Journal of Polymers and the Environment

, Volume 23, Issue 3, pp 383–391 | Cite as

Preparation and Characterization of Bio-based Degradable Plastic Films Composed of Cellulose Acetate and Starch Acetate

  • Zhibin Fei
  • Shaobin Huang
  • Jiazhi Yin
  • Fuqian Xu
  • Yongqing Zhang
Original Paper

Abstract

Bio-based degradable plastic is superior to petroleum-based plastic in terms of environmental protection and preservation of resources. A novel cross-linking system using tributyl citrate (TBC) as a cross-linking agent was used to create a bio-based degradable plastic via acetylation modified starch acetate (SA) and cellulose acetate (CA). Fourier transform infrared spectroscopy of the new plastic films revealed that a cross-Claisen ester condensation reaction had indeed occurred among TBC, CA and SA in the cross-linking system. Thermogravimetric analysis, X-ray diffraction, Scanning electron microscopy and mechanical properties tests confirmed that the fabricated films had mechanical properties and thermal stability that were comparable to conventional plastic films. A degradation-in-soil test showed that the fabricated films have controllable biodegradation properties by adjusting the amount of SA added. The tensile stress of two films—one with mass ratio of SA to CA1:3 and the other with mass ratio of 2:3—reached 3.5 and 3.0 MPa, respectively, the corresponding tensile strains were 22.3 and 17.9 %. The highest thermal stability temperature for both films was 205 °C. After being buried in soil for 35 days, the first film was 36 % degraded, and the second film was 41 % degraded. This paper is expected to promote the study and fabricate of bio-based degradable plastic film.

Keywords

Starch acetate Cellulose acetate Bio-based degradable plastic film Controllable degradation 

Introduction

In recent years, the pollution problems associated with traditional petroleum-based plastics have become increasingly prominent [1], much attention has been paid to developing naturally degradable materials to replace the traditional plastic, in a cost-effective manner [2, 3, 4]. The development of degradable plastics has become a highlight of the sustainable development and circular economy movements [5]. Bio-based degradable plastics are promising materials because during biological degradation, they produced only water, carbon dioxide and inorganic compounds without leaving any toxic residues [6].

Bio-based plastics [3] are high molecular weight polymer materials with plastic properties directly synthesized by living organisms (i.e., animals, plants and microorganisms), such as polyhydroxyalkanoate (PHA) [7] or biological polymers, such as starch, cellulose, lignin, chitin, proteins, peptides and polysaccharides. Bio-based plastics can also be blends of compounds with the above polymer materials serving as the main component, such as polylactic acid, poly amino acids, starch-based plastics, plant fiber molding products, modified cellulose, modified protein and bio-based polyamides.

Starch-based plastics [8] constitute a new type of biodegradable plastics with potential for further development. There have been many studies on the preparation of thermoplastics using modified starch, such as starch acetate (SA) [9, 10, 11, 12, 13, 14]. With the addition of ester groups, the association of the hydroxyl group in the starch macromolecule is weakened, so the poor water resistance and heat resistance of starch are reduced to some extent, and the film-forming property of the material is enhanced. However, compared with other polymers, the disadvantages of low degree of polymerization, high crystallinity, and poor solvent blending properties limit the application of starch-based materials in plastic industry.

Cellulose [15], a naturally occurring linear polymer of 1,4-linked ß-d-glucose, has become one of the most abundant natural polymer and an important substitute for traditional plastics [15, 16, 17]. Cellulose acetate (CA) [18], the acetate ester of cellulose, is an environmental friendly product from sustainable resources that is available at a low price and has good biocompatibility. As a result, CA has become one of the most important bio-based plastics and is widely used in the manufacture of paint, textile fiber, packaging materials, film, artificial kidney and reverse osmosis membrane [1, 4, 16, 19, 20]. However, when compared with SA, CA has the disadvantage of degrading slowly in the natural environment [21, 22].

