改性淀粉/PVA生物降解材料性能的研究

以BPO为引发剂、正庚烷为溶剂在66℃下制得马来酸酐接枝淀粉。将其与聚乙烯醇(PVA)、增塑剂及加工助剂等于HAAKE密炼机中共混,制备了可生物降解热塑性淀粉塑料。研究了接枝改性淀：粉／PVA共混物的力学性能、生物降解性能及热性能等,并用SEM研究了共混物的微观形态。结果表明接枝改性淀粉／PVA共混物拉伸强度为27．57Mpa,60d失重率达65．1％。     

改性淀粉/聚乳酸共混体系增容方法的研究

研究了聚乳酸和改性淀粉共混挤出前的固相酯化反应对共混体系的增容作用。比较挤出样条经二氯甲烷抽提后剩余物的固体13C-NMR光谱谱图,发现未经酯化反应时剩余物为淀粉,经酯化反应后剩余物的固体13C-NMR光谱谱图在20ppm和170ppm处出现聚乳酸特征的碳吸收峰,说明剩余物中含有聚乳酸和淀粉的接枝物。由共混物中聚乳酸的端羧基含量的测定结果也能说明酯化反应后共混物剩余物中含有聚乳酸和淀粉的接枝物。考察了生成的接枝物对共混体系相容性的影响,扫描电镜分析结果表明,经过预处理酯化反应后共混物相容性得到了提高。挤出样条取向拉伸后进行力学性能测试,发现酯化反应明显提高了力学性能。该方法可以通过设计共混挤出过程实现改变共混物相容性的目的,具有广阔的前景和很强的应用价值。     

应力引发官能化EPDM/HDPE及其对PA66/EPDM/HDPE 共混物相形态和力学性能的影响

通过提高双螺杆挤出机螺杆转速的方法,研究了熔融挤出过程中高剪切应力对马来酸酐(MAH)官能化三元乙丙橡胶(EPDM)与高密度聚乙烯(HDPE)共混物的接枝率、熔体流动速率及凝胶含量的影响.随着双螺杆挤出机螺杆转速的增加,强烈的机械剪切应力引发EPDM/HDPE共混物大分子链的断链反应形成大分子自由基,从而引发接枝反应制...     

侧链带羧酸基团聚甲基硅氧烷的合成及其共混物润湿性的研究

合成了单体烯丙氧基苯甲酸，通过接枝共聚合的方法把它接枝到含氢硅氧烷上，得到共聚物，这些共聚物具有较高的，Ｔｇ和热分解温度，在空气中热失重为２％，５％时相对应的分别为３５０℃和４８６℃，粘度测定表明，它们在低浓度时，η／Ｃ反应而较高，具有离聚物的溶液性能；把它作为增容剂与聚乙烯和尼龙６６在２６５℃下共混，该共混物恶性循环随尼龙６６含量的增加而增加。     

马来酸酐改性聚乙烯的制备及其与尼龙的共混物

本文叙述了在聚乙烯-马来酸酐熔融接枝反应过程中,伴随着聚乙烯分子之间的交联反应,少量的己内酰胺添加剂可以有效地阻止交联反应的发生,改善体系的流变性能,而不明显地降低它的接枝率。这种马来酸酐化聚乙烯作为界面相容剂可使尼龙6-聚乙烯共混物的简支梁抗冲击强度比没有界面相容剂的共混物增加近4倍。     

国家自然科学基金资助课题

 本文叙述了在聚乙烯-马来酸酐熔融接枝反应过程中,伴随着聚乙烯分子之间的交联反应,少量的己内酰胺添加剂可以有效地阻止交联反应的发生,改善体系的流变性能,而不明显地降低它的接枝率。这种马来酸酐化聚乙烯作为界面相容剂可使尼龙6-聚乙烯共混物的简支梁抗冲击强度比没有界面相容剂的共混物增加近4倍。     

