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.     

An Investigation Into the Formation of Plasticizer Channels in Plasticized Polymer Films

The effects of plasticizer, polyethylene glycol (PEG-600), on the sucrose permeability, void volume and morphology of cellulose acetate free films were investigated. The sucrose permeability of cellulose acetate free films was found to decrease with increasing PEG-600 to a minimum and increase dramatically when they were plasticized by over 30% (w/w) PEG-600. The decrease in sucrose permeability of cellulose acetate free films with increasing plasticizer at low plasticizer concentrations could be interpreted by the antiplasticization effect, and the dramatic increase of sucrose permeability of cellulose acetate free films at high plasticizer level could be explained by the formation of plasticizer channels. The void volume of cellulose acetate free films were calculated by determining the water content in the films, and the effect of PEG-600 on the morphology of cellulose acetate free films was studied by using the scanning electron microscopy (SEM). Both the void volume and SEM studies supported the assumption that the plasticizer channels would be formed in the polymer films which contain high concentration of plasticizer.     

An Investigation Into the Formation of Plasticizer Channels in Plasticized Polymer Films

Abstract

The effects of plasticizer, polyethylene glycol (PEG-600), on the sucrose permeability, void volume and morphology of cellulose acetate free films were investigated. The sucrose permeability of cellulose acetate free films was found to decrease with increasing PEG-600 to a minimum and increase dramatically when they were plasticized by over 30% (w/w) PEG-600. The decrease in sucrose permeability of cellulose acetate free films with increasing plasticizer at low plasticizer concentrations could be interpreted by the antiplasticization effect, and the dramatic increase of sucrose permeability of cellulose acetate free films at high plasticizer level could be explained by the formation of plasticizer channels. The void volume of cellulose acetate free films were calculated by determining the water content in the films, and the effect of PEG-600 on the morphology of cellulose acetate free films was studied by using the scanning electron microscopy (SEM). Both the void volume and SEM studies supported the assumption that the plasticizer channels would be formed in the polymer films which contain high concentration of plasticizer.     

Studies of the drug permeability and mechanical properties of free films prepared by cellulose acetate pseudolatex coating system

Free films produced with cellulose acetate (CA) pseudolatex were prepared by the casting method. The effects of plasticizer concentration, drying temperature, and drying time on drug permeability and mechanical properties of free films were investigated by three-factor spherical second-order composite experimental design. The results were analyzed by the multivariable regression method. The experimental results indicated that plasticizer concentration, drying temperature, and drying time had complex effects on free film permeability and mechanical behavior. These results probably arise from the film-forming ability of CA pseudolatex particles at various conditions and the evaporation of plasticizer during the film-forming process     

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.     

Influence of Aging on the Physical-Mechanical Properties of Acrylic Resin Films Cast from Aqueous Dispersions and Organic Solutions

The physical-mechanical properties of the enteric copolymers, poly(methacrylic acid, ethyl acrylate) Eudragit® L100-55, and Eudragit® L30D have been investigated. Free films of the copolymer containing varying levels of glyceryl triacetate (triacetin) and citrate ester (Citroflex®) plasticizers were prepared by both aqueous and solvent casting techniques. Conditioned films were stored at different humidities and temperatures for predetermined time periods prior to testing. Free films with plasticizer concentration ranging from 0 to 30% by weight of the polymer demonstrated that physical aging at room temperature resulted in physical-mechanical changes as the stress-strain curves indicated a decrease in the percent elongation with increases in the tensile strength. Films prepared from the aqueous latex approached a constant state of equilibrium at a faster rate than films prepared from isopropyl alcohol, where the mechanical properties approach a relatively constant value. Free films containing varying amounts of the plasticizer, triethyl citrate, were stored under different humidity and temperature conditions. In addition, a headspace-gas chromatography (HSGC) method was developed to correlate solvent residues with mechanical properties. The results indicated that an increase in temperature and humidity accelerated the rate of solvent evaporation as a function of time. High vacuum and low humidity conditions were demonstrated to be ineffective conditions for solvent removal. Solvent residues were found in all films after 48 hours of exposure to temperatures up to 60°C and/or exposure to relatively high humidity conditions. A direct relationship between plasticizer content and rate of solvent evaporation from the film was established. Higher concentrations of the plasticizer were found to augment the evaporation of the solvents. This enhanced evaporation was due to the stronger molecular interaction forces between the polymer and the plasticizer than between the polymer and the solvent.     

