尿素/甲酰胺增塑PVA的性能研究

采用流延成膜法制备了以尿素/甲酰胺为复配增塑剂改性的聚乙烯醇(PVA)改性薄膜。采用FTIR研究了复配增塑剂尿素/甲酰胺和PVA之间的相互作用,采用XRD、DSC、TGA和拉伸性能测定对改性后的PVA膜性能进行了测试表征。结果表明,尿素/甲酰胺能与PVA形成氢键作用,破坏PVA的结晶结构,降低PVA膜的结晶度。尿素/甲酰胺的加入降低了PVA的熔点,提高了PVA的热分解温度。改性后的PVA膜的拉伸强度降低,断裂伸长率提高。     

长链乙烯酯改性聚乙烯醇热塑加工性能的研究

通过山梨醇和甘油复配增塑改善长链乙烯酯改性聚乙烯醇(PVA)的热塑加工性能,采用差示扫描量热仪、高压毛细管流变仪、万能试验机等研究了复配增塑剂与改性PVA的相互作用及其对改性PVA热性能、流变性能、力学性能、溶胀性能等的影响。结果表明,山梨醇和甘油复配增塑剂中的羟基可与改性PVA分子链中的羟基形成氢键,减小了PVA分子链间氢键相互作用,使体系黏度减小,分子链的活动性增强,降低了改性PVA熔点,改善了PVA熔体流动性,有利于实现PVA的热塑加工。复配增塑剂增加了PVA的自由体积,使PVA分子链的运动更加容易,提高了材料的柔韧性及断裂伸长率,减少PVA对水的吸收。当增塑剂含量为10%时,复配增塑剂不易析出,可同时改善改性PVA的流变性并使材料保持优异的力学性能。     

TPS/PVA共混物的热降解行为

以热塑性木薯淀粉(TPS)为研究对象,甘油或甲酰胺/尿素为增塑剂,通过熔融共混法制备TPS/聚乙烯醇(PVA)共混物,利用热重分析仪研究增塑剂种类、用量及PVA对TPS热降解行为的影响。结果表明:添加甘油的TPS热降解温度高于添加甲酰胺/尿素复配增塑剂;随着甘油用量的增加,TPS热降解温度降低;添加PVA后,TPS热降解温度降低,且随着PVA用量的增加而降低;TPS热降解过程分为3个阶段,TPS/PVA共混物的热降解分为4个阶段;随着升温速率的增加,TPS的热降解温度升高;采用Kissinger研究了TPS/PVA共混物的热降解动力学,PVA的加入降低了TPS的热降解活化能。     

己内酰胺/氯化镁复配增塑聚乙烯醇的性能研究

采用己内酰胺/氯化镁为复配增塑剂,通过流延法制备出了增塑改性的聚乙烯醇(PVA)膜。采用DSC、TGA、XRD分析和力学性能与熔体流动性能测试的方法考察了己内酰胺/氯化镁复配增塑剂对PVA性能的影响。结果表明:氯化镁与己内酰胺复配具有良好的协同增塑效应,其对PVA的增塑效果优于单独使用己内酰胺;复配增塑剂能够有效破坏PVA分子间的氢键,降低PVA的结晶度;加入复配增塑剂后,PVA的熔点降低,热稳定性提高,熔体流动性有所改善,拉伸强度降低,断裂伸长率上升。     

热塑性木薯淀粉/聚乙烯醇复合材料的制备、结构与性能研究

采用熔融法制备热塑性木薯淀粉(TPS)/聚乙烯醇(PVA)复合材料,研究PVA和增塑剂的种类、用量对TPS/PVA复合材料的加工、力学性能、回生行为及结构影响。研究结果发现随着PVA用量的增加,TPS/PVA复合材料的塑化时间缩短、塑化扭矩和平衡扭矩增大;随着甘油增塑剂用量的增加,TPS/PVA复合材料的塑化时间、扭矩降低。TPS/PVA-1788复合材料的塑化时间、塑化扭矩和平衡扭矩均比TPS/PVA-1799复合材料的小;采用尿素/甲酰胺复配增塑TPS/PVA复合材料的塑化时间、塑化扭矩和平衡扭矩比使用甘油小。随着PVA用量的增加,TPS/PVA复合材料的拉伸强度增加;TPS/PVA-1799复合材料的拉伸强度比TPS/PVA-1788复合材料的高。使用甘油增塑TPS/PVA复合材料的拉伸强度高于使用尿素/甲酰胺复配增塑剂。随着回生时间增加,TPS/PVA复合材料的回生焓增加。添加PVA加速TPS的回生过程,随着PVA用量进一步增加,TPS/PVA复合材料回生降低。PVA能削弱TPS的氢键作用,提高TPS塑化程度,有利于TPS/PVA复合材料的均匀性。     

