接枝淀粉浆料生物降解性的研究

探讨接枝淀粉浆料接枝支链化学结构与接枝淀粉生物降解性的内在联系,为接枝淀粉浆料的分子结构设计奠定基础。以Fe⁽²⁺⁾-H_2O_2为引发剂,分别引发丙烯酸(AA)、丙烯酰胺(AM)、丙烯酸甲酯(MA)、丙烯酸乙酯(EA)、丙烯酸丁酯(BA)、甲基丙烯酸甲酯(MMA)和甲基丙烯酸丁酯(BMA)与玉米淀粉进行接枝共聚合,制备了淀粉接枝共聚物。采用扫描电镜(SEM)、热重分析(TGA)对淀粉接枝共聚物形态及热稳定性进行表征。然后以COD,BOD5及BOD5/COD为评价指标,探讨了接枝支链的化学结构与接枝淀粉浆料生物降解性的对应关系,并通过改变接枝率研究了接枝率对淀粉浆料的生物降解性的影响。结果表明,对淀粉进行接枝改性,能够提高淀粉的热稳定性。随着接枝支链结构单元烷基碳原子数的增加,接枝淀粉浆料的生物降解性下降;α-甲基的存在,不利于接枝淀粉浆料的生物降解性;接枝率与接枝淀粉浆料的生物降解性呈现负相关性。     

接枝淀粉浆料生物降解性的研究

探讨接枝淀粉浆料接枝支链化学结构与接枝淀粉生物降解性的内在联系,为接枝淀粉浆料的分子结构设计奠定基础。以Fe~(2+)-H_2O_2为引发剂,分别引发丙烯酸(AA)、丙烯酰胺(AM)、丙烯酸甲酯(MA)、丙烯酸乙酯(EA)、丙烯酸丁酯(BA)、甲基丙烯酸甲酯(MMA)和甲基丙烯酸丁酯(BMA)与玉米淀粉进行接枝共聚合,制备了淀粉接枝共聚物。采用扫描电镜(SEM)、热重分析(TGA)对淀粉接枝共聚物形态及热稳定性进行表征。然后以COD,BOD5及BOD5/COD为评价指标,探讨了接枝支链的化学结构与接枝淀粉浆料生物降解性的对应关系,并通过改变接枝率研究了接枝率对淀粉浆料的生物降解性的影响。结果表明,对淀粉进行接枝改性,能够提高淀粉的热稳定性。随着接枝支链结构单元烷基碳原子数的增加,接枝淀粉浆料的生物降解性下降;α-甲基的存在,不利于接枝淀粉浆料的生物降解性;接枝率与接枝淀粉浆料的生物降解性呈现负相关性。     

热塑性木薯淀粉/PVA/SiO_2共混材料的稳定性能研究

通过添加聚乙烯醇(PVA)、二氧化硅(SiO2)到木薯淀粉中,采用熔融密炼法制备热塑性木薯淀粉(TPS)/PVA/SiO2共混材料,研究共混材料的吸水性、生物降解与熔融行为。研究结果表明:随着SiO2用量的增加,TPS/PVA/SiO2共混体系的吸水率增加,TPS/PVA(1799)/SiO2共混材料的吸水率高于TPS/PVA(1788)/SiO2共混物。表面改性后SiO2的TPS/PVA/SiO2共混物的吸水率低于未改性SiO2。随着SiO2用量的增加,TPS/PVA/SiO2共混物的生物降解降低,共混物的熔融峰增高,而熔融焓降低。     

改性淀粉/LLDPE共混体系生物降解材料性能的研究

将自制接枝改性淀粉与LLDPE、玉米淀粉以及另外两种相容剂进行共混。通过对共混体系的形态结构、力学性能、流变性能、热性能以及对共混物薄膜的生物降解性能等的研究说明:复合相容剂MAH-g-PE+LA-g-starch的加入改善了淀粉和LLDPE的相容性,使得共混物体系具有适宜的拉伸强度及断裂伸长率;LLDPE/淀粉/(MAH-g-PE+LA-g-starch)共混物薄膜具有很好的生物降解性能。     