Novel low-molecular-weight hypromellose polymeric films for aqueous film coating applications

The concentration of hypromellose (HPMC) is known to significantly impact the viscosity of coating solutions. The purpose of this study was to determine the viscosity of novel low-molecular-weight (LMW) HPMC products as a function of polymer concentration. The mechanical properties and water vapor permeability of free films prepared from these novel LMW HPMC polymers were also determined and the results were compared with films prepared with conventional HPMC. Solutions of LMW and conventional HPMC 2910 and 2906 containing up to 40% polyethylene glycol (PEG) 400 were prepared and the viscosities were measured using a Brookfield viscometer. Solutions were then cast onto glass plates and stored at 30?C and 50% relative humidity until films were formed. A Chatillon digital force gauge attached to a motorized test stand was used to quantify the mechanical properties of the films, whereas water vapor permeabilities were determined according to the ASTM E96 M-05 water method. As expected, the novel LMW polymer solutions exhibited significantly lower viscosities than the conventional comparators at equivalent polymer concentrations. Film strength of the LMW materials was lower than films prepared from the conventional HPMC solutions, although this effect was not as evident for the HPMC 2906 chemistry. Increasing concentrations of the plasticizer resulted in decreased tensile strength and Young?s modulus and increased elongation as well as increased water vapor permeability, irrespective of polymer type. No statistical difference was found between the tensile strength to Young?s modulus ratios of the F chemistry LMW and conventional HPMC polymer films.     

A facile approach to prepare regenerated cellulose/graphene nanoplatelets nanocomposite using room-temperature ionic liquid

This study presents the preparation of regenerated cellulose (RC)/graphene nanoplatelets (GNPs) nanocomposites via room temperature ionic liquid, 1-ethyl-3-methylimidazolium acetate (EMIMAc) using solution casting method. The thermal stability, gas permeability, water absorption and mechanical properties of the films were studied. The synthesized nanocomposite films were characterized by Fourier transform infrared (FTIR), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The T20 decomposition temperature of regenerated cellulose improved with the addition of graphene nanoplatelets up to 5 wt%. The tensile strength and Young's modulus of RC films improved by 34 and 56%, respectively with the addition of 3 wt% GNPs. The nanocomposite films exhibited improved oxygen and carbon dioxide gas barrier properties and water absorption resistance compared to RC. XRD and SEM results showed good interaction between RC and GNPs and well dispersion of graphene nanoplatelets in regenerated cellulose. The FTIR spectra showed that the addition of GNPs in RC did not result in any noticeable change in its chemical structure.     

甘油含量对NMMO工艺天然纯纤维素膜性能的影响

以棉纤维素为原料,以NMMO(N-甲基吗啉-N-氧化物)为溶剂,以甘油为增塑剂制取天然纯纤维素包装膜,研究了不同甘油含量对纤维素膜性能的影响。结果表明,随着甘油含量的增加,纤维素膜的断裂伸长率随之增加,拉伸强度随之降低,二者变化幅度都很大;当甘油含量从2%增加到5%,纤维素膜的透油系数增加了13.4%,氧气透过率增加了3.0%,透湿系数增加了16.7%,透光率增加了22.4%,横向热收缩率增加了58.8%,纵向热收缩率增加了54.7%。可见,甘油含量对膜的透氧性影响较为微弱,但对力学性能、透油性、透湿性、透明度、热收缩率影响均较为显著。     