复配增塑剂改性聚乙烯醇的热塑加工性能研究

以甘油/二缩三乙二醇(GP)为主增塑剂,N-甲基吡咯烷(NMP)辅助增塑剂,对聚乙烯醇(PVA)进行增塑改性,研究了增塑剂类别和配比对PVA的增塑效果。通过红外光谱分析(FTIR)研究了复配增塑剂与PVA间的相互作用,采用X射线衍射分析(XRD)、差示扫描量热分析(DSC)、热失重分析(TGA)表征了改性PVA的结晶性能和热性能,采用熔融指数仪和转矩流变仪研究了改性后PVA的热塑加工性能。结果表明:复配增塑剂能有效地破坏PVA自身的氢键,降低PVA的熔融温度和结晶度,改善PVA的热塑加工性能,并成功实现了改性PVA的注塑成型。通过注塑成型的PVA具有较好的力学性能,拉伸强度为28.6 MPa,断裂伸长率为534%。     

PVA增塑性能正交试验研究

利用正交试验设计增塑剂与聚乙烯醇(PVA)共混配方,并进行熔融共混模压成型制备增塑PVA薄膜,通过对薄膜的力学性能、熔点、耐水性等性能进行测试,运用正交试验法研究复配增塑剂配方中蒸馏水、甘油、己内酰胺和二甲基亚砜的用量对薄膜拉伸强度、熔点和吸水率的影响。结果表明:增塑改性PVA的复配增塑配方中己内酰胺对拉伸强度影响程度最大,蒸馏水对熔点和吸水率的影响较大。较优的改性PVA复配增塑剂配方为:蒸馏水10 g,甘油10 g,己内酰胺20 g,二甲基亚砜8 g。     

淀粉/三聚氰胺增塑PVA熔融加工膜的制备及性能

以淀粉/三聚氰胺为复配增塑剂,利用熔融加工工艺制备聚乙烯醇(PVA)膜,采用差示扫描量热(DSC)、热失重分析(TG)和力学性能测试等考察了增塑剂含量对PVA膜性能的影响.结果表明,复配增塑剂能有效破坏分子链间氢键,对PVA的增塑作用明显.随增塑剂含量增大,PVA膜的力学性能和熔体质量流动速率呈先增大后减小的趋势,熔点...     

碳酸钙高填充聚乙烯醇复合材料热塑加工性能研究

采用分子复合和增塑,以水、多元醇和含酰胺基团化合物组成复配增塑剂,通过热塑加工制备了碳酸钙(CaCO3)高填充聚乙烯醇(PVA)复合材料,采用差示扫描量热仪(DSC)、热重分析(TG)、高压毛细管流变仪等研究了复合材料的热性能、流变性能,探讨了复合材料中增塑剂的迁移率及其对制品尺寸稳定性的影响。结果表明,通过分子复合和增塑后,改性PVA及PVA/CaCO3复合材料获得较宽热塑加工窗口,当CaCO3含量为70%时热塑加工窗口达85.5℃;PVA/CaCO3复合材料的熔体为假塑性流体,其黏度满足传统挤出或注塑加工的黏度需要;随环境湿度增加,复合材料中增塑剂迁移率增加,CaCO3可抑制复合材料中增塑剂的迁移,一定程度上提高了复合材料的尺寸稳定性。     

PVA/PTMG共混膜制备及性能研究

采用流延成膜的方法制备了聚乙烯醇(PVA)/聚四氢呋喃(PTMG)共混薄膜,当PTMG摩尔分数小于8%时,可以得到均一连续的共混膜。通过拉伸测试和示差扫描量热仪(DSC)等手段对PVA/PTMG共混膜的性能进行了研究。实验结果表明,PTMG可以与PVA形成分子间氢键,破坏了PVA分子内及分子间氢键,进而改善了PVA薄膜的性能。     

Effect of urea and formamide plasticizers on starch/PVA bioblend sheets

The starch/polyvinyl alcohol (PVA) bioblend sheets containing urea and formamide as plasticizers were prepared through melt processing in presence of water. The experiments indicated that urea and formamide plasticizers could form strong hydrogen bonds with starch/PVA molecules. Urea exhibited better plasticizing effect than formamide. Urea also could greatly destroy the crystal structures of PVA component in the blends, leading to the decreased crystallinity of the blends. Formamide was a good solvent for urea and could prevent urea separating from the blends, resulting in the improved stability of plasticizing systems. The blends exhibited good flexibility. Therefore, the incorporation of both urea and formamide into starch/PVA blends could exhibit synergistic effects to ensure the blends with both good plasticizing effect and the stability of the plasticizing systems. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42311.     

