PVA/淀粉薄膜挤出吹塑工艺及性能研究

采用挤出造粒和吹塑工艺连续制备了聚乙烯醇/淀粉薄膜.探讨了淀粉含量、增塑剂含量、增塑剂中水含量和混料条件对PVA/淀粉薄膜加工温度、熔体流动性和薄膜力学性能的影响.结果表明,随着淀粉含量的增加,增塑剂含量的增加,物料的加工温度降低;随着增塑剂中水含量的增加,挤出造粒温度升高,吹膜温度不变;PVA/淀粉共混物优选的造粒温度是165～180℃.吹膜温度是205～220℃;淀粉含量为35%～50%,增塑荆含量60份以上,增塑剂中的水含量为1/6～1/3时,共混物有较好的加工流动性;分批逐滴加入增塑剂并在80～110℃下混料,可以使PVA/淀粉充分溶胀.利于热塑性加工;淀粉含量为40%、增塑剂含量为60份、增塑剂中的水含量为33%时,薄膜力学性能最佳.     

PVA/淀粉共混物的动态流变行为和相转变

用复合增塑剂在哈克流变仪上制备了热塑性聚乙烯醇(PVA)/淀粉共混物,研究了共混体系的动态流变行为,观察了共混物的微观结构.结果表明: PVA/淀粉共混物熔体的动态流动行为与其组分的熔体类似,都表现为类固态行为,显示出假塑性流体的流动特征; PVA/淀粉熔体随着组成的变化存在一次相逆转,其复数黏度、储能模量和损耗模量均随着淀粉含量的变化出现了正-负偏差,这说明共混体系出现了相转变,转变点在淀粉质量分数为80% 处.     

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。     

热塑性淀粉/聚乳酸完全生物降解塑料的制备

研究以植物油为增塑剂通过双螺杆挤出机制备热塑性淀粉的方法,分析了挤出螺杆扭矩、热塑性淀粉黏度等技术指标,考察了植物油/淀粉质量比、植物油种类、加工温度对热塑性淀粉黏性的影响;将制备的热塑性淀粉和聚乳酸共混造粒,考察热塑性淀粉/聚乳酸质量比对共混材料的拉伸强度、断裂伸长率、弯曲强度的影响,并对共混材料进行DTA/DTG测试,观察其热性能。     

PVA/接枝改性淀粉热塑性生物降解材料的制备及应用

以过硫酸铵为引发剂,采用固相法合成了乙酸乙烯酯(VAC)/玉米淀粉接枝共聚物.将其与聚乙烯醇(PVA)、加工助剂在流变仪中共混,制备了PVA/接枝改性淀粉热塑性生物降解材料;分别研究了淀粉接枝共聚物对PVA/淀粉/接枝改性淀粉共混物的加工流动性、耐水性、力学性能和生物降解性能及形态结构的影响.结果表明,PVA/淀粉/接...     

全生物降解淀粉塑料的研究进展

介绍了全生物降解淀粉塑料的研究目的及意义,综述了热塑性淀粉塑料、淀粉/可降解聚合物共混物和淀粉/天然高分子共混物3种全生物降解淀粉塑料的研究进展,包括热塑性淀粉塑料的生产原理和优势、增塑剂的选择与配比对热塑性淀粉塑料的影响、淀粉与聚丁二酸丁二醇酯、聚乙烯醇、聚己内酯、聚乳酸、纤维素、木质素、蛋白质等共混后的性能。最后分析了全生物降解淀粉塑料研究中存在的问题,并对全生物降解淀粉塑料进行了展望。     

复合增塑体系对聚乙烯醇加工性能的影响

为实现聚乙烯醇(PVA)的熔融加工成型,将不同聚合度的2种PVA共混,并分别加入甘油/增塑剂1或甘油/增塑剂2复合增塑剂。X射线衍射仪、差示扫描量热仪及热失重分析仪等测试结果表明,复合增塑体系的加入使PVA的结晶度降低,熔点从225℃降低到206℃,热分解温度基本不变,PVA热塑性加工有望得到实现。     

淀粉基生物降解塑料制备研究进展

简介了热塑性淀粉(TPS)的性质,分别总结了TPS/聚乳酸(PLA)共混物、TPS/聚己内酯(PCL)共混物、TPS/醇酸共聚酯共混物、TPS/聚碳酸亚丙酯(PPC)共混物、TPS/聚乙烯醇(PVA)共混物等热塑性淀粉与合成聚合物共混体系研究现状,以及TPS与天然大分子的共混体系研究现状,并提出了淀粉基生物降解塑料目前存在的问题及今后发展方向。     

热塑性淀粉/黄麻复合材料的研究

以玉米淀粉为原料,以甘油和尿素为增塑剂制备了热塑性淀粉(TPS),并与黄麻(F)进行共混制备了复合材料(TPS/F).对共混条件以及黄麻用量对材料力学性能和耐水性的影响进行了研究.结果表明:在转矩流变仪中转速越高越有利于淀粉的塑化.以尿素为增塑剂制备的热塑性淀粉(UTPS)的拉伸强度(13 MPa)高于以甘油为增塑剂的热塑性淀粉(GTPS)的拉伸强度(7 MPa),而在加入黄麻后,当黄麻质量分数为20%时,GTPS/F的拉伸强度高达26.8 MPa,高于UTPS/F.黄麻的加入也提高了UTPS的耐水性,但GTPS的耐水性仍较差.     