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。     

Cellulose nanocrystal-filled carboxymethyl cellulose nanocomposites

Polymer nanocomposites are one of the important application areas for nanotechnology. Naturally derived organic nanophase materials are of special interest in the case of polymer nanocomposites. Carboxymethyl cellulose is a polyelectrolyte derived from natural materials. It has been extensively studied as a hydrogel polymer. Methods to modify the mechanical properties of gels and films made from CMC are of interest in our lab and in the commercial marketplace. The effect of nano-sized fillers on the properties of CMC-based composites is of interest in the development of novel or improved applications for hydrogel polymers in general and CMC in particular. This project investigated cellulose nanocrystals (CNXLs) as a filler in CMC and compared the effects to microcrystalline cellulose (MCC). The composite material was composed of CMC, MCC or CNXL, with glycerin as a plasticizer. CNXL and MCC concentrations ranged from 5% to 30%. Glycerin concentrations were kept constant at 10%. CNXLs improved the strength and stiffness of the resulting composite compared to MCC. In addition, a simple heat treatment was found to render the nanocomposite water resistant.     

聚乳酸/乙基纤维素复合膜的制备及其性能

以烯基琥珀酸酐( ASA) 作为新型增塑剂, 使用三氯甲烷作为聚乳酸( PLA) 和乙基纤维素( EC) 的共溶剂, 采用溶液浇铸法成功制备了聚乳酸/ 乙基纤维素复合膜。用红外光谱( FT IR) 、X 射线衍射(XRD) 表征了复合膜结构, 并测试了其吸水性和力学性能。FTIR 测试结果显示, 复合膜中存在强烈的氢键相互作用。XRD 表明,ASA 显著提高了PLA 和EC 2 种高聚物的界面黏合性。力学测试结果表明, ASA 对该复合膜具有良好的增塑效果。当膜中PLA 质量分数[ 37%时, PLA 对复合膜起增强作用。复合膜的吸水性随ASA 含量的增大而降低, 随PLA 含量的增大而提高。该复合膜作为一种潜在的药物缓释材料, 将具有广阔应用前景。      

Preparation and Characterization of Cellulose Acetate Butyrate/Organoclay Nanocomposites Produced by Extrusion

Nanocomposite films based on cellulose acetate butyrate, modified montmorillonite (Cloisite^® 30B), plasticizer (triethyl citrate) and antimicrobial compounds (carvacrol and cinnamaldehyde) were prepared by extrusion. The effects of the Cloisite^® 30B content and antimicrobial compound types on the morphology of the nanocomposite films were investigated by X‐ray diffraction and transmission electron microscopy. The thermal characteristics of films were analysed by thermogravimetry and differential scanning calorimetry; oxygen and water vapour permeability and tensile strength were determined. The film's antimicrobial behaviour against Listeria innocua, Staphylococcus aureus, Escherichia coli O157:O7 and Saccharomyces cerevisiae was investigated and determined using a viable cell count method. Nanocomposites with a Cloisite^® 30B content of 3 wt% showed better dispersion than nanocomposites with a 5 wt% content. For films with antimicrobial compounds, tensile strength and Young's modulus decreased and water vapour permeability increased (150%) because of the plasticization effect of the antimicrobial compounds (essential oils). The nanocomposites with carvacrol and cinnamaldehyde were effective against the tested Gram‐positive bacteria (reduction of at least 3.0 log CFU/ml) and yeast (reduction of at least 4.0 log CFU/ml). This study demonstrates that antimicrobial cinnamaldehyde and carvacrol can be successfully incorporated into cellulose acetate butyrate nanocomposites and that they have an inhibitory effect against microbial growth in solid medium. It shows the potential use of cellulose acetate butyrate for food packaging applications. Copyright © 2013 John Wiley & Sons, Ltd.     