SA and CA are both environmental friendly, economical materials that, if combined with a suitable cross-linking agent that could couple their complementary properties [8, 23], a new polymer blend might be synthesized that would have significant environmental and economic benefits. To date, little information is available in the literature regarding the fabrication of plastic films using SA and CA [24]. However, it is known that part or all of the acetic esters in glucose ring of SA and CA can participate in a cross-Claisen ester condensation reaction [25, 26, 27] with tributyl citrate (TBC) (See Fig. 1.). In the SA molecule, the α carbon atom in the acetic ester of glucose ring loses a hydrogen atom and combines with the TBC molecule, which loses varying amount of butoxy during the reaction, The reaction results in diverse β-keto ester cross-linked products and a by-product of butanol. During the reaction, the molecules of the cross-linked products become entangled with each other and form an effective three-dimensional grid structure. Using TBC as intermediate, the straight molecular chain of starch can be efficiently connected, and the cross-linking degree of the products are enhanced. A similar reaction can also occur between CA and TBC, the only difference is that while the glycosidic bond of SA is via the α acetal group, in CA the bond is via the β-acetal group. A single TBC molecule can have cross-Claisen ester condensation reactions with up three molecules of SA and/or CA, resulting in a product in which the SA and CA are well-blended.
Fig. 1

Cross-Claisen condensation of starch acetate and cellulose acetate with tributyl citrate

The aim of the present work is to develop a simple and cost-effective route to fabricate bio-based degradable plastic film. SA and CA are employed as raw materials, a novel cross-linking system was designed to thoroughly dissolve them and cross-link them into biodegradable plastic films using TBC as a cross-linking agent. The films were characterized by means of Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), X-ray diffraction (XRD), a universal material test machine and a soil burial test. The results show that the fabrication procedure is a simple method for producing plastic films at a low price that also have a controllable extent of degradation under natural conditions.

Experimental

Materials

Corn starch, refined cotton fiber and TBC were purchased from Guangdong Shangjiu Bio-degradable Plastics Co., Ltd. (Dongguan, China). Acetic anhydride and concentrated sulfuric acid were purchased from Guangzhou Chemical Reagent factory (Guangzhou, China). Glacial acetic acid, methanol and anhydrous ethanol were purchased from Baishi Chemical Industry Co. Ltd. (Tianjin China). Dibutyltin dilaurate (DBTDL) was purchased from Tianjin FuChen Chemical Reagent factory (Tianjin China). Acetone and dichloromethane were purchased from KaiXin Chemical Reagent Co. Ltd. (Hengyang, China). Sodium ethoxide (SE) was purchased from KeLong Chemical Reagent factory (Chengdu, China).

Preparation of Films

As summarized in Fig. 2, corn starch was placed into three-necked flask along with acetic anhydride and glacial acetic acid for acetylated modification [28], as well as concentrated sulfuric acid as catalyst. The molar proportions of corn starch, acetic anhydride, glacial acetic acid and sulfuric acid were 1:3:3:0.1. The contents of the three-necked flask were stirred at 600 rpm in a thermostat water bath at 80 °C for 2 h, After cooling to room temperature, the resulting reaction product was washed with distilled water to pH = 7 and, then separated with 200 mesh sieve. CA was prepared in a similar fashion.
Fig. 2

Preparation process of bio-based degradable films

The films were prepared by the phase inversion method [29]. SA and CA were dissolved in acetone (the composition of casting solution was shown in Table 1) at 60 °C, stirred at 600 rpm for 4 h, and allowed to settle for 8 h. The resulting casting solution was spread into films on glass plates. After the solvent volatilized in air for 20 min, the fabricated films were put into 20 wt% ethanol solution at 50 °C for 10 h, washed thoroughly with distilled water to remove residual solvent, and then submerged in deionized water until testing.
Table 1

The compositions of casting solution of bio-based degraded films

Membrane

SA (g)

CA (g)

Acetone (ml)

TBC (ml)

SE (ml)

DBTDL (ml)

#1

0.4

3.6

50.0

4.0

0.2

0.5

#2

1.0

3.0

50.0

4.0

0.2

0.5

#3

1.6

2.4

50.0

4.0

0.2

0.5

#4

2.2

1.8

50.0

4.0

0.2

0.5

#5

2.8

1.2

50.0

4.0

0.2

0.5

Characterization of the Fabricated Films

The Degree of Substitution and Polymerization of CA and SA

The degree of substitution (DS) values were obtained using a acid–base titration method [30]. The degree of polymerization (DP) was determined by viscosimetry [31] with dichloromethane/methanol as solvent. Each film was tested at least three times and an average taken.

The Thickness and Mechanical Properties of the Films

The thickness of the fabricated films were measured by micrometer (0–25 screw-thread micrometer, Cangzhou Jilu experiment instrument Co. Ltd. China), and the mechanical properties were determined using the 5,565 Electronical Universal Material Test instrument (Instron Corporation, USA). The samples were 50 mm × 10 mm (width × length) in size, the stretching velocity was set as 5 mm/min, and each sample was tested lengthways three times and an average taken.

