The Effect of Plasticizers on the Properties of Polyvinyl Alcohol Films

Abstract

The effect of water-soluble plasticizers viz propylene glycol (PG), glycerol and polyethylene glycol 600 (PEG) on the morphology and water resistance of polyvinyl alcohol (PVA) films was investigated. Polyvinyl alcohol films were cast from aqueous solutions, and their morphology studied using differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). Water resistance was characterized by the extent of film dissolution and the water uptake capacity of remnant films after immersion of the films in distilled water for 3 days at 37° C. DSC thermograms showed that crystallite formation in the PVA films was affected to different extent by addition of the three plasticizers. The plasticizers not only reduced the degree of crystallinity in the films, but also lowered the crystalline melting temperatures probably by introducing defects into the crystal lattice. This factor, coupled with leaching of the water-soluble plasticizers from the films when immersed in distilled water, lowered the water resistance of the plasticized PVA films. The influence of plasticizers on the properties of PVA films was further related to the degree of compatibility between the plasticizers and PVA.     

Drug release from heat-treated polyvinyl alcohol films

Polyvinyl alcohol (PVA) films containing 10% w/w of a model drug, sulphathiazole, were cast from aqueous solutions and subjected to heat treatment at specific temperatures for known periods of time. Heat treatment at temperatures above the T_g of the PVA films slowed down the rate of drug release from the films. Increasing the temperature of heat treatment from 120°C to 160°C further decreased the rate of drug release. On the other hand, if the heat treatment were conducted at a temperature below the T_g e.g. at 80°C, there were insignificant differences between the release profile of sulphathiazole from heat-treated films and that from untreated films. The duration of heat treatment affected the rate of drug release to a smaller extent compared to the temperature of heat treatment. These results correlated with the heat induced changes in the morphology of, and in the extent of water uptake by the PVA films.     

Drug release from heat-treated polyvinyl alcohol films

Abstract

Polyvinyl alcohol (PVA) films containing 10% w/w of a model drug, sulphathiazole, were cast from aqueous solutions and subjected to heat treatment at specific temperatures for known periods of time. Heat treatment at temperatures above the T_g of the PVA films slowed down the rate of drug release from the films. Increasing the temperature of heat treatment from 120°C to 160°C further decreased the rate of drug release. On the other hand, if the heat treatment were conducted at a temperature below the T_g e.g. at 80°C, there were insignificant differences between the release profile of sulphathiazole from heat-treated films and that from untreated films. The duration of heat treatment affected the rate of drug release to a smaller extent compared to the temperature of heat treatment. These results correlated with the heat induced changes in the morphology of, and in the extent of water uptake by the PVA films.     

增塑剂对马铃薯淀粉基复合膜物理机械性能的影响

以马铃薯淀粉、普鲁兰多糖、明胶为成膜物质,氯化钙为交联剂,甘油、山梨醇、聚乙二醇为增塑剂,采用流延法制备了马铃薯淀粉基复合膜,研究了3种增塑剂对复合膜物理机械性能的影响。结果表明:复合膜的抗拉强度和弹性模量均随增塑剂含量的增加而显著减小,断裂伸长率随甘油和山梨醇含量的增加而显著增加,聚乙二醇对其影响不显著;复合膜的水蒸气透过率和水溶性均随增塑剂含量的增加而增加;聚乙二醇能够显著降低复合膜的透光率。     

完全醇解型PVA包装薄膜的耐水性研究

目的在保持聚乙烯醇(PVA)良好的水溶性、成膜性及生物降解性的基础上,提高聚乙烯醇薄膜的耐水性。方法采用完全醇解型PVA制备水溶性PVA包装薄膜,对薄膜进行化学交联处理、热处理,以及化学交联处理及热处理相结合等3种方式,研究其对薄膜结构和性能的影响。结果经饱和硼酸溶液化学交联处理后,PVA薄膜的吸湿率明显降低,大致可以确定硼酸浴液的最佳温度为70℃,最佳浸渍时间为5 min;经热处理后的PVA薄膜耐水性得到改善。结论经2种方式综合处理的PVA薄膜,既发生了化学交联又产生了结晶结构,其分子内亲水性羟基数量减少的同时,分子链的排列也更加规整有序,与单一处理方式相比,耐水性能得到较大改善。     