乙酰淀粉/PBS/PVA共混体系流变性能及力学性能研究

采用转矩流变仪模拟了乙酰淀粉/聚丁二酸丁二醇酯(PBS)/聚乙烯醇(PVA)三元共混体系的挤出加工过程,考察了PBS/PVA比例、增塑剂、转速、温度对共混体系转矩流变性能的影响;通过电子扫描显微镜观察了共混物的表面形态,并进行了力学性能表征。结果表明:在160℃、转速15r/min条件下,每50phr乙酰淀粉加入10phr甘油、30phrPVA和10phrPBS,共混体系具有较好的流变性能;PVA和PBS的适量加入可有效改善共混物的力学性能。     

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.     

纳米SiO_2对聚乙烯醇/淀粉熔融吹塑薄膜性能的影响

用甘油和水为增塑剂对高醇解度聚乙烯醇和玉米淀粉复配增塑改性,并选用不同的纳米SiO2,对聚乙烯醇/玉米淀粉基体进行纳米改性,熔融吹塑制备聚乙烯醇/玉米淀粉/纳米SiO2薄膜。结果表明:加入纳米SiO2后,聚乙烯醇/玉米淀粉/纳米SiO2薄膜的拉伸性能显著提高,热性能也发生了较明显的变化;探讨了纳米SiO2对薄膜性能影响的机理。     

Plasma treatment for enhancing mechanical and thermal properties of biodegradable PVA/starch blends

Two series of biodegradaable polyvinyl alcohol (PVA)/starch blends, i.e., PVA with/without plasma treatment (PP/P series), were produced by single‐screw extruder. The influences of plasma pretreatment and PVA content on the tensile properties, thermal behaviors, melt flow index, and biodegradability of blends were investigated. PVA pretreated by plasma (PPVA) reacted with glycerol was found not only to mechanically strengthen the PPVA/starch blend but also to improve the compatibility of PPVA and starch. Compared with PVA/starch blends, the melt flow indices of PPVA/starch blends were improved significantly by 200–300% and their tensile strength also increased two‐to‐three‐fold. Thermogravimetry analysis (TGA) showed that the thermal stability of PPVA/starch (85/300g) blend was better than PVA/starch blend at processing temperature and outperformed than PVA and starch at high temperature. Both the PPVA/starch and PVA/starch blends finished biodegradation within 9–10 weeks in soil burial tests. The esterification reaction of PPVA and glycerol was characterized by FTIR spectroscopic measurement and TGA test. The morphologic evolutions of the blend during biodegradation were investigated carefully by scanning electron microscope (SEM) imaging. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermal,mechanical, and surface characterization of starch–poly(vinyl alcohol) blends and borax‐crosslinked films

Starch–poly(vinyl alcohol) (PVA) blends with different compositions were prepared and crosslinked with borax by in situ and posttreatment methods. Various amounts of glycerol and poly(ethylene glycol) with a molecular weight of 400 were added to the formulations as plasticizers. The pure starch–PVA blends and the crosslinked blends were subjected to differential scanning calorimetry, thermogravimetry, and X‐ray photoelectron spectroscopic studies. Broido and Coats–Redfern equations were used to calculate the thermal decomposition kinetic parameters. The tensile strengths and elongation percentages of the films were also evaluated. The results suggested that the glass‐transition temperature (T_g) and the melting temperature strongly depended on the plasticizer concentration. The enthalpy relaxation phenomenon was dependent on the starch content in the pure blend. The crosslinked films showed higher stability and lower T_g's than pure PVA and starch–PVA blends, respectively. High‐resolution X‐ray photoelectron spectroscopy provided a method of differentiating the presence of various carbons associated with different environments in the films. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1313–1322, 2005     

淀粉/PVA在自然土壤环境下的生物降解性能研究

将淀粉与聚乙烯(醇PVA进)行共混,研究了共混物在自然土埋环境中的生物降解过程。结果表明:淀粉的加入可促进PVA的微生物降解速度,使淀粉/PVA试样在120d后分解成小碎片,失重率达到67.8%;对降解不同时间的淀粉/PVA(60/40)片材进行DSC和TG测试发现,降解使材料结晶度和热稳定性提高,说明体系的降解是在无定形区开始的;淀粉/PVA试样的降解过程中,淀粉首先分解,然后是PVA的非晶部分,最后才是PVA的结晶部分。     

