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Article history: Poly(propylene carbonate) (PPC) is a biodegradable and partially renewable polymer that is synthesized
Received 22 July 2016 from CO2. PPC is a suitable alternative to non-degradable polymers and a possible option for effectively
Received in revised form recycling CO2. In this study, the properties of PPC are compared with other commercial polymers. It is
23 August 2016
demonstrated that while the mechanical properties of PPC are comparable to non-degradable poly-
Accepted 27 August 2016
ethylene, its permeability to oxygen and water vapor are remarkably lower. PPC degradation in compost
Available online 29 August 2016
soil is nearly 9% within six months that is comparable with biodegradable polymers such as Eco-Flex.
Meanwhile, PPC is chemically stable when exposed to a broad range of simulated media such as low
Keywords:
Poly(propylene carbonate)
or high pH as negligible mass loss and molecular weight deductions are detected after six months
Biodegradable polymer exposure to these media. Therefore, PPC is deemed to be an ideal polymer for food packaging and many
Compostable other applications such as biomedical devices. The application of PPC can significantly reduce the
Packaging disposal of non-degradable polymers in landfills and minimize the reliance on fossil fuel based polymers.
© 2016 Published by Elsevier Ltd.
1. Introduction such as poly (lactic acid), for biomedical applications [7]. PPC's
degradation products are not acidic; this benign degradation
The broad use and application of non-degradable plastics in behavior in the body eradicates the risk of inflammation. However,
recent decades has led to major environmental issues, such as the the broad commercial application of PPC as a plastic has been
lowering capacity of landfills, and the exposure of the ecosystem to obstructed due to the low glass transition temperature (25e45 C)
hazardous pollutants [1,2]. As a results of this impact many coun- of the polymer [8].
tries has banned to use non-degradable polymer for food pack- In the previous attempts to increase the glass transition tem-
aging. Introducing biodegradable plastics, like Poly (propylene perature of PPC, the polymer was composited with different fillers
carbonate) (PPC), is deemed as a promising solution. Poly (pro- such as starch and cellulose [9,10]. For instance, the mechanical
pylene carbonate) (PPC) degrades enzymatically into water and CO2 properties of PPC-starch blends are comparable with polyesters and
that are non-hazardous. The polymer is synthesized by copoly- their composition can be tuned and varied for different applications
merization of CO2 and propylene oxide [3]. Converting CO2, that [7,11]. The addition of filler generally decreases the elongation at
attributes to the global warming into a biodegradable plastic with break, whilst enhancing the overall tensile strength. Low molecular
favorable properties can mitigate some of environmental issues interaction between PPC and the filler might result in heteroge-
arise from using non-degradable polymers [4,5]. neous distribution of the filler within the polymer structure and
PPC is produced in commercial scale by several companies such thus might be due to low elongation strength of the composite.
as Novomer and AZO-materials as a binder, plasticizer, and adhe- However, PPC-starch blends have increased water sorption and
sive [5]. PPC can also be used for the fabrication of agricultural hydrolysis and a tensile strength that is 20% greater than that of
mulches because of its biodegradability, transparency, and re- pure PPC [12]. This effect is attributed to a hydrogen bonding that
sistivity to moisture [6]. Our recent study showed the superior exists between the hydroxyl groups of starch and the carbonyl
properties of PPC when compared to polyester based polymers groups of PPC [7]. The interaction between PPC and starch can be
improved by using less polar derivatives of starch such as starch
acetate (SA) [13]. The tensile strength of PPC- 20 wt% SA is 50%
higher than neat PPC. In yet another study, the tensile strength of
* Corresponding author.
PPC was increased from 1.8 to 19 MPa and its Young's modulus was
E-mail address: fariba.dehghani@sydney.edu.au (F. Dehghani).
http://dx.doi.org/10.1016/j.polymdegradstab.2016.08.014
0141-3910/© 2016 Published by Elsevier Ltd.
B. Bahramian et al. / Polymer Degradation and Stability 133 (2016) 174e181 175
enhanced from 201 to 1414 MPa by the addition of 1 wt% cellulose samples was 5 cm2 and Mocon self-adhesive foil masks were used
nanocrystals (CNCs) [14]. on both sides of films to seal each test specimen. Pure Oxygen were
In recent years Cardia Bioplastics has introduced a new type of applied in 30 C and dry condition (<3% relative humidity).
biodegradable plastic bag that is fabricated from a blend of PPC and water vapor transmission rate (WVTR): Mocon Permatran W 3/31
starch [15]. However, the hurdle for the broad application of this was applied to test WVTR of thin films (~500 mm) of polymers ac-
composite is the high level of metal based catalyst residue in PPC; cording to ASTM F 1249-06. The test area of samples was nearly
the acceptable threshold for metal catalyst according to the stan- 5 cm2. The analysis was conducted at 37.8 C (estimated tempera-
dards for compostable and biodegradable polymers is 150 ppm ture uncertainty ±0.5 C) and 90% RH for a period of 2 days.