高性能改性聚乙烯醇薄膜的制备及性能表征

作为可生物降解型的聚乙烯醇薄膜,其环保特性已得到了全世界的广泛承认,但是由于聚乙烯醇分子中含有大量的亲水性基团,导致成膜的耐水性差,这很大程度上限制了它的推广和应用。通过采用戊二醛、尿素对聚乙烯醇进行缩醛交联,并通过添加不同种类的增塑剂(丙三醇、PEG-400、MgCl2)破坏PVA的氢键作用,降低其结晶度,从而达到增塑改性效果,最后通过红外光谱FTIR、热重TG分析、物理机械性能以及接触角来鉴定物质的结构以及对其性能进行表征。结果表明:通过戊二醛、尿素与PVA羟基缩醛交联反应可以提高PVA成膜的耐水性能和热稳定性能,丙三醇、PEG-400、MgCl2等可以提高PVA的断裂伸长率和拉伸强度,当涂膜中交联剂戊二醛4%、尿素0.5%,增塑剂丙三醇4%、PEG-400为6%、MgCl2为2%时,成膜的机械性能最优,断裂伸长率达136.7%,拉伸强度达3.48MPa。     

Mechanical and Water Vapor Transmission Properties of Polysaccharide Films

The film-forming properties of chitosan, chitosan glutamate, sodium alginate, and hydroxypropyl methylcellulose (HPMC) were investigated. Films were produced by a casting/solvent evaporation method from plasticizer-free and plasticizer-containing aqueous solutions. The water vapor transmission and mechanical properties (puncture strength and % elongation) of the films were investigated as a function of the polymer type and viscosity, plasticizer type (glycerin, propylene glycol, polyethylene glycol, triethyl citrate), plasticizer concentration, and type and concentration of acid used to dissolve chitosan. The effect of storage humidity was also examined. Glycerin and water were good plasticizers for chitosan glutamate. The chitosan film properties were dependent on the type and concentration of acid used to dissolve it, citric acid being a good plasticizer. The mechanical and water vapor transmission properties of alginate and HPMC films were less influenced by the investigated variables.     

Mechanical and Water Vapor Transmission Properties of Polysaccharide Films

Abstract

The film-forming properties of chitosan, chitosan glutamate, sodium alginate, and hydroxypropyl methylcellulose (HPMC) were investigated. Films were produced by a casting/solvent evaporation method from plasticizer-free and plasticizer-containing aqueous solutions. The water vapor transmission and mechanical properties (puncture strength and % elongation) of the films were investigated as a function of the polymer type and viscosity, plasticizer type (glycerin, propylene glycol, polyethylene glycol, triethyl citrate), plasticizer concentration, and type and concentration of acid used to dissolve chitosan. The effect of storage humidity was also examined. Glycerin and water were good plasticizers for chitosan glutamate. The chitosan film properties were dependent on the type and concentration of acid used to dissolve it, citric acid being a good plasticizer. The mechanical and water vapor transmission properties of alginate and HPMC films were less influenced by the investigated variables.     

The influence of different plasticizers and polymers on the mechanical and thermal properties, porosity and drug permeability of free shellac films

The effect of triethyl citrate (TEC) and different molecular weights and concentrations of polyethylene glycol (PEG), in addition to the effect of different water-soluble polymers and dispersions at different levels, hydroxypropyl methylcellulose (HPMC), methylcellulose (MC), carbomer 940, polyvinyl alcohol (PVA), ethyl cellulose (EC), on the mechanical and thermal properties, drug permeability, and porosity of free shellac films were investigated. Shellac films were cast from aqueous solutions, and their mechanical properties were studied by tensile test. Thermal analyses were performed using differential scanning calorimetry (DSC).

The results showed that the addition of plasticizer caused a decrease in both elastic modulus and glass transition temperature (T_g) and an increase in elongation at break of free shellac films. This effect was related to the concentrations of plasticizers. Different molecular weights of PEGs have different plasticization mechanisms.

Moreover, the incorporation of different amounts of HPMC, MC, or carbomer in free shellac films caused an increase in the flexibility, decrease in T_g, and a marked increase in drug permeability of free shellac films, whereas the addition of PVA caused a decrease in flexibility and drug permeability and an increase in T_g. Addition of EC resulted in a slight decrease of the elasticity and a small decrease in drug permeability. However it does not show a considerable effect on the T_g. In addition, it was found that the drug permeability is directly related to the mechanical properties and T_g of shellac films.     

