Degradation of Polylactic Acid/Polypropylene Carbonate Films in Soil and Phosphate Buffer and Their Potential Usefulness in Agriculture and Agrochemistry
Abstract
:1. Introduction
2. Results
2.1. Weight Changes in Polymer Samples
2.1.1. Weight Loss of Sample in Soil
2.1.2. Weight Loss of Samples in PBS
2.2. Changes in Molecular Weight of Incubated Samples
2.2.1. Degradation of Samples in Soil
2.2.2. Degradation of Samples in PBS
2.3. Changes in Blends Compositions
2.4. Changes in Blends Crystallinity
2.5. Surface Films Erosion
2.6. Plant Growth Tests
3. Discussion
4. Materials and Methods
4.1. Materials
4.2. Preparation of Polymer Films
4.3. Soil Burial Test
4.4. Incubation in PBS
4.5. Determination of the Weight Loss
4.6. pH Changes
4.7. Gel Permeation Chromatography (GPC)
4.8. Proton Nuclear Magnetic Resonance (1H NMR) Spectroscopy
4.9. Differential Scanning Calorimetry (DSC)
4.10. Surface Erosion of Polymer Films
4.11. Plant Growth Test of PPC
5. Conclusions
- (i)
- The degradation rate of the PLA/PPC blends was dependent on the ratio of both components regardless of the degradation medium; however, their time degradation was not satisfied from the mulching film application point of view;
- (ii)
- PPC demonstrated the highest degradation rate compared to all the other tested samples, and its presence in the blend facilitated the degradation of PLA/PPC blends. For this reason, PPC is a highly promising material for further searching for more enzymatically degraded compatible blends;
- (iii)
- Blends consisting of amorphous PLA and PPC demonstrated a faster degradation rate compared to their analogous blends based on the PLA grade that has the ability to crystalize;
- (iv)
- The phytotoxicity test of PPC did not show any harmful effect of this polymer on monocotyledonous and dicotyledonous plants; however, the highest concentration slightly inhibited the development of oat roots, which requires attention and further research. In this respect, this polymer can be successfully used for environmental protection and agricultural purposes, including mulching films and CRFs of agrochemicals (pesticides, fertilizers).
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Incubation in Soil | |||||||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Samples | Before Incubation | 3 Months | 9 Months | 18 Months | 24 Months | ||||||||||
