Sulfur-Based Copolymeric Polyamidoamines as Efficient Flame-Retardants for Cotton
Abstract
:1. Introduction
2. Materials and Methods
2.1. Materials
2.2. Methods
2.3. Synthesis of Homopolymeric PAAs
2.4. Synthesis of Copolymeric PAAs
2.5. Treatment of Cotton Fabrics
2.6. Combustion Tests
3. Results and Discussion
3.1. Synthesis of Homopolymeric and Copolymeric PAAs
3.2. Thermal Stability of PAAs
3.3. FT-IR and Morphological Characterization of PAA-Treated Cotton Fabrics
3.4. Thermal Characterization of PAA-Treated Cotton Fabrics
3.5. Combustion Characterization of PAA-Treated Cotton Fabrics
3.5.1. Vertical Flame Spread Tests
3.5.2. Horizontal Flame Spread Tests (HFST)
3.5.3. Cone Calorimetry Tests
3.5.4. Morphological Characterization and EDX Elemental Analysis of Combustion Residues
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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PAA | G/C Molar Ratio | [M] (g, mmol) | [G] (g, mmol) | [C] (g, mmol) | LiOH·H2O (g, mmol) | H2O (mL) | N (%) | S (%) |
---|---|---|---|---|---|---|---|---|
M–G | - | 3.08, 19.98 | 1.49, 19.98 | - | 0.87, 20.07 | 8.10 | 18.3 | - |
M–C | - | 1.54, 9.99 | - | 2.41, 9.99 | 0.86, 20.50 | 7.00 | 14.2 | 16.2 |
M–G70–C30 | 0.7/0.3 | 1.04, 6.75 | 0.35, 4.72 | 0.49, 2.05 | 0.37, 8.82 | 3.30 | 16.6 | 6.9 |
M–G60–C40 | 0.4/0.6 | 1.54, 9.99 | 0.45, 5.99 | 0.96, 3.99 | 0.60, 14.30 | 5.30 | 16.1 | 8.7 |
M–G50–C50 | 0.5/0.5 | 1.01, 6.55 | 0.24, 3.20 | 0.77, 3.22 | 0.42, 10.00 | 3.67 | 15.7 | 10.3 |
M–G30–C70 | 0.3/0.7 | 1.01, 6.55 | 0.15, 1.99 | 1.09, 4.54 | 0.48, 11.44 | 4.15 | 15.0 | 13.0 |
Cotton Sample | Add-on 1 (%) |
---|---|
Copolymers | |
COT/M–G70–C30 | 16.4 |
COT/M–G60–C40 | 16.3 |
COT/M–G50–C50 | 16.0 |
COT/M–G30–C70 | 16.2 |
Blends | |
COT/(M–G/M–C)70/30 | 16.2 |
COT/(M–G/M–C)50/50 | 16.5 |
COT/(M–G/M–C)30/70 | 16.5 |
Layers | |
COT/M–G/M–C | 16.1 |
COT/M–C/M–G | 16.2 |
PAA | Add-on (%) | Tonset10% 1 (°C) | Tmax1 2 (°C) | Tmax2 3 (°C) | RMF at 750 °C 4 (%) |
---|---|---|---|---|---|
Nitrogen | |||||
M–G | 16.0 | 146 | 144, 268 5 | - | 11.5 |
M–C | 16.0 | 154 | 146, 208, 246 5 | - | 4.0 |
M–G70–C30 | 16.4 | 152 | 2485, 322, 410 | - | 6.5 |
M–G60–C40 | 16.3 | 159 | 2465, 386, 410 | - | 5.5 |
M–G50–C50 | 16.0 | 158 | 213, 2535, 408 | - | 9.5 |
M–G30–C70 | 16.2 | 149 | 213, 2435, 408 | - | 2.0 |
Air | |||||
M–G | 16.0 | 148 | 139, 272 5 | 468 | 8.5 |
M–C | 16.0 | 170 | 221, 225, 250 5 | 449 | 22.0 |
M–G70–C30 | 16.4 | 154 | 155, 251 5 | 445 | 11.5 |
M–G60–C40 | 16.3 | 161 | 156, 243 | 444 | 18.0 |
M–G50–C50 | 16.0 | 161 | 162, 253 5 | 449 | 12.0 |
M–G30–C70 | 16.2 | 138 | 201, 240 5 | 449 | 9.0 |
Sample | Add-on (%) | Tonset10% 1 (°C) | Tmax1 2 (°C) | Tmax2 3 (°C) | RMF at 750 °C 4 (%) |
---|---|---|---|---|---|
Nitrogen | |||||
COT | - | 319 | 365 | - | 12.0 |
COT/M–G70–C30 | 16.4 | 251 | 327 | - | 18.0 |
COT/M–G60–C40 | 16.3 | 251 | 329 | - | 18.0 |
