亲水性单体丙烯酰胺的接枝共聚反应为淀粉团粒表面控制.     

交联玉米淀粉-醋酸乙烯酯接枝共聚乳液的制备及性能

碱性条件下,玉米淀粉经环氧氯丙烷交联处理后,在引发剂存在下,与醋酸乙烯酯进一步接枝共聚制得了交联玉米淀粉-醋酸乙烯酯乳液,经红外光谱确认了共聚物,较好的乳液制备工艺:m(淀粉)∶m(环氧氯丙烷)=25∶1,90°C交联1 h,加入过硫酸铵,按m(醋酸乙烯酯)∶m(淀粉)=3∶1,在70°C接枝共聚3 h。各种淀粉胶液的性能对比结果表明:交联玉米淀粉-醋酸乙烯酯接枝聚合乳液冷热稳定性好,耐水性≥54 h,储存期360 d,剪切强度达9.1 MPa。     

淀粉醋酸酯与醋酸乙烯接枝共聚制备白乳胶

提出了用淀粉醋酸酯与醋酸乙烯接枝共聚制备白乳胶的新工艺。结果表明制得的白乳胶与单独用PVA作为保护胶体制得的白乳胶相比,粘度和耐水性得到改善,粘接强度均能达到使用标准。作为一种新型胶粘剂,其与环境相容性好,前景广阔。     

木薯淀粉/VAc-MA接枝共聚物的合成研究

通过正交试验设计,研究醋酸乙烯酯和丙烯酸甲酯两种单体接枝改性木薯淀粉的影响因素。利用SAS统计分析得出适宜的工艺条件:引发剂浓度16mmol.L-1,总单体浓度1.45mol.L-1,两单体配比(VAc/MA)为30/70,反应温度65℃,反应时间5h。采用红外光谱对该接枝共聚物结构进行了分析。     

Controlled grafting of poly(vinyl acetate) onto starch via RAFT polymerization

A structure‐exact starch‐based xanthate agent was prepared and used as chain transfer agent to mediate RAFT polymerization of vinyl acetate, which offered a convenient way to well control the structure and composition of starch‐g‐poly(vinyl acetate). The structures of the intermediate and the polymer were verified with FTIR and ¹H‐NMR. Gel permeation chromatography measurement results indicated that the polymerization was performed as expected. It was found that the relationship between number average molecular weight and monomer conversion was linear. The polydispersity index of grafted side‐chain ranged from 1.19 to 1.53 and most of them were around 1.2. There was one more degradation stage appeared on the thermogravimetric analysis profile of starch‐g‐poly(vinyl acetate) than that of starch. TEM observation exhibited that the product was able to self‐assemble into micelles in aqueous solution, which suggested the copolymer was amphiphilic. Both the thermal and amphiphilic properties demonstrated the starch‐g‐poly(vinyl acetate) was successfully synthesized as well. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

醋酸乙烯共聚反应的研究

以醋酸乙烯和共聚改性单体为原料，对制备醋酸乙烯共聚体的工艺条件进行了研究。当反应温度为７０～７２℃、反应时间为２ｈ时，共聚物的收率约为９５％，粘度为３０００～５０００ｍＰａ·ｓ，固含量为４０％左右，ｐＨ值为４～５．其性能优于市售白胶。     

氯乙烯-醋酸乙烯酯共聚反应后醋酸乙烯酯的回收

介绍了氯乙烯-醋酸乙烯酯共聚后未转化VAC的回收工艺;比较了减压、常压两种工业化生产回收方案,结果表明,常压回收方案的VAC回收率基本在90%以上,优于减压回收方案。     

Grafting of vinyl acetate onto low density polyethylene—starch biodegradable films for printing and packaging applications

Starch‐based biodegradable low‐density polyethylene (LDPE) films were used for graft copolymerization of vinyl acetate with ceric ammonium nitrate (CAN) in aqueous acidic medium as redox initiator with nitric acid. The extent of grafting was examined by Fourier‐transform infrared (FTIR) spectroscopy, attenuated total reflectance (ATR) spectroscopy, X‐ray diffraction (XRD) and scanning electron microscopy (SEM). The objective behind the grafting of vinyl acetate onto the LDPE–starch biodegradable films is to make these suitable for printing and packaging applications without affecting the biodegradability of the original films. Copyright © 2004 Society of Chemical Industry     

Graft polymerization of vinyl acetate onto silica

The free‐radical graft polymerization of vinyl acetate onto nonporous silica particles was studied experimentally. The grafting procedure consisted of surface activation with vinyltrimethoxysilane, followed by free‐radical graft polymerization of vinyl acetate in ethyl acetate with 2,2′‐azobis(2,4‐dimethylpentanenitrile) initiator. Initial monomer concentration was varied from 10 to 40% by volume and the reaction was spanned from 50 to 70°C. The resulting grafted polymer, which was stable over a wide range of pH levels, consisted of polymer chains that are terminally and covalently bonded to the silica substrate. The experimental polymerization rate order, with respect to monomer concentration, ranged from 1.61 to 2.00, consistent with the kinetic order for the high polymerization regime. The corresponding rate order for polymer grafting varied from 1.24 to 1.43. The polymer graft yield increased with both initial monomer concentration and reaction temperature, and the polymer‐grafted surface became more hydrophobic with increasing polymer graft yield. The present study suggests that a denser grafted polymer phase of shorter chains was created upon increasing temperature. On the other hand, both polymer chain length and polymer graft density increased with initial monomer concentration. Atomic force microscopy–determined topology of the polymer‐grafted surface revealed a distribution of surface clusters and surface elevations consistent with the expected broad molecular‐weight distribution for free‐radical polymerization. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 300–310, 2003     

Room temperature-initiated and self-heating copolymerization of acrylonitrile with vinyl acetate

A novel polymerization method [Ruckenstein and Li, Polymer Bull., 37, 43 (1996)]—room temperature-initiated, self-heating polymerization—was applied to both bulk and concentrated emulsion copolymerization of acrylonitrile (AN) with vinyl acetate (VAc). A redox system was employed as an initiator, with the oxidant dissolved in the monomers and the reductants (two reductants were employed) in the aqueous phase. In the bulk polymerization, the oxidant (cumene hydroperoxide) was dissolved in the mixture of monomers, and the two reductants (sodium metabisulfite and ferrous sulfate) were introduced as an aqueous solution. In the concentrated emulsion polymerization, a mixture of the monomers containing dissolved oxidant was first used as the dispersed phase of a concentrated emulsion in water, and the aqueous solution of reductants was subsequently added to the concentrated emulsion. In both cases, the polymerization started at room temperature, just after the reductants were introduced. Because the reactor was insulated, the heat generated by the reaction was mostly used to accelerate the polymerization, which reached a high conversion in 30 min. The effects of various parameters on the polymerization were investigated. Optimum values were found for the volume fraction of the dispersed phase, for the wt ratios of the two reductants and of the oxidant to reductants, and for the surfactant and reductant concentrations. One concludes that the concentrated emulsion polymerization method is particularly suitable for the room temperature-initiated, self-heating polymerization. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 999–1011, 1998