Mw [g/mol] | Mn [g/mol] | Đ [−] | Mw [%] | Mn [%] | Đ [−] | Mw [%] | Mn [%] | Đ [−] | Mw [%] | Mn [%] | Đ [−] | Mw [%] | Mn [%] | Đ [−] | |
PPC | 211,200 | 40,000 | 5.28 | 99.0 | 103.0 | 5.09 | 88.8 | 81.5 | 5.76 | 93.2 | 85.5 | 5.75 | 69.3 | 80.8 | 4.54 |
crystPLA | 249,200 | 125,500 | 1.99 | 95.5 | 98.7 | 1.91 | 100.4 | 128.6 | 1.55 | 89.5 | 120.5 | 1.47 | 46.8 | 50.9 | 1.82 |
amorphPLA | 173,700 | 91,500 | 1.90 | 92.8 | 92.0 | 1.91 | 92.6 | 120.8 | 1.46 | 85.7 | 116.1 | 1.40 | 43.1 | 42.8 | 1.90 |
crystPLA/PPC 75/25 | 240,300 | 90,500 | 2.66 | 94.9 | 96.4 | 2.62 | 80.0 | 36.4 | 5.87 | 97.1 | 114.4 | 2.26 | 59.3 | 76.8 | 2.05 |
crystPLA/PPC 50/50 | 231,400 | 65,500 | 3.53 | 96.8 | 97.7 | 3.50 | 88.0 | 55.7 | 5.58 | 87.3 | 59.1 | 5.21 | 67.4 | 103.5 | 2.30 |
crystPLA/PPC 25/75 | 223,000 | 52,000 | 4.29 | 100.2 | 102.1 | 4.20 | 97.7 | 65.6 | 6.40 | 95.3 | 49.6 | 5.95 | 78.7 | 142.5 | 2.37 |
amorphPLA/PPC 75/25 | 185,700 | 78,400 | 2.37 | 92.1 | 93.6 | 2.33 | 102.8 | 71.9 | 3.39 | 106.1 | 111.4 | 2.26 | 49.2 | 50.9 | 2.29 |
amorphPLA/PPC 50/50 | 195,400 | 62,100 | 3.15 | 98.2 | 97.8 | 3.16 | 100.3 | 53.0 | 5.95 | 102.8 | 77.8 | 4.16 | 69.1 | 85.5 | 2.54 |
amorphPLA/PPC 25/75 | 206,300 | 48,200 | 4.28 | 96.8 | 95.2 | 4.35 | 99.1 | 65.6 | 6.47 | 99.9 | 68.0 | 6.25 | 74.6 | 119.3 | 2.68 |
Incubation in PBS | |||||||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Samples | Before Incubation | 1 Month | 3 Months | 6 Months | 12 Months | ||||||||||
Mw [g/mol] | Mn [g/mol] | Đ [−] | Mw [%] | Mn [%] | Đ [−] | Mw [%] | Mn [%] | Đ [−] | Mw [%] | Mn [%] | Đ [−] | Mw [%] | Mn [%] | Đ [−] | |
PPC | 211,200 | 40,000 | 5.28 | 83.4 | 81.0 | 5.43 | 83.4 | 72.0 | 6.11 | 84.1 | 81.8 | 5.43 | 62.6 | 100.8 | 3.28 |
crystPLA | 249,200 | 125,500 | 1.99 | 92.5 | 124.9 | 1.47 | 69.7 | 78.2 | 1.77 | 53.0 | 54.1 | 1.95 | 4.4 | 4.9 | 1.76 |
amorphPLA | 173,700 | 91,500 | 1.90 | 90.7 | 77.7 | 2.22 | 66.0 | 76.6 | 1.64 | 42.2 | 50.5 | 1.59 | N/D* | N/D* | N/D* |
crystPLA/PPC 75/25 | 240,300 | 90,500 | 2.66 | 93.6 | 72.7 | 3.42 | 88.8 | 91.4 | 2.58 | 72.5 | 67.5 | 2.85 | 24.0 | 21.4 | 3.02 |
crystPLA/PPC 50/50 | 231,400 | 65,500 | 3.53 | 104.8 | 97.1 | 3.81 | 92.8 | 74.1 | 4.43 | 88.8 | 84.7 | 3.71 | 46.3 | 57.4 | 2.85 |
crystPLA/PPC 25/75 | 223,000 | 52,000 | 4.29 | 99.5 | 85.8 | 4.97 | 96.6 | 87.3 | 4.75 | 93.3 | 84.4 | 4.73 | 62.6 | 92.7 | 2.90 |