FT-IR, XRD, SEM and TGA Measurements

A Fourier transform infrared spectrophotometer (FT-IR, Vector 33, Bruker Optics, Germany) was used to investigate the chemical composition and functional groups in the raw material and prepared films. Each spectrum was captured by 32 scans at a resolution of 2 cm−1 in the wavenumber range of 350–4,000 cm−1.

The crystal structure of the raw material and prepared films were analyzed by X-ray diffractometer (XRD, D8 ADVANCE, RIGAKU, Japan), under the following conditions: Copper target, LynxExe array detector,40 kV–40 mA;at the scanning rate of 0.02º/s in the range of 2θ between 4° and 60°.

The cross-section and surface morphologies of the fabricated films were observed by scanning electron microscopy (SEM, EVO LS10, Zeiss Corporation, Germany).

The thermal stability of the fabricated films was studied using thermogravimetry (TGA, TG 209 F1, Netzsch Corporation, Germay) at a heating rate of 20 °C/min over a temperature range of 30–600 °C under a nitrogen atmosphere.

Soil Burial Test

The degradation ratio (R) of fabricated films was determined by the soil burial test [32, 33]. Films dried to constant weight (m0) were buried in soil 10 cm below the surface, then removed at certain time intervals, washed with water and anhydrous ethanol, dried and weighed (m1). The degradation ratio (R) was calculated using the following expression:
$$ R = \frac{{m_{0} - m_{1} }}{{m_{0} }} \times 100\% $$
Three samples of each film were measured and the average R determined.

Result and Discussion

Characterization of the Fabricated Films and its Raw Materials

The thickness of the fabricated films were in the range of 60–180 μm. For CA, the DS was 2.85, the DP was 245, while for SA, the corresponding values were 2.82 and 165.

FT-IR spectroscopic analysis can provide important information about molecular structures. Figure 3 presents the FT-IR spectra of films of different compositions and their raw materials. The SA and CA show similar spectral features, with absorption frequencies in the regions of 1,750 cm−1 (the acetate C=O stretching mode), 1,240 cm−1 (the acetate C–O–C stretching mode), and 1,372 cm−1 (the acetate H3C–), which is consistent with the study of Gulec et al. [34]. Many of the absorption peaks of the fabricated films were similar to that of CA and SA because the cross-linked products have essentially the same functional groups. However the SA and CA in the cross-linked films have more complicated structures that result in the characteristic acetate peaks in the blended film being weaker than in the SA-alone film and stronger than in the CA-alone film.
Fig. 3

FT-IR spectra of fabricated films of different compositions and its raw materials

The result of cross-Claisen ester condensation reaction can also be seen in Fig. 3, where an hydrogen atom was replaced from the α carbon atoms in the acetic ester of the glucose ring of both SA and CA molecules, thereby decreasing the content of H3C–, while increasing the content of the –OH with the TBC involvement. So inspecting the characteristic peak around 1,220 cm−1, it is evident that the characteristic deformation peaks in the region around 1,030 cm−1 (–OH) were strengthened, while the deformation peaks around 1,369 cm−1 (H3C–) were weakened, indicating that the cross-Claisen condensation reaction had occurred between TBC and SA and/or CA.

XRD is the most extensively employed technique in studying polymer nanocomposite structure. The XRD patterns of the films of different compositions and their raw materials are shown in Fig. 4. CA exhibits five weak diffraction peaks between 2θ of 8º and 23º and no clear Bragg diffraction peaks shows that the CA is present in small particles and has a low degree of crystallinity. This observation is in accord with previous work of Qi Zhou and Ahmad, A. L and others [35, 36]. In contrast, there are two broad diffraction peaks around 2θ of 10º and 20º for SA, which are stronger than those seen in CA, indicating that although SA is also an amorphous material, it has a relatively higher degree of crystallinity, because the organization of starch was not completely destroyed after acetylation [37], a small amount of organic crystals were formed between the SA molecules.
Fig. 4

X-ray diffraction patterns of fabricated films of different compositions and its raw materials