环氧化淀粉基核壳纳米粒子增韧聚乳酸的研究

通过酰氯接枝反应在淀粉大分子链上引入长烷基链和碳碳双键,使淀粉具有自乳化性能并增加反应位点,采用无皂乳液聚合将丙烯酸乙酯(EA)与酯化改性淀粉接枝共聚制备以淀粉为核的核壳粒子,即核壳粒子为硬核软壳的结构,通过添加甲基丙烯酸缩水甘油醚(GMA)进一步制备环氧化核壳粒子.将环氧化核壳粒子与聚乳酸(PLA)进行熔融共混改性,研究不同环氧化程度的核壳粒子对PLA性能的影响.结果表明,环氧化淀粉核壳粒子粒径约250 nm,与PLA共混改性后,环氧化核壳粒子能够明显提高PLA的韧性,而且其拉伸强度维持在较高水平,共混物缺口冲击强度提高至纯PLA的17倍.进一步研究表明环氧官能团的引入提高了核壳粒子与PLA的相容性同时增加了界面相互作用.     

烯类单体与可溶性淀粉的接技共聚

甲基丙烯酸与可溶性淀粉在硝酸铈氨(CAN)、高锰酸钾及Fenton’。试剂(Fe~(2+)—H_2O_2)引发下的接枝反应,经历了不同的反应历程。对可溶性淀粉而言,采用Fenotn‘s试剂为引发剂,水—丙酮混合液为介质,可以有效地控制反应,并获得高转化率和高接枝率的最佳效果。通过溶解度参数估算及拟均相反应设计,选择二甲基亚砜(DMSO)为中介溶剂,通过链转移引发完成了油溶性单体苯乙烯与可溶性淀粉间的有效接枝共聚,确定了转化率高、接枝率高、均聚物含量少的最佳反应条件,突破了多年来用相类似化学引发体系引发在苯乙烯与淀粉接枝时转化率低下及均聚物含量高的局限。在上述研究基础上,对反应介质与条件对油溶性烯类单体与可溶性淀粉接枝聚合之接枝参数的影响进行了探讨。     

聚酰胺1010／聚乙烯—马来酸酐接枝共聚物共混物力学和热学性能研究

为了表明马来酸酐接枝聚烯烃后对聚酰胺的相容作用，本文研究了聚酰胺１０１０／聚乙烯－马来酸酐接枝共聚物 共混物在不同ＭＡＨ接枝量下的结晶性与力学性能。在一定的ＭＡＨ含量内，标题共混物 具有协同效应。     

聚丙烯共混物一步法反应共混增容的研究

研究了影响聚丙烯／（丙烯腈 苯乙烯）共聚物（ＰＰ／ＡＳ）合金反应挤出生成的各项因素,发现在过氧化二异丙苯（ＤＣＰ）存在的条件下进行反应共混可以发生接枝反应,生成ＰＰ与ＡＳ的相互接枝物．接枝物的生成显著地细化了分散相粒子,改善了合金相形态．为抑制反应共混过程中聚丙烯的降解,同时促进接枝反应,在ＰＰ／ＡＳ／ＤＣＰ反应共混中加入了含适量双键组分的添加剂亚油酸三甘酯（ＧＴＬ）．结果发现,较少量ＧＴＬ的加入就显著抑制了聚丙烯的降解,且进一步改善了合金的相形态．在合适的ＧＴＬ与ＤＣＰ用量下,反应共混不但显著改善了ＰＰ／ＡＳ合金的相形态,而且提高了合金的力学性能,初步确立了聚丙烯共混物一步反应共混挤出增溶的方法．     

Starch/Polycaprolactone Blends Compatibilized with Starch Modified Polyurethane

Starch modified polyurethane(St-PCL) was synthesized via chemical modification of corn starch with hexamethylene diisocyanate terminated polycaprolactone. The obtained St-PCL with different grafting rates was used as compatibilizer of starch/polycaprolactone(St/PCL) blend. The structure of St-PCL was confirmed by FTIR, and the grafting rate could reach as high as 64%. In addition, a lower St-PCL amount can effectively improve the compatibility of St/PCL blends. And the thermal, mechanical and hydrophobic properties of St/PCL blends could be tailored by the amount of St-PCL.     