淀粉/PVA可生物降解塑料的研究进展

详细阐述了淀粉/PVA(聚乙烯醇)材料的生物降解机理,从淀粉预处理和PVA预处理这两方面分别对淀粉/PVA可生物降解塑料的热塑性及生物降解性研究进展进行了重点介绍,还对目前国内外淀粉/PVA材料的热塑加工方式进行了综述。     

异丁基乙烯基醚/马来酸酐共聚物改性聚乙烯醇的研究

采用异丁基乙烯基醚/马来酸酐共聚物对聚乙烯醇(PVA)进行共混改性,研究了改性 PVA 的耐水性及力学性能,发现改性后的 PVA 的耐水性及力学性能有明显提高,其中当异丁基乙烯基醚/马来酸酐共聚物的含量为2%时,共混薄膜的断裂伸长率达到300%。同时从增塑性及结晶性等多方面对共混体系的改性机理进行了分析。     

羟基丁酸-戊酸共聚物与聚丙烯酸丁酯的反应性共混

采用反应性共混的方法对羟基丁酸－戊酸共聚物进行改性,使具有生物活性的丙烯酸丁酯在羟基丁酸－戊酸共聚物上接枝聚合,达到提高产物机械性能的同时,保持其生物降解性的目的。系统地研究了反应条件和改性物配比对产物接枝率及共混材料相容性等的影响,发现加料顺序和丙烯酸丁酯用量对产物的接枝率和相容性有很大影响,丙烯酸丁酯含量为２０％～３０％,产物接枝率最高可达２０％以上;在加工时填充４％～６％的滑石粉补强,羟基丁酸－戊酸共聚物／丙烯酸丁酯复合材料的机械性能明显提高。     

马来酸酐接枝共聚物增容聚乳酸/改性淀粉复合材料的制备与性能研究

采用熔融共混方法制备聚乳酸/改性淀粉复合材料。研究了不同含量的马来酸酐接枝共聚物对聚乳酸/改性淀粉复合材料力学性能的影响,并且采用差示扫描量热(DSC)仪和扫描电子显微镜(SEM)对复合材料的微观结构进行分析。结果表明,马来酸酐接枝共聚物的加入改善了聚乳酸与淀粉的相容性,提高了复合材料的力学性能,添加量为0.5份时复合材料的拉伸强度提高了61.6%,断裂伸长率提高了53.1%,弯曲强度提高了104.7%,同时还能提高复合材料的热变形温度和耐水性;改性淀粉与聚乳酸两相紧密连接。     

选择性透过CO2气体PVA/淀粉膜制备及性能研究

对聚乙烯醇(PVA)/淀粉膜进行接枝改性,引入含有叔胺基团的甲基丙烯酸二甲氨基乙酯(DMAEMA),使其对CO₂气体具有选择性透过功能,并对CO₂透过量进行优化,研究其分子结构与性能的关系。红外光谱、X射线光电子能谱、原子力显微镜照片及透气测试结果证明,加入淀粉接枝DMAEMA共聚物后,PVA/淀粉改性膜对CO₂具有选择透过性。接枝共聚物的接枝率和添加量影响CO₂透过量,当添加1.5%(质量分数,下同)的接枝率为55.3%的接枝共聚物,膜的CO₂透过量由1.577 cm³/(m²·24 h·0.1 MPa)提高到45.786 cm³/(m²·24 h·0.1 MPa),提高了28.03倍。X射线光电子能谱测试结果显示,改性膜透过CO₂后,N1s谱图中399.8 eV处的结合能减小,在401.8 eV结合能增大,可能CO₂与膜上叔胺基团发生反应,实现...     