amorphPLA/PPC 75/25 | 185,700 | 78,400 | 2.37 | 106.7 | 56.5 | 4.47 | 95.0 | 66.8 | 3.37 | 88.2 | 62.0 | 3.37 | 21.1 | 10.7 | 4.65 |
amorphPLA/PPC 50/50 | 195,400 | 62,100 | 3.15 | 109.4 | 69.9 | 4.92 | 105.2 | 76.5 | 4.33 | 102.1 | 73.4 | 4.37 | 51.6 | 21.1 | 7.70 |
amorphPLA/PPC 25/75 | 206,300 | 48,200 | 4.28 | 92.3 | 59.9 | 6.59 | 93.3 | 68.3 | 5.84 | 95.3 | 80.3 | 5.08 | 60.7 | 57.9 | 4.50 |
Incubation in Soil | |||||
---|---|---|---|---|---|
Sample | Before Incubation | 3 Months | 9 Months | 18 Months | 24 Months |
crystPLA/PPC 75/25 | 79/21 | 78/22 | 83/17 | 84/16 | 78/22 |
crystPLA/PPC 50/50 | 56/44 | 56/44 | 60/40 | 62/38 | 57/43 |
crystPLA/PPC 25/75 | 31/69 | 31/69 | 29/71 | 30/70 | 33/67 |
amorphPLA/PPC 75/25 | 79/21 | 79/21 | 78/22 | 77/23 | 80/20 |
amorphPLA/PPC 50/50 | 56/44 | 56/44 | 55/45 | 54/46 | 56/44 |
amorphPLA/PPC 25/75 | 31/69 | 31/69 | 29/71 | 19/81 | 33/67 |
Incubation in PBS | |||||
Sample | Before incubation | 1 month | 3 months | 6 months | 12 months |
crystPLA/PPC 75/25 | 79/21 | 78/22 | 79/21 | 79/21 | 77/23 |
crystPLA/PPC 50/50 | 56/44 | 57/43 | 56/44 | 59/41 | 55/45 |
crystPLA/PPC 25/75 | 31/69 | 31/69 | 33/67 | 34/66 | 39/61 |
amorphPLA/PPC 75/25 | 79/21 | 79/21 | 81/19 | 80/20 | 76/24 |
amorphPLA/PPC 50/50 | 56/44 | 56/44 | 57/43 | 56/44 | 54/46 |
amorphPLA/PPC 25/75 | 31/69 | 30/70 | 29/71 | 31/69 | 29/71 |
(°C) | (°C) | Tcc (°C) | ΔHcc (J/g) | Tm (°C) | ΔHm (J/g) | χC (%) | |
---|---|---|---|---|---|---|---|
Before Incubation | |||||||
PPC | N/D | 11.8 | N/D | N/D | N/D | N/D | N/D |
crystPLA | 44.6 | N/D | 104.6 | 22.6 | 139.8 144.4 | −25.0 | 2.58 |
amorphPLA | 38.5 | N/D | N/D | N/D | N/D | N/D | N/D |
crystPLA/PPC 75/25 | 38.6 | 19.1 | 103.8 | 19.9 | 137.2 143.4 | −21.1 | 1.79 |
crystPLA/PPC 50/50 | 35.5 | 14.3 | 101.6 | 13.7 | 135.5 143.0 | −14.9 | 2.58 |
crystPLA/PPC 25/75 | 36.8 | 17.1 | 101.8 | 7.41 | 137.6 144.6 | −8.48 | 4.60 |
amorphPLA/PPC 75/25 | 35.0 | 16.1 | N/D | N/D | N/D | N/D | N/D |
amorphPLA/PPC 50/50 | 32.3 | 15.1 | N/D | N/D | N/D | N/D | N/D |
amorphPLA/PPC 25/75 | 31.9 | 14.6 | N/D | N/D | N/D | N/D | N/D |
3 months | |||||||
PPC | N/D | 18.6 | N/D | N/D | N/D | N/D | N/D |
crystPLA | 45.5 | N/D | 106.1 | 23.5 | 140.1 145.2 | −27.5 | 4.39 |
amorphPLA | 41.5 | N/D | N/D | N/D | N/D | N/D | N/D |
crystPLA/PPC 75/25 | 40.4 | 19.0 | 105.8 | 19.8 | 138.1 144.4 | −20.2 | 0.66 |
crystPLA/PPC 50/50 | 41.0 | 19.1 | 105.5 | 15.4 | 139.7 145.2 | −15.8 | 0.80 |