Structural changes of starch/polyvinyl alcohol biocomposite films reinforced with microcrystalline cellulose due to biodegradation in simulated aerobic compost environment

Starch/Polyvinyl alcohol (PVA) based biocomposite films reinforced with micro crystalline cellulose (MCC) (10 wt %) particles were prepared by solution casting method, incorporating glycerol as plasticizer. These biocomposite films were subjected to biodegradation at ambient temperature in a simulated aerobic compost pit. The extent of biodegradation of these films was studied in terms of weight loss. The corresponding changes in the structure of the films were observed using scanning electron microscopy, X‐Ray diffraction study, and differential scanning calorimetry. The melting point of PVA component of the biocomposite film shifted from 204 to 223°C with increase in biodegradation time and a remarkable difference was observed in their melt crystallization behavior. The unreinforced films also showed a similar trend, but the increase in the crystallinity of PVA was more pronounced in MCC reinforced films than that observed in the unreinforced ones. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Development of polyvinyl alcohol/intercalated MMT composite foams fabricated by melt extrusion

In this work, novel polyvinyl alcohol (PVA)/intercalated montmorillonite (MMT) nanocomposite foams were fabricated by melt extrusion with fixed amount of foaming agent, and the structure and properties were investigated with X‐ray diffraction, transmittance electron microscope, differential scanning calorimetry, plate rheometer, scanning electron microscope, density analysis, and mechanical testing in detail. The results revealed that pristine MMT could be intercalated by PVA during melt‐extrusion. Both exfoliation and intercalation structure was formed in the composites. The strong interaction between PVA and MMT restricted the motion of PVA molecules, leading to the enhanced complex viscosity, storage modulus, and melt flow index, suggesting the improved melt elasticity and melt strength. The improved melt strength of PVA through MMT incorporation facilitated the foaming process. With the increase of MMT, cell rupture was limited and the thickness of cell‐wall decreased, leading to the decreased density. The homogeneous cells and the closed cell structure with the foaming density of 0.35 g/cm³ could be formed with 2 wt % MMT incorporation. With the increase of MMT, the tensile strength of PVA/MMT foams decreased because of the enlarged foaming ratio and decreased density. This work aims to pave a simple and convenient way to produce biodegradable foams. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42706.     

Studies on the properties of poly(vinyl alcohol) film plasticized by urea/ethanolamine mixture

This study investigated the effects of urea/ethanolamine mixture (UE) on the crystallinity, thermal, and mechanical properties of poly(vinyl alcohol) (PVA) films. PVA films were prepared from solutions containing PVA, urea, ethanolamine, and water by casting and evaporating at 50°C for 12 h. The plasticization efficiency of UE was compared with that of glycerol (GL), the conventional plasticizer for PVA. The properties of PVA films plasticized by UE and GL, abbreviated to UE-plasticized PVA film and GL-plasticized PVA film, respectively, were investigated by Fourier-transform infrared spectroscopy, X-ray diffraction, differential scanning calorimetry, thermogravimetric analysis, and mechanical testing. It was proved that UE could form more stable hydrogen bonding with the hydroxyl group of PVA molecule and was more effective in breaking the hydrogen bonds between the hydroxyl groups. Thus, the crystallinity of UE-plasticized PVA films was lower than that of GL-plasticized PVA films. The melting temperatures of UE-plasticized PVA films were lower than those of GL-plasticized PVA films. It was found that UE-plasticized PVA film showed a higher degradation temperature compared with GL-plasticized PVA film. The degree of swelling of UE-plasticized PVA film was higher than that of GL-plasticized PVA film but solubility (S) of UE-plasticized PVA film was lower in aqueous solution. Furthermore, UE-plasticized PVA films show lower tensile strength and higher elongation at break (E) than those of GL-plasticized PVA films. The tensile strength, E, and Young's modulus of PVA film containing 30% UE mixture reached 50.78 MPa, 591.19% and 76.9 MPa, respectively. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and properties of novel polyvinyl alcohol–lactic acid gels