[16]. We have recently developed a novel solvent free process that
tackled this issue and efficiently removed the level of metal resi- 2.5. Chemical resistance to food simulated media
dues to below the accepted level for composting [17]. With this
advancement, we are able to access several pathways for the future Polymer samples with the dimension of 5 mm 5 mm were
and wide-ranging applications of PPC and its derivatives. The aim of immersed in various food simulated media such as acidic (pH 4),
current study is therefore to assess the practical feasibility of using neutral (pH 7) and basic (pH 10) buffers, 50% ethanol/water solu-
PPC as an alternative plastic in different commodity products. To tion and edible olive oil for a period of 6 months at ambient con-
this end, the physico-mechanical properties of PPC alone and its dition. The media was changed on a weekly basis and samples were
composites are systematically compared with commercially avail- kept in sterile conditions to avoid the effect of microbial contami-
able plastics, e.g. low density polyethylene (LDPE), polybutyrate nation on degradation. The samples were removed from buffer
adipate terephthalate (Eco-Flex), and polyethylene/starch blend solutions at different time intervals and washed by milliQ water to
(commercial name: BLFO2). Primarily, the mechanical strength, remove all media residues and then were dried. The samples
biodegradability, chemical stability and high resistivity to oxygen incubated in olive oil were washed by ethanol prior to milliQ water
and water penetration were measured. to remove the residual of oil. Subsequently, the weight loss of
samples at each time point was recorded. Three samples were
2. Experimental collected at each condition to acquire statistically valid data.
Poly(propylene carbonate) resin with the molecular weight of Soil burial biodegradation test was conducted in pots contained
463 KDa and poly dispersity of 2.03 was kindly supplied by Growth 10 cm mature compost soil made from food and garden organics
Technology International Pty Ltd. Eco-Flex and PE/Starch blend (containing active fungi, yeast, actinomycetes and Photosynthetic
(70% starch) with the commercial name of BLFO2 were supplied by Bacteria) sandwiched between 10 cm layers of wood chips to
Cardia Bioplastics Ltd. LDPE was purchased from Sigma-Aldrich. maintain the moisture content. Polymer films (thickness
Buffer solutions of pH 4, pH 7 and pH 10 were purchased from 800e1000 mm) with the dimension of 4 cm 4 cm were buried in
Ajax Finechem. Edible olive oil was used as fatty food simulated the middle part of the mature compost soil. The pots were main-
media. Cellulose powder (~50 mm), soluble starch powder tained in a controlled temperature and moisture incubator
(~200 mm) and Dimethylacetamide (DMAC) were purchased from (T ¼ 40 C, RH ¼ 60e70%). The relative humidity of the chamber
Sigma-Aldrich. Sodium chloride was supplied form Merck and the was controlled by using supersaturated sodium chloride solution
mature compost soil from Landtasia Organic Farms. and measured on a regular basis [19]. To avoid water loss by
evaporation, known amount of water was added to the soil every
2.2. Preparation of polymer films other day. Samples were removed from the soil to assess their
biodegradation rate in predetermined time intervals of up to 6
Thin films of each polymer (thickness 500e1000 mm) were months. After removal from the soil, samples were washed with
prepared by hot melt compression above their melting tempera- milliQ water twice to remove soil residue and dirt and dried in
ture (130 C for PPC, 150 C for Eco-Flex, LDPE and BLFO2, PPC-St vacuum oven until observing a constant weight. The degree of
50-50, PPC-Cell 75-25) and under the pressure of 10 kPa for PPC, biodegradation of samples at each stage was assessed by measuring
2 kPa for Eco-Flex, LDPE and BLFO2, and 7 kPa for PPC-St 50-50, their weight loss, surface morphology, molecular weight, tensile
PPC-Cell 75-25 in a period of 60 min for PPC, PPC-St 50-50, PPC-Cell properties and chemical structure.
75-25, and 20 min for Eco-Flex, LDPE and BLFO2.