crystPLA/PPC 25/75 | 41.5 | 21.3 | 112.0 | 5.09 | 143.2 | −5.70 | 2.62 |
amorphPLA/PPC 75/25 | 39.0 | 21.8 | N/D | N/D | N/D | N/D | N/D |
amorphPLA/PPC 50/50 | 37.2 | 18.1 | N/D | N/D | N/D | N/D | N/D |
amorphPLA/PPC 25/75 | 39.1 | 21.2 | N/D | N/D | N/D | N/D | N/D |
9 months | |||||||
PPC | N/D | 20.9 | N/D | N/D | N/D | N/D | N/D |
crystPLA | 43.8 | N/D | 104.0 | 27.1 | 138.5 146.2 | −27.7 | 0.66 |
amorphPLA | 41.9 | N/D | N/D | N/D | N/D | N/D | N/D |
crystPLA/PPC 75/25 | 42.4 | 21.0 | 107.6 | 22.4 | 139.8 146.0 | −23.4 | 1.51 |
crystPLA/PPC 50/50 | 42.3 | 19.4 | 106.4 | 15.3 | 140.1 146.1 | −16.0 | 1.38 |
crystPLA/PPC 25/75 | 44.1 | 26.3 | 112.6 | 4.50 | 144.2 149.9 | −4.81 | 1.33 |
amorphPLA/PPC 75/25 | 41.4 | 23.1 | N/D | N/D | N/D | N/D | N/D |
amorphPLA/PPC 50/50 | 40.4 | 22.0 | N/D | N/D | N/D | N/D | N/D |
amorphPLA/PPC 25/75 | 44.4 | 27.9 | N/D | N/D | N/D | N/D | N/D |
18 months | |||||||
PPC | N/D | 21.8 | N/D | N/D | N/D | N/D | N/D |
crystPLA | 54.9 | N/D | 114.7 | 31.7 | 146.5 | −31.7 | 0.00 |
amorphPLA | 40.6 | N/D | N/D | N/D | N/D | N/D | N/D |
crystPLA/PPC 75/25 | 46.3 | 24.6 | 106.2 | 24.7 | 141.2 148.1 | −24.7 | 0.00 |
crystPLA/PPC 50/50 | 40.3 | 20.1 | 103.4 | 18.6 | 138.9 146.8 | −18.6 | 0.00 |
crystPLA/PPC 25/75 | 43.9 | 25.0 | 112.7 | 7.5 | 143.8 149.8 | −7.5 | 0.00 |
amorphPLA/PPC 75/25 | 39.8 | 20.3 | N/D | N/D | N/D | N/D | N/D |
amorphPLA/PPC 50/50 | 40.6 | 22.6 | N/D | N/D | N/D | N/D | N/D |
amorphPLA/PPC 25/75 | 42.6 | 24.8 | N/D | N/D | N/D | N/D | N/D |
24 months | |||||||
PPC | N/D | 22.8 | N/D | N/D | N/D | N/D | N/D |
crystPLA | 45.2 | N/D | 101.1 | 38.6 | 136.9 146.6 | −33.1 | 0.00 |
amorphPLA | 42.1 | N/D | N/D | N/D | N/D | N/D | N/D |
crystPLA/PPC 75/25 | 42.1 | 20.4 | 104.3 | 27.60 | 137.8 145.9 | −25.18 | 0.00 |
crystPLA/PPC 50/50 | 41.9 | 20.3 | 102.1 | 19.25 | 138.5 146.6 | −17.86 | 0.00 |
crystPLA/PPC 25/75 | 45.9 | 26.9 | 114.4 | 6.69 | 144.5 * | −6.34 | 0.00 |
amorphPLA/PPC 75/25 | 40.1 | 21.8 | N/D | N/D | N/D | N/D | N/D |
amorphPLA/PPC 50/50 | 39.7 | 21.8 | N/D | N/D | N/D | N/D | N/D |
amorphPLA/PPC 25/75 | 43.7 | 27.4 | N/D | N/D | N/D | N/D | N/D |
PPC Concentration in Soil (mg/kg of Soil Dry Weight) | OAT | RADISH | ||
---|---|---|---|---|
Number of Emerged Seedlings | Germination % | Number of Emerged Seedlings | Germination % | |
Control | 18 | 100 | 18 | 100 |
100 | 19 | 104 | 18 | 96 |
250 | 19 | 104 | 17 | 93 |