There are two board diffraction peaks around 2θ of 8° and 20° in the fabricated films that are obvious weaker than those of CA and SA. Based on the spectra, it is clear that after cross-Claisen ester condensation reaction, the crystallinity of the fabricated films decreased, and the films had better flexibility and mechanical properties, because the molecular orientation of SA and CA were broken, most of the crystalline substance of the SA and CA had turned into a more amorphous form, and the intertwining of the molecular chains reduced the mobility of the cross-linked product, inhibiting the crystallization process, the granule of the films become refined. Compared with CA or SA, the fabricated films had a more uniform microstructure, furthermore, the fabricated films have the same raw materials, so the peaks around 8° remained basically unchanged regardless of the SA: CA ratio and smaller than that of either CA or SA alone, the peaks of film#1, #2, #3 and #4 around 20° were in the same situation. While the peak of film #5 around 20° became close to that of SA slightly, it may be because SA became a majority in film #5 with the SA: CA ratio up to 7:3, so the films demonstrate more like SA in XRD patterns, then the peak at 20° became close to SA.

The cross-section and surface morphologies of the fabricated films were characterized by SEM. As can be seen in Fig. 5, films #1, #2 and #3 displayed the typical homogeneous structures. There is no significant interface between the dispersion phase and continuous phase, and no obvious aggregations of CA or SA particles were observed in the films’ cross-section images, indicating that SA and CA were almost fully compatible in the casting solution and were homogeneously dispersed throughout the films matrix, they have relatively less SA and have dense and smooth surface, while #4 and #5 have more SA and have much rougher surfaces, on which there are some white crystalline substances and micropores. The cross-section morphologies seen on the SEM images show that #1, #2 and #3 have a neat and compact structure, while #4 and #5 have relatively loose microporous structures with an obscure stratification that also leads to poorer mechanical properties. With the increase in SA content, the films will perform more like SA than CA with a low polymerization degree, high crystallinity. So films #1, #2 and #3 with mass ratio of SA to CA 1:9, 1:3 and 2:3, respectively, are better than the others in morphologies and mechanical properties. It appears from the SEM images that the film #2 with a mass ratio of SA to CA 1:3 is the best one, in which both SA and CA entered into cross-Claisen ester condensation reactions with an adequate amount of TBC to form chemical bonds between the molecules of the film and generate a close three-dimensional network structure that gives the film considerable mechanical property and thermal stability (See below).
Fig. 5

SEM micrographs of the (a) surface and (b) cross-section of fabricated films of different compositions

Performance of the Fabricated Films

The thermal stability of the different films was studied by TGA. Figure 6 shows TGA and DTG curves of the fabricated films of different compositions and their raw materials. For SA and CA, the thermograms show two regions of weight loss. The first one between 30 and 82 °C corresponded to water and solvents losses; the second one corresponded to thermal degradation and starts around 230 °C for SA and 330 °C for CA (Fig. 6a), and shows maximum weight loss rate peaks around 367 °C (Fig. 6b), these results are consistent with the study of Huang and Li [38].
Fig. 6

TGA (a) and DTG (b) curves of fabricated films of different compositions and its raw materials

For the fabricated films, there is little difference in their TGA curves; i.e., their thermal degradation started around 205 °C and ending around 450 °C (Fig. 6a), showed two maximum weight loss rate peaks around 275 and 340 °C (Fig. 6b). The films have the same raw materials SA and CA, but differ in their relative composition, so it is reasonable that the thermogravimetric properties are similar. While the thermal degradation of SA and CA strated at different temperatures; i.e., 230 and 330 °C, respectively. Therefore, the thermal degradation of the fabricated films started with the CA component first, then the SA component. This behavior is why the TGA curves present two thermal degradation weight loss regions.

On the other hand, in the cross-linking system, the cross-linker TBC with a boiling point of 234 °C has a relative poor thermal stability, as part of the films, it will very likely decrease the thermal degradation temperature of the fabricated films. Furthermore, the polymer with the lower crystallinity can be more easily thermal degraded [38], so that the thermal degradation temperature of the films was lower than that of either of CA and SA. Even so, the films barely decomposed below 205 °C. Such thermal performance can meet the needs of and industrial applications.