The Influence of Different Plasticizers and Polymers on the Mechanical and Thermal Properties,Porosity and Drug Permeability of Free Shellac Films

ABSTRACT

The effect of triethyl citrate (TEC) and different molecular weights and concentrations of polyethylene glycol (PEG), in addition to the effect of different water-soluble polymers and dispersions at different levels, hydroxypropyl methylcellulose (HPMC), methylcellulose (MC), carbomer 940, polyvinyl alcohol (PVA), ethyl cellulose (EC), on the mechanical and thermal properties, drug permeability, and porosity of free shellac films were investigated. Shellac films were cast from aqueous solutions, and their mechanical properties were studied by tensile test. Thermal analyses were performed using differential scanning calorimetry (DSC).

The results showed that the addition of plasticizer caused a decrease in both elastic modulus and glass transition temperature (T_g) and an increase in elongation at break of free shellac films. This effect was related to the concentrations of plasticizers. Different molecular weights of PEGs have different plasticization mechanisms.

Moreover, the incorporation of different amounts of HPMC, MC, or carbomer in free shellac films caused an increase in the flexibility, decrease in T_g, and a marked increase in drug permeability of free shellac films, whereas the addition of PVA caused a decrease in flexibility and drug permeability and an increase in T_g. Addition of EC resulted in a slight decrease of the elasticity and a small decrease in drug permeability. However it does not show a considerable effect on the T_g. In addition, it was found that the drug permeability is directly related to the mechanical properties and T_g of shellac films.     

The effect of different plasticizer molecular weights and concentrations on mechanical and thermomechanical properties of free films

Plasticizers are usually added to improve the mechanical and conditional (thermomechanical) quality of film coatings. Different molecular weights and concentrations of polyethylene glycol were incorporated as plasticizers in hydroxypropylmethylcellulose (HPMC) films. Thermomechanical and mechanical properties of cast films were tested using tensile and dynamic mechanical thermal analysis (DMTA) testing, respectively.

The results, as expected, showed that addition of plasticizer caused a decrease in both mechanical and thermomechanical properties, but lower grades had more effect than higher molecular weights and concentrations.

The conclusion could be drawn that combining different grades of plasticizers to optimize mechanical and thermomechanical properties is more efficient than using different concentrations of plasticizers.     

Influence of plasticizers and drugs on the physical-mechanical properties of hydroxypropylcellulose films prepared by hot melt extrusion

Hydroxypropylcellulose (HPC) films containing drugs or hydrophilic or hydrophobic plasticizers were prepared by a hot melt extrusion process. Polyethylene glycol 8000 (PEG 8000) 2%, triethyl citrate (TEC) 2%, acetyltributyl citrate (ATBC) 2%, and polyethylene glycol 400 (PEG 400) 1% were the plasticizing agents studied. In addition, either hydrocortisone (HC) 1% or chlorpheniramine maleate (CPM) 1% was incorporated into the films as a model drug. The physical-mechanical properties of the films that were investigated included tensile strength (TS), percentage elongation (%E), and Young's modulus (YM). Differential scanning calorimetry (DSC) was utilized to determine glass transition temperatures (T_g' s). These parameters were studied as a function of time and temperature. The glass transition temperatures initially decreased with the inclusion of the drugs and plasticizers. However, after 6 months aging, films containing PEG 400 and HC showed a marked increase in T_g. The films containing PEG 400 showed physical-mechanical instability in all parameters studied. All extruded films exhibited a marked decrease in TS in contrast to a large increase in %E when testing was performed perpendicular to flow versus in the direction of flow. In addition, a consistent film of HPC in the absence of drugs or plasticizers could not be extruded due to the excessive stress on the equipment. Although the theoretical percentage of CPM on aging remained fairly constant over the processing temperature ranges in this study, the HC levels remaining in the extruded films during storage were a function of time and temperature.     