COT/M–G50–C50 | 16.0 | 251 | 328 | - | 18.0 |
COT/M–G30–C70 | 16.2 | 250 | 329 | - | 18.0 |
Air | |||||
COT | - | 304 | 345 | 480 | 0 |
COT/M–G70–C30 | 16.4 | 256 | 319 | 487 | 1.5 |
COT/M–G60–C40 | 16.3 | 256 | 319 | 492 | 2.0 |
COT/M–G50–C50 | 16.0 | 264 | 322 | 444 | 2.0 |
COT/M–G30–C70 | 16.2 | 242 | 317 | 500 | 4.0 |
Sample | Add-on (%) | Note | Combustion Time 1 (s) | Extinguishment (YES/NO) | RMF 2 (%) |
---|---|---|---|---|---|
COT | - | Flaming | 33 | NO | 2 |
Cotton fabrics treated with PAA copolymers | |||||
COT/M–G70–C30 | 16.4 | Flaming | 76 | NO | 31 |
COT/M–G60–C40 | 16.3 | Flaming | 191 | NO | 41 |
COT/M–G50–C50 | 16.0 | No flaming, only afterglow | 24 | YES | 95 |
COT/M–G30–C70 | 16.2 | No flaming, only afterglow | 23 | YES | 96 |
Cotton fabrics treated with PAA blends | |||||
COT/(M–G/M–C)70/30 | 16.2 | Flaming | 74 | NO | 27 |
COT/(M–G/M–C)50/50 | 16.5 | Flaming | 58 | NO | 32 |
COT/(M–G/M–C)30/70 | 16.5 | Flaming | 82 | NO | 35 |
Cotton fabrics treated with PAA layers | |||||
COT/M–G/M–C | 16.1 | Flaming | 73 | NO | 37 |
COT/M–C/M–G | 16.2 | Flaming | 112 | NO | 29 |
Sample | Add-on (%) | Combustion Time 1 (s) | Extinguishment (YES/NO) | RMF 2 (%) |
---|---|---|---|---|
COT | - | 50 | NO | 1 |
Cotton fabrics treated with PAA copolymers | ||||
COT/M–G70–C30 | 16.4 | 28 | YES | 94 |
COT/M–G60–C40 | 16.3 | 27 | YES | 82 |
COT/M–G50–C50 | 16.0 | 27 | YES | 85 |
COT/M–G30–C70 | 16.2 | 21 | YES | 88 |
Cotton fabric treated with PAA blend | ||||
COT/(M–G/M–C)50/50 | 16.5 | 34 | YES | 85 |
Cotton fabric treated with PAA layer | ||||
COT/M–G/M–C | 16.2 | 23 | YES | 80 |
Sample | Add-on (%) | TTI 1 (s) | PHRR 2 (kw m−2) | FRI 3 | THR 4 (MJ m−2) | [CO] (kg kg−1) | [CO2] (kg kg−1) | RMF 5 (%) |
---|---|---|---|---|---|---|---|---|
COT | - | 12 ±4 | 116 ±6 | - | 2.2 ±0.1 | 0.065 ±0.003 | 1.90 ±0.01 | - |
COT/M–G50–C50 copolymer | 16.0 | 18 ±1 | 53 ± 3 (−55%) 6 | 3.6 | 2.0 ±0.1 | 0.052 ±0.003 (−20%) 6 | 1.35 ±0.01 (−29%) 6 | 8.0 ± 0.5 |
COT/(M–G/M–C)50/50 blend | 16.5 | 14 ±1 | 66 ± 3 (−44%) 6 | 1.7 | 2.6 ±0.1 | 0.063 ±0.003 (−4%) 6 | 1.61 ±0.01 (−15%) 6 | 7.0 ± 0.5 |
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Beduini, A.; Carosio, F.; Ferruti, P.; Ranucci, E.; Alongi, J. Sulfur-Based Copolymeric Polyamidoamines as Efficient Flame-Retardants for Cotton. Polymers 2019, 11, 1904. https://doi.org/10.3390/polym11111904
Beduini A, Carosio F, Ferruti P, Ranucci E, Alongi J. Sulfur-Based Copolymeric Polyamidoamines as Efficient Flame-Retardants for Cotton. Polymers. 2019; 11(11):1904. https://doi.org/10.3390/polym11111904
Chicago/Turabian StyleBeduini, Alessandro, Federico Carosio, Paolo Ferruti, Elisabetta Ranucci, and Jenny Alongi. 2019. "Sulfur-Based Copolymeric Polyamidoamines as Efficient Flame-Retardants for Cotton" Polymers 11, no. 11: 1904. https://doi.org/10.3390/polym11111904