含二烯丙基双酚A醚相容剂对HDPE/PC共混体系的影响

用低密度聚乙烯接枝二烯丙基双酚Ａ醚（ＬＤＰＥ ｇ ＤＢＡＥ）作为高密度聚乙烯／聚碳酸酯（ＨＤＰＥ／ＰＣ）共混体系的增容剂,研究了其对ＨＤＰＥ／ＰＣ共混体系的影响．通过共混物形态观察、热力学性能测试和结晶性分析,发现ＬＤＰＥ ｇ ＤＢＡＥ对ＨＤＰＥ／ＰＣ共混体系有良好的增容效果．并发现了增容剂在共混物中的最佳用量为１０ｐｈｒ,提高增容剂的接枝率更有利于改善共混物的性能     

Mathematical modeling of the graft reaction between polystyrene and polyethylene

Polystyrene (PS) and polyethylene (PE) are two major components of household plastic waste whose blends are immiscible. Recycling them together is an attractive option that requires a compatibilization process to improve the blend mechanical properties. If a PE/PS copolymer is added or formed in situ, it may act as compatibilizer. The structure and molecular properties of this copolymer are key factors to assure its effectivity as a compatibilizer. In this work, we study the graft copolymerization reaction between polystyrene and polyethylene using the catalytic system composed of AlCl₃ and styrene. We develop a model of this process which considers that PE/PS grafting and PS degradation occur simultaneously. We propose a kinetic mechanism for the whole process and apply the method of moments to solve the mass balance equations. The model is able to calculate average molecular weights as well as the amount of grafted PS. It accurately describes the available experimental data, constituting a valuable tool for simulation and optimization purposes.     

阴离子聚合制备聚乙烯-g-聚氧化乙烯接枝共聚物

聚烯烃 (聚乙烯 ,聚丙烯等 )的化学改性一直是科学研究和实际生产的一个热点 ,改性过的聚烯烃可以广泛应用到高分子共混物和复合材料中 .在众多聚烯烃中 ,聚乙烯产量最大 ,但因其惰性也最难于化学改性 .我们采取的改性方法是在聚合物中引入反应性基团 ,可以在温和条件下进行有选择的而且高效的化学改性 .由于两亲性共聚物可用作乳液聚合和悬浮聚合中的表面活性剂及稳定剂 ,塑料的表面改良剂和聚合物的共混相容剂等[1,2 ] ,因此人们对该共聚物的研究越来越多 .过去 ,多数两亲性共聚物的研究局限于聚苯乙烯 (ＰＳ)和聚氧化乙烯 (ＰＥＯ)接枝共…     

Effects of the compatibilizer PE‐g‐GMA on the mechanical,thermal and morphological properties of virgin and reprocessed LDPE/corn starch blends

The effects of the compatibilizer polyethylene grafted with glycidyl methacrylate (PE‐g‐GMA) on the properties of low‐density polyethylene (LDPE) (virgin and reprocessed)/corn starch blends were studied. LDPE (virgin and reprocessed)/corn starch blends containing 30, 40 and 50 wt% starch, with or without compatibilizer, were prepared by extrusion and characterized by the melt flow index (MFI), tensile test, dynamic mechanical analysis (DMTA) and light microscopy. The addition of starch to LDPE reduced the MFI values, the tensile strength and the elongation at break, whereas the modulus increased. The decreases in the MFI and tensile properties were most evident when 40 and 50 wt% starch were added. Blends containing 3 wt% PE‐g‐GMA had higher tensile strength values and lower MFI values than blends without compatibilizer. Light microscopy showed that increasing the starch content resulted in a continuous phase of starch. Copyright © 2005 John Wiley & Sons, Ltd.     