Effects of Plasticizers on Water Permeation and Mechanical Properties of Cellulose Acetate: Antiplasticization in Slightly Plasticized Polymer Film

The effects of plasticizers, triacetin and three different molecular weights of polyethylene glycol, on the water permeation and mechanical properties of cellulose acetate were investigated. At 37°C, the water permeability of cellulose acetate was found to decrease with increasing plasticizer to a minimum and then to increase with higher concentrations of plasticizer. Low plasticizer concentrations caused a decrease in water permeability by antiplasticization. Antiplasticization arose from an interaction between the polymer and the plasticizer molecules and decreases the molecular mobility of the polymer. This effect was confirmed by mechanical measurements of polymer free films at the same experimental temperature. However, when the temperature was raised above the glass transition temperature, T_g, of the polymer films, the polymer films contain enough energy to overcome the interaction between the polymer and plasticizer molecules, and the antiplasticization effect disappeared.     

Study of some physical properties of biodegradable films based on blends of gelatin and poly(vinyl alcohol) using a response-surface methodology

The aim of this work was to study the effect of the hydrolysis degree (HD) and the concentration (C_PVA) of two types of poly(vinyl alcohol) (PVA) and of the type (glycerol and sorbitol) and the concentration (C_P) of plasticizers on some physical properties of biodegradable films based on blends of gelatin and PVA using a response-surface methodology. The films were prepared with a film forming solutions (FFS) with 2 g of macromolecules (gelatin+PVA)/100 g de FFS. The responses analyzed were the mechanical properties, the solubility, the moisture content, the color difference and the opacity. The linear model was statistically significant and predictive for puncture force and deformation, elongation at break, solubility in water, moisture content and opacity. The C_PVA affected strongly the elongation at break of the films. The interaction of the HD and the C_P affected this property. Moreover, the puncture force was affected slightly by the C_PVA. Concerning the solubility in water, the reduction of the HD increased it and this effect was greater for high C_PVA values. In general, the most important effect observed in the physical properties of the films was that of the plasticizer type and concentration. The PVA hydrolysis degree and concentration have an important effect only for the elongation at break, puncture deformation and solubility in water.     

Effects of Plasticizers on Water Permeation and Mechanical Properties of Cellulose Acetate: Antiplasticization in Slightly Plasticized Polymer Film

Abstract

The effects of plasticizers, triacetin and three different molecular weights of polyethylene glycol, on the water permeation and mechanical properties of cellulose acetate were investigated. At 37°C, the water permeability of cellulose acetate was found to decrease with increasing plasticizer to a minimum and then to increase with higher concentrations of plasticizer. Low plasticizer concentrations caused a decrease in water permeability by antiplasticization. Antiplasticization arose from an interaction between the polymer and the plasticizer molecules and decreases the molecular mobility of the polymer. This effect was confirmed by mechanical measurements of polymer free films at the same experimental temperature. However, when the temperature was raised above the glass transition temperature, T_g, of the polymer films, the polymer films contain enough energy to overcome the interaction between the polymer and plasticizer molecules, and the antiplasticization effect disappeared.     

纳米纤维素晶体和柠檬酸改性聚乙烯醇薄膜的制备及性能

以球形纳米纤维素晶体(NCC)作增强相、柠檬酸作交联剂对聚乙烯醇(PVA)进行改性,制备了PVA/NCC纳米复合薄膜和柠檬酸交联PVA/NCC纳米复合薄膜。通过热重分析、差热分析、吸水实验和拉伸实验考察了NCC的添加和柠檬酸的交联对薄膜热性能、耐水性和力学性能的影响。结果表明,与纯PVA薄膜相比,改性PVA薄膜的起始分解温度升高、熔融/结晶峰向高温方向移动、吸水率降低;只用NCC或柠檬酸对PVA改性时,所得PVA/NCC纳米复合薄膜、柠檬酸交联PVA薄膜的力学性能均对环境湿度敏感;同时用NCC(m(NCC)/m(PVA)=6/100)和柠檬酸(m(柠檬酸)/m(PVA)=3/100或m(柠檬酸)/m(PVA)=4.5/100)对PVA改性时,所得柠檬酸交联PVA/NCC纳米复合薄膜的力学性能不随环境湿度变化。     

Influence of Plasticizers and Drugs on the Physical-Mechanical Properties of Hydroxypropylcellulose Films Prepared by Hot Melt Extrusion