This article describes a process for esterifying polyvinyl alcohol (PVA) with L‐lactide (LLA) and D,L‐lactic acid (LA), using ethyl acetate and N,N′‐dimethyl formamide at temperatures varying from 120 to 150°C. The grafting process was carried out under nitrogen to avoid possible oxidation or other degradation of the process ingredients and product. Lower T_g values were obtained for the PVA/LLA graft copolymers of higher LLA content suggesting some compatibility in the amorphous phase. Higher T_g values were observed for PVA/LA graft copolymers that yielded tough polymer films. The structure of the copolymers was studied by solid‐state ¹³C‐NMR, infrared spectroscopy, and differential scanning calorimetry (DSC). The PVA/LA films exhibited melt processability and good mechanical properties such as yield strength, tensile energy at break, modulus, and elongation at break. The polymer films produced through compression molding at 100°C showed good swelling properties. The transport coefficient (n) values determined from the plot of log(M_t/M_∞) vs. log t indicate Fickian behavior, and they are consistent with the reported literature values for other PVA systems. The nature of water in gels [bound water (W_b), freezing (W_f), and freezing bound (W_fb), and water content (W_t)] was evaluated from DSC data. The results demonstrate that PVA/LA hydrogels with good combination of thermal, physicomechanical, and swelling properties can be prepared via the lactic acid esterification of PVA polymer process described. Besides being melt processable, the PVA/LA gels exhibit a melting point, which indicates possibly use of higher temperatures. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Fabrication of water‐soluble poly(vinyl alcohol)‐based composites with improved thermal behavior for potential three‐dimensional printing application

Water‐soluble support materials are essential for fabrication of three‐dimensional printing component, in particular of fused deposition modeling (FDM) process. Poly(vinyl alcohol) (PVA) was considered as a potential ideal candidate used in rapid prototyping technology, while its properties and process‐ability need to be improved for the wide application. This article attempts to use urea/caprolatam (UC) as modification additive for tuning the thermal and mechanical properties of PVA. PVA‐based films with different content of additives were prepared by solution casting method. The results showed that with the increase of UC, PVA films showed decreased crystallinity and melting temperature, while the initial degradation temperature and melt index were increased. The corporation of UC decreased the melting temperature to 173.04 °C and PVA composite with 4.5% crystallinity was fabricated. Due to the formation of hydrogen bonding between UC and the hydroxyl group of PVA, the tensile strength and modulus of PVA were slightly decreased, while strain‐at‐break was significantly enhanced, as high as 470.24%, indicating UC behaved as good plasticizing effect. The microstructure examination via scanning electron microscopy showed that when the content of UC was less than 30% in the composites, homogeneous phase could be observed, indicating good compatibility between these two components. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44966.     

季铵醚化-辛烯基琥珀酸酯化淀粉与PVA共混膜力学性能研究

为克服淀粉膜脆且硬的缺陷,制备季铵醚化-辛烯基琥珀酸酯化淀粉（QAS）,并将它与聚乙烯醇（PVA）进行混合来制备共混膜;用X射线衍射仪进行共混膜结晶度测定,用扫描电子显微镜观察共混膜的表面形貌,研究QAS/PVA共混比和PVA结构对共混膜力学性能的影响。结果表明,QAS/PVA共混膜的结晶度比QAS膜的结晶度有所降低;随着QAS含量的增加,共混膜的断裂伸长率逐渐减小,断裂强度先减小后增大,当QAS/PVA共混比为50/50（质量比,下同）时,断裂强度达到最小值;随着PVA聚合度和醇解度的增加,共混膜的断裂强度和断裂伸长率也随之增大。     

Structure‐property and swelling behavior of electron beam irradiated poly(vinyl alcohol)/acrylamide/sodium montmorillonite clay composites

Composites based on poly(vinyl alcohol) (PVA), acrylamide monomer (AM) and sodium montmorillonite clay (MMT) were prepared, in the form of thin films, by solution casting. The PVA/AM/MMT composites films were then exposed to electron beam irradiation to form crosslinked network structure. The structure‐property behavior of PVA/AM/MMT hybrids was demonstrated by x‐ray diffraction (XRD), scanning electron microscopy, gel content, color intensity, thermogravimetric analysis (TGA) and swelling behavior in aqueous solutions. The results indicated that the introduction of MMT clay ratio up to 5% decreased the gel content of PVA/AM hydrogels. The color measurements indicated that the introduction of MMT clay ratio up to 5% was shown to affect the color intensity of composite films. It was found that both PVA/AM hydrogels and PVA/AM/MMT composites reached the equilibrium swelling state in water after four hours; however PVA/AM/MMT composites displayed higher swelling than PVA/AM hydrogels. However, the swelling of PVA/AM hydrogels or their composites at the equilibrium state increased with increasing temperature up to 60°C. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011