羟基丁酸—戊酸共聚物与聚内烯酸丁酯的反应性共混

采用反应性共混的方法对羟基丁酸－戊酸共聚物进行改性，使具有生物活性的丙烯酸丁酯在羟基丁酸－戊酸共聚物上接枝聚合，达到提高产物机械性能的同时，保持其生物降解性的目的。系统地研究了反应条件和改性物配比对产物接枝率及共混材料相容性等的影响，发现加料顺序和丙烯酸丁酯用量对产物的接枝率和相容性有很大影响，丙烯酸丁酯含量为２０％￣３０％，产物接枝率最高可达２０％以上；在加工时填充４％￣６％的滑石粉补强，羟基丁     

淀粉基聚乙烯醇完全生物降解塑料薄膜的结构与性能

通过优化工艺条件，制备了高淀粉填充量的淀粉／聚乙烯醇完全生物降解塑料薄膜，研究了提高淀粉用量对淀粉／聚乙烯醇（PVA）完全生物降解塑料薄膜的力学性能和耐水性影响；并分析了耐水改性助剂尿素用量对薄膜的吸水率和生物降解性能的影响。结果表明，通过先糊化、后共混、再交联的薄膜制备工艺过程，能够获得高淀粉填充量的淀粉／聚乙烯醇完全生物降解塑料薄膜；先糊化打破了淀粉颗粒的原有形态结构，促进了淀粉与聚乙烯醇的共混相容性，从而获得了优良的力学性能；耐水改性助剂尿素的使用，能够大幅度地降低材料的吸水率，同时提高材料的生物降解性和环境友好程度。     

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     

PVAL/改性淀粉复合发泡材料的制备及性能

以玉米淀粉为原料,通过丙烯酸塑化改性法制备玉米改性淀粉。以柠檬酸和NaHCO_3作为复合发泡剂,甘油、二乙醇胺和山梨醇作为复合增塑剂改性聚乙烯醇(PVAL),与改性淀粉辅以其它加工助剂,利用模压成型发泡制备了一种可生物降解的PVAL/改性淀粉复合发泡材料。重点探究了改性淀粉含量对复合发泡材料生物降解性能和发泡形态的影响,NaHCO_3发泡剂含量对复合材料耐水性能、力学性能和发泡性能的影响,助剂滑石粉含量对复合材料发泡性能的影响。结果表明,当改性淀粉质量分数为40%,复合发泡剂NaHCO_3、滑石粉及柠檬酸质量分数均为4.0%时,所得发泡材料的生物降解性能较好,拉伸强度为2.134 MPa,断裂伸长率为79.1%,泡孔分布均匀,泡孔结构良好,形状较规整。     

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。     

SA/PVA可降解复合塑料膜的制备与性能研究

对木薯原淀粉进行乙酰化改性,合成低酯化度的木薯淀粉醋酸酯(SA);经增塑、交联后与聚乙烯醇(PVA)合成可降解的SA/PVA复合塑料膜,重点研究了PVA、甘油、乙二醛的用量及SA的酯化度对复合膜力学性能的影响,并对复合膜性能进行了表征。结果表明:在PVA质量分数为40%,甘油质量分数为14%,乙二醛质量分数为4%时,可以得到力学性能较好的复合塑料膜;与原淀粉/PVA复合膜相比,复合膜致密性提高,玻璃化转变温度降低,结晶度下降,表现出更好的力学性能。     

Hybrid composite based on poly(vinyl alcohol) and fillers from renewable resources

Hybrid composite laminates consisting of polyvinyl alcohol (PVA) as continuous phase (33% by weight) and lignocellulosic fillers, derived from sugarcane bagasse, apple and orange waste (22% by weight) were molded in a carver press in the presence of water and glycerol such as platicizers agents. Corn starch was introduced as a biodegradation promoter and gluing component of the natural filler and synthetic polymeric matrix in the composite (22% by weight). The prepared laminates were characterized for their mechanical properties and degradative behavior in simulated soil burial experiments. The fibers type and content in composite impacted mechanical properties. Materials based on PVA and starch with apple wastes and sugarcane bagasse fillers were much harder (Young's Modulus respectively, 57, 171 MPa) than materials prepared with orange wastes (17 Mpa). Respirometric test revealed that soil microbes preferentially used natural polymers and low molecular weight additive as a carbon source compared to biodegradable synthetic polymer. The presence of PVA in formulations had no negative effect on the degradation of lignocellulosic fibers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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。     