2.7. Gel permeation chromatography (GPC)
2.3. Mechanical properties
The molecular weight of samples from biodegradation test was
The tensile test was conducted according to ASTM standard measured using the Gel Permeation Chromatography on a Shi-
using dumbbell shaped samples that were cut from polymer films madzu CBM-20A system with an Agilent Polargel-M guard column
(thickness 500e1000 mm). Universal testing instrument (Instron and three Phenomenex Phenogel columns using dimethyl acet-
5543) equipped with a 100 N load cell was used to measure tensile amide (Containing LiBr 0.03% w/w to avoid precipitation of the
strength of these samples. In addition, the tear resistance of spec- polymer) as a mobile phase at a flow rate of 1.0 ml/min at 50 C. The
imens were determined using Universal testing instrument (Ins- system was equipped with a Shimadzu RID-10A differential
tron 5543) equipped with a 100 N load cell. This test was conducted refractive index detector and Wyatt MiniDawn TREOS light scat-
using standard trouser-shaped test specimens [18]. tering. The GPC system was calibrated with narrow polystyrene
(PS) standards (PDI < 1.1).
2.4. Barrier properties
2.8. Nuclear magnetic response (1HNMR)
oxygen transmission rate (OTR): Mocon Ox-Tran 2/21 instrument
was used to conduct OTR analysis for thin films of polymers Chemical structure of PPC during the biodegradation test was
(~500 mm) according to ASTM D3985-05. The test area for the determined by proton nuclear magnetic response (1HNMR)
176 B. Bahramian et al. / Polymer Degradation and Stability 133 (2016) 174e181
100
The surface morphology of PPC films from biodegradation and
chemical resistance tests was observed by the SEM (Zeiss ULTRA 80
Plus SEM) at 15 kV. Prior to this analysis PPC samples were 60
mounted on aluminum stubs, using conductive carbon paint, and
40
then gold sputtered using the Emitech K550X sputter coater.
20
0
3.1. Mechanical properties Eco-Flex BL-FO2
BLFO2 LDPE PPC
120
The mechanical properties are critical in the selection of poly- C
mers for different applications. Any impact during the handling,
100
*
shipment and storage of food may affect the safety and the quality
Tear Resistance (N/mm)
Fig. 4. SEM images of the PPC films A) before incubation and after 6 months incubation in B) acidic, C) basic and D) 50% ethanol E) fatty food simulated media.
90 Table 1
Molecular weight and PDI of the PPC films before and after soil burial
80 LDPE biodegradation.
PPC
70 Eco-Flex PPC sample Mw PDI
Weight Loss (%)
x BLFO2
60 Control (month 0) 463,746 3.26
Second months 417,026 4.69
50 Third months 409,809 5.58
Sixth month 394,721 6.23
40
30
Fig. 7. The images of A) PPC, B) LDPE, C) Eco-flex, D) BLFO2 and E) SEM images of PPC films at different time points of soil burial.
250 forth. Therefore, these blends could not be used for the applications
** in which the high tear force is critical. However, the lower amount
200 of starch in composite may have less impact on this property of PPC.
Tensile Modulus (MPa)
2
1000
900 A ** * 1
800
Tensile Modulus (MPa)
700 0
600 0 50 100 150 200
500 Time (day)
5
400 pH4
pH7 B
300
4 pH10
200 x 50% Ethanol
weight Loss (%)
100
3 * Olive Oil
0
PPC PPC-St 50-50 PPC-Cell 75-25
18 2
16
B *
14 1
Ultimate Strength (MPa)
12
10 0
0 50 100 150 200
8
Time (day)
6
Fig. 11. Degradation of A) PPC-St 50e50 and B) PPC-Cell 75-25 films in various media
4
in six months period.
2
0
PPC PPC-St 50-50 PPC-Cell 75-25 60
PPC
80 PPC-Cell 75-25
C ** 50 x PPC-St 50-50
Weight Loss (%)
**
Tear Resistance (N/mm)
60 40
30
40
20
20
10
0 0
PPC PPC-St 50-50 PPC-Cell 75-25 0 50 100 150 200
Time (Day)
Fig. 10. A)Tensile Modulus, B) Ultimate Strength, and C) Tear Resistance of PPC and PPC
composites with natural polymers. Fig. 12. The weight loss of polymer films in compost soil as a function of time.
B. Bahramian et al. / Polymer Degradation and Stability 133 (2016) 174e181 181
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