Studies on compatibility of biodegradable starch/polyvinyl alcohol blends

Compatibility of starch/polyvinyl alcohol (PVA) blends, prepared by solution cast method, is dependent on the blend composition. Crystallinity of the blend, as measured by X‐ray diffraction (XRD) and differential scanning calorimeter (DSC), decreases with increase in starch content. Thermogravimetric analysis (TGA) shows that the broadness in the peak width at the degradation region increases with increase in starch content in the starch/PVA blend. Dynamic mechanical thermal analysis (DMTA) reveal that the broadness of the relaxation peaks is due to the partial compatibility of the glycerol plasticized starch/PVA blends. The tensile property decreases with increase in starch content and the 30/70 starch/PVA blend shows maximum ductility in respect to both the percentage of elongation and energy at break. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Super‐tough biodegradable poly(vinyl alcohol)/poly(vinyl pyrrolidone) blends plasticized by glycerol and sorbitol

Tough biodegradable films were prepared using a poly(vinyl alcohol) (PVA)/poly(vinyl pyrrolidone) (PVP) (1:1) blend with plasticizers of glycerol (GLY), sorbitol (SOR), and their (one to one) mixture. We studied the effect of plasticization on the structural, thermal, and mechanical properties of the PVA/PVP blend films. Fourier transform infrared spectra indicated good miscibility of the two components due to the H‐bonding between the PVA and PVP molecules. The addition of plasticizers reduced the interaction between PVA and PVP, evidenced by an increase in the intensity of PVA diffraction peaks observed in the X‐ray diffraction (XRD) characterization. Thermal degradation of the blends increased as a function of the plasticizer used. GLY affected thermal degradation more than SOR and the mixtures. The incorporation of the plasticizers promoted the growth of PVA crystals as evidenced by XRD patterns and the enthalpy of fusion (ΔH_f) obtained by differential scanning calorimetry measurements. The introduction of SOR to the binary blend increased toughness seven times and imparted simultaneous and pronounced improvements to maximum tensile stress and elongation at break. This behavior holds out great promise for the development of a new generation of mechanically robust, yet thoroughly biodegradable materials that could effectively supplant conventional polymers in demanding applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46406.     

Dynamic mechanical properties of photopolymerizable poly(vinyl alcohol)–acrylate monomer blends

Dynamic mechanical properties of photopolymerizable poly(vinyl alcohol) (PVA)–monoacrylate blends were investigated by measuring dynamic shear modulus G′ and loss tangent, tan δ. The dynamic mechanical properties of the blends before being exposed to UV irradiation were governed by the weight percent of the monomers which act as plasticizers. On the other hand, the UV-irradiated blends seemed to be typical two-phase materials since they revealed two tan δ maxima whose positions were independent of the monomer content. Those two maxima were assigned to PVA and photopolymerized acrylates with reference to the dynamic mechanical data of PVA and a PVA-polyacrylamide polyblend. Those dynamic mechanical data suggested that insolubilization of the blend type photopolymers should be caused by a decrease in solubility due to graft polymerization of acrylate monomers onto PVA.     

Synthesis of starch‐based plastic films by electron beam irradiation

Starch‐based plastic films were prepared by the electron beam irradiation of starch and poly(vinyl alcohol) (PVA) in a physical gel state at room temperature. The influence of starch/PVA composition, irradiation dose, and plasticizer (glycerol) on the properties of the plastic films was investigated. The gel fraction of the starch/PVA films increased with both the radiation dose and PVA content in the plastic film and decreased with increasing glycerol concentration. The starch/PVA compatibility was determined by measurement of the thermal properties of the starch/PVA blends with various compositions with differential scanning calorimetry. The swelling of the starch/PVA films increased with increasing PVA content and decreasing irradiation dose. Mechanical studies were carried out, and the tensile strength of the films decreased at high starch ratios in the starch‐based mixture. This was due to the decrease in the degree of crosslinking of starch. Furthermore, when PVA, a biodegradable and flexible‐chain polymer, was incorporated into the starch‐based films, the properties of the films, such as the flexibility (elongation at break), were obviously improved. The tensile strength of the films decreased with increasing glycerol concentration, but elongation at break increased up to a maximum value at a 20% glycerol concentration, and then, it leveled off and decreased slightly. Biodegradation of the starch/PVA plastic films was indicated by weight loss (%) after burial in soil and morphological shape, which was detected by scanning electron microscopy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 504–513, 2007