Thermogravimetric and dynamic mechanical analysis of LLDPE/EMA blends

The thermal stability of linear low density polyethylene (LLDPE)/ethylene methyl acrylate (EMA) blends was studied using thermogravimetry. The blend ratio as well as the presence of compatibilizer has significant effect on thermal stability of the blends. The compatibilization of the blends using LLDPE-g-MA has increased the degradation temperature. Phase morphology was found to be one of the most decisive factors that affected the thermal stability of both uncompatibilized and compatibilized blends. Dynamic mechanical behavior of the blend was studied by dynamic mechanical analysis. The storage modulus of the blends decreased with increase in EMA content. When compatibilized with LLDPE-g-MA the storage modulus of the blend increases. LLDPE-g-MA is an effective compatibilizer as it increases the thermal stability and modulus of the blend.     

Grafting of Preformed Polyethylene Oxide on Dialdehyde Starch by Acetal Formation

The acid-catalyzed reaction of dialdehyde starch with diethylene glycol and polyethylene oxide-400 under anhydrous conditions was studied as a new approach to the preparation of graft polymers of polyalkylene oxides on starch, the attachment of the side chains being through acetal linkages. The reaction was carried out in DMF in the presence of p-toluene sulfonic acid. It was found that increasing the reaction temperature, the diol concentration, or the reaction time led to an increase in the degree of grafting, as seen from the decrease in the dicarbonyl content of the products. Fusible graft polymers, soluble in water and in organic solvents, were obtained.     

High-Toughness Poly(lactic Acid)/Starch Blends Prepared through Reactive Blending Plasticization and Compatibilization

In this study, poly(lactic acid) (PLA)/starch blends were prepared through reactive melt blending by using PLA and starch as raw materials and vegetable oil polyols, polyethylene glycol (PEG), and citric acid (CA) as additives. The effects of CA and PEG on the toughness of PLA/starch blends were analyzed using a mechanical performance test, scanning electron microscope analysis, differential scanning calorimetry, Fourier-transform infrared spectroscopy, X-ray diffraction, rheological analysis, and hydrophilicity test. Results showed that the elongation at break and impact strength of the PLA/premixed starch (PSt)/PEG/CA blend were 140.51% and 3.56 kJ·m⁻², which were 13.4 and 1.8 times higher than those of pure PLA, respectively. The essence of the improvement in the toughness of the PLA/PSt/PEG/CA blend was the esterification reaction among CA, PEG, and starch. During the melt-blending process, the CA with abundant carboxyl groups reacted in the amorphous region of the starch. The shape and crystal form of the starch did not change, but the surface activity of the starch improved and consequently increased the adhesion between starch and PLA. As a plasticizer for PLA and starch, PEG effectively enhanced the mobility of the molecular chains. After PEG was dispersed, it participated in the esterification reaction of CA and starch at the interface and formed a branched/crosslinked copolymer that was embedded in the interface of PLA and starch. This copolymer further improved the compatibility of the PLA/starch blends. PEGs with small molecules and CA were used as compatibilizers to reduce the effect on PLA biodegradability. The esterification reaction on the starch surface improved the compatibilization and toughness of the PLA/starch blend materials and broadens their application prospects in the fields of medicine and high-fill packaging.     

Synthesis and characterization of starch-graft-polycaprolactone as compatibilizer for starch/polycarprolactone blends

Polycaprolactone (PCL) was grafted onto starch through introduction of urethane linkages. The grafting reaction was carried out in two steps. The first step was the reaction of hydroxyl-terminated PCL with 2,4-tolylene diisocyanate. The isocyanate terminated PCL was then reacted with starch to obtain starch-graft-polycaprolactone (starch-g-PCL). The grafting reaction was confirmed by FT-IR spectroscopy. The compatibility of the starch/PCL blend was enhanced with a compatibilizer, starch-g-PCL, whose amount was 3 wt.-% of the blend. The tensile strength and morphology of the compatibilized blend were determined. It was found that the compatibilized starch/PCL blend has finer phase domains and an improved interfacial adhesion. Mechanical properties of the compatibilized blend were found to be significantly higher than those of the corresponding uncompatibilized starch/PCL blend.