Figure 7 summarizes the mechanical performance of the fabricated films. It is clear that as the SA content of the film increased, the tensile stress decreased while the tensile strain initially increased and then generally decreased, The tensile strength of films decreased with increasing SA content, moving from 3.62 MPa for #1, to 2.06 MPa for #5 with corresponding, tensile strains for #1 of 20.3 % increasing to 22.3 % for #2, and then decreasing to 13.6 % for #5. Among these films, #2, #3 had the best mechanical performance, which is close to or partly exceeds the Chinese national standards of polyethylene blown mulch film for agricultural uses (GB/T13735—1992, http://www.pv265.com/gjbz/201206/73745.html), indicating that the plastic films fabricated under this system have mechanical properties that are comparable to those of petroleum-based films. This result suggests there is a wide field of possible applications for these bio-based films.
Fig. 7

Tensile test curves of fabricated films of different compositions

Degradation Properties of Films of Different Compositions

Both biological and non-biological mediated processes contribute to the degradation of the polymer films, and both aerobic and anaerobic microorganisms can produce hydrolases, including esterases, which are necessary to degrade acetylated polysaccharides [16, 21]. So the fabricated films can be well-degraded in natural environments, such as in the atmosphere, water, and soil. Figure 8 shows the degradation of films of different compositions in the soil burial test. In the first 24 days, all of the films experienced their highest degradation rate; at the end of the first 24 days, the CA film had degraded 26.01 %, while the degradation ratios of fabricated films increased from film #1 (28.08 %) to #5 (43.51 %). This result differs from that reported in the study of Nishida and Tokiwa [39], in which they observed that the degradability of a polymer decreased as its overall crystallinity increased. Our results may reflect the fact that SA can be easily hydrolysed and act as a suitable carbon source for microorganisms, properties that would increase the degradability of the SA-containing films. This behavior is a result of the fact that SA degrades more quickly than CA in the natural environment. Therefore, the degradation of the fabricated film can be controlled by changing the mass ratio of SA in the film.
Fig. 8

Soil-burial degradation rate of fabricated films of different composition and CA

The degradation rate of all the tested films slowed after 50 days, with the greatest degradation ratio after 120 days being 52.43 %, during this period, the films’ integral structures were degraded due to chemical hydrolysis and biological action of microorganism in soil. The un-decomposed polymer contained a large amount of acetyl esters, which have no toxic effects in either soil or water after disintegration. Theoretically, they too, will degraded after few months via deacetylation and de-esterification produced by microorganism [40]. The important feature from the soil burial test is that the biodegradation of the film increases with increasing amounts of SA.

Conclusions

In this work, a novel cross-linking system has been shown to be effective in preparing bio-based degradable plastic film, using the cross-Claisen ester condensation reaction between TBC and mixtures of SA and CA. The films combine the advantages of CA and SA, while reduce their disadvantages. For example, the SA film is fragile and easily torn, the CA film degrades slowly when buried in soil. However by changing the proportion of SA, the mechanical properties of the film improve and the degradation properties can be controlled. The film #2 (25 wt% SA) and film #3 (40 wt% SA) have a smooth surface and tight structure. Their tensile stress can reach 3.5 MPa and 3.0 MPa; their tensile strain can reach 22.3 and 17.9 %. The soil burial degradation ratio at 35 days can reach 40.37 and 35.82 %, respectively. The highest thermal stability temperature for both films is above 200 °C.

These films can be produced at a low price from readily available stocks of both starch and cellulose. As a result, they not only have high economic and industrial value but also have considerable environmental benefits to the extent that they replace petroleum-based, non-degrading plastics.

Notes

Acknowledgments

This research was financially supported by the National Natural Science Foundation of China (Grants No. 51378217 and No. U1360101), Guangdong Natural Science and Foundation (No. S2012020010887), Research Project of Guangdong Provincial Department of Science and Technology Department (Grants No. 2012A010800006).

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Copyright information

© Springer Science+Business Media New York 2015

Authors and Affiliations

  • Zhibin Fei
    • 1
  • Shaobin Huang
    • 1
    • 2
    • 3
  • Jiazhi Yin
    • 1
  • Fuqian Xu
    • 1
  • Yongqing Zhang
    • 1
  1. 1.Guangdong Provincial Key Laboratory of Atmospheric Environment and Pollution Control, School of Environment and EnergySouth China University of TechnologyGuangzhouPeople’s Republic of China
  2. 2.State Key Laboratory of Pulp and Paper EngineeringSouth China University of TechnologyGuangzhouPeople’s Republic of China
  3. 3.The Key Lab of Pollution Control and Ecosystem Restoration in Industry ClustersMinistry of Education, South China University of TechnologyGuangzhouPeople’s Republic of China

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