Mechanical Behavior and Biodegradation of Poly(ε-caprolactone)/Starch Blends with and without Expansor

Summary The use of biodegradable polymers has provided an alternative to the problem of polymer-based products discarded in the environment. Poly(ε-caprolactone) (PCL) is a biodegradable polymer that has been used industrially, but it is very expensive. Starch is a potentially useful material for biodegradable plastics because of its natural abundance and low cost. The aim of this work was to examine the effect of adding azodicarbonomide (ADC) as an expansor to blends of PCL with corn starch. Different proportions, of ADC (0.1%, 0.2% and 0.3%, w/w) were added to pure PCL and to PCL/starch (50/50) blends and their properties were studied. Biodegradable blends of PCL with starch had a higher density than PCL alone and the addition of ADC reduced the density of the materials. The incorporation of starch increased the water absorption and ADC did not significantly alter this property. The incorporation of starch into PCL reduced the tensile strength and the elongation at break; ADC enhanced these reductions and also decreased the Young’s modulus of PCL. SEM showed that blends prepared with starch were immiscible, had a homogeneous dispersion of starch, and poor interfacial adhesion. The addition of ADC resulted in cells in the interior of the polymers. The 50/50 PCL/starch blends biodegraded faster than PCL, and ADC had no significant influence on the biodegradation of the blends but inhibited the biodegradation of PCL.     

Mixture design applied for the development of films based on starch,polyvinyl alcohol,and glycerol

Starch and polyvinyl alcohol (PVA) are biodegradable materials with potentiality to replace the conventional polymers in some applications. The aim of this work was to produce biodegradable films of PVA, cassava starch, and glycerol by thermoplastic extrusion using a mixture design to evaluate the effects of each component in the blend properties. Six formulations were prepared using a twin‐screw extruder coupled with a calender. All the materials were visually homogeneous and presented good processability. Mechanical properties were dependent on both the relative humidity conditioning and the formulation; higher relative humidities detracted the mechanical properties, which was associated to plasticizer effect of the water. Furthermore, the mechanical properties were better when higher concentrations of PVA were used, resulting in films with lower opacity, lower water vapor permeability, and higher thermal stability, according to TGA. Biodegradable materials based on starch, PVA, and glycerol have adequate mechanical and processing properties for commercial production. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42697.     

Characterization of linear low‐density polyethylene/poly(vinyl alcohol) blends and their biodegradability by Vibrio sp. isolated from marine benthic environment

Increasing amounts of plastic waste in the environment have become a problem of gigantic proportions. The case of linear low‐density polyethylene (LLDPE) is especially significant as it is widely used for packaging and other applications. This synthetic polymer is normally not biodegradable until it is degraded into low molecular mass fragments that can be assimilated by microorganisms. Blends of nonbiodegradable polymers and biodegradable commercial polymers such as poly (vinyl alcohol) (PVA) can facilitate a reduction in the volume of plastic waste when they undergo partial degradation. Further, the remaining fragments stand a greater chance of undergoing biodegradation in a much shorter span of time. In this investigation, LLDPE was blended with different proportions of PVA (5–30%) in a torque rheometer. Mechanical, thermal, and biodegradation studies were carried out on the blends. The biodegradability of LLDPE/PVA blends has been studied in two environments: (1) in a culture medium containing Vibrio sp. and (2) soil environment, both over a period of 15 weeks. Blends exposed to culture medium degraded more than that exposed to soil environment. Changes in various properties of LLDPE/PVA blends before and after degradation were monitored using Fourier transform infrared spectroscopy, a differential scanning calorimeter (DSC) for crystallinity, and scanning electron microscope (SEM) for surface morphology among other things. Percentage crystallinity decreased as the PVA content increased and biodegradation resulted in an increase of crystallinity in LLDPE/PVA blends. The results prove that partial biodegradation of the blends has occurred holding promise for an eventual biodegradable product. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012