500 | 19 | 104 | 17 | 95 |
1000 | 19 | 104 | 17 | 93 |
LSDS = 1 LSDC = 2 | LSDS = 1 LSDC = 1 |
PPC Conc. (mg/kg of Soil) | ||||||||
---|---|---|---|---|---|---|---|---|
Fresh Mass (g/pot) | Fresh Mass Related to Control [%] | Dry Weight (mg/g of Fresh Weight) | Dry Mass Related to Control [%] | Average Shoot Height [cm] | Average Shoot Height Related to Control [%] | Average Root Length [cm] | Average Root Length Related to Control [%] | |
Oat | ||||||||
0 | 2.34 | 100 | 0.2264 | 100 | 20.0 | 100 | 11.5 | 100 |
250 | 2.36 | 100.7 ± 5.3 | 0.2282 | 100.8 ± 4.1 | 19.6 | 98 ± 1.1 | 11.4 | 99.1 ± 2.2 |
500 | 2.30 | 98.4 ± 6.5 | 0.2190 | 96.7 ± 5.8 | 19.1 | 95.5 ± 0.9 | 10.9 | 94.8 ± 2.6 |
750 | 2.41 | 102.9 ± 3.7 | 0.2158 | 95.3 ± 2.6 | 19.5 | 97.5 ± 0.8 | 10.5 | 91.3 ± 3.4 |
1000 | 2.36 | 100.7 ± 2.2 | 0.1908 | 84.3 ± 7.4 | 19.2 | 96 ± 1.3 | 9.8 | 85.2 ± 1.9 |
Radish | ||||||||
0 | 2.42 | 100 | 0.1679 | 100 | 9.1 | 100 | 8.5 | 100 |
250 | 2.94 | 121.4 ± 3.7 | 0.2005 | 119.4 ± 6.0 | 8.9 | 97.8 ± 1.6 | 8.8 | 103.5 ± 1.5 |
500 | 2.89 | 119.6 ± 12.4 | 0.2012 | 119.8 ± 14.5 | 9.2 | 101.1 ± 3.3 | 8.8 | 103.5 ± 1.8 |
750 | 3.17 | 131.3 ± 10.4 | 0.2151 | 128.1 ± 20.0 | 8.8 | 96.7 ± 1.2 | 8.6 | 101.2 ± 2.5 |
1000 | 3.10 | 128.2 ± 5.4 | 0.2186 | 130.0 ± 4.9 | 8.8 | 96.7 ± 1.5 | 8.4 | 98.8 ± 1.4 |
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Szymanek, I.; Cvek, M.; Rogacz, D.; Żarski, A.; Lewicka, K.; Sedlarik, V.; Rychter, P. Degradation of Polylactic Acid/Polypropylene Carbonate Films in Soil and Phosphate Buffer and Their Potential Usefulness in Agriculture and Agrochemistry. Int. J. Mol. Sci. 2024, 25, 653. https://doi.org/10.3390/ijms25010653
Szymanek I, Cvek M, Rogacz D, Żarski A, Lewicka K, Sedlarik V, Rychter P. Degradation of Polylactic Acid/Polypropylene Carbonate Films in Soil and Phosphate Buffer and Their Potential Usefulness in Agriculture and Agrochemistry. International Journal of Molecular Sciences. 2024; 25(1):653. https://doi.org/10.3390/ijms25010653
Chicago/Turabian StyleSzymanek, Izabela, Martin Cvek, Diana Rogacz, Arkadiusz Żarski, Kamila Lewicka, Vladimir Sedlarik, and Piotr Rychter. 2024. "Degradation of Polylactic Acid/Polypropylene Carbonate Films in Soil and Phosphate Buffer and Their Potential Usefulness in Agriculture and Agrochemistry" International Journal of Molecular Sciences 25, no. 1: 653. https://doi.org/10.3390/ijms25010653