纳米纤维素/壳聚糖复合膜的制备和性能

目的获得力学性能和阻隔性能优异的食品包装用壳聚糖膜。方法通过超声法由糠醛渣纤维素制备纳米纤维素(NCC),将其与壳聚糖(CS)共混流延制备纳米纤维素/壳聚糖复合膜(NCC-CS)。结果复合膜中NCC质量分数为5%时,NCC-CS的拉伸强度比纯CS膜提高了30%,NCC-CS的透湿量比纯CS膜降低了24%。SEM分析结果表明NCC-CS复合膜微观结构致密。FT-IR和XRD的分析结果表明CS与NCC间存在着较强的相互作用。结论 NCC的加入对CS膜的力学性能和阻隔性能的提高有促进作用。     

羧甲基纤维素增强膜的制备及性能

目的为了获得一种可用于食品包装的羧甲基纤维素增强膜。方法以羧甲基纤维素(CMC)为成膜基底,甘油为增塑剂,分别将质量分数为1%,3%,5%和10%的纳米纤维素(NCC)添加到CMC中,共混流延制备羧甲基纤维素增强膜(CMC-NCC)。结果 NCC的加入,提高了CMC的力学性能和对水蒸气的阻隔性能,还提高了CMC的热性能。FT-IR分析结果表明,CMC与NCC两者间形成了分子间氢键;XRD分析结果表明,NCC可以改变CMC的结晶排列。当添加质量分数为5%的NCC时,CMC-NCC的拉伸强度比纯CMC膜提高了25.6%,断裂伸长率降低了21.3%,透湿量降低了9%,热稳定性提高了2%,透光率维持在87%以上。结论 CMC增强膜具有力学性能高、阻湿性能好等优点,NCC提高了CMC的成膜品质。     

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.     

Thermomechanical properties of poly(vinyl alcohol) plasticized with varying ratios of sorbitol

The objective of this work is to study the thermal and mechanical properties of films based on blends of poly(vinyl alcohol) (PVA) with different weight percent of sorbitol. Solid-state PVA/sorbitol polymer membranes were prepared by a solution casting method. The characteristic properties of these polymer membranes were examined by thermo-gravimetric analysis (TGA), differential scanning calorimetry (DSC), nanoindentation methods and by Fourier Transform Infrared (FTIR) spectroscopy. It was found that the thermal properties (glass transition, T_g, melting point, T_m and decomposition temperature, T_d) for PVA blends showed a decrease proportional to the sorbitol concentrations. The hardness and elastic modulus obtained from nanoindentation test were also found to decrease with increase in plasticizer concentration. FTIR confirmed the reduction in hydrogen bonding between PVA chains in favour of formation new bonding between the plasticizer and the PVA chains.     

Properties of Aqueous, Plastic Izer-Containing Ethyl Cellulose Dispersions and Prepared Films in Respect to the Production of oral Extended Release Formulations

Plasticized aqueous ethyl cellulose (EC) dispersions (Aquacoat^R ECD-30) are incompatible with concentrated electrolytes but stable with nonelectrolytes. The minimum film formation temperature (MFT) decreases with increasing plasticizer content, from 81°C to about 30°C with 20% dibutyl sebacate (DBS) in the resulting film. The plasticiser has to penetrate completely into the EC particles before film formation to obtain optimal plastification, the lowest film formation temperature and high permeability of the resulting film. This takes more than 5 hours with 20% DBS. Films prepared from plasticized dispersion with short standing times show craters of former plasticizer droplets. With increasing plasticizer content the sticking point of the films decreases. The plasticizer induce a high water absorption of the films: more than 30% with 23-26% DBS or diethyl phthalate (DEP). DBS is hardly released from the films within 5 hours, in contrast to DEP. Thus, the absorbed water is completely swelling water in case of DBS and partially also substitution water in case of DEP. The films squeeze out cetylalcohol (CA) and also sodium lauryl sulfate (NaLS) during storage, this may change the permeability of the films. EC contains a small amount of carboxylic groups which explains the pH dependent release of drugs from pellets coated with aqueous EC dispersions.     

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.