Determination of Residual Diisocyanates and Related Diamines in Biodegradable Mulch Films Using N-Ethoxycarbonylation Derivatization and GC-MS
Abstract
:1. Introduction
2. Results and Discussion
2.1. Optimization of Ultrasonic Hydrolysis and Extraction
2.2. Optimization of N-Ethoxycarbonylation Derivatization
2.3. Mass Spectra Identification of N-Ethoxycarbonylation Derivatives
2.4. Validation of Analytical Parameters
2.5. Analysis of Residual Diisocyanates and Related Diamines in PBAT Mulch Film Samples
3. Materials and Method
3.1. Chemicals and Reagent
3.2. Preparation of Standard Solution and Biodegradable Mulch Film Samples
3.3. Ultrasonic Hydrolysis and Extraction of Residual Diisocyanates and Related Diamines
3.4. N-Ethoxycarbonylation Derivatization of Diamines
3.5. Instruments and Chromatographic Conditions
3.6. Statistical Analysis
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
References
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Uncoded (Coded) Variables | Average Hydrolysis Efficiency of Each Class Diisocyanates | |||||||
---|---|---|---|---|---|---|---|---|
No | A/v/w | B/W | C/°C | D/min | Aliphatic | Cycloaliphatic | Amino Acid Ester | Aromatic |
1 | 60 (0) | 300 (1) | 50 (0) | 30 (−1) | 0.758 | 0.765 | 0.695 | 0.643 |
2 | 60 (0) | 200 (0) | 50 (0) | 60 (0) | 0.848 | 0.855 | 0.795 | 0.732 |
3 | 60 (0) | 300 (1) | 50 (0) | 90 (1) | 0.854 | 0.865 | 0.823 | 0.746 |
4 | 40 (−1) | 200 (0) | 70 (1) | 60 (0) | 0.911 | 0.923 | 0.652 | 0.795 |
5 | 80 (1) | 100 (−1) | 50 (0) | 60 (0) | 0.945 | 0.956 | 0.885 | 0.822 |
6 | 80 (1) | 200 (0) | 70 (1) | 60 (0) | 0.932 | 0.941 | 0.692 | 0.805 |
7 | 40 (−1) | 100 (−1) | 50 (0) | 60 (0) | 0.921 | 0.935 | 0.855 | 0.792 |
8 | 60 (0) | 200 (0) | 50 (0) | 60 (0) | 0.885 | 0.891 | 0.791 | 0.761 |
9 | 40 (−1) | 300 (1) | 50 (0) | 60 (0) | 0.862 | 0.885 | 0.785 | 0.751 |
10 | 60 (0) | 300 (1) | 30 (−1) | 60 (0) | 0.885 | 0.902 | 0.812 | 0.755 |
11 | 80 (1) | 200 (0) | 50 (0) | 90 (1) | 0.928 | 0.914 | 0.845 | 0.777 |
12 | 60 (0) | 300 (1) | 70 (1) | 60 (0) | 0.882 | 0.896 | 0.675 | 0.764 |
13 | 80 (1) | 200 (0) | 30 (−1) | 60 (0) | 0.905 | 0.912 | 0.821 | 0.812 |
14 | 60 (0) | 200 (0) | 50 (0) | 60 (0) | 0.865 | 0.885 | 0.818 | 0.752 |
15 | 60 (0) | 100 (−1) | 50 (0) | 30 (−1) | 0.865 | 0.883 | 0.754 | 0.761 |
16 | 60 (0) | 200 (0) | 50 (0) | 60 (0) | 0.892 | 0.912 | 0.789 | 0.785 |
17 | 40 (−1) | 200 (0) | 30 (−1) | 60 (0) | 0.918 | 0.932 | 0.849 | 0.798 |
18 | 80 (1) | 200 (0) | 50 (0) | 30 (−1) | 0.801 | 0.825 | 0.662 | 0.711 |
19 | 60 (0) | 100 (−1) | 50 (0) | 90 (1) | 0.932 | 0.918 | 0.835 | 0.794 |
20 | 60 (0) | 100 (−1) | 70 (1) | 60 (0) | 0.952 | 0.934 | 0.701 | 0.811 |
21 | 40 (−1) | 200 (0) | 50 (0) | 90 (1) | 0.912 | 0.915 | 0.823 | 0.799 |
22 | 60 (0) | 200 (0) | 30 (−1) | 90 (1) | 0.885 | 0.899 | 0.785 | 0.765 |
23 | 40 (−1) | 200 (0) | 50 (0) | 30 (−1) | 0.792 | 0.784 | 0.652 | 0.671 |
24 | 60 (0) | 100 (−1) | 30 (−1) | 60 (0) | 0.915 | 0.922 | 0.829 | 0.794 |
25 | 60 (0) | 200 (0) | 30 (−1) | 30 (−1) | 0.762 | 0.766 | 0.652 | 0.645 |
26 | 60 (0) | 200 (0) | 50 (0) | 60 (0) | 0.871 | 0.896 | 0.828 | 0.752 |
27 | 60 (0) | 200 (0) | 50 (0) | 60 (0) | 0.852 | 0.882 | 0.811 | 0.745 |
28 | 60 (0) | 200 (0) | 70 (1) | 90 (1) | 0.871 | 0.881 | 0.628 | 0.761 |
29 | 60 (0) | 200 (0) | 70 (1) | 30 (−1) | 0.785 | 0.795 | 0.605 | 0.682 |
30 | 80 (1) | 300 (1) | 50 (0) | 60 (0) | 0.835 | 0.845 | 0.802 | 0.722 |
ANOVA | Model p-value | <0.0001 | <0.0001 | <0.0001 | <0.0001 | |||
Lack of fit p-value | 0.2638 | 0.3110 | 0.0712 | 0.3418 | ||||