Hydroxypropylcellulose (HPC) films containing drugs or hydrophilic or hydrophobic plasticizers were prepared by a hot melt extrusion process. Polyethylene glycol 8000 (PEG 8000) 2%, triethyl citrate (TEC) 2%, acetyltributyl citrate (ATBC) 2%, and polyethylene glycol 400 (PEG 400) 1% were the plasticizing agents studied. In addition, either hydrocortisone (HC) 1% or chlorpheniramine maleate (CPM) 1% was incorporated into the films as a model drug. The physical-mechanical properties of the films that were investigated included tensile strength (TS), percentage elongation (%E), and Young's modulus (YM). Differential scanning calorimetry (DSC) was utilized to determine glass transition temperatures (T_g' s). These parameters were studied as a function of time and temperature. The glass transition temperatures initially decreased with the inclusion of the drugs and plasticizers. However, after 6 months aging, films containing PEG 400 and HC showed a marked increase in T_g. The films containing PEG 400 showed physical-mechanical instability in all parameters studied. All extruded films exhibited a marked decrease in TS in contrast to a large increase in %E when testing was performed perpendicular to flow versus in the direction of flow. In addition, a consistent film of HPC in the absence of drugs or plasticizers could not be extruded due to the excessive stress on the equipment. Although the theoretical percentage of CPM on aging remained fairly constant over the processing temperature ranges in this study, the HC levels remaining in the extruded films during storage were a function of time and temperature.     

载Ag改性桑枝韧皮纤维素/聚乙烯醇复合膜的制备及表征

采用流延法制备了载Ag改性桑枝韧皮纤维素/聚乙烯醇（Ag-T-CMC/PVA）复合膜,并利用XRD、SEM、DSC等分析测试方法研究了该复合膜的结构和性能。结果表明:随着Ag-T-CMC含量增加,Ag-T-CMC/PVA复合膜的力学性能、耐水性及抗菌性能均有提高。当Ag-T-CMC与PVA质量比为2%时,力学性能达到最佳,拉伸强度提高了3.4%。SEM分析表明:Ag-T-CMC均匀分散于Ag-T-CMC/PVA复合膜中,表现出良好的相容性;随着Ag-T-CMC含量的增加,断层逐渐变得光滑平面,在Ag-T-CMC与PVA质量比为2%时,断层最光滑。吸水性能测试表明:Ag-T-CMC能明显降低Ag-T-CMC/PVA复合膜的吸水性。抑菌性能测试表明:Ag-T-CMC/PVA复合膜对大肠杆菌和金黄色葡萄球菌有一定的抑菌效果,且随着Ag-T-CMC含量的增大,抑菌圈直径变大,抑菌效果增强。      

聚乙烯醇/二氧化硅共混膜的制备及耐温、耐溶剂性能研究

以聚乙烯醇（PVA）和正硅酸乙酯（TEOS）为原料,通过溶胶－凝胶（Sol-Gel)方法,制备出不同二氧化硅含量的聚乙烯醇／二氧化硅（PVA／SiO2)共混均质膜。通过热重分析（TGA）、示差扫描量热法（DSC）和动态力学分析（DMA）研究了共混膜的热性能。结果表明,与PVA膜相比,PVA／SiO2共混膜具有更高的热稳定性,随SiO2含量的增大,共混膜的分解温度升高,玻璃化温度也略有提高。以水为溶剂,测定了共混膜的耐溶剂性能。与PVA膜相比,PVA／SiO2共混膜的耐溶剂性能有显著的提高。     

柠檬酸/PVA抗菌薄膜性能的研究

目的研究柠檬酸添加量对聚乙烯醇薄膜性能的影响。方法将柠檬酸颗粒溶解到质量分数为10%的PVA母液中,通过流延法制备柠檬酸/PVA抗菌薄膜。结果添加柠檬酸可降低薄膜吸水性和溶解性,随着柠檬酸质量分数的增加,透湿系数减小。观察扫描电镜表明,柠檬酸在聚乙烯醇中溶解均匀。以大肠杆菌和金黄色葡萄球菌为指标的抗菌性能测试表明,柠檬酸对大肠杆菌和金黄色葡萄球菌均有较强的抑制作用。结论柠檬酸的添加可降低PVA薄膜的吸水性、溶解性和水蒸气透过系数,并使薄膜具有抗菌性。