Coefficient of variation % | 2.49 | 2.53 | 3.61 | 2.72 | ||||
R2 | 0.9115 | 0.9018 | 0.9385 | 0.9034 |
Diamines | N-Ethoxycarbonyl Derivative of Diamines | ||||||
---|---|---|---|---|---|---|---|
Diamines | Structure | Class | pKa | Log Kow | RT a/min | RI b | Characteristic Ions c/m/z |
DAB | Aliphatic diamine | 10.51 | −0.69 | 25.487 | 1863.8 | 102; 142; 159; 187; 232 | |
DAP (IS) | Aliphatic diamine | 10.51 | −0.16 | 27.681 | 1974.3 | 102; 156; 128; 201; 246 | |
HDA | Aliphatic diamine | 10.51 | 0.04 | 29.562 | 2077.1 | 102; 130; 158; 215; 260 | |
IPDA | Cycloaliphatic diamine | 10.54 | 0.96 | 30.472 | 2185.7/ 2264.1 | 123; 212; 241; 269; 314 | |
LEE | Amino acid ester | 7.33 | — | 32.374 | 2264.1 | 156; 128; 226; 171; 272; 318 | |
2, 6 -TDA | Aromatic diamine | 8.42 | 2.34 | 39.626 | 2401.1 | 266; 121; 147; 194; 220 | |
2, 4 -TDA | Aromatic diamine | 9.31 | 1.99 | 40.239 | 2360.2 | 266; 121; 147; 194; 220 | |
DDCM | Cycloaliphatic diamine | 10.87 | 1.59 | 42.482 | 2384.5 | 128; 184; 265; 309; 354 |
Diamines | Linear Range/µg/mL | Regression Equation | R | LOD/µg/mL | LOQ/µg/mL | Stability |
---|---|---|---|---|---|---|
DAB | 0.02~2.00 | y = 0.385x + 0.0146 | 0.9999 | 0.0043 | 0.013 | 0.66 |
HDA | 0.04~4.00 | y = 0.315x + 0.0220 | 0.9997 | 0.0051 | 0.016 | 0.76 |
IPDA | 0.02~2.00 | y = 0.560x + 0.0265 | 0.9995 | 0.0025 | 0.0079 | 0.81 |
LEE | 0.02~2.00 | y = 0.359x − 0.00458 | 0.9992 | 0.0047 | 0.015 | 1.09 |
2, 6-TDA | 0.04~4.00 | y = 0.441x − 0.00637 | 0.9996 | 0.0036 | 0.011 | 2.35 |
2, 4-TDA | 0.04~4.00 | y = 0.487x + 0.00311 | 0.9996 | 0.0031 | 0.0097 | 1.57 |
DDCM | 0.02~2.00 | y = 0.269x + 0.00950 | 0.9990 | 0.0057 | 0.018 | 1.03 |
Diamines | Content/ µg/g | Concentration/µg/g | Recovery (Repeatability)/% | Reproducibility/% | ||
---|---|---|---|---|---|---|
Low Spiked | High Spiked | Low Spiked | High Spiked | |||
DAB | — | 0.10 | 1.00 | 98.3 (1.25) | 99.6 (0.89) | 2.12 |
HDA | — | 5.00 | 10.00 | 97.2 (2.00) | 101.2 (1.45) | 3.08 |
IPDA | — | 0.10 | 1.00 | 97.6 (2.44) | 99.7 (2.02) | 2.98 |
LEE | — | 0.10 | 1.00 | 95.5 (4.89) | 98.2 (3.18) | 6.12 |
2, 6-TDA | 21.85 | 10.00 | 20.00 | 94.7 (6.74) | 97.7 (4.65) | 8.34 |
2, 4-TDA | 63.81 | 30.00 | 60.00 | 93.9 (8.12) | 98.1 (6.24) | 10.56 |
DDCM | — | 0.10 | 1.00 | 95.3 (3.45) | 99.3 (2.77) | 5.11 |
Content/µg/g | PBAT-1 | PBAT-2 | PBAT-3 |
---|---|---|---|
DAB | ND a | ND | ND |
HDA | ND | ND | 10.23 ± 0.28 |
IPDA | ND | ND | ND |
LEE | ND | ND | ND |
2, 6-TDA | 0.69 ± 0.08 | 21.85 ± 1.64 | ND |
2, 4-TDA | 1.43 ± 0.15 | 63.81 ± 4.05 | ND |
DDCM | ND | ND | ND |
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Cai, K.; Lin, Y.; Ma, Y.; Yang, Z.; Yu, L.; Zhang, J.; Xu, D.; Zeng, R.; Gao, W. Determination of Residual Diisocyanates and Related Diamines in Biodegradable Mulch Films Using N-Ethoxycarbonylation Derivatization and GC-MS. Molecules 2022, 27, 6754. https://doi.org/10.3390/molecules27196754
Cai K, Lin Y, Ma Y, Yang Z, Yu L, Zhang J, Xu D, Zeng R, Gao W. Determination of Residual Diisocyanates and Related Diamines in Biodegradable Mulch Films Using N-Ethoxycarbonylation Derivatization and GC-MS. Molecules. 2022; 27(19):6754. https://doi.org/10.3390/molecules27196754
Chicago/Turabian StyleCai, Kai, Yechun Lin, Yunfei Ma, Zhixiao Yang, Lei Yu, Jie Zhang, Dongqing Xu, Rong Zeng, and Weichang Gao. 2022. "Determination of Residual Diisocyanates and Related Diamines in Biodegradable Mulch Films Using N-Ethoxycarbonylation Derivatization and GC-MS" Molecules 27, no. 19: 6754. https://doi.org/10.3390/molecules27196754